JPH0637453B2 - Chloroacetic ester derivative - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to 4,5-dihydro-1H-as a herbicide.
The present invention relates to a chloroacetic acid ester derivative as an intermediate raw material for a 1,2,4-triazole-3-carboxylic acid amide derivative.

2. Description of the Related Art Chloro (arylhydrazono) acetic acid esters represented by the general formula (I ') are known.

For example, in Pharmaco Edizione Scientifica Vol. 40, p. 272 (1985), R ¹ of the general formula (I ′) is —CH ₂ CH ₃ and R ² is —CF ₃ , —NO ₂ , —Cl, —NHCOCH ₃
Or R a -N _(CH 3) describes a compound which is COCH _3, West Germany general formula Patent Publication 2017762 (I ')
^1, with _-CH ² CH ₃ ^R 2 is -OCF ₂ CH ₂ F, -
_{OCF 2 CHClF, -OCF 2 CHCl 2} , -OCF
_{2 CHFCF 3, -OCF 2 CHF 2} , -OCF 3, -
SCF _3, compounds of -CClF ₂ or -CH ₃ are described.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present inventors have shown excellent herbicidal effects and studied rice herbicides that do not harm crops such as wheat and corn, and as a result, a general formula having an excellent selective herbicidal effect. (II): (In the formula, R is a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, and a carbon atom. It represents an alkynyl group having 3 to 8 carbon atoms, an alkoxyalkyl group having 3 to 8 carbon atoms, a phenyl group, a halogen-substituted phenyl group, an aralkyl group, or an alkyl group having 2 to 8 carbon atoms substituted with fluorine). 4,5-dihydro-1H-1,2,4
A chloroacetic acid ester derivative useful as an intermediate raw material for a -triazole-3-carboxylic acid amide derivative was found, and the present invention was completed based on this finding.

Composition of the Invention The compounds of the present invention have the general formula (I): Is a chloroacetic acid ester derivative.

In the above formula, R is a linear alkyl group having 1 to 8 carbon atoms, preferably 3 to 6 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms, a phenyl group, halogen, preferably 1 ~
3 is a phenyl group substituted with halogen, an aralkyl group having 7 to 9 carbon atoms, or an alkyl group having 2 to 8 carbon atoms, preferably 2 to 7 carbon atoms, substituted with fluorine, preferably 1 to 15 fluorine.

Table 1 shows the chloroacetic acid ester derivative represented by the general formula (I) and its physicochemical properties, and Table 2 shows the elemental analysis results of these compounds.

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

(In the formula, R has the same meaning as described above.) That is, the aniline derivative (III) is converted to a diazonium salt (IV) by using sodium nitrite in hydrochloric acid,
The desired compound represented by the general formula (I) can be synthesized by reacting with 2-chloroacetoacetic acid ester (V) at preferably -10 to 50 ° C by the method described in JP-B-58-4035. .

The compound of the general formula (III), which is the starting material of the present invention, can be obtained by the following reaction.

(In the formula, R has the same meaning as described above.) First, 3-nitrobenzyl chloride (VI) and general formula (VI
The compound represented by the formula (I) is reacted in the presence of a hydrogen chloride scavenger such as KOH or NaH, preferably at -10 to 150 ° C to obtain a nitrobenzene derivative represented by the general formula (VIII). Then, this nitrobenzene derivative is reduced by a conventional method to easily obtain the aniline derivative represented by the general formula (III).

The compound of the general formula (I)
The reaction for synthesizing the compound of I) is as follows.

(In the formula, R has the same meaning as described above.) Ammonia is reacted with a chloroacetic ester derivative of the general formula (I) in an alcohol at a temperature of preferably -10 ° to 50 ° C, more preferably 0 to 30 ° C. Then, an oxamide derivative represented by the general formula (IX) is obtained. When benzaldehyde (X) is dehydrated and condensed in the presence of an acid catalyst such as acetic acid or p-toluenesulfonic acid at -10 to 150 ° C, 4,5-dihydro-1 represented by the general formula (II) is obtained. A 2,2,4-triazole-3-carboxylic acid amide derivative is obtained.

EFFECTS OF THE INVENTION The chloroacetic acid ester derivative represented by the general formula (I) of the present invention is 4,5-dihydro-containing compound represented by the general formula (II).
It is a compound useful as a raw material of a 1,2,4-triazole-3-carboxylic acid amide derivative (a compound useful as a herbicide, JP-A-63-230676).

The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples.

Example 1 Synthesis of chloro [3-[(3-methylbutoxy) methyl] phenylhydrazono] acetic acid methyl ester (Compound No. 4): 3-[(3-Methylbutoxy) methyl] aniline 19.3 g
(0.1 mol) is dissolved in 30 ml of acetic acid, 26 ml of concentrated hydrochloric acid is added, and the temperature is 0 ° C.
Cooled to. 6.9g of sodium nitrite while stirring
(0.1 mol) dissolved in 12 ml of water, the reaction temperature is 5 ℃
A diazonium salt solution was prepared by dropping so as to keep the content below. 15.1 g (0.1 mol) of 2-chloroacetoacetic acid methyl ester was added to a mixture of 70 ml of methanol, 50 ml of water and 40.8 g (0.3 mol) of sodium acetate trihydrate and cooled to 0 ° C.
Add the diazonium salt solution prepared above to this over 15 minutes,
The mixture was stirred at 0 ° C for 1 hour and at room temperature for 3 hours. 100 ml of water was added, and the mixture was extracted twice with 150 ml of benzene. The organic layer was washed with water, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous sodium sulfate. The extract obtained by distilling off the solvent was purified by silica gel chromatography (developing solution; dichloromethane) to obtain 29.3 g (93.8% yield) of a pale yellow extract.

Example 2 Synthesis of chloro [3- (phenoxymethyl) phenylhydrazono] acetic acid methyl ester (Compound No. 7): 10.0 g (0.05 mol) of 3- (phenoxymethyl) aniline was dissolved in 15 ml of acetic acid and 13 ml of concentrated hydrochloric acid was added. The mixture was cooled to 0 ° C. A solution of 3.5 g (0.05 mol) of sodium nitrite dissolved in 6 ml of water was added dropwise while maintaining the temperature at 5 ° C or lower to prepare a diazonium solution. 7.5 g of 2-chloroacetoacetic acid methyl ester (0.0
35 mol of methanol, 25 ml of water and sodium acetate
The mixture was added to a mixture of 20.4 g (0.15 mol) of trihydrate and cooled to 0 ° C. The above diazonium salt solution was added dropwise to this at 0 ° C for 1
For 3 hours at room temperature. Remove the deposited crystals,
It was washed with water and dried. This was recrystallized from dichloromethane-carbon tetrachloride to obtain 14.6 g (91.2% yield) mp.

Reference Example 1 Synthesis of 1-[(3-methylbutoxy) methyl] -3-nitrobenzene (a compound in which R represents a 3-methylbutyl group in the general formula (VIII)): 158.1 g (0.92 mol) of 3-nitrobenzyl chloride 3-
It was dissolved in a mixture of 500 ml of methyl-1-butanol (4.59 mol, 5 eq) and 140 ml of dimethylformamide. 78 g of KOH pellets while stirring vigorously while cooling in a water bath
(1.39 mol, 1.5 eq) was added. The reaction temperature rose to 43 ° C and then gradually returned to room temperature. The stirring reaction was completed for 7 hours at room temperature.

The solid of the reaction solution was separated, the solution was adjusted to pH 2 with hydrochloric acid, and then excess alcohol and dimethylformamide were distilled off. The residue was dissolved in a mixed solvent of n-hexane (450 ml) -ethyl acetate (50 ml), washed successively with 1N-HCl and saturated brine, and dried over magnesium sulfate. After distilling off the solvent, fractional distillation was carried out to obtain 185.2 g of the target product at bp 116-117 ° C (0.08 mmHg).
(90.1% yield) was obtained.

Reference Example 2 Synthesis of 3-[(3-methylbutoxy) methyl] aniline (a compound in which R represents a 3-methylbutyl group in the general formula (III)): 130 g (0.58 mol) of the nitrobenzene derivative obtained in Reference Example 1
Is dissolved in 150 ml of ethanol, and 0.6 g of 10% palladium on carbon is dissolved.
Was added. While stirring, 89 ml (1.84 mol) of hydrazine hydrate was added dropwise at a rate at which foaming did not become severe. After completion of dropping, the reaction was completed by refluxing for 3 hours on a hot water bath. After allowing the reaction solution to cool, the catalyst was separated and washed with ethanol. The solution was concentrated, then dissolved in 300 ml of dichloromethane, washed successively with a 10% aqueous sodium carbonate solution and saturated brine, and dried over anhydrous potassium carbonate. The solvent is distilled off, the residue is fractionally distilled and bp10
109.2 g (97.1% yield) of the desired product was obtained at 5-6 ° C (0.19 mmHg).

Reference Example 3 Synthesis of oxamide 3-[(3-methylbutoxy) methyl] phenylhydrazone (a compound in which R represents a 3-methylbutyl group in the general formula (IX)): 15.9 g of chloroacetic acid ester derivative (Compound No. 4) A solution of 0.05 mol) in 20 ml of dichloromethane was carefully poured into 100 ml of ice-cooled ammonia-methanol solution (containing 20% of ammonia), stirred for 30 minutes, sealed, and left overnight. The solvent was evaporated and the obtained residue was dispersed in ethyl acetate and water to separate the organic layer. The extract was washed with water and saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated. The brown oil was purified by silica gel chromatography (developing solution; dichloromethane / ethyl acetate = 4/1, V / V) to give a pale yellow oil (11.4 g, 80.6%).
Yield) was obtained.

Reference Example 4 4,5-dihydro-1- [3-[(3-methylbutoxy) methyl] phenyl] -5-phenyl-1H-1,
Synthesis of 2,4-triazole-3-carboxylic acid amide [a compound in which R represents a 3-methylbutyl group in the general formula (II)]: 2.78 g (0.01 mol) of the oxamide derivative obtained in Reference Example 3 was saturated with nitrogen. Benzaldehyde 1.17 dissolved in 12 ml acetic acid
g (0.011 mol) was added under a nitrogen atmosphere and the mixture was stirred as it was for 16 hours at room temperature. Water saturated with nitrogen was added to collect precipitated crystals, which were dried in vacuum. Recrystallization from ethyl acetate-n-hexane substituted with nitrogen gave yellow needle crystals 3.11 g (84.4%
The desired product (yield), mp 144-6 ° C., was obtained.

Reference Example 5 [4,5-Dihydro-1,2,4-triazole-3-
Example of weeding test of carboxylic acid amide (general formula II)) Sand loam soil was packed into a planter (650 × 210 × 220 mm) to form a field, and a certain amount of plant seed was sown to cover the soil.

50 parts of the compound represented by the general formula (II), 5 parts of lignin sulfonate, 3 parts of alkyl sulfonate and 42 parts of diatomaceous earth were mixed and pulverized to prepare a wettable powder, which was diluted with water to a predetermined concentration and then spray gun. The amount of the active ingredient was 200 g / 10a was evenly sprayed on the soil surface, and then the glass was grown and controlled at room temperature.
On the 21st day from the above treatment, the herbicidal effect against each weed and the phytotoxicity against the crops were observed and evaluated according to the following criteria to obtain the results shown in Table 3.

Evaluation criteria: 0 ……… No effect 1 ………… Less than 30% herbicidal effect 2 ……… 31-50% herbicidal effect 3 ………… 51-70% herbicidal effect 4 ………… 71 ～ 90% herbicidal effect 5 ………… 91 ～ 100% herbicidal effect Chemical damage degree －－ …… Harmless, ± …… Slight harm, + …… Intermediate harm …… Strong harm,… Major harm

Claims (1)

[Claims] 1. General formula (I): (In the formula, R is a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, a phenyl group, a halogen-substituted phenyl group, an aralkyl group, or a fluorine-substituted C 2 to 2 Which represents the alkyl group of 8).