compost, herbicide composition, herbicide mixtures, method for controlling the growth of unwanted ve

专利摘要:
The present invention relates to compounds of Formula 1, including all stereoisomers, N-oxides, and their salts, wherein Q, Z, R2, R3 and m are as defined in the present invention. The present invention also relates to compositions containing the compounds of Formula 1 and methods for controlling unwanted vegetation which comprises contacting the unwanted vegetation or its environment with an effective amount of a compound or composition of the present invention.
公开号:BR112016016443B1
申请号:R112016016443-1
申请日:2015-01-09
公开日:2020-07-28
发明作者:Nicholas Ryan Deprez；Ravisekhara P. Reddy；Paula Louise Sharpe；Thomas Martin Stevenson
申请人:Fmc Corporation；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] The present invention relates to certain pyrimidinyloxy benzene derivatives, their N-oxides and salts, and the compositions and methods of their use for the control of unwanted vegetation. BACKGROUND OF THE INVENTION
[002] The control of unwanted vegetation is extremely important to achieve high crop efficiency. The selective control of weed growth, especially in useful crops such as rice, soybeans, sugar beet, corn, potatoes, wheat, barley, tomatoes and plantation crops, among others, is highly desired. The uncontrolled growth of weeds in such useful crops can cause a significant reduction in productivity and therefore result in increased costs for the consumer. The control of unwanted vegetation in uncultivated areas is also important. Many products are commercially available for these purposes, but the need continues for new compounds that are more effective, less expensive, less toxic, environmentally safe or that have different mechanisms of action.
[003] JP 61,236,766 A (Sumitomo, 1986) describes certain carbon-linked pyrimidinyloxy derivatives as herbicides. WO 1994/17059 (Nippon Soda, 1994) describes certain carbon-linked pyrimidinyloxy benzene derivatives as herbicides. BRIEF DESCRIPTION OF THE INVENTION
[004] The present invention relates to the compounds of Formula 1 (including all stereoisomers), (N-oxides and their salts), the agricultural compositions containing them and their use as herbicides:
- Q is a 5- or 6-membered aromatic heterocyclic ring, linked to the rest of Formula 1 through a carbon atom, and optionally substituted by 1 to 4 R1; - Z is O or S; - each R1, independently, is halogen, cyan, nitro, SFs, CHO, C (= O) NH2, C (= S) NH2, SO2NH2, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, haloalkyl C1-C4, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C4-C8 cycloalkylalkyl, C2-C6-cycloalkyl, alkoxycarbonyl, alkoxycarbonyl C3-C7, C2-C8 alkylaminocarbonyl, C3-C10 dialkylaminocarbonyl, C1-C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-C4 haloalkoxy, C3-C4 haloalkoxy, C3-C4 halo, alkoxyalkyl C3-C6, C4-C8 cycloalkylalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 alkoxyalkyl, C2-C6 alkoxyalkyl, C2-C4alkylalkyl, C2-C6alkyl, alkoxy C2-C6, alkali C2-C4, SOnR1A, Si (CH3) 3 OR B (-OC (R1B) 2C (R1B) 2O-); OR a phenyl ring optionally substituted by up to 5 substituents independently selected from R1C; or a 5- or 6-membered heteroaromatic ring containing the ring members selected from carbon atoms and up to 4 heteroatoms independently selected from atoms of up to 2 O, up to 2 S and up to 4 N, each ring optionally substituted by up to 3 substituents independently selected from R1C on the carbon atom ring members and R1D on the nitrogen atom ring members; - R2 is halogen, cyano, nitro, C1-C4 alkoxy, C1-C4 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, SOnR4, C1-C4 haloalkyl or C3-C6 cycloalkyl; - each R3, independently, is halogen, cyano, hydroxy, nitro, amino, CHO, C (= O) NH2, C (= S) NH2, SO2NH2, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl , C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl C2-C6alkylalkyl, C2-C6alkyl, C2-C6alkyl, C2-C6alkyl , C3-C7 cycloalkylcarbonyl, C1-C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-C4 haloalkoxy, C3-C4 haloalkyloxy C3-C4 haloalkynoxy C3-C6 cycloalkyl C3-C6 cycloalkyl, C6-C6 cycloalkyl , C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 alkoxyalkyl, C2-C6 alkoxyalkyl, C2-C4 alkylcarbonyloxy, C2-C6 cyanoalkyl, C2-C6 cyanoalkoxy, C3-C3- (CH3) 3, C (= O) N (R3A) (R3B), C (= NOR3C) H, C (= NR3D) H, SOnR3E; or a phenyl ring optionally substituted by up to 5 substituents independently selected from R3F; or a 5- or 6-membered heteroaromatic ring containing the ring members selected from carbon atoms and up to 4 heteroatoms independently selected from atoms of up to 2 O, up to 2 S and up to 4 N, each ring optionally substituted by up to 3 substituents independently selected from R3F on the ring members of carbon atoms and R3G on the ring members of nitrogen atoms; or pyrimidinyloxy; - m is 0, 1,2 or 3; - each n, independently, is 0, 1 or 2; each R1A, R2, and R3E, independently, is C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkylamino or C2-C6 dialkylamino; - each R1B, independently, is H or C1-C4 alkyl, - each R1 independently, is 0 hydroxy, halogen, cyano, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy or Ci-Ce haloalkoxy; each R1D independently is 0 cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy or C2-C6 alkylcarbonyl; each R3A independently is C1-C4 alkyl or C1-C4 haloalkyl; each R3B independently is H, C1-C4 alkyl or C1-C4 haloalkyl; - each R3C, independently, is H or C1-C4 alkyl; - each R30, independently, is H, amino, C1-C4 alkyl or C1-C4 alkylamino; each R3F independently is hydroxy, halogen, cyano, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy or Ci-Ce haloalkoxy; and - each R3G, independently, is 0 cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy or C2-C6 alkylcarbonyl;
[005] More particularly, the present invention relates to a compound of Formula 1 (including all stereoisomers), an A / -oxide or a salt thereof. The present invention also relates to a herbicidal composition comprising a compound of the present invention (i.e., in an amount effective as a herbicide) and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents . The present invention further relates to a method for controlling the growth of unwanted vegetation which comprises contacting the vegetation or its environment with a herbicidal amount of a compound of the present invention (for example, such as a composition described herein) ).
[006] The present invention also relates to a herbicide mixture comprising (a) a compound selected from Formula 1, its N-oxides, and its salts, and (b) at least one additional active ingredient selected from (b1) to (b16); and the salts of compounds from (b1) to (b16). DETAILED DESCRIPTION OF THE INVENTION
[007] As used herein, the terms "comprises", "which comprises", "includes", "including", "has", "having", "contains", "containing", "characterized by" or any other variations, are intended to cover non-exclusive inclusion, subject to any explicitly stated limitations. For example, a composition, mixture, process, method, which comprises a list of elements is not necessarily limited to just those elements, but may include other elements that are not expressly listed or inherent in that composition, mixture, process or method.
[008] The transition phrase “which consists of” excludes any unspecified element, step or ingredient. If in the claim, this would restrict the claim to include materials other than those cited, except for impurities normally associated with the same materials. When the phrase "consisting of" appears in a clause in the body of a claim, instead of immediately after the preamble, it will only limit the element presented in that clause; other elements are not excluded from the claim as a whole.
[009] The transition phrase “which essentially consists of” is used to define a process or method of composition that includes materials, steps, characteristics, components or elements, in addition to those described literally, provided that these additional materials, steps, characteristics, components or elements do not materially affect the basic and innovative feature (s) of the claimed invention. The term "which essentially consists of" occupies an intermediate position between "that comprises" and "that consists of".
[010] In the event that the Depositors have defined an invention or a part of it with an open term, such as “that it understands” it should be easily understood that (unless otherwise stated) the description should be interpreted also describing that invention, using the terms “which essentially consists of” or “which consists of”.
[011] Furthermore, unless otherwise specified, “or” refers to an inclusion and not an exclusion. For example, a condition A or B is satisfied by any of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
[012] Furthermore, the indefinite articles "one" and "one" that precede an element or component of the present invention are intended to be non-restrictive in terms of the number of cases (i.e., occurrences) of the element or component. Therefore, "one" or "one" should be read including one or at least one, and the form of the singular word for the element or component also includes the plural, unless the number obviously means the singular.
[013] As mentioned in the present, the term “seedling”, used alone or in combination of words means a young plant developing from the embryo of a seed.
[014] As referred to herein, the term “broad leaf” used alone or in terms such as “broad leaf weeds” means dicotile or dicotyledonous, a term used to describe a group of angiosperms characterized by embryos that have two cotyledons .
[015] As used herein, the term "alkylating agent" refers to a chemical compound, in which a carbon-containing radical is attached through a carbon atom to an leaving group such as halide or sulfonate, which is displaced by the attachment of a nucleophile to said carbon atom. Unless otherwise indicated, the term "alkylation" does not limit the radical containing carbon to alkyl; the carbon-containing radicals in the alkylating agents include a series of carbon-linked substituent radicals specified for Q, R1 and R3
[016] In the above quotations, the term "alkyl", used alone or in compound words, such as "alkylthio" or "haloalkyl", includes straight or branched chain alkyl, such as methyl, ethyl, n-propyl , / '- propyl or the different isomers of butyl, pentyl or hexyl. The term "alkenyl" includes straight or branched chain alkenes such as ethylene, 1 propenyl, 2 propenyl, and the different isomers of butenyl, pentenyl and hexenyl. The term "alkenyl" also includes polyenes such as 1,2-propadienyl and 2,4 hexadienyl. The term "alkynyl" includes straight or branched chain alkines such as ethynyl, 1 propynyl, 2 propynyl and the different isomers of butynyl, pentynyl and hexynyl.
[017] The term "alkoxy", for example, includes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different isomers of butoxy, pentoxy and hexyloxy. The term "alkoxyalkyl" means the substitution of alkoxy to alkyl. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2. The term "alkenyloxy" includes straight or branched chain alkenyloxy moieties. Examples of "alkenyloxy" include H2C = CHCH2O, (CH3) 2C = CHCH2O, (CH3) CH = CHCH2O, (CH3) CH = C (CH3) CH2O and CH2 = CHCH2CH2O. The term "alkynyloxy" includes straight or branched chain alkynyloxy moieties. Examples of "alkynyloxy" include HC = CCH2O, CHsC ^ CCFW and CHsC ^ CCFhCFhO. The term "alkylthio" includes straight or branched chain alkylthio moieties such as methylthio, ethylthio, and the different isomers of propylthio, butylthio, pentylthio and hexylthio. The term "alkylthioalkyl" means the substitution of alkylthio in alkyl. Examples of "alkylthioalkyl" include CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2 and CH3CH2SCH2CH2. The term "alkylthioalkoxy" means the substitution of alkylthio in alkoxy. The term "cyanoalkyl" means an alkyl group substituted by a cyano group. Examples of "cyanoalkyl" include NCCH2, NCCH2CH2 and CH3CH (CN) CH2. The term "alkylamino", "dialkylamino", and the like, are defined analogously to the above examples.
[018] The term "cycloalkyl", for example, includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "halogen", alone or in compound words such as "haloalkyl", or when used in descriptions, such as "halogen substituted alkyl" includes fluorine, chlorine, bromine or iodine. In addition, when used in compound words, such as “haloalkyl”, or when used in descriptions, such as “halogen substituted alkyl”, said alkyl can be partially or completely replaced by halogen atoms, which can be the same or many different. Examples of "haloalkyl" or "halogen substituted alkyl" include F3C-, CICH2-, CF3CH2- and CF3CCI2. The term "haloalkoxy" and the like is defined analogously to the term "haloalkyl". Examples of "haloalkoxy" include CF3O-, CCI3CH2O-, HCF2CH2CH2O- and CF3CH2O-. The term "alkylcarbonyl" means straight or branched chain alkyl moieties attached to a -C (= O) moiety. Examples of "alkylcarbonyl" include CH3-C (= O) -, CH3CH2CH2-C (= O) - and (CH3) 2CH-C (= O) -. Examples of "alkoxycarbonyl" include CH3O-C (= O) -, CH3CH2O-C (= O) -, CH3CH2CH2O-C (= O) -, (CH3) 2CHO-C (= O) - and the different isomers butoxy or pentoxycarbonyl.
[019] The total number of carbon atoms in a substituent group is indicated by the prefix “Ci-Cf, where i and j are numbers from 1 to 6. For example, C1-C4 alkylsulfonyl means from methylsulfonyl to butylsulfonyl; alkoxyalkyl C2 designates CH3OCH2-; C3 alkoxyalkyl means, for example, CH3CH (OCH3) -, CH3OCH2CH2- or CH3CH2OCH2-; and C4 alkoxyalkyl refers to the various isomers of an alkyl group substituted by an alkoxy group containing a total of four carbon atoms, examples include CH3CH2CH2OCH2- and CH3CH2OCH2CH2-.
[020] When a compound is replaced by a substituent that supports a subscript that indicates the number of said substituents may exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents, (for example, [R3) n], n is 0, 1, 2 or 3). Furthermore, when the subscript indicates a range, for example, (R) H, therefore, the number of substituents can be selected from the integers between i and j, inclusive. When a group containing a substituent that may be 0 hydrogen, for example, (where m = 0), therefore, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said unsubstituted group. When a variable group is shown to be optionally attached to a position, (for example, R1n), linked to the Q where n can be 0, therefore, the hydrogen can be in the position, even if not recited in the definition of the group variable. When it is said that one or more positions in a group are "unsubstituted" or "unsubstituted", therefore, the hydrogen atoms are attached to assume any free valence.
[021] Unless otherwise indicated, a "ring" as a component of Formula 1 (for example, the Q substituent) is carbocyclic or heterocyclic. The term "ring member" refers to an atom or hetero atom forming the main chain of a ring. When a completely unsaturated carbocyclic ring meets Hückel's rule, therefore, this ring is also called an "aromatic ring". The term "saturated carbocyclic" refers to a ring that has a backbone consisting of carbon atoms linked together through simple bonds; unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms.
[022] The terms "heterocyclic ring", "heterocycle" mean a ring in which at least one ring atom forming the main chain is not carbon, for example, it is nitrogen, oxygen or sulfur. Normally, a heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygen atoms and no more than 2 sulfur. Unless otherwise indicated, a heterocyclic ring can be a saturated, partially unsaturated, or totally unsaturated ring. When a totally unsaturated heterocyclic ring meets Hückel's rule, then this ring is also called a "heteroaromatic ring" or "aromatic heterocyclic ring". Unless otherwise indicated, heterocyclic rings can be linked through any available carbon or nitrogen atom by replacing a hydrogen in said carbon or nitrogen.
[023] The term "aromatic" indicates that each of the ring atoms is essentially on the same plane and has a p orbital perpendicular to the ring plane, and that (4n + 2) TT electrons, where n is a positive integer, are associated with the ring to comply with Hückel's rule.
[024] The term "optionally substituted" in connection with heterocyclic rings refers to groups that are unsubstituted or, at least, have a substituent other than hydrogen that does not extinguish the biological activity possessed by the unsubstituted analog. As used herein, the following definitions apply, unless otherwise stated. The term “optionally substituted” is used interchangeably with the phrase “substituted or not substituted” or with the term “(not) substituted”. Unless otherwise indicated, an optionally substituted group may contain a substituent at each substitution position in the group, and each substitution is independent of the other.
[025] When Q is a 5- or 6-membered heterocyclic ring (containing nitrogen), it can be linked to the rest of Formula 1 through any available carbon or nitrogen ring atom, unless otherwise stated. As noted above, Q may be (among others) phenyl optionally substituted by one or more substituents selected from a group of substituents as defined in the Brief Description of the Invention. An example of phenyl optionally substituted with one to five substituents is the ring illustrated as U-1 in Exhibit 1, where Rv is R1, as defined in the Brief Description of the Invention for Q and r is an integer (from 0 to 4).
[026] As noted above, Q can be (among others) a 5- or 6-membered aromatic heterocyclic ring, which can be saturated or unsaturated, optionally substituted by one or more substituents selected from a group of substituents as defined in Brief Description of the Invention. Examples of a 5- or 6-membered unsaturated aromatic heterocyclic ring optionally substituted by one or more substituents include the rings from U 2 to U-61 illustrated in Exhibit 1, where Rv is any substituent as defined in the Brief Description of the Invention for Q (ie, R1) and er is an integer from 0 to 4, limited to the number of positions available in each U group. Like U-29, U-30, U-36, U-37, U-38, U-39, U-40, U-41, U-42 and U-43 have only one position available, for these groups U, r is limited to integers 0 or 1, and r being 0 means that the group U is not substituted and a hydrogen atom is present at the position indicated by (Rv) r.

[027] Although the Rv groups are shown in structures from U-1 to U-61, it should be noted that they do not need to be present since they are the optional substituents. Note that when Rv is H when attached to an atom, this is the same as if that atom was unsubstituted. The nitrogen atoms that require replacement to fill their valence are replaced by H or Rv. Note that when the connection point between (Rv) r and the group U is illustrated as floating, the (Rv) r can be attached to any available carbon atom or nitrogen atom in the group U. Note that when the attachment point in the group U is shown as floating, the U group can be linked to the rest of Formula 1 through any carbon or the nitrogen available from the U group by replacing a hydrogen atom. Note that some U groups can only be replaced by groups less than 4 Rv (for example, from U-2 to U-47 and from U-52 to U-61).
[028] A wide variety of synthetic methods are known in the art to enable the preparation of aromatic and non-aromatic heterocyclic rings and ring systems; for extensive evaluations see the set of eight volumes of Comprehensive Heterocyclic Chemistri, AR editors-in-chief Katritzki and CW Rees, Pergamon Press, Oxford, 1984 and the set of twelve volumes of Comprehensive Heterociclic Chemistri II, AR Katritzki, editors-in-chief CW Rees and EFV Scriven, Pergamon Press, Oxford, 1996.
[029] The compounds of the present invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. Stereoisomers are isomers of identical constitution, but which differ in the arrangement of their atoms in space and include enantiomers, diastereomers, cis-trans isomers (also known as geometric and atropisomers). Atropisomers result from restricted rotation around simple connections where the rotation barrier is high enough to allow the isolation of isomeric species. A person skilled in the art will consider that a stereoisomer may be more active and / or may exhibit beneficial effects when enriched in relation to the other stereoisomer (s) or when separated from the other stereoisomer (s) ). In addition, a person skilled in the art knows how to separate, enrich and / or selectively prepare said stereoisomers. The compounds of the invention can be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
[030] Formula 1 compounds usually exist in more than one form, and Formula 1 therefore includes all crystalline and non-crystalline forms of the compounds it represents. Non-crystalline forms include embodiments that are solid, such as waxes and gums, as well as embodiments that are liquid, such as solutions and melts. Crystalline forms include the embodiments that essentially represent a single type of crystal and the embodiments, which represent a mixture of polymorphs (i.e., different crystalline types). The term "polymorph" refers to a particular crystalline form of a chemical compound that can crystallize into different crystalline forms, those forms with different arrangements and / or conformations of the molecules in the crystalline structure. Although the polymorphs may have the same chemical composition, they may also differ in composition due to the presence or absence of cocrystallized water or other molecules, which may be weakly or strongly bound in the structure. Polymorphs can differ in such chemical, physical and biological properties as crystal form, density, hardness, color, chemical stability, melting point, hygroscopicity, suspension, dissolution rate and biological availability. One skilled in the art will consider that a polymorph of a compound of Formula 1 may have beneficial effects (for example, suitability for the preparation of useful formulations, better biological performance) over another polymorph or a mixture of polymorphs of the same represented compound by Formula 1. The preparation and isolation of a special polymorph of a compound represented by Formula 1 can be obtained by methods known to those skilled in the art, including, for example, crystallization, using the selected solvents and temperatures. For a comprehensive discussion of polymorphism, see R. Hilfiker, Ed., Polimorphism in the Pharmaceutical Industri, Wilei-VCH, Weinheim, 2006.
[031] A person skilled in the art will understand that not all heterocycles containing nitrogen can form N-oxides since nitrogen requires an available pair for oxidation to oxide; a person skilled in the art will recognize the nitrogen-containing heterocycles that can form N-oxides. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation of N-oxides of heterocycles and tertiary amines are well known to a person skilled in the art, including the oxidation of heterocycles and tertiary amines with peroxy acids, such as peracetic acid and m-chloroperbenzoic acid (MCPBA) , hydrogen peroxide, alkyl hydroperoxides, such as t-butyl hydroperoxide, sodium perborate, and dioxirans, such as dimethyldioxirane. These methods for the preparation of N-oxides are extensively described and reviewed in the literature, see, for example: T. L. Gilchrist in Comprehensive Organic Sinthesis, volume 7, pages 748 to 750, S. V. Lei, ed., Pergamon Press; Tisler M. and B. Stanovnik in Comprehensive Heterociclic Chemistri, volume 3, pages 18 to 20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterociclic Chemistri, volume 43, pages 149 to 161, A. R. Katritzki, ed., Academic Press; Tisler M. and B. Stanovnik in Advances in Heterociclic Chemistri, volume 9, pages 285 to 291, A. R. Katritzki and A. J. Boulton, Eds. Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterociclic Chemistri, volume 22, pages 390 to 392, A. R. Katritzki and A. J. Boulton, Eds., Academic Press.
[032] A person skilled in the art recognizes that because in the environment and under physiological conditions the salts of chemical compounds are in balance with their corresponding non-salt forms, the salts share the biological utility of non-salt forms. Therefore, a wide variety of salts of the compounds of Formula 1 are useful for the control of invertebrate pests (that is, they are agriculturally suitable). The salts of Formula 1 compounds include acid addition salts with inorganic or organic acids, such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic acids , salicylic, tartaric, 4-toluenesulfonic or valeric. When a compound of Formula 1 contains an acidic unit, such as a carboxylic acid or phenol, salts include those formed with organic or inorganic bases, such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or sodium carbonates, potassium, lithium, calcium, magnesium or barium. Accordingly, the present invention comprises compounds selected from Formula 1, their A / -oxides and agriculturally suitable salts.
[033] The embodiments of the present invention, as described in the Brief Description of the Invention, include (wherein Formula 1, as used, in the following embodiments, includes its A-oxides and salts):
[034] Realization 1. A compound of Formula 1, where Q is selected from:

-where r is 0, 1,2 or 3; es is 0 or 1.
[035] Realization 2. A compound of Realization 1, where Q is selected from Q-1 to Q-42.
[036] Realization 3. A compound of Realization 2, where Q is selected from Q-7 to Q-24.
[037] Realization 4. A compound of Realization 3, where Q is selected from Q-16 and Q-18.
[038] Realization 5. A compound of Realization 4, where Q is Q-16.
[039] Realization 6. A compound of Realization 4, where Q is Q-18.
[040] Realization 7. A compound from Realization 1, where Q is selected from Q-43 to Q-55.
[041] Embodiment 8. A compound from Embodiment 7, where Q is selected from Q-43, Q-44, Q 45, Q-48, Q-49 and Q-50.
[042] Realization 9. A compound of Realization 8, where Q is selected from Q-43, Q-44 and Q-45.
[043] Realization 10. A compound of Realization 9, where Q is Q-43.
[044] Realization 11. A compound of Realization 10, where Q is Q-45.
[045] Embodiment 12. A compound of Formula 1 or any of Embodiments 1 through 11, singly or in combination, where Z is O.
[046] Embodiment 13. A compound of Formula 1 or any of Embodiments 1 through 12, alone or in combination, in which each R1, independently, is halogen, cyan, SFs, CHO, C1-C4 alkyl, alkenyl C2-C4, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1-C4alkoxy, C1-4 alkoxy, C1-4 alkoxy C3-C4, C1-C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkynoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 cyanoalkyl, C1-C4 hydroxyalkyl, C1-C2-alkyl, Alkylalkyl
[047] Embodiment 14. A compound from Embodiment 13, wherein each R1, independently, is halogen, cyano, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2- haloalkenyl C4, C2-C4 haloalkyl, C1-C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkynoxy, C2-C6alkoxyalkyl, C2-C6alkyl, haloalkyl C4, C2-C4 alkylthioalkyl or SOnR
[048] Embodiment 15. A compound from Embodiment 14, wherein each R1, independently, is 0 halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy or S0nR1A.
[049] Embodiment 16. A compound from Embodiment 15, wherein each R1, independently, is halogen, C1-C4 alkyl, C1-C4 haloalkyl or C1-C4 haloalkoxy.
[050] Embodiment 17. A compound from Embodiment 16, wherein each R1, independently, is halogen, C1-C4 haloalkyl or C1-C4 haloalkoxy.
[051] Realization 18. A compound of Realization 17, where each R1, independently, is halogen or haloalkyl C1-C4.
[052] Embodiment 19. A compound from Embodiment 18, wherein each R1, independently, is F, Cl, Br, CF3, CHF2 or CH2F.
[053] Realization 20. A compound of Formula 1 or any of Realizations 1 to 19, alone or in combination, where r is 0, 1 or 2.
[054] Achievement 20a. A compound from Realization 20, where r is 1.
[055] Embodiment 21. A compound of Formula 1 or any of Embodiments 1 through 19, singly or in combination, where s is 1.
[056] Achievement 21a. A compound of Formula 1 or any of Embodiments 1 through 20a, alone or in combination, wherein, when Q is Q-16 and r is 1, therefore, R1 is attached at the 5-position of the Q-16 ring.
[057] Output 21b. A compound of Formula 1 or any of Embodiments 1 through 20a, alone or in combination, where, when Q is Q-18 and r is 1, therefore, R1 is attached at position 3 of the Q-18 ring.
[058] Realization 22. A compound of Formula 1 or any of Realizations 1 to 21b, alone or in combination, where R2 is halogen, C1-C4 alkyl or C1-C4 haloalkyl.
[059] Embodiment 23. A compound from Embodiment 22, where R2 is halogen or C1-C4 alkyl.
[060] Realization 24. A compound from Realization 23, where R2 is halogen or CH3.
[061] Realization 25. A compound from Realization 24, where R2 is 0 halogen.
[062] Realization 26. A compound of Realization 25, where R2 is F, Cl or Br.
[063] Embodiment 27. A compound of Formula 1 or any of Embodiments 1 through 26, singly or in combination, where m is 0, 1 or 2.
[064] Realization 28. A compound of Realization 27, where m is 0 or 1.
[065] Realization 29. A compound of Realization 28, where m is 1.
[066] Realization 30. A compound of Realization 27, where m is 0 (that is, in positions 3, 4, 5 and 6 are not replaced by R3).
[067] Embodiment 31. A compound of Formula 1 or any of Embodiments 1 to 30, singly or in combination, where each R3, independently, is halogen, cyano, CHO, C1-C4 alkyl, C2- alkenyl C4, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C4 haloalkyl, C2-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C2-C6 alkylcarbonyl, C2-C6alkyl, haloalkylcarbonyl C6, C1-C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkyloxy, C3-C6 cycloalkoxy, C3-C6alkylalkoxy, C3-alkoxyalkyl C6, C2-C4 alkylcarbonyloxy, C2-C6 cyanoalkyl, C (= O) N (R3A) (R3B), C (= NOR3C) H, SOnR3E; or a phenyl ring optionally substituted by up to 5 substituents independently selected from R3F; or a 5- or 6-membered heteroaromatic ring containing the ring members selected from carbon atoms and up to 4 heteroatoms independently selected from atoms of up to 2 O, up to 2 S and up to 4 N, each ring optionally substituted by up to 3 substituents independently selected from R3F on the carbon atom ring members and R3G on the nitrogen atom ring members.
[068] Embodiment 32. A compound from Embodiment 31, wherein each R3, independently, is halogen, cyano, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2- haloalkenyl C4, C2-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1-C4 alkoxy, C1-40 haloalkyl, alkoxy2-alkoxy6 C6, C2-C6 cyanoalkyl, SOnR3E; or a 5- or 6-membered heteroaromatic ring containing the ring members selected from carbon atoms and up to 4 heteroatoms independently selected from atoms of up to 2 O, up to 2 S and up to 4 N, each ring optionally substituted by up to 3 substituents independently selected from R3F on the carbon atom ring members and R3G on the nitrogen atom ring members.
[069] Embodiment 33. A compound from Embodiment 32, wherein each R3, independently, is halogen, cyano, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C4 alkoxy, C1-C4 haloalkoxy, C2-C6 alkoxyalkyl or C2-C6 haloalkoxyalkyl.
[070] Embodiment 34. A compound from Embodiment 33, wherein each R3, independently, is halogen, cyano, C1-C4 alkyl or C1-C4 haloalkyl.
[071] Realization 35. A compound of Realization 34, where each R3, independently, is halogen or cyan.
[072] Realization 36. A compound of Realization 35, in which each R3 independently, is halogen.
[073] Embodiment 37. A compound of Formula 1 or any of Embodiments 1 through 36, alone or in combination, where R3 is linked to the rest of Formula 1 in position 3.
[074] Embodiment 38. A compound of Formula 1 or any of Embodiments 1 to 37, alone or in combination, wherein each R1A independently is C1-C4 alkyl or C1-C4 haloalkyl.
[075] Embodiment 39. A compound from Embodiment 38, wherein each R1A, independently, is C1-C4 haloalkyl.
[076] Embodiment 40. A compound of Formula 1 or any of Embodiments 1 to 39, singly or in combination, where each R3E, independently, is C1-C4 alkyl.
[077] Embodiment 41. A compound of Formula 1 or any of Embodiments 1 to 40, alone or in combination, in which each R3A independently is C1-C4 alkyl.
[078] Embodiment 42. A compound of Formula 1 or any of Embodiments 1 to 41, singly or in combination, wherein each R3B, independently, is H or C1-C4 alkyl.
[079] Embodiment 43. A compound of Formula 1 or any of Embodiments 1 through 42, alone or in combination, wherein each R3C, independently, is H or C1-C4 alkyl.
[080] Embodiment 44. A compound of Formula 1 or any of Embodiments 1 to 43, alone or in combination, wherein each R3D, independently, is H or C1-C4 alkyl.
[081] Realization 45. A compound of Formula 1 or any of Realizations 1 to 44, singly or in combination, where each n, independently, is 0 or 2.
[082] Realization 46. A compound of Realization 45, where n is 2.
[083] Realization 47. A compound of Realization 45, where n is 0.
[084] Embodiment 48. A compound of Formula 1 or any of Embodiments 1 to 47, alone or in combination, provided that (i) when Q is 5-chloro-2-pyridinyl; Z is O; and R3 is 4-chlorine, therefore, R2 is different from Cl or Br; (ii) when Q is 4-CFs-2-pyrimidinyl; Z is O; and m is 0, therefore R2 is different from Cl or Br; and (iii) when Q is 6-CF3-2-pyridinyl; Z is O; and m is 0, therefore R2 is different from Br.
[085] The Realizations of the present invention as described in the Brief Description of the Invention and Realization AAA also include the following:
[086] Realization 1P. A Formula 1 compound (including all stereoisomers), its N-oxides, and their salts, the agricultural compositions containing them and their use as herbicides, as described in the Brief Description of the Invention.
[087] 2P realization. A compound from Embodiment 1, where Q is a 5- or 6-membered aromatic heterocyclic ring, attached to the remainder of Formula 1 via a carbon atom, and optionally substituted by 1 to 3R1.
[088] 3P realization. A realization 2 compound, where Q is selected from


- r is 0, 1,2 or 3; and
[089] Realization 4P. A compound from any of Embodiments 1 through 3, where Q is a 5-membered aromatic heterocyclic ring, attached to the remainder of Formula 1 via a carbon atom, optionally substituted by R1, and is selected from Q- 1 to Q-41.
[090] Achievement 5P. A compound from Realization 4, where Q is selected from Q-7 to Q-24.
[091] Realization 6P. A compound of Realization 5, where Q is selected from Q-9, Q-11, Q-12, Q-16, Q-18, Q-22, Q-23, Q-24 and Q-25.
[092] Realization 7P. A compound from Realization 6, where Q is selected from Q-11, Q-18 and Q-22.
[093] Achievement 8P. A compound from any of Embodiments 1 through 3, where Q is a 6-membered heterocyclic aromatic ring, attached to the remainder of Formula 1 via a carbon atom, optionally substituted by R1, and is selected from Q- 42 to Q 54.
[094] Achievement 9P. A compound from Realization 8, where Q is selected from Q-42, Q-43, Q 44, Q-47, Q-48 and Q-49.
[095] Achievement 10P. A compound from Realization 9, where Q is selected from Q-42, Q-43, Q-47 and Q-48.
[096] Achievement 11P. A compound from Realization 10, where Q is selected from Q-42, Q-47 and Q-48.
[097] 12P realization. A compound from Realization 11, where Q is selected from Q-42.
[098] Accomplishment 13P. A composite of Realization 12, where Q
[099] Achievement 14P. A compound from any of Achievements 1 through 3, where Q is selected from Q-7 to Q-24, Q-42, Q- 43, Q-44, Q-47, Q-48 and Q- 49.
[0100] Realization 15P. A compound from Realization 14, where Q is selected from Q-9, Q-11, Q-12, Q-16, Q-18, Q-22, Q-23, Q-24, Q-25, Q-42, Q-43, Q-47 and Q-48.
[0101] 16P realization. A compound from Realization 1, where Q is phenyl substituted by 1 to 3 R1.
[0102] Realization 17P. A compound from Embodiment 16, where Q is phenyl substituted by 1 to 2 R1.
[0103] Realization 18P. A compound from Embodiment 17, where Q is phenyl substituted by 1 R1 in positions 3 or 4 (i.e., meta or stops with respect to the phenyl bond to the rest of Formula 1).
[0104] Realization 19P. A compound from Realization 1, where when Q is phenyl substituted by 1 to 3 R1, m is 1,2 or 3.
[0105] 20P realization. A compound from Realization 1, where, when Q is 1 to 3 substituted phenyl R1, m is 1 or 2.
[0106] Achievement 21P. A compound from Embodiment 1, where Q is different from phenyl substituted by 1 to 4 R1.
[0107] Realization 22P. A compound of any of Embodiments 1 to 21, wherein R1 is halogen, cyano, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkoxy, C3-C4 alkenyloxy, C3 alkynyloxy - C4, C1-C4 haloalkyl, C1-C4 haloalkoxy, C2-C4 alkoxyalkyl, C2-C4 alkylthioalkyl or S0nR1A
[0108] 23P realization. A compound of Embodiment 22, wherein R1 is halogen, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, or SCF3.
[0109] 24P realization. A compound of Embodiment 23, wherein R1 is halogen, C1-C4 alkyl or C1-C4 haloalkyl or C1-C4 haloalkoxy.
[0110] Realization 25P. A compound of Embodiment 24, wherein R1 is halogen, C1-C4 haloalkyl or C1-C4 haloalkoxy.
[0111] Achievement 26P. A compound from Realization 25, where R1 is Cl, Br, CF3 or OCF3.
[0112] Realization 27P. A compound of any of Achievements 1 through 22, where each n, independently, is 0, 1 or 2.
[0113] Achievement 28P. A compound of Realization 27, where each n, independently, is 0.
[0114] Realization 29P. A compound of Realization 28, where each n, independently, is 2.
[0115] Realization 30P. A compound of any of Embodiments 1 through 29, wherein R2 is halogen, C1-C4 alkyl or C1-C4 haloalkyl.
[0116] Achievement 31P. A compound of Embodiment 30, wherein R2 is halogen or C1-C4 alkyl.
[0117] Achievement 32P. A compound from Realization 31, where R2 is halogen or CH3.
[0118] Achievement 33P. A compound of Realization 32, where R2 is halogen.
[0119] Achievement 34P. A compound of Realization 33, wherein R2 is F, Cl or Br.
[0120] Achievement 35P. A compound of any of Achievements 1 through 34, where m is 0, 1 or 2.
[0121] Achievement 36P. A compound of Realization 35, where m is 0 or 1.
[0122] Achievement 37P. A compound from Realization 36, where m is 1.
[0123] Achievement 38P. A compound of Embodiment 37, where m is 0 (i.e., at positions 3, 4, 5 and 6 of the benzene ring are not replaced by R3).
[0124] Achievement 39P. A compound of any of Embodiments 1 to 37, wherein each R3, independently, is halogen, cyano, hydroxy, nitro, amino, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4, C alkynyl = O) N (R3A) (R3B), C (= NOR3C) H, C (= N) (R3D) H, C1-C4 alkoxy, C2-C4 cyanoalkoxy, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, C2 alkylcarbonyloxy -C4, C2-C4 alkoxyalkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, C3-C6 cycloalkyl or SOnR3E
[0125] Achievement 40P. A compound of Embodiment 39, wherein each R3, independently, is halogen, cyano, amino, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkoxy, C2-C4 alkoxycarbonyl, C2-C4 alkylcarbonyloxy , C2-C4 alkoxyalkyl or C1-C4 haloalkyl.
[0126] Achievement 41P. A compound of Realization 40, wherein each R3, independently, is halogen, cyano, amino or C1-C4 alkyl.
[0127] Achievement 42P. A compound of Realization 41, where each R3, independently, is cyan.
[0128] Achievement 43P. A compound of any of Achievements 1 to 37 or 39 to 42, where each R3 is linked to the rest of Formula 1 in positions 3, 4 or 6.
[0129] Achievement 44P. A composite of Achievements 43, where each R3 is linked to the rest of Formula 1 in positions 3 or 4.
[0130] 45P realization. A compound from Realization 44, in which R3 is linked to the remainder of Formula 1 at position 3.
[0131] Achievement 46P. A compound of any of Embodiments 1 to 22 or 27 or 29 to 45, wherein R1A is C1-C4 alkyl or C1-C4 haloalkyl.
[0132] Realization 47P. A compound of Embodiment 46, wherein R1A is C1-C4 haloalkyl.
[0133] Achievement 48P. A compound of any of Embodiments 1 through 37 or 39, wherein R3E is C1-C4 alkyl.
[0134] Achievement 49p. A compound of any of Embodiments 1 through 37 or 39, wherein R3A is C1-C4 alkyl.
[0135] Achievement 50P. A compound of any of Embodiments 1 through 37 or 39, wherein R3B is H or C1-C4 alkyl.
[0136] Achievement 51P. A compound of any of Embodiments 1 through 37 or 39, wherein R3C is H or C1-C4 alkyl.
[0137] Achievement 52P. A compound of any of Embodiments 1 through 37 or 39, wherein R3D is H or C1-C4 alkyl.
[0138] Realization 53P. A compound of any of Achievements 1 through 52, where Z is O.
[0139] Achievement 54P. A compound of any of Embodiments 1 through 53, wherein when m is 1, R3 is positioned in one of positions 3, 5 or 6 (that is, in positions 3, 5 and 6 positions of the benzene ring).
[0140] Realization 55P. A compound of any of Realizations 1 through 53, where when m is 1, R3 is different from Cl in position 4.
[0141] The embodiments of the present invention, including embodiments 1 to 48 and 1P to 55P above, as well as any other embodiments described herein, can be combined in any way, and the descriptions of the variables in the embodiments refer not only to to a Formula 1 compound, but also to the starting compounds and intermediate compounds useful for the preparation of the Formula 1 compounds. In addition, the embodiments of the present invention, including Embodiments 1 to 48 and 1P to 55P above, as well as any other embodiments described herein, and any combinations thereof, belong to the compositions and methods of the present invention.
[0142] AAA realization. A Formula 1 compound, where - Q is a 5- or 6-membered aromatic heterocyclic ring, attached to the remainder of Formula 1 via a carbon atom, and optionally substituted by 1 to 4 R1; or - Q is phenyl substituted by 1 to 4 R1; - Z is O or S; - R1 is halogen, cyano, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-4 haloalkyl, C1-C4 haloalkoxy, C2-C4 alkoxyalkyl, C2-C4 alkylthioalkyl, SOnR1A, C2-C6 dialkylamino, C1-C4 cyanoalkyl, C1-C4 hydroxyalkyl, CH (-NOH) or Cs-Ce cycloalkyl; or unsubstituted phenyl; or unsubstituted pyridyl; - R2 is halogen, cyano, nitro, C1-C4 alkoxy, C1-C4 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, SOnR4 or C1-C4 haloalkyl; - each R3, independently, is halogen, cyano, hydroxy, nitro, amino, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C (= O) N (R3A) (R3B), C ( = NOR3C) H, C (= N) (R3D) H, C1-C4 alkoxy, C2-C4 cyanoalkoxy, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, C2-C4 alkylcarbonyloxy C2-C4 alkoxyalkyl, C1-C4 alkoxyalkyl, C1-C4-haloalkyl halo C1-C4, SOnR3E or C3-C6 cycloalkyl; or phenyl optionally substituted by cyano, halogen or C1-C4 alkyl, - m is 0, 1,2 or 3; each R1A, R2A and R3E, independently, is C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkylamino or C2-C6 dialkylamino; - R3A is C1-C4 alkyl or C1-C4 haloalkyl; - R3B is H, C1-C4 alkyl or C1-C4 haloalkyl; - R3C, independently, is H or C1-C4 alkyl; - R3D, independently, is H or C1-C4 alkyl; and - n is 0, 1, or 2; - provided that the Formula 1 compound is other than 5-chloro-2- [(4'-methyl [1,1'-biphenyl] 2-yl) oxy] pyrimidine (CAS # 107492-74-0), 5- chloro-2 - [(4'-chloro [1,1'-biphenyl] 2-yl) oxy] pyrimidine (CAS # 107492-72-8), 5-chloro-2 - [(3'-chloro [1, 1'-biphenyl] 2-yl) oxy] pyrimidine (CAS # 107492-76-2) and 5 chloro-2 - [[3'- (trifluoromethyl) [1,1'-biphenyl] 2-yl] oxy] pyrimidine (CAS # 107492-75-1); and provided that (i) when Q is 5-chloro-2-pyridinyl; Z is O; and R3 is 4-chlorine, therefore, R2 is different from Cl or Br; (ii) when Q is 4-CF3-2-pyrimidinyl; Z is O; and m is 0, therefore R2 is different from Cl or Br; and (iii) when Q is 6-CF3-2-pyridinyl; Z is 0 O; and m is 0, therefore R2 is different from Br.
[0143] AA realization. A compound of the AAA Realization or a Formula 1 compound as described in the Brief Description of the Invention, where - Q is a 5- or 6-membered aromatic heterocyclic ring, attached to the remainder of Formula 1 via a carbon atom, and optionally substituted through 1 to 4 R1; - Z is 0 O or S; - each R1, independently, is halogen, cyan, nitro, SFs, CHO, C (= O) NH2, C (= S) NH2, SO2NH2, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, haloalkyl C1-C4, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C4-Cs cycloalkylalkyl, C2-C6-cycloalkyl, cycloalkylalkyl, alkoxycarbonyl C3-C7, C2-C8 alkylaminocarbonyl, C3-C10 dialkylaminocarbonyl, C1-C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-C4 haloalkoxy, C3-C4 haloalkoxy, C3-C4 halo, alkoxyalkyl C3-C6, C4-C8 cycloalkylalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 alkoxyalkyl, C2-C6 alkoxyalkyl, C2-C4alkylalkyl, C2-C6alkyl, alkoxy C2-C6alkyl, alkali C2-C4, SOnR1A, Si (CH3) 3 OR B (-OC (R1B) 2C (R1B) 2O-); OR a phenyl ring optionally substituted by up to 5 substituents independently selected from R1C; or a 5- or 6-membered heteroaromatic ring containing the ring members selected from carbon atoms and up to 4 heteroatoms independently selected from atoms of up to 2 O, up to 2 S and up to 4 N, each ring optionally substituted by up to 3 substituents independently selected R1C from ring members of carbon atoms and R4 in ring members of nitrogen atoms, R2 is 0 halogen, cyano, nitro, C1-C4 alkoxy, C1-C4 alkyl, C2-C6 alkenyl , C2-C6 alkynyl, SOnR2 ^, C1-C4 haloalkyl or C3-C6 cycloalkyl; - each R3, independently, is halogen, cyano, hydroxy, nitro, amino, CHO, C (= O) NH2, C (= S) NH2, SO2NH2, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl , C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl C2-C6alkyl, C2-C6alkyl, C2-C6alkyl, C2-C6alkyl , C3-C7 cycloalkylcarbonyl, C1-C4 alkoxy, C3-C4 alkenyloxy, C3-C4 cycloalkyl, C1-C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkyl, C3-cycloalkoxy C3-cycloalkoxy C3-cycloalkoxy C8, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 alkoxyhaloalkyl, C2-C6 alkoxyalkoxy, C2-C4 alkylcarbonyloxy, C2-C6 cyanoalkyl, C2-C6 cyanoalkyl, C3-C3 (C3-C3) alkyl CH3) 3, C (= O) N (R3A) (R3B), C (= NOR3C) H, C (= NR3D) H, SOnR3E; or a phenyl ring optionally substituted by up to 5 substituents independently selected from R3F; or a 5- or 6-membered heteroaromatic ring containing the ring members selected from carbon atoms and up to 4 heteroatoms independently selected from atoms of up to 2 O, up to 2 S and up to 4 N, each ring optionally substituted by up to 3 substituents independently selected R3F from ring members of carbon atoms and R3G from ring members of nitrogen atoms; or idinyloxy pyrim; - m is 0, 1,2 or 3; - each n, independently, is 0, 1 or 2; each R1A, R2A and R3E, independently, is C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkylamino or C2-C6 dialkylamino; - each R1B, independently, is H or C1-C4 alkyl; - each R10, independently, is hydroxy, halogen, cyano, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy or Ci-Ce haloalkoxy; each R1D independently, is cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy or C2-C6 alkylcarbonyl; each R3A independently is C1-C4 alkyl or C1-C4 haloalkyl; each R3B independently is H, C1-C4 alkyl or C1-C4 haloalkyl; each R3C independently, is H or C1-C4 alkyl; - each R3D independently, is H, amino, C1-C4 alkyl or C1-C4 alkylamino; each R3F independently is 0 hydroxy, halogen, cyano, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy or Ci-Ce haloalkoxy; and - each R3G independently is cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy or C2-C6 alkylcarbonyl;
[0144] Realization A. A compound of Realization AA where - Q is selected from Q-1 to Q-55 where r is 0, 1,2 or 3, and s is 0 or 1; - each R1, independently, is halogen, cyano, SFs, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C2-C6 alkylcarbonyl , C2-C6 haloalkylcarb, C2-C6 alkoxycarbonyl, C1-C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-C4 haloalkoxy, C3-C4 haloalkenyl, C3-C6-alkoxy , C2-C6 cyanoalkyl, C1-C4 hydroxyalkyl, C2-C4 alkylthioalkyl or SOnR1A; - R3, independently, is halogen, cyano, CHO, C-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C4 haloalkyl, C2-C4 haloalkyl, C3-C6 cycloalkyl, C3 halocycloalkyl -C6, C4-C8 alkylcycloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1-C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkylene C1-C4-alkoxy, halo C1-C4-alkoxy, C1-C4-alkoxy -C4, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C4 alkylcarbonyloxy, C2-C6 cyanoalkyl, C (= O) N (R3A) (R3B), C (C3) ) H, SOnR3E; or a phenyl ring optionally substituted by up to 5 substituents independently selected from R3F; or a 5- or 6-membered heteroaromatic ring containing the ring members selected from carbon atoms and up to 4 heteroatoms independently selected from atoms of up to 2 O, up to 2 S and up to 4 N, each ring optionally substituted by up to 3 substituents independently selected R3F from ring members of carbon atoms and R3G from ring members of nitrogen atoms; - Z is O; and - m is 0, 1 or 2.
[0145] Realization B. The compound of Realization A, wherein - each R1, independently, is halogen, cyano, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2 haloalkenyl -C4, C2-C4 haloalkyl, C1-C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkyloxyC2-C6alkylalkyl, C2-C6alkylalkyl, C2-C6alkyl -C4, C2-C4 alkylthioalkyl or SOnR1A, - R2 is halogen, C1-C4 alkyl or C1-C4 haloalkyl; - each R3, independently, is halogen, cyano, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkyl, C3-C6 cycloalkyl, halocycloalkyl C3-C6, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6, C6-C6-C6-C6, C2-C6; or a 5- or 6-membered heteroaromatic ring containing the ring members selected from carbon atoms and up to 4 heteroatoms independently selected from atoms of up to 2 O, up to 2 S and up to 4 N, each ring optionally substituted by up to 3 substituents independently selected R3F from ring members of carbon atoms and R3G from ring members of nitrogen atoms; and - m is 0 or 1.
[0146] Realization Ci. A compound of Realization B where - Q is selected from Q-7 to Q-24; - each R1, independently, is halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy or SOnR1A; - R2 is 0 halogen or C1-C4 alkyl; - each R3, independently, is halogen, cyano, C-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1- alkoxy C4, C1-C4 haloalkoxy, C2-C6 alkoxyalkyl or C2-C6 haloalkoxyalkyl; and - each R1A, independently, is C1-C4 alkyl or C1-C4 haloalkyl.
[0147] Realization C2. A compound from Realization B where - Q is selected from Q-43, Q-44, Q-45, Q-48, Q-49 and Q-50; - each R1, independently, is halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy or SQnR1A; - R2 is halogen or C1-C4 alkyl; - each R3, independently, is halogen, cyano, C-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1- alkoxy C4, C1-C4 haloalkoxy, C2-C6 alkoxyalkyl or C2-C6 haloalkoxyalkyl; and - each R1A, independently, is C1-C4 alkyl or C1-C4 haloalkyl.
[0148] Realization D1. A compound from Realization C1 where - Q is selected from Q-16 and Q-18; - each R1, independently, is halogen, C1-C4 alkyl, C1-C4 haloalkyl or C1-C4 haloalkoxy; - R2 is halogen or CH3; and - each R3, independently, is halogen, cyano, C1-C4 alkyl or C1-C4 haloalkyl.
[0149] Realization D2. A compound from Realization C2 where - Q is selected from Q-43, Q-44 and Q-45; - each R1, independently, is halogen, C1-C4 alkyl, C1-C4 haloalkyl or C1-C4 haloalkoxy; - R2 is halogen or CH3; and - each R3, independently, is halogen, cyano, C1-C4 alkyl or C1-C4 haloalkyl.
[0150] Specific achievements include Formula 1 compounds selected from the group consisting of: - 5-chloro-2- [2- (5-chloro-2-pyridinyl) phenoxy] pinmidine (Compound 1), 5- chloro-2- [2- [5- (fluoromethyl) -3-isoxazolyl] phenoxy] pyrimidine (Compound 32), - 2- [2- (3-bromo-5-isoxazolyl) phenoxy] -5-chloro-pyrimidine ( Compound 12), 5-chloro-2- [2- [5- (trifluoromethyl) -2-pyridinyl] phenoxy] pyrimidine (Compound 27), 5-chloro-2- [3-chloro-2- (5-chloro- 2-pyridinyl) phenoxy] pyrimidine (Compound 23), 4- [2 - [(5-bromo-2-pyrimidinyl) oxy] phenyl] -2- (tnfluoromethyl) pinmidine (Compound 21), 2- [2- (2 -brorno-5-thiazolyl) phenoxy] -5- (trifluoromethyl) pyrimidine (Compound 15), - 5-chloro-2- [4-methyl-2- [2- (tnfluoromethyl) -4-pyridinyl] phenoxy] pinmidine ( Compound 24), 5-chloro-2- [2- [5- (difluoromethyl) -3-isoxazolyl] phenoxy] pyrimidine (Compound 35), 5-chloro-2- [2- [3- (difluoromethyl) -5- isoxazolyl] phenoxy] pyrimidine (Compound 53), 5-chloro-2- [2- [5- (difluoromethyl) -3-isoxazolyl] -3-fluorophenoxy] pyrimidine (Compound 55), 5-bromo-2- [2- [5- (difluoromet yl) -3-isoxazolyl] phenoxy] pyrimidine (Compound 62), 5-chloro-2- [2- [3- (trifluoromethyl) -5-isoxazolyl] phenoxy] pyrimidine (Compound 63), 5-chloro-2- [ 2- [3- (difluoromethyl) -5-isoxazolyl] -3-fluorophenoxy] pyrimidine (Compound 144), 5-bromo-2- [2- [3- (difluoromethyl) -5-isoxazolyl] -3-fluorophenoxy] pyrimidine (Compound 145), 5-chloro-2- [2- [5- (trifluoromethyl) -3-isoxazolyl] -3-fluorophenoxy] pyrimidine (Compound 168) and 5-chloro-2- [2- [5- (trifluoromethyl ) -3-isoxazolyl] phenoxy] pyrimidine (Compound 200).
[0151] The embodiments of the present invention as described in the Brief Description of the Invention and Realization AAA also include the following:
[0152] Realization Ap. A compound of the Brief Description of the Invention, where - Q is an aromatic heterocyclic ring with 5 or 6 members, linked to the rest of Formula 1 through a carbon atom, and optionally substituted by 1 to 3 R1; or - Q is phenyl substituted by 1 to 3 R1; - R1 is halogen, cyano, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-4 haloalkyl, C1-C4 haloalkoxy, C2-C4 alkoxyalkyl, C2-C4 alkylthioalkyl or SOnR1A; - each n, independently, is 0, 1 or 2 - R2 is halogen, C1-C4 alkyl or C1-C4 haloalkyl; - m is 0, 1 or 2; - each R3, independently, is 0 halogen, cyano, hydroxy, nitro, amino, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C (= O) N (R3A) (R3B), C ( = NOR3C) H, C (= N) (R3D) H, C1-C4 alkoxy, C2-C4 cyanoalkoxy, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, C2-C4 alkylcarbonyloxy C2-C4 alkoxyalkyl, C1-C4 alkoxyalkyl, C1-C4-haloalkyl halo C1-C4, SOnR3E or Cs-Ce cycloalkyl; - each R3 is linked to the rest of Formula 1 in positions 3, 4 or 6; - R1A is C1-C4alkyl or C1-C4 haloalkyl; - R3E is C1-C4 alkyl; - R3A is C1-C4 alkyl; - R3B is H or C1-C4 alkyl; - R3C is H or C1-C4 alkyl; and - R3D is H or C1-C4 alkyl.
[0153] Realization Bp. A compound from Realization A, where - Q is selected from Q-1 to Q-54 (i.e., as described in Realization 3); - Z is O; - R1 is halogen, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, or SCF3; - R2 is halogen or C1-C4 alkyl; - m is 0 or 1; - each R3, independently, is halogen, cyano, amino, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkoxy, C2-C4 alkoxycarbonyl, C2-C4 alkylcarbonyloxy, C2-C4 alkoxyalkyl or haloalkyl C1-C4; and - each R3 is linked to the rest of Formula 1 in position 3 or 4.
[0154] Cp. A compound from Realization B, where - Q is a 5-membered aromatic heterocyclic ring, attached to the remainder of Formula 1 through a carbon atom, optionally substituted by R1, and is selected from Q-1 to Q-41 ; - R1 is halogen, C1-C4 haloalkyl or C1-C4 haloalkoxy; - R2 is 0 halogen or CH3; and - each R3, independently, is halogen, cyano, amino or C1-C4 alkyl.
[0155] Realization Dp. A Realization C compound, where - Q is a 6-membered heterocyclic aromatic ring, attached to the remainder of Formula 1 through a carbon atom, optionally substituted by R1, and is selected from Q-42 to Q-54; - R1 is halogen, C1-C4 haloalkyl or C1-C4 haloalkoxy; - R2 is halogen or CH3; and - each R3, independently, is halogen, cyano, amino or C1-C4 alkyl.
[0156] Realization Ep. A realization compound D, where - Q is selected from Q-42, Q-43, Q-44, Q-47, Q-48 and Q- 49; - R1 is Cl, Br, CF30U OCF3; - R2 is halogen; and - each R3, independently, is cyan.
[0157] Specific embodiments include a compound of Formula 1, selected from the group consisting of: - 5-chloro-2- [2- (5-chloro-2-pyridinyl) phenoxy] pyrimidine (Compound 1); 5-chloro-2- [2- [5- (fluoromethyl) -3-isoxazolyl] phenoxy] pyrimidine (Compound 32); - 2- [2- (3-bromo-5-isoxazolyl) phenoxy] -5-chloro-pyrimidine (Compound 12); 5-chloro-2 - [[4 '- (trifluoromethoxy) [1,1' -biphenyl] -2-yl] oxy] pyrimidine (Compound 42); 5-chloro-2- [2- [5- (trifluoromethyl) -2-pyridinyl] phenoxy] pyrimidine (Compound 27); 5-chloro-2- [3-chloro-2- (5-chloro-2-pyridinyl) phenoxy] pyrimidine (Compound 23); 4- [2 - [(5-bromo-2-pyrimidinyl) oxy] phenyl] -2- (trifluoromethyl) pyrimidine (Compound 21); 2- [2- (2-bromo-5-thiazolyl) phenoxy] -5- (trifluoromethyl) pyrimidine (Compound 15); and - 5-chloro-2- [4-methyl-2- [2- (trifluoromethyl) -4-pyridinyl] phenoxy] pyrimidine (Compound 24).
[0158] The present invention also relates to a method for the control of unwanted vegetation which comprises the application, at the vegetation site, of herbicidal amounts of the compounds of the present invention (for example, as a composition described herein). Of interest as realizations, in relation to the methods of use are those involving the compounds of the realizations described above. The compounds of the present invention are especially useful for the selective control of weeds in cereal crops such as wheat, barley, corn, soybeans, sunflower, cotton, rapeseed and rice, and special crops, such as cane crops. sugar, citrus fruits, fruits and nuts.
[0159] Also of interest, as embodiments are the herbicidal compositions of the present invention, which comprise the compounds as described in the above embodiments.
[0160] The present invention also includes a herbicidal mixture comprising (a) a compound selected from Formula 1, A / -oxides, and its salts, and (b) at least one additional active ingredient selected from (b1) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS) inhibitors, (b3) acetyl-CoA carboxylase inhibitors (ACCase), (b4) auxin mimics, and (b5) inhibitors of synthase of 5-enol-pyruvylshiquimato-3-phosphate (EPSP), (b6) electron deflectors from photosystem I, (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b8), glutamine synthetase (GS) inhibitors, (b9 ) very long chain fatty acid elongase inhibitors (VLCFA), (b10) auxin transport inhibitors, (b11), phytene desaturase inhibitors (PDS), (b12) 4-hydroxyphenyl pyruvate dioxigenase inhibitors ( HPPD), (b13) homogeneous soleneyltransererase (HST) inhibitors, (b14) cellulose biosynthesis inhibitors, (b15) other herbicides s including mitotic disruptors, organic arsenicals, asulam, bromobutide, cinmethyline, cumilurone, dazomet, difenzoquat, dimrone, etobenzanid, flurenol, phosamine, phosamine ammonium, metam, methyldimrone, oleic acid, oxaziclomefone, pelargonic acid and bicarb and e ) herbicidal protection agents; and salts of compounds from (b1) to (b16).
[0161] “Photosystem II inhibitors” (b1) are chemical compounds that bind to the D-1 protein in the QB binding niche and therefore block the transport of electrons from QA to QB in the chloroplast thylakoid membranes . The electrons blocked from passing through photosystem II are transferred through a series of reactions to form the toxic compounds that disrupt cell membranes and cause chloroplast swelling, membrane leakage, and ultimately cell destruction. The QB binding niche has three different binding sites: binding site A binds triazines, such as atrazine, triazinones such as hexazinone and uracils such as bromacila, binding site B binds phenylureas such as diurone , and the binding site C binds benzothiadiazoles such as bentazone, nitriles, such as bromoxynil and phenyl pyridazines, such as pyridate. Examples of photosystem II inhibitors include ametrine, amicarbazone, atrazine, bentazone, bromacil, bromophenoxin, bromoxynil, chlorobromurone, chloridazone, chlortolurone, chloroxurone, cumilurone, cyanazine, daimurone, desmediphone, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine, dimethine and dimethine, dimethine, dimethine, dimethine, dimethine and dimethine, dimethine, dimethine and dimethine, dimethine and dimethine, dimethine, dimethine, dimethine and dimethine and dimethine, dimethylamine and , fluometurone, hexazinone, ioxynil, isoproturone, isourone, lenacil, linurone, metamitrone, metabenzthiazurone, metobromurone, methoxyurone, metribuzin, monolinurone, neburone, pentanochlor, fenemedifame, prometon, promethine, propanil, pyrethine, pyrethine, pyrethine, pyrethine, pyrethine, pyrethine, pyrethine, pyrethine, pyrethine, pyrethine, pyrethine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine. , tebutiurone, terbacil, terbumetone, terbuthylazine, terbutrin and trietazine.
[0162] "AHAS inhibitors" (b2) are chemical compounds that inhibit acetohydroxy acid synthase (AHAS), also known as acetolactate synthase (ALS), and therefore kill plants by inhibiting production of branched-chain aliphatic amino acids, such as valine, leucine and isoleucine, which are necessary for protein synthesis and cell growth. Examples of AHAS inhibitors include amidosulfurone, azimsulfurone, benssulfuron-methyl, bispyribac-sodium, chloransulam-methyl, chlorimuron-ethyl, chlorsulfurone, cinosulfurone, cyclosulfamurone, diclosulam, etametsulfuron-methyl, flasulfazuran, flushassulfan flumetsulam, flupirsulfuron-methyl, flupirsulfuron-sodium, foramsulfurone, halosulfuron-methyl, imazametabenz-methyl, imazamox, imazapyr, imazaquin, imazetapyr, imazosulfurone, iodosulfuron-methyl (including sodium-iodine (2-sodium-2) ( (4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl] -benzene-sulfonamide) of iofensulfurone, mesosulfuron-methyl, (3-chloro-4 (5,6-dihydro -5-m ethyl 1-1,4,2-dioxazin-3-yl) -N - [[(4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] -1-methyl-1 H-pyrazol-5 - sulfonamide) of metazosulfurone, metosulam, metsulfuron-methyl, nicosulfurone, oxasulfurone, penoxsulam, primisulfuron-methyl, propoxycarbazon-sodium, (2-chloro-N - [[(4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] - 6-propylimidazo [1,2-b] pyridazine-3-sulfonamide) of propyrisulfurone, prosulfurone, pyrazosulfuron-ethyl, pyribenzoxy, pyriftalid, pyriminobac-methyl, piritiobac-sodium, rimsulfurone, sulfometuron-methyl, sulfosulfurone, thiensarbazone N- [2 - [(4,6-dimethoxy-1,3,5-triazin-2-yl) carbonyl] -6-fluorophenyl] -1,1-difluoro-N-methylmethanesulfonamide) of triafamone, triasulfurone, tribenuron- methyl, trifloxysulfurone (including the sodium salt), triflussulfuron-methyl and tritosulfurone.
[0163] "ACCase inhibitors" (b3) are the chemical compounds that inhibit the acetyl-CoA carboxylase enzyme, which is responsible for catalyzing an initial step in the synthesis of lipids and fatty acids in vegetables. Lipids are essential components of cell membranes, and without them, new cells cannot be produced. The inhibition of acetyl-CoA carboxylase and the subsequent lack of lipid production lead to losses in the integrity of the cell membrane, especially in regions of active growth, such as meristems. Eventually, sprout and rhizome growth stops, and the rhizome sprout and bud meristems begin to die. Examples of ACCase inhibitors include aloxidim, butroxidim, cletodim, clodinafop, cycloxidime, cyhalofop, diclofop, fenoxaprop, fluazifop, haloxifop, pinoxadene, profoxidim, propaquizafop, quizalofop, setoxidim, such as tepraloxime, fenoxaprop-P, fluazifop-P, haloxifop-P and quizalofop-P and ester forms, such as clodinafop-propargil, cihalofop-butyl, diclofop-methyl and phenoxaprop-P-ethyl.
[0164] Auxin is a plant hormone that regulates growth in many plant tissues. The "auxin mimics" (b4) are chemical compounds that mimic the auxin plant growth hormone, therefore causing uncontrolled and disorganized growth leading to the death of the plant in sensitive species. Examples of auxin mimics include aminocyclopyrachlor (6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid) and its methyl and ethyl esters and their sodium and potassium salts, aminopyralid benazoline acetate, chloramben, clacifos, clomeprop, clopyralid, dicamba, 2,4-D, 2,4-DB, dichlorprop, fluroxypyr, (4-amino-3-chloro-6- (4-chloro-2-fluoro-3-methoxyphenyl acid) ) -2-pyridinecarboxylic) of halauxifene, (4-amino-3-chloro-6- (4-chloro-2-fluoro-3-methoxyphenyl) -2-methyl pyridinocarboxylate) of halauxifen-methyl, MCPA, MCPB, mecoprope , picloram, quinclorac, quinmerac, 2,3,6-TBA, triclopyr, and 4-amino-3-chloro-6- (4-chloro-2-fluoro-3-methoxyphenyl) -5-fluoro-2-pyridinocarboxylate methyl.
[0165] "EPSP inhibitors (5-enol-pyruvylshiquimato-3-phosphate synthase)" (b5) are the chemical compounds that inhibit the enzyme, 5-enol-pyruvylshiquimato-3-phosphate synthase, which is involved in synthesis of aromatic amino acids such as tyrosine, tryptophan and phenylalanine. Herbicidal EPSP inhibitors are easily absorbed through the plant's foliage and translocated in the phloem to the growth points. Glyphosate is a relatively non-selective post-emergence herbicide that belongs to this group. Glyphosate includes ammonium esters and salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimesium (alternatively called sulfosate).
[0166] The “diverters from electron photosystem I” (b6) are the chemical compounds that accept the electrons of Photosystem I and then several cycles generate hydroxyl radicals. These radicals are extremely reactive and quickly destroy unsaturated lipids, including membrane fatty acids and chlorophyll. This destroys the integrity of the cell membrane, so that the cells and organelles “leak”, causing the leaf to quickly wither and desiccate, and eventually the death of the plant. Examples of this second type of photosynthesis inhibitor include paraquat and diquat.
[0167] The “PPO inhibitors” (b7) are the chemical compounds that inhibit the protoporphyrinogen oxidase enzyme, resulting in the rapid formation of highly reactive compounds in plants that break cell membranes, causing cell fluids to leak. Examples of PPO inhibitors include acifluorfen-sodium, azafenidin, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, clomethoxyfen, cinidon-ethyl, fluazolate, flufenpir-ethyl, flumiclorac-pentyl, fluoroglobulin, fluoroglobulin methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazone, oxyfluene, pentoxazone, profluazole, pyraclonil, piraflufen-ethyl, saflufenacil, sulfentrazone, aclonifen, (N- [2 - [[2-chloro-5- [3,6-dihydro -3-methyl-2,6-dioxo-4- (trifluoromethyl) -1 (2H) -pyridinyl] -4-fluorophenyl] thio] -1-oxopropyl] - [methyl 3-alaninate) of thiafenacil and 3- [7-fluoro-3,4-dihydro-3-oxo-4- (2-propin-1-yl) -2 H-1,4-benzoxazin-6-yl] dihydro-1,5-dimethyl-6- thioxo-1,3,5-triazin-2,4 (1H, 3H) -dione.
[0168] "GS (glutamine synthase) inhibitors" (b8) are chemical compounds that inhibit the activity of the glutamine synthase enzyme, which plants use to convert ammonia to glutamine. Consequently, ammonia accumulates and reduces glutamine levels. Plant damage is likely to occur due to the combined effects of ammonia toxicity and amino acid deficiency needed for other metabolic processes. GS inhibitors include glufosinate and its esters and salts, such as ammonium glufosinate and other phosphinothricin derivatives, glufosinate-P ((2S) -2-amino-4- (hydroxymethylphosphinyl) butanoic acid) and bilanafos.
[0169] "VLCFA elongase inhibitors (very long chain fatty acids)" (b9) are herbicides that have a wide variety of chemical structures, which inhibit elongase. Elongase is one of the enzymes located in or near the chloroplasts that are involved in the biosynthesis of VLCFAs. In vegetables, very long chain fatty acids are the main constituents of hydrophobic polymers that prevent desiccation on the leaf surface and provide stability to pollen grains. These herbicides include acetochlor, alachlor, butachlor, cafenstrol, dimetachlor, dimethenamide, diphenamide, (3 - [[(2,5-dichloro-4-ethoxyphenyl) methyl] sulfonyl] -4,5-dihydro-5,5-dimethylisoxazole ) of phenoxasulfone, fentrazamide, flufenacet, indanofan, mefenacet, metazachlor, metolachlor, naproanilide, napropamide, napropamid-M ((2R) -N, N-diethyl-2- (1-naphthalenyloxy) -propanamide, pesticide, poxamide, poxamide, poxamide, petoxamide, poxamide, poxamide, pesticide; , propachlor, propisochlor, pyroxasulfone, and tenylchlor, including resolved forms, such as S-metolachlor and chloroacetamides and oxyacetamides.
[0170] "Auxin transport inhibitors" (B10) are chemicals that inhibit auxin transport in vegetables, such as by binding with an auxin transport protein. Examples of auxin transport inhibitors include naptalam (also known as N- (1-naphthyl) phthalamic acid and 2 - [(1-naphthalenylamino) carbonyl] benzoic acid).
[0171] The “PDS (phytoene desaturase inhibitors) (b11) are the chemical compounds that inhibit the carotenoid biosynthesis pathway in the Phytene desaturase stage. Examples of PDS inhibitors include beflubutamide, diflufenican, fluridone, flurochloridone, norflurzone, flurtamone and picolinafen.
[0172] "HPPD inhibitors (4-hydroxyphenylpyruvate dioxygenase)" (b12) are chemicals that inhibit the synthesis biosynthesis of 4-hydroxyphenyl-pyruvate dioxigenase. Examples of HPPD inhibitors include benzobicyclone, benzofenap, (4-hydroxy-3 - [[2- [(2-methoxyethoxy) methyl] -6- (trifluoromethyl) -3-pyridinyl] carbonyl] bicycle [3.2.1] bicyclopyrone oct-3- en-2-one, (2 - [[8-chloro-3,4-dihydro-4- (4-methoxyphenyl) -3-oxo-2-quinoxalinyl] carbonyl] -1,3 -cyclohexanedione) of phenquinotrione, isoxaclortol, isoxaflutole, mesotrione, pirasulfotole, pyrazolinate, pyrazoxifene, sulcotrione, tefuriltrione, tembotrione, topramezone, 5-chloro-3 - [(2-hydroxy-6-oxo-1-cyclohex-1-cyclohex-1-cyclohex il) carbon il] -1 - (4-methoxyphenyl) -2- (1 H) -quinoxalinone, 4- (2,6-diethyl I-4-methylphenyl) -5-hydroxy-2,6-dimethyl-3 (2H) -pyridazinone, 4- (4-fluorophenyl) -6 - [(2-hydroxy-6-oxo-1-cyclohexen-1 -i I) carbonyl] -2-m and i 1-1,2, 4-triazin-3,5 (2H, 4H) - dione, 5 - [(2-hydroxy-6-oxo-1-cyclohexen-1-yl) carbonyl] -2- (3-methoxyphenyl) -3- (3 - methoxypropyl) -4 (3H) -pyrimidinane, 2-methyl-N- (4-methyl-1,2,5-oxadiazol-3-yl) -3- (methylsulfinyl) -4- (trifluoromethyl) benzamide and 2- methyl-3- (methylsulfonyl) -N- (1 - methyl-1 H-tetrazol-5- il) -4- (trifluoromethyl) benzamide.
[0173] The "HST inhibitors" (homogentisate solenesyltransererase) (b13) unbalance the plant's ability to convert homogentisate to 2-methyl-6-solanyl-1,4-benzoquinone, thereby interrupting the biosynthesis of carotenoids. Examples of HST inhibitors include haloxidine, pyrichlorine, 3- (2-chloro-3,6-difluorophenyl) -4-hydroxy-1-methyl-1,5-naphthyridin-2 (1 H) -one, 7- (3,5-dichloro-4-pyridyl) -5- (2,2-difluoroethyl) -8-hydroxypyrido [2,3-b] pyrazin-6 (5H) -one and 4- (2,6 -diethyl-4-methylphenyl) -5-hydroxy-2,6-dimethyl-3 (2H) -pyridazinone.
[0174] HST inhibitors also include compounds of Formulas A and B.
- where Rd1 is H, Cl or CF3; Rd2 is H, Cl or Br; Rd3 is H or Cl; Rd4 is H, Cl or CF3; Rd5 is CH3, CH2CH3 or CH2CHF2; and Rd6 is OH, or OC (= O) -i-Pr; and Re1 is H, F, Cl, CH3 or CH2CH3; Re2 is H or CF3; Re3 is H, CH3OU CH2CH3; Re4 is H, F or Br; Re5 is Cl, CH3, CF3, OCF3 or CH2CH3; Re6 is H, CH3, OR CH2CHF2 C = CH; Re7is OH, OC (= O) Et, OC (= O) - / - Pr or OC (= O) -t-Bu; and Ae8 is N or CH.
[0175] Cellulose biosynthesis inhibitors (b14) inhibit cellulose biosynthesis in certain plants. They are most effective when using pre- and early post-application on young or rapidly growing vegetables. Examples of cellulose biosynthesis inhibitors include chlortiamid, diclobenyl, flupoxam, indaziflam (N2 - [(1 R, 2S) - 2,3-dihydro-2,6-dim eti 1-1 H-inden-1 - yl] -6- (1-fluoroethyl) -1,3,5-triazine-2,4-diamine), isoxaben and triaziflam.
[0176] Other herbicides (b15) include herbicides that act through a variety of different modes of action, such as mitotic disrupters (eg, flamprop-M-methyl and flamprop-M-isopropyl) organic arsenicals (eg , DSMA, and MSMA), 7,8-dihydropteroate synthase inhibitors, isoprenoid synthesis inhibitors and cell wall chloroplast biosynthesis inhibitors. Other herbicides include herbicides with unknown modes of action or do not fall into a specific category listed in (b1) to (b14) or act through a combination of the modes of action listed above. Examples of other herbicides include aclonifen, asulam, amitrol, bromobutide, cinmethyline, clomazone, cumilurone, cyclopyrimorate (6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-morpholinecarboxylate), daimuratone, , etobenzanid, fluometurone, flurenol, phosamine, phosamine ammonium, dazomet, dimrone, (1 - (2,4-dichlorophenyl) -N- (2,4-d if fluorophen i I) -1,5-dihydro- N- (1-methylethyl) -5-oxo-4H- 1,2,4-triazole-4-carboxamide) of ipfencarbazone, metam, methyldimrone, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb and 5 - [[(2, 6- difluorophenyl) methoxy] methyl] -4,5-dihydro-5-methyl-3- (3-methyl-2-thienyl) isoxazole.
[0177] "Herbicidal protection agents" (b16) are substances added to a herbicidal formulation to eliminate or reduce the herbicide's phytotoxic effects for certain crops. These compounds protect crops from damage by herbicides, but usually do not prevent the herbicide from controlling unwanted vegetation. Examples of herbicide protection agents include, but are not limited to, benoxacor, cloquintocet-mexila, cumilurone, ciometrinil, cyprosulfamide, daimurone, dichlormide, dicyclone, dimepiperate, phenclorazol-ethyl, fenclorim, flurazol, fluxofenil, isofluidol, furofenil, isofilimol, furofenoxy , mefenpyr-diethyl, mefenate, methoxyphenone, naphthalic anhydride, oxabetrinyl, N- (aminocarbonyl) -2-methylbenzenesulfonamide and N- (aminocarbonyl) -2-fluorobenzenesulfonamide, 1-bromo-4- [(chloromethyl) 2- sulfonyl] benzene (dichloromethyl) -2-methyl-1,3-dioxolane (MG 191), 4- (dichloroacetyl) -1-oxa-4-azospiro [4,5] decane (MON 4660).
[0178] The compounds of Formula 1 can be prepared using the general methods known in the art of synthetic organic chemistry. One or more of the following methods and variations, as described in Schemes 1 to 9, can be used to prepare the compounds of Formula 1. The definitions of Q, R1, R2 and R3 in the compounds of Formulas 1 to 11 below are as defined above in the Brief Description of the Invention, unless otherwise indicated. The compounds of Formulas 1A to 1C, 2A to 2F, 4A and 8A are several subsets of the compounds of Formula 1, 2, 4 and 8, and all substituents for Formula 1A to 1C, from 2A to 2F, 4A and 8A are as defined above for Formula 1, unless otherwise stated.
[0179] One or more of the following methods and variations, as described in Schemes 1 to 9, can be used to prepare the compounds of Formula 1. The definitions of Q, R1, R2 and R3 in the compounds of Formulas 1 to 11 to below are as defined above in the Brief Description of the Invention, unless otherwise stated.
[0180] As shown in Scheme 1 a Formula 1 compound can be prepared by nucleophilic substitution by heating a Formula 2 compound in a suitable solvent, such as acetonitrile, tetrahydrofuran or N, N-dimethylformamide in the presence of a base such as potassium hydroxide or cesium carbonate, at temperatures ranging from 50 to 110 ° C, with a compound of Formula 3, (where LG is halogen or SCteMe). The reaction is normally conducted at temperatures ranging from 50 to 110 ° C.
[0181] Alternatively, as shown in Scheme 2, Formula 5 boron compounds or Formula 6 tin compounds can be coupled with Formula 4 intermediates, under Suzuki or Stille conditions, to provide the compounds of Formula 1. Suzuki couplings are usually performed in the presence of Pd (0) or Pd (ll) salts, a suitable binder, and a base. Suitable bases for this transformation include potassium carbonate or cesium carbonate, while Pd (ll) salts such as Pd (OAc) 2 or PdCl2 can be used in conjunction with binders such as triphenylphosphine or 1,1 ' - bis (diphenylphosphine) ferrocene (dppf). The conditions for Suzuki couplings are described in the literature (see, for example, Angewandte Chemie International Edition2006, 45, 3,484 and Tetrahedron Letters2002, 58 (14), 2885). The boron intermediates of Formula 5 are commercially available or can be prepared from the corresponding halides or trifluoromethanesulfonates using methods known in the literature (see, for example, PCT patent publication WO 2007/043278, US patent 8,080,566, Organic Letters2011, 13 (6), 1,366 and Organic Letters, 2012, 14 (2), 600). Stille couplings can normally be conducted in the presence of the salt of Pd (0) or Pd (ll), a binder and a salt of Cu (l), such as copper iodide (l). The reaction can be carried out in a solvent such as dioxane, 1,2 dimethoxyethane or toluene, at a temperature ranging from room temperature to reflux. For conditions and reagents used in Stille couplings see Chemical Reviews from 2007, 107 (1), 133-173.
[0182] As shown in Scheme 3, a Formula 2C compound (that is, a Formula 2 compound where Z is O) can be prepared by deprotecting a Formula 2B compound (that is, a Formula compound 2A where Z is O, and RA is CH3 or -C (= O) CH3) with a suitable deprotecting agent. Suitable methoxy deprotection reagents (ie when RA is CH3) such as BBrs, AICI3 and HBr in acetic acid can be used in the presence of solvents, such as toluene, dichloromethane and dichloroethane, at a temperature of from -80 to 120 ° C. Suitable acetoxy deprotection reagents (that is, when RA is -C (= O) CH3) include potassium carbonate in methanol or ammonium acetate in aqueous methanol at room temperature, be used as discussed in Das, et al., Tetrahedron, 2003, 59, 1.049-1.054 and methods cited herein. Alternatively, a Formula 2B compound can be combined with Amberlist 15® in methanol (as discussed in Das, et al. Tet. Lett., 2003, 44, 5,465-5,468) or in combination with sodium acetate in ethanol (as discussed in Narender, T., et al. Sinthetic Communications, 2009, 39 (11), 1,949-1,956) to obtain a Formula 2C compound. Other suitable phenolic protecting groups useful for use in the preparation of a Formula 2C compound can be found in Greene, T. W .; Wuts, P.G.M, Protective Groups in Organic Sinthesis, 4th Ed .; Wilei: Hoboken, New Jersey, 1991.
[0183] A Formula 2B intermediate can be prepared as shown in Scheme 4 through a Formula 7 intermediate using a variety of methods known to a person skilled in the art. Formula 2B compounds can be accessed by coupling Formula 7 precursors, where J is Br, Cl, I or trifluoromethanesulfonate with heterocycles containing a boronate or trialkyl tin group (i.e., Formula 5 or Formula compounds 6 using the Suzuki conditions or the Stille conditions in Scheme 2). Alternatively, the Formula 7 compounds, where J is a boronate or trialkyl tin group, can be coupled with the halogen-substituted Q-X heterocycles using the methods shown in Scheme 2 to produce the Formula 2B compounds. The person skilled in the art will understand that, with the prudent selection of groups X and J in reactions involving the compounds of Formula 7 and QX, he can synthesize intermediate 2b, using various cross-coupling procedures such as Kumada coupling, coupling of Hiiama or Negishi coupling described in “Metal-Catalized Cross- Coupling Reaction“, Eds. A. de Meijere and F. Diederich, Wilei-VCH, Weinheim, 2004, Volumes 1 and 2.
[0184] When J in Formula 7 is an alkene, alkaline, oxime, nitrile or ketone, several heterocycles can be prepared using the methods described in Katritski, Advances in Heterociclic Chemistri, Vol. 1-104, Elsevier. In cases where regioisomeric mixtures are produced, the desired product can be isolated using routine separation techniques known in the art.
[0185] As shown in Scheme 5, a Formula 4A compound can be prepared by coupling Formula 9 phenols with a Formula 3 compound under the nucleophilic substitution conditions described in Scheme 1.
[0186] As shown in Scheme 6, a compound of Formula 1B, (ie, a compound of Formula 1 where Z is O; m and is 1 at position 3) can be prepared by “CH activation” of a compound Formula 1A (a Formula 1 compound where Z is O; em is 0). For example, palladium (II) acetate, together with either an N-halosuccinimide, Phl (OAc) 2, N-fluoropyridinium tetrafluoroborate, or a lower alkyl boronic acid can be used to introduce the variable R3 such as I, Br, Cl, -OAc, F, and the lower alkyl substituents, respectively. These methods are detailed in evaluations of selective activation of C-H bonds, in Chemical Reviews, 2010, 110, 575-1211 and the references cited in the present. Methods for “CH activation” can also be found in Wencel-Delord et al., Nature Chemistri, 2013, 5, 369-375 and a series of “CH activation” assessments in Accounts of Chemical Research, 2012, 45, 777-958 and the references cited herein. The Formula 1B iodides and bromides can then be further functionalized through the various cross-coupling procedures described in “Metal-Catalized Cross-Coupling Reactions", Eds A. de Meijere and F. Diederich, Wilei-VCH, Weinheim, 2004, Volumes 1 and 2.
[0187] Chemistry based on “CH activation” can also be used to prepare a Formula 2D compound (ie, a Formula 2 compound where Z is O; RA is -C (O) CHs; in is 1 in position 3) as shown in Scheme 7, using palladium (II) acetate and (diacetoxyiodine) benzene as described above for Scheme 6. A compound of Formula 2D can later be converted using the methods described in Schemes 1 and 6, to provide a Formula 1 compound.
[0188] Similarly, chemistry based on "CH activation" can be used to prepare a Formula 2F compound (i.e., a Formula 2A compound where Z is S) as shown in Scheme 8. A compound of Formula 8 can first be converted to a Formula 8A compound (that is, a Formula 6 compound in which the ortho "H" is X; and X is Br or I) through the use of a gradual introduction of substituents using “CH activation”. The Formula 8A iodides and bromides can then additionally be functionalized through copper-mediated cross coupling with thiourea, as described in Qi, Junsheng, Chin. J. Chem., 2010, 28, 1.441-1.443 to provide aryl thiol after acid deprotection. The catalyzed cross-coupling reactions of aryl halide palladium can provide the protected thiols which, in turn, can be unprotected, under acidic conditions or basic conditions (for example, cesium fluoride) to provide a Formula 2F compound. These conditions are discussed in Organ, Michael G., Angew. Chem. Int. Ed., 2012, 51, 3.314-3.322 and the references cited in the present. In addition, the relevant conditions can be found in Takashiro Itoh, J. Org. Chem., 2006, 71, 2,203-2,206. A Formula 2F compound can then be converted using the methods described in Schemes 1 and 7 to provide a Formula 1 compound.
[0189] In Scheme 9, phenol, 2E is reacted with N, N-dimethyl thiocarbamoyl chloride in N, N-dimethylformamide, in the presence of a strong tertiary amine base such as 1,4-diazabicyclo [2.2 .2] octane or N-methylmorpholine for acidic phenols (for less acidic phenols, previous deprotonation with sodium hydrate may be advantageous) to form Formula 10 O-aryl N, N-dimethylthiocarbamate. The rearrangement of Newman-Kwart of a Formula 10 compound at temperatures ranging from 200 to -300 ° C provides the Formula 11 S-aryl dimethylthiocarbamate intermediate. Deprotection of only one container of a Formula 11 compound is easily achieved using 10% aqueous sodium hydroxide or methanolic potassium hydroxide to obtain the corresponding aryl thiol. The subsequent reaction with a Formula 3 compound at room temperature slightly above provides the product 1C (i.e., a Formula 1 compound where Z is S). Methods for Newman-Kwart rearrangements are found in Lloid-Jones, Gui C., Sinthesis, 2008, 661-689.
It is recognized by a person skilled in the art that different functional groups can be converted to others to provide a different compound of Formula 1. For a valuable resource that illustrates the interconversion of functional groups in a simple and straightforward way, see Larock, RC, Comprehensive Organic Transformations: A Guide to Functional Group Preparations, 2aed, Wilei-VCH, New York, 1999. For example, intermediates for the preparation of a Formula 1 compound may contain aromatic nitro groups, which can be reduced to amino groups, and , then be converted by reactions well known in the state of the art such as the Sandmeier reaction, into various halides, providing a compound of Formula 1. The above reactions can also, in many cases, be carried out alternatively.
[0190] It is recognized that some reagents and reaction conditions described above for the preparation of a compound of Formula 1 may not be compatible with certain functionalities present in the intermediates. In such cases, the incorporation of protection / deprotection sequences or interconversions of functional groups in the synthesis will help to obtain the desired products. The use and selection of protection groups will be evident to a person skilled in the art in chemical synthesis (see, for example, Greene, TW; Wuts, PG Protective Groups M. in Organic Sinthesis, 4aed .; Wilei: Hoboken, New Jersey, 1991 ). A person skilled in the art will recognize that, in some cases, after the introduction of a particular reagent, as described in any individual scheme, it may be necessary to perform additional routine synthetic steps, not described in detail to complete the synthesis of compounds of Formula 1. A person skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the diagrams above in an order different from that implied by the special presented to prepare a Formula 1 compound.
[0191] A person skilled in the art will also recognize that a Formula 1 compound and the intermediates described herein can be subjected to various organometallic, electrophilic, nucleophilic, radical reduction and oxidation reactions, to add substituents or modify existing substituents.
[0192] Without further elaboration, it is believed that a technician in the subject, using the previous description, can use the present invention to its maximum extent. The following Examples, therefore, can be interpreted as merely illustrative, and do not limit the description in any way. The steps in the following Examples illustrate a procedure for each Step in a general synthetic transformation, and the starting material for each Step may not necessarily have been prepared by a special preparatory operation whose procedure is described in other Steps and Examples. The percentages are by weight, except for mixtures of chromatographic solvents or where otherwise indicated. The parts and percentages of the chromatographic solvent mixtures are by volume, unless otherwise specified. The NMR 1H spectra are described in ppm from tetramethylsilane in CDCI3 solution unless otherwise specified; "S" stands for singlet, "d" stands for doublet, "t" stands for triplet, "q" stands for quartet, "m" stands for doublet, "dt" stands for doublet of triplets, "bs" stands for broad singlet.
[0193] It is recognized by a person skilled in the art that different functional groups can be converted into others to provide different Formula 1 compounds. For a valuable resource that illustrates the interconversion of functional groups in a simple and straightforward way, see Larock, RC, Comprehensive Organic Transformations: A Guide to Functional Group Preparations, 2aed, Wilei-VCH, New York, 1999. For example, intermediates for the preparation of Formula 1 compounds may contain aromatic nitro groups, which can be reduced to amino groups, and then be converted by reactions well known in the state of the art such as the Sandmeier reaction, into various halides, providing the compounds of Formula 1. The above reactions can also, in many cases, be carried out alternatively .
[0194] It is recognized that some reagents and reaction conditions described above for the preparation of compounds of Formula 1 may not be compatible with certain functionalities present in the intermediates. In such cases, the incorporation of protection / deprotection sequences or interconversions of functional groups in the synthesis will help to obtain the desired products. The use and selection of protection groups will be evident to a person skilled in the art in chemical synthesis (see, for example, Greene, T. W .; Wuts, P. G. Protective Groups M. in Organic Sinthesis, 2nd ed .; Wilei: New York, 1991). A person skilled in the art will recognize that, in some cases, after the introduction of a particular reagent, as described in any individual scheme, it may be necessary to perform additional routine synthetic steps, not described in detail to complete the synthesis of compounds of Formula 1. A person skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the schemes above in an order different from that implied by the special one presented to prepare the Formula 1 compounds.
[0195] A person skilled in the art will also recognize that the compounds of Formula 1 and the intermediates described herein may be subjected to various organometallic, electrophilic, nucleophilic, radical reduction and oxidation reactions to add the substituents or modify the existing substituents.
[0196] Without further elaboration, it is believed that a technician in the subject, using the previous description, can use the present invention to its maximum extent. The following Examples, therefore, can be interpreted as merely illustrative, and do not limit the description in any way. The steps in the following Examples illustrate a procedure for each Step in a general synthetic transformation, and the starting material for each Step may not necessarily have been prepared by a special preparatory operation whose procedure is described in other Steps and Examples. The percentages are by weight, except for mixtures of chromatographic solvents or where otherwise indicated. The parts and percentages of the chromatographic solvent mixtures are by volume, unless otherwise specified. NMR 1H spectra are described in ppm from tetramethylsilane at 500 MHz in CDCh, unless otherwise stated; “S” stands for singlet, “d” stands for doublet, “t” stands for triplet, “q” stands for quartet, “m” stands for multiplet, “dd” stands for doublet of doubles and “dt” stands for doublet of triplets. EXAMPLE OF SUMMARY 1
[0197] Synthesis of 3- [2 - [(5-chloro-2-pyrimidinyl) oxy] phenyl] -5-isoxazolemethanol (Compound 31). STEP A
[0198] Synthesis of 5-chloro-2- [2- [5 - [[[(1,1-dimethylethyl) diphenylsilyl] oxy] methyl] -3-isoxazolyl] phenoxy] pyrimidine.
[0199] To a solution of 3- (2-methoxyphenyl) -5-isoxazolemethanol (prepared as described in Bioorganic Med. Chem. 2004, 12, 3,965 (0.500 mg, 0.243 mmol) in tetrahydrofuran (25 ml_) was added the chloride of f-butyldiphenylsilyl (0.804 mg, 2.92 mmol) followed by imidazole (0.199 mg, 2.92 mmol). After 2 h, the solvent was removed in vacuo. Purification using silica gel chromatography eluting with 0 to 100% ethyl acetate in hexanes to provide the intermediate 5 - [[[(1,1-dimethylethyl) diphenylsilyl] oxy] methyl] -3- (2-methoxyphenyl) isoxazole and the material was taken without further purification.
[0200] To a solution of 5 - [[[(1,1-dimethylethyl) diphenylsilyl] oxy] methyl] -3- (2-methoxyphenyl) isoxazole (3.10 g, 0.699 mmol) in dichloromethane (35 mL) to 0 ° C a boron tribromide solution (34.9 ml) was added and the 1.0 M reaction was stirred at this temperature for 1 h. The reaction was quenched with a saturated solution of sodium bicarbonate. The phases were separated, and the aqueous layer was washed with additional dichloromethane. The combined organic phases were combined, dried with MgSO4 and concentrated in vacuo. Purification by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes provided 2- [5- [[[1,1-dimethylethyl) diphenylsilyl] oxy] methyl] -3-isoxazolyl] phenol that was taken to the next step without further purification.
[0201] To a solution of 2- [5 - [[[(1,1-dimethylethyl) diphenylsilyl] oxy] methyl] - 3-isoxazolyl] phenol (2.78 g, 6.47 mmol) in acetonitrile (60 mL ) were added to 2,5-dichloropyrimidine (1.15 g, 7.70 mmol) and potassium carbonate (2.24 g, 16.2 mmol) and the reaction was heated at 80 ° C for 6 h. The reaction mixture was allowed to warm to room temperature and the solvent was removed in vacuo. Purification by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes provided the title compound (2.27 g).
[0202] NMR 1H õ 8.41 (s, 2H), from 8.00 to 7.97 (m, 1H), from 7.67 to 7.61 (m, 4H), from 7.56 to 7, 50 (m, 1H), 7.47 to 7.36 (m, 7H), 7.28 to 7.26 (m, 1H), 6.56 (t, 1H), 1.05 (s, 9H). MS (AP +) = 542. STEP B
[0203] Synthesis of 3- [2 - [(5-chloro-2-pyrimidinyl) oxy] phenyl] -5-isoxazolemethanol.
[0204] To a solution of 5-chloro-2- [5 - [[[(1,1-dimethylethyl) diphenylsilyl] oxy] methyl] -3-isoxazolyl] phenoxy] pyrimidine (i.e., the product of Step A) (2.27 g, 4.19 mmol) in tetrahydrofuran (15 mL) was added acetic acid (0.50 mL) followed by a 75% solution of tetrabutylammonium fluoride in water (2.9 mL) and the reaction was left to stir for 2 h. The reaction was brusquely cooled with a saturated sodium bicarbonate solution and the phases were shared and the aqueous phase was further washed with ethyl acetate. The combined organic phases were combined, dried over MgSCU and concentrated in vacuo. Purification by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes provided the title compound, a compound of the present invention (1.21 g).
[0205] NMR 1H δ 8.45 (s, 2H), 7.99 to 7.95 (m, 1H), 7.56 to 7.52 (m, 1H), 7.42 to 7, 38 (m, 1H), from 7.28 to 7.25 (m, 1H), from 6.64 to 6.61 (m, 1H), from 4.77 to 4.73 (m, 2H). EXAMPLE OF SUMMARY 2
[0206] Synthesis of 3- [2 - [(5-chloro-2-pyrimidinyl) oxy] phenyl] -5-isoxazolecarboxaldehyde (Compound 33). STEP A
[0207] Synthesis of 3- [2 - [(5-chloro-2-pyrimidinyl) oxy] phenyl] -5-isoxazolecarboxaldehyde.
[0208] The pyridinium chlorochromate (263 mg, 1.22 mmol) and silica gel (200 mg) were combined and mixed as solids. This mixture was then added to a stirred solution of 3- [2 - [(5-chloro-2-pyrimidinyl) oxy] phenyl] -5-isoxazolemethanol (i.e., the product obtained in Step A of Example 1) (309 mg, 1.02 mmol) in dichloromethane (5.0 ml) and the reaction was allowed to stir for 18 h. The solution was filtered to remove the silica gel and the organic phase was washed with a 1 M hydrochloric acid solution. The organic phase was dried with MgSCM and concentrated in vacuo. Purification by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes provided the title compound, a compound of the present invention (0.307 g).
[0209] NMR 1H δ 9.95 (s, 1H), 8.46 (s, 2H), from 8.06 to 8.01 (m, 1H), from 7.61 to 7.56 (m, 1H ), from 7.47 to 7.41 (m, 1H), 7.38 (s, 1H), from 7.32 to 7.29 (m, 1H). MS (AP +) = 302. EXAMPLE OF SUMMARY 3
[0210] Synthesis of 5-chloro-2- [2- [5- (difluoromethyl) -3-isoxazolyl] phenoxy] pyrimidine (Compound 35). STEP A
[0211] Synthesis of 5-chloro-2- [2- [5- (difluoromethyl) -3-isoxazolyl] phenoxy] pyrimidine.
[0212] To a stirred solution of 3- [2 - [(5-chloro-2-pyrimidinyl) oxy] phenyl] -5-isoxazolecarboxaldehyde (i.e., the product from Step A of Example 2) (100 mg, 0.332 mmol ) in dichloromethane (3.0 ml), at -78 ° C, Desoxo-Fluor® (161 mg, 0.729 mmol) was added and the reaction was allowed to return to room temperature. After consuming the starting material as evidenced by thin layer chromatography, the solvent was removed in vacuo. Purification by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes provided the title compound, a compound of the present invention (36.3 mg).
[0213] NMR 1H õ 8.46 (s, 2H), from 8.01 to 7.96 (m, 1H), from 7.59 to 7.54 (m, 1H), from 7.44 to 7, 38 (m, 1H), from 7.31 to 7.27 (m, 1H), from 6.98 to 6.96 (s, 1H), from 6.83 to 6.60 (m, 1H). MS (ESP) = 324. EXAMPLE OF SUMMARY 4
[0214] Synthesis of 2- [2- (3-bromo-5-isoxazolyl) phenoxy] -5-chloropyrimidine (Compound 12). STEP A
[0215] Synthesis of 3-bromo-5- (2-methoxyphenyl) isoxazole.
[0216] To a solution of 1-ethynyl-2-methoxybenzene (0.78 g, 5.92 mmol) in dichloromethane (10 mL) was added to dibromoformaldoxima (1.00 g, 4.93 mmol). The mixture was cooled to 0 ° C and potassium bicarbonate (1.48 g, 14.8 mmol) was added, followed by heating at 40 ° C for 18 h. Water was added to the reaction mixture, the phases were separated, and the aqueous layer was washed again with dichloromethane. The combined organic phases were dried over MgSO4, concentrated in vacuo, and purified by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes to provide the title compound, a compound of the present invention (1, 04 g).
[0217] NMR 1H δ 7.94 (dd, 1H), from 7.47 to 7.42 (m, 1H), 7.09 (dd, 1H), 7.02 (dd, 1H), 6.85 (s, 1H), 3.97 (s, 3H). MS (AP +) = 254. STEP B
[0218] Synthesis of 2- (3-bromo-5-isoxazolyl) phenol.
[0219] To a solution of 3-bromo-5- (2-methoxyphenyl) isoxazole (i.e., the product of Step A) (0.50 g, 1.97 mmol) in dichloromethane (20 mL) was added a solution at 1 M boron tribromide in dichloromethane (9.86 mmol) at -78 ° C and the solution was allowed to warm to room temperature and stirred for 18 h. Dichloroethane (20 ml) was added, and the reaction mixture was concentrated to remove excess dichloromethane. Boron tribromide in dichloromethane (9.86 mmol) was added again and the reaction was heated to 80 ° C until completion, as evidenced by thin layer chromatography. The reaction mixture was allowed to cool to room temperature and quenched with a saturated solution of sodium bicarbonate. The phases were separated and the aqueous layer was washed again with dichloromethane. The combined organic phases were dried with MgSCU, concentrated in vacuo, and purified by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes to provide the title compound (0.395 g).
[0220] NMR 1H õ 7.76 (dd, 1H), from 7.39 to 7.33 (m, 1H), from 7.09 to 7.02 (m, 1H), from 6.96 to 6, 93 (m, 1H), 6.02 (s, 1H). MS (AP-) = 238. ETAPAC
[0221] 2- [2- (3-bromo-5-isoxazolyl) phenoxy] -5-chloropyrimidine.
[0222] To a solution of 2- (3-bromo-5-isoxazolyl) phenol (i.e., the product from Step B) (100 mg, 0.417 mmol) in acetonitrile (5 mL) was added to 2,5-dichloropyrimidine (75.0 mg, 0.503 mmol) and potassium carbonate (288 mg, 2.08 mmol), then the solution was stirred at room temperature for 18 h. The reaction was then heated to 40 ° C for 2 h followed by 80 ° C for two hours. The solution was then cooled to room temperature, water was added, the phases were separated and the aqueous layer was washed again with dichloromethane. The combined organic phases were dried over MgSCH, concentrated in vacuo, and purified by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes to provide the title compound, a compound of the present invention (122 mg ).
[0223] NMR 1H δ 8.49 (s, 2H), 8.03 (dd, 1H), from 7.58 to 7.53 (m, 1H), 7.43 (dt, 1H), 7.29 (dd, 1H), 6.74 (s, 1H). MS (AP +) = 352. EXAMPLE OF SUMMARY 5
[0224] Synthesis of 5-chloro-2- [2- [4- (trifluoromethyl) -2-pyridinyl] phenoxy] pyrimidine (Compound 25). STEP A
[0225] Synthesis of 2- [4- (trifluoromethyl) -2-pyridinyl] phenol.
[0226] 2-chloro-4-trifluoromethylpyridine (1.0 g, 5.5 mmol) and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenol ( 1.57 g, 7.16 mmol) were combined in dimethoxyethane (18 ml) and water (1.8 ml). To this mixture were added sodium carbonate (2.28 g, 16.5 mmol) and tetrakis (triphenylphosphine) palladium (0) (0.32 g, 0.27 mmol). The reaction was heated to 90 ° C for 2.5 h and allowed to stir at 23 ° C for 18 h. The mixture was diluted with water (20 ml) and dichloromethane (20 ml) and the layers were separated. The aqueous layer was washed with dichloromethane (10 ml). The combined dichloromethane layers were washed with a saturated aqueous sodium chloride solution (10 ml) and dried over sodium sulfate. After filtration, the organic phase was evaporated and then the solid obtained was triturated with hexanes (20 ml). The filtrate was concentrated to provide 1.18 g of the title compound as a yellow solid, which was used in Step B without further purification.
[0227] NMR 1H δ 13.61 (s, 1H), 8.72 (d, 1H), 8.12 (s, 1H), 7.83 (d, 1H), 7.47 (m, 1H) , 7.36 (s, 1H), 7.06 (d, 1H), 6.96 (t, 1H). STEP B
[0228] Synthesis of 5-chloro-2- [2- [4- (trifluoromethyl) -2-pyridinyl] phenoxy] pyrimidine.
[0229] 2- [4- (trifluoromethyl) -2-pyridinyl] phenol (i.e., the product of Step A) (0.20 g, 0.84 mmol) and 2.5-dichloropyrimidine (0.14 g , 0.92 mmol) were dissolved in acetonitrile (2 mL) and treated with powdered potassium carbonate (0.34 g, 2.5 mmol). The mixture was heated to 80 ° C for 18 h. After cooling, the reaction mixture was diluted with water (10 ml) and ethyl acetate (10 ml) and the layers were separated. The aqueous layer was washed with ethyl acetate (10 ml). The combined ethyl acetate solution was washed with a saturated aqueous sodium chloride solution (10 mL) and dried over MgSCU. The filtrate was evaporated under reduced pressure and subjected to chromatography through 12 g of silica gel eluting with 10 to 20% ethyl acetate in hexanes. The appropriate fractions were combined and evaporated to provide the title compound, a compound of the present invention (0.2 g) as a clear oil.
[0230] NMR 1H δ 8.75 (d, 1H), 8.39 (s, 2H), 7.91 (s, 1H), 7.88 (m, 1H), 7.54 (m, 1H) , 7.44 (m, 1H), 7.37 (d, 1H), 7.28 (m, 1H). EXAMPLE OF SUMMARY 6
[0231] Synthesis of 5-chloro-2- [4-methyl-2- [6- (trifluoromethyl) -3-pyridinyl] phenoxy] pyrimidine (Compound 22). STEP
[0232] Synthesis of 2- (2-bromo-4-methylphenoxy) -5-chloropyrimidine.
[0233] 2-bromo-4-methylphenol (280 mg, 1.5 mmol) and 2,5-dichloropyrimidine (246 mg, 1.65 mmol) were combined in 6 mL of acetonitrile under an atmosphere of nitrogen. Powdered potassium carbonate (455 mg, 3.3 mmol) was added and the resulting mixture was heated to reflux for 6 h. The reaction mixture was cooled and diluted with deionized water and ethyl acetate. The aqueous layer was separated and extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over MgSCM, filtered and concentrated under reduced pressure. The resulting residue was purified by medium pressure liquid chromatography on silica gel eluting with 0 to 15% ethyl acetate in hexanes to produce the title compound (270 mg).
[0234] NMR 1H δ 8.48 (s, 2H), 7.47 (d, 1H), 7.18 (m, 1H), 7.11 (m, 1H), 2.37 (s, 3H) . STEP B
[0235] Synthesis of 5-chloro-2- [4-methyl-2- [6- (trifluoromethyl) -3-pyridinyl] phenoxy] pyrimidine.
[0236] A mixture of 2- (2-bromo-4-methylphenoxy) -5-chloropyrimidine (ie, the product of Step A; 190 mg, 0.63 mmol), B- [6- (trifluoromethyl) - 3-pyridinyl] -boronic (133 mg, 0.70 mmol), sodium carbonate (0.6 mL of a 2 M aqueous solution, 1.26 mmol) and tetrakis (triphenylphosphine) palladium (0) (73 mg, 0 , 06 mmol) in toluene (9 ml) and ethanol (1 ml) was heated to 90 ° C for 2 h. The reaction mixture was then concentrated under reduced pressure, and the residue was purified by medium pressure liquid chromatography on the silica gel eluted with 0 to 10% ethyl acetate in hexanes to produce the title compound, a compound of the present invention (190 mg).
[0237] NMR 1H δ 8.77 (d, 1H), 8.36 (s, 2H), 8.02 (m, 1H), 7.64 (d, 1H), 7.31 (m, 2H) , 7.15 (d, 1H), 2.45 (s, 3H). EXAMPLE OF SUMMARY 7
[0238] Synthesis of 5-chloro-2- [2- [3- (difluoromethyl) -5-isoxazolyl] phenoxy] pyrimidine (Compound 53). STEP A
[0239] Synthesis of 2- (3-difluoromethyl-5-isoxazolyl) phenol.
[0240] To a solution of 25% sodium methoxide in methanol (5 ml) and tetrahydrofuran (10 ml), acetophenone (1 g, 7.3 mmol) and difluoroacetate (1 g, 8.1 mmol) in tetrahydrofuran (2 ml) were added and heated to 60 ° C for 5 h. The reaction was cooled to room temperature and treated with 36% aqueous hydrochloric acid (4 ml) and stirred at 60 ° C for 2 h. The reaction was quenched by the addition of water (15 ml) and the organic solvent was removed in vacuo. The precipitated product of 2-difluoromethyl-4-chromenone (1.4 g) was filtered and dissolved in ethanol (5 ml). To this solution, hydroxylamine acetate (22 mmol) in water (5 ml) was added and the mixture was heated at 60 ° C for 3 h. After cooling the reaction to room temperature, 4,4-difluoro-1- (2-hydroxyphenyl) -butane-1,3-dione-3-oxime was precipitated with the addition of water (20 ml). This product was collected by filtration and suspended in acetic acid (5 ml) and 36% aqueous hydrochloric acid (1.8 ml) at room temperature and stirred at 80 ° C for 15 minutes to obtain the title compound as a solid. beige (800 mg).
[0241] NMR 1H δ 7.82 (m, 1 H), 7.36 (s, 1 H), 7.07 (m, 1 H), 6.95 (m, 2H), 6.82 (t , 1H), 6.05 (s, 1H). MS (ESI +) = 212 ETAPAB
[0242] Synthesis of 5-chloro-2- [2- [3- (difluoromethyl) -5-isoxazolyl] phenoxy] - pyrimidine.
[0243] To a solution of 2- (3-difluoromethyl-5-isoxazolyl) phenol (i.e., the product of Step A) (2.1 g, 9.71 mmol) in N, N-dimethylformamide (8 mL) 2,5-dichloropyrimidine (1.5 g, 10.2 mmol) and potassium carbonate (2.9 g, 21.3 mmol) were added. The reaction was heated to 90 ° C for 1 h. The solution was cooled to room temperature and diluted with water. The phases were separated and the aqueous phase was washed with additional ethyl acetate. The organic phases were combined, dried with magnesium sulfate and concentrated in vacuo. Purification by chromatography on silica gel eluting with 0 to 10% ethyl acetate in hexanes provided the title compound, a compound of the present invention, as a solid (2.2 g) -
[0244] NMR 1H δ 8.49 (s, 2H), 8.06 (m, 1H), 7.57 (m, 1H), 7.44 (m, 1H), 7.31 (m, 1H) , 6.88 (s, 1H), 6.74 (t, 1H). MS (ESI +) = 324 EXAMPLE OF SUMMARY 8
[0245] Synthesis of 5-chloro-2- [2- [3- (difluoromethyl) -5-isoxazolyl] -3-fluorophenoxy] pyrimidine (Compound 144). STEP A
[0246] Synthesis of 4,4-difluoro-1- (2-fluoro-6-methoxyphenyl) butane-1,3-dione.
[0247] To a solution of 1- (2-fluoro-6-methoxyphenyl) ethanone (2.6 g, 15.5 mmol) and difluoroacetic acid ethyl ester (3.9 mL, 31.0 mmol) in N , N-dimethylformamide at 0 ° C sodium hydride (1.2 g, 31.0 mmol) was added. The reaction mixture was heated to 80 ° C for 1 h. The reaction was then cooled to 0 ° C, diluted with ethyl acetate and acidified with 1 N aqueous hydrochloric acid. The phases were separated and the aqueous phase was washed with additional ethyl acetate. The organic phases were combined and dried with magnesium sulfate and concentrated in vacuo. Purification by chromatography on silica gel eluting with 0 to 15% ethyl acetate in hexanes provided the title compound (2.5 g).
[0248] NMR 1H δ 7.39 (m, 1H), 6.77 (m, 2H), 6.24 (s, 1H), 6.01 (t, 1H), 3.87 (s, 3 H ). MS (ESP) = 247. STEP B
[0249] Synthesis of 3-difluoromethyl-5- (2-fluoro-6-methoxyphenyl) isoxazole.
[0250] A solution of 4,4-difluoro-1- (2-fluoro-6-methoxyphenyl) butane-1,3-dione (i.e., the product of Step A) (2.5 g, 10 mmol) and hydroxylamine hydrochloride (2.1 g, 30 mmol) in ethanol (25 ml) was stirred at 80 ° C. After 1 h, the solvent was removed in vacuo. The resulting residue was diluted with water and extracted with dichloromethane. The organic phase was dried with magnesium sulfate and concentrated in vacuo. Purification by chromatography on silica gel eluting with 0 to 15% ethyl acetate in hexanes provided the title compound (1.5 g).
[0251] NMR 1H δ 7.41 (m, 1 H), from 6.69 to 6.98 (m, 4H), 3.93 (s, 3 H). MS (ESP) = 244 STEP C
[0252] Synthesis of 2- (3-difluoromethyl-5-isoxazolyl) -3-fluorophenol.
[0253] To a solution of 3-difluoromethyl-5- (2-fluoro-6-methoxyphenyl) isoxazole (i.e., the product of Step B) (1.5 g, 6.2 mmol.) In dichloromethane (10 mL ) at 0 ° C a 1.0 M solution of boron tribromide in dichloromethane (31 mL, 31 mmol) was added. The reaction mixture was warmed to room temperature and stirred for 6 h. The reaction was cooled to 0 ° C and slowly abruptly cooled with a saturated aqueous solution of sodium bicarbonate. The biphasic mixture was stirred at room temperature for 1 h. The phases were separated and the aqueous phase was extracted with dichloromethane. The combined organic phases were dried and concentrated in vacuo. The crude residue was purified by chromatography on silica gel, eluting with 0 to 10% ethyl acetate in hexanes, to provide the title compound (980 mg).
[0254] 1H NMR δ 7.33 (m, 1 H), from 6.66 to 6.99 (m, 4 H). MS (ESP) = 230 STEP D
[0255] Synthesis of 5-chloro-2- [2- [3- (difluoromethyl) -5-isoxazolyl] -3-fluorophenoxy] pyrimidine.
[0256] To a solution of 2- (3-difluoromethyl-5-isoxazolyl) -3-fluorophenol (i.e., the product of Step C) (120 mg, 0.5 mmol) in N, N-dimethylformamide (2 mL ) were added to 2,5-dichloropyrimidine (85 mg, 0.57 mmol) and potassium carbonate (244 mg, 1.04 mmol). The reaction was heated to 80 ° C for 4 h. The mixture was cooled to room temperature and diluted with water. The phases were separated and the aqueous phase was washed with additional ethyl acetate. The organic phases were combined, dried with magnesium sulfate and concentrated in vacuo. Purification by chromatography on silica gel eluting with 0 to 15% ethyl acetate in hexanes provided the title compound, a compound of the present invention, as a solid (110 mg).
[0257] NMR 1H δ 8.46 (s, 2H), 7.56 (m, 1H), 7.21 (m, 1H), 7.13 (m, 1H), 6.87 (m, 1 H ), 6.74 (t, 1H). MS (ESP) = 342 EXAMPLE OF SUMMARY 9
[0258] Synthesis of 5-chloro-2- [2- [5- (difluoromethyl) -3-isoxazolyl] -3-fluorophenoxy] pyrimidine (Compound 55). STEP A
[0259] Synthesis of 4,4-difluoro-1- (2-fluoro-6-methoxyphenyl) butane-1,3-dione.
[0260] A solution of 2-fluoro-6-methoxyacetophenone (6.83 g, 40.6 mmol) and ethyl difluoroacetate (7.45 g, 60 mmol) in tetrahydrofuran (35 mL) was added dropwise to a solution tetrahydrofuran (20 mL) and 25% sodium methoxide (10.2 g, 47.2 mmol) for 15 minutes. The reaction was complete in 3 hours, as determined by high pressure liquid chromatography. The reaction mixture was partially concentrated in vacuo to remove most of the tetrahydrofuran and methanol, and then diluted with toluene and water. The aqueous phase was acidified with 37% hydrochloric acid (5 g), followed by extraction with toluene. The combined organic phases were concentrated in vacuo to provide the title compound (7.98 g).
[0261] NMR 1H õ 7.39 (td, 1 H) from 6.72 to 6.81 (m, 2 H) 6.25 (d, 1 H) from 5.87 to 6.14 (m, 1 H) 3.88 (s, 3 H). STEP B
[0262] Synthesis of 5- (difluoromethyl) -3- (2-fluoro-6-methoxyphenyl) -4H-isoxazol-5-ol.
[0263] To a solution of 4,4-difluoro-1- (2-fluoro-6-methoxyphenyl) butane-1,3-dione (i.e., the product of Step A) (7.98 g, 32.4 mmol) in 35 mL of methanol at room temperature, a 50% hydroxylamine solution (2.78 g, 42.1 mmol) and 1 N sodium hydroxide (1.50 mL, 1.50 mmol) was added followed by heating at 65 ° C for 2h. The reaction was cooled to room temperature and diluted with water and toluene. The phases were separated and the organic phase was concentrated in vacuo, to provide the title compound (7.99 g).
[0264] NMR 1H õ 7.36 (td, 1 H) from 6.73 to 6.82 (m, 2 H) from 5.79 to 6.05 (m, 1 H) 3.88 (s, 3 H) from 3.67 to 3.73 (m, 1 H) from 3.47 to 3.51 (m, 1 H) from 3.34 to 3.42 (m, 1 H). STEP C
[0265] Synthesis of 5- (difluoromethyl) -3- (2-fluoro-6-methoxyphenyl) isoxazole.
[0266] To toluene (80 mL) was added 5- (difluoromethyl) -3- (2-fluoro-6-methoxyphenyl) -4H-isoxazol-5-ol (i.e., the product of Step B) (7, 99 g, 30.6 mmol) followed by p-toluenesulfonic acid monohydrate (0.700 g, 3.68 mmol). The mixture was heated to a vigorous reflux (from 107 to 111 ° C) for two hours, at which point, high pressure liquid chromatography determined that the reaction was complete. The cooled reaction mixture was washed with a saturated sodium bicarbonate solution, followed by water. The organic phase was concentrated in vacuo, to provide the title compound (7.44 g).
[0267] NMR 1H δ 7.40 (td, 1 H) from 6.69 to 6.94 (m, 4 H) 3.88 (s, 3 H). STEP D
[0268] Synthesis of 2- [5- (difluoromethyl) -3-isoxazolyl] -3-fluorophenol.
[0269] To a solution of 5- (difluoromethyl) -3- (6-methoxyphenyl-2-fluoro) isoxazole (i.e., the product of Step C) (3.72 g, 15.3 mmol) in dichloromethane (15 ml) at 3 ° C a 1 M solution of boron tribromide in dichloromethane (18.0 ml, 18 mmol) was added over 5 min. The reaction was then allowed to warm to room temperature. After 90 minutes, the reaction was determined to be complete using high pressure liquid chromatography and the reaction was treated with a 10% aqueous solution of potassium bicarbonate (10 mL). The phases were separated and the organic phase was concentrated in vacuo. The resulting brown solid was triturated with a water / methanol solution (about 1/2) providing the title compound (3.34 g).
[0270] NMR 1H δ from 9.63 to 9.75 (m, 1 H) 7.33 (td, 1 H) 7.21 (ddd, 1H), from 6.71 to 6.96 (m, 3 H). STEP
[0271] Synthesis of 5-chloro-2- [2- [5- (difluoromethyl) -3-isoxazolyl] -3-fluorophenoxy] pyrimidine.
[0272] To a solution of 2- [5- (difluoromethyl) -3-isoxazolyl] -3-fluorophenol (i.e., the product of Step D) (1.61 g, 7.02 mmol) and 5-methyl- 2-methylsulfonylpyrimidine (1.49 g, 7.72 mmol) in N, N-dimethylformamide (9 mL) potassium carbonate (4.24 g, 17.5 mmol) was added and the reaction was allowed to stir at temperature room for 24 h. The reaction was diluted with water and toluene, the phases were separated and the organic solvent was removed in vacuo. To the resulting oil, 8 ml of methanol and a brown paste formed were added, after dilution with a methanol / water solution (20 ml), the precipitate was filtered providing the title compound, a compound of the present invention (2.24 g) .
[0273] NMR 1H δ 8.45 (s, 2 H) 7.54 (td, 1 H) 7.19 (ddd, 1H), 7.14 (dt, 1H), 6.88 (dt, 1H) from 6.61 to 6.85 (m, 1 H). EXAMPLE OF SUMMARY 10
[0274] Preparation of 5-chloro-2- [3-cyano-2- [4- (trifluoromethyl) -2-pyridinyl] phenoxy] pyrimidine (Compound 158).
[0275] A solution of 5-chloro-2- [2- [4- (trifluoromethyl) -2-pyridinyl] phenoxy] pyrimidine (i.e., the product of Example 5, Step B) (0.30 g, 0.853 mmol ) in 4.27 mL of N, N-dimethylformamide under a nitrogen atmosphere was treated with copper (II) bromide (0.19 g, 0.853 mmol), palladium (II) acetate (9 mg, 0.0426 mmol) and potassium ferricyanide (0.06 g, 0.17 mmol). The mixture was heated at 130 ° C for 18 hours. The mixture was then cooled, diluted with diethyl ether and water, filtered through a pad of celite and rinsed with ethyl acetate and water. The phases were separated and the aqueous phase was extracted twice with diethyl ether. The combined organic phases were washed twice with water and saturated aqueous sodium chloride, dried over magnesium sulfate, and concentrated to provide 0.21 g of the crude product. The crude product was purified with 12 g of Teledine Isco silica gel column eluting with 10 to 30% EtOAc-hexanes gradient to provide the title compound, a compound of the present invention as a solid (0.23 g) .
[0276] NMR 1H δ 8.86 (d, 1H), 8.40 (s, 2H), 7.78 (d & s, 2H), 7.62 (t, 1H), 7.52 (d, 1H), 7.50 (d, 1H). EXAMPLE OF SUMMARY 11
[0277] Synthesis of 5-chloro-2- [2- [5- (trifluoromethyl) -2-pyridinyl] phenoxy] pyrimidine (Compound 27). STEP A
[0278] Synthesis of 2- [5- (trifluoromethyl) -2-pyridinyl] phenol.
[0279] 2-chloro-5- (tnfluoromethyl) pyridine (1.0 g, 5.50 mmol) and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl ) phenol (1.57 g, 7.16 mmoles) were combined in 16 ml of 1,2-dimethoxyethane and 1.8 ml of deionized water, under an atmosphere of nitrogen. Solid sodium carbonate (2.28 g, 16.5 mmoles) and then tetrakis (triphenylphosphine) palladium (0) (0.32 g, 0.27 mmoles) were added. The reaction was heated to reflux for about 90 minutes. The reaction was cooled, diluted with dichloromethane and filtered through a pad of celite, washed with dichloromethane and then with deionized water. The phases were separated. The aqueous phase was extracted twice with dichloromethane. The combined organic phases were washed with saturated aqueous sodium chloride, dried over magnesium sulfate, filtered and concentrated to provide a solid. A solid was filtered over hexanes to provide 34 mg. A second collection was obtained from the filtrate in hexanes to obtain 506 mg of a light brown-orange solid of the title compound.
[0280] NMR 1H δ 8.81 (s, 1H), 8.04 (m, 2H), 7.83 (d, 1H), 7.38 (t, 1H), 7.07 (d, 1H) , 6.98 (t, 1H). ETAPAB
[0281] Synthesis of 5-chloro-2- [2- [5- (trifluoromethyl) -2-pyridinyl] phenoxy] - pyrimidine.
[0282] A mixture of 2- [5- (trifluoromethyl) -2-pyridinyl] phenol (i.e., the product of Step A) (0.20 g, 0.836 mmol) and 2.5-dichloropyrimidine (0.14 g , 0.919 mmol) in 2.0 mL of N, N-dimethylformamide was stirred under an atmosphere of nitrogen. Powdered potassium carbonate (0.35 g, 2.51 mmoles) was added and the mixture was heated to 80 ° C overnight. The reaction was cooled before diluting with deionized water and diethyl ether. The phases were separated. The aqueous phase was extracted twice with diethyl ether. The combined organic phases were washed three times with deionized water, dried over sodium sulfate, filtered and concentrated to 0.37 g of solid. A solid was filtered from hexanes and some diethyl ether to provide 103 mg of the title compound, a compound of the present invention.
[0283] NMR 1H δ 8.84 (s, 1H), 8.40 (s, 2H), 7.92 (d, 1H), 7.87 (sed, 2H), 7.54 (t, 1H) , 7.45 (t, 1H), 7.27 (d, 1H). EXAMPLE OF SUMMARY 12
[0284] Preparation of 5-chloro-2- [2- [5- (trifluoromethyl) -2-pyridinyl] -3-chlorophenoxy] pyrimidine (Compound 160).
[0285] A 5-chloro-2- [2- [5- (trifluoromethyl) -2-pyridinyl] phenoxy] -pinmidine (i.e., the product of example 11, step B) (0.14 g, 0.398 mmol) was dissolved in 2 ml of acetic acid. Palladium acetate (0.01 g, 0.039 mmol) and N-chlorosuccinimide (0.11 g, 0.796 mmol) were added and the mixture was heated at 100 ° C for three hours. The mixture was cooled overnight at room temperature and then diluted with toluene and ethyl acetate. The mixture was filtered through a pad of celite, washed with toluene and then with ethyl acetate. The filtrate was washed twice with saturated aqueous sodium hydrogen carbonate, saturated aqueous sodium chloride, dried over magnesium sulfate and concentrated to a crude product. The crude product was purified with 12 g of a Teledine Isco silica gel column eluting with 10 to 30% EtOAc-hexanes gradient to provide the title compound, a compound of the present invention as a solid (40 mg).
[0286] NMR 1H δ 8.82 (s, 1H), 8.41 (s, 2H), 7.93 (d, 1H), 7.52 (d, 1H), 7.47 (m, 2H) , 7.19 (m, 1H). EXAMPLE OF SUMMARY 13
[0287] Synthesis of 5-bromo-2- [2- [5- (difluoromethyl) -3-isoxazolyl] phenoxy] pyrimidine (Compound 62). STEP A
[0288] Synthesis of 5- (difluoromethyl) -3- (2-methoxyphenyl) isoxazole.
[0289] To a solution of acetophenone (3.0 g, 20 mmol) in methanol (15 mL) was added 30% sodium methoxide in methanol solution (5.0 mL) and the reaction was stirred for five minutes . Then ethyl difluoroacetate (2.97 g, 24 mmol) was added and the reaction was heated to reflux for 18 h. The reaction was allowed to cool to room temperature and the solvent was removed in vacuo. To the residue, 1 M hydrochloric acid and ethyl acetate were added, the phases were separated, the organic phase was dried using magnesium sulfate and the solvent was removed in vacuo. Purification by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes provided the desired product, which was taken directly. A solution of 4,4-difluoro-1- (2-methoxyphenyl) butane-1,3-dione from the previous Step in ethanol (30 ml) was added dropwise to a hydroxylamine hydrochloride solution (1.4 g, 20 mmol) in 1 M sodium hydroxide (21 mL). The reaction was then heated to reflux for 2 h, followed by cooling to room temperature. The product was precipitated from the solution by adding water and collected through vacuum filtration to provide the desired product, which was directly taken (AP + 244, NMR 1H õ ppm 7.79 (d, 1 H) from 7 , 38 to 7.46 (m, 1 H) from 6.93 to 7.04 (m, 2 H) from 5.76 to 6.04 (m, 1 H) 3.88 (s, 3 H) of 3.67 to 3.80 (m, 1 H) from 3.49 to 3.55 (m, 1 H)). Then, a solution of 5- (difluoromethyl) -3- (2-methoxyphenyl) -4H-isoxazol-5-ol from the previous Step was taken up in trifluoroacetic acid (20 ml) and heated at 70 ° C for 18 h . The reaction was cooled to room temperature and the solvent was removed in vacuo. The resulting residue was dissolved in dichloromethane and washed with a saturated sodium bicarbonate solution. The phases were separated, the organic phase was dried using magnesium sulfate and the solvent was removed in vacuo. Purification by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes provided the title compound (2.0 g, AP + = 226).
[0290] NMR 1H õ 7.91 (dd, 1 H) from 7.42 to 7.50 (m, 1 H) from 6.98 to 7.12 (m, 3 H) from 6.66 to 6, 93 (m, 1 H) 3.92 (s, 3 H). STEP B
[0291] Synthesis of 2- [5- (difluoromethyl) -3-isoxazolyl] phenol.
[0292] To a solution of 5- (difluoromethyl) -3- (2-methoxyphenyl) isoxazole (i.e., the product of Step A) (2.01 g, 8.92 mmol) in dichloromethane (50 mL) at 0o A 1 M solution of boron tribromide in dichloromethane (13.3 ml, 13.3 mmol) was added and the reaction was allowed to warm to room temperature over three hours. The solvent was removed in vacuo and purified by chromatography on silica gel, eluting with 0 to 100% ethyl acetate in hexanes to provide the title compound (1.66 g, AP = 210).
[0293] NMR 1H õ 9.14 (s, 1 H) 7.51 (dd, 1 H) 7.39 (ddd, 1 H) 7.11 (dd, 1 H) from 6.97 to 7.04 (m, 2 H) from 6.70 to 6.95 (m, 1 H). STEP C
[0294] Synthesis of 5-bromo-2- [2- [5- (difluoromethyl) -3-isoxazolyl] phenoxy] -pyrimidine.
[0295] To a solution of 2- [5- (difluoromethyl) -3-isoxazolyl] phenol (i.e., the product of Step B) (427 mg, 2.01 mmol) and 5-bromo-2-chloro-pyrimidine (468 mg, 2.42 mmol) in acetonitrile (10 mL) potassium carbonate (695 mg, 5.03 mmol) was added and the reaction was heated at 80 ° C for 18 h. The solvent was removed in vacuo and purified by chromatography on silica gel, eluting with 0 to 100% ethyl acetate in hexanes to provide the title compound, a compound of the present invention, as a solid (555 mg, mp = 88.9 to 92.8 ° C).
[0296] NMR 1H δ 8.53 (s, 2 H) 7.98 (dd, 1 H) from 7.53 to 7.60 (m, 1 H) 7.41 (td, 1 H) 7.28 (dd, 1 H) 6.97 (t, 1H) from 6.59 to 6.84 (m, 1 H). EXAMPLE OF SUMMARY 14
[0297] Synthesis of 5-chloro-2- [2- [5- (trifluoromethyl) -3-isoxazolyl] -3-fluorophenoxy] pyrimidine (Compound 168). STEP A
[0298] Synthesis of 5- (difluoromethyl) -3- (2-methoxyphenyl) -4H-isoxazol-5-ol.
[0299] To a solution of 2-fluoro-6-methoxyacetophenone (1.0 g, 5.9 mmol) in tetrahydrofuran (2 mL) was added 30% sodium methoxide in methanol solution (1.4 mL) . To this mixture, a solution of ethyl trifluoroacetate (0.805 g, 6.49 mmol) in tetrahydrofuran (1 ml) was added dropwise and the reaction was stirred at room temperature for 2 h. To the reaction, a 1 M solution of hydrochloric acid and ethyl acetate was added, the phases were separated and the aqueous phase was washed again with ethyl acetate. The combined organic phases were dried with magnesium sulfate and concentrated in vacuo to provide the desired product (AP_ = 263) which was taken directly to the next step. Then, to a solution of 4,4,4-trifluoro-1- (2-fluoro-6-methoxyphenyl) butane-1,3-dione (from the previous Step) in ethanol (14 ml) was added a hydroxide solution 1 M sodium hydroxide (7 mL) followed by hydroxylamine hydrochloride (410 mg, 5.9 mmol) and the reaction was stirred overnight at room temperature. The solvent was removed in vacuo and the residue was purified by chromatography on silica gel, eluting with 0 to 100% ethyl acetate in hexanes with 0 to 20% methanol in dichromethane to provide the product (AP + = 280, NMR 1H õ ppm 7.37 (td, 1 H) from 6.74 to 6.83 (m, 2 H) 3.89 (s, 3 H) 3.79 (d, 1 H) 3.50 (dd , 1 H)), which was taken directly to the next stage. To a solution of 3- (2-fluoro-6-methoxy-phenyl) -5- (trifluoromethyl) -4H-isoxazol-5-ol (from the previous Step) in dichloromethane (20 ml) at 0 ° C was added 1 M solution of boron tribromide in dichloromethane (11.8 ml, 11.8 mmol) and the reaction was allowed to warm to room temperature over 2 h. The solvent was removed in vacuo. The residue was dissolved in dichloromethane and washed with a saturated solution of sodium bicarbonate, the aqueous phase was washed with dichloromethane. The combined organic phases were dried with magnesium sulfate, concentrated in vacuo and purified by chromatography on silica gel, eluting with 0 to 100% ethyl acetate in hexanes, providing the title compound (606 mg, AP = 264).
[0300] NMR 1H õ 9.86 (s, 1 H) 7.32 (td, 1 H) from 6.84 to 6.90 (m, 1 H) 6.68 (ddd, 1H), of 3, 86 to 3.94 (m, 1 H) 3.75 (dd, 1 H) 3.56 (s, 1H). STEP B
[0301] Synthesis of 5-chloro-2- [2- [5- (trifluoromethyl) -3-isoxazolyl] -3-fluorophenoxy] pyrimidine.
[0302] To a solution of 3- (2-fluoro-6-hydroxyphenyl) -5- (trifluoromethyl) -4H-isoxazol-5-ol (i.e., the product of Step a) (606 mg, 2.29 mmol ) in dimethylsulfoxide (15 mL) was added to 5-chloro-2-methylsulfonyl-pyrimidine (527mg, 2.74 mmol) followed by cesium carbonate (1.1 g, 3.43 mmol) and the reaction was stirred for 18 H. The reaction was partitioned between water and ethyl acetate, the phases were separated and the aqueous layer was washed again with ethyl acetate. The combined organic phases were dried with magnesium sulfate and concentrated in vacuo. The residue was purified by chromatography on silica gel, eluting with 0 to 100% ethyl acetate, to provide the title compound, a compound of the present invention, (198 mg, AP + = 360).
[0303] NMR 1H õ 8.46 (s, 2 H) 7.56 (td, 1 H) 7.21 (ddd, 1H), 7.15 (dt, 1 H) 7.02 (dd, 1 H ). EXAMPLE OF SUMMARY 15
[0304] Synthesis of 5-chloro-2- [2- [3- (trifluoromethyl) -5-isoxazolyl) phenoxy] pyrimidine (Compound 63). STEP A
[0305] Synthesis of 2- (trifluoromethyl) -4H-1-benzopyran-4-one.
[0306] 2-hydroxyacetophenone (10 g, 66.7 mmol) was dissolved in trifluoroacetic anhydride (19 mL, 133.3 mmol) and pyridine (10.8 mL, 133.3 mmol). The reaction mixture was heated to 70 ° C and stirred for 12 h. After cooling, the reaction mixture was diluted with methylene chloride and 1 M hydrochloric acid and washed with water. The organic phase was dried with magnesium sulfate and concentrated in vacuo. Purification by chromatography on silica gel eluting with 0 to 5% ethyl acetate in hexanes provided the title compound (10.5 g) as a pale yellow solid.
[0307] NMR 1H δ 8.21 (m, 1 H), 7.76 (m, 1H), 7.77 (d, 1H), 7.46 (m, 1H), 6.73 (s, 1H ). MS (ESP) = 215 STEP B
[0308] Synthesis of 2- [3- (trifluoromethyl) -5-isoxazolyl] phenol.
[0309] To a solution of 2- (trifluoromethyl) -4H-1-benzopyran-4-one (i.e., the product of Step a) (10.5 g, 48.8 mmol) in ethanol (50 mL), hydroxylamine acetate (146 mmol) in water (50 ml) was added. The mixture was heated to 60 ° C for 4 h. After cooling, the reaction to room temperature, 4,4,4-trifluoro-1- (2-hydroxyphenyl) -butane-1,3-dione-3-oxime was precipitated with the addition of water (200 mL) .
[0310] NMR 1H δ 9.30 (s, 1H), 7.37 (m, 1H), 7.19 (m, 1H), 7.06 (m, 1H), 6.94 (m, 1H) , 3.87 (d, 1H), 3.69 (d, 1H).
[0311] This product was collected through filtration and suspended in acetic acid (30 ml) and 36% aqueous hydrochloric acid (10.8 ml) at room temperature. The mixture was stirred at 80 ° C for 30 min to provide the title compound as a white solid (4.6 g).
[0312] NMR 1H δ 7.88 (m, 1H), 7.37 (m, 1H), 7.08 (m, 1H), 7.01 (s, 1H), 6.95 (m, 1H) . MS (ESP) = 230 STEP C
[0313] Synthesis of 5-chloro-2- [2- [3- (trifluoromethyl) -5-isoxazolyl) phenoxy] -pyrimidine.
[0314] To a solution of 2- [3- (trifluoromethyl) -5-isoxazolyl] phenol (i.e., the product of Step B) (2.2 g, 9.4 mmol) in N, N-dimethylformamide (10 ml) were added to 2,5-dichloropyrimidine (1.5 g, 10.3 mmol) and potassium carbonate (2.9 g, 20.6 mmol). The reaction was heated to 80 ° C for 2 h. The solution was cooled to room temperature and diluted with water. The phases were separated and the aqueous phase was washed with additional ethyl acetate. The organic phases were combined, dried with magnesium sulfate and concentrated in vacuo. Purification by chromatography on silica gel eluting with 0 to 5% ethyl acetate in hexanes provided the title compound, a compound of the present invention, as a solid (2.1 g) -
[0315] NMR 1H δ 8.49 (s, 2H), 8.08 (m, 1H), 7.58 (m, 1H), 7.45 (m, 1H), 7.32 (m, 1H) , 6.91 (s, 1H). MS (ESP) = 342. Melting point: from 114 to 115 ° C EXAMPLE OF SUMMARY 16
[0316] Synthesis of 5-bromo-2- [2- [3- (difluoromethyl) -5-isoxazolyl] -3-fluorophenoxy] pyrimidine (Compound 145). STEP
[0317] Synthesis of 4,4-difluoro-1- (2-fluoro-6-methoxyphenyl) butane-1,3-dione.
[0318] To a solution of 1- (2-fluoro-6-methoxyphenyl) ethanone (2.6 g, 15.5 mmol) and difluoroacetic acid ethyl ester (3.9 mL, 31.0 mmol) in N , N-dimethylformamide at 0 ° C, sodium hydride (1.2 g, 31.0 mmol) was added. The reaction mixture was heated to 80 ° C for 1 h. The reaction was then cooled to 0 ° C, diluted with ethyl acetate and acidified with 1 N aqueous hydrochloric acid. The phases were separated and the aqueous phase was washed with additional ethyl acetate. The organic phases were combined and dried with magnesium sulfate and concentrated in vacuo. Purification by chromatography on silica gel eluting with 0 to 15% ethyl acetate in hexanes provided the title compound (2.5 g).
[0319] NMR 1H δ 7.39 (m, 1H), 6.77 (m, 2H), 6.24 (s, 1H), 6.01 (t, 1H), 3.87 (s, 3 H ). MS (ESP) = 247 STEP B
[0320] Synthesis of 3- (difluoromethyl) -5- (2-fluoro-6-methoxyphenyl) isoxazole.
[0321] A solution of 4,4-difluoro-1- (2-fluoro-6-methoxyphenyl) butane-1,3-dione (i.e., the product of Step A) (2.5 g, 10 mmol) and hydroxylamine hydrochloride (2.1 g, 30 mmol) in ethanol (25 ml) was stirred at 80 ° C. After 1 h, the solvent was removed in vacuo. The resulting residue was diluted with water and extracted with dichloromethane. The organic phase was dried with magnesium sulfate and concentrated in vacuo. Purification by chromatography on silica gel eluting with 0 to 15% ethyl acetate in hexanes provided the title compound (1.5 g).
[0322] 1H NMR δ 7.41 (m, 1 H), from 6.69 to 6.98 (m, 4H), 3.93 (s, 3 H). MS (ESP) = 244 STEP C
[0323] Synthesis of 2- [3- (difluoromethyl) -5-isoxazolyl] -3-fluorophenol.
[0324] To a solution of 3- (difluoromethyl) -5- (6-methoxyphenyl-2-fluoro) isoxazole (i.e., the product of Step B) (1.5 g, 6.2 mmol) in dichloromethane (10 ml) at 0 ° C a 1.0 M solution of boron tribromide in dichloromethane (31 ml, 31 mmol) was added. The reaction mixture was warmed to room temperature and stirred for 6 h. The reaction was cooled to 0 ° C and slowly treated with a saturated aqueous solution of sodium bicarbonate. The biphasic mixture was stirred at room temperature for 1 h. The phases were separated and the aqueous phase was extracted with dichloromethane. The combined organic phases were dried and concentrated in vacuo. The crude residue was purified by chromatography on silica gel, eluting with 0 to 10% ethyl acetate in hexanes, to provide the title compound (980 mg).
[0325] 1H NMR δ 7.33 (m, 1 H), from 6.66 to 6.99 (m, 4 H). MS (ESP) = 230 STEP D
[0326] Synthesis of 5-bromo-2- [2- [3- (difluoromethyl) -5-isoxazolyl] -3-fluorophenoxy] pyrimidine.
[0327] To a solution of 2- [3- (difluoromethyl) -5-isoxazolyl] -3-fluorophenol (i.e., the product of Step C) (229 mg, 1 mmol) in anhydrous N, N-dimethylformamide (2 , 5 ml) were added to 5-bromo-2-chloropyrimidine (212 mg, 1.1 mmol) and potassium carbonate (304 mg, 2.2 mmol). The reaction was heated to 80 ° C for 1 h. The solution was cooled to room temperature and diluted with water. The phases were separated and the aqueous layer was washed with additional ethyl acetate. The organic phases were combined, dried with magnesium sulfate and concentrated in vacuo. Purification by chromatography on silica gel eluting with 0 to 15% ethyl acetate in hexanes provided the title compound, a compound of the present invention, as a solid (320 mg).
[0328] NMR 1H δ 8.54 (s, 2H), 7.54 (m, 1H), 7.20 (m, 1H), 7.13 (m, 1H), 6.86 (m, 1 H ), 6.75 (t, 1H). MS (ESP) = 387
[0329] Using the procedures described herein together with methods known in the art, the following compounds from Tables 1 to 1,584 can be prepared. The following abbreviations are used in the following Tables: t means tertiary, s means secondary, n means normal, i means iso, c means cycle, Me means methyl, Et means ethyl, Pr means propyl, Bu means butyl, i-Pr isopropyl means, Bu means butyl, c-Pr cyclopropyl, c-Bu means cyclobutyl, Ph means phenyl, OMe means methoxy, OEt means ethoxy, SMe means methylthio, SEt means ethylthio, NHMe means methylamino, -CN means cyan, Pi means pyridinyl , NO2 means nitro, tzl means triazole, pzl means pyrazole, izl means imidazole, odzl means oxadiazole, tdzl means thiadiazole and SCteMe means methylsulfonyl.
- R2 = Cl; Z = O; and R3 = H (m = 0); - and Q is: Isoxazol-5-yl













[0330] The present invention also includes Tables 2 through 1,584. Each Table is constructed in the same manner as Table 1 above, except that the title line in Table 1 (that is, “R2 = Cl; Z = O; and R3 = H (m = 0)”) is replaced by the respective line title shown below. For example, the first entry in Table 2 is a compound of Formula 1, where R1 is H, R2 is Cl, Z is O, R3 is H (m = 0), and Q is isoxazole-5 -il (ie, the unsubstituted isoxazole attached to the rest of Formula 1 in position 5). The remainder of Table 2 is constructed in the same manner, and therefore the remainder of Tables 3 to 1,584 is constructed in a similar manner.


























[0331] Solid diluents, for example, include clays such as bentonite, montmorillonite, atapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (eg lactose, sucrose) , silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate and sodium sulfate. Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carries, 2aEd., Dorland Books, Caldwell, New Jersey.
[0332] Liquid diluents, for example, include water, N, N-dimethylalkanamides (eg N; N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (eg N-methylpyrrolidone), alkyl phosphates (eg triethyl phosphate), ethylene glycol, triethylene glycol, polypropylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (eg white mineral oils, normal paraffin, isoparaffins ), alkylbenzenes, alkylnaphthalenes, glycerin, glycerol triacetate, sorbitol, aromatic hydrocarbons, aliphatic dearomatizers, alkylbenzenes, alkylnaphthalenes, ketones, such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-acetan-2-methyl-2-methyl-2-methyl , such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate, other esters, such as alkylated lactate esters, dibas esters alkyl and aryl benzoates and y-butyrolactone, and alcohols, which can be linear, branched, saturated or unsaturated, such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, n-hexanol , 2-ethylexanol, n-octanol, decanol, isodecyl alcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol and benzyl alcohol. Liquid thinners also include glycerol esters of saturated and unsaturated fatty acids (usually C6-C22), such as vegetable seeds and fruit oils (for example, olive, castor, flax, sesame, corn oils maize), peanuts, sunflower, grape seed, saffron, cottonseed, soy, rapeseed, coconut and palm kernel), animal fats (eg beef tallow, pork tallow, pork lard , cod liver oil, fish oil) and their mixtures. Liquid diluents also include alkylated fatty acids (for example, methylated, ethylated, butylated), where fatty acids can be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation. Liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.
[0333] The solid and liquid compositions of the present invention, in general, include one or more surfactants. When added to a liquid, surfactants (also known as “surfactants”), in general, modify, most of the time, reduce the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in a surfactant molecule, surfactants can be useful as wetting, dispersing, emulsifying or foaming agents.
[0334] Surfactants can be classified as non-ionic, anionic or cationic. Nonionic surfactants useful for the present composition include, but are not limited to, alkoxylated alcohol, such as alkoxylated alcohol based on natural and synthetic alcohols (which can be branched or linear) and prepared from alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, ethoxylated alkanolamides and alkanolamides; alkoxylated triglycerides, such as ethoxylated soy, castor and rapeseed oils; alkylphenol alkoxylates, such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol ethoxylates and dodecyl phenol ethoxylates (prepared from phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers, wherein the terminal blocks are prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenol (including those prepared from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylated esters, such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters and polyethoxylated glycerol fatty acid esters, other sorbitan derivatives, such as sorbitan esters; polymeric surfactants, such as random copolymers, block copolymers, alkyl PEG resins (polyethylene glycol), grafted or comb polymers and star-type polymers; polyethylene glycols (PEGs); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar derivatives, such as sucrose esters, alkyl polyglycosides and alkyl polysaccharides.
[0335] Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated or alkylphenol ethoxylated alcohol; diphenyl sulfonate derivatives; lignin and lignin derivatives, such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters, such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styrene phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styrene phenol ether sulfate; sulfates and sulfonates from oils and fatty acids; ethoxylated alkylphenol sulfates and sulfonates; alcohol sulfates; ethoxylated alcohol sulfates; amine and amide sulfonates, such as A / N-alkyltaurates; benzene, cumene, toluene, xylene sulfonates, and dodecyl and tridecylbenzenes; condensed naphthalene sulfonates; naphthalene and alkyl naphthalene sulfonates; fractionated petroleum sulfonates; sulfosuccinamates; and sulfosuccinates and their derivatives, such as the dialkyl sulfosuccinate salts.
[0336] Useful cationic surfactants include, but are not limited to: ethoxylated amides and amides; amines, such as N-alkyl propanodiamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts, such as amine acetates and diamine salts; quaternary ammonium salts, such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides, such as alkyldimethylamine oxides and bis- (2-hydroxyethyl) -alkylamine oxide.
[0337] Mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants are also useful for the present composition. Nonionic, anionic and cationic surfactants and their recommended uses are described in a variety of published References including McCutcheon's Emulsifiers and Detergents, annual American and International Editions published bi McCutcheon's Division, The Manufacturing confectioner Publishing Co .; Siseli and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. S. Davidson and B. Milwidski, Sinthetic Detergents, 7th edition, John Wilei and Sons, New York, 1987.
[0338] The compositions of the present invention may also contain formulation aids and additives, known to those skilled in the art as formulation aids (some of which may function as solid diluents, liquid diluents or surfactants). Such formulation aids and additives can control: pH (buffers), foaming during processing (defoamers, such as polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), microbial growth in containers (antimicrobials) ), freezing product (antifreeze), color (dyes / pigment dispersions), washing (film or adhesive formers), evaporation (evaporation retardants) and other formulation attributes. Film makers, for example, include polyvinyl acetates, polyvinyl acetate copolymers, vinyl acetate - polyvinylpyrrolidone copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes. Examples of formulation aids and additives include those listed in McCutcheon's Volume 2: Functional Materials, annual International and North American editions published by McCutcheon's Division, The Manufacturing confectioner Publishing Co .; and PCT Publication WO 2003/024222.
[0339] Formula 1 compounds and other active ingredients are usually incorporated into the present compositions, dissolving the active ingredient in a solvent or by grinding it in a liquid or dry diluent. Solutions, including emulsifiable concentrates, can be prepared by just mixing the ingredients. If the solvent in a liquid composition intended for use as an emulsifiable concentrate is immiscible with water, an emulsifier is usually added to emulsify the solvent containing the active in the water dilution. The sludge of the active ingredient with particle diameters up to 2,000 pm can be wet milled using the medium mills to obtain particles with average diameters less than 3 pm. The aqueous sludge can be made from finished suspension concentrates (see, for example, US patent 3,060,084) or further processed by spray drying to form the water dispersible granules. Dry formulations usually require dry milling processes, which produce average particle diameters in the range of 2 to 10 pm. Dry powders and dust can be prepared by mixing and, in general, grinding (such as in a hammer mill or a fluid energy mill). Granules and pellets can be prepared by spraying the active material on preformed granular vehicles or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pages 147 - 48, Perri's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New lock, 1963, pages 8-57 and following, and the publication WO 1991/13546. Pellets can be prepared as described in US patent 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in US patents 4,144,050, US 3,920,442 and DE 3,246,493. The tablets can be prepared as taught in US patents 5,180,587, US 5,232,701 and US 5,208,030. Films can be prepared as taught in GB 2,095,558 and US 3,299,566.
[0340] For more information regarding the formulation technique, see TS Woods, The Formulator's Toolbox - Product Forms for Modern Agriculture in Pesticide Chemistri and Bioscience, The Food-Environment Challenge, T. Brooks and TR Roberts, Eds., Proceedings of the 9th International congress on Pesticide Chemistri, The Roial Societi of Chemistri, Cambridge, 1999, pages 120-133. See also US patent 3,235,361, from column 6, line 16 to column 7, line 19 and Examples 10 to 41; US patent 3,309,192, from column 5, line 43 to column 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138 to 140, 162 to 164 , 166, 167 and 169 to 182; US patent 2,891,855, from column 3, line 66 to column 5, line 17 and Examples 1 to 4; Klingman, Weed controls Science, John Wlei and Sons, Inc., New York, 1961, pages 81 to 96; and Hance et al., Weed control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technologi, PJB Publications, Richmond, United Kingdom, 2000.
[0341] In the following Examples, all formulations are prepared in conventional ways. The compound numbers refer to the compounds in the Index Tables A. Without further elaboration, it is believed that a person skilled in the art, using the above description, can use the present invention to its fullest extent. The following Examples, therefore, are to be construed as merely illustrative, and not limiting the present description in any way. The percentages are by weight, unless otherwise stated. EXAMPLE A
EXAMPLE B
EXAMPLE C
EXAMPLE D
EXAMPLE E
EXAMPLE F
EXAMPLE G
EXAMPLE H
EXAMPLE
EXAMPLE

[0342] The test results indicate that the compounds of the present invention are highly active pre-emergent and / or post-emergent herbicides and / or plant growth regulators. The compounds of the present invention, in general, show high weed control activity in post-emergence (ie applied, after weeds emerge from the soil) and in pre-emergence of weed control (ie applied, before weeds emerge from the soil). Many of them are useful for a broad spectrum of pre- and / or post-emergence weed control in areas where complete control of all vegetation is desired, such as around fuel storage tanks, industrial storage areas, parks parking, parking in theaters, airfields, river banks, irrigation and other water courses, around billboards and road and railway structures. Many of the compounds of the present invention, due to selective metabolism in crops against weeds, or due to selective activity at the locus of physiological inhibition of crops and weeds, or by selective placement on or within the environment of a mixture of crops and herbs weeds are useful for the selective control of grass and broadleaf weeds within a crop / weed mix. One skilled in the art will recognize that the preferred combination of these selectivity factors within a compound or group of compounds can be easily determined by performing routine biological and / or biochemical analyzes. The compounds of the present invention may show tolerance for important agronomic crops, including, but not limited to, alfalfa, barley, cotton, wheat, rapeseed, sugar beet, corn (millet), sorghum, soy, rice, oats, peanuts, vegetables , tomato, potato, perennial crops such as coffee, cocoa, palm oil, rubber, cane, citrus, grape, fruit trees, nut trees, banana, banana, pineapple, hops, tea and forests, such as eucalyptus and conifers (for example, Pinus taeda) and grass species (for example, Kentucki blue grass, St. Augustine grass, Kentucki fescue and Bermuda grass). The compounds of the present invention can be used in genetically transformed or bred crops to incorporate herbicide resistance, express proteins toxic to invertebrate pests (such as Bacillus thuringiensis toxin), and / or express other useful characteristics. Those skilled in the art will find that not all compounds are equally effective against all weeds. Alternatively, the compounds in question are useful for modifying the growth of vegetables.
[0343] Since the compounds of the present invention exhibit pre-emergent and post-emergent herbicidal activity, to control unwanted vegetation, killing or harming vegetation or reducing its growth, the compounds can be usefully applied across a variety of methods that involve contacting a herbicidal amount of a compound of the present invention, or a composition comprising said compound and at least one of a surfactant, a solid diluent or a liquid diluent, to the foliage or other part of the unwanted vegetation or to the environment of unwanted vegetation, such as soil or water, where unwanted vegetation is growing or surrounding the seed or other propagule of unwanted vegetation.
[0344] An herbicidal amount of the compounds of the present invention is determined by a number of factors. These factors include: the selected formulation, application method, quantity and type of vegetation present, growing conditions, and so on. In general, an herbicidal amount of the compounds of the present invention is about 0.001 and 20 kg / ha, with a preferred range of about 0.004 to 1 kg / ha. A person skilled in the art can easily determine the amount of herbicide needed for the desired level of weed control.
[0345] The compounds of the present invention are useful in the treatment of all plants and parts of plants. The varieties and cultivars of vegetables and seeds can be obtained using conventional propagation and reproduction methods or through genetic engineering methods. Genetically modified vegetables (transgenic vegetables) are those in which a heterologous gene (transgene) has been stably integrated into the genome of the plant or seed. A transgene that is defined by its special location in the plant's genome is called a transgenic transformation or event.
[0346] Genetically modified vegetable cultivars that can be treated according to the present invention include those that are resistant to one or more biotic strains (pests, such as nematodes, insects, mites, fungi, and the like. ) or abiotic stresses (aridity, cold temperature, soil salinity, and the like), or that contain other desired characteristics. Vegetables can be genetically modified to show aspects, for example, tolerance to herbicides, resistance to insects, tolerance to aridity or modified oil profiles. Useful genetically modified plants that contain the individual genetic transformation events or combinations of transformation events are listed in Exhibit C. Additional information for the genetic modifications listed in Exhibit C can be obtained from publicly maintained databases, for example , by the US Department of Agriculture.
[0347] The following abbreviations, from 1 to 37, are used in Exhibit A for the characteristics. One means that the entry is not available. - * Argentina (Brassica napus), ** Polish (B. rapa), # Eggplant
DISPLAY C






[0348] The treatment of genetically modified vegetables with the compounds of the present invention can result in superadditive or synergistic effects. For example, the reduction in application rates, broadening of the activity spectrum, increased tolerance to abiotic / biotic stress or enhanced storage stability may be greater than expected from the only simple additive effects of applying the compounds of the present invention to genetically modified vegetables.
[0349] The compounds of the present invention can also be mixed with one or more other biologically active compounds or agents, including herbicides, herbicide protection agents, fungicides, insecticides, nematocides, bactericides, acaricides, growth regulators, such as inhibitors from insect seedling and rooting stimulants, chemosterilizers, semi-chemicals, repellents, attractants, pheromones, food stimulants, other biologically active compounds or entomopathogenic bacteria, viruses or fungi to form a multi-component pesticide providing an even broader spectrum of agricultural protection . Mixtures of the compounds of the invention with other herbicides can broaden the spectrum of activity against additional weed species, and suppress the proliferation of any resistant biotypes. Accordingly, the present invention also relates to a composition comprising a compound of Formula 1 (in an amount effective as a herbicide) and at least one additional biologically active compound or agent (in a biologically effective amount) and may further comprise at least one of a surfactant, a solid diluent or a liquid diluent. The other biologically active compounds or agents can be formulated in compositions that comprise at least one of a surfactant, a solid or liquid diluent. For the mixtures of the present invention, one or more other biologically active compounds or agents can be formulated together with a Formula 1 compound, to form a premix, or one or more other biologically active compounds or agents can be formulated separately at from the Formula 1 compound, and the combined formulations before application (for example, in a spray tank) or, alternatively, applied in succession.
[0350] A mixture of one or more of the following herbicides with a compound of the present invention can be especially useful for weed control: acetochlor, acifluorphene and its sodium salts, aclonifene, acrolein (2-propenal), alachlor, aloxidim, ametrine, amicarbazone, amidosulfurone, aminocyclopyrachlor and its esters (eg, methyl, ethyl) and their salts (eg, sodium, potassium), aminopyralid, amitrol, ammonium sulfamate, anilophos, asulam, atrazine, azimsulfurone , beflubutamide, benazoline, benazolin-ethyl, bencarbazone, benfluralin, benfuresate, benssulfuron-methyl, bensulide, bentazone, benzobicyclone, benzofenap, bicyclopyrone, biphenox, bilanafos, bispiribac and its sodium salt, bromoboxin, bromoboxin, bromoboxin, bromoboxin, bromoboxin, bromoboxin, bromoboxin, bromoboxin, bromoboxin, bromoboxane, bromoboxide bromoxynil, butachlor, butafenacil, butamiphos, butralin, butroxidim, butylate, cafenstrol, carbetamide, carfentrazon-ethyl, catechin, clomethoxyfen, chloramben, chlorobromurone, chlorflurenol-methyl, chloridazon a, clorimuron ethyl, chlorotolurone, clorprofam, chlorsulfurone, chlortal-dimethyl, chlortiamid, cinidon-ethyl, cinmetilina, kynosulphurone, clacifos, clefoxidim, cletodim, clodinafop-propargilo, clomazone, clomeprop, cloppropyl, clopylamine, clopylamine cyanazine, cycloate, cyclosulfamurone, cycloxidim, cihalofop-butyl, 2,4-D and its butotyl, butyl, isooctyl and isopropyl esters and their dimethylammonium, diolamine and trolamine salts, daimurone, dalapon, dalapon sodium, dazomet, 2, 4-DB and its salts of dimethylammonium, potassium and sodium, demedify, demetrine, dicamba and its salts of diglycolamonium, dimethylammonium, potassium and sodium, diclobenyl, dichorprop, diclofop-methyl, diclosulam, difenzoquat, diflufen, diflufenican methyl sulfate dimepiperate, dimetachlor, dimetamethrin, dimethenamide, dimethenamide-P, dimethypine, dimethylarsinic acid and its sodium salt, dinitramine, dinoterb, diphenamide, diquat dibromide, dithiopir, diurone, DNOC, end otal, EPTC, esprocarb, etalfluralin, etametsulfuron-methyl, ethiozine, etofumesate, ethoxyfen, ethoxysulfurone, etobenzanid, phenoxaprop-ethyl, phenoxaprop-P-ethyl, phenoxasulfone, phenquinotrione, fentrazamide, methacrone, flampropane, phenurone, flamprop, M-isopropyl, flamprop-M-methyl, flazassulfurone, florasulam, fluazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone, flucetosulfurone, flucloraline, flufenacet, flufenpir, flufenpiryl, flumetsulam, flumetsulam fluoroglycofen acetate, flupoxam, flupirsulfuron-methyl and its sodium salts, flurenol, flurenol-butyl, fluridone, flurochloridone, fluroxypyr, flurtamone, fluoroglycophen-ethyl, fomesafen, foramosulfate, ammonium phosphates, glufos, glufos such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimesium (alternatively, called sulfosate), halauxifen, halauxifen-methyl, halosulfuron-methyl, halox ifop-etothil, haloxifop-methyl, hexazinone, imazametabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazaquin ammonium, imazetapyr, imazetapyr ammonium, imazosulfurone, indanofan, indaziflamine, iofensulfuronate, iodine sulfurone, iodine sulfurone, iodine sulfurone, iodine sulfurone sodium, ipfencarbazone, isoproturone, isourone, isoxaben, isoxaflutol, isoxaclortol, lactophen, lenacil, linurone, maleic hydrazide, MCPA and their salts (eg MCPA-dimethylammonium, MCPA-potassium and MCPA-sodium, esters (eg -2-ethylhexyl, MCPA-butotyl) and thioesters (for example, MCPA-thioethyl), MCPB and its salts (for example, MCPB-sodium) and esters (for example, MCPB-ethyl), mecoprop-P, mefenacet , mefluidide, mesosulfuron-methyl, mesotrione, sodium metam, metamifop, metamitrone, metazachlor, metazosulfurone, metabenzthiazurone, methiozoline, methyl methanesonic acid and its calcium, monoammon, monosodium and disodium salts, methyldimrone, metobromoluron, metobromolurone, metosu lam, methoxyurone, metribuzin, metsulfuron-methyl, molinate, monolinurone, naproanilide, napropamide, napropamide-M, naptalam, neburone, nicosulfurone, norflurazon, orbencarb, orthosulfamurone, orizalin, oxadiargyl, oxaduroxy, oxaldexyl, oxaldexyl, oxidase pebulate, pelargonic acid, pendimethalin, penoxsulam, pentanochlor, pentoxazone, perfluidone, petoxamide, petoxiamid, fenmedifam, picloram, picloram-potassium, picolinafen, pinoxadene, piperofós, pretilachlor, propisoxymethyl, propisoxymethyl, propisoxymethyl, propisoxymethyl, propisulfuron-propisoxymethyl, propylsulfone , propaquizafop, propazin, profam, propisochlor, propoxycarbazone, propizamide, prosulfocarb, prosulfurone, piraclonil, piraflufen-ethyl, pyrazogyl, pyrazolinate, pyrazolinate, pyrazoxifene, pyrazosulfuron-ethyl, pyribenzoxim, pyributicarb, pyributicarb, pyributicarb, pyributicarb , piritiobac-sodium, pyroxassulfone, piroxsulam, quinclorac, quinmerac, quinoclamine, quizalo fop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuril, rimssulfurone, saflufenacil, setoxidim, sidurone, simazine, simetrine, sulcotrione, sulfentrazone, sulfometuron-methyl, sulfosulfurone, 2,3,6-TBA, TCA, TCA, TCA, TCA sodium, tebutam, tebuturon, tefuriltrione, tembotrione, tepraloxidim, terbacil, terbumeton, terbuthylin, terbutrin, tenylchlorine, thiazopyr, tiencarbazone, tifenssulfuron-methyl, thiobencarb, thiafenacyl, trifamily, triamfon, trilone methyl, triclopyr, triclopyr-butothyl, triclopyr-triethylammonium, tridiphane, trietazine, trifloxysulfurone, trifluralin, triflussulfuron-methyl, trifloxysulfurone, vernolate, 3- (2-chloro-3,6-difluorophenyl-1-hydroxy-1-hydroxy-1-hydroxy-1-hydroxy-1-hydroxy 1,5-naphthyridin -2 (1 H) -one, 5-chloro-3 - [(2-hydroxy-6-oxo-1-cyclohexen-1-yl) carbonyl] -1 - (4-methoxyphenyl) -2 (1 H) - quinoxalinone, 2-chloro-N- (1-methyl-1 H-tetrazol-5-yl) -6- (trifluoromethyl) -3-pyridinecarboxamide, 7- (3,5-dichloro-4 -pyridinyl) -5- (2,2-difluoroethi l) -8-hydroxypyrido [2,3-b] pyrazin-6 (5H) -one), 4- (2,6-diethyl-4-methylphenyl) -5-hydroxy-2,6-dimethyl-3 (2H ) -pyridazinone), 5 - [[(2,6-difluorophenyl) methoxy] methyl] -4,5-dihydro-5-methyl- 3- (3-methyl-2-thienyl) isoxazole (formerly metioxolin), 3- [7-fluoro-3,4-dihydro-3-oxo-4- (2-propin-1-yl) -2 H-1,4-benzoxazin-6-yl] dihydro-1,5-dimethyl-6- thioxo-1,3,5-triazin-2,4 (1 H, 3H) -dione, 4- (4-fluorophenyl) -6 - [(2-hydroxy-6-oxo-1-cyclohexen-1 - yl) carbonyl] -2-methyl-1,2,4-triazin-3,5 (2H, 4H) -dione, 4-amino-3-chloro-6- (4-chloro-2-fluoro-3-methoxyphenyl) - Ethyl 5-fluoro-2-pyridinecarboxylate, 2-methyl-3- (methylsulfonyl) -N- (1-methyl- (trifluoromethyl) -benzamide, and 2-methyl-N- (4-methyl-1,2,5 - oxadiazol-3-yl) -3- (methylsulfinyl) -4- (1 H-tetrazol-5-yl) -4-trifluoromethyl) benzamide. Other herbicides also include bioherbicides such as Alternaria destruensSimmons, Colletotrichum gloeosporioides (Penz.) Penz. & Sacc, Drechsiera monoceras (MTB-951), Mirothecium verrucaria (Albertini & Schweinitz) Ditmar: Fries, Phitophthora palmivora (Butl.) Butl. and Puccinia thlaspeos Schub.
[0351] The compounds of the present invention can also be used in combination with plant growth regulators, such as aviglycine, A / - (phenylmethyl) -1 / - / - purin-6-amine, epocoleone, gibberellic acid, gibberellin A4 and A , harpin protein, mepiquat chloride, calcium proexadione, proidrojasmon, sodium nitrophenolate and methyl trinexapac and plant growth modification organisms, such as Bacillus cereus, strain BP01.
[0352] General references for agricultural protectors (ie herbicides, herbicidal protection agents, insecticides, fungicides, nematocides, acaricides and biological agents) include The Pesticide Manual, 13th edition, CDS Tomlin, ed., British Crop Protection Council, Farnham, Surrei, United Kingdom, 2003 and The BioPesticide Manual, 2nd Edition, LG Copping, ed., British Crop Protection Council, Farnham, Surrei, United Kingdom, 2001.
[0353] For embodiments, in which one or more of these different mixing partners are used, the weight ratio of these different mixing partners (in total) to the Formula 1 compound is normally between about 1: 3,000 to about 3,000: 1. Of interest are weight ratios between about 11: 300 to about 300: 1 (for example, ratios between about 1:30 to about 30: 1). A person skilled in the art can easily determine by simple experimentation the biologically effective amounts of the active ingredients needed for the desired spectrum of biological activity. It is evident that the inclusion of these additional components could broaden the spectrum of controlled weeds beyond the spectrum controlled by the Formula 1 compound alone.
[0354] In certain cases, combinations of a compound of the present invention with other biologically active compounds or agents (ie, active ingredients) (especially herbicides) may result in a more than additive (ie, synergistic) effect on weeds and / or a less than additive (ie, protective) effect on desired crops or other vegetables. Reducing the amount of active ingredients released into the environment, ensuring effective pest control is always advantageous. The ability to use greater amounts of active ingredients to provide more effective control of weeds without excessive damage to the crop is also desired. When the synergism of herbicidal active ingredients occurs with weeds at application rates providing satisfactory agronomic levels of weed control, such combinations can be advantageous for reducing crop production costs and reducing the environmental burden. When protection from herbicidal active ingredients occurs in crops, such combinations can be advantageous to increase crop protection, reducing weed competition.
[0355] Of interest is a combination of a compound of the present invention with at least one other herbicidal active ingredient. Of special interest is a combination in which the other herbicidal active ingredient has a different site of action than the compound of the present invention. In certain cases, a combination of at least one other herbicidal active ingredient has a similar spectrum of control, but a different site of action will be especially advantageous for the administration of resistance. Therefore, a composition of the present invention can still comprise (in an amount effective as a herbicide), at least one additional herbicidal active ingredient has a similar spectrum of control at a different site of action.
[0356] The compounds of the present invention can also be used in combination with herbicide protection agents, such as allidochlor, benoxacor, cloquintocet-mexila, ciometrinil, cyprosulfonamide, dichlormide, dicyclone, diethylate, dimepiperate, fenclorazol-ethyl, phenclorimim , flurazole, fluxofenim, furilazol, isoxadifen-ethyl, mefenpir-dietila, mefenato, methoxyphenone naphthalic anhydride (1,8-naphthyl anhydride), oxabetrinyl, N- (aminocarbonyl) -2-methylbenzenesulfonamide, N- (aminocarbon), N- (aminocarbon) 1-bromo-4- [(chloromethyl) sulfonyl] benzene (BCS), 4- (dichloroacetyl) -1-oxa-4-azospiro [4,5] decane (MON 4660), 2- (dichloromethyl) -2-methyl -1,3-dioxolane (MG 191), 1,6-dihydro-1- (2-methoxyphenyl) -6-oxo-2-phenyl-5-pyrimidinecarboxylate, 2-hydroxy-N, N-dimethyl-6 - (trifluoromethyl) pyridine-3-carboxamide, and 3-oxo-1-cyclohexen-1-yl 1- (3,4-dimethylphenyl) -1,6-dihydro-6-oxo-2-phenyl-5- pyrimidine carboxylate to increase safety for certain crops. The antidote effective amounts of the herbicidal protection agents can be applied at the same time as the compounds of the present invention, or applied as seed treatments. Therefore, an aspect of the present invention relates to a herbicidal mixture that comprises a compound of the present invention and an amount effective as antidotes to the herbicidal protection agents. Seed treatment is especially useful for selective weed control, since it physically restricts the antidote to crop vegetables. Accordingly, an especially useful embodiment of the present invention is a method for the selective control of the growth of unwanted vegetation in a crop comprising contacting the site of the crop with an herbicidal amount of a compound of the present invention, wherein the seed that the crop is grown is treated with an effective amount as antidotes to the protective agents. The effective antidote amounts of the protective agents can be easily determined by a person skilled in the art through simple experimentation.
[0357] Of interest is a composition comprising a compound of the present invention (in an amount effective as a herbicide), at least one additional active ingredient selected from the group consisting of other herbicides and herbicidal protection agents (in an amount effective), and at least one component selected from the group consisting of surfactants, solid thinners and liquid thinners.
[0358] Table A1 lists the specific combinations of a Component (a) with Component (b) illustrating the mixtures, compositions and methods of the present invention. Compound 1 in Component (a) of the column is identified in Index Table A. The second column of Table A1 lists the Compound of the specific component (b) (for example, “2,4-D” in the first row). The third, fourth and fifth columns of Table A1 list the ranges of ratios by weight of the rates, in which the compound of Component (a) is normally applied to a field-grown crop in relation to Component (b) (i.e., ( a) :( b)). Therefore, for example, the first row of Table A1 specifically describes the combination of Component (a) (i.e., Compound 1 in Index table A) with 2,4-D, it is usually applied in a weight ratio between 1: 168 to 6: 1. The remaining rows in Table A1 should be constructed in a similar manner. TABLE A1




[0359] Table A2 is constructed similarly to Table A1 above, except that the entries under the column heading “Component (a)” are replaced by the Column Entry for the respective Component (a) shown below. Compound 1 in the Component (a) column is identified in Index Table A. Therefore, for example, in Table A2 the entries under the column title “Component (a)” all recited “Compound 12” (ie, Compound 12 identified in Table of Index A), and the first line below the column headings in Table A2 specifically, describe a mixture of Compound 12 with 2,4-D. Tables A3 to A9 are constructed in a similar way.

[0360] Preferably for better control of unwanted vegetation (eg lower utilization rate such as synergism, wider spectrum of controlled weeds, or enhanced crop safety) or to prevent the development of resistant weeds are mixtures of a compound of the present invention with a herbicide selected from the group consisting of chlorimuron-ethyl, nicosulfuran, diurone, hexazinone, tifensulfuran-methyl and S-metolachlor.
[0361] The compounds of the present invention are useful for controlling weed species that are resistant to herbicides with the AHAS inhibitor or (b2) mode of action [chemical compound that inhibits acetohydroxy acid synthase (AHAS), also known as acetolactate synthase (ALS)].
[0362] The following tests demonstrate the effective control of the compounds of the present invention against specific weeds. The weed control provided through the compounds, however, is not limited to these species. See Table of Index A for descriptions of the compounds. The mass spectra are described as the molecular mass of parent ion high isotopic abundance (M + 1) formed by adding H + (molecular weight of 1) to the molecule, observed through mass spectrometry using chemical ionization of atmospheric pressure (AP +) or electrospray ionization (ESI). The following abbreviations are used in the following Index Table A: Ph is phenyl, pyridyl is pyridinyl, OEt is ethoxy, CN is cyano, CHO is formyl, t-Bu is tert-butyl, i-Pr is iso-propyl, c-Pr is cyclopropyl, Me is methyl, Et is ethyl and C (= O) CH3 is acyl. The abbreviation “Ex.” means "Example" and followed by a number that indicates in which Example the compound is prepared. ES +, bAP; c M + Na. * See Index table B for NMR 1H data. - & 4-Br-1 H-pyrazol-1 – il TABLE OF CONTENTS A








TABLE OF INDEXB


-z NMR 1H data is in ppm from tetramethylsilane at 500 MHz unless otherwise noted. The couplings are called singlet (s), (d) doublet and (m) multiplet. BIOLOGICAL EXAMPLES OF THE INVENTION TEST A
[0363] Seeds of plant species selected from grassy brome (Bromus tectorum), burrow (common bream, Xanthíum strumarium), oats, wild (Avena fatua), rice grass (Echinochloa crusgalli), large mattress grass (Lg ) (Digitaria sanguinalis), giant fox's tail (Setaria faberii), morning glory (Ipomoea spp.), Velvet leaf (Abutilon theophrasti), and sorghum (Sorghum vulgare) were planted in clayey soil and pre-emergence treated by irrigation of the soil using a chemical test formulated in a non-phytotoxic solvent mixture that included a surfactant. At the same time, these species were also pre-emergence treated with a runoff spray using a test chemical formulated in the same way.
[0364] The vegetables vary in height from 2 to 18 cm and were in the stage of one to two leaves for treatment in the post-emergence. Treated vegetables and untreated controls were kept in an oven for about 11 days, after which all treated vegetables were compared with untreated controls and visually assessed for damage. Evaluations of plant responses, summarized in Table A, are based on a scale of 0 to 100, where 0 means no effect and 100 is complete control. A dash response (-) means that there is no test result.
TEST B
[0365] Seeds of plant species selected from rice grass (Echinochloa crusgalli), kochia (Kochia scoparia), ambrosia (common ambrosia, Ambrosia elatior), Italian ryegrass (Lolium multiflorum), large mattress grass (Lg) ( Digitaria sanguinalis), giant fox tail (Setaria faberii), morning glory (Ipomoea spp.), Tingling herb (Amaranthus retroflexus), velvet leaf (Abutilan theophrasti), wheat (Triticum aestivum), and corn (Zea plus) were planted in a mixture of clayey soil and sand and pre-emergence treated with a spray of directed to the soil using test chemicals formulated in a non-phytotoxic solvent mixture that included a surfactant.
[0366] At the same time, the vegetables selected from these crop and weed species and also from the black grass (Alopecurus miosuroides) and gallium (straw bed weed, Galium aparine) were planted in pots containing the same mixture of clay soil and sand mixture and treated with post-emergence applications of test chemicals formulated in the same way. The vegetables varied in height from 2 to 10 cm and were in the stage of one to two leaves for treatment in the post-emergence. Treated vegetables and untreated controls were kept in a greenhouse for about 10 days, after which all treated vegetables were compared with untreated controls and visually assessed for damage. Evaluations of plant responses, summarized in Table B, are based on a scale of 0 to 100, where 0 means no effect and 100 is the complete control. A dash response (-) means that there is no test result. TABLE B

















TESTEC
[0367] The species of the vegetables in the soaked test selected from rice (Oríza satíva), small-flowered ciperacea (Ciperus difformís), ducksalad (Heteranthera limosa) and rice grass (Echinochloa crusgallí) were grown for the stage 2 sheets for testing. At the time of treatment, the test pots were soaked to 3 cm above the soil surface, treated by applying the test compounds directly to the rice irrigation water, and then maintained at that water depth for the duration of the test.
[0368] The treated vegetables and controls were kept in a greenhouse for 13 and 15 days, after which all species were compared with the controls and visually evaluated. Evaluations of plant responses, summarized in Table C, are based on a scale of 0 to 100, where 0 means no effect and 100 is complete control. A dash response (-) means that there is no test result. TABLE C

TEST D
[0369] Seeds of plant species selected from black grass (Alopecurus miosuroides), Italian ryegrass (Lolium multiflorum), winter wheat (Triticum aestivum), gallium (straw bed weeding, Galium aparine), corn (Zea plus), large mattress grass (Lg) (Digitaria sanguinalis), giant mile (Setaria faberii), massambará (Sorghum halepense), lambsquarters (Chenopodium album), morning glory (Ipomoea coccinea), yellow peppermint (Ciperus esculentus), grass anthill (Amaranthus retroflexus), ambrosia (common ambrosia, Ambrosia elatior), soy (Glicine max), rice grass (Echinochloa crusgallí), rapeseed (Brassica napus), amaranth (common amaranth, Amaranthus rudis), and velvet leaf (Abutilan theophrasti) were planted in a mixture of clay soil and sand and pre-emergence treated with test chemicals formulated in a non-phytotoxic solvent mixture that included a surfactant.
[0370] At the same time, the vegetables selected from these crops and weed species and also the kochia (Kochia scoparia), wild oats (Avena fatua) and bird chick (common bird chick, Stellaria media) were planted in pots containing Redi-Earth® planting medium (Scotts Company, 14,111 Scottslawn Road, Marisville, Ohio 43041) comprising paghnum peat moss, videmiculite, wetting agent and starting nutrients and treated with post-emergence applications test chemicals formulated in the same way.
[0371] The species of vegetables in the soaked test selected from rice (Oriza sativa), peppermint, small flowered umbrella peppermint (Ciperus difformis), ducksalad (Heteranthera limosa) and rice grass (Echinochloa crusgalli) were grown for the 2-sheet stage for testing. At the time of treatment, the test pots were soaked to 3 cm above the soil surface, treated by applying the test compounds directly to the rice irrigation water, and then maintained at that water depth for the duration of the test.
[0372] The treated vegetables and controls were kept in a greenhouse for 13 and 15 days, after which all species were compared with the controls and visually evaluated. Evaluations of plant responses, summarized in Table D, are based on a scale of 0 to 100, where 0 means no effect and 100 is complete control. A dash response (-) means that there is no test result. TABLE D













TEST AND
[0373] Seeds of the plant species selected from blue grass (annual blue grass, Poa annua), black grass (Alopecurus miosuroides), yellow grass (Phalaris minor), chickweed (common chickweed, Stellaria media) , gallium (straw bed weed, Galium aparine), grassy brome (Bromus tectorum), wild poppy (Papa ver rhoeas), wild violet (Viola arvensls), mile, green (Setaria viridis), nettle (henbit nettle) , Lamium amplexicaule), Italian ryegrass (Lollum multiflorum), kochia (Kochia scoparia), lambsquarters (Chenopodium album), rapeseed oil (Brassica napus), anthill (Amaranthus retroflexus), Russian thistle (Iberian salsola), chamomile (odorless chamomile) , Matricaria inodora), veronica (panoramic veronica, Veronica persica), spring barley (Hordeum vulgare), spring wheat (Triticum aestivum), wild buckwheat (Poligonum convolvulus), wild mustard (Slnapls arvensls), oats, wild (Avena fatua), wild radish (Avena fatua), wild radish (Raphanus raphanistrum), wind grass (Apera spicaventi), winter barley (Hordeum vulgare), and winter wheat (Triticum aestivum) were planted in a clayey soil and pre-emergence treated with test chemicals formulated in a non-phytotoxic solvent mixture that included a surfactant.
[0374] At the same time, these species were planted in pots containing Redi-Earth® planting medium (Scotts Company, 14.111 Scottslawn Road, in Marisville, Ohio 43041) which comprises the spaghnum peat moss, videmiculite, wetting agent and nutrients and treated with post-emergence applications of test chemicals formulated in the same way.
[0375] The vegetables varied in height from 2 to 18 cm (stage from 1 to 4 leaves) for post-emergence treatments. The treated vegetables and controls were kept in a greenhouse for 7 to 21 days, after which all species were compared with the controls and visually evaluated. The evaluations of plant responses, summarized in Table E, are based on a scale from 0 to 100, where 0 means no effect and 100 is the complete control. A dash response (-) means that there is no test result. TABLE E





TEST F
[0376] Seeds of plant species selected from corn (Zea plus), soybeans (Glicine max), (Abutilan theophrasti), lambsquarters (Chenopodium album), wild peanuts (wild peanuts, Euphorbia heterophilla), palmer anthill herb (Amaranthus palmeri), amaranth (common amaranth, Amaranthus rudis), brachiar grass (Brachiaha decumbens), large mattress grass (Lg) (Digitaria sanguinalis), Brazilian mattress grass (Digitaria horizontalis), autumn panicum (Panicum dichotomiflorum), giant mile (Setaria faberii), green mile (Setaria viridis), goose grass (Eleusine indica), massambará (Sorghum halepense), ambrosia (common ambrosia, Ambrosia elatior), rice grass (Echinochloa crusgalli), sandbur (southern sandbur, Cenchrus echinatus), guanxuma (Sida rhombifolia), Italian ryegrass (Lolium multiflorum), trapoeraba (Virginia trapoeraba (VA), Commelina virginica), field creeper (Convolvulus arvensis), tick (common tick, Xanthium strumarium), morning glory (Ipod a coccinea), nightshade (oriental nightshade, Solanum pticanthum), kochia (Kochia scoparia), yellow peppermint (Ciperus esculentus) and black peacock (Bidens pilosa), were planted in a clayey and pre-emergence soil treated with chemicals from test formulated in a non-phytotoxic solvent mixture that included a surfactant.
[0377] At the same time, vegetables from these crop and weed species and also amaranth_RES1, (common amaranth resistant to ALS and triazine, Amaranthus rudís) and amaranth_RES2, (common amaranth resistant to ALS & HPPD Amaranthus rudis) were treated with post-emergence applications of test chemicals formulated in the same way. The vegetables varied in height from 2 to 18 cm (stage from 1 to 4 leaves) for post-emergence treatments.
[0378] The treated vegetables and controls were kept in a greenhouse for 14 to 21 days, after which all species were compared with the controls and visually evaluated. Evaluations of plant responses, summarized in Table F, are based on a scale of 0 to 100, where 0 means no effect and 100 is complete control. A dash response (-) means that there is no test result. TABLE F





TEST G
[0379] Three plastic pots (about 16 cm in diameter) per fee were partially filled with sterile clay soil Tama, which comprises a proportion of sand, mud and clay and 2.6% of organic matter of 35:50:15 . The separate plantings for each of the three pots were as follows. The seeds of the USA of monochoria (Monochoria vaginalis), ciperacea small flower umbrella (Ciperus difformis), reed, hard stem (hard reed stem, Scirpus juncoides), and red stem (purple red stem, Ammannia coccinea), were planted in 16 cm pots for each rate. US seeds of flatsedge, rice (rice flatsedge, Ciperus would), sprangletop, Brdd. (Bearded Sprangletop, Leptochloa fascicularis), an easel of 9 or 10 seedlings of rice seeded water (Indica rice, Oriza sativa), and two easels of 3 or 4 seedlings of rice, transplanted {Oriza sativa cv “Japonica - M202”) were planted in a 16 cm pot for each rate. The US seeds of rice grass (Echinochloa crusgalli), water plant (common water plant, Alisma plantago-aquatica) and water grass, afternoon (late water grass, Echinochloa orizicola) were planted in a 16 cm pot for each fee. The plantations were sequential so that the crop and weed species were in the 2.0 to 2.5 leaf stage at the time of treatment.
[0380] The potted vegetables were grown in a greenhouse with day / night temperature settings of 30/27 ° C and supplementary balanced lighting was provided to maintain a 16 h photoperiod. The test vessels were kept in the greenhouse until the test was completed.
[0381] At the time of treatment, the test vessels were soaked 3 cm above the soil surface, treated by applying test compounds directly to the rice water, and then kept at that depth of water for the test duration. The effects of treatments on rice and weeds were visually assessed by comparison with untreated controls after 21 d. Assessments of plant responses, summarized in Table G, are based on a scale of 0 to 100 where 0 means no effect and 100 controls is complete. A dash response (-) means that there is no test result.

权利要求:
Claims (15)
[0001]
1. COMPOUND, characterized by being selected from Formula 1, N-oxides and their salts,
[0002]
2. COMPOUND, according to claim 1, characterized in that: - Q is selected from
[0003]
3. COMPOUND according to claim 2, characterized in that: - each R1, independently, is halogen, cyano, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2- haloalkenyl C4, C2-C4 haloalkyl, C1-C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkynoxy, C2-C6alkoxyalkyl, C2-C6alkyl, haloalkyl C4, C2-C4 alkylthioalkyl or SOnR1A; - R2 is halogen, C1-C4 alkyl or C1-C4 haloalkyl; - each R3, independently, be halogen, cyano, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C4 haloalkyl, C2-C4 haloalkyl, C3-C6 cycloalkyl, C3 halocycloalkyl -C6, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1-C4 alkoxy, C1-C6 haloalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6, C3-C6, SO6; or a 5- or 6-membered heteroaromatic ring containing the ring members selected from carbon atoms and up to 4 heteroatoms independently selected from atoms of up to 2 O, up to 2 S and up to 4 N, each ring optionally substituted with up to 3 substituents independently selected R3F from ring members of carbon atoms and R3G from ring members of nitrogen atoms; and - m is 0 or 1.
[0004]
4. COMPOUND, according to claim 3, characterized in that: - Q is selected from Q-7 to Q-24; - each R1, independently, be halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy or SOnR1A; - R2 is halogen or C1-C4 alkyl; - each R3, independently, be halogen, cyano, C-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1-C4 alkoxy , C1-C4 haloalkoxy, C2-C6 alkoxyalkyl or C2-C6 haloalkoxyalkyl; and - each R1A, independently, is C1-C4 alkyl or C1-C4 haloalkyl.
[0005]
5. COMPOUND, according to claim 4, characterized in that: - Q is selected from Q-16 and Q-18; - each R1, independently, be halogen, C1-C4 alkyl, C1-C4 haloalkyl or C1-C4 haloalkoxy; - R2 is halogen or CH3; and - each R3, independently, be halogen, cyano, C1-C4 alkyl or C1-C4 haloalkyl.
[0006]
6. COMPOUND, according to claim 3, characterized in that: - Q is selected from Q-43, Q-44, Q-45, Q-48, Q-49 and Q-50; - each R1, independently, be halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy or SQnR1A; - R2 is halogen or C1-C4 alkyl; - each R3, independently, be halogen, cyano, C-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1-C4 alkoxy , C1-C4 haloalkoxy, C2-C6 alkoxyalkyl or C2-C6 haloalkoxyalkyl; and - each R1A, independently, is C1-C4 alkyl or C1-C4 haloalkyl.
[0007]
7. COMPOUND, according to claim 6, characterized in that: - Q is selected from Q-43, Q-44 and Q-45; - each R1, independently, be halogen, C1-C4 alkyl, C1-C4 haloalkyl or C1-C4 haloalkoxy; - R2 is halogen or CH3; and - each R3, independently, be halogen, cyano, C1-C4 alkyl or C1-C4 haloalkyl.
[0008]
8. COMPOUND according to claim 1, characterized in that it is selected from the group consisting of - 5-chloro-2- [2- (5-chloro-2-pyridinyl) phenoxy] pinmidine, - 5-chloro- 2- [2- [5- (fluoromethyl) -3-isoxazolyl] phenoxy] pyrimidine, - 2- [2- (3-bromo-5-isoxazolyl) phenoxy] -5-chloropyrimidine, - 5-chloro-2- [ 2- [5- (trifluoromethyl) -2-pindinyl] phenoxy] pyrimidine, - 5-chloro-2- [3-chloro-2- (5-chloro-2-pyridinyl) phenoxy] pyrimidine, - 4- [2- [(5-bromo-2-pinmidinyl) oxy] phenyl] -2- (tnfluoromethyl) pyrimidine, - 2- [2- (2-bromo-5-thiazolyl) phenoxy] -5- (trifluoromethyl) pyrimidine, - 5- chloro-2- [4-methyl-2- [2- (trifluoromethyl) -4-pindinyl] phenoxy] pyrimidine, - 5-chloro-2- [2- [5- (difluoromethyl) -3-isoxazolyl] phenoxy] pyrimidine , - 5-chloro-2- [2- [3- (difluoromethyl) -5-isoxazolyl] phenoxy] pyrimidine, -5-chloro-2- [2- [5- (difluoromethyl) -3-isoxazolyl] -3- fluorophenoxy] pyrimidine, - 5-bromo-2- [2- [5- (difluoromethyl) -3-isoxazolyl] phenoxy] pyrimidine, - 5-chloro-2- [2- [3- (trifluoromethyl) -5-isoxazolyl] phenoxy] pyrimidine, -5-chloro-2- [2- [3- (difluoromethyl) -5-i soxazolyl] -3-fluorophenoxy] pyrimidine, -5-bromo-2- [2- [3- (difluoromethyl) -5-isoxazolyl] -3-fluorophenoxy] pyrimidine, -5-chloro-2- [2- [5- (trifluoromethyl) -3-isoxazolyl] -3-fluorophenoxy] pyrimidine, - 5-chloro-2- [2- [5- (trifluoromethyl) -3-isoxazolyl] phenoxy] pyrimidine, -5-chloro-2- [2- [5- (difluoromethyl) -3-isoxazolyl] -3-difluoromethoxyphenoxy] -pyrimidine, -5-chloro-2- [2- [5- (cyclopropyl) -3-isoxazolyl] -3-fluorophenoxy] pyrimidine, -5 -chloro-2- [2- [5- (trifluoromethyl) -3-isoxazolyl] -3-chlorophenoxy] pyrimidine, -5-chloro-2- [2- [5- (difluoromethyl) -3-isoxazolyl] -3- chlorophenoxy] pyrimidine, -5-chloro-2- [2- [3- (trifluoromethyl) -5-isoxazolyl] -3-chlorophenoxy] pyrimidine, -5-chloro-2- [2- [3- (trifluoromethyl) -5 -isoxazolyl] -3-fluorophenoxy] pyrimidine, -5-chloro-2- [2- [5- (trifluoromethyl) -3-isoxazolyl] -3-bromophenoxy] pyrimidine, -5-chloro-2- [2- [3 - (difluoromethyl) -5-isoxazolyl] -3-chlorophenoxy] pyrimidine, -5-bromo-2- [2- [3- (difluoromethyl) -5-isoxazolyl] -3-chlorophenoxy] pyrimidine, -5-bromo-2 - [2- [3- (methyl) -5-isoxazolyl] -3-chlorophenoxy] pyrimidine, -5-c loro-2- [2- [3- (difluoromethyl) -5-isoxazolyl] -3-bromophenoxy] pyrimidine, and -5-chloro-2- [2- [5- (difluoromethyl) -3-isoxazolyl] -3- bromophenoxy] pyrimidine.
[0009]
9. HERBICIDE COMPOSITION, characterized in that it comprises a compound as defined in any one of claims 1 to 8 and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.
[0010]
10. HERBICIDE COMPOSITION, characterized in that it comprises a compound, as defined in any one of claims 1 to 8, at least one additional active ingredient selected from the group consisting of other herbicides and herbicide phytoprotectants, and at least one component selected from the group consisting of surfactants, solid thinners and liquid thinners.
[0011]
11. HERBICIDE MIXTURE, characterized by comprising (a) a compound as defined in any one of claims 1 to 8, and (b) at least one additional active ingredient selected from (b1) inhibitors of photosystem II, (b2 ) acetohydroxy acid synthase inhibitors (AHAS), (b3) acetyl-CoA carboxylase inhibitors (ACCase), (b4) auxin mimics, and (b5) 5-enol-pyruvylshiquime-3-phosphate synthase inhibitors ( EPSP), (b6) electron shunt of photosystem I, (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b8), glutamine synthase (GS) inhibitors, (b9) very fatty acid elongase inhibitors (VLCFA), (b10) auxin transport inhibitors, (b11), phytene desaturase inhibitors (PDS), (b12) 4-hydroxyphenyl-pyruvate dioxigenase inhibitors (HPPD), (b13) solene homogentisate inhibitors (HST), (b14) cellulose biosynthesis inhibitors, (b15) other herbicides including disruptives s mitotic, organic arsenicals, asulam, bromobutide, cinmethyline, cumilurone, dazomet, difenzoquat, dimrone, etobenzanid, flurenol, phosamine, phosamine ammonium, metam, methyldimrone, oleic acid, oxaziclomefone, pelargonic acid and pyributicarb agents, and (b) 16 protection herbicides and salts of compounds from (b1) to (b16).
[0012]
12. METHOD FOR THE CONTROL OF UNWANTED VEGETATION GROWTH, characterized by understanding the contact of vegetation or its environment with a herbicide-effective amount of a compound, as defined in any of claims 1 to 8.
[0013]
13. METHOD FOR THE CONTROL OF UNWANTED VEGETATION GROWTH IN THE HARVEST OF GENETICALLY MODIFIED VEGETABLES that exhibit the characteristics of glyphosate tolerance, tolerance to glufosinate, tolerance to ALS herbicide, tolerance to dicamba, tolerance to imidazolinone herbicides, tolerance to 2,4 -D, tolerance to HPPD and tolerance to mesotrione, characterized by understanding the contact of vegetation or its environment with an effective herbicidal amount of a compound, as defined in any of claims 1 to 8.
[0014]
14. HERBICIDE MIXTURE, characterized by comprising (a) a compound, as defined in any of claims 1 to 8, and (b) at least one additional active ingredient selected from (b1) inhibitors of photosystem II, (b2 ) acetohydroxy acid synthase (AHAS) inhibitors, (b4) auxin mimics, (b5) 5-enol-pyruvylshiquimate-3-phosphate (EPSP) inhibitors, (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b8), (b9) very long chain fatty acid elongase inhibitors (VLCFA), and (b12) 4-hydroxyphenylpyruvate dioxigenase (HPPD) inhibitors.
[0015]
15. HERBICIDE MIXTURE, characterized by comprising (a) a compound, as defined in any of claims 1 to 8, and (b) at least one additional active ingredient selected from the group consisting of 2,4-D, acetochlor, alachlor, atrazine, bromoxynil, bentazone, bicyclopyrone, carfentrazon-ethyl, cloransulam-methyl, dicamba, dimetenamid-P, florassulame, flufenacete, flumioxazin, flupirssulfuron-methyl, fluroxifyr-isoxy-pyrol, -pyroxy-pyrol, -oxy-pyrol, -pyroxy-pyrol, mesotrione, metolachlor, metsulfuron-methyl, nicosulfuone, pirasulfotol, pyroxsulfone, pyroxsulam, rimsulfurone, saflufenacil, tembotrione, tifensulfuron-methyl, topramazone and tribenurone.

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法律状态:
2018-03-06| B07D| Technical examination (opinion) related to article 229 of industrial property law [chapter 7.4 patent gazette]|

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2018-08-28| B25A| Requested transfer of rights approved|Owner name: FMC CORPORATION (US) |

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2019-07-16| B07G| Grant request does not fulfill article 229-c lpi (prior consent of anvisa) [chapter 7.7 patent gazette]|Free format text: NOTIFICACAO DE DEVOLUCAO DO PEDIDO POR NAO SE ENQUADRAR NO ART. 229-C DA LPI. |

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2019-07-30| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-04-28| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-05-19| B09X| Republication of the decision to grant [chapter 9.1.3 patent gazette]|

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2020-07-28| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/01/2015, OBSERVADAS AS CONDICOES LEGAIS. |

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2020-09-01| B16C| Correction of notification of the grant [chapter 16.3 patent gazette]|Free format text: REF. RPI 2586 DE 28/07/2020 QUANTO AO ENDERECO. |

优先权:

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申请号 | 申请日 | 专利标题

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US201461928129P| true| 2014-01-16|2014-01-16|

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US61/928,129|2014-01-16|

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PCT/US2015/010823|WO2015108779A1|2014-01-16|2015-01-09|Pyrimidinyloxy benzene derivatives as herbicides|

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