JPS58194866A - Triazole derivative and herbicide containing the same - Google Patents

Abstract

NEW MATERIAL:A 1,2,4-triazole derivative of formula I (R1 is H, alkyl, hydroxyalkyl, cyanoalkyl, acetyl, halogenoacetyl, methoxyacetyl, amino, methoxy, hydroxyl; R3, R4 are H, alkyl, halogen). USE:Herbicide: especially it shows high herbicidal effect against broad-leaf plants. PREPARATION:The reaction of a 4-phenylhydrazono-2-phenyloxazoline-5-derivative with an appropriate amine derivative of formula III is carried out in acetone or dioxane to give a compound of formula I where R2 is a substituent other than acetyl, halogenacetyl and methoxyacetyl. Or the acylation of a 1,2,4- triazole derivative of formula IV with an acid chloride is effected in an inert solvent to give the compound of formula I where R2 is acetyl, halogenoacetyl or methoxyacetyl.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (1) (wherein ■ represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group, and R2 represents a hydrogen atom, an alkyl group, a halogenoalkyl group, or a hydroxyalkyl group).

cyanoalkyl group, acetyl group, halogenoacetyl group,
Represents a methoxyacetyl group, amine group, methoxy group or hydroxyl group, R3, 'it, 'l each represent a hydrogen atom,
The present invention relates to a novel 1,2,4-1J azoyl derivative represented by an alkyl group or a halogen atom, and a herbicide containing the same as an active ingredient.

As a result of various researches, the present inventors have discovered that the 1,2,4-to-IJ azole derivative represented by the above general formula (R) has an excellent practical herbicidal effect, leading to the present invention. .

The compound of general formula (1) of the present invention (hereinafter referred to as the compound of the present invention) does not cause any chemical damage to rice, wheat, corn core, etc., and has been tested in herbicidal tests such as seed germination tests, soil treatment tests, and foliar spray treatment tests. It was discovered that it exhibited herbicidal activity against broad-leaved plants and gramineous plants, and in particular, it had a herbicidal activity that was ineffective against broad-leaved plants (purslane, whitewort, chickweed, aspergillus, etc.). Its application range as a herbicide is paddy fields,
In addition to agricultural land such as fields and orchards, use for floriculture is discouraged.

The compound of the present invention can be synthesized by any of the following reaction formulas.

1) General formula (when R1 in the formula represents a substituent other than an acetyl group, a halogenoacetyl group, or a methoxyacetyl group: As shown in reaction formula 1, 4-phenylhydrazono-
2-phenyloxazoline-5-derivative (II) in acetone or dioxane with a suitable amine derivative (1)
It can be easily synthesized by reacting and then cyclizing using hydrochloric acid.

2) When R in general formula 0) represents an acetyl group, a halogenoacetyl group, or a methoxyacetyl group: 1.2.4-) Riazole visiting conductor (■) as shown in reaction formula 2
' can be easily synthesized by acylating with acid chloride or acid anhydride in an inert solvent such as benzene or toluene.

Shown in Table 1.

-8- Next, the entire synthesis of the compound of the present invention is shown below. Compound numbers correspond to those shown in Table 1.

Synthesis Example 1z Synthesis of Compound No. 2 4-()-, tylphenylhydrazono)-2-phenyloxazolin-5-one (In formula n, R5 is a hydrogen atom R64 represents a methyl group at the 3-position) 2.8f ( 0,0
1 mol) was suspended in 30 ml of acetone, and 4
0% methylamine water 1. Of (0,013 moles) force 0
reflux for 30 minutes, and after cooling, convert the concentrated 4-acid into 1.5-
Drip. After dropping, the mixture is refluxed again for 5 minutes.

After cooling, the precipitate was poured into water of reaction i'i 300-, and the precipitate was recrystallized from ni*, total ethanol-water (10 m-2yd) to obtain colorless crystals of 1.81. Melting point 13
5-6°C, yield 61.7%.

Synthesis Example 2z Synthesis of Compound No. 3 4-(3-methylphenylhydrazono)-2-phenyloxazolin-5-one (In the formula (■), R1 represents a hydrogen atom and R14 represents a methyl group at the 3-position) 2.8 r (
0.01 mol) in addition to 30 ml of dioxane, Anili 7
Add 1.3r (0,013 mol) and reflux for 4 hours.

After cooling, 1.5-ml of concentrated hydrochloric acid was added dropwise and heated at 40°C for 5 minutes. After cooling, the reaction solution was poured into 50 ml of water, the precipitate was collected by filtration, and the precipitate was dissolved in ethanol-dioxane (40 ml-20 ml).
Recrystallization with l) gives pale yellow crystals of 2.42. Melting point: 204-61Q Yield: 66.7% Synthesis Example 3: Synthesis of Compound No. 7 4-(3-Methylphenylhydrazono)'-2-phenyloxazolin-5-one (In formula 2, R8 is a hydrogen atom + R4 is 3-position methyl group) 2.8f (0,0
1 mol) in dioxane 20- and at room temperature 0.9 y (o,ot3 mol) of hydroxyamine hydrochloride are added.

Next, 0.5 y (0,013 mol) of caustic soda? Add 3 tnl Q of the dissolved aqueous solution dropwise. After dropping, 40℃
Heat for 30 minutes. After cooling, 1.5 g of concentrated hydrochloric acid is added dropwise. The container was cooled again to 40°C for 5 minutes. Reaction Q 7z was poured into 200 ml of water, and the precipitate was collected by filtration and washed with acetone-water to obtain light brown crystals of 1.92. Melting point: 155-8°C, yield: 64.
6% Synthesis Example 4: Synthesis of Compound No. 26 1-(3-Me+ruphenyl)-5-phenyl-1,2,
4-) Riazole-3-carboxamide (in the formula (2), R2 and R8 represent hydrogen atoms, and 1t4 represents a methyl group at the 3-position) 2.89 (0.01 mol) was dissolved in 50v of toluene!
Trichloroacetyl chloride 2.29
(0,012 mol) was added in total and refluxed for 2 hours.

The reaction mixture was reduced by km and washed with a small amount of ethanol, resulting in 2
, 5v colorless crystals are obtained. Melting point 161-2°C, yield 59.0% 1-(3-methulfenyl)-5-phenyl-1,2,
4-triazole-3-carboxamide (in the formula ①, R2 and R3 are hydrogen atoms, 1t is a methyl group at the 3-position) 2.8 f (0.01 mol) (i7 toluene 5
Suspend in 0 ml of methoxyacetyl chloride 1.3
y (0,012 mol) and refluxed for 2 hours.

The reaction mixture was concentrated and washed with a small amount of ethanol, resulting in 2
．． 12 colorless crystals are obtained. jslt points 128-30
℃, yield 60% Next, some examples will be given, but the mixing ratio of the phase (1 @ diluent) and the auxiliary agent and the active ingredients can be varied within a wide range.

Example 1; Wettable powder compound A3 50 parts lignin sulfonate 5 parts alkyl sulfonate 3 parts diatomaceous earth
All 42 parts are mixed and crushed and used as an irrigation agent.
Use by diluting with water.

Example 2: Emulsion compound 10 parts 25 parts xylene 65 parts polyoxyethylene alkyl allyl ether 10 parts are uniformly mixed to form an emulsion, which is diluted with water and used.

Example 3: Granule compound @ Genus 12 8 parts bentonite 40 parts clay
45 parts lignin sulfonate
Mix 7 parts uniformly, add water, knead, grind into granules using an extrusion granulator, and dry to make granules.

Next, some test examples will be shown to demonstrate the effectiveness of the compounds of the present invention.

Trial employment example T: 411 was used to test the herbicidal effect of pre-emergence soil treatment.The soil was packed in a planter (F150 x 210 x 200 gourd) to make it look like a field, and after sowing a certain number of yuzu needles of the test plant and covering the soil, the compounds of the present invention were tested. - A diluted solution adjusted to cover 50% of the soil was uniformly spread on the soil surface, and growth was managed in a greenhouse. After 25 days of treatment, evaluation was made based on the following criteria.

Evaluation criteria O No herbicide effect 1 20% weed killing effect 240% 360% 480% 5100% The results of the above tests are shown in Table 2.

The seeds were sown in the same manner as in Test Example 1, and when the plants reached the 1-2 leaf stage, 50? A considerable amount of water suspension was uniformly sprayed on the soil surface of the shoots and leaves, and growth was managed in a greenhouse. The same investigation as in Test Example 1 was conducted 25 days after the treatment.

The results of the above tests are shown in Table 3.

Figure 1 shows compound number 1, Figure 2 shows compound number 2, and Figure 3 shows compound number 3. Figure 4 shows compound number 4. Figure 5 shows compound number 5. Figure 6 shows compound number 6. Figure 7 shows compound number 7. Figure 8 shows compound number 8. Figure 9 shows compound number 9. Figure 10 shows compound number 10. Figure 11 shows compound number 11.
Figure 12 shows compound number 12. Figure 13 shows compound number 13.
．． Figure 14 shows compound number 14. Figure 15 shows compound number 1.
5. Figure 16 shows compound number 16. Figure 17 shows compound number 17. Figure 18 shows compound number 18. Figure 19 shows compound number 19. Figure 20 shows compound number 20°. Figure 21 shows compound number 21. Figure 22 shows compound number 22. Figure 23 shows compound number 23. Figure 24 shows compound number 24. Figure 25 shows compound number 25. Figure 26 shows compound number 26°. Figure 27 shows compound number 27. Figure 28 shows compound number 2B.

Figure 29 shows the infrared absorption spectrum of Compound No. 29, complete procedure amendment, Commissioner of the Japan Patent Office, Kazuo Wakasugi, 1, case description, 1981, Patent Application No. 77010, 2.
, Title of the invention Triazole derivatives and herbicides containing said derivatives 3, Relationship with the case of the person making the amendment Patent applicant 4, Agent Yamada Building 7, 1-1-14 Shinjuku, Shinjuku-ku, Tokyo, Subject of the amendment Specification 8, Inclusion of amendment (amended as "J" on the bottom line of page 2 of the 11th specification.

(2) Amend page 7 of the specification as per Section 4i).

Claims (2)

[Claims] (1) General formula (I) 4 (wherein R, l"j represents a hydrogen atom, an alkyl group or a hydroxyalkyl group, R2 is a hydrogen atom, an alkyl group,
R3,R represents a halogenoalkyl group, a hydroxyalkyl group, a cyanoalkyl group, an acetyl group, a )-logenoacetyl group, a methoxyacetyl group, an amine group, a methoxy group, or a hydroxyl group; each represents a hydrogen atom, an alkyl group or a halogen atom. ) All 1,2.4-) lyazole derivatives. (2) A herbicide containing a 1,2,4-triazole derivative having the general formula (1) (wherein 1 + "2 + R8 + "4 has the same meaning as above).