JPH07611B2 - Pyridine derivative, method for producing the same, and herbicide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a compound of the general formula (I): [In the formula, W represents an oxygen atom or a sulfur atom. X is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms
Lower alkoxymethyl group, lower alkylthiomethyl group having 1 to 4 carbon atoms, lower haloalkyl group having 1 to 4 carbon atoms,
A lower alkylsulfonylmethyl group having 1 to 4 carbon atoms, a benzyl group, an optionally substituted phenyl group or a pyridyl group (as the substituent, a lower alkyl group having 1 to 4 carbon atoms, a lower alkyl group having 1 to 4 carbon atoms) Represents an alkoxy group, a halogen atom, a nitro group, a cyano group or a trifluoromethyl group.).

Y is an oxygen atom, a sulfur atom, a mono-substituted nitrogen atom (as the substituent, a lower alkyl group having 1 to 4 carbon atoms, 1 carbon atom)
To 4 lower alkoxy groups, 1 to 4 carbon lower alkoxycarbonylamino groups or optionally substituted phenyl groups or pyridyl groups (this substituent includes 1 to 4 carbon lower alkyl groups, 1 carbon atoms 4 represents a lower alkoxy group, a halogen atom, a nitro group, a cyano group or a trifluoromethyl group. } Or a di-substituted carbon atom {the di-substituents are each independently a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower haloalkyl group having 1 to 4 carbon atoms, or 3 to 6 carbon atoms. Cycloalkyl group or optionally substituted phenyl group or pyridyl group (this substituent has 1 to 4 carbon atoms)
Lower alkyl group, lower alkoxy group having 1 to 4 carbon atoms,
Indicates a halogen atom, nitro group, cyano group or trifluoromethyl group. ) Further, the di-substituents are taken together to form a ring and represent a cycloalkyl group having 3 to 6 carbon atoms which may be substituted by a lower alkyl group having 1 to 3 carbon atoms. } Is represented.

R is a hydrogen atom, a di-lower alkylimino group, an optionally substituted lower alkyl group having 1 to 5 carbon atoms (as the substituent, a lower alkoxy group having 1 to 3 carbon atoms, a hydroxy group, a carbon number 3) ~ 6 halocycloalkyl group, carboxyl group, lower alkoxycarbonyl group, cyano group, dialkylphosphonyl group, halogen atom, benzyloxy group, tri-lower alkylammonium group or optionally halogen atom, lower alkyl having 1 to 4 carbon atoms Group, carbon number 1
4 shows a phenyl group which may be substituted with a lower alkoxy group or a nitro group. ), An optionally substituted lower alkenyl group having 2 to 5 carbon atoms (as the substituent, a lower alkoxy group having 1 to 3 carbon atoms, a lower alkoxycarbonyl group, two lower alkoxy groups having 1 to 3 carbon atoms) Group, or a phenyl group), a lower alkynyl group having 2 to 5 carbon atoms, an oxacycloalkyl group having 5 to 6 carbon atoms, and 2 carbon atoms
-5 mono-, di- or trihaloalkenyl groups, haloalkynyl groups having 2-5 carbon atoms, glycidyl groups, alkylthioalkyl groups, cycloalkyl having 3-6 carbon atoms which may be substituted with alkyl groups having 1-3 carbon atoms Represents a group or a cation selected from alkali metal atoms, alkaline earth metal atoms, ammonium or organic ammonium.

R ¹ represents a lower alkyl group having 1 to 4 carbon atoms.

R ² is a lower alkyl group having 1 to 4 carbon atoms or 3 to 4 carbon atoms
6 represents a cycloalkyl group.

Further, R ¹ and R ² represent a cycloalkyl group having 3 to 6 carbon atoms, which can form a ring together and which may be substituted with a lower alkyl group having 1 to 3 carbon atoms.

R ³ is a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms.
Represents an alkylthio group, a phenoxy group, a haloalkyl group having 1 to 4 carbon atoms, a haloalkoxy group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms. ] The pyridine derivative represented by or an optical isomer of the derivative (provided that R ¹ and R ² are not the same), a method for producing these, and a derivative or an optical isomer of the derivative (provided that R ¹ and R ²
R ² is not the same) as an active ingredient.

The compound of the present invention is a novel compound not described in the literature and has excellent physiological activity as a herbicide. Conventionally, it has been generally pointed out that the economic cost of using a herbicide depends on the amount of the active ingredient treated per unit area when using the herbicide. The research of the compound showing is has been continued for many years.

As a result of many years of study, the present inventors have found that the compounds of the present invention have a significantly higher herbicidal effect than conventional herbicides, and most of the compounds of the present invention are contained in some crops, particularly legumes such as soybeans. The present invention has been found to be practically useful because it has selectivity for crops such as

That is, the compound of the present invention can significantly reduce the amount of the active ingredient dropped per unit area as compared with these conventionally known compounds, its economic effect is extremely large as compared with the conventional herbicides, and moreover, a large amount of pesticides is used. It can be said to be an epoch-making herbicide that can significantly reduce the risk of environmental pollution due to application.

The compound (I) of the present invention represented by the general formula (I) can be easily produced by the following reaction.

Reaction formula 1 (In the formula, W, X, Y, R, R ¹ , R ² and R ³ have the same meanings as described above.) That is, 1 to 10 equivalents of the pyridine derivative (II) (R = H) is hydroxylated. Heating to a temperature between room temperature and 100 ° C in an aqueous solution of an alkali metal hydroxide such as sodium, potassium hydroxide or magnesium hydroxide or an alkaline earth metal hydroxide having a concentration between 1% and 50%. Thus, the compound (I) of the present invention (R = Na, K, Mg, etc.) is obtained. The compound (I) of the present invention (R = H) is obtained by neutralizing this with a mineral acid such as hydrochloric acid or sulfuric acid.

By treating this with ammonia and organic amine,
The compound (I) of the present invention (R = ammonium, cation of organic ammonium) is obtained.

The compound (I) of the present invention can be obtained by esterifying the compound (I) of the present invention (R = H) with an alcohol ROH corresponding to various R in an acid catalyst. Alternatively, the compound (I) (R = H 3) of the present invention is treated with diazomethane in an inert solvent, or treated with dimethyl sulfate and Meyerbaine reagent to obtain the compound (I) (R = CH ₃ ) of the present invention. Further, the compound (I) of the present invention can be obtained by transesterification thereof with an alcohol ROH corresponding to various R. The starting pyridine derivative (II) (R = H) can be synthesized according to the synthetic route of the following [Method A].

[Method A] (In the formula, W, X, Y, R ¹ , R ² and R ³ have the same meanings as above.) That is, Synthesis. 902. Published in 1983 (Synthesis 9
02 (1983)), Chemical Reviews. 161 pages. Published 1964 (Chem Rev.161 (1964)), Chemical and Pharmaceuticals. Bretan. 26, 1201, published in 1978 (C
The compound (III) (Y = carbonyl group) can be synthesized in high yield by referring to the method described in hem, pharm. Bull 26 1201 (1978), etc. Also, Journal of the American Chemical Society, Vol. 73, page 4380.
Published 1951 (Journal of the American Chemical Socie
ty 73 4380 (1951), Journal of the American Chemical Society, Vol. 74, p. 1489, published in 1952 (Jo
urnal of the American Chemi-cal Society 74 1489 (1
952)) with reference to compound (III) (Y = oxygen atom)
By reacting ethoxymethylene oxaloacetate with a suitable solvent (eg, diethyl ether, ethanol, acetic acid, benzene, etc.), the pyridine-2,3-dicarboxylic acid diester (IV) (Y = oxygen atom) yields a high yield. You get at a rate.

Corresponding dicarboxylic acid compound (V) by treating diester compound (IV) (Y = oxygen atom) with a water-alcohol solution containing 2 equivalents or more of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. (Y = oxygen atom) is obtained.

Further, the diester (IV) (Y = oxygen atom) is reduced in a suitable solvent, preferably diethyl ether, methanol or a metal hydride such as sodium borohydride in a water solvent, and the obtained compound is appropriately dehydrated. agent, preferably sulfuric acid, can be sulfate, compound by dehydrating with p-toluenesulfonic acid ^{(IV) (Y = R 5} -C-R 6) is synthesized.

Sodium hydroxide or 2 equivalents of diester of ^{(IV) (Y = R 5} -C-R 6), water containing an alkali metal hydroxide such as potassium hydroxide - by treating with an alcohol solution, or diesters obtaining a body (IV) the corresponding dicarboxylic acid derivative by ^{(Y = R 5 -C-R} 6) is treated with a mineral acid such as sulfuric acid ^{(V) (Y = R 5} -C-R 6).

The dicarboxylic acid derivative (V) thus obtained is heated with acetic anhydride, trifluoroacetic anhydride or the like to a temperature between room temperature and reflux temperature, preferably 60 to 100 ° C. Object (VI) is obtained. Carboxamide derivative (II) (R = H) by reacting acid anhydride (VI) with α-aminoamide compound (VII) in an inert solvent (eg, acetonitrile, acetone, methylene chloride, pyridine, picoline, etc.) Can be obtained.
Carboxamide derivative (II ′) (R =
H) may be produced as a by-product.

(In the formula, W, X, Y, R, R ¹ , R ² and R ³ have the same meanings as described above.) Reaction formula 2 (In the formula, W, X, Y, R, R ¹ , R ² and R ³ have the same meanings as described above.) That is, if a pyridine derivative (II) (R = methyl or ethyl) or the like is necessary, benzene is used. The compound (I) of the present invention (R = methyl or ethyl) can be obtained by treatment with phosphorus oxychloride, phosphorus pentachloride, sodium hydride or the like in an inert solvent such as hexane, hexane or ether.

The compound (I) of the present invention (R = methyl or ethyl) can be converted to the compound (I) of the present invention by hydrolysis or by esterification, transesterification or the like as shown in Reaction Scheme 1. . Raw pyridine derivative (I
I) (R = methyl or ethyl) can be synthesized according to the synthetic route of the following [Method B].

[Method B-1] [Method B-2] (In the formula, W, X, Y, R, R ¹ , R ² and R ³ have the same meanings as described above.) That is, the half-ester form (VIII) (R = methyl or ethyl) is the corresponding diester (IV ) (R = ethyl)
Semi-hydrolysis reaction or acid anhydride (VI) methanol,
Alternatively, it can be synthesized by ethanol decomposition. Compound (VIII)
(R = methyl or ethyl) is converted to an acid chloride with thionyl chloride or the like, or converted to an active ester with chloroformate or the like, and then reacted with α-aminoamide (VII) to give compound (II) (R = methyl or ethyl). Or ethyl) can be obtained. Or acid anhydride (VI)
-The compound (X) is obtained by reacting with aminonitrile (IX) in an inert solvent, removing the solvent, and heating with acetic anhydride solvent in the presence of catalytic amounts of sodium acetate and potassium acetate.

Then, the compound (XI) (W = O) is obtained by treating with a strong acid such as sulfuric acid, if necessary, in a halogenated hydrocarbon solvent such as chloroform, methylene chloride, carbon tetrachloride and the like. The compound (II) (R ≠ H) is obtained by treating the compound (XI) (W═O) thus obtained with an alkoxy anion corresponding to R in an alcohol solvent corresponding to R.
Is obtained.

Reaction formula 3 (In the formula, W, X, Y, R, R ¹ , R ² and R ³ have the same meanings as described above.) That is, the compound (XII) or (XIII) is treated with an inert aprotic solvent such as tetrahydrofuran or dioxane. Alcohol ROH corresponding to various R, etc.
If necessary at a temperature between 0 ° C and 50 ° C, the compound (I) of the present invention can be obtained by adding an organic base such as sodium hydride or triethylamine as a catalyst and reacting.

The compounds (XII) and (XIII) as raw materials are the following [Method C].
Can be synthesized according to the synthetic route of.

[C method]

(In the formula, W, X, Y, R, R ¹ , R ² and R ³ have the same meanings as described above.) Compound (I) (R = H) is mixed with dicyclohexylcarbodiimide (DCC), acetic anhydride and trihydrate. If necessary, a dehydration condensing agent such as fluoroacetic acid is allowed to act in a halogenated hydrocarbon or an ether (eg, tetrahydrofuran) solvent, or the compound (XI) is hydrogenated in an aromatic hydrocarbon solvent such as benzene, toluene, or xylene. Alkali metal hydrides such as sodium, 1,8-diazabicyclo [5.4.0]-
Compounds (XII) and (XIII) can be obtained by treating with a base such as 7-undecene (DBU).

Intermediate compound (II) (II ') used in the present invention
(IV) [However, (X = CH ₃ , Y = O, R ³ = CH ³ ) is excluded],
(V) [However, (X = CH ₃ , Y = O, R ³ = CH ₃ ) is excluded],
(VI) (VIII) (X) (XI) (XII) (XIII) are novel compounds.

This will be specifically described by the following synthesis example.

Synthesis example 1 1-Amino-1-buten-3-one 10.0 g (0.118 mol), ethylethoxymethylene oxaloacetate 28.0
g (0.115 mol) was dissolved in 50 ml of diethyl ether and stirred at room temperature for 12 hours. A saturated aqueous solution of sodium hydrogen carbonate was added to the reaction solution, extracted with diethyl ether, washed with water, dried and the solvent was distilled off to obtain a crude product of the title compound, which was distilled and purified under reduced pressure to obtain 14.0 g of the title compound. (0.054
A yield of 47% was obtained.

[Light yellow liquid, boiling point 160-183 ℃ (0.3mmHg), refractive index ▲ n
²⁰ _D ▼ 1.5170, PMR (δ value (CDCl ₃ )): 1.41 (t, J = 6.5Hz, 3
H), 1.38 (t, J = 6.5Hz, 3H) 2.17 (8,3H), 4.40 (q, J =
6.5Hz, 2H), 4.51 (q, J = 6.5Hz, 2H), 8.67 (d, J = 2Hz, 1
H), 9.23 (d, J = 2Hz, 1H)] Synthesis example 2 1-phenyl-3-amino-2-propen-1-one 1
4.7 g (0.10 mol) and 22.0 g (0.098 mol) of ethylethoxymethylene oxaloacetate were dissolved in tetrahydrofuran, stirred at room temperature for 5 hours, heated to reflux temperature, and further reacted for 1 hour. After distilling off the solvent under reduced pressure, saturated aqueous sodium hydrogencarbonate solution was added to the reaction solution, extraction was performed with diethyl ether, the organic layer was washed with water, dried and the solvent was distilled off to obtain a crude product of the title compound. This was purified by column chromatography to give 24.0 g (0.0
A yield of 75% was obtained.

[Light yellow crystal, PMR (δ value (CDCl ₃ ) 1: 1.37 (t, J = 6.5Hz, 3
H), 1.41 (t, J = 6.5Hz, 3H), 4.38 (q, J = 6.5Hz, 2H), 4.
45 (q, J = 6.5Hz, 2H), 7.30 to 8.10 (m, 5H), 8.48 (d, J =
2Hz, 1H), 8.96 (d, J = 2Hz, 1H)] Synthesis example 3 0.5 g of sodium borohydride was added to a solution of 6.0 g (0.023 mol) of pyridinecarboxylic acid diethyl ester synthesized in Synthesis Example 1 in 100 ml of methanol, and the mixture was stirred at room temperature for 3 hours, diluted hydrochloric acid was added to the reaction solution, and the mixture was extracted with diethyl ether. did. The organic layer was washed with water, dried and the solvent was distilled off to obtain 5.4 g (0.020 mol) of a crude alcohol product in a yield of 88%. Crude alcohol product (5.4 g, 0.020 mol), paratoluene sulfonic acid (0.1 g) and xylene (50 ml) were reacted at reflux temperature for 24 hours while separating water using a moisture meter. After cooling, the solvent was distilled off under reduced pressure, water was added and the mixture was extracted with chloroform. The organic layer was washed with water, dried and the solvent was distilled off to obtain a crude product of the title compound, which was purified by column chromatography. Thus, 1.85 g (0.074 mol) of the title compound was obtained in a yield of 37%.
[Oil, refractive index ▲ n ²⁰ _D ▼ 1.5106, PMR (δ value (CDCl ₃ )):
1.40 (t, J = 6Hz, 3H), 1.38 (t, J = 6Hz, 3H), 4.42 (q, J
= 6Hz, 2H), 4.38 (q, J = 6Hz, 2H), 5.50 (d, J = 11Hz, 1
H), 5.74 (d, J = 17Hz, 1H), 6.77 (dd, J = 11Hz, 17Hz, 1
H), 8.12 (d, J = 2Hz, 1H), 8.70 (d, J = 2Hz, 1H)] Synthesis example 4 5-Acetyl-6-methylpyridine-2,3-dicarboxylic acid diethyl ester 10.0 g (0.036 mol) of methanol 10
After adding 0.7 g of sodium borohydride to the 0 ml solution and stirring at room temperature for 3 hours, the reaction solution was acidified with diluted hydrochloric acid and extracted with diethyl ether. The organic layer was dried and the solvent was distilled off to give a crude alcohol product 9.6 g (0.034 mol) yield 95
Earned%. [PMR (δ value (CDCl ₃ )): 1.35 (t, J = 6Hz, 3
H), 1.33 (t, J = 6Hz, 3H), 1.44 (d, J = 6Hz, 3H), 2.53
(S, 3H), 2.93 (bs, 1H), 4.32 (q, J = 6Hz, 2H), 4.38
(Q, J = 6Hz, 2H), 5.09 (q, J = 6Hz, 1H), 8.27 (s, 1H)] 8.0g (0.028mol) of alcohol crude product, 0.5g of paratoluenesulfonic acid, 100ml of xylene are refluxed. The reaction was carried out all day and night while separating water using a water separator at temperature. After cooling, the solvent was distilled off under reduced pressure, water was added, and the mixture was extracted with chloroform. The organic layer was washed with water and dried, and then the solvent was distilled off to obtain a crude product of the title compound. This was purified by column chromatography to obtain 4.3 g (0.0163 mol) of the title compound in 58% yield. [Oil substance, refractive index ▲ n ²⁰ _D ▼ 1.5324, PMR (δ value (CDCl ₃ )): 1.40 (t, J = 6
Hz, 3H), 1.39 (t, J = 6Hz, 3H), 2.62 (s, 3H), 4.39 (q, J
= 6Hz, 2H), 4.43 (q, J = 6Hz, 2H), 5.53 (d, J = 10Hz, 1
H), 5.75 (d, J = 17Hz, 1H), 6.86 (d ・ d, J = 10Hz.17Hz,
1H), 8.15 (s, 1H)] Synthesis example 5 1-amino-4-methyl-1-penten-3-one 3.4 g
(0.03 mol) and 7.3 g (0.03 mol) of ethylethoxymethylene oxaloacetate were dissolved in 50 ml of ethanol and stirred at room temperature for 12 hours. The solvent was evaporated under reduced pressure, saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with diethyl ether,
After washing with water and drying, the solvent was distilled off to obtain a crude product of the title compound, which was purified by column chromatography to obtain 1.3 g (4.4 mmol) of the title compound in a yield of 15%.

[Oil, PMR (δ value (CDCl ₃ )): 1.24 (d, J = 6.5Hz, 6H),
1.38 (t, J = 6.5Hz, 3H), 1.41 (t, J = 6.5Hz, 3H), 3.52
(7th, J = 6.5Hz, 1H), 4.40 (q, J = 6.5Hz, 2H), 4.47 (q,
J = 6.5Hz, 2H), 8.13 (d, J = 2Hz, 1H), 9.18 (d, J = 2Hz, 1
H)] Synthesis example 6 Pyridinedicarboxylic acid diester synthesized in Synthesis Example 1.
0 g (0.0189 mol) was added to a mixed solution of 30 ml of methanol, 30 ml of water and 2.0 g (0.045 mol) of sodium hydroxide, and the mixture was stirred at room temperature for 12 hours. Next, after neutralizing with hydrochloric acid, the solvent was completely distilled off under reduced pressure, 200 ml of ethanol was added, and the solvent was distilled off from the liquid to obtain 3.6 g (0.0172 mol) of the title compound in a yield of 91%. . [White crystals, melting point 127-138 ° C (decomposition), PMR (δ value (DMSO-d ₆ )): 2.70 (s, 3H), 7.90-9.0
5 (bs, 2H), 8.68 (d, J = 2Hz, 1H), 9.24 (d, J = 2Hz, 1
H)] Synthesis example 7 Pyridine dicarboxylic acid diester 1 synthesized in Synthesis Example 2
2.5 g (0.038 mol) was added to a mixed solution of 90 ml of methanol, 90 ml of water and 6.0 g of sodium hydroxide, the mixture was refluxed for 2.5 hours, the solvent was distilled off under reduced pressure and the resulting residue was washed with water. When dissolved in and acidified with concentrated hydrochloric acid, white crystals were broken out. Separate the white crystals and dry to give the title dicarboxylic acid 8.
A yield of 4 g (0.031 mol) 82% was obtained.

(Pale yellow crystal, PMR (δ value (DMSO-d ₆ )): 7.20 ~ 8.00 (m,
5H), 8.53 (d, J = 2Hz, 1H), 9.04 (d, J = 2Hz, 1H), 10.50
~ 11.30 (bs, 2H)] Synthesis Example 8 2.1 g (0.01 mol) of pyridinedicarboxylic acid synthesized in Synthesis Example 6 and 100 ml of acetic anhydride were heated and stirred at 90 to 100 ° C. for 8 hours. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain 1.8 g of the title compound.
(9.4 mmol) was obtained. (Gray white crystals, PMR (δ value (CDC1
₃ )): 2.77 (s, 3H), 8.61 (d, J = 2Hz, 1H), 9.00 (d, J = 2
Hz, 1H)] Synthesis example 8 ' 5-acyl-6-methylpyridine-2,3-dicarboxylic acid diethyl ester 3.5 g, acetic acid 5 ml, 32% hydrobromic acid aqueous solution
3.2 g was cooled to 0 ° C., 4.0 g of pyridine hydrobromide perbromide dissolved in 50 ml of acetic acid was added dropwise thereto, and the temperature was gradually raised from 0 ° C. to room temperature. Water was added to the reaction solution and extracted with diethyl ether. The organic layer was washed with water, dried and the solvent was evaporated to obtain 3.85 g of the title compound (purity 80%).
[Oil, refractive index ▲ n ²⁰ _D ▼ 1.5402, PMR (δ value (CDCl ₃ )):
1.37 (t, J = 6.5Hz, 3H), 1.35 (t, J = 6.5Hz, 3H), 2.72
(S, 3H), 4.31 (s, 2H), 4.31 (q, J = 6.5Hz, 2H), 4.36
(Q, J = 6.5 Hz, 2H), 8.26 (s, 1H)] In the same manner as in Synthesis Example 1 to Synthesis Example 8 ', the compounds (IV), (shown in Tables 1, 2 and 3) V) and (VI) were synthesized.

Next, the compound of the present invention represented by the general formula (I) can be synthesized by any one of the above-mentioned (reaction formula 1), (reaction formula 2) or (reaction formula 3). Specific examples are shown in Table 4. However, the compound of the present invention is not limited to these.

The compound No. of the present invention in Table 4 is referred to for the following synthesis examples, formulation examples and test examples.

Next, the compound of the present invention will be described with some specific synthetic examples. However, it is not limited to these.

Synthesis example 9 Diethyl pyridinedicarboxylate synthesized in Synthesis Example 4 3.0 g
(12 mmol) was hydrolyzed in the same manner as in Synthesis Example 6 to give 5-ethynylpyridine-2,3-dicarboxylic acid.
Obtained 2.5 g. Add 20 ml of acetic anhydride to it at 90-100 ° C for 5
The mixture was heated and stirred for an hour. Compound (VI) was obtained by distilling off the solvent under reduced pressure.
(X = H, Y = CH 2 R 3 = H) to give the crude product. 2-Amino-2,3-dimethylbutanamide (VII) was added to the crude product.
^{(W = O, R 1 =} CH 3, R 2 = CH (CH 3) 2) was vigorously stirred overnight at room temperature by addition of 1.6 g.

The solvent was distilled off under reduced pressure to remove compound (II) (W = O, X = H, Y = CH
_2, R = H, to give a ^{_{R 1 = CH 3, R 2}} = CH (CH 3) 2) of the crude product. 25 ml of water and 1.4 g of sodium hydroxide were added to this crude product, and stirring was continued at a temperature of 80 ° C. for 3 hours. After cooling, the solution was made acidic with concentrated hydrochloric acid, extracted with chloroform, the organic layer was washed with water, dried and the solvent was distilled off to obtain a crude product of the title compound. Further, this was purified by column chromatography to obtain 1.3 g of white crystals of the compound No. 1 of the present invention.

Synthesis example 10 Compound (VI) (X = H, Y = CH 2, R 3 = CH 3) 2.0g, 2- amino-2,3-dimethylbutane amide (VII) (W = O, R 1 = CH 3,
R ² = CH (CH ₃ ) ₂ ) (1.5 g) and pyridine (50 ml) were vigorously stirred at room temperature for one day. The solvent was distilled off under reduced pressure to give compound (II) (W
= O, X = H, Y = CH 2, R = H, R 1 = CH 3, R 2 = CH (CH 3) 2, R 3 = C
To give the crude product of H _3). Water (25 ml) and sodium hydroxide (1.4 g) were added to the crude product, and stirring was continued at a temperature of 80 ° C. for 3 hours.
After cooling, the insoluble matter was removed, and hydrochloric acid was added to make the solution acidic. The product was extracted with ethyl acetate, the organic layer was washed with water and dried, and then the solvent was distilled off to obtain a crude product of the title compound. Further, the compound N of the present invention was purified by column chromatography.
1.1 g of white crystals of o.2 was obtained.

Synthesis example 11 Compound (VI) synthesized in Synthesis Example 8 (X = CH ₃ , Y = O, R ³ =
H) 7.1 g, 2-amino-2,3-dimethylbutanamide (VI
I) (W = O, R 1 = CH 3, R 2 = CH (CH 3) 2) 5.4g, 4- picoline 2
0 ml was vigorously stirred overnight at room temperature. Compound solvent was evaporated under reduced pressure (II) (W = O, X = CH 3, Y = O, R = H, R 1 = CH 3, R
^{_{2 = CH (CH 3) 2}} , to obtain a R ³ = H) of the crude product. 25 ml of water and 6.1 g of sodium hydroxide were added to this crude product, and the mixture was stirred at a temperature of 80 ° C. for 3 hours. After cooling, the insoluble matter was removed in excess and hydrochloric acid was added to acidify the mixture. The organic layer was extracted with chloroform, washed with water, dried and the solvent was distilled off to obtain a crude product of the title compound. Further, this was purified by column chromatography to obtain 4.0 g of white crystal of the compound No. 3 of the present invention.

Synthesis Example 12 2.0 g of compound (I) (compound No. 4 of the present invention) and 20 ml of acetic acid were slowly added dropwise with 2.0 g of bromine. After stirring at room temperature for 5 hours, the solvent was distilled off under reduced pressure, and the mixture was extracted with chloroform. The organic layer was washed with water, dried and the solvent was distilled off to obtain the title compound.

Synthesis example 13 1.0 g of compound (I) (Compound No. 4 of the present invention), 0.67 g of ethyl carbazate, and 20 ml of ethyl alcohol were refluxed for 3 hours.
After cooling, the solvent was distilled off under reduced pressure, and the remaining residue was dissolved in tetrahydrofuran. The insoluble material was removed in excess, and the solution was concentrated under reduced pressure. When isopropyl ether was added to the residue, white crystals were precipitated. The crystals were separated and dried to obtain 0.72 g of white crystals of compound No. 9 of the present invention.

The compound (I) of the present invention shown in Table 5 by utilizing the reaction of any one of (Scheme 1), (Scheme 2) or (Scheme 3).
Can be synthesized.

When the compound of the present invention is applied as a herbicide or a plant growth regulator, it is generally a suitable carrier, for example, solid carrier such as clay, talc, bentonite, diatomaceous earth or water, alcohols (methanol, ethanol, etc.), aromatic carbonization. Hydrogens (benzene, toluene, xylene, etc.),
It can be used by mixing it with a liquid carrier such as chlorinated hydrocarbons, ethers, ketones, esters (ethyl acetate, etc.), acid amides (dimethylformamide, etc.). Add turbidity agents, penetrants, spreading agents, stabilizers, etc. to prepare liquids, emulsions, wettable powders, powders, granules,
It can be put to practical use in any dosage form such as a flowable agent. The content of the active ingredient compound in these preparations is not particularly limited, but is generally desirable to be in the range of 1.0 to 90.0% by weight. In addition, if necessary, it may be mixed with other types of herbicides, various insecticides, fungicides, plant growth regulators, synergists and the like at the time of formulation or spraying. The types of herbicides to be mixed include, for example, the compounds described in Farm Chemicals Hand-book, 70th edition (1984).

In addition, the compound of the present invention can be applied to the control of various weeds in non-agricultural fields such as athletic fields, open spaces, and track ends, as well as agricultural and horticultural fields such as upland fields, paddy fields and orchards. Although there are differences depending on the time of application, method of application, target grass species, cultivated crops, etc., generally an effective amount of about 0.005 to 10 kg per hectare is appropriate.

Next, formulation examples of a herbicide and a plant growth regulator containing the compound of the present invention as an active ingredient will be shown, but the invention is not limited thereto. In the following formulation examples, "part" means part by weight.

The above is uniformly mixed and pulverized to obtain a wettable powder. Before use, dilute the wettable powder 50 to 10,000 times and spray it so that the amount of active ingredient is 0.005 kg to 10 kg per hectare.

The above is uniformly mixed to obtain an emulsion. When used, the emulsion is diluted 50 to 1,000 times and sprayed so that the amount of active ingredient is 0.005 kg to 10 kg per hectare.

The above is uniformly mixed and pulverized, a small amount of water is added, and the mixture is stirred and mixed, granulated by an extrusion granulator, and dried to obtain a granule. When using, the amount of active ingredient in the above granules is 0 per hectare.
Sprinkle so that it is 005kg-10kg.

Solpol 3353, Lunox 1000C and a 1% xanthan gum aqueous solution were uniformly dissolved in water, and then compound No. 1 of the present invention was added.
After adding well and stirring well, wet grind with a sand mill to obtain a flowable agent. At the time of use, the flowable agent is diluted 50 to 1,000 times and sprayed so that the amount of active ingredient is 0.005 kg to 10 kg per hectare.

The above is uniformly mixed and pulverized to obtain a wettable powder.

Next, the herbicidal effect of the compound of the present invention will be specifically described with reference to test examples.

Test Example-1 Herbicidal effect test by soil treatment Put sterilized diluvial soil in a plastic box having a length of 30 cm, a width of 22 cm, and a depth of 6 cm, and cultivated rice, novier, cypress, dogpea, dog pepper, corn, wheat, soybean,
After sowing cotton and barley stalks and covering them with soil for about 1.5 cm, the active ingredients were sprayed uniformly on the soil surface so that the amount of active ingredient was a predetermined ratio. The chemical liquid for spraying was prepared by diluting the wettable powder, emulsion or flowable agent of the above-mentioned formulation example with water and spraying it over the entire surface with a small spray. The herbicidal effect against various weeds was investigated 3 weeks after spraying the chemical solution according to the following criteria.

Judgment criteria 5 ... Herbicide rate 90% or more (almost complete death) 4 ... Herbicide rate 70-90% 3 ... Herbicide rate 40-70% 2 ... Herbicide rate 20-40% 1 ... Herbicide rate 5-20% 0 ... Herbicide rate 5% or less (almost no effect) However, the above-mentioned herbicidal rate is obtained by measuring the above-ground vegetation weight of the chemical treatment area and the above-ground vegetation weight of the non-treatment area by the following formula.

In addition, the chemical damage to various crops was investigated according to the following criteria. The results are shown in Table 6.

Criteria 5: Almost complete death of crops 4 ... Remarkable phytotoxicity to crops 3 ... Recognizing phytotoxicity to crops 2 ... Recognizing some phytotoxicity to crops 1 ... Almost no phytotoxicity to crops 0 ... Recognizing phytotoxicity to crops No Test Example-2 Herbicidal effect test by stalk treatment 30 cm long, 22 cm wide, 6 cm deep in plastic box with sterilized diluvial soil, rice, novier, cyperaceae, dogwood, dog pepper, oysters, corn, wheat , Soybean, cotton, and beet seeds were sown in spots and covered with soil for about 1.5 cm. When various plants reached the 2-3 leaf stage, the active ingredients were sprayed evenly on the stalks so as to have a predetermined ratio.

The chemical solution for spraying was prepared by diluting the wettable powder, emulsion or flowable agent of the above-mentioned formulation example with water and spraying it over the entire stalks of various weeds and crops with a small spray. Four weeks after spraying the chemical solution, the herbicidal effect on various weeds and the chemical damage on various crops were investigated according to the criteria of Test Example-1.

The results are shown in Table 7.

Control compound (A) in Table 6 [generic name: Linuron (Li
nuron)] has the structural formula Is.

The structural formula of the reference compound (B) [general name: Acifluorfen-Sodium] in Table 7 is Is.

Test Example-3 Applicability test during soybean cultivation (spodoptera treatment) Sterilized diluvial soil was placed in a plastic pot with a diameter of 30 cm and a depth of 12 cm, soybean, Johnsongrass, millet, green locust, Ohashiba, Onami fir, Korean ginseng Morning glory,
The seeds of Malaga morning glory, velvetleaf, stag deer, stag beetle, and Tsunokusa nem were sown and covered with soil for about 1.5 cm.
In addition, plant the bud nuts and seeds in separate pots at a depth of 1.5 cm. When various crops reached the first leaf stage, the active ingredients were sprayed evenly on the stalks so that the amount of the active ingredient was a predetermined ratio.

The chemical solution used for spraying was prepared by diluting the wettable powder of the above-mentioned formulation example with water and spraying it over the entire stalks of various plants with a small spray. The effect on various plants was investigated 4 weeks after the application of the drug solution according to the criteria of Test Example 1 above.

The results are shown in Table 8.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tsutomu Namaki 1470 Shiraoka, Shiraoka-cho, Minamisaitama-gun, Saitama Nissan Biochemical Laboratory Co., Ltd. Masato Ikeda Examiner, Biochemistry Research Institute, Chemical Industry Co., Ltd.

Claims (3)

[Claims] 1. General formula (I): [In the formula, W represents an oxygen atom or a sulfur atom. X is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms
Lower alkoxymethyl group, lower alkylthiomethyl group having 1 to 4 carbon atoms, lower haloalkyl group having 1 to 4 carbon atoms,
A lower alkylsulfonylmethyl group having 1 to 4 carbon atoms, a benzyl group, an optionally substituted phenyl group or a pyridyl group (as the substituent, a lower alkyl group having 1 to 4 carbon atoms, a lower alkyl group having 1 to 4 carbon atoms) Represents an alkoxy group, a halogen atom, a nitro group, a cyano group or a trifluoromethyl group.). Y is an oxygen atom, a sulfur atom, a mono-substituted nitrogen atom (as the substituent, a lower alkyl group having 1 to 4 carbon atoms, 1 carbon atom)
To 4 lower alkoxy groups, 1 to 4 carbon lower alkoxycarbonylamino groups or optionally substituted phenyl groups or pyridyl groups (this substituent includes 1 to 4 carbon lower alkyl groups, 1 carbon atoms 4 represents a lower alkoxy group, a halogen atom, a nitro group, a cyano group or a trifluoromethyl group. } Or a di-substituted carbon atom {the di-substituents are each independently a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower haloalkyl group having 1 to 4 carbon atoms, or a lower alkyl group having 3 to 6 carbon atoms. A cycloalkyl group or an optionally substituted phenyl group or pyridyl group (this substituent has 1 to 4 carbon atoms)
Lower alkyl group, lower alkoxy group having 1 to 4 carbon atoms,
Indicates a halogen atom, nitro group, cyano group or trifluoromethyl group. ) Further, the di-substituents are taken together to form a ring and represent a cycloalkyl group having 3 to 6 carbon atoms which may be substituted by a lower alkyl group having 1 to 3 carbon atoms. } Is represented. R is a hydrogen atom, di-lower alkylimino group, optionally substituted carbon atoms 1 to
5 lower alkyl group (This substituent has 1 to 1 carbon atoms.
3 lower alkoxy group, hydroxy group, halocycloalkyl group having 3 to 6 carbon atoms, carboxyl group, lower alkoxycarbonyl group, cyano group, dialkylphosphonyl group,
Halogen atom, benzyloxy group, tri-lower alkylammonium group or optionally halogen atom, carbon number 1-4
Represents a lower alkyl group, a lower alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may be substituted with a nitro group. ), An optionally substituted lower alkenyl group having 2 to 5 carbon atoms (as the substituent, a lower alkoxy group having 1 to 3 carbon atoms, a lower alkoxycarbonyl group, two lower alkoxy groups having 1 to 3 carbon atoms) Group, or a phenyl group), a lower alkynyl group having 2 to 5 carbon atoms, or 5 carbon atoms
6 oxacycloalkyl group, C2-5 mono-, di- or trihaloalkenyl group, C2-5 haloalkynyl group, glycidyl group, alkylthioalkyl group,
3 carbon atoms which may be substituted with an alkyl group having 1 to 3 carbon atoms
~ 6 cycloalkyl groups or cations selected from alkali metal atoms, alkaline earth metal atoms, ammonium or organic ammonium. R ¹ represents a lower alkyl group having 1 to 4 carbon atoms. R ² represents a lower alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Further, R ¹ and R ² represent a cycloalkyl group having 3 to 6 carbon atoms, which can form a ring together and which may be substituted with a lower alkyl group having 1 to 3 carbon atoms. R ³ is a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms.
Represents an alkylthio group, a phenoxy group, a haloalkyl group having 1 to 4 carbon atoms, a haloalkoxy group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms. ] A pyridine derivative represented by or an optical isomer of the derivative (provided that R ¹ and R ² are not the same). 2. General formula (II): [In the formula, W represents an oxygen atom or a sulfur atom. X is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms
Lower alkoxymethyl group, lower alkylthiomethyl group having 1 to 4 carbon atoms, lower haloalkyl group having 1 to 4 carbon atoms,
A lower alkylsulfonylmethyl group having 1 to 4 carbon atoms, a benzyl group, an optionally substituted phenyl group or a pyridyl group (as the substituent, a lower alkyl group having 1 to 4 carbon atoms, a lower alkyl group having 1 to 4 carbon atoms) Represents an alkoxy group, a halogen atom, a nitro group, a cyano group or a trifluoromethyl group.). Y is an oxygen atom, a sulfur atom, a mono-substituted nitrogen atom (as the substituent, a lower alkyl group having 1 to 4 carbon atoms, 1 carbon atom)
To 4 lower alkoxy groups, 1 to 4 carbon lower alkoxycarbonylamino groups or optionally substituted phenyl groups or pyridyl groups (this substituent includes 1 to 4 carbon lower alkyl groups, 1 carbon atoms 4 represents a lower alkoxy group, a halogen atom, a nitro group, a cyano group or a trifluoromethyl group. } Or a di-substituted carbon atom {the di-substituents are each independently a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower haloalkyl group having 1 to 4 carbon atoms, or 3 to 6 carbon atoms. Cycloalkyl group or optionally substituted phenyl group or pyridyl group (this substituent has 1 to 4 carbon atoms)
Lower alkyl group, lower alkoxy group having 1 to 4 carbon atoms,
Indicates a halogen atom, nitro group, cyano group or trifluoromethyl group. ) Further, the di-substituents are taken together to form a ring and represent a cycloalkyl group having 3 to 6 carbon atoms which may be substituted by a lower alkyl group having 1 to 3 carbon atoms. } Is represented. R is a hydrogen atom, a di-lower alkylimino group, an optionally substituted lower alkyl group having 1 to 5 carbon atoms (as the substituent, a lower alkoxy group having 1 to 3 carbon atoms, a hydroxy group, a carbon number 3) ~ 6 halocycloalkyl group, carboxyl group, lower alkoxycarbonyl group, cyano group, dialkylphosphonyl group, halogen atom, benzyloxy group, tri-lower alkylammonium group or optionally halogen atom, lower alkyl having 1 to 4 carbon atoms Group, carbon number 1
4 shows a phenyl group which may be substituted with a lower alkoxy group or a nitro group. ), An optionally substituted lower alkenyl group having 2 to 5 carbon atoms (as the substituent, a lower alkoxy group having 1 to 3 carbon atoms, a lower alkoxycarbonyl group, two lower alkoxy groups having 1 to 3 carbon atoms) Group, or a phenyl group), a lower alkynyl group having 2 to 5 carbon atoms, an oxacycloalkyl group having 5 to 6 carbon atoms, and 2 carbon atoms
-5 mono-, di- or trihaloalkenyl groups, haloalkynyl groups having 2-5 carbon atoms, glycidyl groups, alkylthioalkyl groups, cycloalkyl having 3-6 carbon atoms which may be substituted with alkyl groups having 1-3 carbon atoms Represents a group or a cation selected from alkali metal atoms, alkaline earth metal atoms, ammonium or organic ammonium. R
¹ represents a lower alkyl group having 1 to 4 carbon atoms. R ² is a lower alkyl group having 1 to 4 carbon atoms or 3 to 4 carbon atoms
6 represents a cycloalkyl group. Further, R ¹ and R ² represent a cycloalkyl group having 3 to 6 carbon atoms which can form a ring together and which may be substituted with a lower alkyl group having 1 to 3 carbon atoms. R ³ is a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms.
Represents an alkylthio group, a phenoxy group, a haloalkyl group having 1 to 4 carbon atoms, a haloalkoxy group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms. ] The pyridine derivative represented by or the optical isomer of the derivative (provided that R ¹ and R ² are not the same) is cyclized with an aqueous solution of an alkali metal hydroxide or an alkaline earth metal hydroxide. Cyclization in the presence of phosphorus oxychloride, phosphorus pentachloride, alkali metal hydride or alkaline earth metal hydride in an inert solvent, or cyclization using a dehydrating reagent such as dicyclohexylcarbodiimide Or, in some cases, esterification or transesterification of the above cyclized product with an alkylating agent such as diazomethane, dialkyl sulfate, Meyerbaine reagent, or alcohol ROH corresponding to R (I): (Wherein W, X, Y, R, R ¹ , R ² and R ³ have the same meanings as described above) or an optical isomer of the pyridine derivative (provided that R ¹ and R ² If the two are not the same). 3. General formula (I): [In the formula, W represents an oxygen atom or a sulfur atom. X is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms
Lower alkoxymethyl group, lower alkylthiomethyl group having 1 to 4 carbon atoms, lower haloalkyl group having 1 to 4 carbon atoms,
A lower alkylsulfonylmethyl group having 1 to 4 carbon atoms, a benzyl group, an optionally substituted phenyl group or a pyridyl group (as the substituent, a lower alkyl group having 1 to 4 carbon atoms, a lower alkyl group having 1 to 4 carbon atoms) Represents an alkoxy group, a halogen atom, a nitro group, a cyano group or a trifluoromethyl group.). Y is an oxygen atom, a sulfur atom, a mono-substituted nitrogen atom (as the substituent, a lower alkyl group having 1 to 4 carbon atoms, 1 carbon atom)
To 4 lower alkoxy groups, 1 to 4 carbon lower alkoxycarbonylamino groups or optionally substituted phenyl groups or pyridyl groups (this substituent includes 1 to 4 carbon lower alkyl groups, 1 carbon atoms 4 represents a lower alkoxy group, a halogen atom, a nitro group, a cyano group or a trifluoromethyl group. } Or a di-substituted carbon atom {the di-substituents are each independently a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower haloalkyl group having 1 to 4 carbon atoms, or a lower alkyl group having 3 to 6 carbon atoms. A cycloalkyl group or an optionally substituted phenyl group or pyridyl group (this substituent has 1 to 4 carbon atoms)
Lower alkyl group, lower alkoxy group having 1 to 4 carbon atoms,
Indicates a halogen atom, nitro group, cyano group or trifluoromethyl group. ) Further, the di-substituents are taken together to form a ring and represent a cycloalkyl group having 3 to 6 carbon atoms which may be substituted by a lower alkyl group having 1 to 3 carbon atoms. } Is represented. R is a hydrogen atom, a di-lower alkylimino group, an optionally substituted lower alkyl group having 1 to 5 carbon atoms (as the substituent, a lower alkoxy group having 1 to 3 carbon atoms, a hydroxy group, a carbon number 3) ~ 6 halocycloalkyl group, carboxyl group, lower alkoxycarbonyl group, cyano group, dialkylphosphonyl group, halogen atom, benzyloxy group, tri-lower alkylammonium group or optionally halogen atom, lower alkyl having 1 to 4 carbon atoms Group, carbon number 1
4 shows a phenyl group which may be substituted with a lower alkoxy group or a nitro group. ), An optionally substituted lower alkenyl group having 2 to 5 carbon atoms (as the substituent, a lower alkoxy group having 1 to 3 carbon atoms, a lower alkoxycarbonyl group, two lower alkoxy groups having 1 to 3 carbon atoms) Group, or a phenyl group), a lower alkynyl group having 2 to 5 carbon atoms, an oxacycloalkyl group having 5 to 6 carbon atoms, and 2 carbon atoms
-5 mono-, di- or trihaloalkenyl groups, haloalkynyl groups having 2-5 carbon atoms, glycidyl groups, alkylthioalkyl groups, cycloalkyl having 3-6 carbon atoms which may be substituted with alkyl groups having 1-3 carbon atoms Represents a group or a cation selected from alkali metal atoms, alkaline earth metal atoms, ammonium or organic ammonium. R
¹ represents a lower alkyl group having 1 to 4 carbon atoms. R ² is a lower alkyl group having 1 to 4 carbon atoms or 3 to 4 carbon atoms
6 represents a cycloalkyl group. Further, R ¹ and R ² represent a cycloalkyl group having 3 to 6 carbon atoms, which can form a ring together and which may be substituted with a lower alkyl group having 1 to 3 carbon atoms. R ³ is a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms.
Represents an alkylthio group, a phenoxy group, a haloalkyl group having 1 to 4 carbon atoms, a haloalkoxy group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms. ] A herbicide containing, as an active ingredient, one or more pyridine derivatives represented by the following formula or optical isomers of the derivatives (provided that R ¹ and R ² are not the same).