method of forming an olefin product in a metathesis reaction from a raw material comprising a first

专利摘要:
METHOD OF FORMING OLEFINS FROM A FIRST OLEFIN AND A SECOND OLEFIN IN A REACTION OF METATHESIS, COMPOUND, USE OF COMPOUND, COMPOSITION AND METHOD FOR INCREASE THE REACTIVITY OF A COMPOUND The invention relates to a method of forming olefins to starting from a first olefin and a second olefin, in a metathesis reaction (double-exchange), comprising the following step (i): (i) reacting the first olefin with the second olefin in the presence of a compound that catalyzes said reaction of double-exchange (metathesis) so that the molar ratio of said compound to the first or second olefin is 1:500 or less, and the conversion of the first or second olefin to said olefin is at least 50%, wherein the compound that catalyzes said metathesis reaction (double-exchange) is a compound with the following chemical formula: wherein M is Mo or W; R' is the aryl, heteroaryl, alkyl or heteroalkyl radical; optionally substituted; R2 and R3 can be the same or different radicals, and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl or heteroaryl; optionally substituted; R 5 is the alkyl, alkoxy, heteroalkyl, aryl, heteroaryl, silylalkyl, silyloxy radical, optionally substituted; (...).
公开号:BR112015023269B1
申请号:R112015023269-8
申请日:2014-03-13
公开日:2021-05-04
发明作者:Levente Ondi；Jeno Varga；Agota Bucsai；Florian Toth；Krisztian Lorincz；Csaba Hegedus；Emmanuel Robe；Geog Frater
申请人:Verbio Vereinigte Bioenergie Ag；
IPC主号:

专利说明:

Description
[0001] This invention relates to alkene metathesis reactions and metathesis catalysts suitable for use in these reactions.
[0002] Alkene metathesis (olefin metathesis) is a reaction between alkenes or olefinic groups, in which, formally, alkadiene groups are exchanged between alkenes or olefinic groups. Examples of metathesis reactions include cross metathesis, that is, the reaction between two different olefins forming a new olefin or new olefins, ring-opening metathesis of cyclic dienes, which can also proceed under polymerization, ring-closing metathesis of a diene, ethenolysis of an olefin containing an internal olefinic double bond to form an olefin containing a terminal olefinic double bond, and the formation of internal olefin(s) from the terminal olefin(s) via homometathesis reaction. The last reaction can be considered as a cross metathesis between two identical olefins. More generally, any two identical olefins can be reacted in a cross homometathesis reaction.
[0003] US 2011/007742 A1 generally refers to catalysts and processes for selective formation of Z-shaping of internal olefin(s) from terminal olefin(s) , via homometathesis reaction. The method comprises reacting a first molecule containing a terminal double bond and a second identical molecule, via homometathesis reaction, to generate a product containing an internal double bond, in which the internal double bond of the product comprises an atom one carbon atom from the terminal double bond of the first molecule, and one carbon atom from the terminal double bond of the second carbon atom, and where at least 60% of the internal double bond of the product is formed as the Z-isomer. formula
wherein M is Mo or W, R1 is aryl, heteroaryl, alkyl, heteroalkyl radical, optionally substituted, R2 and R3 may be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl radical or heteroaryl, optionally substituted, and R4 and R5 may be the same or different and are an optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, silylalkyl or silyloxy radical, wherein at least one of R4 or R5 is a linker containing an oxygen bond with M. Preferably, bidentate structures are used as the R4 linker. Other compounds based on Mo and W, useful as catalysts in metathesis reactions, are known from US 6,121,473, US 2008/0119678 and US 2011/0015430.
[0004] Such catalysts are generally applied, or should be applied, in a metathesis reaction in a relatively high molar amount in relation to the molar amount of olefin or olefins, in order to achieve a sufficient degree of conversion of the olefin(s) (s) used as starting material. It is known that a molar ratio of up to 1:500 with respect to the applied olefin(s) (molar ratio of catalyst: olefin(s)) is required in order to achieve a conversion of 30 % or more. Hence, and since these catalysts are relatively slow, such reactions are slow on an industrial scale and therefore often lack industrial applicability.
[0005] This is an object of the invention, to provide a process for producing an olefin in a metathesis reaction and compounds useful as metathesis catalysts that carry out metathesis in a molar quantity as small as possible, in relation to the molar quantity of the applied olefin(s), and still allows a high conversion while optionally predicting a stereoselectivity, and also optionally, not only allowing the increasing formation of Z isomers in a homometathesis reaction, but it can be nephically catalyze other metathesis reactions, such as cross metathesis or ethenolysis of an olefin containing an internal olefinic double bond. Consequently, the process and compounds must be capable of allowing a conversion to a metathesis reaction of at least 30%, when applied in a molar ratio of less than 1:500, relative to the olefin(s) to be reacted. Such conversion and molar ratio are considered to allow a beneficial reaction on an industrial scale. First aspect of the invention - Metathesis reactions according to the invention and compounds used in the metathesis reactions according to the invention
[0006] According to a first aspect, this objective is achieved with a method of forming an olefin from a first olefin and a second olefin in a metathesis reaction comprising step (i): (i) reacting the first olefin with the second olefin, in the presence of a compound that catalyzes said metathesis reaction, such that the molar ratio of said compound to the first or second olefin is less than 1:500, and the conversion is at least 30% , wherein, as a compound that catalyzes said metathesis reaction, a compound with the following general formula is used:
where M = Mo or W, and R1, R2, R3, R5 are selected from commonly used residues for catalysts of the above formula and R4 is selected to be an R6-X- residue, where X = O and R6 is aryl radical, optionally substituted; or X = S and R6 is aryl radical, optionally substituted; or X = O and R6 is silyl radical; or X = O and R6 is a residue which is attached to the oxygen atom via a tertiary carbon atom; or R4 and R5 are linked together and are linked to M via oxygen, respectively.
[0007] In a modality, R1 to R5 are selected so that the conversion rate is at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90% is achieved.
[0008] In one embodiment, R1 to R5 are selected such that the molar ratio of the compound of the above formula to the first or second olefins is 1:1000 or less, or 1:2500 or less, or 1: 5000 or less, or 1:7500 or less, or 1:10000 or less, in order to achieve the object of the invention.
[0009] In one modality, R1 to R5 are selected so that the molar ratio is less than 1:500, and the corresponding conversion rate is at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%.
[0010] In one modality, R1 to R5 are selected so that the molar ratio is 1:1000 or less, and the corresponding conversion rate is at least 30%, or at least 40%, or at least 50% , or at least 60%, or at least 70%, or at least 80%, or at least 90%.
[0011] In one modality, R1 to R5 are selected so that the molar ratio is 1:2500 or less, and the corresponding conversion rate is at least 30%, or at least 40%, or at least 50% , or at least 60%, or at least 70%, or at least 80%, or at least 90%.
[0012] In an embodiment, R1 to R5 are selected so that the molar ratio is 1:5000 or less, and the corresponding conversion rate is at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%.
[0013] In one modality, R1 to R5 are selected so that the molar ratio is 1:7500 or less, and the corresponding conversion rate is at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%.
[0014] In one embodiment, R1 to R5 are selected so that the molar ratio is 1:10000 or less, and the corresponding conversion rate is at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%.
[0015] In one modality, R1 to R5 are selected so that the molar ratio is 1:20000 or less, or 1:50000 or less, or 1:100000 or less, or 1:500000 or less, or 1:1000000 or less, and the corresponding conversion rate is at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90 %, respectively.
[0016] In one embodiment, the upper limit of the molar ratio of said compound that catalyzes said metathesis reaction, relative to the first or second olefins, is 1:2,000,000.
[0017] In other embodiments, R1 to R5 are selected so that the molar ratio is from less than 1:500 to 1:50000 or less, and the corresponding conversion rate is from 30 to 100%, or from 50 to 100 %, or from 60 to 100%.
[0018] In one embodiment, R1 at which the molar ratio is 1:1000 and the corresponding conversion is from or from 60 to 100%.
[0019] In one embodiment, R1 at which the molar ratio is 1:2500 the corresponding conversion is from or from 60 to 100%.
[0020] In one modality, R1 to R5 are selected so that the molar ratio is from 1:5000 to 1:30000 or less, or from 1:10000 to 1:30000, or from 1:15000 to 1:30000, and the corresponding conversion rate is from 30 to 100%, or from 50 to 100%, or from 60 to 100%, respectively.
[0021] In one embodiment, the method consists of step (i).
[0022] In one embodiment, the first olefin has a terminal olefinic double bond, and the second olefin has a terminal olefinic double bond, wherein the first and second olefins are identical. Therefore, this reaction can be denoted as homometathesis reaction. This reaction results in an olefin containing an internal olefinic double bond, which is made from an olefin with a terminal olefinic double bond. Such a reaction can also be called a cross metathesis reaction between two identical olefins (homometathesis cross reaction).
[0023] Then, in this embodiment, the invention reports a method of forming an olefin containing an internal olefinic double bond, from an olefin containing a terminal olefinic double bond, in a metathesis reaction comprising step (i. 1): (i.(1) reaction of the first olefin with the second olefin, in the presence of a compound that catalyzes said metathesis reaction, such that the molar ratio of said compound to the first or second olefin is less than 1 :500, and the conversion is at least 30%, where the first and second olefins are identical, a compound with the following general formula is used:
where M = Mo or W, and R1 to R5 are selected in order to achieve the object of the invention.
[0024] The reaction, as defined in step (i.1), can be carried out according to methods and conditions known from the prior art, for example known from document US 2011/0077421.
[0025] In one embodiment, at least 50% of the internal double bonds are formed as the Z-isomer, preferably more than 60%, even more preferably more than 70%, or more than 80%, or more than 90%.
[0026] In another embodiment, the first and second olefins are different from each other. Such a reaction can be termed a cross-metathesis reaction between two different olefins.
[0027] Thus, in another embodiment, the invention refers to a method of forming olefin (or olefins) from a first olefin and a second olefin, in a metathesis reaction, comprising step (i .2): (i.(2) reaction of the first olefin with the second olefin, in the presence of a compound that catalyzes said metathesis reaction, so that the molar ratio of said compound to the first olefin or the second olefin is less than 1:500, and the conversion rate is at least 30%, where the first and second olefins are different from each other; where, as a compound that catalyzes said metathesis reaction, a compound with the following general formula is used:
where M = Mo or W, and R1 to R5 are selected in order to achieve the object of the invention.
[0028] In one embodiment, the first and second olefins contain an internal olefinic double bond, respectively.
[0029] In another embodiment, the first and second olefins contain a terminal olefinic double bond, respectively.
[0030] In another embodiment, the first olefin has a terminal olefinic double bond, and the second olefin contains an internal olefinic group, or vice versa.
[0031] In one embodiment, the first olefin is an olefin containing an internal olefinic double bond and the second olefin is ethylene. Such a metathesis reaction can be called etenolysis. This ethenolysis reaction results in an olefin or olefins containing a terminal olefinic double bond, respectively.
[0032] Thus, in another embodiment, the invention relates to a method of forming an olefin containing a terminal olefinic double bond, from a first olefin containing an internal olefinic double bond, and a second olefin, where the second olefin is ethylene, comprising step (i.3): (i.(3) reacting the first olefin with the second olefin, in the presence of a compound that catalyzes said metathesis reaction, so that the molar ratio of said compound with respect to the first or second olefin is less than 1:500, and the conversion rate is at least 30%, where the first and second olefins are different from each other; where as a compound that catalyzes the said metathesis reaction, a compound with the following general formula is used:
where M = Mo or W, and R1 to R5 are selected in order to achieve the object of the invention.
[0033] In one embodiment, the first olefin is a cyclic olefin, and the second olefin is a cyclic olefin, wherein the metathesis reaction is a ring-opening metathesis polymerization.
[0034] Thus, in one embodiment, the invention relates to a polymer formation method comprising internal olefinic double bond, from a first cyclic olefin and a second cyclic olefin, in a polymerization by metathesis of ring opening, comprising step (i.4): (i.(4) reacting the first cyclic olefin with the second cyclic olefin, in the presence of a compound that catalyzes said metathesis reaction, so that the molar ratio of said compound with respect to the first or second olefins is less than 1:500, and the conversion rate is at least 30%, where the first and second olefins are identical or different from each other; wherein, as a compound that catalyzes said metathesis reaction, a compound with the following general formula is used:
where M = Mo or W, and R1 to R5 are selected in order to achieve the object of the invention.
[0035] In one embodiment, the first olefin is identical to the second olefin. In one embodiment, the olefin is selected from norbornene or cyclopentadiene.
[0036] In an embodiment, the method consists of steps (i.1) or step (i.2) or step (i.3) or step (i.4).
[0037] In a more specific embodiment, the invention relates to a method of forming an olefin from a first olefin and a second olefin, in a metathesis reaction, comprising step (i): olefin is less than 1:500, and the conversion rate of the first or second olefins to said olefin is at least 30%, wherein, as a compound that catalyzes said metathesis reaction, a compound with the following general formula is used:
where M = Mo or W; R1 is aryl, heteroaryl, alkyl or heteroalkyl radical; optionally substituted; R2 and R3 may be the same or different and are hydrogen, alkyl (alcoyl), alkenyl (alkenyl), heteroalkyl, heteroalkenyl, aryl or heteroaryl, optionally substituted; R5 is an optionally substituted alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy radical; and R4 is an R6-X- residue, where X = O and R6 is aryl radical, optionally substituted; or X = S and R6 is aryl radical, optionally substituted; or X = O and R6 is (R7, R8, R9)Si; where R7, R8, R9 are alkyl or phenyl radicals, optionally substituted; or X = O and R6 is (R10, R11, R12)C, where R10, R11, R12 are independently selected from phenyl, alkyl radicals; optionally substituted; or R4 and R5 are linked together and are linked to M via oxygen, respectively.
[0038] In one modality, M = Mo or W; R1 is aryl, or adamant-1-yl radical; optionally substituted; R2 is an alkyl or cycloalkyl radical which is attached to M via a tertiary carbon atom, such as -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is optionally substituted alkoxy, heteroaryl, silyloxy, aryloxy radical; and R4 is an R6-X- residue, where X = O and R6 is phenyl radical substituted with up to five substituents independently selected from alkyl radical, preferably C1-C4 alkyl, such as methyl, isopropyl or t-butyl , alkoxy, preferably C1-C4 alkoxy, halogen, phenoxy, optionally substituted, phenyl optionally substituted; or X = S and R6 is phenyl substituted with up to five substituents independently selected from the alkyl radical, preferably C1-C4 alkyl, such as methyl, isopropyl or t-butyl, alkoxy, preferably C1-C4 alkoxy, halogen, phenyl , optionally substituted, phenoxy, optionally substituted; or X = O and R6 is triphenylsilyl radical, optionally substituted; or triisopropylsilyl; or X = O and R6 is triphenylmethyl radical; optionally substituted; or X = O and R6 is 9-phenyl-fluoren-9-yl radical; or X = O and R6 is 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl, or 2-methyl-1,1,1,3,3,3-hexafluoro radical -prop-2-yl; or X = O and R6 is t-butyl radical.
[0039] In one modality, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-di-t-butylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 9-phenyl-fluorene-9-yloxy; 2,6-diphenylphenoxy; t-butyloxy; and R4 is R6-X-, where X = O and R6 is phenyl substituted with up to five substituents independently selected from an alkyl radical, preferably C1-C4 alkyl, such as methyl, isopropyl or t-butyl, alkoxy, preferably C1 -C4 alkoxy, phenoxy, phenyl, halogen, optionally substituted; or X = S and R6 is phenyl substituted with up to five substituents independently selected from alkyl radical, preferably C1-C4 alkyl, such as methyl, isopropyl or t-butyl, alkoxy, preferably C1-C4 alkoxy, halogen, phenyl , optionally substituted, phenoxy, optionally substituted; or X = O and R6 is triphenylsilyl radical, optionally substituted; or triisopropylsilyl; or X = O and R6 is triphenylmethyl radical, optionally substituted; or X = O and R6 is 9-phenyl-fluoren-9-yl radical; or X = O and R6 is 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl or 2-methyl-1,1,1,3,3,3-hexafluoro-prop -2-yl; or X = O and R6 is t-butyl radical.
[0040] In one modality, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl and 2,5-dimethyl-pyrrol-1-yl; and R4 is R6-X-, where X = O and R6 is phenyl substituted with up to five substituents independently selected from an alkyl radical, preferably C1-C4 alkyl such as methyl, isopropyl or t-butyl, alkoxy, preferably C1- C4 alkoxy, halogen, phenoxy, optionally substituted, phenyl, optionally substituted; or X = S and R6 is phenyl substituted with up to five substituents independently selected from alkyl radical, preferably C1-C4 alkyl, such as methyl, isopropyl or t-butyl, alkoxy, preferably C1-C4 alkoxy, halogen, phenoxy , optionally substituted, phenyl, optionally substituted; or X = O and R6 is triphenylsilyl; or triisopropylsilyl; or X = O and R6 is triphenylmethyl or tri(4-methylphenyl)methyl; or X = O and R6 is 9-phenyl-fluoren-9-yl; or X = O and R6 is 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl or 2-methyl-1,1,1,3,3,3-hexafluoro-prop -2-yl; or X = O and R6 is t-butyl radical.
[0041] In one modality, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from triphenylsilyloxy or triisopropylsilyloxy; and R4 is R6-X-, where X = O and R6 is phenyl substituted with up to five substituents independently selected from alkyl, preferably C1-C4 alkyl, such as methyl, isopropyl or t-butyl, alkoxy, preferably C1- C4 alkoxy, halogen, phenoxy, optionally substituted, phenyl, optionally substituted; or X = S and R6 is phenyl substituted with up to five substituents independently selected from alkyl, preferably C1-C4 alkyl, such as methyl, isopropyl or t-butyl, alkoxy, preferably C1-C4 alkoxy, halogen, phenyl, optionally substituted, phenoxy, optionally substituted; or X = O and R6 is triphenylsilyl or triisopropylsilyl; or X = O and R6 is triphenylmethyl or tri(4-methylphenyl)methyl; or X = O and R6 is 9-phenyl-fluoren-9-yl; or X = O and R6 is 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl or 2-methyl-1,1,1,3,3,3-hexafluoro-prop -2-yl; or X = O and R6 is t-butyl.
[0042] In one modality, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from 9-phenyl-fluoren-9-yloxy; and R4 is R6-X-, where X = O and R6 is phenyl substituted with up to five substituents independently selected from alkyl, preferably C1-C4 alkyl, such as methyl, isopropyl or t-butyl, alkoxy, preferably C1- C4 alkoxy, halogen, phenoxy, optionally substituted, phenyl, optionally substituted; or X = S and R6 is phenyl substituted with up to five substituents independently selected from alkyl, preferably C1-C4 alkyl, such as methyl, isopropyl or t-butyl, alkoxy, preferably C1-C4alkoxy, halogen, phenoxy, optionally substituted, phenyl, optionally substituted; or X = O and R6 is triphenylsilyl or triisopropylsilyl; or X = O and R6 is triphenylmethyl or tri(4-methylphenyl)methyl; or X = O and R6 is 9-phenyl-fluoren-9-yl; or X = O and R6 is 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl or 2-methyl-1,1,1,3,3,3-hexafluoro-prop -2-yl; or X = O and R6 is t-butyl radical.
[0043] In one modality, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy or 2-methyl-1,1,1,3,3,3-hexafluoro-prop -2-yloxy; and R4 is R6-X-, where X = O and R6 is phenyl substituted with up to five substituents independently selected from alkyl, preferably C1-C4 alkyl, such as methyl, isopropyl or t-butyl, alkoxy, preferably C1- C4 alkoxy, halogen, phenoxy, optionally substituted, phenyl, optionally substituted; or X = S and R6 is phenyl substituted with up to five substituents independently selected from alkyl, preferably C1-C4 alkyl, such as methyl, isopropyl or t-butyl, alkoxy, preferably C1-C4 alkoxy, halogen, phenoxy, optionally substituted, phenyl, optionally substituted; or X = O and R6 is triphenylsilyl or triisopropylsilyl; or X = O and R6 is triphenylmethyl or tri(4-methylphenyl)methyl; or X = O and R6 is 9-phenyl-fluoren-9-yl; or X = O and R6 is 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl or 2-methyl-1,1,1,3,3,3-hexafluoro-prop -2-yl; or X = O and R6 is t-butyl radical. In one embodiment, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 2,6-diphenylphenoxy; 9-phenyl-fluoren-9-yloxy; t-butyloxy; and R4 is R6-X-, where X = O and R6 is a phenyl radical bearing two substituents in the ortho position with respect to O, or bearing two substituents in the ortho position with respect to O and at least one additional substituent in the position to, in relation to O; X = O and R6 is triphenylsilyl; optionally substituted; or triisopropylsilyl; or X = O and R6 is triphenylmethyl or tri(4-methylphenyl)methyl; or X = O and R6 is 9-phenyl-fluoren-9-yl; or X = O and R6 is 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl or 2-methyl-1,1,1,3,3,3-hexafluoro-prop -2-yl; or X = O and R6 is t-butyl radical.
[0044] In one modality, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 2,6-diphenylphenoxy; 9-phenyl-fluoren-9-yloxy; t-butyloxy; and R4 is selected from 4-bromo-2,6-diphenylphenoxy, 4-fluoro-2,6-diphenylphenoxy, 4-methyl-2,6-diphenylphenoxy, 4-methoxy-2,6-diphenylphenoxy, 2 ,4,6-triphenylphenoxy, 4-fluoro-2,6-dimethylphenoxy, 4-bromo-2,6-di-tert.-butylphenoxy, 4-methoxy-2,6-di-tert.-butylphenoxy, 4 -methyl-2,6-di-tert.-butyl-phenoxy, 4-dimethylaminophenyl-2,6-diphenylphenoxy, 2,4,6-tri-tert.-butylphenoxy, 4-bromo-2,3,5,6 -tetraphenylphenoxy; 4-bromo-2,6-di(4-bromophenyl)-3,5-diphenylphenoxy; or
where TBS is t-butyldimethylsilyl; or

[0045] where Me = methyl; or 2,6-diphenylphenoxy, 2,3,5,6-tetraphenylphenoxy, 2,6-di(tert.-butyl)phenoxy; 2,6-di(2,4,6-triisopropylphenyl)phenoxy; or Triphenylsilyloxy or triisopropylsilyloxy; or triphenylmethyloxy or tri(4-methylphenyl)methyloxy; or 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy or 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; or 9-phenyl-fluoren-9-yloxy; or t-butyloxy.
[0046] In one embodiment, the residues R4 and R5 are linked and are linked to M via oxygen, respectively. An example of such a linked residue is the corresponding residue in compounds 105 and 114:

[0047] The catalyst can be prepared according to known methods or known methods from patents US 2011/0077421 A1, US 6,121,473, US 2008/0119678 and US 2011/0015430.
[0048] The compounds can be advantageously used in the metathesis reactions specified above. Without being bound by theory, it is believed that in particular R4, as selected and defined, provides high yield and stereoselectivity in the various types of metathesis reactions. Furthermore, the catalyst starting materials, in particular the starting materials used to introduce the residue R4 into compounds of Mo or W, are mostly commercially available or can simply be prepared according to known methods. This makes the selected catalysts specifically applicable for industrial purposes, that is, for alkene (alkene) metathesis reactions carried out on an industrial scale.
[0049] Consequently, said catalysts can be advantageously applied in various types of metathesis reactions.
[0050] In an embodiment of the method according to the invention, the first olefin has a terminal olefinic double bond, and the second olefin has a terminal olefinic double bond, wherein the first and second olefins are identical.
[0051] In another modality, the first and second olefins are different from each other.
[0052] In yet another embodiment, the first olefin has an internal olefinic double bond and the second olefin is an ethylene. In one modality, when M = Mo; R1 is 2,6-diisopropylphenyl; R2 is -C(CH3)2C6H5; R3 is H; R4 is 1-(4-bromo-2,6-diphenylphenoxy); R5 is 2,5-dimethyl-pyrrol-1-yl; or when M is Mo; R1 is 2,6-dimethylphenyl; R2 is -C(CH3)2C6H5; R3 is H; R4 is 4-bromo-2,3,5,6-tetraphenylphenoxy; R5 is 2,5-dimethyl-pyrrol-1-yl; the catalysts allow ethenolysis, resulting in a high yield of an olefin with a terminal olefinic double bond.
[0053] Other chosen compounds have the following structures: M = Mo; R1 is 2,6-dimethylphenyl; R2 is -C(CH3)2CGH5; R3 is H; R4 is 4-bromo-2,3-diphenylphenoxy; R5 is 2,5-dimethyl-pyrrol-1-yl; or M is Mo; R1 is 2,6-diisopropylphenyl; R2 is -C(CH3)2C6H5; R3 is H; R4 is 4-bromo-2,3,5,6-tetraphenylphenoxy; R5 is 2,5-dimethyl-pyrrol-1-yl; or M is Mo; R1 is 2,6-diisopropylphenyl; R2 is -C(CH3)2C6H5; R3 is H; R4 is 4-methyl-2,3-di-t-butylphenoxy; R5 is pyrrol-1-yl; or M is Mo; R1 is 2,6-diisopropylphenyl; R2 is -C(CH3)2C6H5; R3 is H; R4 is 4-bromo-2,3-di-t-butylphenoxy; R5 is pyrrol-1-yl; or M is Mo; R1 is 2,6-diisopropylphenyl; R2 is -C(CH3)2C6H5; R3 is H; R4 is 2,4,6-tri-t-butylphenoxy; R5 is pyrrol-1-yl; or M is Mo; R1 is 2,6-diisopropylphenyl; R2 is -C(CH3)2C6H5;R3 is H; R4 is 4-methoxy-2,3-di-t-butylphenoxy; R5 is pyrrol-1-yl.
[0054] Additional preferred compounds used as catalysts in the method according to the invention are the following compounds from 1 to 291:































[0055] The following compounds are known from:

Purification of the first and/or second olefin, respectively purification of a raw material comprising the first and/or second olefin
[0056] It was further discovered, unexpectedly, that the molar ratio of the metathesis catalyst of the first or second olefins, or first and second olefins, can be further reduced if the raw material containing said first and/or second olefins , which will be subjected to said metathesis reaction, is purified before its reaction on the catalyst.
[0057] In one modality, the purification is carried out so that the by-products (contaminants) contained in the raw material are subjected to a physical purification. Preferably, the term "physical purification" encompasses: distilling said by-products for removal, or distilling the raw material, or adsorbing said by-products. Therefore, said by-products can be partially or completely removed from the raw material, in such a way that they do not negatively affect the use of the catalyst.
[0058] Possible by-products accompanying said first and second olefins, which are contained in the raw material, are, for example, water, alcohols, aldehydes, peroxides, hydroperoxides, protic materials, polar materials, Lewis base catalyst poison and two or more of them. Then, the by-products are selected from the group consisting of water, alcohols, aldehydes, peroxides, hydroperoxides, protic materials, polar materials, Lewis base catalyst poisons and two or more thereof.
[0059] In another embodiment, the purification is a chemical purification. Preferably, the term “chemical purification” encompasses: subjecting the by-products to a chemical reaction.
[0060] Therefore, through a suitable reaction, the by-product(s) can be converted to another compound, which does not negatively affect the use of the catalyst.
[0061] In one embodiment, physical purification comprises media selected from the group consisting of heat (preferably distillation), molecular sieves, alumina, silica gel, montmorillonite clay, Fuller's earth, bleaching clay, diatomaceous earth, zeolites, kaolin, activated metals, metal sulfates, metal halides, metal silicates, activated carbon and sodium carbonate.
[0062] In one embodiment, chemical purification comprises media selected from the group consisting of metal carbonates and metal hydrogencarbonates, acid anhydrides, metal hydrides, phosphorus pentoxide, aluminum metal hydrides, alkyl aluminum hydrides, trialkyl aluminum, metal borohydrides, organometallic reagents, metal amides, and combinations thereof.
[0063] In one embodiment, a by-product is a compound that contains at least one proton suitable for reacting with a compound selected from the group consisting of metal carbonates and metal hydrogen carbonates, acid anhydrides, metal hydrides, phosphorus pentoxide, metal hydrides of aluminum, alkylaluminum hydrides, trialkylaluminum, metal borohydrides, organometallic reagents, metal amides, and combinations thereof.
[0064] In another embodiment, purification is carried out by means selected from the group consisting of molecular sieves optionally heat treated, activated alumina optionally heat treated, activated acidic alumina optionally heat treated, activated neutral alumina optionally heat treated , optionally heat treated activated basic alumina, alkaline earth metal hydrides, alkaline earth metal sulphates, alkali metal sulphates, alkaline earth metal halides, alkali metal aluminum hydrides, alkali metal boron hydrides, chemical reagents Grignard; organolithium reagents, trialkylaluminum, bis(trimethylsilyl)amide, and combinations thereof.
[0065] In another modality, purification is performed by means selected from the group consisting of CaH2, activated copper (Cu), activated magnesium (Mg), acetic anhydride, calcium sulfate, magnesium sulfate, potassium sulfate, aluminum sulfate, magnesium potassium sulfate, sodium sulfate, calcium carbonate, sodium carbonate, magnesium silicate, potassium chloride, LiAlH4, NaAlH4, iBu2AlH, n-butyl lithium, t-butyl lithium sec-butyl lithium, triethyl aluminum , tributylaluminum, triisopropylaluminum, trioctylaluminum, lithium diisopropyl amide, KHMDS, and combinations thereof.
[0066] Consequently, in an embodiment, where said first and said second olefins are contained in a raw material, wherein said raw material further comprises at least one by-product selected from the group consisting of water, alcohols, aldehydes, peroxides, hydroperoxides, decomposition products of peroxides, protic materials, polar materials, basic Lewis catalyst poisons, or mixture of two or more of these, the method still comprises step (0) before step (i) : (0) subjecting said raw material to a physical or chemical, or physical and chemical purification step, preferably in which the physical purification is carried out before the chemical purification step, in which the physical purification step comprises: distilling at least one of said by-products, or distilling said raw material, or absorbing at least one of the by-products; and wherein the chemical purification step comprises: subjecting at least one of the by-products to a chemical reaction.
[0067] In one embodiment, said first and second olefins are comprised in a raw material, wherein said raw material further comprises at least one by-product selected from the group consisting of water, alcohols, aldehydes , peroxides and hydroperoxides, peroxide decomposition products, protic materials, polar materials, Lewis base catalyst poison, or mixture of two or more of these, the method further comprises step (0) before step (i) submit at least one of the by-products in said raw material to a chemical reaction.
[0068] In one embodiment, the first and second olefins are identical.
[0069] In one embodiment, the raw material comprises at least 99% by weight of the first and second olefins, based on the total weight of the raw material, the remainder being by-products, or at least 99.5% in Weight.
[0070] After the purification step, in one embodiment, the raw material comprises at least 99.9% by weight of the first and second olefins, or at least 99.99% by weight, or at least 99.999%.
[0071] Without being limited by theory, it is believed that said step (0) transfers by-products that are contained in the olefin and that can react with a metathesis catalyst and thus can destroy the activity of the same, in non-reactive species thereby further favorably lowering the molar ratio of catalyst to olefin.
[0072] In one modality, the by-products of the raw material are subjected to an anhydride of an organic acid. Suitable anhydrides are preferably aliphatic, cyclic anhydrides, alicyclic organic acids containing from 1 to 10 carbon atoms, or aromatic organic acids containing from 6 to 10 carbon atoms. These compounds are known in the literature or can be produced according to known methods.
[0073] In one embodiment, the organic anhydride is acetic anhydride.
[0074] In another modality, the by-products of the raw material are subjected to an organometallic aluminum compound.
[0075] In one embodiment, the organometallic compound is of the formula R1R2R3Al, wherein R1, R2 and R3 are independently selected from aliphatic, cyclic, alicyclic residues containing 1 to 10 carbon atoms, or from residues aromatics containing from 6 to 10 carbon atoms. Such compounds are known in the literature or can be produced according to known methods.
[0076] In one embodiment, the organometallic aluminum compound is triethylaluminum, tributylaluminum, triisobutylaluminum, triisopropylaluminum or trioctyl.
[0077] Trioctylaluminum is particularly preferred, since said compound is stable in contact with air, i.e. it is not flammable in contact with air, unlike, for example, triethylaluminum. This makes said compound particularly suitable for industrial scale applications.
[0078] For the practical realization of the chemical purification step, in one modality, the amount of by-products can be determined, for example, by known methods such as chromatographic methods. Then, the theoretical amount of compound needed to convert reactive groups of the by-products into non-reactive groups, preferably organic anhydride or organometallic aluminum compound, is added.
[0079] In one embodiment, per mole of by-product, a slight excess of organic anhydride or organometallic aluminum compound, preferably a trialkylaluminum compound, preferably trioctylaluminum, is added in order to convert said by-product into a non-reactive species to the catalyst.
[0080] In one embodiment, if a trialkylaluminum compound, preferably trioctylaluminum, is used in the chemical purification step, per 1 mol of by-product, preferably 1 to 2 mol of trialkylaluminum compound, preferably trioctylaluminum, is preferably used 1 to 1.5 mol, more preferably 1.25 mol.
[0081] In another embodiment, any excess organometallic aluminum compound can be destroyed or removed.
[0082] In one modality, step (0) and step (i) can be performed spatially separated from each other. Thus, step (0) can be performed at a single location or in one reactor, and step (i) is performed at another location or another reactor.
[0083] In another modality, step (0) and step (i) are performed spatially not separated from each other. Thus, step (0) is carried out in a single place or in a reactor, and step (i) is carried out in the same place or in the same reactor.
[0084] Typically there are several options of different and often complementary media from which to choose for the preparation to purify a contaminated raw material, comprising said first and said second olefins, before a metathesis reaction according to the invention. While not wishing to be bound by any particular theory, nor intending to limit in any way the scope of the appended claims or their equivalents, it is currently believed that the following list of representative non-exhaustive and non-limited purification methodologies may be useful in treating of raw materials that contain, alongside the first and second olefins, specific contaminants [rovided that the media are compatible with any functional group in the raw material and/or with the by-products (contaminants) themselves, etc.]: ( a) a heat treatment—for example, heating (and/or distilling) a raw material or a by-product (for example, between about 100 °C and 250 °C, or around 200 °C in some modalities — depending on the boiling point of the raw material, optionally with a purging of an inert gas such as N2 and/or the like) and/or treatment with an adsorbent (eg alumina and the like) may be useful in both contaminant decomposition s of peroxides and/or decomposition products thereof or adsorbent contaminants; (b) treatment with acid anhydride (eg, acetic anhydride, Ac2O) can be useful in removing moisture, materials containing active hydroxyl group (eg, alcohols), and hydroperoxides (via acetylation); (c) treatment with a desiccant (eg, silica gel, molecular sieves, magnesium sulfate, calcium sulfate, and the like, and combination thereof) and/or an organometallic reagent (eg, t-butyl lithium, tri- aluminum ethyl, aluminum tributyl, aluminum triisobutyl, aluminum triisopropyl, aluminum trioctyl, and the like, and combinations thereof) and/or metal hydrides (for example, CaH2 and the like) and/or acid anhydrides (for example, acetic anhydride and the like) can be useful in removing moisture; (d) treatment with an adsorbent (eg, alumina, silica gel, and the like, and combinations thereof) and/or an organometallic reagent (eg, t-butyl lithium, triethylaluminum, tributylaluminum, triisobutylaluminum, tri -isopropylaluminum, trioctylaluminum, and the like, and combinations thereof) and/or a metallic amide (e.g., LDA, KHMDA, and the like) may be useful in removing protic materials; (e) treatment with an adsorbent (eg, alumina, silica gel activated carbon, and the like, and combinations thereof) can be useful in removing polar materials; (f) treatment with an organometallic reagent (for example, t-butyl lithium, triethylaluminum, tributylaluminum, triisobutylaluminum, triisopropylaluminum, trioctylaluminum, and the like, and combinations thereof) may be useful in removing basic catalyst poison of Lewis; etc.
[0085] In some embodiments, the medium used to purify said raw material, prior to the metathesis reaction, comprises an adsorbent which, in some embodiments, is selected from the group consisting of silica gel, alumina, clay of bleaching, activated carbon, molecular sieves, zeolites, Fuller's earth, diatomaceous earth and the like, and combinations thereof. In some embodiments, the medium is selected from the group consisting of optionally heat treated molecular sieves, optionally heat treated alumina, and combinations thereof. In some embodiments, the adsorbent comprises optionally heat-treated activated alumina which, in some embodiments, is selected from the group consisting of optionally heat-treated activated acidic alumina, optionally heat-treated activated neutral alumina, optionally heat-treated activated basic alumina, and combinations thereof . In some embodiments, the adsorbent comprises optionally heat-treated activated neutral alumina, which can be useful in treating substrates (e.g., olefins) that are susceptible to acid-catalyzed isomerization and/or rearrangement.
[0086] For modalities in which the means for purification comprises an adsorbent (e.g., molecular sieves, alumina etc.), it is currently believed that the treatment of raw material with adsorbent is carried out more effectively by the flow of material. press through the means for purification using a percolation or flow-type system (eg column chromatography) as opposed to simply adding adsorbent to the substrate in a vial. In some embodiments, about 20% by weight of alumina is used in a column. While not wishing to be bound by any particular theory, nor intending to limit in any way the scope of the appended claims or their equivalents, it is currently believed to treat a feedstock with alumina at a basis ratio of about 5 to 1 weight -weight is effective for some modalities. However, it should be understood that the amount of alumina used is not restricted and will be dependent on both the raw material and impurities, in addition to being influenced by the form of the alumina, its activation process and the precise method of treatment (for example, flow through a column versus direct addition to the vial). In some embodiments, the medium used to purify the raw material prior to the metathesis reaction comprises a trialkylaluminum which, in some embodiments, is selected from the group consisting of triethylaluminum, tributylaluminum, triisobutylaluminum, triisopropylaluminum , trioctylaluminum, and the like, and combinations thereof. While not wishing to be bound by any particular theory, nor intending to limit in any way the scope of the appended claims or their equivalents, it is believed that treating a substrate with trialkyl aluminum significantly improves the conversion of the raw material at low concentrations of metathesis catalyst, but that, in the presence of excess aluminum trialkyl, the catalyst performance is negatively affected. Thus, in some embodiments, the use of a continuous agent to treat the substrate can comprise an adsorbent that can remove excess aluminum trialkyl. In other embodiments, the amount of trialkylaluminum used to treat the raw material can be reduced by pre-treating the raw material with a form other than a medium described herein (e.g., an adsorbent including, but not limited to, molecular sieves, alumina, and/or the like), followed by the introduction of aluminum trialkyl as a second (subsequent) means to remove residual contaminants. In any event, while not wishing to be bound by any particular theory, nor intending to limit in any way the scope of the appended claims or their equivalents, it is believed that the removal of excess trialkyl aluminum from organic products should be carried out with Great caution, as using the wrong adsorbent can be unsafe.
[0087] In some embodiments, molecular sieves can be used as a method of drying most of the raw material, heat-treated alumina can then be used as a second means to remove additional moisture, and finally, molecular sieves they can be used at the end as a third means of removing additional residual moisture. In another embodiment, molecular sieves can be used as the first means to dry most of the raw material, heat-treated alumina can be used as a second means to remove additional moisture, and finally a trialkylaluminum (eg, aluminum triethyl, aluminum tributyl, aluminum triisobutyl, aluminum triisopropyl, aluminum trioctyl, and the like, and combinations thereof) can be used as a third means for removing any still residual moisture.
[0088] In a particular modality, activated copper powder is used alone or in combination with another treatment. For example, in some embodiments, activated copper powder is used in combination with heat (eg 200 °C for at least 2 hours under nitrogen gas), molecular sieves, and/or a trialkyl aluminum treatment. In another modality, activated magnesium ingots (shavings) are used alone or in combination with another treatment. For example, in some embodiments, activated magnesium ingots are used in combination with heat (eg 200 °C for at least 2 hours under nitrogen gas), molecular sieves, and/or a trialkyl aluminum treatment.
[0089] In a particular modality, acetic anhydride is used alone or in combination with another treatment/medium. For example, in some embodiments, acetic anhydride is used in combination with alumina (aluminum oxide) and/or treatment with a trialkylaluminum. In other embodiments, acetic anhydride is used in combination with alumina, distillation, molecular sieves, and/or treatment with a trialkylaluminum. In addition, percolation over activated alumina or molecular sieves can be applied before or instead of trialkyl aluminum treatment. In another embodiment, alumina is used alone or in combination with another treatment/agent. In one embodiment, alumina is used in combination with a palladium on carbon (Pd/C) catalyst and/or treatment with an aluminum trialkyl.
[0090] It was further discovered, unexpectedly, that the purification period of the raw material can significantly influence the effectiveness of the chemical purification step. Thus, prolonged periods of purification can improve the catalytic activity of compounds used as catalysts in metathesis reactions according to the invention.
[0091] In one embodiment, preferably when a trialkylaluminum compound is used for purification, preferably trioctylaluminum, the raw material is subjected to said compound for a period of 2 to 100 hours, preferably 5 to 90 hours, more preferably 10 to 80 hours, and even more preferably 15 to 70 hours.
[0092] In some embodiments, purification of the raw material reduces the level of at least one by-product, to an amount sufficient to allow the metathesis reaction to proceed at a molar ratio of the compound of the above formula to the first and/or second olefins of 1:1,000 or less, or 1:2,500 or less, or 1:5,000 or less, or 1:7,500 or less, or 1:10,000 or less.
[0093] In one embodiment, the purification of the raw material reduces the level of at least one by-product to an amount sufficient to allow the metathesis reaction to proceed at a molar ratio of the compound of formula above to the first and/ or second olefins of less than 1:500, and the corresponding conversion rate is at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%.
[0094] In one embodiment, the purification of the raw material reduces the level of at least one by-product, to an amount sufficient to allow the metathesis reaction to proceed at a molar ratio of the compound of the above formula to the first and /or second olefins of 1:1,000 or less, and the corresponding conversion rate is at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least at least 80%, or at least 90%.
[0095] In one embodiment, the purification of the raw material reduces the level of at least one by-product, to an amount sufficient to allow the metathesis reaction to proceed at a molar ratio of the compound of the above formula to the first and /or second olefins of 1:2,500 or less, and the corresponding conversion rate is at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least at least 80%, or at least 90%.
[0096] In one embodiment, purification provides a molar ratio of 1:5,000 or less, and the corresponding conversion rate is at least 30%, or at least 40%, or at least 50%, or at least 60% , or at least 70%, or at least 80%, or at least 90%.
[0097] In one embodiment, the purification of the raw material reduces the level of at least one by-product, to an amount sufficient to allow the metathesis reaction to proceed at a molar ratio of the compound of the above formula to the first and /or second olefins 1:7,500 or less, and the corresponding conversion rate is at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%.
[0098] In one embodiment, the purification of the raw material reduces the level of at least one by-product, to an amount sufficient to allow the metathesis reaction to proceed at a molar ratio of the compound of the above formula to the first and /or second olefins of 1:10,000 or less, and the corresponding conversion rate is at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least at least 80%, or at least 90%.
[0099] In one embodiment, the purification of the raw material reduces the level of at least one by-product, to an amount sufficient to allow the metathesis reaction to proceed at a molar ratio of the compound of the above formula to the first and /or second olefins of 1:20,000 or less, or 1:50,000 or less, or 1:100,000 or less, or 1:500,000 or less, or 1:1,000,000 or less, and the corresponding conversion rate is at least at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%, respectively.
[0100] In one embodiment, purification provides a lower limit of the compound of the above formula with respect to the first and/or second olefins, molar ratio of 1:2,000,000, or 1:3,000,000 or 1:4,000,000 , respectively.
[0101] In other modalities, the purification of the raw material reduces the level of at least one by-product, to an amount sufficient to allow the continuation of the metathesis reaction at a molar ratio of the compound of the above formula in relation to the first and/or second olefins from less than 1:500 to 1:50,000 or less, and the corresponding conversion rate is from 30 to 100%, or from 50 to 100%, or from 60 to 100%.
[0102] In one embodiment, the purification of the raw material reduces the level of at least one by-product, to an amount sufficient to allow the metathesis reaction to proceed at a molar ratio of the compound of the above formula to the first and /or second olefins from 1:1,000 to 1:40,000 or less, and the corresponding conversion rate is from 30 to 100%, or from 50 to 100%, or from 60 to 100%.
[0103] In one embodiment, the purification of the raw material reduces the level of at least one by-product, to an amount sufficient to allow the metathesis reaction to proceed at a molar ratio of the compound of the above formula to the first and /or second olefins from 1:2,500 to 1:30,000 or less, and the corresponding conversion rate is from 30 to 100%, or from 50 to 100%, or from 60 to 100%.
[0104] In one embodiment, the purification of the raw material reduces the level of at least one by-product, to an amount sufficient to allow the metathesis reaction to proceed at a molar ratio of the compound of the above formula to the first and /or second olefins from 1:5,000 to 1:30,000 or less, or from 1:10,000 to 1:30,000, or from 1:15,000 to 1:30,000, and the corresponding conversion rate is from 30 to 100%, or from 50 to 100%, or 60 to 100%, respectively.
[0105] In one modality, said method consists of steps (0) and (i). Method of adding the catalyst to the raw material comprising the first olefin and/or the second olefin
[0106] In another embodiment, it has been even more unexpectedly considered that the effectiveness of the compound of the above formula used as a metathesis catalyst can be improved by slowly adding the catalyst to the first and/or second olefins.
[0107] The effectiveness can be, for example, evaluated by calculating the turn-over number (TON). In some embodiments, the total catalyst load (catalyst amount per unit amount of reactant) may be reduced by at least 10%, at least 20%, or at least 30% compared to achieving the same TON in an isolated batch full charge.
[0108] The slow addition of the total catalyst charge may comprise the fractional addition of catalyst charge to the substrate at an average rate of approximately 10 ppm by weight of catalyst per hour (ppm by weight/h), 5ppm by weight/h, 1ppm wt/hr, 0.5ppm wt/hr, 0.1ppm wt/hr, 0.05ppm wt/hr, or 0.01 ppm wt/hr. In other embodiments, the catalyst is added slowly at a rate of between about 0.01-10 ppmw/hr, 0.05-5 ppmw/hr, or 0.1-1 ppmw/hr. The slow addition of catalyst can be conducted in batch loading at frequencies of every 5 minutes, 15 minutes, 30 minutes, 1 hour, 2 hours, 4 hours, 12 hours, or 1 day. In other embodiments, slow addition is conducted in a continuous addition process.
[0109] In one embodiment, catalyst is slowly added to the substrate at a rate of 0.01-10 ppm by weight of catalyst per hour.
[0110] In one modality, the catalyst is added in portions.
[0111] In some embodiments, the raw material comprising the first and/or second olefins is purified with at least one method, as described in detail above, before the slow addition of the catalyst. In other embodiments, slow addition of catalyst improves catalyst efficiency, independent of any substrate treatment.
[0112] In one modality, the raw material is purified by applying prolonged periods of purification, followed by a slow addition of catalyst. Second aspect of the invention - Selected suitable compounds for use in metathesis reactions and metathesis reactions according to the invention
[0113] According to the second aspect, the invention relates to the compounds that can be used in the method as defined in the first aspect of the invention and in any embodiments defined herein.
[0114] In one embodiment, the invention relates to a formula compound
where M is Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-di-iso-propylphenyl, 2,6-di-t-butylphenyl, 2,6-diclophenyl, adamant-1-yl; R2 is —C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from depyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 9-phenyl-fluene-9-yloxy; 2,6-diphenylphenoxy; t-butyloxy; and R4 is R6-X-, where X = O and R6 is the phenyl radical, which bears at least two substituents, or bears two substituents in the ortho position to O, or bears two substituents in the ortho position to O to the O, and a substituent in the para position with respect to the O; or X = O and R6 is the triphenylsilyl radical; optionally substituted, or triisopropylsilyl; or optionally substituted phenyltriphenylsilylor isopropyl or X = O and R6 is the triphenylmethyl radical; optionally substituted; or optionally substituted phenylmethyltriphenylmethyl or X = O and R6 is the 9-phenyl-fluoroene-9-yl radical; or X = O and R6 is the 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl or 2-methyl-1,1,1,3,3,3-hexafluoro radical -prop-2-yl; or X = O and R6 is the t-butyl radical with the proviso that the following compounds are excluded: M = Mo; R1 = 2,6-diisopropylphenyl; R2 = -C(CH3)2C6H5; R3 = H; R5 = 2,5-dimethylpyrrol-1-yl; R4 = 2,6-diphenylphenoxy; M = Mo; R1 = 2,6-diisopropylphenyl; R2 = -C(CH3)2C6H5; R3 = H; R5 = 2,5-dimethylpyrrol-1-yl; R4 = 2,3,5,6-tetraphenylphenoxy; M = W; R1 = 2,6-diisopropylphenyl; R2 = -C(CH3)2C6H5; R3 = H; R5 = 2,5-dimethylpyrrol-1-yl; R4 = triphenylsilyloxy; and M = Mo; R1 = 2,6-diisopropylphenyl; R2 = -C(CH3)2C6H5; R3 = H; R5 = 2,5-dimethylpyrrol-1-yl; R4 = triphenylsilyloxy; and M = W; R1 = 2,6-diisopropylphenyl; R2 = -C(CH3)2C6H5; R3 = H; R5 = 2,5-dimethylpyrrol-1-yl; and R4 =

where R19 is F, Cl, Br, or I.
[0115] In one embodiment, R6 is phenyl, which bears two substituents in the ortho position, relative to O, or which bears two substituents in the ortho position, relative to O, and one substituent in the para position, relative to O, wherein the two substituents at the ortho position are identical.
[0116] In one mode, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R2 is —C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 2-methyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 9-phenyl-fluenyl-9-oxy; 2,6-diphenylphenoxy; t-butyloxy; and R4 is selected from 4-bromo-2,6-diphenylphenoxy, 4-fluouo-2,6-diphenylphenoxy, 4-methyl-2,6-diphenylphenoxy, 4-dimethylamino-2,6-diphenylphenoxy, 4 -methoxy-2,6-diphenylphenoxy, 2,4,6-triphenylphenoxy, 4-fluoro-2,6-dimethylphenoxy, 4-bromo-2,6-di-tert-butylphenoxy, 4-methoxyoxy-2,6 -di-tert-butylphenoxy, 4-methyl-2,6-di-tert-butylphenoxy, 2,4,6-tri-tert-butylphenoxy, 4-bromo-2,3,5,6-tetraphenylphenoxy; 4-bromo-2,6-di(4-bromophenyl)-3,5-diphenylphenoxy.
[0117] In one mode, M = Mo or W; R1 is selected from methylphenyl2,6-dimethylphenyl, isopropylphenyl2,6-diisopropylphenyl, or phenyl2,6-dichlorophenyl, adamant-1-yl; R2 is —C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrole-1-ylc; methyl2,5-dimethyl-pyrrol-1-yl; phenyltriphenylsiloxy; isopropylsilyloxytriisopropylsilyloxy; phenylor1,1,1,3,3,3-hexafluouo-prop-2-yl2-phenyl-1,1,1,3,3,3-hexafluoo-propyl-2-oxy; phenylor9-phenyl-fluenyl-9-yl9-phenyl-fluenyl-9-oxy; methylor1,1,1,3,3,3-hexafluo-prop-2-yl2-methyl-1,1,1,3,3,3-hexafluoo-propyl-2-oxy; phenylphenoxy2,6-diphenylphenoxy; and R4 is selected from
wherein TBS is the t-butyldimethylsilyl radical;
where Me = methylmethyl; with the proviso that the following compounds are excluded: M = W; R1 = isopropylphenyl2,6-diisopropylphenyl; R2 = —C(CH3)2C6H5; R3 = H; R5 = methyl2,5-dimethylpyrrol-1-yl; and R4 =
wherein TBS is the t-butyldimethylsilyl radical; and M = Mo; R1 = isopropylphenyl2,6-diisopropylphenyl, methylphenyl2,6-dimethylphenyl, or phenyl2,6-dichlorophenyl, adamant-1-yl; R2 = -C(CH3)2CβH5; R3 = H; R5 = methyl2,5-dimethylpyrrol-1-yl; and R4 =

[0118] In one modality, M is Mo or W; R1 is methylphenyl2,6-dimethylphenyl, isopropylphenyl2,6-diisopropylphenyl, or phenyl2,6-dichlorophenyl, adamant-1-yl; R2 is -C(CH3)2CGH5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 2-methyl-1,1,1,3,3,3-hexafluoro-propyl-2- oxy; 9-phenyl-fluorenyl-9-oxy; 2,6-diphenyl-phenoxy; t-butyloxy; and R4 is selected from 2,6-diphenylphenoxy, 2,3,5,6-tetraphenylphenoxy, 2,6-di(tert-butyl)phenoxy; with the proviso that the following compounds are excluded: M = Mo; R1 = 2,6-diisopropylphenyl; R2 = -C(CH3)2C6H5; R3 = H; R5 = 2,5-dimethylpyrrol-1-yl; R4 = 2,6-diphenylphenoxy; and M = Mo; R1 = 2,6-diisopropylphenyl; R2 = -C(CH3)2C6H5; R3 = H; R5 = 2,5-dimethylpyrrol-1-yl; R4 = 2,3,5,6-tetraphenylphenoxy.
[0119] In one modality, M is Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R2 is —C(CH3)2CGH5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 2-methyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 9-phenyl-fluorenyl-9-oxy; 2,6-diphenyl-phenoxy; t-butyloxy; and R4 is an R6-X- residue, wherein X = O and R6 is triphenylsilyl radical; with the proviso that the following compounds are excluded: M = W; R1 = 2,6-diisopropylphenyl; R2 = -C(CH3)2C6H5; R3 = H; R5 = 2,5-dimethylpyrrol-1-yl; R4 = triphenylsilyloxy; and M = Mo; R1 = 2,6-diisopropylphenyl; R2 = -C(CH3)2C6H5; R3 = H; R5 = 2,5-dimethylpyrrol-1-yl; R4 = triphenylsilyloxy.
[0120] In one modality, M i is Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R2 is —C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 2-methyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 9-phenyl-fluorenyl-9-oxy; t-butyloxy; and R4 is an R6-X- residue, wherein X = O and R6 is selected from triphenylmethyl or tri(4-methylphenyl)methyl; or 1,1,1,3,3,3-hexafluoro-prop-2-yl; 9-phenyl-fluoren-9-yl.
[0121] In another embodiment, the invention relates to the formula compound
where M is Mo or W; R1 is aryl, ouadamant-1-yl radical; optionally substituted; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is alkoxy, heteroaryl, silyloxy radical; optionally substituted; and R4 is an R6-X- residue, where X = O and R6 is an aryl residue, which assumes a substituent in the para position, relative to O.
[0122] In one embodiment, R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-di-t-butylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R2 is -C(CH3)2CGH5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 2-methyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 9-phenyl-fluorenyl-9-oxy; t-butyloxy; and R4 is R6-X-, where R6 = phenyl radical substituted in the para position, relative to O and with up to four additional substituents, wherein the substituents are independently selected from alkyl radical, preferably C1-C4 alkyl , such as methyl, isopropyl or t-butylmethylisopropylout-butyl, alkoxy, preferably C1-C4 alkoxy, halogenphenoxy, optionally substituted phenyl, optionally substituted.
[0123] In one embodiment, R4 is selected from 4-bromo-2,6-diphenylphenoxy, 4-fluoro-2,6-diphenylphenoxy, 4-methyl-2,6-diphenylphenoxy, 4-methoxy-2 ,6-diphenylphenoxy, 2,4,6-triphenylphenoxy, 4-fluoro-2,6-dimethylphenoxy, 4-bromo-2,6-di-tert-butylphenoxy, 4-methoxy-2,6-di-tert-butylphenoxy , 4-methyl-2,6-di-tert-butylphenoxy, 2,4,6-tri-tert-butylphenoxy, 4-bromo-2,3,5,6-tetraphenylphenoxy, phenyl4-bromo-2,6-di (4-bromophenyl)-3,5-diphenylphenoxy;
wherein TBS is the t-butyldimethylsilyl radical;
where Me = methyl.
[0124] In one embodiment, R4 is selected from 4-bromo-2,6-diphenylphenoxy, 4-fluoro-2,6-diphenylphenoxy, 4-methyl-2,6-diphenylphenoxy, 4-methoxy-2 ,6-diphenylphenoxy, 2,4,6-triphenylphenoxy, 4-fluoro-2,6-dimethylphenoxy, 4-bromo-2,6-di-tert-butylphenoxy, 4-methoxy-2,6-di-tert-butylphenoxy , 4-methyl-2,6-di-tert-butylphenoxy, 2,4,6-tri-tert-butylphenoxy, 4-bromo-2,3,5,6-tetraphenylphenoxy, 4-bromo-2,6-di (4-bromophenyl)-3,5-diphenylphenoxy.
[0125] In one embodiment, the invention relates to the formula compound
where M is Mo or W; R1 is aryl, or adamant-1-yl radical; optionally substituted; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is alkoxy, heteroaryl, silyloxy; optionally substituted; and R4 is an R6-X- residue, where X = O and R6 is an aryl radical residue, which bears two substituents in the ortho position, with respect to O; with the proviso that the following compounds are excluded: M = Mo; R1 = 2,6-diisopropylphenyl; R2 = —C(CH3)2CβH5; R3 = H; R5 = 2,5-dimethylpyrrol-1-yl; R4 = 2,6-diphenylphenoxy (compound 1); M = Mo; R1 = 2,6-diisopropylphenyl; R2 = —C(CH3)2CβH5; R3 = H; R5 = 2,5-dimethylpyrrol-1-yl; R4 = 2,3,5,6-tetraphenylphenoxy (compound 10).
[0126] In one embodiment, R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, t-butyl2,6-di-t-butylphenyl, 2,6-dichlorophenyl, adamant-1-yl ; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 2-methyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 9-phenyl-fluorenyl-9-oxy; t-butyloxy; and R4 is R6-X-, wherein X = O and R6 is phenyl radical substituted with up to two additional substituents in the ortho position, relative to O, and wherein all substituents are independently selected from the alkyl radical, preferably C1-C4 alkyl, such as methyl, isopropyl or t-butyl, alkoxy, preferably C1-C4 alkoxy, phenoxy, phenyl, halogen, optionally substituted.
[0127] In one embodiment, R4 is selected from 2,6-diphenylphenoxy, 2,3,5,6-tetraphenylphenoxy, 2,6-di(tert-butyl)phenoxy.
[0128] In one embodiment, the invention relates to a compound of formula
where M = Mo or W; R1 is aryl, or adamant-1-yl radical; optionally substituted; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is alkoxy, heteroaryl, silyloxy; optionally substituted; and R4 is an R6-X- residue, wherein X = O and R6 is triphenylsilyl or triisopropylsilyl radical; with the proviso that the following compounds are excluded: M = W; R1 = 2,6-diisopropylphenyl; R2 = —C(CH3)2C6H5; R3 = H; R5 = 2,5-dimethylpyrrol-1-yl; R4 = triphenylsilyloxy; and M = Mo; R1 = 2,6-diisopropylphenyl; R2 = -C(CH3)2CGH5; R3 = H; R5 = 2,5-dimethylpyrrol-1-yl; R4 = triphenylsilyloxy.
[0129] In one embodiment, R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyl; triisopropylsilyl; 2-phenyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 2-methyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 9-phenyl-fluorenyl-9-oxy; t-butyloxy.
[0130] In one embodiment, the invention relates to a compound of formula
where M = Mo or W; R1 is aryl, ouadamant-1-yl radical; optionally substituted; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is alkoxy, heteroaryl, silyloxy; optionally substituted; and R4 is an R6-X- residue, wherein X = O and R6 is selected from triphenylmethyl or tri(4-methylphenyl)methyl; 1,1,1,3,3,3-hexafluoro-prop-2-yl; 9-phenyl-fluoren-9-yl.
[0131] In one embodiment, R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyl; triisopropylsilyl; 2-phenyl1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 2-methyl1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 9-phenyl-fluorenyl-9-oxy; t-butyloxy.
[0132] In one mode, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl and 2,5-dimethyl-pyrrol-1-yl; R4 is R6-X-, wherein R6-X- is selected from 1-(2,6-di-t-butylphenoxy); wherein the phenyl radical of the phenoxy residue preferably bears up to three substituents independently selected from alkyl radical, preferably C1-C4 alkyl, such as methyl, isopropyl out-butyl, alkoxy, such as C1-C4 alkoxy , phenoxy, phenyl, halogen.
[0133] In one mode, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl and 2,5-dimethyl-pyrrol-1-yl; R4 is R6-X-, wherein R6-X- is selected from 4-methyl-2,6-di-t-butylphenoxy or 4-methoxy-2,6-di-t-butylphenoxy or 4-bromo-2 ,6-di-t-butylphenoxy or 2,4,6-tri-t-butylphenoxy.
[0134] In one mode, M = W; R1 is 2,6-dichlorophenyl; R2 is —C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is pyrrol-1-yl; R4 is 4-bromo-2,6-di-t-butylphenoxy or 2,4,6-tri-t-butylphenoxy or 4-methoxy-2,6-di-t-butylphenoxy.
[0135] In one modality, M = Mo; R1 is 2,6-diisopropylphenyl; R2 is -C(CH3)2C6H5 or -C(CHs)3; R3 is H; R5 is pyrrol-1-yl; R4 is 4-methyl-2,6-di-t-butylphenoxy or 4-bromo-2,6-di-t-butyl-phenoxy or 2,4,6-tri-t-butylphenoxy or 4-methoxy-2, 6-di-t-butylphenoxy.
[0136] In one mode, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl and 2,5-dimethyl-pyrrol-1-yl; R4 is R6-X-, wherein R6-X- is selected from 2,6-di-phenylphenoxy; wherein the phenyl radical of the phenoxy residue preferably bears up to three substituents independently selected from alkyl radical, preferably C1-C4 alkyl, such as methyl, isopropyl or t-butyl, alkoxy, such as C1-C4 alkoxy, halogen , phenoxy, phenyl, optionally substituted, respectively.
[0137] In one mode, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl and 2,5-dimethyl-pyrrol-1-yl; R4 is R6-X-, wherein R6-X- is selected from 2,6-diphenylphenoxy, 4-chloro-2,6-diphenylphenoxy, 4-bromo-2,6-diphenylphenoxy, 4-fluoro-2, 6-diphenylphenoxy, 4-fluoro-2,6-di(2,4,6-trimethylphenyl)phenoxy, 2,3,5,6-tetraphenylphenoxy or 4-chloro-2,3,5,6-te- traphenylphenoxy or 4-bromo-2,3,5,6-tetraphenylphenoxy or 4-fluoro-2,3,5,6-tetraphenylphenoxy or 4-bromo-3,5-diphenyl-2,6-di(4-bromophenyl) phenoxy or 4-dimethylaminophenyl-2,6-diphenyl-phenoxy or 2,6-di(2,4,6-triisopropylphenyl)phenoxy.
[0138] In one modality, M = Mo; R1 is selected from 2,6-diisopropylphenyl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is pyrrol-1-yl; R4 is 2,6-diphenylphenoxy, 4-bromo-2,6-diphenylphenoxy, 4-fluoro-2,6-diphenylphenoxy, 4-fluoro-2,6-di(2,4,6-trimethylphenyl)phenoxy.
[0139] In one mode, M = Mo; R1 is selected from 2,6-dimethylphenyl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is 2,5-dimethyl-pyrrol-1-yl; R4 is selected from 2,6-diphenylphenoxy, 4-fluoro-2,6-di(2,4,6-trimethylphenyl)phenoxy.
[0140] In one modality, M = Mo; R1 is selected from adamant-1-yl; R2 is -C(CHs)2C6H5 or -C(CHs)3; R3 is H; R5 is 2,5-dimethyl-pyrrol-1-yl; R4 is 2,6-diphenylphenoxy.
[0141] In one modality, M = Mo; R1 is 2,6-dimethylphenyl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is 2,5-dimethyl-pyrrol-1-yl; R4 is selected from 4-bromo-2,6-diphenylphenoxy, 4-fluoro-2,6-di(2,4,6-trimethylphenyl)phenoxy.
[0142] In one modality, M = Mo; R1 is 2,6-dimethylphenyl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; R4 is 9-phenyl-fluorenyl-9-oxy.
[0143] In one modality, M is Mo; R1 is or 2,6-dichlorophenyl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; R4 is 9-phenyl-fluorenyl-9-oxy.
[0144] In one modality, M = Mo; R1 is 2,6-diisopropylphenyl; R2 is -C(CH3)2C6H5 or -C(CHs)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; R4 is 2-phenyl-1,1,1,3,3,3-hexafluoropropyl-2-oxy.
[0145] In one modality, M = Mo; R1 is 2,6-diisopropylphenyl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; R4 is triphenylsilyloxy.
[0146] In one modality, M = W; R1 is selected from 2,6-diisopropylphenyl, 2,6-dichlorophenyl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is 2,5-dimethyl-pyrrol-1-yl; R4 is triphenylsilyloxy.
[0147] In one modality, M = Mo; R1 is selected from 2,6-diisopropylphenyl; 2,6-dichlorophenyl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is pyrrol-1-yl; R4 is triphenylmethyloxy.
[0148] In one modality, M = Mo; R1 is 2,6-dichlorophenyl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is 2,5-dimethyl-pyrrol-1-yl; R4 is triphenylmethyloxy.
[0149] In one embodiment, R1 is 2,6-dimethylphenyl or 2,6-diisopropylphenyl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R4 is 4-bromo-2,6-diphenylphenoxy or 4-bromo-2,3,5,6-tetraphenylphenoxy; R5 is pyrrol-1-yl or 2,5-dimethyl-pyrrol-1-yl.
[0150] In one modality, M = Mo; R1 is 2,6-dimethylphenyl or 2,6-diisopropylphenyl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R4 is 4-bromo-2,6-diphenylphenoxy; R5 is 2,5-dimethyl-pyrrol-1-yl.
[0151] In yet another embodiment, M = Mo; R1 is 2,6-dimethylphenyl or 2,6-diisopropylphenyl; R2 is -C(CH3)2CGH5 or -C(CH3)3; R3 is H; R4 is 4-bromo-2,3,5,6-tetraphenylphenoxy; R5 is 2,5-dimethyl-pyrrol-1-yl.
[0152] In one modality, M = Mo; R1 is 2,6-diisopropylphenyl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R4 is 2,6-di-t-butylphenoxy; wherein the phenyl radical of the phenoxy residue preferably bears up to three substituents independently selected from alkyl radical, preferably C1-C4 alkyl, such as methyl or t-butyl, alkoxy, such as C1-C4 alkoxy, phenoxy, phenyl, halogen ; R5 is pyrrol-1-yl.
[0153] In one modality, M = Mo; R1 is 2,6-diisopropylphenyl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R4 is 4-methyl-2,6-di-t-butylphenoxy or 4-methoxy-2,6-di-t-butylphenoxy or 4-bromo-2,6-di-t-butylphenoxy or 2,4,6- tri-t-butylphenoxy; R5 is pyrrol-1-yl.
[0154] In one mode, M = W; R1 is 2,6-dichlorophenyl; R2 is -C(CH3)3; R3 is H; R5 is pyrrol-1-yl; R4 is 4-methoxy-2,6-di-t-butylphenoxy or 4-bromo-2,6-di-t-butylphenoxy or 2,4,6-tri-t-butylphenoxy.
[0155] Each of these three W-based compounds, of the aforementioned modality, when used as a catalyst in a cross metathesis reaction, can provide excellent Selectivity for the Z conformation, which can be around 90% of Z and around 10% of E.
[0156] In one modality, M = Mo; R1 is 2,6-diisopropylphenyl; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R4 is 4-bromo-2,6-diphenylphenoxy or 4-bromo-2,3,5,6-tetraphenylphenoxy; R5 is pyrrol-1-yl.
[0157] In one modality, M = Mo; or W; R1 is selected from 2,6-dimethylphenyl; 2,6-diisopropylphenyl; or 2,6-dichlorophenyl; R2 is -C(CH3)2C6H5 or -C(CHs)3; R3 is H; R4 is 2,6-diphenylphenoxy or 2,6-di-t-butylphenoxy; wherein the phenyl radical of the phenoxy residue, preferably, in addition to the two phenyl or t-butyl residues, bears up to three substituents independently selected from the alkyl radical, preferably C1-C4 alkyl, such as methyl or t-butyl, alkoxy, such as C1-C4 alkoxy, phenoxy, phenyl, halogen; R5 is pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl.
[0158] In one modality, M = Mo; or W; R1 is selected from 2,6-dimethylphenyl; 2,6-diisopropylphenyl; or 2,6-dichlorophenyl; R2 is -C(CH3)2C6H5; -C(CH3)3; R3 is H; R4 is 2,6-diphenylphenoxy or 2,6-di-t-butylphenoxy; wherein the phenyl radical of the phenoxy residue, in addition to the two phenyl or t-butyl residues, bears up to three substituents independently selected from the alkyl radical, preferably C1-C4 alkyl, such as methyl or t-butyl, alkoxy, such as C1-C4 alkoxy, halogen, phenoxy, phenyl, optionally substituted, respectively; R5 is pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl.
[0159] In one modality, M is Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-di-t-butylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R2 is -C(CH3)2CGH5 or -C(CH3)3; R3 is H; R5 is selected from triphenylsilyloxy; and R4 is R6-X-, where X = O and R6 is triphenylmethyl; optionally substituted; or X = O and R6 is 9-phenyl-fluoren-9-yl; or X = O and R6 is 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl or 2-methyl-1,1,1,3,3,3-hexafluoro-propyl -2-oxy.
[0160] In one mode, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-di-t-butylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R2 is -C(CH3)2CGH5 or -C(CH3)3; R3 is H; R5 is selected from 9-phenyl-fluorenyl-9-oxy; and R4 is R6-X-, where X = O and R6 is triphenylmethyl; optionally substituted; or X = O and d R6 is 9-phenyl-fluoren-9-yl; or X = O and R6 is 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl or 2-methyl-1,1,1,3,3,3-hexafluoro-propyl -2-oxy.
[0161] In one mode, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-di-t-butylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R2 is -C(CH3)2CGH5 or -C(CH3)3; R3 is H; R5 is selected from 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-oxy or 2-methyl-1,1,1,3,3,3-hexafluoro-propyl- 2-oxy; and R4 is R6-X-, where X = O and R6 is triphenylmethyl; optionally substituted; or X = O and R6 is 9-phenyl-fluoren-9-yl; or X = O and R6 is 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl or 2-methyl-1,1,1,3,3,3-hexafluoro-pro- pil-2-oxy; or t-butyloxy.
[0162] In one modality, M = W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R2 is -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; R4 is
where TBS is t-butyldimethylsilyl;
where M = methyl;
[0163] In one mode, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R2 is -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; 9-phenyl-fluorenyl-9-oxy; 2-phenyl-1,1,1,3,3,3-hexafluoropropyl-2-oxy; R4 is R6-X-, where X = O and R6 is phenyl radical substituted with up to five substituents independently selected from alkyl radical, preferably C1-C4 alkyl, such as methyl, isopropyl or t-butyl , alkoxy, preferably C1-C4 alkoxy, halogen, phenoxy, phenyl, optionally substituted, respectively; or X = S and R6 is phenyl radical substituted with up to five substituents independently selected from alkyl radical, preferably C1-C4 alkyl, such as methyl, isopropyl or t-butyl, alkoxy, preferably C1-C4 alkoxy , halogen, phenoxy, phenyl, optionally substituted, respectively; or X = O and R6 is triphenylsilyl or triisopropylsilyl; or X = O and R6 is triphenylmethyl or tri(4-methylphenyl)methyl; or X = O and R6 is 9-phenyl-fluoren-9-yl; or X = O and R6 is 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl or 2-methyl-1,1,1,3,3,3-hexafluoro-propyl -2-oxy; or X = O and R6 is t-butyloxy.
[0164] In one mode, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl; R2 is -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; R4 is selected from 2,6-diphenylphenoxy, 4-bromo-2,6-diphenylphenoxy, 4-fluoro-2,6-diphenylphenoxy, 4-methyl-2,6-diphenylphenoxy, 4-dimethylamino-2, 6-diphenylphenoxy, 2,6-di(2,4,6-triisopropylphenyl)phenoxy, 4-fluoro-2,6-dimethylphenoxy, 2,6-di-tert-butyl-phenoxy, 4-bromo-2, 6-di-tert-butylphenoxy, 4-methoxy-2,6-di-tert-butylphenoxy, 4-methyl-2,6-di-tert-butylphenoxy, 2,4,6-tri-tert-butylphenoxy, 2, 3,5,6-tetraphenylphenoxy, 4-bromo-2,3,5,6-tetraphenylphenoxy, 2,6-di(4-bromophenyl)-3,5-diphenyl-phenoxy, phenyl4-bromo-2,6-di (4-bromophenyl)-3,5-diphenylphenoxy,
wherein TBS represents a t-butyldimethylsilyl group, and
where Me represents a methyl group; or R4 is R6-X-, where X = O and R6 is triphenylsilyl or triisopropylsilyl; or X = O and R6 is triphenylmethyl or tri(4-methylphenyl)methyl; or X = O and R6 is 9-phenyl-fluoren-9-yl; or X = O and R6 is 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl or 2-methyl-1,1,1,3,3,3-hexafluoro-propyl -2-oxy; or X = O and R6 is t-butyl.
[0165] In one embodiment, the invention relates to a compound of structure 2, 3, 4, 5, 6, 7, 8, 11, 12, 13, 14, 15, 16, 17, 18, 19 , 20, 21, 23, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46 , 47, 48, 50, 51, 52, 53, 54, 55, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 73, 74, 75 , 77, 79, 81, 82, 83, 84, 85, 86, 89, 91, 94, 95, 97, 99, 100, 104, 105, 107, 108, 109, 111, 114, 115, 116, 117,119 , 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 145, 146 , 148, 149, 150, 151, 152, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 175 , 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190, 191, 192, 195, 196, 197, 198, 199, 200, 201, 202 , 203, 204, 205, 207, 208, 209, 210, 212, 213, 214, 216, 217, 218, 219, 220, 232, 233, 246, 247, 261, 262, 263, 264, 269, 270 , 271, 272, 273, 274, 280, 281, 282, 283, 284, 288 , 289, 290, 291.
[0166] In one embodiment, compounds are preferably selected from the group consisting of structures 11, 32, 36, and 162. Also preferred are compounds selected from the group consisting of structures 30, 123, 142, 154, 168, and 178. Also preferred is the compound of structure 21. Third aspect of the invention - Use of the compounds as defined in the second aspect of the invention
[0167] According to the third aspect, the invention relates to the use of a compound, as defined in the second aspect or in any embodiment of the second aspect, as a catalyst, preferably in which the catalyst catalyzes a metathesis reaction. Hence, the compounds can be used in a metathesis reaction or as a catalyst in a metathesis reaction.
[0168] In one embodiment, the metathesis reaction is selected from cross metathesis, ring opening metathesis, polymerization by ring opening metathesis, ring closing metathesis, ethenolysis, homometathesis.
[0169] Cross metathesis can, for example, be performed as a cross homometathesis, that is, metathesis reaction between identical olefins (HCM), or as cross heterometathesis, that is, reaction between two different olefins. Fourth aspect of the invention - Use of compounds in a kit
[0170] According to the fourth aspect, the invention relates to a kit comprising an organometallic aluminum compound, of formula R1R2R3Al, wherein R1, R2, and R3 are independently selected from aliphatic, cyclic, alicyclic residue containing from 1 to 10 carbon atoms, or from aromatic residues containing from 6 to 10 carbon atoms; and a compound used in the method of the invention, preferably a compound selected from one or more of structures 1-291.
[0171] In one embodiment, the organometallic aluminum compound used in the kit is trioctylaluminum.
[0172] In one embodiment, the invention relates to a kit consisting of said organometallic aluminum compound, of formula R1R2R3Al, and said compound selected from one or more of said structures 1 to 291. Fifth Aspect of the Invention - Method of Purifying an Olefin
[0173] According to the fifth aspect, the invention relates to a method of purification of a raw material comprising the first and second olefins, which may be identical or which may be different from each other, and by-products, which are selected from the group consisting of water, alcohols, aldehydes, peroxides, hydroperoxides, peroxide decomposition products, protic materials, polar materials, Lewis base catalyst poisons, or a mixture of two or more of these, comprising: (0 ) subjecting said raw material to a physical or chemical, or physical and chemical purification step, preferably in which said physical purification is carried out before the chemical purification step, in which the physical purification step comprises: distilling the said by-products, or distilling the raw material, or adsorbing said by-products; and wherein the chemical purification step comprises: subjecting at least one of the by-products to a chemical reaction; or (0) subjecting at least one of the by-products in said raw material to a chemical reaction.
[0174] In one modality, the by-products of the raw material are subjected to an anhydride of an organic acid; preferably wherein said anhydrides are anhydrides of aliphatic, cyclic, alicyclic organic acids containing from 1 to 10 carbon atoms, or an aromatic organic acid containing from 6 to 10 carbon atoms;
[0175] In another modality, the raw material by-products are subjected to an organometallic aluminum compound; preferably wherein the organometallic aluminum compound is of formula R1R2R3Al, wherein R1, R2, and R3 are independently selected from aliphatic, cyclic, alicyclic residue containing 1 to 10 carbon atoms, or aromatic residues containing de 6 to 10 carbon atoms.
[0176] In one embodiment, the anhydride of an organic acid is acetic acid; or the organometallic aluminum compound is trioctylaluminum.
[0177] In one modality, said method consists of step (0). Sixth aspect of the invention - A composition comprising a compound that catalyzes metathesis of a first and/or a second olefin and a purified raw material
[0178] According to the sixth aspect, the invention relates to a composition comprising a compound, as defined in any of the embodiments consequently with the first aspect, or a compound, as defined in any of the embodiments consequently with the second aspect, which catalyzes metathesis of a first and/or a second olefin, and a first and/or a second olefin that are contained in a raw material, wherein said raw material further comprises at least one by-product selected from the group consisting of of water, alcohols, aldehydes, peroxides, hydroperoxides, peroxide decomposition products, protic materials, polar materials, Lewis base catalyst poisons, or a mixture of two or more of these, and wherein said raw material was subjected to a purification step, as defined in any of the respective modalities according to the first aspect.
[0179] In one embodiment, the invention relates to a composition consisting of said compound and said first and/or second olefins; or consisting of said compound and a raw material containing said first and/or second olefins. Seventh aspect of the invention - Method of increasing the reactivity of a compound that catalyzes the metathesis reaction
[0180] According to the seventh aspect, the invention relates to a method for increasing the reactivity of a compound, as defined in any of the embodiments consequently with the first aspect, which catalyzes the metathesis reaction of a first and a second olefins, so that the molar ratio of said compound to the first or second olefin is less than 1:500, and the conversion rate of the first or second olefin is at least 30%, wherein said first and said second olefins are contained in a raw material, wherein said raw material further comprises at least one by-product selected from the group consisting of water, alcohols, aldehydes, peroxides, hydroperoxides, peroxide decomposition products , protic materials, polar materials, Lewis base catalyst poisons, or a mixture of two or more of these, comprising step (0) and optionally subsequent to step (0), the following step (i): ( 0) submit said raw material to a physical or chemical, or physical and chemical purification step, preferably wherein said physical purification is carried out before the chemical purification step, wherein the physical purification step comprises: distilling at least one of said by-products, or distilling said raw material, or adsorbing at least one of said by-products; and wherein the chemical purification step comprises: subjecting at least one of said by-products to a chemical reaction; (i) reacting the first olefin with the second olefin, in the presence of said compound that catalyzes said metathesis reaction.
[0181] In one embodiment, preferably, when a trialkylaluminum compound, preferably trioctylaluminum, is used for purification, the raw material is subjected to said compound for a period of 2 to 100 hours, preferably 5 to 90 hours , more preferably from 10 to 80 hours, and even more preferably from 15 to 70 hours.
[0182] In another embodiment of this aspect, the catalyst is slowly added to the substrate, at a rate of 0.01-10 ppm by weight of catalyst per hour.
[0183] In one modality, said method consists of steps (0) and (i). Eighth aspect of the invention - Method of altering or causing alteration by metathesis
[0184] According to the eighth aspect, the invention relates to a method of altering or causing alteration (metathesizing) to a first olefin and/or a second olefin, comprising at least steps (i) to (iii): (i) stipulating at least one compound to be used as a metathesis catalyst, as defined in any of the embodiments consequently with the first aspect of the invention, or consequently with the second aspect of the invention; (ii) stipulating a first and/or a second olefin; and (iii) slowly adding the catalyst to the first and/or second olefins to cause metathesizing in the first and/or second olefins; wherein the step of slowly adding the catalyst to the first and/or second olefin allows the metathesis reaction to proceed at a molar ratio of catalyst to first and/or second olefin of less than 1:7500.
[0185] In one embodiment, the catalyst is slowly added to the first and/or second olefins at a rate of 0.0110 ppm by weight of catalyst per hour, or any other rate as defined in the first aspect of the invention.
[0186] In one embodiment, the catalyst is added at a rate to allow the metathesis reaction to proceed at a molar ratio of catalyst to first and/or second olefins of 1:7,500 or less, and the corresponding conversion rate is at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%.
[0187] In one embodiment, the catalyst is added at a rate to allow the metathesis reaction to proceed at a molar ratio of the catalyst to the first and/or second olefins of 1:10,000 or less, and the corresponding conversion rate is at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%.
[0188] In one embodiment, the catalyst is added at a rate to allow the metathesis reaction to proceed at a molar ratio of catalyst to first and/or second olefins of 1:20,000 or less, or 1:50,000 or less , or 1:100,000 or less, or 1:500,000 or less, or 1:1,000,000 or less, and the corresponding conversion rate is at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%, respectively.
[0189] In one embodiment, the catalyst is added at a rate to allow the metathesis reaction to proceed at a molar ratio of catalyst to first and/or second lower limit olefins of 1:2,000,000, or 1:3,000 .000 or 1:4,000,000, respectively.
[0190] In other embodiments, the catalyst is added at a rate to allow the metathesis reaction to proceed at a molar ratio of the catalyst to the first and/or second olefins of 1:500 to 1:50,000 or less, and the corresponding conversion rate is from 30 to 100%, or from 50 to 100%, or from 60 to 100%.
[0191] In one embodiment, the catalyst is added at a rate to allow the metathesis reaction to proceed at a molar ratio of catalyst to first and/or second olefins of from 1:1000 to 1:40,000 or less, and at corresponding conversion rate is from 30 to 100%, or from 50 to 100%, or 60 to 100%.
[0192] In one embodiment, the catalyst is added at a rate to allow the metathesis reaction to proceed at a molar ratio of catalyst to first and/or second olefins of 1:2,500 to 1:30,000 or less, and at corresponding conversion rate is from 30 to 100%, or from 50 to 100%, or 60 to 100%.
[0193] In one embodiment, the catalyst is added at a rate to allow the metathesis reaction to proceed at a molar ratio of catalyst to first and/or second olefins of from 1:5,000 to 1:30,000 or less, or of 1:10,000 to 1:30,000, or 1:15,000 to 1:30,000, and the corresponding conversion rate is 30 to 100%, or 50 to 100%, or 60 to 100%, respectively.
[0194] In one modality, said method consists of steps (i) to (iii). Other Preferred Modalities and Compounds
[0195] In a ninth aspect, the invention relates to a compound of formula:
where M = Mo or W; R1 is an aryl, heteroaryl, alkyl, or heteroalkyl radical; optionally replaced; R2 and R3 may be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, arylheteroaryl; optionally substituted; R5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy radical, optionally substituted; and R4 is an R6-X- residue, where X = O and R6 is a phenyl ring which is substituted at least at the 4 position (para position) relative to O; or X = S and R6 is a phenyl ring which is substituted at least in position 4 relative to S.
[0196] In a first modality, R6 is substituted in positions 2 and 4, with respect to O.
[0197] In a second modality, R6 is substituted in positions 3- and 4-.
[0198] In a third modality, R6 is substituted in the 2-, 3- and 4-positions.
[0199] In a fourth modality, R6 is substituted in positions 2-, 5- and 4-.
[0200] In a fifth modality, R6 is substituted in positions 3-, 5- and 4-.
[0201] In a sixth modality, R6 substituted in positions 2, 6 and 4.
[0202] In a seventh modality, R6 is substituted in the 2-, 3-, 5-, and 4-positions.
[0203] In an eighth modality, R6 is substituted in the 2-, 3-, 6-, and 4-positions.
[0204] In a ninth modality, R6 is substituted in the 2-, 3-, 5-, 6-, and 4-positions.
[0205] The substituent of the residue R6 at the 4-position may be independently selected from the group consisting of: halogen, dialkylamino, cyano, optionally substituted alkyl, optionally substituted alkyloxy, optionally substituted aryl, optionally substituted aryloxy.
[0206] The other substituents of the R6 residue, if any, i.e. a 2-position substituent, relative to O, or 3-position, or 2- and 3-position, or 2- and 5-position, or 3-position substituents 3 and 5, or in positions 2 and 6, or in positions 2, 3 and 5 or in positions 2, 3 and 6 or in positions 2, 3, 5 and 6, may be the same or may be different from the substituent at position 4 , and can be independently selected from the group consisting of: halogen, dialkylamino, cyano, optionally substituted alkyl, optionally substituted alkyloxy, optionally substituted aryl, optionally substituted aryloxy.
[0207] In one embodiment, R1 is phenyl or alkyl radical; optionally substituted; R2 and R3 can be the same or different and are hydrogen, optionally substituted alkyl; R5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted; and the substituent of residue R6 at position 4 may be independently selected from the group consisting of: halogen, C1-4 dialkylamino, optionally substituted C1-4 alkyl, optionally substituted C1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy; and the other substituents of the residue R6, that is, a substituent in position 2, relative to O, or in position 3, or in positions 2 and 3, or in positions 2 and 5, or in positions 3 and 5, or at the 2 and 6 positions, or at the 2, 3 and 5 positions or at the 2, 3 and 6 positions or at the 2, 3, 5 and 6 positions, may be the same or may be different from the substituent at position 4, and may be independently selected from the group consisting of halogen, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
[0208] In one embodiment, R 1 is phenyl or alkyl radical, optionally independently substituted with halogen, C 1-4 dialkylamino, C 1-4 alkyl, C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy, respectively; R2 and R3 can be the same or different and are hydrogen or optionally substituted alkyl; R5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted; and the residue substituent R6 at position 4 may be independently selected from the group consisting of: halogen, C1-4 dialkylamino, optionally substituted C1-4 alkyl, optionally substituted C1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy phenyl; and the other substituents of the residue R6, that is, a substituent in position 2, relative to O, or in position 3, or in positions 2 and 3, or in positions 2 and 5, or in positions 3 and 5, or at positions 2 and 6, or at positions 2, 3, 5 and 6, which may be the same or may be different from the substituent at position 4 and may be independently selected from the group consisting of halogen, C1- 4 di-alkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
[0209] In one embodiment, R 1 is phenyl or alkyl radical, optionally independently substituted with halogen, C 1-4 dialkylamino, C 1-4 alkyl, C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy; R2 and R3 can be the same or different and are hydrogen, C(CH3)3 or C(CH3)2C6H5; R5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted; and the substituent of the residue R6 at position 4 may be independently selected from the group consisting of: halogen, C1-4 dialkylamino, optionally substituted C1-4 alkyl, optionally substituted C1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy; and the other substituents of the residue R6, that is, a substituent in position 2, relative to O, or in position 3, or in positions 2 and 3, or in positions 2 and 5, or in positions 3 and 5, or at the 2 and 6 positions, or at the 2, 3 and 5 positions or at the 2, 3 and 6 positions or at the 2, 3, 5 and 6 positions, which may be the same or different from the substituent at position 4 and may be independently selected from the group consisting of: halogen, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
[0210] In one mode, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, 2,3,4,5,6-pentafluorophenyl, 2-trifluoromethyl, 2,6-di(trifluoromethyl) phenyl, adamant-1-yl; R2 is —C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; ytriisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 2-methyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 2,6-diphenylphenoxy; 9-phenyl-fluorenyl-9-oxy; t-butyloxy; and the substituent of the residue R6 at the 4-position may be independently selected from the group consisting of: halogen, C1-4 dialkylamino, optionally substituted C1-4 alkyl, optionally substituted C1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy; and the other substituents of the residue R6, that is, a substituent in position 2, relative to O, or in position 3, or in positions 2 and 3, or in positions 2 and 5, or in positions 3 and 5, or at the 2 and 6 positions, or at the 2, 3 and 5 positions or at the 2, 3 and 6 positions or at the 2, 3, 5 and 6 positions, which may be the same or different from the substituent at position 4 and may be independently selected from the group consisting of: halogen, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
[0211] In one embodiment, the substituent of R6 at position 4 can be independently selected from the group consisting of: fluorine, chlorine, bromine, dimethylamino, diethylamino, methyl, ethyl, propyl, isopropyl, butyl, t-butyl , methoxy, ethoxy, propyloxy, butyloxy, t-butyloxy, trifluoromethyl, phenyl optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy: phenoxy optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy; and the other substituents of the residue R6, i.e., substituent at position 2, relative to O, or at position 3, or at positions 2 and 3, or at positions 2 and 5, or at positions 3 and 5, or at positions 2 and 6, or at the 2, 3 and 5 positions or at the 2, 3 and 6 positions, or at the 2, 3, 5 and 6 positions, which may be the same or may be different from the substituent at position 4 and may be independently selected from the group consisting of: fluorine, chlorine, bromine, dimethylamino, diethylamino, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, methoxy, ethoxy, propyloxy, butyloxy, t-butyloxy, trifluoromethyl, phenyl optionally substituted with halogen , alkyl, alkyloxy, phenyl, phenoxy; phenoxy optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy.
[0212] In a preferred embodiment, according to the sixth embodiment, the residue R6 is a phenyl ring which is independently substituted at the 2 and 4 positions with halogen, and at the 6 position with a phenyl radical, which may optionally be substituted with halogen, alkyl, alkyloxy, phenyl, optionally substituted by halogen, alkyl, alkyloxy, phenyl, phenoxy, phenoxy, optionally substituted by halogen, alkyl, alkyloxy, phenyl, phenoxy.
[0213] In one mode, M = Mo or W; R1 is selected from 2,6-diisopropylphenyl, 2,6-dichlorophenyl; R2 is —C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; R4 is an R6-X- residue, where X = O and R6 is independently substituted at the 2 and 4 positions with halogen, and at the 6 position with phenyl radical, which may optionally be substituted with halogen, alkyl, alkyloxy , phenyl, optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy; phenoxy, optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy.
[0214] This type of catalyst, according to the invention, is represented, for example, by compounds 183 and 184.
[0215] In other embodiments, said phenyl ring R6 may bear - in addition to the substituents at positions 2, 6 and 4, in relation to O - also substituents at positions 3 and/or 5.
[0216] Therefore, in a modality, M = Mo or W; R1 is an aryl, heteroaryl, alkyl, or heteroalkyl radical; optionally replaced; R2 and R3 may be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; optionally substituted; R5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted; and R4 is an R6-X- residue, where X = O and R6 is a phenyl ring bearing at least three substituents, wherein said phenyl ring is independently substituted at the 2 and 4 positions with halogen, and at the position 6 with phenyl radical which optionally may be substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy; phenoxy, optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy.
[0217] In another preferred embodiment, according to the sixth embodiment, R6 is a phenyl ring which is substituted at positions 2 and 6 by substituents via carbon atoms, and at position 4 by a substituent via any atom.
[0218] The term "any atom" used herein encompasses halogen, carbon, nitrogen, oxygen.
[0219] Thus, in a modality, M = Mo or W; R1 is an aryl, heteroaryl, alkyl, or heteroalkyl radical; optionally replaced; R2 and R3 may be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; optionally substituted; R5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted; and R4 is an R6-X- residue, where X = O and R6 is a phenyl ring which is substituted at positions 2 and 6, by substituents via carbon atoms, and at position 4 by substituents via any atom.
[0220] In one mode, M = Mo or W; R1 is phenyl or alkyl radical, optionally independently substituted by halogen, C1-4 dialkylamino, C1-4 alkyl, C1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy; R2 and R3 can be the same or different and are hydrogen, C(CH3)3, or C(CH3)2C6H5; R5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted; and the substituent of the residue R6 at position 4 can be selected from the group consisting of: halogen, C1-4 dialkylamino, optionally substituted C1-4 alkyl, optionally substituted C1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy; and the other substituents of the residue R6, i.e., substituents at positions 2 and 6, relative to O, may be the same or may be different from one another, and may be selected from the group consisting of C1-4 alkyl optionally substituted, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
[0221] In one mode, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, 2,3,4,5,6-pentafluorophenyl, 2-trifluoromethyl, 2,6-di(trifluoromethyl) phenyl, adamant-1-yl; R2 is —C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; the substituent of residue R6 at position 4 may be selected from the group consisting of: halogen, C1-4 dialkylamino, optionally substituted C1-4 alkyl, optionally substituted C1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy; and the other substituents of the residue R6, i.e., substituents at positions 2 and 6, may be the same or may be different from one another, and may be selected from the group consisting of optionally substituted C1-4 alkyl, C1- 4 optionally substituted alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
[0222] Examples are compounds 3, 4, 5, 7, 14, 15, 17, 18, 19, 70, 33, 34, 35, 36, 37, 41, 42, 43, 44, 63, 64, 65 , 66, 67, 68, 69, 120, 121, 122, 125, 126, 127, 130, 131, 132, 133, 134, 135, 140, 141, 142, 146, 149, 150, 155, 156, 157 , 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 173, 187, 188.
[0223] These compounds are particularly efficient in ethenolysis reaction.
[0224] In other embodiments, said phenyl ring R6 may bear - in addition to the substituents at positions 2, 6 and 4 in relation to O - also substituents at positions 3 and/or 5.
[0225] Therefore, in one modality, M = Mo or W; R1 is an aryl, heteroaryl, alkyl, or heteroalkyl radical; optionally replaced; R2 and R3 may be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; optionally substituted; R5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted; and R4 is an R6-X- residue, wherein X = O and R6 is a phenyl ring bearing at least three substituents, wherein said phenyl ring is substituted at positions 2 and 6 by substituents via carbon atoms, and at 4-position and 3- and/or 5-position by substituents via any atom, respectively.
[0226] In one mode, M = Mo or W; R1 is phenyl or alkyl, optionally independently substituted with halogen, C1-4 dialkylamino, C1-4 alkyl, C1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy; R2 and R3 can be the same or different and are hydrogen, C(CH3)3, C(CH3)2C6H5; R5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silyalkyl, silyloxy, optionally substituted; and the substituent of the residue R6 at position 4 can be selected from the group consisting of: halogen, C1-4 dialkylamino, optionally substituted C1-4 alkyl, optionally substituted C1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy; and the substituents of the residue R6 at positions 2 and 6, may be the same or may be different from each other, and may be selected from the group consisting of optionally substituted C1-4 alkyl, optionally substituted C1-4 alkyloxy, optionally substituted phenyl , optionally substituted phenyloxy; and the other substituents at positions 3 and/or 5 may be selected from the group consisting of: halogen, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy .
[0227] In one mode, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, 2,3,4,5,6-pentafluorophenyl, 2-trifluoromethyl, 2,6-di(trifluoromethyl) phenyl, adamant-1-yl; R2 is —C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; and the substituent of the R6 residue at the 4 position can be selected from the group consisting of: halogen, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, phenyloxy optionally substituted; and the substituents of the residue R6 at positions 2 and 6, may be the same or may be different from each other, and may be selected from the group consisting of optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, phenyl optionally substituted, optionally substituted phenyloxy; and the other substituents at positions 3 and/or 5 may be selected from the group consisting of: halogen, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C14 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
[0228] In a specific yet preferred modality, according to the ninth modality, M = Mo or W; R1 is an aryl, heteroaryl, alkyl, or heteroalkyl radical; optionally substituted; R2 and R3 may be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; optionally substituted; R5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted; and R4 is an R6-X- residue, where X = O and R6 is a phenyl ring substituted at the 4 position with halogen, preferably bromine, and at the 2, 3, 5 and 6 positions with phenyl, respectively, wherein said phenyl residue can be independently substituted with fluorine, chlorine, bromine, dimethylamino, diethylamino, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, methoxy, ethoxy, propyloxy, butyloxy, t-butylt-butyloxy, trifluoromethyl, phenyl optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy; phenoxy optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy.
[0229] In a preferred embodiment, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, 2,3,4,5,6-pentafluorophenyl, 2-trifluoromethyl, 2,6-di(trifluoromethyl) phenyl, adamant-1-yl; R2 is —C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; R4 is an R6-X- residue, where X = O and R6 is a phenyl ring substituted at the 4 position with bromine, and at the 2, 3, 5 and 6 positions with phenyl, respectively, wherein said phenyl residue may be independently substituted with fluorine, chlorine, bromine, dimethylamino, diethylamino, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, methoxy, ethoxy, propyloxy, butyloxy, t-butylt-butyloxy, trifluoromethyl, phenyl optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy; phenoxy optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy.
[0230] Examples are compounds 11, 13, 16, 32, 60, 123,136, 145, 189, 261,
[0231] These compounds, which bear a 4-bromo-(2,3,5,6-tetraphenyl)phenyl radical, may have a positive effect on the catalytic activity, compared to their bromine analogues, that is, they are substituted in the position 4 with hydrogen. This positive effect can result in a high conversion, in the range of 10-30%.
[0232] Furthermore, such compounds exhibit good activity in the ethenolysis reaction.
[0233] In a tenth aspect, the invention relates to a compound of formula:
where M = Mo or W; R1 is an aryl, heteroaryl, alkyl, or heteroalkyl radical; optionally substituted; R2 and R3 may be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; optionally substituted; R5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted; and R4 is an R6-X- residue, wherein X = O and R6 is a phenyl ring substituted in positions 2 and 6 with phenyl, respectively, optionally substituted; or X = S and R6 is a phenyl ring substituted in positions 2 and 6 with phenyl, respectively, optionally substituted.
[0234] In one mode, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, 2,3,4,5,6-pentafluorophenyl, 2-trifluoromethyl, 2,6-di(trifluoromethyl) phenyl, adamant-1-yl; R2 is —C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; R4 is an R6-X- residue, where X = O and R6 is substituted at the 2 and 6 positions with phenyl, which optionally may be independently substituted with halogen, alkyl, preferably C1-4 alkyl, alkyloxy, preferably C1 -4-alkyloxy, phenyl, optionally substituted with halogen, alkyl, alkyloxy, diallylamino, phenyl, phenoxy; phenoxy optionally substituted with halogen, alkyl, alkyloxy, di-alkylamino, phenyl, phenoxy.
[0235] Such compounds exhibit good activity in the ethenolysis reaction.
[0236] Compounds are, for example, compounds 178 and 233.
[0237] In an eleventh aspect, the invention relates to a compound of formula
where M = Mo or W; R1 is an aryl, heteroaryl, alkyl, or heteroalkyl radical; optionally replaced; R2 and R3 may be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; optionally substituted; R5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted; and R4 is [8-(naphthalen-1-yl)-naphthalen-1-yl]oxy, optionally substituted.
[0238] The term "[8-(naphthalen-1-yl)-naphthalen-1-yl]oxy, optionally substituted" encompasses the replacement of one or both of the naphthyl rings, with one or more substituents, selected from the group consisting of: halogen, hydroxy, protected hydroxy, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted C 1-4 phenyl, optionally substituted phenyloxy.
[0239] In one mode, M = Mo or W; R1 is phenyl or alkyl, optionally independently substituted with halogen, C1-4 dialkylamino, C1-4 alkyl, C1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy; R2 and R3 can be the same or different and are hydrogen, C(CH3)3, or C(CH3)2C6H5; R5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted; and R4 is [8-(naphthalen-1-yl)-naphthalen-1-yl]oxy, optionally substituted.
[0240] In one mode, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, phenyl2,6-dichlorophenyl, 2,3,4,5,6-pentafluorophenyl, 2-trifluoromethyl, 2,6-di(trifluoromethyl) phenyl, adamant-1-yl; R2 is —C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; methyl2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; isopropylsilyloxy; triisopropylsilyloxy; R4 is [8-(naphthalen-1-yl)-naphthalen-1-yl]oxy, optionally substituted.
[0241] Examples are compounds 192, 196, 214, 217, 220.
[0242] Such compounds can have a positive impact on catalytic activity in relation to ethenolysis, cross metathesis and homometathesis.
[0243] In a twelfth aspect, the invention relates to a compound of formula
where M = Mo or W; R1 is an aryl, heteroaryl, alkyl, or heteroalkyl radical; optionally substituted; R2 and R3 may be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; optionally substituted; R5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted; and R4 is (8-phenylnaphthalen-1-yl)oxy, optionally substituted.
[0244] The term "optionally substituted 8-phenylnaphthalen-1-yl)oxy" encompasses the replacement of the phenyl ring or naphthyl ring, or the phenyl ring and naphthyl ring, with one or more substituents selected from the group consisting of : halogen, hydroxy, protected hydroxy, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
[0245] In one mode, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, 2,3,4,5,6-pentafluorophenyl, 2-trifluoromethyl, 2,6-di(trifluoromethyl) phenyl, adamant-1-yl; R2 is —C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; (8-phenylnaphthalen-1-yl)oxy, optionally substituted; R4 is (8-phenylnaphthalen-1-yl)oxy, optionally substituted.
[0246] Examples are compounds 218, 216, 247, 246, 288,269.
[0247] In a thirteenth aspect, the invention relates to a compound of formula:
where M = Mo or W; R1 is an aryl, heteroaryl, alkyl, or heteroalkyl radical; optionally substituted; R2 and R3 may be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; optionally substituted; R5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted; and R4 is an R6-X- residue, where X = O and R6 is quinolin-8-yl, optionally substituted.
[0248] The term "optionally substituted quinoline-8-yl" encompasses replacement of the ring system with one or more substituents selected from the group consisting of: halogen, hydroxy, protected hydroxy,, C 1-4 dialkyl- mino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
[0249] In one embodiment, M = Mo or W;R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, 2,3,4,5,6-pentafluorophenyl , 2-triflutrifluoromethyl, 2,6-di(trifluoromethyl)phenyl, adamant-1-yl; R2 is —C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; R4 is an R6-X- residue, where X = O and R6 is quinolin-8-yl, optionally substituted.
[0250] In the fourteenth aspect, the invention relates to a compound of formula:
where M = Mo or W; R1 is an aryl, heteroaryl, alkyl, or heteroalkyl radical; optionally substituted; R2 and R3 may be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; optionally substituted; R5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted; and R4 is an R6-X- residue, where X = O and R6 is a phenyl ring, substituted in position 2 with respect to O;
[0251] Under the condition that compound 153 is excluded.
[0252] The substituent at position 2 can be selected from the group consisting of: halogen, hydroxy, protected hydroxy, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
[0253] In one modality, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, 2,3,4,5,6-pentafluorophenyl, 2-trifluoromethyl, 2,6-di(trifluoromethyl) phenyl, adamant-1-yl; R2 is —C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; phenyl1,1,1,3,3,3-hexafluoro-prop-2-yl;2-phenyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 2-methyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 9-phenyl-fluoren-9-yl; 2,6-diphenylphenoxy; t-butyloxy R4 is an R6-X- residue, where X = O and R6 is phenyl substituted in position 2 with respect to O, where the substituent is selected from the group consisting of: halogen, hydroxy, protected hydroxy, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy; provided that compound 153 is excluded.
[0254] An exemplary compound is compound 152.
[0255] In a fifteenth aspect, the invention relates to a compound of formula:
where M = Mo or W; R1 is an aryl, heteroaryl, alkyl, or heteroalkyl radical; optionally substituted; R2 and R3 may be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; optionally substituted; R5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted; and R4 is an R6-X- residue, where X = O and R6 is a phenyl ring substituted in positions 2 and 6 with respect to O; under the condition that compounds 1, 9, 88, 101, 118, 174 are excluded.
[0256] Substituents at positions 2 and 6 can be independently selected from groups consisting of: halogen, hydroxy, protected hydroxy, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally phenyl substituted, optionally substituted phenyloxy.
[0257] In one mode, M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, 2,3,4,5,6-pentafluorophenyl, 2-trifluoromethyl, 2,6-di(trifluoromethyl) phenyl, adamant-1-yl; R2 is —C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; -phenyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 2-methyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 9-phenyl-fluoren-9-yl; 2,6-diphenylphenoxy; t-butyloxy; R4 is an R6-X- residue, where X = O and R6 is a phenyl ring substituted at the 2 and 6 positions relative to O, where the substituents at the 2-and 6-positions can be independently selected from the group consisting of: halogen, hydroxy, protected hydroxy, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy, under the condition that compounds 1, 9, 88, 101 , 118, 174 are excluded.
[0258] Exemplary compounds are compounds 73, 74, 84, 85, 89, 6, 8, 62, 175, 176, 177, 178, 179, 185, 195, 199, 202, 203, 204, 205, 232, 233, 270, 271, 272, 273, 274. Definitions used in the sense of the invention
[0259] The term “metathesis” refers to the metathesis of alkenes (olefins).
[0260] The term "cross metathesis" encompasses the reaction between two different olefins.
[0261] The term "ring opening metathesis" encompasses the ring opening of a cyclic olefin.
[0262] The term "polymerization via ring opening metathesis" encompasses the ring opening of a cyclic olefin, wherein the product of the ring opening polymerizes in a growing polymerization chain to form a polymer containing olefinic bonds.
[0263] The term "ring-closing metathesis" encompasses the closure of the ring of a diene.
[0264] The term "ethenolysis" encompasses the reaction of an olefin containing an internal olefinic bond with ethylene.
[0265] The term "homometathesis" encompasses the formation of an internal olefin from two identical olefins. The term "conversion" or "degree of conversion" is defined as 100 (final moles of first or second olefins * 100% / initial moles of first or second olefins).
[0266] The term "olefinic double bond" refers to carbon-carbon double bond or ethylenic double bond.
[0267] The term "olefin" refers to any species containing at least one ethylenic double bond, such as straight and branched chain aliphatic olefin, cycloaliphatic olefins, aryl radical substituted olefins. Olefins can comprise terminal double bonds (terminal olefin) and/or internal double bonds (internal olefin), and can be cyclic or acyclic, linear or branched, optionally substituted. The total number of carbon atoms can be from 1 to 100, or from 1 to 40; the double bonds of a terminal olefin can be mono- or bi-substituted, and the double bond of an internal olefin can be bi-tri- or tetra-substituted. In some cases, an internal olefin is bisubstituted. Unlimited examples of molecules comprising terminal olefins are substituted or unsubstituted linear alkyl internal olefins, such as C4-C30 olefins (eg, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, allylbenzene, allyltrimethylsilane, methyl-10-undecenoate, pinacol ester allylboronic acid, allylphenylether, N-allyl-4-methylbenzensulfonamide, allylaniline, methyl-9-decenoate, allyloxy(t-butyl)dimethyl silane, allylcyclohexane etc.).
[0268] In one embodiment, the olefin containing terminal olefinic double bond is of the formula RCH=CH2, wherein R is selected from H, alkyl, alkenyl, aryl, hetero-alkyl, heteroalkenyl, heteroaryl, or acyl, optionally substituted.
[0269] The term "cyclic olefin" refers to any cyclic species comprising at least one ethylenic double bond in a ring. Ring atoms can be optionally substituted. The ring can comprise any number of carbon atoms and/or heteroatoms. The ring can comprise at least 3, at least 4, at least 5, at least 6, at least 7, at least 8 or more atoms. Unlimited examples of cyclic olefins include norbornene, dicyclopentadiene, bicyclic compounds, oxabicyclic compounds, and the like, all optionally substituted. "Bicyclic compounds" are a class of compounds consisting of just two rings, containing two or more atoms in common. "Oxabicyclic compounds" are a class of compounds consisting of just two rings, containing two or more atoms in common, at least one of which comprises an oxygen atom.
[0270] The term "substituted" is contemplated to include all permissible organic compound substituents, "permitted" being, in the context of the chemical rules of valence, known to those skilled in the art. Examples of the substituents include, but are not limited to aryl, arylalkyl, cyclic alkyl, heterocycloalkyl, hydroxyl, alkoxy, aryloxy, peraloalkoxy, arylalkoxy, heteroaryl, heteroaryloxy, heteroarylalkyl, heteroarylalkoxy, azido, amino, halogen, alkylthio, oxo , acylalkyl, carboxyl esters, carboxyl, -carboxamido, nitro, acyloxy, aminoalkyl, alkylaminoaryl, alkylaryl, alkylaminoalkyl, alkoxyaryl, arylamino, arylalkylamino, alkylsulfonyl, -carboxamidoalkylaryl, -carboxamidoalkylaryl, -carboxyamidoalkylaryl, -carboxamidoalkylaryl, -carboxamidoalkylaryl, , alkylaminoalkylcarboxy-, aminocarboxamidoalkyl-, cyano, alkoxyalkyl, perhaloalkyl, arylalkyloxyalkyl.
[0271] The term "alkyl" embraces saturated aliphatic groups, including straight-chain alkyl groups, branched-chain alkyl groups, cycloalkyl (alicyclic) groups, alkyl substituted with cycloalkyl group, and cycloalkyl substituted with alkyl groups. In certain embodiments, a straight-chain or branched-chain alkyl radical has about 30 carbon atoms or less in its backbone (eg, C1-C30 for straight chain, C3-C30 for branched chain) and, alternatively, about of 20 or less. Likewise, the cycloalkyl radical has about 3 to 10 carbon atoms in its ring structure and, alternatively, about 5, 6 or 7 carbons in the ring structure. In some embodiments, an alkyl group can be a lower alkyl group, where a lower alkyl group comprises 10 or fewer carbon atoms in its backbone (e.g., C1-C10 for straight chain lower alkyl).
[0272] In one embodiment, the term alkyl encompasses C1-C4 alkyl such as methyl, isopropyl or t-butyl.
[0273] The term "alkyl" also encompasses transposed hydrocarbon residues such as adamantyl residue, particularly the adamant-1-yl residue. Such a residue is, for example, described in compounds 9, 16, 46, 48, 49 as residue R1.
[0274] The term "alkyl" also encompasses conjugated ring systems such as fluoren-9-yl residue such as 9-phenyl-fluoren-9-yl residue.
[0275] The term “t-Bu” denotes a tertiary butyl group.
[0276] The term "alkoxy" refers to the group alkyl -O-, wherein alkyl has the meaning as defined above, in connection with the term alkyl.
[0277] A preferred alkoxy residue is 9-phenylfluorenyl-9-oxy, described in compounds 28, 29, 30, 47, 49, 53, 58, 72 as residue R4, and in compounds 49 and 72 as residues R4 and R5 .
[0278] A further preferred alkoxy residue is triphenylmethyloxy (triphenylmethoxy), described in compounds 23, 25, 27, 45, 52 as R4 residue.
[0279] A further preferred alkoxy residue is tri(4-methylphenyl)methyloxy, described in compound 62 as R4 residue.
[0280] A further preferred alkoxy residue is 2-phenyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy, described in compound 39 as R4 residue, and in compounds 38, 40 as residue R4 and residue R5.
[0281] A further preferred alkoxy residue is 2-methyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy, described in compound 71 as residue R4, and in compound 72 as residue R4 and residue R5.
[0282] A further preferred alkoxy residue is t-butyloxy, described in compound 90 as R4 residue and R5 residue.
[0283] A further preferred alkaloxy residue is 9-phenyl-9-fluorenyl-9-oxy, described in compounds 29, 30, 47, 53, 58 as R4 and in compounds 49 and 81 as R4 and R5.
[0284] The term "alkenyl" refers to olefinic groups as described above. The alkenyl radical can be optionally substituted with the substituents defined above.
[0285] The term "aryl" refers to optionally substituted carbocyclic aromatic groups having single ring (eg phenyl), multiple rings (eg biphenyl), or multiple conjugated rings, wherein at least one it is aromatic (for example, 1,2,3,4-tetrahydronaphthyl, naphthyl, anthryl, or phenanthryl). That is, at least one ring must have a π-conjugated electron system, while other adjacent rings can be cycloalkyl, cycloalkene, cycloalkyne, aryl, and/or heterocyclyl. The aryl group can be optionally substituted as described herein.
[0286] The term "carbocyclic aryl groups" as used herein refers to aryl groups in which the ring atoms in the aromatic ring are carbon atoms. Carbocyclic aryl groups include monocyclic and polycyclic carbocyclic aryl groups or conjugated compounds (for example, two or more adjacent ring atoms are common to two adjacent rings), such as naphthyl groups. In some cases, aryl groups may include monocyclic and polycyclic carbocyclic aryl groups or compounds (for example, two or more adjacent ring atoms are common to two adjacent rings), such as a naphthyl group. Non-limited examples of aryl groups include phenyl, naphthyl, tetrahydronaphthyl, indanyl, indenyl, and the like.
[0287] A preferred aryl residue is 2,6-diisopropylphenyl as defined in compounds 1, 2, 6, 7, 8, 10, 11, 14, 17, 18, 19, 22, 23, 24, 25, 28, 29, 31, 32, 33, 34, 35, 36, 37, 38, 39, 41, 42, 43, 44, 50, 54, 56, 57, 58, 60 as residue R1.
[0288] An additionally preferred aryl residue is 2,6-dichlorophenyl as defined in compounds 3, 4, 5, 20, 21, 26, 27, 30, 52, 53, 59, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71 as residue R1.
[0289] An additionally preferred aryl residue is 2,6-dimethylphenyl as defined in compounds 8, 12, 13, 15, 39, 40, 45, 47, 51, 55, 61 as R1 residue.
[0290] The term “phenoxy” refers to the group C6H5O-.
[0291] The term "thiophenoxy" refers to the group C6H5S-.
[0292] This phenoxy or thiophenoxy residue may be substituted with up to five substituents independently selected from alkyl, preferably C1-C4 alkyl, such as methyl, isopropyl or t-butyl, alkoxy, preferably C1-C4 alkoxy, phenoxy, phenyl, halogen.
[0293] A preferred phenoxy residue is 2,6-diphenylphenoxy as defined in compounds 1, 6, 8, 9 as R4 residue.
[0294] An additionally preferred phenoxy residue is 4-bromo-2,6-diphenylphenoxy as defined in compounds 14, 15, 33, 68 as R4 residue.
[0295] An additionally preferred phenoxy residue is 4-fluoro-2,6-diphenylphenoxy as, for example, disclosed in compounds 34, 36, 63, 67 as R4 residue.
[0296] An additionally preferred phenoxy residue is 4-methyl-2,6-diphenylphenoxy as defined in compounds 41, 42, 65 as R4 residue.
[0297] An additionally preferred phenoxy residue is 2,4,6-triphenylphenoxy as defined in compounds 43, 44, 64, 66 as R4 residue.
[0298] An additionally preferred phenoxy residue is 4-fluoro-2,6-dimethylphenoxy as defined in compounds 35, 37, 69 as R4 residue.
[0299] An additionally preferred phenoxy residue is 2,6-di-t-butylphenoxy as defined in compounds 59, 62 as R4 residue.
[0300] A further preferred phenoxy residue is 4-bromo-2,6-di-t-butylphenoxy as defined in compounds 3, 17 as R4 residue.
[0301] An additionally preferred phenoxy residue is 4-methoxy-2,6-di-tert-butylphenoxy as defined in compounds 5, 19 as R4 residue.
[0302] An additionally preferred phenoxy residue is 4-methyl-2,6-di-tert-butylphenoxy as defined in compound 7 as R4 residue.
[0303] An additionally preferred phenoxy residue is 2,4,6-tri-tert-butylphenoxy as defined in compounds 4, 18 as R4 residue.
[0304] An additionally preferred phenoxy residue is 2,3,5,6-tetraphenylphenoxy as defined in compounds 10, 12 as R4 residue.
[0305] An additionally preferred phenoxy residue is 4-bromo-2,3,5,6-tetraphenylphenoxy as defined in compounds 11, 13, 16 as R4 residue.
[0306] A further preferred phenoxy residue is 2,6-di(4-bromophenyl)-3,5-diphenylphenoxy as defined in compounds 53, 54 as R4 residue.
[0307] A further preferred phenoxy residue is 4-bromo-2,6-di(4-bromophenyl)-3,5-diphenylphenoxy as defined in compounds 32, 60 as R4 residue.
[0308] An additionally preferred phenoxy residue is
as defined in compound 56 as residue R4. TBS represents a t-butyldimethylsilyl group.
[0309] An additionally preferred phenoxy residue is
as defined in compound 58 as residue R4. It represents me a methyl group.
[0310] An additionally preferred phenoxy residue is 4-dimethylaminophenyl-2,6-diphenylphenoxy as residue R4 as, for example, defined in structures 159, 160, 161, 162,167, 168, 169, 170.
[0311] An additionally preferred phenoxy residue is 2,6-di(2,4,6-triisopropylphenyl)phenoxy as residue R4 as, for example, defined in structure 174.
[0312] Another preferred residue is quinolone-8-oxy as the R4 residue as, for example, defined in structures 94 and 97.
[0313] A preferred thiophenoxy residue is 2,6-diphenyl-thiophenoxy, 4-bromo-2,6-diphenylthiophenoxy, 4-fluoro-2,6-diphenylthiophenoxy, 4-methyl-2,6-diphenylthiophenoxy, 2 ,4,6-triphenyl-thiophenoxy, 4-fluoro-dimesitylthiophenoxy, 2,6-di-tert-butylthiophenoxy, 4-bromo-2,6-di-tert-butylthiophenoxy, 4-methoxy-2,6-di -tert-butylthiophenoxy, 4-methyl-2,6-di-tert-butylthiophenoxy, 2,4,6-tri-tert-butylthiophenoxy, 2,3,5,6-tetraphenylthiophenoxy, 4-bromo-2,3,5 ,6-tetraphenylthiophenoxy, 2,6-di(4-bromophenyl)-3,5-diphenylthiophenoxy, 4-bromo-2,6-di(4-bromophenyl)-3,5-diphenylthiophenoxy as residue R4.
[0314] The term "heteroaryl" as used herein, refers to aryl groups, as described herein, wherein one or more atoms is an optionally substituted heteroatom (e.g., oxygen, nitrogen, sulfur, and the like). Examples of aryl and heteroaryl groups include, but are not limited to, phenyl, aryloxy, pyrrolyl, furanyl, thiophenyl, imidazolyl, oxazolyl, thiazolyl, triazolyl, pyrazolyl, pyridinyl, pyrazinyl, pyridazinyl and pyrimidinyl, and the like.
[0315] A preferred heteroaryl residue is the pyrrol-1-yl residue as, for example, disclosed in compounds 2, 3, 4, 5, 6, 7, 17, 18, 19, 20, 25, 28, 33 , 34, 37, 41, 43, 51, 52, 58, 59, 62, 65, 66, 67, 68, 69, 70 as residue R5.
[0316] An additionally preferred heteroaryl residue is the 2,5-dimethylpyrrol-1-yl residue as, for example, disclosed in compounds 1, 8, 9, 10, 11, 12, 13, 14, 15, 16, 21, 22, 23, 24, 26, 27, 29, 30, 31, 32, 35, 36, 39, 42, 45, 44, 47, 57, 61, 63, 64 as residue R5.
[0317] The term "heteroalkyl" refers to alkyl groups as described herein, in which one or more atoms are heteroatoms (for example, oxygen, nitrogen, sulfur and the like). Examples of heteroalkyl groups include, but are not limited to, alkoxy, poly(ethylene glycol)-, substituted alkyl amino, tetrahydrofuranyl, piperidinyl, morpholinyl, etc.
[0318] The term "halogen" refers to F, Cl, Br, I.
[0319] The term "acyl" refers to H, alkyl, alkenyl, aryl, heteroalkyl and heteroaryl groups, as defined above, in which they are attached to another atom or to another group, such as an olefinic double bond via the group. carbonyl.
[0320] The term "triphenylsilyloxy" refers to the preferred group (C6H5)3SiO which is, for example, disclosed in compounds 2, 20, 21, 22, 24, 46, 49, 50 as residue R4 and in compounds 46, 50 additionally as residue R5.
[0321] The term "triisopropylsilyloxy" refers to the preferred group (CH3)2CHSiO as, for example, disclosed in compound 137.
[0322] The term "comprising" is used to mean "including, but not limited by".
[0323] The term “consisting of” is used to mean “including and limited by”.
[0324] The term "raw material" covers the compounds used as starting material in the reaction, according to the invention, that is, first olefin and/or said second olefin and other products accompanied by said olefin(s). Said other olefins are called “by-products”. In one embodiment, the raw material comprises at least 99% by weight of the first and/or second olefins, based on the total weight of the raw material, with the remainder being by-products, or at least 99.5% by weight. By-products are, for example, water, alcohols, aldehydes, peroxides, hydroperoxides.
[0325] The term "first or second olefins" is, in one embodiment, used synonymously with the term "first and second olefins".
[0326] The term “by-product” is used synonymously with the term “contaminant”.
[0327] The term “physical purification” includes: distilling said by-products, or distilling said raw material or adsorbing said by-products.
[0328] The term “chemical purification” covers: subjecting the by-products to a chemical reaction.
[0329] The term "chemical reaction" encompasses a reaction in which at least one compound, such as a by-product accompanied by said first and/or second olefins, is converted into another compound. Thus, the term “chemical reaction” refers to a process in which, in a compound, a new bond is formed.
[0330] The term “substrate” encompasses the first and/or second olefins, that is, the olefin(s) to be converted in a metathesis reaction.
[0331] The term "protic material" encompasses any material that is suitable for releasing a proton, or from which protons can be removed.
[0332] The term "polar material" encompasses any material that has polar groups, such as hydroxyl groups, carboxylic groups, aldehyde groups, cyano groups, nitrile groups, sulfonate groups, phosphate groups, ester groups.
[0333] The term "Lewis basic catalyst poison" encompasses any compound that has a free pair of electrons.
[0334] The term "means/methods" in connection with purification encompasses any method or material that is suitable to, at least partially, destroy or remove a by-product that is contained in a raw material, comprising a first and a second olefin.
[0335] The term "optionally substituted", as used herein, encompasses the replacement of a phenyl ring or an alkyl chain with one or more substituents selected from the group consisting of: halogen, hydroxy, protected hydroxy, C 1 -4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
[0336] The term "protected hydroxyl" encompasses protection with Si-containing groups, such as trimethylsilyl (TMS), triethylsilyl (TES), t-butyldimethylsilyl (TBS, TBDMS), triisopropylsilyl (TIPS), and t- butyldiphenylsilyl (TBDPS). Examples l. Catalyst synthesis
[0337] All reactions were carried out in suitable dry glassware (120 °C), under an inert atmosphere of N2, unless otherwise indicated. Alcohols were dried by azeotropic distillation, with C6D6, before being used in reactions with reagents based on Mo- or W-. 1H NMR were recalled on a spectrometer, at an XL-200(200MHz) range. Chemical shifts are reported in ppm from tetramethylsilane with the resonance of tetramethylsilane as its internal reference (δ 0.00). Data are reported as follows: chemical shift, integration, multiplicity (s=singlet, d=doublet, t=triplet, hept=heptate, br=broad, m=multiplet).
[0338] Example 1: N-[(2,5-dimethyl-1H-pyrrol-1-yl)(2-methyl-2-phenylpropylidene)2,4,6-triphenylphenoximolibdeniolidene]-2,6- bis(propan-2-yl)aniline (new compound 44)
[0339] In a chamber filled with N2, a 100mL pear-shaped flask with magnetic stir bar was charged with N-[bis(2,5-dimethyl-1H-pyrrol-1-yl)(2-methyl- 2-phenylpropylidene)-molybdeniolidene]-2,6-bis(propan-2-yl)aniline (959.5mg, 1.6mmol) and Et2O (16mL). A 30ml vial was loaded with 2,4,6-triphenylphenol (522.8mg, 1.6mmol) and Et2O (4ml). The Mo-bis(pyrrolide) solution was allowed to stir and the phenol solution was added by pipette. The flask containing the phenol was rinsed with Et2O (2mL), which was similarly transferred to the reaction mixture. After 2h at 22°C, volatiles were removed under reduced pressure and the resulting red oil was triturated with n-pentane (10ml) to provide an orange precipitate. The vial was sealed and allowed to cool to -38 °C (chamber cooler) for 12 h. The orange precipitate was collected by vacuum filtration and washed with cooled pentane (~5mL) to provide the subject compound as an orange powder (1.1g, 1.3mmol, 82.8% yield). 1H NMR (200MHz, C6D6): δ 11.42 (1H, s), 7.63-7.56 (8H, m), 7.226.88(17H, m), 6.10 (2H, s), 3.13(2H, hept), 2.25 (6H, br s), 1.54 (3H, s), 1.21 (3H, s), 0.96 (6H, d), 0.84 ( 6H, d).
[0340]
[0341] Example 2: 2,6-dichloro-N-[(2,5-dimethyl-1H-pyrrol-1-yl)(2,2-dimethylpropylidene)4-fluoro-2,6-diphenylphenoxy-tungsteniolidene]aniline (new compound 63)
[0342] In a chamber filled with N2, a 100mL pear-shaped flask with magnetic stir bar was charged with N-[bis(2,5-dimethyl-1H-pyrrol-1-yl)(2,2-dimethylpro - pilidene)tungsteniolidene]-2,6-dichloroaniline (1.5g, 2.5mmol) and Et2O (19ml). A 30mL vial was loaded with 4-fluoro-2,6-diphenylphenol (658.3mg, 2.5mmol) and Et2O (6mL). The W-bis(pyrrolide) solution was left under stirring and the phenol solution was added by pipette. The flask containing the phenol was rinsed with Et2O (2ml), which was similarly transferred to the reaction mixture. After 2h at 22°C, volatiles were removed under reduced pressure and the resulting orange solid was triturated with n-pentane (15ml) to provide a yellow precipitate. The vial was sealed and allowed to cool to -38 °C (chamber cooler) for 12 h. The orange precipitate was collected by vacuum filtration and washed with cooled pentane (~5mL) to provide the subject compound as an orange powder (1.6g, 2.1mmol, 83.3% yield). 1H NMR (200 MHz, C6D6): δ 8.06 (1H, s), 7.39-7.35 (4H, m), 7.10-6.78(10H, m), 6.18 (1H, , t), 6.13 (2H, s), 2.17 (6H, s), 1.00 (9H, s).
[0343] The compounds were characterized by the 1H NMR spectroscopy method and the respective displacement (ppm) of the respective alkylidene or H (C6D6) as shown in the following Table 1:






*In the case of compound 154, a chemical shift of the complex alkylidene signal (7.86 ppm) detected was different from that described in the literature US 20110077421, WO 2011040963 (11.04 ppm) which is strangely high for this type of complex.
[0344] The compounds from 180 to 291 were also characterized by 1H NMR spectroscopy method and the respective displacement (ppm) of the respective alkylidene H (C6D6) as shown in the respective formulas. Additionally, the formula weight is indicated. 2.Display of the various compounds in ring closing metathesis (RCM) of diethyl diallylmalonate, according to the following scheme 1:
[0345]

[0346] Metathesis catalysts were tested in the ring closure reaction (RCM) of diethyl diallylmalonate. The reaction was characterized by conversion data. Compounds 1, 10 and 154 are known compounds, compounds 11, 42, 123, 142, 162, 168, 178 are new. Results are summarized in Table 2.
Conversion = [(area of diethyl cyclopent-3-ene-1,1-dicarboxylate 2) / (area of diethyl cyclopent-3-ene-1,1-dicarboxylate 2 ) + (area of di-ethyl diallylmalonate 1) ] without calibration.
[0347] Input 1-2, 4-9: All manipulation was carried out under the inert atmosphere of the chamber. Diethyl diallylmalonate (2.5 mmol, 604 µL) (substrate) was measured in a 10 ml glass vial and dissolved in toluene (1.9 ml abs). 0.1 M stock solution (1 μmol, 10 μL) of the catalyst was added at room temperature and the flask was covered with a perforated lid to exhale the evolution of ethylene. The reaction mixture was kept under stirring, at the same temperature, for 4h and then it was removed from the chamber, and its volume was diluted to 10 mL with EtOAc. 1 mL of this solution was poured on top of a silica column (1.0 mL) and eluted with EtOAc (10 mL). The collected eluate was analyzed by GCMS (gas chromatography - mass spectrometry).
[0348] Entry 3: The manipulation was carried out under the inert atmosphere of the chamber. Diethyl diallylmalonate (2.5 mmol, 604 µL) was measured in a 10 ml glass vial and dissolved in toluene (1.9 ml abs). 0.05 M stock solution (1 µmol, 20 µL) of catalyst 154 was added at room temperature and the flask was covered with a perforated cap to exhale the ethylene evolution. The reaction mixture was kept under stirring at the same temperature for 4h and then it was removed from the chamber, and its volume was diluted to 10mL with EtOAc. 1 mL of this solution was poured on top of a silica column (1.0 mL) and eluted with EtOAc (10 mL). The collected eluate was analyzed by GCMS. Materials: Diethyldiallylmalonate was purchased from Sigma-Aldrich company. It was purged with nitrogen and transferred to the chamber. It was percolated twice over 2 x 25% by weight of activated alumina and stored in a molecular sieve.
[0349] All reactions under the chamber were carried out in dry glassware (140°C), under an inert atmosphere of N2, unless otherwise indicated. Every catalyst was used as a 0.1M stock solution in C6D6 or benzene except compound 154, which was used with a 0.05M solution in C6D6. GCMS chromatograms were saved to a Shimadzu GC2010 Plus instrument. 3. Display of the various compounds in cross homometathesis (HCM) of 2-allylphenylacetate Preparation of 2-allylphenylacetate according to scheme 2

[0350] 2-allylphenol (0.5 mol) was dissolved in CH2Cl2 (1L) under nitrogen. Et3N (139 mL, 1 mol,) and DMAP (1.83 g, 0.015 mol) were added in one portion. The mixture was cooled to 0°C with an ice bath and acetic anhydride was added thereto dropwise, keeping the temperature below 10°C. The reaction mixture was stirred for 2 h at 0-5 °C and monitored by TLC (10% EtOAc in heptane). The ice bath was removed, the reaction mixture was extracted with water (2x500ml) and brine (300ml). The solvent was evaporated and the product purified by vacuum distillation (bp: 101°C at 11 Torr). The main fraction was purged with nitrogen; transferred to a nitrogen-filled chamber, and filtered through an activated alumina sieve (20% wt) to transform 2 into a clear liquid. (50 ml, 58.6%). GC-MS: 99.6%, [Allylphenol traces (0.037%) were also detected], 1H NMR (200 MHz, Chloroform-d): δ 2.23 (s, 3H), 3.23 (s, 2H ), 4.94-4.98 (m, 1H), 5.03-5.04 (m, 1H), 5.73-5.93 (m, 1H), 6.94-7.22 (m) , 4H), consistent.
[0351] Before the metathesis reaction the substrate was stirred with 0.037-0.1 mol% triethylaluminum (room temperature for 1 h) to deactivate the free phenol and traces of water.
[0352] 2-allylphenylacetate was subjected to HCM according to Scheme 3

[0353] Metathesis catalysts were tested in 2-allylphenylacetate HCM using different substrate/catalyst ratios. The reaction was characterized by conversion data. The catalysts according to the invention were compared with the known compounds 1 and 10. Before the metathesis reaction, the new compound 2 was purified by the Et3Al method.
[0354] Compound 162 provided a remarkable result. A high conversion was detected in the case of the known compound 1 for a high load with elephine. Compounds 11, 42 and 162 are new. The results are summarized in Table 3.
Table 3. Allylphenylacetate autometathesis results (2) in the presence of different metathesis catalysts at 760 Torr bConversion = [(1,4-di(2-acetyloxyphenyl)-2-butene 3) area x 2) / area of ((1,4-di(2-acetyloxyphenyl)-2-butene 3) x 2 + area of 2-allylphenylacetate 2)]. (based on calibrated GCMS data) The E/Z isomers were separated in GC. E-isomer could be isolated by flash chromatography and characterized by NMR. TON = Number of Turn Over. Experimental:
[0355] Entry 1. All manipulation was carried out under the inert atmosphere of the chamber. 2-allylphenylacetate was pretreated with 0.1 mol% Et3Al (25 wt% in toluene). The substrate from the pretreated stock solution (171 µl, 1 mmol) was measured in a 4 ml glass vial. 0.1 M catalyst 11 stock solution (1 μmol, 10 μL) was added at room temperature and the flask was covered with a perforated lid to exhale the evolution of ethylene. The reaction mixture was kept under stirring, at the same temperature, for 2.5h. The reaction mixture was removed from the chamber and cooled with ethyl acetate. Internal standards, mesitylene (c=60mg/ml) and pentadecane (c=60mg/ml) were added, the solution was poured onto the top of a silica column (1.0ml) and eluted with EtOAc (10ml) ). The collected eluate was analyzed by GCMS. Conversion: 93%, TON: 456, Z/E Isomer Ratio: 17/83.
[0356] Entry 9. All manipulation was carried out under the inert atmosphere of the chamber. 2-Allylphenylacetate was pretreated with 0.085 mol% Et3Al (25 wt% in toluene). The pretreated stock solution substrate (1711 µl, 10 mmol) was measured in a 10 ml glass vial. 0.1 M of compound 162 stock solution (1 µmol, 10 µL) was added at room temperature and the bottle was covered with a perforated cap to exhale the evolution of ethylene. The reaction mixture was kept under stirring, at the same temperature, for 2.5h. The reaction mixture was removed from the chamber and cooled with ethyl acetate. Internal standards, mesitylene (c=60 mg/ml) and pentadecane (c=60 mg/ml) were added and the volume of the mixture was diluted to 10ml. 1 mL of the solution was poured onto the top of a silica column (1.0 mL) and eluted with EtOAc (10 mL). The collected eluate was analyzed by GCMS. Conversion: 67%, TON: 3299, Z/E Isomer ratio: 18/82. General:
[0357] All reactions under the chamber were carried out in dry glassware (140°C), under an inert atmosphere of N2, unless otherwise indicated. Every catalyst was used as a 0.1 M stock solution in C6D6 or benzene.
[0358] TLC was performed on 0.25 mm of Merck silica gel, 60 F254 plates and visualized under UV light (254 nm) and iodine vapor. GCMS chromatograms were saved to a Shimadzu GC2010 Plus instrument. 1H NMR were saved to the Varian XL-200 (200MHz) spectrometer. Chemical shifts are reported in ppm of tetramethylsilane with the tetramethylsilane resonance as an internal reference (δ 0.00). Data are reported as follows: chemical shifts, integration, multiplicity (s=singlet, d=doublet, t=triplet, hept=heptate, br=broad, m=multiplet).4.Display of the various compounds in a homometa reaction - allylbenzene cross-thesis (HCM) at different catalyst loads, according to the following scheme 4:
[0359]
4.1 Purification of crude allylbenzene by physical-chemical pretreatment
[0360] The crude allylbenzene (substrate) was distilled under atmospheric pressure. Its peroxide content was determined by titration and found to be 0.01 mol%. Then, the substrate was percolated in 20% by weight of aluminum oxide 90 (active base). By this method, the hydroperoxide content could be reduced below the detection limit and the water content below 5 ppms. The percolated substrate was stored on a molecular sieve and applied in a self-metathesis reaction using different catalysts.
[0361] The reaction was tested with the new compound 11 using different molar ratios of catalyst/substrate. The results are summarized in Table 4. The selected catalyst gives practically complete conversion after 1h.

Table 4. Allylbenzene results (1) autometathesis in the presence of new compound 11
[0362]aConversion = [(1,4-diphenylbutene area 2) x 2 / ((1,4-diphenylbutene area 2) x) 2 + allylbenzene area 1]. bE/Z isomers were separated in GC. The mixture was measured by 1H NMR, and the chemical shifts of the isomers were compared to literature data. The main component was found to be the E-isomer of the catalyst. It was used from 0.1M stock solution in C6D6 or benzene
[0363] The reaction was performed with other catalysts, as shown in Table 5 below. Compound 10 is known, compounds 11, 21, 30, 32, 36, 42 are new.
Table 5. Selected results of allylbenzene (1) autometathesis in the presence of various catalysts aConversion = [(1,4-diphenylbutene area 2) x 2 / ((1,4-diphenylbutene area 2) x) 2 + area of allylbenzene 1]. bThe E/Z isomers were separated in GC. The mixture was measured by 1H NMR, and the chemical shifts of the isomers were compared to literature data. The main component was found to be the E-isomer. Experimental:
[0364] Reactions in Table 5 were carried out according to the following protocol: All manipulation was carried out under an inert atmosphere of the chamber. Allylbenzene (20 mmol, 2650 µL) was measured in a 10 mL glass vial. 0.1 M catalyst stock solution (1 μmol, 10 μL) was added at room temperature and the reaction mixture was kept under stirring, at the same temperature, for 2h. 100 µl of sample was removed from the chamber and cooled with 2 ml EtOAc. The solution was poured over the top of the silica column (1.0 ml) and eluted with EtOAc (10 ml). 200 μL of the collected eluate were analyzed by GCMS. 4.2 Allylbenzene purification by chemical purification step: reaction of by-products with trioctylaluminum
[0365] Allylbenzene was purchased from Sigma-Aldrich company (A29402-100ML, Lot No.: 55496LMV, Certificate of Analysis: 99.9%). In GCMS analysis: 99.64% allylbenzene, 0.27% cinnamaldehyde, 0.07% unknown impurities. Hydroperoxide content: 0.68 mol% by titration. Water content by KF titration: 973 ppm, 0.63 mol%.
[0366] Crude allylbenzene was pretreated with different amount of Oc3Al. After pretreatment, the raw substrate was applied in metathesis reaction. The reaction was characterized by the conversion data and the required amount of Oc3Al could be optimized.
[0367] 0.8-1.2 mol% Oc3Al efficiently removed impurities. The ideal was not determined due to the high conversion at each point. Results with known catalyst 1 are listed in Table 6.
Table 6. Pretreatment with application of Oc3Al in allylbenzene autometathesis in the presence of 100 mol ppm of the catalyst 1 Allylbenzene quality: crude, hydroperoxide/water content = 0.68%/0.63%, Additive: Oc3Al (25 % in hexane weight), pre-treatment conditions: 18 h agitation at rt, Catalyst: 1, S/C=10 000, Metathesis conditions: 4 h, room temperature aConversion = [(1,4-diphenylbutene area 2) x 2 / ((1,4-diphenyl-butene area 2) x) 2 + allylbenzene area 1]. bThe E/Z isomers were separated in GC.
[0368] Table 7 shows the application of Oc3Al in the pre-treatment of allylbenzene auto-metathesis, in the presence of 50 mol ppm of the known catalyst 1 and the new catalysts 178, 162, 168, 183, 184 and 123:
Table 7. Application of Oc3Al in allylbenzene pretreatment (1) autometathesis in the presence of 50 mol ppm catalyst Pretreatment conditions: 18 h under stirring at rt, Catalyst/substrate =1:20,000, metathesis: 4h, room temperature
[0369] Table 8 presents the effect of pretreatment time. It was found that, under the indicated conditions, the reaction is practically complete within 2 to 4 hours.
Table 8. Study of the effect of crude allylbenzene pretreatment time on autometathesis catalyzed by the known catalyst 1 Allylbenzene quality: crude, hydroperoxide/water content = 0.68%/0.63%, Additive: 0.9 ml% Oc3Al (25 wt% hexane), catalyst: 1, Catalyst/Substrate =1:10,000, Metathesis Conditions: 4h, room temperature aConversion = [(1,4-diphenylbutene area 2 ) x 2 / ((1,4-diphenylbutene area 2) x) 2 + allylbenzene area 1]. cThe E/Z isomers were separated in GC. Experimental:
[0370] If the catalyst/substrate ratio = 1:10 000, (100 mol ppm catalyst), reactions in Table 7 and Table 8 were carried out according to the following protocol: All manipulation was carried out under the inert atmosphere of the chamber. 662 µl (5 mmol) of allylbenzene (H2O content 973 ppm, 0.63%, peroxide content 0.68%) was measured in a 5 mL glass vial. Oc3Al (25% sol. in hexane) was added thereto and the mixture was kept under stirring for 1-18h. Then 0.1 M catalyst stock solution (5 μl, 1 μmol, 100 mol ppm) was added at room temperature and the reaction mixture was kept under stirring, at the same temperature, for 4h. Then, the reaction mixture was removed from the chamber and air-cooled with 100 µL of MeOH. Internal standards were added: mesitylene in EtOAc and pentadecane (1 mL, c=60 mg/mL). The volume was diluted to 5 mL. 1 mL of this solution was poured onto the top of silica column 1 (mL) and eluted with EtOAc (10 mL). From the collected eluate, 100 μL is anylized by GC or GCMS.
[0371] If the catalyst/substrate ratio = 1:20,000, (50 mol ppm catalyst), reactions in Table 7 were carried out according to the following protocol: All manipulation was carried out under the inert atmosphere of the chamber. 1362 µl (10 mmol) of allylbenzene (H2O content 973 ppm, 0.63%, peroxide content 0.68%) was measured in a 10 mL glass vial. Oc3Al (25% sol. in hexane) was added thereto and the mixture was kept under stirring for 18h. Then 0.1 M catalyst stock solution (5 μl, 0.5 μmol, 50 mol ppm) was added at room temperature and the reaction mixture is kept under stirring, at the same temperature, for 4 h. Then the reaction mixture was removed from the chamber and cooled with 100 µL of MeOH. Internal standards were added: mesitylene in EtOAc and pentadecane (1 ml, c=60 mg/ml). The volume was diluted to 10 ml. 1 mL of this solution was poured onto the top of a column of silica 1 (mL) and eluted with EtOAc (10 mL). From the collected eluate, 100 µL is analyzed by GC or GCMS.
[0372] Trioctylaluminum, which allows safe handling, efficiently destroy impurities in allylbenzene substrate and allow to achieve high conversion even at low catalyst load, such as 50 mol ppm. 5. Display of compounds in ring closing metathesis (RCM) of diethyl diallylmalonate (DEDAM) depending on purification
[0373] Crude diethyl diallylmalonate was purchased from Sigma-Aldrich company, its water content by Karl-Fischer titration was 346 ppm in weight (0.46 mol%). The crude substrate solution was pretreated (shaking) with Oc3Al and then applied in RCM reaction using the new compound 11 as catalyst under standard conditions. Diethyl diallylmalonate was pre-dried in molecular sieve at 20% by weight for 24 h. Its water content was reduced to 346 ppm by weight (0.46 mol%) to 14.7 ppm by weight, 0.019 mol%. Without Oc3Al purification, no metathesis reaction can be performed (Table 9, entry 1). After 0.175 mol% treatment with trioctylaluminum, metathesis can be performed at high conversion rates (Table 9, entry 8).
Table 9. Diethyl diallylmalonate results (1) RCM reaction after substrate pre-drying in molecular sieve and subsequent pre-treatment with Oc3Al (purification) bConversion = [(area of diethyl cyclopent-3-ene-1,1-dicarboxylate 2) / (area of diethyl cyclopent-3-ene-1,1-dicarboxylate 2 ) + (area of diethyl diallylmalonate (1)] without calibration. Pretreatment conditions: CDEDAM = 1 M in toluene, 0-0.2% Oc3Al, 1h, room temperature Metathesis conditions: catalyst/substrate = 1:2500, catalyst load 11 = 400 mole ppm, 4h, room temperature
[0374] Table 10 shows the results of the improved conversion, if the purification period is extended:

Table 10. Diethyl diallylmalonate results (1) RCM reaction after Oc3Al purification time, using 24 h purification time bConversion = [(area of diethyl cyclopent-3-ene-1,1-dicarboxylate 2) / ( area of diethyl cyclopent-3-ene-1,1-dicarboxylate 2) + (area of diethyl diallylmalonate (1)] without calibration. Purification conditions: CDEDAM = 1 M in toluene, 0-1.75% Oc3Al; 24h, room temperature Metathesis conditions: catalyst/substrate = 1:2500, catalyst load 11 = 400 mole ppm, 4h, room temperature 6. Display of compound 11 in allylbenzene cross homometathesis (HCM) depending on purification and mode of addition of catalyst
[0375] Allylbenzene containing 973 ppm (0.6 mol %) of water was pretreated with 1 mol % of Oc3Al for a period of 18 h. Subsequent to purification, 33 mol% of the new compound 11 was added in one go. After a period of 4 h the conversion was 81 %.
[0376] The experiment was repeated with the difference that the pre-treatment time was extended to 60 h, and that the catalyst was added in portions of 8.25 mol %, respectively. After a period of 2 h, subsequent to the addition of the first portion, the conversion was 38%. Soon the second portion was added. After a further 2 h the conversion was 84%. Then the third portion was added. After a further 2 h the conversion was 93%. When the last portion was added. After a further 2 h the conversion was 94%. 7. Display of the various compounds in ethenolysis
[0377] The performance of the catalyst was compared in the ethenolysis of purified unsaturated triglycerides. The purification method was a chemical pretreatment with trialkylaluminum. Triglycerides were subjected to ethylene at a temperature of 50 °C and a pressure of 10 bar for 18 hours, using various amounts of catalyst.
[0378] The metathesis reaction was characterized by the conversion data. As the catalysts were used in the same amount of [1000 ppm (weight) - 250 ppm (weight) - 25 ppm (weight) respectively], their molar ratio is dependent on their molecular weight. Normalized conversion was obtained by linear extrapolation of the real conversion, calculated from the real molar quantity.
[0379] Table 11 shows the superior results of the new catalysts 123 and 124 where R6 is phenyl substituted with phenyl at the 2-, 3-, 5- and 6-positions, and the 4 position is substituted with bromine, compared to the catalyst known 154, which supports hydrogen at the 4 position of the phenyl moiety.

[0380] Table 12 shows the results of catalysts where R6 is a phenyl ring, which is substituted at the 2-, 4- and 6-positions, where the 2 and 6-positions are substituted by substituents via carbon atom, and the substituent at position 4 can be attached to the phenyl ring via any atom. Compound 113 is known, the other compounds are new.

[0381] Table 13 shows the results of the other catalysts in which R6 is a phenyl ring, which is substituted in the 2-, 4- and 6-positions, in which the 2 and 6-positions are replaced by substituents via carbon atoms, and the substituent at position 4 is fluorine. Compounds 35, 122, 127, 131 and 135 are new.

[0382] Table 14 shows the results of the new catalysts 178 and 233 where R6 is a phenyl ring that is substituted at the 2 and 6 positions via a phenyl moiety.
8. Display of various compounds bearing an [8-(naphthalen-1-yl)-naphthalen-1-yl]oxy linker or an (8-phenylnaphthalen-1-yl)oxy linker as R4
[0383] Table 15 shows the efficiency of novel compounds 192, 196, 214, 216, 217, 220, 246, 247, 269, 288 in methyldecenoate cross homometathesis (DAME HCM), in cross homometathesis of allylbenzene (HCM from AB), in the ring-closing metathesis of diethyl diallylmalonate (RCM from DEDAM) and in the ethenolysis of unsaturated glycerides. S/C is the molar ratio of substrate to catalyst:


[0384] Table 16 shows the efficiency of the new catalysts 207, 208, 214, 216, 220 in allylbenzene HCM. Allyl-benzene was physicochemically treated before the metathesis reaction, which means that it was percolated into a base layer of activated alumina (20% by weight). It was then allowed to rest 20% in a molecular sieve, for at least 1 day, before the metathesis reaction.
9. Display of compounds supporting 2,6-diphenyl phenol and 2-Br-6-arylphenol as R4 linker in allylbenzene HCM reaction using chemically treated substrate
[0385] HCM reactions were carried out in a glovebox atmosphere at room temperature for 4h, in a vented flask. Typical substrate/catalyst ratios are: 20,000 = 50 ppm mol catalyst loading, 30,000 = 33 ppm mol catalyst loading. After the reaction was quenched by “wet” EtOAc, samples were filtered through a silica pad and analyzed by GCMS-FID. The catalysts used are all new.
[0386] The results are summarized in table 17:
10. Display of compounds bearing a 2,3,5,6-tetraphenylphenoxy radical as R4 linker in methyl deceneate (DAME) HCM using a physically pretreated substrate, according to scheme 5

[0387] The substrate was purified through a physical treatment method, that is, percolation in activated alumina layer. The reaction was characterized by conversion data. Data are summarized in Table 18.

[0388] Compounds 10, 11 and 32 are Mo complexes, while compounds 154, 123 and 124 are W complexes. Compounds 10 and 154 are known, compounds 11, 32, 123 and 124 are new.
[0389] Compound 10 has a 2,3,5,6-tetraphenyl-phenoxy compound as R4 linker, while compound 11 is the respective 4-bromo-2,3,5,6-tetraphenylphenoxy compound and compound 32 is the 4-bromo-2,6-di(4-bromophenyl)-3,5-diphenylphenoxy analogue. R1 in each case is 2,6-diisopropylphenyl.
[0390] Compound 154 bears a 2,3,5,6-tetraphenylphenoxy residue as linker R4, while compound 123 is the respective 4-bromo-2,3,5,6- compound and compound 124 , the 4-bromo-2,6-di(4-bromophenyl)-3,5-diphenylphenoxy analogue. R1 in each case is 2,6-dichlorophenyl.
[0391] The new catalyst has excellent activity.

权利要求:
Claims (13)
[0001]
1. Method of forming an olefin product in a metathesis reaction from a raw material comprising a first olefin and a second olefin characterized in that said raw material comprises at least one by-product selected from the group consisting of water, alcohols, aldehydes, peroxides, hydroperoxides, peroxide decomposition products, protic materials, polar materials, basic Lewis catalyst poison, and mixtures thereof, the method comprising step (i), and subsequently to step (i), the following step (ii): (i) removing, at least partially, said at least one by-product from the raw material by subjecting said raw material to (1) a chemical purification step or ( 2) both a physical purification step and a chemical purification step, wherein the physical purification step comprises subjecting said raw material to at least one distillation step or an adsorption step; and wherein the chemical purification step comprises subjecting said raw material to a chemical reaction, wherein said raw material is subjected to an anhydride of an organic acid or an organometallic aluminum compound; (ii) reacting the first olefin with the second olefin in the presence of a compound that catalyzes said metathesis reaction, so that the molar ratio of said compound to the first or second olefin is less than 1:500, and the conversion of the first or second olefin to said olefin product is at least 30%, wherein the compound catalyzing said metathesis reaction has the following general formula (A):
[0002]
2. Method according to claim 1, characterized in that the organometallic aluminum compound is trioctyl aluminum.
[0003]
3. Method according to claim 1, characterized in that the organometallic aluminum compound is a trialkyl aluminum compound, and in which the raw material is subjected to the trialkyl aluminum compound for a period of 10 to 80 hours.
[0004]
4. Method according to claim 1, characterized in that the raw material is subjected to the organometallic aluminum compound, and in which the organometallic aluminum compound is added to the first and second olefins at a rate of 0.01 - 10 ppm (weight of organometallic aluminum compound) per hour.
[0005]
5. Method according to claim 1, characterized in that in the compound of general Formula (A): M = Mo or W; R1 is phenyl or adamantyl, each of which is optionally substituted; R2 is -C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is a straight chain alkoxy group having 1 to 30 carbon atoms, or a branched chain alkoxy group having 3 to 20 carbon atoms, or a cycloalkoxy group having 3 to 10 carbon atoms, pyrrolyl group, silyloxy , or phenoxy, each of which is optionally substituted; and R4 is an R6-X- residue, where X = O and R6 is phenyl substituted with up to five substituents independently selected from straight chain alkyl having 1 to 30 carbon atoms, or branched chain alkyl having 3 to 20 carbon atoms, or cycloalkyl group having from 3 to 10 carbon atoms, phenoxy, phenyl, each of which is optionally substituted, halogen; or X = O and R6 is 8-(naphthalen-1-yl)-naphthalen-1-yl, optionally substituted; or X = O and R6 is 8-phenylnaphthalen-1-yl, optionally substituted; or X = O and R6 is quinolin-8-yl, optionally substituted; or X = S and R6 is phenyl substituted with up to five substituents independently selected from straight chain alkyl having 1 to 30 carbon atoms, or branched chain alkyl having 3 to 20 carbon atoms, or cycloalkyl group having 3 to 10 carbon atoms, phenoxy, phenyl, each of which is optionally substituted, halogen; or X = O and R6 is triphenylsilyl; optionally substituted; or triisopropylsilyl; or X = O and R6 is triphenylmethyl; optionally substituted; or X = O and R6 is 9-phenyl-fluoren-9-yl; or X = O and R6 is 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl, or 2-methyl-1,1,1,3,3,3-hexafluoro- prop-2-yl; or X = O and R6 is t-butyl; or wherein in the compound of general Formula (A): M = Mo or W; R1 is selected from 1-(2,6-dimethylphenyl), 1-(2,6-diisopropylphenyl), 1-(2,6-di-t-butylphenyl), 1-(2,6-dichlorophenyl), adamant-1-yl; R2 is —C(CH3)2C6H5 or C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 2-methyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 9-phenyl-fluorenyl-9-oxy; 2,6-diphenylphenoxy; t-butyloxy; and R4 is R6-X-, where X = O and R6 is the phenyl radical substituted with up to five substituents independently selected from straight chain alkyl having 1 to 30 carbon atoms, or branched chain alkyl having 3 to 20 carbon atoms, or cycloalkyl group having 3 to 10 carbon atoms, straight chain alkoxy having 1 to 30 carbon atoms, or branched chain alkoxy having 3 to 20 carbon atoms, or cycloalkoxy group having 3 to 10 carbon atoms, phenoxy, phenyl, each of which is optionally substituted, halogen; or X = O and R6 is 8-(naphthalen-1-yl)-naphthalen-1-yl, optionally substituted; or X = O and R6 is 8-phenylnaphthalen-1-yl, optionally substituted; or X = O and R6 is quinolin-8-yl, optionally substituted; or X = S and R6 is substituted phenyl, with up to five substituents independently selected from straight chain alkyl having 1 to 30 carbon atoms, or branched chain alkyl having 3 to 20 carbon atoms, or cycloalkyl group having to 3 to 10 carbon atoms, phenoxy, phenyl, each of which is optionally substituted, halogen; or X = O and R6 is triphenylsilyl; or triisopropylsilyl; or X = O and R6 is triphenylmethyl or tri(4-methylphenyl)methyl; or X = O and R6 is 9-phenyl-fluoren-9-yl; or X = O and R6 is 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl; or 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yl; or X = O and R6 is t-butyl.
[0006]
6. Method according to claim 1, characterized in that in the compound of general Formula (A): M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R2 is —C(CH3)2C6H5 or -C(CH3)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy, triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 2-methyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 9-phenyl-fluorenyl-9-oxy; 2,6-diphenylphenoxy; t-butyloxy; and R4 is R6-X-, where X = O and R6 is the phenyl radical, which bears two substituents in the ortho position with respect to O, or bears at least three substituents, of which two are in the ortho position, with respect to O, and a substituent is in the para position, relative to the O; or X = O and R6 is the 8-(naphthalen-1-yl)-naphthalen-1-yl radical, optionally substituted; or X = O and R6 is the optionally substituted 8-phenylnaphthalen-1-yl radical; or X = O and R6 is the optionally substituted quinolin-8-yl radical; or X = O and R6 is the triphenylsilyl radical; or triisopropylsilyl; X = O and R6 is the triphenylmethyl or tri(4-methylphenyl)methyl radical; or X = O and R6 is the 9-phenyl-fluoren-9-yl radical; or X = O and R6 is the 2-phenyl-1,1,1,3,3,3-hexafluoroprop-2-yl radical; or 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yl; or X = O and R6 is the t-butyl radical.
[0007]
7. Method according to claim 1, characterized in that the compound is selected from the following structures:
[0008]
8. Method according to claim 1, characterized in that, in the compound of General Formula (A): M = Mo or W; R1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-di-tert-butylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R2 is -C(CHs)2C6H5 or -C(CHs)3; R3 is H; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrole-1-triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 2-methyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 9-phenyl-fluorenyl-9-oxy; 2,6-diphenylphenoxy; tert-butoxy; and R4 is R6 - X, where X = O and R6 is the phenyl radical which bears at least two substituents, or bears two substituents in ortho position to O, or bears two substituents in ortho position to O and one substituent in para position with respect to O; or X = O and R6 is the triphenylsilyl radical, optionally substituted; or X = O and R6 is the triphenylmethyl radical; optionally substituted; or X = O and R6 is the 9-phenyl-fluoren-9-yl radical; or X = O and R6 is the 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl or 2-methyl-1,1,1,3,3,3-hexafluoro radical -prop-2-yl; or X = O and R6 is the tert-butyl radical; X = O and R6 is the t-butyl radical; with the proviso that the following compounds are excluded: M = Mo; R1 = 2,6-diisopropylphenyl; R2 = —C(CH3)2CβH5; R3 = H; R5 = 2,5-dimethylpyrrol-1-yl; R4 = 2,6-diphenylphenoxy; M = Mo; R1 = 2,6-diisopropylphenyl; R2 = —C(CH3)2CβH5,' R3 = H; R5 = 2,5-dimethylpyrrol-1-yl; R4 = 2,3,5,6-tetraphenylphenoxy; M = W; R1 = 2,6-diisopropylphenyl; R2 = —C(CH3)2CβH5; R3 = H; R5 = 2,5-dimethylpyrrol-1-yl; R4 = triphenylsilyloxy; M = Mo; R1 = 2,6-diisopropylphenyl; R2 = —C(CH3)2CβH5; R3 = H; R5 = 2,5-dimethylpyrrol-1-yl; R4 = triphenylsilyloxy; and M = W; R1 = 2,6-diisopropylphenyl; R2 = —C(CH3)2CβH5; R3 = H; R5 = 2,5-dimethylpyrrol-1-yl; R4 =
[0009]
9. Method according to claim 1, characterized in that, in the compound of general Formula (A): X = O and R6 is a phenyl ring that is substituted at least in position 4 with respect to O.
[0010]
10. Method according to claim 9, characterized in that the substituent of the residue R6 at position 4 is selected from the group consisting of: halogen, dialkylamino, cyano, optionally substituted alkyl, optionally substituted alkyloxy, wherein the term " alkyl" means a straight chain alkyl group having 1 to 30 carbon atoms, or a branched chain alkyl group having 3 to 20 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms, or optionally phenyl substituted, optionally substituted phenyloxy; wherein the other substituents on the R6 residue are the same or different from the substituents at the 4-position, and are independently selected from the group consisting of: halogen, dialkylamino, cyano, optionally substituted alkyl, optionally substituted alkyloxy, wherein the term " alkyl" means a straight chain alkyl group having 1 to 30 carbon atoms, or a branched chain alkyl group having 3 to 20 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms, optionally substituted phenyl , optionally substituted phenyloxy; or wherein R 1 is phenyl or alkyl, each of which is optionally independently substituted with halogen, wherein the term "alkyl" means a straight chain alkyl group having from 1 to 30 carbon atoms, or a branched chain alkyl group having from 3 to 20 carbon atoms, or a cycloalkyl group having from 3 to 10 carbon atoms, C1-4 dialkylamino, C1-4 alkyl, C1-4 alkyloxy, phenyl, phenyloxy, each of which is optionally substituted, R2 and R3 are the same or different and are hydrogen, C(CH3)3, or C(CH3)2C6H5; R5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy, 2-phenyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 2-methyl-1,1,1,3,3,3-hexafluoro-propyl-2-oxy; 2,6-diphenylphenoxy; 9-phenyl-fluorenyl-9-oxy; t-butyloxy; and the substituent of residue R6 at position 4 is selected from the group consisting of: halogen, C1-4 dialkylamino, C1-4 alkyl, C1-4 alkyloxy, phenyl, phenyloxy, each of which is optionally substituted; and the other substituents on the R6 residue are the same as or different from the substituent at the 4-position, and are independently selected from the group consisting of halogen, C1-4 dialkylamino, C1-4 alkyl, C1-4 alkyloxy, phenyl, phenyloxy, each one of which is optionally substituted; or wherein R6 is a phenyl ring which is independently substituted at the 2 and 4 positions with halogen, and at the 6 position with phenyl, which is optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy; or phenyl or phenoxy optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy, respectively, wherein the term "alkyl" means a straight chain alkyl group having from 1 to 30 carbon atoms, or a branched chain alkyl group having from 3 to 20 carbon atoms, or a cycloalkyl group having from 3 to 10 carbon atoms; or wherein R6 is a phenyl ring substituted at positions 2 and 6 by substituents via carbon atoms, and at position 4 by substituents via any atom; or wherein R6 is a phenyl ring substituted at the 4 position with bromine and at the 2, 3, 5 and 6 positions with phenyl, respectively, wherein said phenyl residues are independently substituted with fluorine, chlorine, bromine, dimethylamino, diethylamino, methyl , ethyl, propyl, isopropyl, butyl, t-butyl, methoxy, ethoxy, propyloxy, butyloxy, t-butyloxy, trifluoromethyl, phenyl optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy; phenoxy optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy, wherein the term "alkyl" means a straight chain alkyl group having 1 to 30 carbon atoms, or a branched chain alkyl group having 3 to 20 atoms carbon, or a cycloalkyl group having 3 to 10 carbon atoms.
[0011]
11. Method according to claim 1, characterized in that, in the compound of general Formula (A): M = Mo or W; R4 is an R6-X- residue, wherein X = O and R6 is a phenyl ring substituted in positions 2 and 6 with phenyl, optionally substituted, respectively; or R4 is [8-(naphthalen-1-yl)-naphthalen-1-yl]oxy, optionally substituted; or R4 is (8-phenylnaphthalen-1-yl)oxy, optionally substituted.
[0012]
12. Method according to claim 1, characterized in that the first olefin has a terminal olefinic double bond, and the second olefin has a terminal olefinic double bond, wherein the first and second olefins are identical; or wherein the first and second olefins are different from each other; or wherein the first olefin has an internal olefinic double bond and the second olefin is ethylene; or wherein the first olefin is a cyclic olefin and the second olefin is a cyclic olefin, wherein the first and second olefins are identical or different from each other.
[0013]
13. Method for increasing the reactivity of a compound of Formula (A): characterized by the fact that M = Mo or W R1 is phenyl; or straight chain alkyl having 1 to 30 carbon atoms, or branched chain alkyl having 3 to 20 carbon atoms, or cycloalkyl having 3 to 10 carbon atoms; each of which is optionally substituted; R2 and R3 are the same and are straight chain alkyl having 1 to 30 carbon atoms, or branched chain alkyl having 3 to 20 carbon atoms, or cycloalkyl having 3 to 10 carbon atoms, or phenyl, each of which is optionally substituted, or hydrogen; R5 is straight chain alkyl having 1 to 30 carbon atoms, or branched chain alkyl having 3 to 20 carbon atoms, or cycloalkyl having 3 to 10 carbon atoms, or phenoxy, or silyloxy, or is pyrrolyl, each of which is optionally substituted; and R4 is an R6-X- residue, where X = O and R6 is phenyl, optionally substituted; or X = S and R6 is phenyl, optionally substituted; or X = O and R6 is (R7)(R8)(R9)Si; wherein R7, R8, R9 are straight chain alkyl having 1 to 30 carbon atoms, or branched chain alkyl having 3 to 20 carbon atoms, or cycloalkyl having 3 to 10 carbon atoms, or phenyl, each one of which is optionally substituted; or X = O and R6 is (R10)(R11)(R12)C, wherein R10, R11, R12 are independently selected from optionally substituted phenyl, or straight chain alkyl having 1 to 30 carbon atoms, or branched-chain alkyl having from 3 to 20 carbon atoms, or cycloalkyl having from 3 to 10 carbon atoms optionally substituted; or X = O and R6 is the optionally substituted quinolin-8-yl radical; or R4 and R5 are linked together and are linked to M via oxygen, respectively; or is selected from one of the following structures: 280, 281, 289, 290, or 291: which catalyzes the metathesis reaction of a raw material comprising a first and a second olefin, so that the molar ratio of said compound to the first or second olefin is less than 1:500, and the conversion of the first or second olefin olefins is at least 30%, wherein said raw material further comprises at least one by-product selected from the group consisting of water, alcohols, aldehydes, peroxides, hydroperoxides, peroxide decomposition products, protic materials, polar materials , Lewis base catalyst poison, and mixtures thereof, the method comprising step (i), and subsequent to step (i), the following step (ii): (i) at least partially removing said at least a by-product from the raw material by subjecting said raw material to a chemical purification step, wherein the chemical purification step comprises subjecting said raw material to a chemical reaction, wherein said raw material is subjected to an anhydride of an organic acid or an organometallic aluminum compound; (ii) reacting the first olefin with the second olefin in the presence of a compound that catalyzes said metathesis reaction, and ee wherein the organometallic aluminum compound of step (i) is of the formula R1R2R3Al, wherein said R1, R2 and R3 in the organometallic aluminum compound are independently selected from aliphatic, cyclic, or alicyclic residues having 1 to 10 carbon atoms, or from aromatic residues having 6 to 10 carbon atoms; and wherein said chemical reaction further comprises: (a) determining an amount of said at least one by-product in the raw material, wherein said at least one by-product comprises at least one reactive group, wherein said at least one group reactive is reactive to said compound that catalyzes said metathesis reaction and to said anhydride of an organic acid or to said organometallic aluminum compound; and adding a theoretical amount of said organic acid anhydride and said organometallic aluminum compound, respectively, which is necessary to convert said at least one reactive group to at least one non-reactive group, wherein said at least one non-reactive group is non-reactive to said compound that catalyzes said metathesis reaction and both to said anhydride of an organic acid and to said organometallic aluminum compound; or (b) adding an excess of said anhydride of an organic acid or of said organometallic aluminum compound per mol of said at least one by-product to convert said at least one by-product into a species that is not reactive to the compound that catalyzes said metathesis reaction. in the presence of a compound that catalyzes said metathesis reaction.

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法律状态:
2019-10-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-02-04| B25A| Requested transfer of rights approved|Owner name: VERBIO VEREINIGTE BIOENERGIE AG (DE) |

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2020-09-08| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-03-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-05-04| 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 13/03/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201361781120P| true| 2013-03-14|2013-03-14|

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EP13001297|2013-03-14|

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EP13001297.4|2013-03-14|

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US61/781,120|2013-03-14|

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PCT/EP2014/000671|WO2014139679A2|2013-03-14|2014-03-13|Metathesis catalysts and reactions using the catalysts|

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