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    • 专利摘要:
    PURPOSE: A herbicidal composition containing pyridine-sulfonylurea derivatives, salt thereof or a stereochemical isomer thereof is provided which is highly effective against an annual and perennial grass weed before germination and/or after germination. CONSTITUTION: This herbicidal composition contains pyridine-sulfonylurea derivatives of formula 1, which derivatives are obtained by reaction of a compound of formula 6 with a compound of formula 7 in the presence or absence of a base in a solvent. In formula, n is an integer from 1 to 3; R is H or C1-4 alkyl; R' is H or C1-4 alkyl, C1-3 haloalkyl, halogen or C1-2 alkoxy; X and Y are each independently C1-2 alkyl, C1-2 alkoxy, C1-2 haloalkoxy or halogen.
    公开号:KR20020029177A
    申请号:KR1020000059990
    申请日:2000-10-12
    公开日:2002-04-18
    发明作者:구석진；조진호；김정수；강승훈；강경구；김대황；장해성；고영관；류재욱
    申请人:성재갑；주식회사 엘지씨아이；
    IPC主号:
    专利说明:

    Herbicidal pyridine sulfonyl urea derivatives
    [1] Pyridinesulfonylurea derivatives of the general formula (1), salts or stereochemical isomers thereof, methods of using the same, preparations thereof, and derivatives thereof, which are useful as pre- and / or post-germination treatment herbicides in rice agriculture. It relates to a herbicide composition characterized in that it contains an intermediate compound, and derivatives thereof.
    [2] [Formula 1]
    [3]
    [4] In the above formula
    [5] n represents an integer of 1 to 3,
    [6] R represents H or C 1 -C 4 -alkyl,
    [7] R 'represents H or C 1 -C 4 -alkyl, C 1 -C 3 -haloalkyl, halogen or C 1 -C 2 -alkoxy,
    [8] X and Y each independently represent C 1 -C 2 -alkyl, C 1 -C 2 -alkoxy, C 1 -C 2 -haloalkoxy or halogen.
    [9] Conventionally, many sulfonylurea derivatives having herbicidal activity in rice farming have been known. For example, Japanese Patent No. 61/191602 reports a compound of the following formula (2), which is currently commercialized and used as a herbicide for rice agriculture under the name of pyrazosulfuron-ethyl.
    [10]
    [11] In addition, the Republic of Korea Patent No. 70757 has been reported a compound of the formula (3).
    [12]
    [13] In the above formula
    [14] R represents haloalkyl,
    [15] X and Y represent CH 3 , OCH 3 or Cl, respectively,
    [16] Z represents CH or N.
    [17] In addition, Korean Patent Application No. 91-3014 discloses a herbicidal sulfonylurea derivative of the following formula (4).
    [18]
    [19] In the above formula
    [20] R, X, Y and Z are as defined in Formula 3,
    [21] R 'represents H or CH 3 ,
    [22] P and Q represent CH or N, respectively, provided that the aromatic ring comprising P and Q is benzene or pyridine.
    [23] In addition, Korean Patent Application No. 93-6915 discloses a herbicidal pyridine sulfonylurea derivative of the formula (5).
    [24]
    [25] In the above formula
    [26] P, Q, R ', X and Y are as defined in formula (4),
    [27] R is H, R a - (C = O) - or R a -X a - (C = O) - denotes a, where R a is C 1 ~ C 4 - alkyl, C 1 ~ C 3 - haloalkyl , C 2 -C 4 -alkenyl or C 2 -C 4 -alkynyl, and X a represents O, S, NH or NR a .
    [28] Existing sulfonylurea herbicidal compounds as described above have excellent control ability against annual and perennial weeds in rice farming, but it is difficult to control it, so it does not have excellent control ability for the most problematic blood or weak against rice. Problems have been found to cause. Accordingly, the present inventors have conducted intensive research to overcome this problem, and as a result, they have developed a pyridinesulfonyl urea derivative having a new structure, and the compound has excellent selectivity against rice and excellent control against blood compared to existing compounds. The present invention was completed by confirming that it can be very usefully used as a herbicide for agriculture.
    [29] Accordingly, an object of the present invention is to provide a pyridinesulfonylurea derivative of the general formula (1), a salt thereof, or a stereochemical isomer thereof.
    [30] The present invention also aims to provide a process for preparing the compound of formula (1).
    [31] The present invention also aims to provide novel intermediate compounds for use in the preparation of compounds of formula (I).
    [32] It is another object of the present invention to provide a method for using the compound of formula (1) for herbicidal purposes for water and herbicidal composition characterized by containing the same.
    [33] Hereinafter, the present invention will be described in more detail.
    [34] The present invention relates to compounds of formula
    [35] [Formula 1]
    [36]
    [37] In the above formula
    [38] n represents an integer of 1 to 3,
    [39] R represents H or C 1 -C 4 -alkyl,
    [40] R 'represents H or C 1 -C 4 -alkyl, C 1 -C 3 -haloalkyl, halogen or C 1 -C 2 -alkoxy,
    [41] X and Y each independently represent C 1 -C 2 -alkyl, C 1 -C 2 -alkoxy, C 1 -C 2 -haloalkoxy or halogen.
    [42] Among the compounds of the general formula (1) which can be used very effectively as water herbicides because of excellent selectivity to rice and excellent control against blood, n is an integer of 1 or 2, R is H or methyl, and R 'is H, halogen or methyl and X and Y are each methoxy.
    [43] Particularly preferred compounds are compounds wherein n is an integer of 1 or 2, R is methyl, R 'is H, Cl, Br or methyl, and X and Y are each methoxy.
    [44] Representative compounds of the most preferred compounds of the formula (1) according to the present invention are listed as follows.
    [45] N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3-sulfonamide.
    [46] N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (2-fluoro-1-hydroxyacetoxy-n-propyl) pyridine-3-sulfonamide.
    [47] N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (2-fluoro-1- (3-hydroxypropion) oxy-n-propyl) pyridine-3- Sulfonamides.
    [48] N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (2-fluoro-1- (3-methoxypropion) oxy-n-propyl) pyridine-3- Sulfonamides.
    [49] N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-methyl-2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3- Sulfonamides.
    [50] N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-chloro-2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3- Sulfonamides.
    [51] N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-bromo-2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3 Sulfonamides.
    [52] Since the compound of Formula 1 includes two asymmetric carbons, it may exist as erythro, threo, or a mixture of these isomers. The compounds of the present invention show stronger activity when in erythro form, but also exhibit sufficient activity even with a suitable ratio of mixture.
    [53] The compound of formula 1 according to the present invention may be prepared by reacting a compound of formula 6 with a compound of formula 7 in the presence or absence of a base in a solvent, and thus, the present invention also provides a method for preparing the compound. The purpose is:
    [54]
    [55]
    [56] In the above formula
    [57] n, R, R ', X and Y are as defined for formula (1).
    [58] Compounds of formula (6) used as starting materials in the process according to the invention may exist as erythro, threo or mixtures thereof, depending on which stereochemical arrangement the compound of formula (6) has This is determined.
    [59] In the above method, any solvent may be used as long as it does not adversely affect the reaction. Preferably, tetrahydrofuran, acetone, acetonitrile, dioxane, methylene chloride, toluene, butanol, pyridine, dimethylformamide, etc. may be mentioned. have. The process also provides a small amount of strong bases, for example triethylamine, hexamethylenetetraamine, pyridine, DBU or DABCO, where DBU is 1,8-diazabicyclo [5,4,0] undec-7- Y, DABCO means 1,4-diazabicyclo [2,2,2] octane, which is the same below) and the like, and the reaction temperature is in the range of 10 to 80 ° C. It is good to keep. Specific reaction conditions may refer to US Pat. No. 4,443,245, which refers to similar reactions, and after completion of the reaction, the desired compound may be obtained by treatment with an acid as described in EP 044,807. If a high purity compound is to be obtained, it is preferable to purify using HPLC.
    [60] The compound of formula 7 can be easily prepared according to the method described in Korean Patent No. 70,675 as a known substance.
    [61] The compound of formula 6 is a novel intermediate initially provided by the present invention which is another subject of the invention which the present invention is intended to provide. The compound of formula 6 may be prepared by leaving the t-butyl group by treating the compound of formula 8 with trifluoroacetic acid (TFA).
    [62]
    [63] Wherein n, R and R 'are as defined for Formula 1, respectively.
    [64] When the compound of Formula 8 is stirred at a temperature of 0 to 80 ° C. using trifluoroacetic acid (TFA) as a solvent, the t-butyl group is released to give a sulfonamide compound of Formula 6. When the obtained compound of formula 6 is present as an erythro-sreo mixture, pure erythro or threo compounds can be obtained by separation using column chromatography or HPLC or preparative-TLC method.
    [65] In addition, the compound of formula (8) can be obtained by acylating the compound of formula (9) in a conventional manner.
    [66]
    [67] Wherein R 'is as defined for Formula (1).
    [68] The compound of formula 9 can be obtained by selectively reducing the compound of formula 10 with an appropriate reducing agent such as, for example, DIBAL.H (Diisobutylaluminum hydride), NaBH 4 , LiAlH 4 , BH 3 .
    [69]
    [70] Wherein R 'is as defined for Formula 1 above.
    [71] In order to clarify the compound of Formula 1 that can be prepared according to the above description as shown in the individual compounds as shown in Table 1 below.
    [72]
    [73] The compounds of formula 1 according to the invention may exist in the form of suitable salts and are also useful as herbicides in the form of salts. Salts can be prepared using known conventional methods. For example, suitable salts can be prepared by contacting a compound of Formula 1 with a hydroxide, alkoxide or carbonate solution of an alkali or alkaline earth metal and salts can be prepared in a similar manner using amine compounds.
    [74] Various salts can also be obtained by exchanging cations with other salts of the compounds of formula (1). Cation exchange can be carried out by directly contacting one salt of the compound of formula 1, for example an aqueous alkali metal salt or quaternary amine salt, with a solution containing the cation to be exchanged. This method is most effective when the desired salt containing the exchanged cation is insoluble in water. Ion exchange may also be carried out by passing a salt of a compound of formula 1, for example an alkali metal salt or quaternary amine salt aqueous solution, through a column packed with a cation exchange resin containing a cation to be exchanged. Here the cation of the resin is exchanged with the cation of the original salt and the desired salt product elutes from the column. This method is particularly effective when the desired salt is water soluble, ie, sodium, potassium or calcium salts.
    [75] Compounds of formula (1) are also usefully used as herbicides in mixtures or complexes with urea or amide compounds, and such mixtures or complexes can be prepared according to conventional methods.
    [76] The preparation or conversion method is briefly summarized, but can be easily performed by those skilled in the art of organic synthesis or synthesis of sulfonylurea derivatives, and includes all modifications. .
    [77] The pyridinesulfonylurea derivatives of the general formula (1) according to the present invention can be usefully used as herbicides as already mentioned. Therefore, the use and the formulation example are demonstrated below.
    [78] [Utility]
    [79] Compounds of formula (1) exhibit excellent selectivity to rice with strong herbicidal activity and are therefore very useful as water herbicides or as components of herbicide compositions in which they are contained.
    [80] As a result, it was confirmed that the herbicides treated with field conditions before or after germination showed extremely high activity, and that they were also extremely high as non-conditioning sleeping or foliage treated herbicides.
    [81] The amount of active compound used depends on a number of factors, including the type of weed to be controlled, climate, weather, formulation, application, and weed size. In general, the amount of active ingredient used is 1g to 1kg per ha, and low doses are used when applied to soils or sandy loams with low organic content, or when plants are young or when short-term continuity is required. The field in which the compound according to the present invention can be particularly effectively used is a weed control in rice farming, and is very effective in controlling annual annual leafy weeds, herbaceous weeds, and perennial weeds, including blood.
    [82] The compound according to the present invention may be used alone, or may be mixed with known agents and used in binary, tertiary or quaternary mixtures.
    [83] [Formulation]
    [84] In the present invention, the compound of formula 1 is used in the form of a conventional composition. The compound of formula (1) may be treated in plants, soil or water, if desired, with other carriers, surfactants or dosage-enhancing additives conveniently used in the formulation art.
    [85] Suitable carriers and additives may be solid or liquid and are useful ingredients in the formulation art, such as natural or synthetic inorganics, solvents, dispersants, wetting agents, adhesives, thickeners, binders and the like.
    [86] Preferred methods of administering a composition comprising a compound of formula (1) are soil or through roots and stems by soaking the plant's habitat in liquid form or incorporating the active ingredient into the soil in solid form, e. It is to reach plants through water. Alternatively, the herbicidal activity can also be exhibited by directly administering to the leaves of the plant (foliar administration). Frequency and rate of administration depend on the plant's biological characteristics, climate and soil environment.
    [87] Combinations of compounds are in unmodified form and are used in conjunction with adjuvants that are conveniently used in the formulation art. These are processed according to known methods, for example, into emulsion concentrates, dilutable liquid formulations, liquid hydrating agents for direct sleep treatment, sleep developing agents, emulsions, hydrating agents, powders, dusting agents, granules, granules or tablets. The nature of the methods and compositions of administration, such as spraying, spraying, and spraying, are selected to suit the intended purpose and surrounding environment. The dosage of the active ingredient mixture is generally 1 g to 1 kg active ingredient / ha, preferably 10 g to 30 g active ingredient / ha.
    [88] According to known methods, the formulation is prepared by, for example, intimately mixing and / or grinding the active ingredient with an extender (eg solvent, solid carrier and, if appropriate, surface-active compound (surfactant)).
    [89] Possible solvents include: aromatic hydrocarbons such as xylene mixtures or substituted naphthalenes; Esters with alcohols such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether and glycols and ethers thereof; Ketones such as cyclohexanone, strong polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide and vegetable oils such as epoxidized or unepoxidized vegetable oils such as epoxidized coconut or soybean oil; Or water. Such solvents may be used as solvents for emulsions and liquid formulations or as cosolvents for granules.
    [90] Solid carriers commonly used in, for example, spraying agents and granular preparations are typically ground natural minerals such as talc, kaolin, montmorillonite, pyrophyllite, bentonite, or calcium carbonate or adsorbent carriers such as zeolites, or sand. In addition, many pre-pulverized inorganic or organic materials can be used.
    [91] Suitable surface-active compounds are selected from nonionic, cationic and / or anionic surfactants which exhibit good dispersion, wetting and lubricating properties depending on the nature of the compound of formula 1 to be formulated. Surfactant also means a mixture of surfactants.
    [92] The herbicide composition according to the invention comprises 0.1 to 99%, preferably 0.1 to 95%, 99.9% to 1%, preferably 99.9% to 5%, and 0 to 25% of a compound of formula 1 And preferably 0.1 to 25%.
    [93] Such compositions also form part of the present invention.
    [94] The preparation and use of the compounds according to the invention will be described in more detail with reference to the following examples. However, these examples are only for the understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense. In the examples below, C18 silica (25-40 μm, 50 mL) equilibrated with acetonitrile / water = 10/90 (v / v) was used as the stationary phase of column chromatography unless otherwise noted.
    [95] Example 1: Synthesis of erythro-N-t-butyl-4-methyl-2- (2-fluoro-1-hydroxy-n-propyl) pyridine-3-sulfonamide
    [96] Erythro-Nt-butyl-2- (2-fluoro-1-hydroxy-n-propyl) pyridine-3-sulfonamide (2.55 g) was dissolved in well-purified THF (150 mL) and -78 ° C under nitrogen gas. 2.5N n-BuLi (13.4 mL) was added slowly. The reaction temperature was raised to -20 ° C and then cooled to -78 ° C. CuI (2.10 g) was added to another flask, and the lithium salt synthesized above was reversely added to the flask. After 10 minutes, CH 3 I (0.83 mL) was added and stirred at −78 ° C. for 30 minutes and then quenched with NH 4 Cl solution. Ethyl acetate was added to the reaction mixture to separate an organic layer. Ethyl acetate was added to the aqueous layer, and the organic layers were combined, dried (MgSO 4 ), filtered and concentrated to give a crude product. This was separated by column chromatography (mobile phase: ethyl acetate / n-hexane = 1/2, v / v) to obtain 0.5 g of the pure title compound.
    [97] 1 H NMR (200 MHz, CDCl 3 ): δ 8.55 (d, 1H, J = 5 Hz), 7.24 (d, 1H, J = 5 Hz), 6.1 (br s, 1H), 4.6-4.9 (m, 3H), 2.76 (s, 3H), 1.35 (dd, 3H, J 1 = 25 Hz, J 2 = 6 Hz), 1.26 (s, 9H)
    [98] Example 2: Synthesis of erythro-4-methyl-2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3-sulfonamide
    [99] Ethlo-Nt-butyl-4-methyl-2- (2-fluoro-1-hydroxy-n-propyl) pyridine-3-sulfonamide (0.7 g) was dissolved in THF (10 mL) and methoxyacetyl chloride ( 0.32 g) was added. 60% NaH (0.13 g) was added at 0 ° C, and stirred for 2 hours at room temperature. The reaction solution was quenched with saturated NH 4 Cl aqueous solution and extracted with ethyl acetate. The organic layer was dried (MgSO 4 ), filtered and concentrated, and the residue was separated and purified by column chromatography (mobile phase: ethyl acetate / n-hexane = 1/3, v / v) to erythro-Nt-butyl-4-methyl 2- (2-Fluoro-1-methoxyacetoxy-n-propyl) pyridine-3-sulfonamide (0.7 g) was obtained.
    [100] CF 3 CO 2 H (10 mL) was added to the obtained product, the mixture was stirred at 60 to 65 ° C for 1 hour, and the reaction solution was concentrated under reduced pressure. The residue was dissolved in methylene chloride and washed with aqueous sodium bicarbonate solution. The organic layer was dried (MgSO 4 ), filtered and concentrated, and the residue was separated and purified by column chromatography (mobile phase: ethyl acetate / methylene chloride = 1/7 → 1/1, v / v) to give pure title compound 0.37 g was obtained.
    [101] 1 H NMR (200 MHz, CDCl 3 ): δ 8.57 (d, 1H, J = 5 Hz), 7.24 (d, 1H, J = 5 Hz), 6.85-6.95 (m, 1H), 5.65 (br s, 2H) , 4.9 to 5.3 (m, 1H), 4.13 (s, 2H), 3.41 (s, 2H), 2.72 (s, 3H), 1.55 (dd, 3H, J 1 = 25 Hz, J 2 = 6 Hz)
    [102] Example 3: Synthesis of erythro-N-t-butyl-4-chloro-2- (2-fluoro-1-hydroxy-n-propyl) pyridine-3-sulfonamide
    [103] Erythro-Nt-butyl-2- (2-fluoro-1-hydroxy-n-propyl) pyridine-3-sulfonamide (0.29 g) was dissolved in well-purified THF (10 mL) and nitrogen gas at -78 ° C. 2.5N n-BuLi (1.52 mL) was added slowly. The reaction temperature was raised to -20 ° C and then cooled to -78 ° C. NCS (N-chlorosuccinimide) (0.2 g) dissolved in THF (5 mL) was slowly injected into the reaction solution. After 30 minutes it was quenched with saturated aqueous ammonium chloride solution. Ethyl acetate was added to the reaction mixture to separate the organic layer, and the aqueous layer was extracted once more with ethyl acetate. The combined organic layers were dried (MgSO 4 ), filtered and concentrated to give crude product, which was then separated by column chromatography (mobile phase: ethyl acetate / n-hexane = 1/2, v / v) to give 0.18 g of the pure title compound. Obtained.
    [104] 1 H NMR (200 MHz, CDCl 3 ): δ 8.61 (d, 1H, J = 5 Hz), 7.50 (d, 1H, J = 5 Hz), 6.05-6.15 (br s, 1H), 5.2 (br s, 1H ), 4.6 to 4.9 (m, 2H), 1.35 (dd, 3H, J 1 = 25 Hz, J 2 = 6 Hz), 1.25 (s, 9H)
    [105] Example 4 Synthesis of Erythro-N-t-butyl-4-chloro-2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3-sulfonamide
    [106] Erythro-Nt-butyl-4-chloro-2- (2-fluoro-1-hydroxy-n-propyl) pyridine-3-sulfonamide (0.75 g) was dissolved in THF (10 mL) and methoxyacetyl chloride ( 0.33 g) was added. The reaction was cooled to 0 ° C. and 60% NaH (0.13 g) was added. After the reaction temperature was raised to room temperature and stirred for 2 hours, the reaction solution was quenched with an aqueous ammonium chloride solution. The reaction solution was extracted with ethyl acetate, and then the organic layer was dried (MgSO 4 ), filtered and concentrated. The residue was separated and purified by column chromatography (mobile phase: ethyl acetate / n-hexane = 1/3, v / v) to give 0.7 g of the pure title compound.
    [107] 1 H NMR (200 MHz, CDCl 3 ): δ 8.60 (d, 1H, J = 5 Hz), 7.46 (d, 1H, J = 5 Hz), 7.05 to 7.15 (m, 1H), 5.45 (br s, 1H) , 4.9 to 5.3 (m, 1H), 2.1 (s, 3H), 1.44 (dd, 3H, J 1 = 25 Hz, J 2 = 6 Hz), 1.31 (s, 9H)
    [108] Example 5: Synthesis of erythro-N-t-butyl-4-bromo-2- (2-fluoro-1-hydroxy-n-propyl) pyridine-3-sulfonamide
    [109] Erythro-Nt-butyl-2- (2-fluoro-1-hydroxy-n-propyl) pyridine-3-sulfonamide (7.0 g) was dissolved in well-purified THF (200 mL) and -78 ° C under nitrogen gas. 2.5N n-BuLi (13.4 mL) was added slowly. The reaction temperature was raised to -20 ° C and then cooled to -78 ° C. NBS (N-bromosuccinimide) (6.4 g) was added to the reaction solution, stirred for 30 minutes, and quenched with saturated aqueous ammonium chloride solution. Ethyl acetate was added to the reaction mixture to separate the organic layer, and the aqueous layer was extracted once more with ethyl acetate. The combined organic layers were dried (MgSO 4 ), filtered and concentrated to give crude product, which was then separated by column chromatography (mobile phase: ethyl acetate / n-hexane = 1/2, v / v) to give 3.9 g of the pure title compound. Obtained.
    [110] 1 H NMR (200 MHz, CDCl 3 ): δ 8.48 (d, 1H, J = 5 Hz), 7.74 (d, 1H, J = 5 Hz), 6.5 (br s, 1H), 5.39 (br s, 1H), 4.6-4.95 (m, 2H), 1.32 (dd, 3H, J 1 = 25 Hz, J 2 = 6 Hz), 1.25 (s, 9H)
    [111] Example 6: Synthesis of erythro-4-bromo-2- (2-fluoro-1-hydroxy-n-propyl) pyridine-3-sulfonamide
    [112] Erythro-Nt-butyl-4-bromo-2- (2-fluoro-1-hydroxy-n-propyl) pyridine-3-sulfonamide (0.5 g) was converted to trifluoroacetic acid (CF 3 CO 2 H; 10 ml) and stirred at 60-65 ° C. for 2 hours. The reaction solution was concentrated under reduced pressure, and the filtrate was diluted with methylene chloride and concentrated. The residue was purified by column chromatography (mobile phase: ethyl acetate / methylene chloride = 1/7 → 1/1, v / v) to give 0.3 g of the pure title compound.
    [113] 1 H NMR (200 MHz, CDCl 3 ): δ 8.49 (d, 1H, J = 5 Hz), 7.75 (d, 1H, J = 5 Hz), 6.0-6.06 (m, 1H), 5.45 (br s, 2H) , 4.15 to 4.55 (m, 1H), 3.46 (br s, 1H), 1.53 (dd, 3H, J 1 = 25 Hz, J 2 = 6 Hz)
    [114] Example 7: erythro-N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-chloro-2- (2-fluoro-1-methoxyacetoxy-n- Propyl) synthesis of pyridine-3-sulfonamide
    [115] Dissolve erythro-4-chloro-2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3-sulfonamide (0.5 g) in acetonitrile (10 mL) and add phenyl (4,6- Dimethoxypyrimidin-2-yl) carbamate (0.86 g) was added at room temperature. After slowly injecting DBU (0.48 g), the reaction solution was stirred for 30 minutes, diluted with methylene chloride (100 mL), and washed with 5% aqueous hydrochloric acid solution (50 mL). The organic layer was dried (MgSO 4 ), filtered and concentrated and the residue was recrystallized from diethyl ether / n-hexane to give 0.61 g of the pure title compound as a white solid.
    [116] Melting Point: 135 ~ 140 ℃
    [117] 1 H NMR (200 MHz, CDCl 3 ): δ 13.2 (br s, 1H), 8.63 (d, 1H, J = 5 Hz), 7.45 (d, 1H, J = 5 Hz), 7.2-7.4 (m, 2H), 5.81 (s, 1H), 4.82 to 5.22 (m, 1H), 3.97 (s, 6H), 1.44 (dd, 3H, J 1 = 25 Hz, J 2 = 6 Hz)
    [118] Example 8 erythro-N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-bromo-2- (2-fluoro-1-methoxyacetoxy-n Synthesis of -propyl) pyridine-3-sulfonamide
    [119] Erythro-4-bromo-2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3-sulfonamide (0.82 g) and phenyl (4,6-dimethoxypyrimidine-2 -Yl) carbamate (0.86 g) was reacted according to the method of Example 7 to yield 0.85 g of the title compound as a white solid.
    [120] Melting Point: 87-89 ℃
    [121] 1 H NMR (200 MHz, CDCl 3 ) δ 8.49 (d, 1H, J = 5 Hz), 7.65 (d, 1H, J = 5 Hz), 7.23 (s, 1H), 7.02-7.1 (m, 1H), 5.80 ( s, 1H), 5.22-5.58 (m, 1H), 4.13 (s, 2H), 3.96 (s, 6H), 3.41 (s, 3H), 1.48 (dd, 3H, J 1 = 25 Hz, J 2 = 6 Hz )
    [122] Example 9: erythro-N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-methyl-2- (2-fluoro-1-methoxyacetoxy-n- Propyl) Synthesis of Pyridine-3-Sulfonamide
    [123] Erythro-4-methyl-2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3-sulfonamide (0.73 g) and phenyl (4,6-dimethoxypyrimidine-2- I) carbamate (0.86 g) was reacted according to the method of Example 7 to obtain 0.75 g of the title compound as a white solid.
    [124] Melting Point: 156-158 ℃
    [125] 1 H NMR (200 MHz, CDCl 3 ) δ 8.58 (d, 1H, J = 5 Hz), 7.23 (d, 1H, J = 5 Hz), 7.21 (br s, 1H), 6.65-6.75 (m, 1H), 5.78 (s, 1H), 5.05-5.38 (m, 1H), 4.13 (s, 2H), 3.97 (s, 6H), 3.41 (s, 3H), 2.89 (s, 3H), 1.47 (dd, 3H, J) 1 = 25 Hz, J 2 = 6 Hz)
    [126] Example 10 erythro-2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3-sulfonamide and threo-2- (2-fluoro-1-methoxyacetoxy- Synthesis of n-propyl) pyridine-3-sulfonamide
    [127] Nt-butyl-2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3-sulfonamide (5.0 g), which is a 1: 1 mixture of erythro and threoisomers, was treated with trifluoroacetic acid ( 20 ml), stirred at 45 ° C. for 12 hours, and then the reaction solution was concentrated under reduced pressure and the residue was dissolved in methylene chloride. The solution was washed with an aqueous solution of sodium bicarbonate, and then the organic layer was dried over anhydrous magnesium sulfate, and the residue was separated by column chromatography (mobile phase: ethyl acetate / methylene chloride = 1/7 → 1/1, v / v) to pure erythride. 1.0 g of the title title compound and 1.0 g of the pure threotype title compound were obtained in the solid phase, respectively.
    [128] Erythro compounds
    [129] 1 H NMR (200 MHz, CDCl 3 ): δ 8.82-8.85 (m, 1H), 8.35-8.38 (m, 1H), 7.43-7.50 (m, 1H), 6.60-6.72 (m, 1H), 5.68 ( brs, 2H), 4.93-5.29 (m, 1H), 4.18 (s, 2H), 3.2 (s, 3H), 1.55 (dd, 3H, J HH = 6.5 Hz, J HF = 25 Hz),
    [130] Threo compounds
    [131] 1 H NMR (270 MHz, CDCl 3 ): δ 8.82-8.85 (m, 1H), 8.35-8.38 (m, 1H), 7.43-7.50 (m, 1H), 6.60-6.72 (m, 1H), 5.58 ( brs, 2H), 5.29-5.40 (m, 1H), 4.18 (s, 2H), 3.43 (s, 3H), 1.20 (dd, 3H, J HH = 6.5 Hz, J HF = 25 Hz)
    [132] Example 11: Synthesis of erythro-2- (2-fluoro-1-hydroxyacetoxy-n-propyl) pyridine-3-sulfonamide
    [133] Dissolve erythro-2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3-sulfonamide (0.5 g) in chloroform (10 mL), add iodotrimethylsilane (0.9 mL), and Stir at 60 ° C. for 12 h. After concentrating the reaction solution, column chromatography (mobile phase: CH 3 CN / H 2 O = 10/90, v / v) was performed using C 18 silica (50 mL) to obtain 0.22 g of the title compound.
    [134] Melting Point: 142-143 ℃
    [135] 1 H NMR (200 MHz, D 2 O): δ 8.82-8.85 (m, 1H), 8.35-8.38 (m, 1H), 7.43-7.50 (m, 1H), 5.0-5.4 (m, 1H), 4.4 ( d, 2H), 1.55 (dd, 3H)
    [136] Example 12 Synthesis of Erythro-2- (2-fluoro-1- (3-methoxypropion) oxy-n-propyl) pyridine-3-sulfonamide
    [137] Erythro-Nt-butyl-2- (2-fluoro-1- (3-methoxypropion) oxy-n-propyl) pyridine-3-sulfonamide (5.0 g) was reacted according to the method of Example 10 to give the title 2.0 g of compound were obtained.
    [138] 1 H NMR (200 MHz, CDCl 3 ): δ 8.82-8.85 (m, 1H), 8.35-8.38 (m, 1H), 7.43-7.50 (m, 1H), 6.60-6.72 (m, 1H), 5.75 ( brs, 2H), 4.93-5.29 (m, 1H), 3.62 (t, 2H), 3.3 (s, 3H), 2.7 (m, 2H), 1.55 (dd, 3H)
    [139] Example 13: Synthesis of erythro-2- (2-fluoro-1- (3-hydroxypropion) oxy-n-propyl) pyridine-3-sulfonamide
    [140] Erythro-2- (2-fluoro-1- (3-methoxypropion) oxy-n-propyl) pyridine-3-sulfonamide (0.56 g) was reacted according to the method of Example 11 to obtain 0.12 g of the title compound. Obtained.
    [141] 1 H NMR (200 MHz, D 2 O): δ 8.8 (m, 1H), 8.4 (m, 1H), 7.45 (m, 1H), 6.9 (brs, 2H), 6.75 (m, 1H), 5.0-5.3 (m, 1H), 3.8 (m, 2H), 2.6 (t, 2H), 1.55 (dd, 3H)
    [142] Example 14 erythro-N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine- Synthesis of 3-sulfonamide
    [143] Dissolve erythro-2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3-sulfonamide (3.9 g) in acetonitrile (20 mL) and phenyl (4,6-dimethoxypy). Rimidin-2-yl) carbamate (3.57 g) was added followed by the slow injection of triethylamine (1.32 g). The reaction solution was stirred for 2 hours and diluted with methylene chloride (20 mL). Washed with 5% aqueous hydrochloric acid solution (10 mL) and water (10 mL), and the organic layer was dried over magnesium sulfate, filtered, and concentrated. The residue was recrystallized from ethyl acetate / hexane / diethyl ether to give 4.5 g of the title compound.
    [144] Melting Point: 175-177 ℃
    [145] 1 H NMR (200 MHz, CDCl 3 ): δ 13.2 (br, 1H), 8.8 (m, 1H), 8.6 (m, 1H), 7.5 (m, 1H), 7.2 (br, 1H), 6.6 (m , 1H), 5.80 (s, 1H), 5.0-5.3 (m, 1H), 4.05 (s, 2H), 3.96 (s, 6H), 3.25 (s, 3H), 1.45 (dd, 3H)
    [146] Example 15: Sreo-N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine Synthesis of 3-Sulfonamide
    [147] Threo-2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3-sulfonamide (1.56 g) and phenyl (4,6-dimethoxypyrimidin-2-yl) carba The mate (2.99 g) was reacted according to the method of Example 14 to obtain 1.8 g of the title compound as a white solid.
    [148] Melting Point: 152-154 ℃
    [149] 1 H NMR (200 MHz, CDCl 3 ): δ 13.2 (br, 1H), 8.81 (m, 1H), 8.67 (m, 1H), 7.50 (m, 1H), 7.49 (br, 1H), 6.67 (m , 1H), 5.80 (s, 1H), 5.0-5.3 (m, 1H), 4.05 (s, 2H), 3.96 (s, 6H), 3.25 (s, 3H), 1.28 (dd, 3H)
    [150] Example 16: erythro-N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (2-fluoro-1-hydroxyacetoxy-n-propyl) pyridine- Synthesis of 3-sulfonamide
    [151] Erythro-2- (2-fluoro-1-hydroxyacetoxy-n-propyl) pyridine-3-sulfonamide (1.2 g) and phenyl (4,6-dimethoxypyrimidin-2-yl) carbamate (1.33 g) was reacted according to the method of Example 14 to obtain 1.5 g of the title compound as a white solid.
    [152] Melting Point: 157-158 ℃
    [153] 1 H NMR (200 MHz, CDCl 3 ): δ 8.8 (m, 1H), 8.05 (m, 1H), 7.5 (m, 1H), 6.7-6.8 (m, 1H), 5.80 (s, 1H), 5.0 -5.3 (m, 1H), 4.2 (m, 2H), 3.95 (s, 6H), 1.45 (dd, 3H)
    [154] Example 17 erythro-N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (2-fluoro-1- (3-hydroxypropion) oxy-n- Propyl) synthesis of pyridine-3-sulfonamide
    [155] Erythro-2- (2-fluoro-1- (3-hydroxypropion) oxy-n-propyl) pyridine-3-sulfonamide (0.11 g) and phenyl (4,6-dimethoxypyrimidine-2- I) carbamate (0.18 g) was reacted according to the method of Example 14 to obtain 0.13 g of the title compound.
    [156] Melting Point: 147-148 ℃
    [157] 1 H NMR (200 MHz, CDCl 3 ): δ 13.3 (br, 1H), 8.8 (m, 1H), 8.65 (m, 1H), 7.6 (m, 1H), 7.3 (br, 1H), 5.80 (s , 1H), 5.0-5.3 (m, 1H), 3.96 (s, 6H), 3.6-3.9 (m, 2H), 3.4 (br, 1H), 2.6 (m, 2H), 1.45 (dd, 3H)
    [158] Example 18 erythro-N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] 2- (2-fluoro-1- (3-methoxypropion) oxy-n-propyl Synthesis of Pyridine-3-Sulfonamide
    [159] Erythro-2- (2-fluoro-1- (3-methoxypropion) oxy-n-propyl) pyridine-3-sulfonamide (0.29 g) and phenyl (4,6-dimethoxypyrimidine-2- I) carbamate (0.53 g) was reacted according to the method of Example 14 to obtain 0.35 g of the title compound.
    [160] Melting Point: 145-146 ℃
    [161] 1 H NMR (200 MHz, CDCl 3 ): δ 8.8 (m, 1H), 8.6 (m, 1H), 7.5 (m, 1H), 7.2 (br, 1H), 6.6 (m, 1H), 5.80 (s , 1H), 4.95-5.25 (m, 1H), 3.95 (s, 6H), 3.45 (t, 2H), 3.2 (s, 3H), 2.5 (m, 2H), 1.5 (dd, 3H)
    [162] Example 19
    [163] The herbicidal effects of the compounds according to the invention and known control compounds shown in Table 2 were assayed in a greenhouse.
    [164]
    [165] Effect, weakness experiment
    [166] Pots with a surface area of 150 cm 2 contained small amounts of fertilizer and sterile sterilized paddy soil 5 cm deep. Five rice seeds, which were minimized, were straightened on the soil surface, and the seedlings of rice seedlings (2 to 3 blades), which had been seeded beforehand, were transferred to a depth of 2 cm, each of 3 pieces per pot. In other pots, seed was sown on the soil surface and incorporated into the soil. After rice sowing, transplanting and sowing, fresh water was grown to a depth of 3 cm and grown in a greenhouse. Rice was treated with the medicine 5 days after sowing and transplanting, and blood was treated within 5 days before sowing, and after germination, when the blood germinated and became 3 leaves (usually 15 days after sowing) It was.
    [167] Preparation of the treatment drug was prepared by mixing 1 part by weight of the active compound with 5 parts by weight of acetone and 1 part by weight of alkylaryl polyglycol ether as an emulsifier, and then diluting with water to a desired concentration.
    [168] After 2 weeks of treatment, the effects on rice and weeds were assessed as a percentage (%) compared to the untreated controls, with 0% being either invalid or unaffected (same as untreated). 100% represents a complete test.
    [169] The non-conditional weakness and efficacy of the compound of formula 1 according to the present invention and known controls are shown in Tables 3a and 3b, respectively.
    [170] Control compound E is pyrazosulfuron-ethyl and is currently the most widely used herbicide. On the other hand, the control materials A, B, C and D is a patent application material having a structure most similar to the compound of the formula (1) according to the present invention.
    [171] Efficacy and Weakness in Paddy Field Conditions of Control compoundRice ( Oryza sativa )Blood ( Echinochloa crus-galli ) Dose (g / ha)Straight wave (before germination)Yiang (Tree Season)Dose (g / ha)GerminationTrifoliate Control A80807030100100 4050402010095 2040301010090 10402056060 Control substance B80706030100100 4050402010090 2040201010090 10302055050 Control C80705030100100 40303020100100 2020201010090 10101054060 Control D80605030100100 40302020100100 2020101010090 1010053050 Control substance E (Pyrazosulfuron-ethyl)803010303020 4020020200 2010010100 1000500
    [172] Experimental results show that the usual dosage of Control E is 20 g / ha, which is almost safe for rice (10%) and less than 30% even for upright rice. However, control substance E was hardly recognized in the amount used (20 g / ha) for blood, the most important weed in rice farming (less than 10%).
    [173] On the contrary, the control substances A ~ D showed very high activity against blood, and at the dose of 20g / ha or more, it showed more than 95% control effect regardless of the pre-emergence or post-emergence (trifoliate) treatment. These control substances (A ~ D) showed a selectivity of 10 to 40% of the harmful to the rice at 20 g / ha level depending on the drug. However, in practice, it is possible to develop only when the dose is higher than 4 times in order to secure safety. The control substances A ~ D showed 50-80% of weakness at 80g / ha, which is 4 times the dose, and practical development was impossible.
    [174] Efficacy and Weakness in Non-conditioning of Compounds According to the Invention compoundRice ( Oryza sativa )Blood ( Echinochloa crus-galli ) Dose (g / ha)Straight wave (before germination)Yiang (Tree Season)Dose (g / ha)GerminationTrifoliate Compound 18030203090100 403010209090 201010108080 100055060 Compound 280301030100100 40201020100100 20001010090 100056050 Compound 380302030100100 403020209590 201010109080 100556060 Compound 480302030100100 40201020100100 2000109590 100056060 Compound 580302030100100 40200209090 20100108070 100055060 Compound 680202030100100 401002010090 2000108070 100056050 Compound 780302030100100 402010209095 2000108080 100056050
    [175] On the other hand, the compound of the formula (1) according to the present invention was found to be a compound that significantly improved the damage to rice while maintaining excellent control of the blood possessed by the control materials A ~ D. As shown in Table 3b, the compound of the present invention showed more than 90% of the blood control value at 20 g / ha depending on the medicinal agent, and was excellent in safety with less than 30% even at 80 g / ha for rice, comparable to Control E.
    [176] Unconditional weed spectrum experiment
    [177] In the above-mentioned method, the soil was contaminated in a pot of 500㎡ of surface area, and the annual weed seeds such as water cane, field grass, node flower, and tadpole were mixed on the soil surface. The tubers of scallops and peels were planted to a depth of 4 cm. 5 days after sowing, the drug was prepared in the same manner as in the above-described method, dipped into the water and irradiated 2 weeks after the treatment. The results are shown in Table 4.
    [178] Weed Spectrum in Non-conditioning of Compounds According to the InventionDose (g / ha)AnnualPerennial Water pinnacleBattlingFlowerTadpoleYou tooOlmeAll fivePeel Compound 220100100100100100959590 Compound 420100100100100100909585
    [179] From the results of Table 4, it was confirmed that the compounds according to the present invention also well control various annual and perennial weeds occurring in paddy fields besides blood.
    [180] In conclusion, the compounds according to the present invention effectively control annual and perennial weeds, including blood, as a new herbicide by pre- and post-germination treatments, and have excellent safety against rice paddy and direct weave. It is expected to be.
    权利要求:
    Claims (12)
    [1" claim-type="Currently amended] Pyridinesulfonylurea derivatives of formula (1), salts or stereochemical isomers thereof
    [Formula 1]
    In the above formula
    n represents an integer of 1 to 3,
    R represents H or C 1 -C 4 -alkyl,
    R 'represents H or C 1 -C 4 -alkyl, C 1 -C 3 -haloalkyl, halogen or C 1 -C 2 -alkoxy,
    X and Y each independently represent C 1 -C 2 -alkyl, C 1 -C 2 -alkoxy, C 1 -C 2 -haloalkoxy or halogen.
    [2" claim-type="Currently amended] The compound of claim 1, wherein n is an integer of 1 or 2, R is H or methyl, R 'is H, halogen or methyl, and X and Y are each methoxy.
    [3" claim-type="Currently amended] The compound of claim 1, wherein n is an integer of 1 or 2, R is methyl, R 'is H, Cl, Br or methyl, and X and Y are each methoxy.
    [4" claim-type="Currently amended] The method of claim 1,
    N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3-sulfonamide,
    N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (2-fluoro-1-hydroxyacetoxy-n-propyl) pyridine-3-sulfonamide,
    N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (2-fluoro-1- (3-hydroxypropion) oxy-n-propyl) pyridine-3- Sulfonamide,
    N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (2-fluoro-1- (3-methoxypropion) oxy-n-propyl) pyridine-3- Sulfonamide,
    N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-methyl-2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3- Sulfonamide,
    N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-chloro-2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3- Sulfonamides, and
    N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-bromo-2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3 A compound selected from the group consisting of sulfonamides.
    [5" claim-type="Currently amended] The compound according to claim 1, which is in erythro stereoisomeric form.
    [6" claim-type="Currently amended] A compound of formula
    [Formula 6]
    In the above formula
    n, R and R 'are as defined in claim 1.
    [7" claim-type="Currently amended] The compound of claim 6, which is 2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3-sulfonamide.
    [8" claim-type="Currently amended] A process for preparing a compound of formula 1 as defined in claim 1 characterized in that the compound of formula 6 is reacted with a compound of formula 7 in the presence or absence of a base in a solvent:
    [Formula 6]
    [Formula 7]
    In the above formula
    n, R, R ', X and Y are as defined in claim 1.
    [9" claim-type="Currently amended] The compound of claim 8, wherein the base is triethylamine, hexamethylenetetraamine, pyridine, 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU) or 1,4-diazabicyclo How to use [2,2,2] octane (DABCO).
    [10" claim-type="Currently amended] A herbicide composition for weed control comprising the compound of formula 1 as defined in claim 1 as an active ingredient together with a carrier.
    [11" claim-type="Currently amended] The composition of claim 10 wherein the compound of Formula 1 is n is an integer of 1 or 2, R is H or methyl, R 'is H, halogen or methyl, and X and Y are each compound representing methoxy.
    [12" claim-type="Currently amended] A method of using the compound of formula 1 as defined in claim 1 to control weeds for rice or wheat in paddy or field conditions.
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    同族专利:
    公开号 | 公开日
    KR100399366B1|2003-09-26|
    TWI258477B|2006-07-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-10-12|Application filed by 성재갑, 주식회사 엘지씨아이
    2000-10-12|Priority to KR10-2000-0059990A
    2002-04-18|Publication of KR20020029177A
    2003-09-26|Application granted
    2003-09-26|Publication of KR100399366B1
    优先权:
    申请号 | 申请日 | 专利标题
    KR10-2000-0059990A|KR100399366B1|2000-10-12|2000-10-12|Herbicidally active pyridine sulfonyl urea derivatives|
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