JP2512303B2 - Phenylhydrazone derivative of 2-oxazoline-4,5-dione - Google Patents

Description

The present invention relates to a phenylhydrazone of 2-oxazoline-4,5-dione useful as an intermediate for the production of phenylhydrazone derivatives of oxamide having excellent selective herbicidal activity. Regarding derivatives.

(Prior Art) Conventionally, several compounds have been reported as phenylhydrazone derivatives of 2-oxazoline-4,5-dione.

For example, Chemical Abstrac
ts) 98 (11), 88326y and tetrahedron, 1975, 25-2
Each 9 discloses a substituted phenylhydrazone of 2-oxazoline-4,5-dione. In addition, JP-A-57-193406
Is an intermediate for producing a 1,2,4-triazole derivative,
The following formula (In the formula, X ¹ represents hydrogen, alkyl having 1 to 3 carbon atoms, fluorine, chlorine, iodine, fluorine-substituted alkyl, nitro, methoxy, X ² represents hydrogen, chlorine, methyl, X ³ is hydrogen, 2-oxazoline-represented by
Disclosed are phenylhydrazone derivatives of 4,5-dione.

(Problems to be Solved by the Invention) The present inventors show excellent herbicidal effect,
As a result of research on herbicides that do not harm crops such as wheat and corn, general formula (II) having excellent selective herbicidal effect: (In the formula, R ¹ is a linear alkyl having 2 to 10 carbons, and 3 to 3 carbons.
10 branched or cyclic alkyl, 4 to 10 carbon atoms
Alkyl substituted with an alicyclic structure, phenyl, halogen-substituted phenyl, aralkyl having 7 to 9 carbon atoms, alkenyl having 3 to 6 carbon atoms, and 2 to 4 carbon atoms substituted with alkoxy having 1 to 4 carbon atoms. Or an alkyl group having 1 to 19 fluorine atoms and having 2 to 10 carbon atoms, and R ² is hydrogen, fluorine, chlorine, methyl or methoxy). 2
A phenylhydrazone derivative of -oxazoline-4,5-dione has been found, and the present invention has been completed based on this finding.

(Structure of the Invention) The compound of the present invention has the general formula (I): Is a phenylhydrazone derivative of 2-oxazoline-4,5-dione.

In the above formula, R ¹ is a linear alkyl having 2 to 10 carbon atoms, preferably 3 to 6 carbon atoms, a branched alkyl or cyclic alkyl having 3 to 10 carbon atoms, preferably 3 to 7 carbon atoms, 4 to 10 carbon atoms, preferably Alkyl substituted with an alicyclic structure of 4 to 7, phenyl,
Phenyl substituted with halogen, preferably halogen of 1 to 3, aralkyl having 7 to 9 carbon atoms, alkenyl having 3 to 6 carbon atoms, and 2 to carbon atoms substituted with alkoxy having 1 to 4, preferably 4 carbon atoms. 4, preferably 2 alkyl or 1 to 19 fluorine, preferably 3 to 12 fluorine substituted alkyl having 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, R ² is hydrogen, fluorine, Represents chlorine, methyl or methoxy.

The phenylhydrazone derivative of 2-oxazoline-4,5-dione represented by the general formula (I) is shown in Table 1, and its physicochemical properties and elemental analysis results are shown in Table 2.

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

(In the formula, R ¹ and R ² have the same meanings as described above.) First, nitrobenzene chloride is reacted with R ¹ OH in the presence of a hydrogen chloride scavenger such as KOH, preferably at −10 to 150 ° C. for etherification. Then, it is reduced by a method such as catalytic reduction to obtain an aniline derivative, and diazotized according to a conventional method to synthesize a diazo compound.

Separately, for example, a hippuric acid derivative is reacted with acetic anhydride to dehydrate and cyclize to synthesize a 2-oxazoline-5-one derivative, and this and a diazo compound are preferably diazo-coupled at −50 to 100 ° C. The compound of the present invention represented by (I) can be synthesized.

The compound of general formula (II) can be easily synthesized according to the following reaction using the compound of general formula (I) of the present invention as a starting material.

(In the formula, R ¹ and R ² have the same meanings as described above.) That is, 2-oxazoline-4,5-of the general formula (I)
When the phenylhydrazone derivative of dione is reacted with ammonia in a solvent such as acetone, preferably at -10 to 50 ° C for 0.1 to 10 hours, the oxamide derivative represented by the general formula (II) is obtained.

EFFECT OF THE INVENTION 2-oxazoline represented by the general formula (I) of the present invention
The phenylhydrazone derivative of 4,5-dione is a compound useful as a raw material for the oxamide derivative represented by the general formula (I), which is a compound useful as a herbicide.

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

Synthesis Example 1 Synthesis of 1- (3-methylbutoxy) methyl-3-nitrobenzene 38.1 g of 3-nitrobenzyl chloride (158.1 g, 0.92 mol)
-Methyl-1-butanol 500 ml (4.59 mol, 5 equivalents)
And 140 ml of dimethylformamide. While stirring vigorously while cooling in a water bath, 78 g of KOH pellets
(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 in 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, the fraction of bp116-117 ℃ (0.08mmHg) is collected by fractional distillation.
185.2 g (90.1% yield) of 1- (3-methylbutoxy) methyl-3-nitrobenzene was obtained.

Synthesis Example 2 Synthesis of 3-[(3-methylbutoxy) methyl] aniline 130 g (0.58 mol) of the nitrobenzene derivative obtained in Synthesis Example 1 was dissolved in 150 ml of ethanol and 10% palladium carbon was added.
0.6g was added. While stirring, 89 ml of hydrazine hydrate (1.
84 mol) was added dropwise at such a rate that foaming did not become violent. 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.
Concentrate the solution and dissolve it in 300 ml of dichloromethane.
% Sodium carbonate aqueous solution and saturated saline solution, and dried over anhydrous potassium carbonate. The solvent was distilled off and the residue was fractionally distilled to obtain bp.
Fraction of 105-6 ℃ (0.19mmHg) was collected and 109.2g (97.1%)
Yield) of 3-[(3-methylbutoxy) methyl] aniline was obtained.

Example 1 2- (2-Fluorophenyl) -2-oxazoline-4,
Synthesis of 4- [3-[(3-methylbutoxy) methyl] phenylhydrazone] of 5-dione (Compound No. 17) 2-fluorohippuric acid 3.94 g, sodium acetate 3.28 g, and acetic anhydride 17.4 ml at 60 ° C. After stirring for 20 minutes to prepare 2- (2-fluorophenyl) -2-oxazolin-5-one, it was quickly cooled with ice water.

On the other hand, 3- [3-methylbutoxy) methyl] aniline
A mixture of 3.48 g (18 mM), 3% HCl (3.4 ml) and acetic acid (12 ml) was stirred under ice-water cooling, 2.8 ml of isopentyl nitrite was added, and the mixture was stirred for 10 minutes to prepare a diazonium salt.

The mixture containing 2- (2-fluorophenyl) -2-oxazolin-5-one prepared above was stirred under ice water cooling. Add the prepared diazonium salt there over 2 minutes, and
Stir for 1 minute and continue stirring for another 1 hour and 30 minutes. Then, ice water (40 ml) and petroleum ether (20 ml) were added and the mixture was stirred for 2 hours. The orange precipitate was collected by filtration and air dried to obtain 2.45 g (35.5% yield) of the desired product.

Example 2 4-Phenyl-2-oxazoline-4,5-dione
[3-[(2,2,3,3-Tetrafluoropropoxy) methyl] phenylhydrazone] (Synthesis of Compound No. 11 60 g of hippuric acid 0.9 g, sodium acetate 0.82 g and acetic anhydride 6 ml)
2-Phenyl-2-oxazoline-
After the 5-one was prepared, it was immediately cooled with ice water.

On the other hand, 3-[(2,
2,3,3-Tetrafluoropropoxy) methyl] aniline
A mixture of 1.07 g, 0.85 ml of 35% HCl and 8 ml of acetic acid was stirred under cooling with ice water, 0.7 ml of isopentyl nitrite was added thereto, and the mixture was stirred for 10 minutes to prepare a diazonium salt.

2-phenyl-2-oxazoline-5-prepared previously
The mixture containing ON was stirred under ice water cooling. The prepared diazonium salt was added thereto over 2 minutes, stirred for 30 minutes, and further stirred at room temperature for 1 hour 30 minutes. Then, 40 ml of ice water and 20 ml of petroleum ether were added, and the mixture was stirred for 2 hours, then the yellow precipitate was collected by filtration and air dried to obtain 1.6 g (87% yield) of the desired product.

Example 3 2- (2-Fluorophenyl) -2-oxazoline-4,
Synthesis of 5-dione 4- [3- (butoxymethyl) phenylhydrazone] (Compound No. 15) 2-fluorohippuric acid 1.97 g, sodium acetate 1.64 g, and acetic anhydride 8.7 ml were stirred at 60 ° C. for 20 minutes. 2- (2-Fluorophenyl) -2-oxazolin-5-one was prepared and immediately cooled with ice water.

On the other hand, 3-synthesized in the same manner as in the methods of Synthesis Examples 1 and 2
(Butoxymethyl) aniline 1.61g (9mM) and 35% HCl1.7
The mixture of 8 ml of acetic acid and 8 ml of acetic acid was stirred under cooling with ice water, 1.4 ml of isopentyl nitrite was added thereto, and the mixture was stirred for 10 minutes to prepare a diazonium salt.

The mixture containing 2- (2-fluorophenyl) -2-oxazolin-5-one prepared above was stirred under ice water cooling. Add the prepared diazonium salt there over 2 minutes, and
The mixture was stirred for 1 minute, and further stirred at room temperature for 1 hour and 30 minutes. Then, 40 ml of ice water and 20 ml of petroleum ether were added, and the mixture was stirred for 2 hours. The yellow-orange precipitate was collected by filtration and air-dried to give 1.2 g (36% yield).
I got the object.

Reference Example 1 1- [3 of 1- (2-fluorobenzoyl) oxamide
Synthesis of-[(3-methylbutoxy) methyl] phenyl] hydrazone (Compound No. 17 ') 1.5 g of 2-oxazoline-4,5-dione phenylhydrazone derivative (Compound No. 17) synthesized in Example 1 The mixture was stirred at room temperature in 30 ml of ether. There 35% NH ₃ water 0.5 ml
Was added and stirred for 30 minutes, 60 ml of hexane was added, and the precipitate was collected by filtration and air-dried to obtain 1.22 g (78% yield) of the desired product having an mp of 138-140 ° C. Table 3 shows the phenylhydrazone derivative of oxamide synthesized in the same manner as above from the phenylhydrazone derivative of 2-oxazoline-4,5-dione.

Reference Example 2 Preparation of wettable powder Compound No. 4'50 parts Lignin sulfonate 5 parts Alkyl sulfonate 3 parts Diatomaceous earth 42 parts are mixed and pulverized to obtain a wettable powder, which is diluted with water and used.

Reference Example 3 Preparation of emulsion Compound No. 4'25 parts xylene 65 parts Polyoxyethylene alkylallyl ether 10 parts are uniformly mixed to form an emulsion, which is diluted with water and used.

Reference Example 4 Preparation of granules Compound No. 17 ′ 8 parts Bentonite 40 parts Clay 45 parts Lignin sulfonate 7 parts Uniformly mixed and further mixed with water Kneaded into granules by an extrusion granulator, dried and granulated And

Reference Example 5 Effect on Upland Weeds (Soil Treatment Before Germination) A planter (650 × 210 × 220 mm) was filled with sandy loam soil to form a field, and Aoyu, Kosendan, wild mustard,
Chickweed, dogwood, velvetleaf, edible millet, crabgrass,
After sowing a certain amount of wheat and corn seeds and covering the soil,
A wettable powder prepared in the same manner as in Reference Example 2 was diluted to a predetermined concentration with water, and a spray gun was used to evenly spray an amount of the active ingredient of 200 g / 10a on the soil surface, and then grow in a glass greenhouse. Managed.

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 4.

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 Effect 5 …… 91 ~ 100% herbicidal effect Chemical damage degree －－ …… No harm ± …… Slight harm + …… Mild harm …… Strong harm …… Major harm Reference Example 6 Effect on upland weeds (post-emergence soil treatment) According to the same procedure as described in Test Example 1, seeds of various plants were sown, and each plant reached the 1-2 leaf stage. Similar to the above, a wettable powder diluted with water is sprayed evenly on the foliage and soil surface of each plant with a spray gun so that the amount of the active ingredient sprayed is 200g / 10a, and then grown again in the glass greenhouse. Then, 21 days after the treatment, the same criteria as those shown in Reference Example 5 were evaluated and the results shown in Table 5 were obtained.

Reference Example 7 Effects and phytotoxicity on paddy field weeds Water is poured into a 1/2000 arel Wagner pot filled with paddy soil to make it a submerged state, and seeds of Taenia cinerea, firefly, Hera modaka, eel, and pearl vine are sown.
Planted tubers of Mizuhaya. Furthermore, after transplanting two paddy rice seedlings (cultivar Sasanishiki) at the two-leaf stage, the pot was grown in a greenhouse for 3 days, and the emulsion prepared in the same manner as in Reference Example 3 was diluted with water to a predetermined concentration, and the effective amount of the active ingredient was 200 g. The amount of / 10a was uniformly dropped on the water surface. Twenty-one days after the chemical treatment, the herbicidal effect and the degree of phytotoxicity of the paddy rice were investigated according to the same criteria as in Reference Example 5, and the results shown in Table 6 were obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroe Shinkawa 14 Suga Nishiki-cho, Iwaki City

Claims (1)

(57) [Claims] 1. A general formula (I) (In the formula, R ¹ is a linear alkyl having 2 to 10 carbons, and 3 to 3 carbons.
10-branched alkyl or cyclic alkyl substituted with an alicyclic structure having 4 to 10 carbon atoms, phenyl, halogen-substituted phenyl, aralkyl having 7 to 9 carbon atoms, alkenyl having 3 to 6 carbon atoms, and 1 carbon atom Represents an alkyl having 2 to 4 carbons substituted with alkoxy of 4 to 4 or an alkyl having 2 to 10 carbons substituted with 1 to 19 fluorine, and R ² represents hydrogen, fluorine, chlorine, methyl or methoxy. A phenylhydrazone derivative of 2-oxazoline-4,5-dione represented by