JP3074403B2 - Pyrimidine derivatives and herbicides containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel pyrimidine derivative and a herbicide containing the same as an active ingredient, which can be applied to paddy fields, uplands and non-agricultural lands.

[0002]

2. Description of the Related Art U.S. Pat. No. 4,248,619 (JP-A-55-24195) and U.S. Pat. No. 4,427,437 (JP-A-54-557) have already been disclosed.
No. 29) and Agricultural and Biological Chemistry (Agric. Biol. Chem.) 30
Vol. 9, No. 896, p. 896 (1966) describes that 2-phenoxypyrimidine derivatives have a herbicidal action.

[0003]

However, the compounds described in these documents have weak herbicidal activity against annual weeds, show little activity against perennial weeds, and some of the compounds have strong herbicidal activity. However, there is a drawback that some useful crops cause harm to useful crops.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies on pyrimidine derivatives with the aim of developing compounds having excellent herbicidal activity without causing phytotoxicity to useful crops. The pyrimidine derivative of the present invention in which a substituent has been introduced at a specific position, shows an excellent herbicidal effect on perennial weeds as well as annual weeds,
The present invention was found to be safe and selective for crops such as rice, wheat, and corn, and completed the present invention.

That is, the present invention relates to a compound represented by the general formula [I]:

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[Where the Het is the formula

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In the formula, X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group, a phenyl group, a substituted phenyl group, a lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group, a cyano group, a nitro group, a lower group. It represents an alkoxycarbonyl group, an amino group, a lower alkylamino group or a lower dialkylamino group, n represents an integer of 1 to 6, and R ¹ represents a lower alkyl group, a phenyl group or a substituted phenyl group.基 represents a group represented by
Is a hydrogen atom, a lower alkyl group, a formula —CH (R ² ) OR
^{3 In the} formula, R ² represents a hydrogen atom or a lower alkyl group;
R ³ is a lower alkyl group, an alkylcarbonyl group, a phenylcarbonyl group, a substituted phenylcarbonyl group, a lower alkoxycarbonyl group or a formula —C (O) NR ⁴ R ⁵ (wherein R ⁴ and R ⁵ are the same or different, Represents a hydrogen atom or an alkyl group.) A group represented by {} or a formula -N = C
And a group represented by (R ⁶ ) ₂ (wherein R ⁶ represents a lower alkyl group). And a salt thereof and a herbicide containing these as an active ingredient.

In the general formula [I], the substituent X on the heterocyclic ring
Examples of the halogen atom include chlorine, bromine, fluorine and iodine atoms. As the lower alkyl group, a linear or branched alkyl group having 1 to 3 carbon atoms, that is, a methyl group, an ethyl group, an n-propyl group, i
-Propyl groups. As the lower haloalkyl group, a haloalkyl group in which part or all of the lower alkyl group is substituted with the halogen atom, for example, a group
CHF ₂ , group CH ₂ Cl, group CBr _{3 and the} like can be exemplified. Examples of the substituted phenyl group include a substituted phenyl group in which part or all of the phenyl group is substituted with the above-described halogen atom, lower alkyl group and lower alkoxy group, for example, 4-chlorophenyl group, 3-methylphenyl group and the like. Can be. As the lower alkoxy group, a linear or branched alkoxy group having 1 to 3 carbon atoms, that is, a methoxy group,
Examples include an ethoxy group, an n-propoxy group, and an i-propoxy group. As the lower haloalkoxy group, a haloalkoxy group in which part or all of the lower alkoxy group is substituted with the halogen atom, for example, a group OCHF ₂ , a group O
CH ₂ Cl, group OCBr _{3 and the} like can be exemplified. Examples of the lower alkylthio group include a linear or branched alkylthio group having 1 to 3 carbon atoms, that is, a methylthio group, an ethylthio group, an n-propylthio group, and an i-propylthio group. As the lower alkoxycarbonyl group,
A carbonyl group to which the lower alkoxy group is bonded, that is, a methoxycarbonyl group, an ethoxycarbonyl group, n-
And a propoxycarbonyl group and an i-propoxycarbonyl group. A lower alkylamino group and a lower dialkylamino group are an amino group in which the lower alkyl group is mono- or di-substituted, for example, a methylamino group,
Examples thereof include a diethylamino group, a methylethylamino group, and an n-propylamino group.

Examples of the lower alkyl group for the substituent R ¹ of some of the hetero rings include the same groups as the lower alkyl groups for the substituent X. Examples of the substituted phenyl group include the same groups as the substituted phenyl group of the substituent X.

Examples of the lower alkyl group for the substituent R of the carboxylic acid include the same groups as the lower alkyl group for the substituent X. Further, the lower alkyl group of the substituents R ² and R ^{3 in} the formula —CH (R ₂ ) OR ³ may be the same as the lower alkyl group of the substituent X. Examples of the alkylcarbonyl group for the substituent R ³ include a carbonyl group having a linear or branched alkyl group having 1 to 7 carbon atoms, such as a methylcarbonyl group, an ethylcarbonyl group, an i-propylcarbonyl group, and an s-butyl group. Carbonyl group, n-pentylcarbonyl group, n-hexylcarbonyl group, group CO
CH ₂ C (CH ₃ ) _{3 and the} like can be exemplified. Examples of the substituted phenylcarbonyl group include a carbonyl group having the same substituted phenyl group as the substituted phenyl group of the substituent X, such as a 4-chlorophenylcarbonyl group and a 3-methylphenylcarbonyl group. Examples of the lower alkoxycarbonyl group include the same groups as the lower alkoxycarbonyl group for the substituent X. Formula -C (O)
NR ⁴ The alkyl group of the substituents R ⁴ and R ⁵ in R ^5, straight-chain or branched alkyl group having 1 to 7 carbon atoms,
For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group,
t-butyl group, n-pentyl group, i-pentyl group, s-
Pentyl group, t-pentyl group, n-hexyl group, group CH ₂ C
(CH ₃ ) ₃ , group CH ₂ CH (CH ₃ ) C ₂ H ₅ , group CH ₂ CH (C ₂ H ₅ ) ₂ , group C ₂ H ₄ C
(CH ₃ ) ₃ , a group CH (CH ₃ ) CH ₂ C (CH ₃ ) _{3 and the} like can be exemplified. The lower alkyl group of the substituents R ⁶ in the formula _{^{-N = C (R 6) 2}} , it may be exemplified the same groups as the lower alkyl group of the substituent X.

Particularly preferred compounds are those in which, in the general formula [I], the substituent X on the heterocyclic ring represents a methoxy group, a methyl group, a trifluoromethyl group and a chlorine atom, and R represents a hydrogen atom and a methoxymethyl group. can give. Next, specific examples of the compound represented by the general formula [I] are shown in Tables 1, 2 and 3A to 3E. The compound numbers will be referred to in the following description.

[0012]

[Table 1]

[0013]

[Table 2]

[0014]

[Table 3A]

[0015]

[Table 3B]

[0016]

[Table 3C]

[0017]

[Table 3D]

[0018]

[Table 3E]

The compound of the present invention can be produced, for example, by the following method. Manufacturing method <A>

[0020]

[Reaction formula 1]

(In the formula, Y represents a halogen atom, a methylsulfonyl group or a benzylsulfonyl group, and Het has the same meaning as described above.) Compound [II] formed from compound [II] and compound [a]
I] is reacted with a compound represented by the general formula [IV] in a solvent in the presence of a base at a reaction temperature of 0 to 200 ° C. for 0.5 to 20.
The compound represented by the general formula [V] can be produced by reacting for an hour and treating the obtained substance with the compound [b]. Here, as the base, an inorganic or organic base such as sodium hydroxide, potassium carbonate, sodium hydrogen carbonate, sodium hydride, triethylamine, pyridine and the like can be used. As the solvent, acetone, acetonitrile, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, benzene, toluene, dichloromethane, chloroform and the like can be used.

Manufacturing method <B>

[Reaction formula 2]

(Wherein, R ⁷ represents a benzyl group or a 2-trimethylsilylethyl group, and Y and Het have the same meanings as described above.) Compound [VII] formed from compound [VI] and compound [VII]
I] is reacted with a compound represented by the general formula [IV] in a solvent in the presence of a base at a reaction temperature of 0 to 200 ° C. for 0.5 to 20.
The reaction is carried out for an hour to produce compound [IX]. Compound (IX)
Is treated with a compound [b] or [c] to produce a compound represented by the general formula [V]. Here, as the base and the solvent, those similar to those described in the production method <A> can be used.

Manufacturing method <C>

[Reaction formula 3] (In the formula, R, Y and Het have the same meaning as described above.)

By reacting the compound represented by the general formula [X] with the compound represented by the general formula [IV] in a solvent in the presence of a base, the compound represented by the general formula [XI] is obtained. Compounds can be prepared. Here, as the base and the solvent, those similar to those described in the production method <A> can be used.

Manufacturing method <D>

[Reaction formula 4] (In the formula, Het and Y have the same meaning as described above.)

The compound [XIII] formed from the compound [XII] and the compound [a] is reacted with the compound represented by the general formula [VII] in a solvent in the presence of a base at a reaction temperature of 0 to 200 ° C.
For 0.5 to 20 hours, and treating the resulting substance with the compound [b] to produce a compound represented by the general formula [V]. Here, as the base and the solvent, those similar to those described in the production method <A> can be used.

Manufacturing method <E>

[Reaction formula 5] (In the formula, R ⁷ , Het and Y have the same meanings as described above.)

Compound [XIV] is dissolved in a solvent in the presence of a base,
The compound represented by the general formula [VII] is reacted at a reaction temperature of 0 to 2
The reaction was carried out at 00 ° C. for 0.5 to 20 hours, and the resulting compound [I
The compound represented by the general formula [V] can be produced by treating X] with the compound [b] or [c]. Here, as the base and the solvent, those similar to those described in the production method <A> can be used.

Manufacturing method <F>

[Reaction formula 6] (In the formula, R, Het and Y have the same meaning as described above.)

By reacting the compound represented by the general formula [XV] with the compound represented by the general formula [VII] in a solvent in the presence of a base, the compound represented by the general formula [XI] is obtained. Can be manufactured. Here, as the base and the solvent, those similar to those described in the production method <A> can be used.

Manufacturing method <G>

[Reaction formula 7]

Wherein R ⁸ is a hydrogen atom, a lower alkyl group, a formula —CH (R ² ) OR ³ , wherein R ² is a hydrogen atom or a lower alkyl group, R ³ is a lower alkyl group, an alkyl group carbonyl group, phenylcarbonyl group, a substituted phenylcarbonyl group, ⁴ R ⁵ (wherein a lower alkoxycarbonyl group, or the formula -C (O) NR, R ⁴ and R ⁵ are the same or different, represent a hydrogen atom or an alkyl group. ) Represents a group represented by｝, Z represents a halogen atom, and Het has the same meaning as described above. ]

The compound represented by the general formula [V] and the compound represented by the general formula [XVI] are reacted in a solvent at a reaction temperature of -10 to 150 ° C for 0.5 to 15 hours in the presence of a base. By reacting, the compound represented by the general formula [XVII] can be produced. Here, as the base and the solvent, those similar to those described in the production method <A> can be used.

Manufacturing method <H>

[Reaction formula 8] (In the formula, Het and R ⁶ have the same meaning as described above.)

The compound represented by the general formula [V] and the compound represented by the general formula [XVIII] are reacted with a base and a phosphoric acid dichloride such as dimethylaminophosphoryl dichloride or phenylphosphorodichloride,
By reacting in a solvent at a reaction temperature of -10 to 100 ° C for 1 to 30 hours, a compound represented by the general formula [ XIX ] can be produced. Here, organic tertiary amines such as pyridine and triethylamine can be used as the base, and N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and the like can be used as the solvent.

Manufacturing method <I>

[Reaction formula 9] (In the formula, Het and R have the same meanings as described above.)

The compound represented by the general formula [XX] is reacted with the compound represented by the general formula [V] and the compound [d] in a solvent at a reaction temperature of -10 to 100 ° C. for 1 to 10 hours. Can be manufactured. Ethyl ether, tetrahydrofuran, dioxane, benzene, toluene and the like can be used as the solvent. The compound represented by the general formula [XXI] was added to the obtained compound [XX] in a solvent at -10 to 1
By reacting at 00 ° C. for 0.5 to 30 hours, compound [XI] can be produced. The same solvent as described above can be used.

Production method <J> General formula [V]

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(Wherein, Het has the same meaning as described above) and a base, and a solvent such as water, alcohol, acetonitrile, acetone, ether, N, N-dimethylformamide, and dimethylsulfoxide. In the reaction, an organic or inorganic salt of the compound represented by the general formula [V] can be produced by reacting at a reaction temperature of 0 to 100 ° C. for 0.2 to 10 hours. Here, as the base, sodium hydroxide, potassium hydroxide, hydroxides of alkali metals or alkaline earth metals such as calcium hydroxide, carbonates such as sodium carbonate, potassium carbonate and calcium carbonate, ammonia, ethylamine, dimethylamine, Primary such as isopropylamine, diisopropylamine, diethanolamine, triethylamine,
Secondary and tertiary amines can be used.

[0041]

EXAMPLES Next, the production method of the present invention will be specifically described with reference to examples. Example 1 Synthesis of 2- (4,6-dimethoxypyrimidin-2-yl) oxy-6- (4,6-dimethoxy-1,3,5-triazin-2-yl) oxybenzoic acid (Compound No. 12) Benzyl 2- (4,6-dimethoxypyrimidin-2-yl) oxy-6-hydroxybenzoate (mp 63-65)
C) 3.8 g (10 mmol), 4,6-dimethoxy-
1.8 g of 1,3,5-triazine and 1.5 g of potassium carbonate
(11 mmol) was suspended in 40 ml of dimethylformamide and stirred at 80 ° C. for 4 hours. The reaction mixture was poured into water and extracted twice with ethyl acetate. The organic layer was washed with water and dried, and then the solvent was distilled off. The resulting viscous liquid was purified by column to give 2- (4,6- 4.0 g of benzyl dimethoxypyrimidin-2-yl) oxy-6- (4,6-dimethoxy-1,3,5-triazin-2-yl) oxybenzoate
Was obtained (77% yield). This is dissolved in ethyl acetate,
Catalytic reduction was carried out by adding hydrogen to the suspension containing 0.3 g of 10% palladium carbon, which had been moistened with ethyl acetate and methanol in advance, and introducing hydrogen at normal pressure. When the absorption of hydrogen stopped, the reaction was terminated and the reaction solution was filtered. After concentrating the filtrate under reduced pressure, toluene and hexane were added to the residue for crystallization to obtain 2.2 g of a white powder having a melting point of 137 to 141 ° C (yield 67%).

Example 2 Sodium 2- (4,6-dimethoxypyrimidin-2-yl) oxy-6- (4,6-dimethoxy-1,3,5-triazin-2-yl) oxybenzoate (Compound No. 1
Synthesis of 3) 0.8 g of 2- (4,6-dimethoxypyrimidin-2-yl) oxy-6- (4,6-dimethoxy-1,3,5-triazin-2-yl) oxybenzoic acid (1. 9 mmol)
Was dissolved in 10 ml of methanol, and 0.4 g of 28% sodium methylate was added thereto. After concentrating the reaction solution, acetone was added, and the precipitated crystals were separated by filtration and washed with hexane to obtain 0.8 g of white crystals having a melting point of 181 to 184 ° C (yield 9).
3%).

Example 3 2- (4,6-dimethoxypyrimidin-2-yl-6-
(5-nitropyridin-2-yl) oxybenzoic acid 1-
Synthesis of ethoxycarbonyloxyethyl (Compound No. 25) 1-ethoxycarbonyloxyethyl 2-hydroxy-6- (5-nitropyridin-2-yl) oxybenzoate 2.0 g (5 mmol), 4,6-dimethoxy- 1.2 g (5.5 mmol) of 2-methylsulfonylpyrimidine and 2.0 g (14.5 mmol) of potassium carbonate were suspended in 5 ml of dimethylformamide and stirred at 80 ° C. for 4 hours. The reaction mixture was poured into water, extracted twice with ethyl acetate, and the organic layer was washed with water and dried, and then the solvent was distilled off. The resulting viscous liquid was subjected to column purification to give a melting point of 43 to 47 ° C. 2.1 g of a pale yellow powder was obtained (76% yield).

Example 4 1-ethoxycarbonyloxyethyl 2- (2-chloro-3-nitropyridin-6-yl) oxy-6- (4,6-dimethoxypyrimidin-2-yl) oxybenzoate (Compound No. 47) 2.0 g (5 mmol) of 1-ethoxycarbonyloxyethyl 2- (4,6-dimethoxypyrimidin-2-yl) oxy-6-hydroxybenzoate, 2,6-dichloro-3- nitropyridine 1 2.0 g (15.2 mmol) of potassium carbonate and 2.0 g (14.5 mmol) of potassium carbonate were suspended in 5 ml of dimethylformamide and stirred at room temperature for 1 hour.
The reaction mixture was poured into water, extracted twice with ethyl acetate, the organic layer was washed with water and dried, and then the solvent was distilled off.The resulting viscous liquid was purified by column to remove the pale yellow candy-like substance. 2.1 g was obtained (yield: 75%).

Example 5 2- {2,6-bis (trifluoromethyl) pyridine-
Synthesis of 1-ethoxycarbonyloxyethyl 4-yl} oxy-6- (4,6-dimethoxypyrimidin-2-yl) oxybenzoate (Compound No. 46) 2- {2,6-bis (trifluoromethyl) pyridine −
1.4 g (2.8 mmol) of 4-yl) oxy-6- (4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid, 0.45 g of 2-chloroethyl ethyl carbonate (2.
9 mmol) and 0.4 g (2.9 mmol) of potassium carbonate were suspended in 5 ml of dimethylformamide.
Stirred at 0 ° C. for 3 hours. The reaction mixture was put into water, extracted twice with ethyl acetate, the organic layer was washed with water and dried, and then the solvent was distilled off.The resulting viscous liquid was purified by column chromatography.
A colorless viscous liquid having a refractive index (Na-D line) of 1.4978 was added to a liquid of 0.10.
5 g was obtained (yield 29%).

Example 6 2- (6-chloropyrazin-2-yl) oxy-6
Synthesis of (4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid (Compound No. 21) Benzyl 2,6-dihydroxybenzoate was converted to a sodium salt with 2-fold molar sodium hydride in tetrahydrofuran under ice-cooling. Later, an equimolar amount of 4,6-dimethoxy-2
-Methylsulfonylpyrimidine was added, and the mixture was stirred overnight while gradually returning to room temperature. After completion of the reaction, the reaction mixture was poured into water, adjusted to pH = 1 with hydrochloric acid, extracted with ethyl acetate, washed with water, dried and concentrated, and the obtained powder was recrystallized from ethanol to give 2- (4,6-dimethoxy). There was obtained benzyl (pyrimidin-2-yl) oxy-6-hydroxybenzoate.
Next, 3.8 g of benzyl 2- (4,6-dimethoxypyrimidin-2-yl) oxy-6-hydroxybenzoate.
(10 mmol) in N, N-dimethylacetamide (1
0 ml), and then cooled to 0.25% with sodium hydride under ice-cooling.
g (10.5 mmol) was added, and the mixture was stirred under ice cooling for 10 minutes and at room temperature for 30 minutes. Further, 4.5 g (30 mmol) of 2,6-dichloropyrazine was added, and the mixture was stirred at 80 to 90 ° C. for 2.5 hours. The reaction mixture was poured into water, extracted twice with ethyl acetate, and the organic layer was washed with water and dried, and then the solvent was distilled off.
(6-chloropyrazin-2-yl) oxy-6- (4,
4.7 g of benzyl 6-dimethoxypyrimidin-2-yl) oxybenzoate were obtained (96% yield). This was dissolved in ethyl acetate, added to a suspension containing 0.4 g of 10% palladium carbon, which had been wetted with ethyl acetate and methanol in advance, and hydrogen was introduced at normal pressure to perform catalytic reduction. The reaction was terminated when the absorption of hydrogen stopped, and the reaction solution was filtered. After the filtrate was concentrated under reduced pressure, chloroform was added to the residue for crystallization to obtain 1.7 g of a white powder having a melting point of 167 to 171 ° C (44% yield).

Example 7 2- (3-chloro-5-trifluoromethylpyridine-
Synthesis of 2-yl) oxy-6- (4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid (Compound No. 28) 2- (4,6-dimethoxypyrimidin-2-yl) oxy-6-hydroxybenzoic acid 3.6 g (12.3 mmol) of the acid was dissolved in 50 ml of tetrahydrofuran, and 2.2 g (13.5 mmol) of carbonyldiimidazole was added thereto.
The mixture was stirred and refluxed for 30 minutes. After returning the reaction solution to room temperature, 1.6 g of 2-trimethylsilylethanol was added thereto.
(13.5 mmol) was added, and the mixture was stirred and refluxed for 8 hours.
After cooling, the reaction solution was filtered, the filtrate was concentrated, and the obtained residue was dissolved in 50 ml of acetonitrile. In addition to this,
1.8 g of dichloro-5-trifluoromethylpyridine
(8.4 mmol) and 1.2 g (8.4 mmol) of potassium carbonate
Was added, and the mixture was stirred and refluxed for 8 hours. After allowing to cool, the reaction solution was filtered, the filtrate was concentrated, and the obtained viscous liquid was purified by column to give 2- (3-chloro-5-trifluoromethylpyridin-2-yl) oxy-6- (4 3.2 g of 2-trimethylsilylethyl 2,6-dimethoxypyrimidin-2-yl) oxybenzoate was obtained (yield 73%). This was dissolved in 30 ml of dimethylformamide, 5.3 g (16.8 mmol) of tetrabutylammonium fluoride trihydrate was added, and the mixture was stirred at room temperature for 30 minutes. The reaction solution was poured into water, a small amount of saturated aqueous potassium hydrogen sulfate was added, and the mixture was extracted with ether. The organic layer was washed and dried with saturated saline, and the solvent was distilled off. After washing with a mixed solvent of ether, 2.3 g of white needles having a melting point of 130 to 133 ° C. was obtained (88% yield).

Example 8 Synthesis of 2- (4,6-dimethoxypyrimidin-2-yl) oxy-6- (pyridin-3-yl) oxybenzoic acid (Compound No. 29) 2-hydroxy-6- (pyridine- 5 g (15 mmol) of 2-trimethylsilylethyl 3-yl) oxybenzoate are dissolved in 50 ml of dimethylformamide,
6-dimethoxy-2-methylsulfonylpyrimidine 3.
6 g (16.5 mmol) and 2.3 g of potassium carbonate (16.5 mmol).
5 mmol) and stirred at 100 ° C. for 3 hours. After cooling down,
The reaction solution was poured into water and extracted twice with ethyl acetate. The organic layer was washed with water and dried, and then the solvent was distilled off. The obtained viscous liquid was purified by column to give 2- (4,6- Dimethoxypyrimidin-2-yl) oxy-6- (pyridin-3-yl)
5.6 g of 2-trimethylsilylethyl oxybenzoate was obtained (yield 79%). This is dimethylformamide 30
Then, 9.4 g (29.8 mmol) of tetrabutylammonium fluoride trihydrate was added, and the mixture was stirred at room temperature for 15 minutes. The reaction solution is poured into water, a small amount of saturated aqueous potassium hydrogen sulfate is added, and the mixture is extracted with ethyl acetate.The organic layer is washed and dried with saturated saline, the solvent is distilled off, and the obtained crystals are washed with hexane. Thus, 2.2 g of a slightly yellow solid having a melting point of 139 to 142 ° C. was obtained (yield: 50%).

Example 9 Synthesis of 4-heptylideneamino 2- (4,6-dimethoxypyrimidin-2-yl) oxy-6- (2-methylpyridin-5-yl) oxybenzoate (Compound No. 34) 1 g (2.6 mmol) of 2- (4,6-dimethoxypyrimidin-2-yl) oxy-6- (2-methylpyridin-5-yl) oxybenzoic acid was added to 20 m of dimethylformamide.
and heptanone oxime (0.3 g, 2.6 mmol) and pyridine (0.4 g, 5.2 mmol) under stirring at room temperature.
After adding l), the reaction solution was cooled to about 0 ° C. and stirred, and 0.5 g (2.9 mmol) of dimethylaminophosphoryl dichloride was added.
l) was slowly added dropwise. After stirring at room temperature for 10 hours, the reaction solution was put into ice water, extracted three times with ethyl acetate, and the organic layer was washed and dried with saturated saline, and then the solvent was distilled off. The viscous liquid was subjected to column purification to obtain 0.3 g of a slightly yellow transparent viscous liquid having a refractive index (Na-D line) of 1.5459 (yield: 23%).

Example 10 Synthesis of isopropylideneamino 2- (4,6-dimethoxypyrimidin-2-yl) oxy-6- (pyridin-3-yl) oxybenzoate (Compound No. 30) 2- (4,6) -Dimethoxypyrimidin-2-yl) oxy-6- (pyridin-3-yl) oxybenzoic acid 0.7
g (1.9 mmol) was dissolved in 20 ml of tetrahydrofuran, and 0.34 g of carbonyldiimidazole (2.3.
1 mmol), and the mixture was stirred and refluxed for 30 minutes. The reaction solution was returned to room temperature, and 0.16 g (2.2 mmol) of acetoxime was obtained.
Was added and the mixture was stirred and refluxed for 10 minutes. After allowing to cool, the reaction solution was put into ice water, extracted twice with ethyl acetate, and the organic layer was washed and dried with a saturated saline solution, and then the solvent was distilled off. Thus, 0.3 g of a slightly yellow transparent viscous liquid was obtained (yield: 38%).

The herbicide of the present invention comprises a pyrimidine derivative represented by the general formula [I] as an active ingredient. To use the compound of the present invention as a herbicide, the compound of the present invention may be used as it is, but a carrier commonly used for formulation, a surfactant, a dispersant or an auxiliary agent, and the like are mixed, and a powder, It can also be formulated and used in wettable powders, emulsions, fine granules or granules.

[0052] Carriers used in the formulation are as follows:
For example, Siegrite, Talc, Bentonite, Clay,
Examples include solid carriers such as kaolin, diatomaceous earth, white carbon, vermiculite, calcium carbonate, slaked lime, silica sand, ammonium sulfate, and urea, and liquid carriers such as isopropyl alcohol, xylene, cyclohexanone, and methylnaphthalene.

Examples of surfactants and dispersants include metal salts of alkyl benzene sulfonic acid, metal salts of dinaphthyl methane disulfonic acid, alcohol sulfates, alkyl aryl sulfonates, lignin sulfonates, polyoxyethylene glycol ethers and polyoxyethylene glycol ethers. Oxyethylene alkyl aryl ether, polyoxyethylene sorbitan monoalkylate and the like can be mentioned. Examples of the adjuvant include carboxymethyl cellulose, polyethylene glycol, gum arabic and the like. When used, they are diluted to an appropriate concentration and sprayed or applied directly.

The herbicide of the present invention can be used for foliage application, soil application or water application. The compounding ratio of the active ingredient is appropriately selected as necessary, but when it is a powder or granule, it is appropriately selected from the range of 0.01 to 10% (weight), preferably 0.05 to 5% (weight). Is good. 1 to 50% when used as emulsion and wettable powder
(Weight), preferably in the range of 5 to 20% (weight).

The application rate of the herbicide of the present invention varies depending on the kind of the compound used, the target weed, the tendency to emerge, the environmental conditions, the dosage form used, and the like. The active ingredient may be appropriately selected from the range of 0.1 g to 5 kg, preferably 1 g to 1 kg per 10 ares. When used in the form of a liquid such as an emulsion and a wettable powder, 0.1 to 50,000 pp
m, preferably in the range of 10 to 10,000 ppm.

The compounds of the present invention may be mixed with insecticides, fungicides, other herbicides, plant growth regulators, fertilizers and the like, if necessary. Next, the preparation method will be specifically described with reference to typical preparation examples. The types and compounding ratios of the compounds and additives are not limited to these and can be changed in a wide range. In the following description, “parts” means parts by weight.

Formulation Example 1 Wettable powder 0.5 part of emulgen (registered trademark of Kao Corporation) 810, 0.5 part of Demol (registered trademark of Kao Corporation) N, kunilite in 10 parts of compound (35) 20 parts of (Kunimine Kogyo Co., Ltd.) 201 and 69 parts of Zikulite (Ziglite Co., Ltd.) CA are mixed and pulverized to obtain a wettable powder.

Formulation Example 2 wettable powder 0.5 part of emulgen 810 was added to 10 parts of compound (12).
Part, 0.5 part of Demol N, 20 of Kunilite 201
Part, 5 parts of Carplex 80, 6 parts of Siegrite CA
4 parts are mixed and pulverized to obtain a wettable powder.

Formulation Example 3 Water-dispersible powder (calcium carbonate formulation) 0.5 part of Demol N and 0.5 part of Emal (registered trademark of Kao Atlas Co., Ltd.) 10 in 10 parts of compound (6)
, 20 parts of Kunilite 301, 5 parts of Carplex 80 and 64 parts of calcium carbonate are mixed and pulverized to obtain a wettable powder.

Formulation Example 4 Emulsion To 30 parts of the compound (32) are added 60 parts of an equal mixture of xylene and isophorone, and 10 parts of a surfactant, Solpol (registered trademark of Toho Chemical Industry Co., Ltd.) 800A, and these are mixed well. Thus, an emulsion is obtained.

Formulation Example 5 Granules 10 parts of compound (25), talc and bentonite in 1:
80 parts of a mixed bulking agent at a ratio of 3; 5 parts of white carbon; 5 parts of surfactant Solpol 800A;
Part, and kneaded well to form a paste.
After extruding through a 7mm sieve hole and drying,
Cut to a length of 1 mm to obtain granules.

Next, the effects of the compound of the present invention will be described with reference to Test Examples. Test Example 1 (Test of herbicidal effect by paddy field soil treatment) A 100 cm ² plastic pot was filled with paddy field soil,
After scratching, foxtail (Ec), conger (Mo) and firefly (Sc)
Were seeded and submerged at a depth of 3 cm. The next day, the wettable powder prepared according to Formulation Example 1 was diluted with water and dropped on the water surface. The application rate was 100 g of the active ingredient per 10 ares. Thereafter, the plants were grown in a greenhouse, and on the 21st day of the treatment, the herbicidal effect was investigated in accordance with the criteria in Table 4. Table 5 shows the results.

[0063]

[Table 4]

[0064]

[Table 5]

Test Example 2 (Test for Herbicidal Effect by Upland Field Soil Treatment) A 120 cm ² plastic pot was filled with upland soil,
Various seeds of edible flies (Ec), P. japonica (Po), Ao-byu (Am), Shiroza (Ch), and Kogo Megatsuri (Ci) were sowed and covered with soil. The wettable powder prepared according to Formulation Example 1 was diluted with water,
100 l per 10 ares was evenly sprayed on the soil surface with a small sprayer so that the active ingredient was 100 g per 0 ares. After that, the plants were grown in a greenhouse, and on the 21st day of the treatment, the herbicidal effect was investigated according to the criteria in Table 4. Table 6 shows the results.

[0066]

[Table 6]

Test Example 3 (Test of Herbicidal Effect by Upland Field Foliar Treatment) A 120 cm ² plastic pot was filled with upland soil,
Various varieties of edible flies (Ec), P. japonicus (Po), Aoubiyu (Am), Shiroza (Ch) and Kogomegatsuri (Ci) were sown, cultivated in a greenhouse for 2 weeks, and then hydrated according to Formulation Example 1. The agent was diluted with water, and 100 l per 10 ares was sprayed with foliage over the whole plant using a small sprayer so that the active ingredient was 100 g per 10 ares. Thereafter, the plants were grown in a greenhouse, and on the 14th day of the treatment, the herbicidal effects were investigated according to the criteria in Table 4. Table 7 shows the results.

[0068]

[Table 7]

Test Example 4 (Test on low herbicidal herbicidal effect by foliar treatment of upland field) A 600 cm ² plastic pot was filled with upland soil,
Edible millet (Ec), Johnson grass (So), black grass
(Al), Greater Polygonum (Po), Aoville (Am), Shiroza (Ch),
After seeding various varieties of strawberry (Ab) and growing them in a greenhouse for 2 weeks,
The wettable powder prepared according to Formulation Example 1 was diluted with water, and 100 l per 10 ares was sprayed with foliage from above the whole plant using a small sprayer so that the active ingredient was 6.3 g per 10 ares. . Thereafter, the plants were grown in a greenhouse, and on the 14th day of the treatment, the herbicidal effects were investigated according to the criteria in Table 4. Table 8 shows the results.

[0070]

[Table 8]

Test Example 5 (Crop Selectivity Test by Paddy Soil Treatment) A 1 / 5000a Wagner pot was filled with paddy field soil, water-filled and scratched, and then seeds of barnyard grass (Ec), oak (Mo) and firefly (Sc) were obtained. , And paddy rice (Or) at the 2.0 leaf stage is transplanted at a depth of 2c.
m, and two were transplanted and submerged at a depth of 3 cm. The next day, the prescribed amount of the active ingredient (ai, g / 10) of the wettable powder prepared according to Formulation Example 1
a) was diluted with water and dropped on the water surface. Thereafter, the plants were grown in a greenhouse, and on the 30th day after the treatment, the herbicidal effect and the phytotoxicity were investigated according to the criteria shown in Table 3. Table 9 shows the results.

[0072]

[Table 9]

[0073]

The compound of the present invention represented by the general formula [I] and a salt thereof are useful for various weeds which are problematic in the field, such as P. japonicus, Aobuyu, Shiroza, Hakobe, Ichibi, American stag, and Acacia catechu. , As well as broadleaf weeds such as morning glory, onyx fir, perennial and annual perennial such as hamazuge, yellow fever, cyperaceae, cyperacea, kogomegayatsuri, etc. It exerts an excellent herbicidal effect over a wide range of growing seasons from before the emergence of weeds. In addition, it can also control annual weeds such as red snapper, tamaya-tsuri and konagi which occur in paddy fields, and perennial weeds such as urikawa, omodaka, suzuka-yatsuri, kuroguwai, firefly, and shiramodaka. In addition, the compounds of the present invention and salts thereof do not harm useful crops such as rice, wheat, and corn.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI A01N 43/66 A01N 43/66 43/76 101 43/76 101 43/78 101 43/78 101 C07D 239/60 C07D 239/60 403/12 403/12 405/12 405/12 409/12 409/12 413/12 413/12 417/12 417/12 Examiner Shunichi Yokoo (56) References JP-A-63-258461 (JP, A) JP-A-1-250365 (JP, A) JP-A-3-115205 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 401/12 A01N 43/54 A01N 43/58 A01N 43/60 A01N 43/66 A01N 43/76 A01N 43/78 C07D 239/60 C07D 403/12 C07D 405/12 C07D 409/12 C07D 413/12 C07D 417/12 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A compound of the general formula [Wherein Het is of the formula: In the formula, X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group, a phenyl group, a substituted phenyl group, a lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group, a cyano group, a nitro group, or a lower alkoxycarbonyl group. , An amino group, a lower alkylamino group or a lower dialkylamino group, n represents an integer of 1 to 6, and R ¹ represents a lower alkyl group, a phenyl group or a substituted phenyl group. R represents a hydrogen atom, a lower alkyl group, a formula —CH (R ² ) OR ³中
² represents a hydrogen atom or a lower alkyl group; R ³ represents a lower alkyl group, an alkylcarbonyl group, a phenylcarbonyl group, a substituted phenylcarbonyl group, a lower alkoxycarbonyl group or a formula —C (O) NR ⁴ R ⁵ (wherein R ⁴ and R ⁵
Are the same or different and represent a hydrogen atom or an alkyl group. )} Or a group represented by the formula —N ＝ C (R ⁶ ) ₂ (wherein R ⁶ represents a lower alkyl group). ] The pyrimidine derivative represented by these, and its salt. 2. A herbicide comprising the pyrimidine derivative according to claim 1 and a salt thereof as an active ingredient.