JPS6281360A - Cyanohexanilide derivative and herbicide for paddy field containing said derivative as active constituent - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (X is halogen, cyano, methyl, trifluoromethyl, etc.; Y is H, halogen, cyano, etc.; X and Y may link to form a ring through 3,4-trimethylene or 3,4-dioxymethylene). EXAMPLE:N-(3-chlorophenyl)-2-cyano-3-methyl-hexanamide. USE:A herbicide for paddy field useful particularly for barnyard grass, bulrush, monochoria, spike-flowered rotala, false pimpernel, long-stemmed waterwort, etc., with very slight phytotoxicity to rice plants. PREPARATION:A 2-cyanoacetanilide expressed by formula II is reacted with a 2-halogenated pentane expressed by formula III (Z is halogen) in a solvent, e.g. acetone, in the presence of a base, e.g. NaOH, at 0-100 deg.C to afford the aimed compound expressed by formula I.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel anohexaani IJ derivative,
The derivatives are useful as herbicides for rice fields.

[Conventional technology]

A chemical compound having herbicidal activity in an anohexaani IJ derivative was described by Arthur B, Gels.
Peet, ic, Sci, 1+ by Sler et al.
452-438 (+980).

Although the above literature describes that N-phenyl-2-cyano-3-methylhexanamide has a herbicidal effect on weeds in fields, it is not clear whether it can be used to control noxious weeds in rice fields. There is no mention of anything about that.

[Problem that the invention seeks to solve]

N-phenyl-2-cyano-3-methylhexanamide described in the above document cannot be used as a herbicide in rice fields because it does not have sufficient herbicidal effects in rice fields and causes chemical damage to crops. There is a desire for a compound that can kill grass weeds without causing any phytotoxic effects.

[Failure to solve the problem]

The present inventor conducted intensive studies on paddy field weed control agents, and as a result, the formula [1] (in the formula, or a halogen atom, a diano group, a methyl group.

Trifluoromethyl group, ethyl group, ethynyl group.

It represents a methoxy group, and Y represents a hydrogen atom, a halogen atom, a cyano group, or a methyl group. However, Y is a halogen atom,
When it represents a cyano group, a methyl group, or a halogen atom, an ano group, or a methyl group. Or also connect with Y, 3.
4-) A ring may be formed by a rimetherene group or a 3,4-dioxymethylene group. The present inventors discovered that the compound represented by ) exhibits strong herbicidal activity and has little toxicity to paddy rice, making it a practical herbicide for paddy fields.This led to the completion of the present invention.

The novel cyanohexanilide derivative represented by formula [1] of the present invention can be produced, for example, by the following method.

Production method A: 2-cyanoacetanilide represented by the following formula (2) (
In the formula, X and Y are the same as in formula (1)) and 2-halogenated pentane represented by formula (3)
f) and acetone, benzene, toluene.

In an inert solvent such as chlorobenzene, DMF,
NaOH, No□co3. KOH, K2CO3, N
O to 100°C, preferably 0 to 100°C in the presence of a base such as aH
It can be synthesized by reacting at 50°C.

Manufacturing method B: (4) (s)! Substituted nitrogen represented by formula (4) (wherein X and Y
is the same as formula (5)) and 1-methylbutyl-cyanoacetic acid tobenzene, toluene, xylene,
0 to 100 in an inert solvent such as chlorobenzene, 1,2-dichloroethane, dichloromethane, ethyl acetate, or chloroform, using a dehydrating agent such as C,C,(N,N'-dicyclohexylcarbodiimide). It can be synthesized by dehydration condensation at a temperature of preferably 0 to 50°C.

The compound of formula (5) as a raw material is R, Alexand
The method of e r et al. (J, Am, Chem, Sac+194
4.66, 686) using an alkali such as NaOH,
It is obtained by hydrolysis in a mixed solvent of water and alcohol, followed by acid precipitation using hydrochloric acid or sulfuric acid to form a carboxylic acid.

Production method C: The compound represented by general formula (1) can also be produced by the above-mentioned Arthu
r E, Gelssler et al.'s method (Pe8tic,
Sci., 11452-438, 1980), the aniline compound represented by the formula (4) (in which X and Y
is the same as formula (1)) and 1-methylbutyl-cyanoacetate represented by formula (6) (in the formula, R is lower alkyl), and the mixture is heated to a temperature higher than the boiling point of the alcohol to be produced, preferably from 180 to 200°C. It is synthesized by dealcoholization and condensation by heating.

At this time, the reaction may be carried out in an inert gas flow such as nitrogen gas or argon gas.

The compound of formula (2) as a raw material can be synthesized in the same manner as the production method B described above, using cyanacetic acid in place of the compound of formula (3), or in place of the compound of formula (6). It can be synthesized in the same manner as the production method C described above using cyanacetic ester.

When using the compounds of the invention as herbicides.

Depending on the purpose of use, it may be used as is or mixed with pesticide adjuvants to enhance or stabilize the effect.

By the method commonly used in the agricultural chemical manufacturing field,
It can be used in the form of powders, fine granules, wettable powders, flowable preparations, emulsions, and the like.

These various formulations are used in actual use.

It can be used directly or diluted with water to the desired concentration.

Agrochemical auxiliaries include carriers (diluents) and other auxiliaries such as spreading agents and emulsifiers.

Wetting agents 1 Dispersants, fixing agents, disintegrants, binders, etc. can be mentioned.

Examples of liquid carriers include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as ligroin and kerosene, alcohols such as methanol, butanol and glycol, ketones such as acetone, amides such as dimethylformamide, dimethyl sulfoxide, etc. sulfoxides, methylnaphthalene, cyclohexane, animal and vegetable oils, fatty acids, fatty acid esters, etc.

Solid carriers include clay, kaolin, and talc.

Diatomaceous earth, silica, calcium carbonate, montmorillonite,
bentonite, feldspar 1 quartz, alumina, potassium chloride,
Sawdust, etc. can be raised.

In addition, surfactants are usually used as emulsifiers or dispersants, such as anionic surfactants such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, lauryl betaine, cationic surfactants, Nonionic surfactants 1 Examples include amphoteric surfactants.

Spreading agents include polyoxyethylene nonylphenyl ether and polyoxyethylene lauryl ether; wetting agents include dialkyl sulfosuccinate,
Polyoxyethylene nonylphenyl ether, etc., fixing agents include carboxymethyl cellulose or polyvinyl alcohol, disintegrants include sodium lignin sulfonate or calcium salts of carboxymethyl cellulose, binding agents include xanthan gum, sodium polyacrylate, etc. .

All formulations can not only be used alone, but also mixed with fungicides, insecticides, plant growth regulators, acaricides, agricultural and horticultural fungicides, soil fungicides, soil conditioners, or nematicides. It can often be used in combination with fertilizers and other herbicides.

The active ingredient compound content in the herbicide of the present invention is 95% (by weight) depending on the formulation form, application method, and other conditions.
Preferably it is in the range of 0.5 to 50% (by weight).

Further, when weeding with the herbicide of the present invention, the amount used varies depending on the compound used and the place of application, but it is usually used within the range of 11, preferably 507 active ingredient compounds per are.

〔Effect of the invention〕

The compound of the present invention has a high herbicidal effect on paddy field weeds such as Japanese millet, bulrush, Japanese grasshopper, Japanese grass weed, azalea, and chickweed, and has extremely low phytotoxicity to rice.

〔Example〕

The present invention will be explained below with reference to Examples.

Synthesis Example 1 Synthesis of N-(3-chlorophenyl)-2-cyano-3-methyl-hexanamide (compound 42) N-(3-chlorophenyl)-2-cyanoacetamide 5g (0,02
6 mol) in N,N-dimethylformamide 20 me, sodium hydride (approximately 60% oily) +, o7
Add. While cooling the reactor with ice water, 3.97 (0,026 mol) of 2-bromopentane is added dropwise.

After stirring at around 0°C for 50 minutes, the mixture was left standing at room temperature overnight.

The reaction solution was poured into water and extracted with ethyl acetate. The organic layer is washed with water, dried over anhydrous sulfuric acid, and concentrated. The obtained oily substance is purified by column chromatography using silica gel to obtain the desired colorless oily substance 5.
・11 was obtained.

(Yield 74%). ? L2D': 1.5413 elemental analysis value C14H17CIN20 calculated value C=65.51%
H = 6.47% N = 13.5 [1% actual value C = 6 M
, 15%H: 6.51% N=lQ, 5Q% Synthesis Example 2 N-(3,5-dimethylphenyl)-2-cyano-3-
Synthesis of methyl-hexanamide (compound &18) 5.5-dimethylaniline 4.259 (0,035 mol) and N,N'-dicyclohexylcarbodiimide CD
, C, C) a, b a? is dissolved in 100R1 dichloromethane. A dichloromethane solution of 6.43r (o, o4t4g) of 1-methylbutylcyanoacetic acid is added dropwise to this at room temperature. After stirring at room temperature for 1 hour, the precipitated crystals are filtered, washed with water, dehydrated with anhydrous sodium sulfate, and concentrated. The obtained oily substance was subjected to column chromatography using silica gel-1? When made by fif, it is 8.91° (
A colorless oil with a yield of 98% was obtained, which after a while turned into white crystals with a slight paste mixture. Melting point 70-
85℃ Elemental analysis value C16H22N20 Calculated value C==74.38%H=13.58%lJ
o, a 4% actual value C=74.50%H=13.5
6%N=10.80% Synthesis Example 5 Synthesis of N-(5-methylphenyl)-2-cyano-3-metalhexanamide (Compound &5) 5-methylaniline 5.569 (0.05 mol) 1-methylbutyl-
7Anoacetic acid ester 9.16 jil (0.05
2 moles) and heated to 180-200℃ under nitrogen gas stream.
Heat for an hour. After cooling, the mixture is extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and concentrated. The obtained crude oily substance was purified by column chromatography using silica gel to obtain a colorless oily substance of 7.59%.

7%'1.52'82 Elemental analysis value C15H2ON20 Calculated value C=73.73%H==8.25%N=11.
46% actual value C=75.90%H==8.14%N=
=11.52% Examples of compounds obtained by the above method are shown in Table 1.

Derivatives shown in Table 1 Next, the formulation examples of the present invention will be explained in more detail.
The types and mixing ratios of additives are not limited to these, and can be used in a wide range. In addition, the parts are the parts by weight.

Formulation Example 1 35 parts of xylene was added to 50 parts of emulsion compound No. 9 to dissolve it, and a mixture of polyoxyethylene alkylphenyl ether and calcium alkylbenzenesulfonate (3:
2) An emulsion is obtained by mixing with 15 parts. To use it, dilute it with water to a concentration of 0.01-1%.

Formulation Example 2 Powder A powder is obtained by adding 95 parts of clay to 5 parts of Compound No. 25 and mixing and pulverizing the mixture. This is used for direct spraying.

Formulation Example 3 Wettable powder Compound No. 20 was mixed with 50 parts of diatom ±10 parts and 32 parts of kaolin.
2. % of the carrier and further mixed with sodium lauryl sulfate.
Eight parts of a mixture of sodium 2'-dinaphthyl methanesulfonate was mixed uniformly and then pulverized to obtain a finely powdered hydrating powder. This product is used as a suspension after diluting O,Q (16-1% concentration).

Formulation Example 4 Granules-1 Put 5 parts of fine powder of Compound No. 22, 70 parts of clay powder, 20 parts of bentonite as a binder, and 5 parts of sodium dodebulpenzenesulfonate as a wetting agent into a suitable mixer, and mix with a suitable mixer. Add moisture, granulate using an extrusion granulator, dry, and sieve to obtain granules.

Formulation Example 5 Granules-2 5 parts of fine powder of Compound No. 17, 93.5 parts of potassium chloride, 1 part of sodium polyacrylate, and 0 xanthan gum.
Put 5 parts into a suitable mixer, add appropriate moisture, granulate with an extrusion granulator, dry, and sieve to obtain granules.

Next, an experimental example will show that the cyanohexanilide derivative represented by formula (1) is useful as an active ingredient of a herbicide for rice fields. The cyanohexanilide derivative represented by formula (1) is shown by the compound number in Table 1, and the compound used for comparison is shown by the compound symbol in Table 2.

Table 2 Experimental Example 1 Pre-flooding treatment before emergence of rice paddy soil A certain amount of paddy soil was filled in a 115,000 are Wagner pot and used as a planting stock to grow Japanese millet, -year-old broad-leaved weeds (Japanese grasshopper, Japanese azalea, azalea, and chickweed), and firefly. A certain amount of seeds were sown.

Furthermore, after water-logging to a depth of 5 crn, the active ingredient compound of the present invention was found to be s per area, 12-12.5? The diluted solution was added dropwise into the flooded water.

Three days later, three paddy rice seedlings (Nihonbare) at the 2.5 leaf stage were transplanted. Thirty days after the chemical treatment, the herbicidal effect and the presence or absence of chemical damage to paddy rice were determined. The test was conducted according to the following criteria and the results shown in Table 3 were obtained.

Weeding effect index Phytotoxicity index 5: Complete weeding 5: Deadness 4: Weeding around 80% 4: Severe damage 5 = around 60% weeding 3: Nakayori 2: Weeding around 40% 2: Shogaku 1: Around 20% Weeding 1: Slight harm O: No effect O: Harmless Table 3 2 3.12 5. B
5.0 4.8 012.5 5.
05.05.0 9 3, +2 4.8 4.0 5.5 0+
2.5 5.0 5.0 5.0 0it
3.12 5.0 5.0 2.0 012.5
5.0 5.0 3.0
012 3.12
5.0 5+0 2.0 012.
5 5.0 5.0 4.
0 017 3.12 5.0 5.
0 2.0 0+2.5 5.0
5. B 3.0 0185 work 12 5.
0 5.0 2.5 012.5 5
．． 0 5.0 5.0 0
21 3.12 5.0
5.0 5.5 012.5
5.0 5.0 5. B
022 3.12 4.5 2.5 0
．． 5 012.5 5.0 5.0 5.0
023 3.12 5.0
5.0 0.5 012.5
5.0 5.0 2.5 024
3.12 5.0 5.0
2.0 012.5 5.0 5.
0 5.0 0 Control Compound A 3.12 2.0 0.0
0 1.012.5 4eO1
,02,Os,.

B 5.12 5.0 4.0
0 2.0 Experimental Example 2 After the emergence of paddy field weeds, submergence treatment A fixed amount of paddy soil was filled in a 115,000 are Wagnerbot, and the soil was used as a planting layer to grow Japanese millet, -year-old broad-leaved weeds (Prunus elegans, Kikashigusa, Azena, Mizopakohe), and Firefly. A certain amount of seeds were sown.

Furthermore, 3 days after the water was flooded to a depth of 3-.

Six paddy rice seedlings (Nihonpare) at the 2.5 leaf stage were transplanted.

After transplantation, when the leaf stage of the Japanese millet reached 2.5 leaves, a diluted solution containing the active ingredient compound of the present invention in an amount of 5.12 to 12.52 per are was dropped into the flooded water.

Thirty days after the chemical treatment, the herbicidal effect and the presence or absence of chemical damage to paddy rice were investigated.

The investigation was conducted based on the following criteria and the results shown in Table 4 were obtained.

Table 4 2 3.12 2.0
4.5 2.5 012.5
5.0 5.0 5.0
05 3.12 2.
0 4.5 2.5
012.5 5.0 5.0
5.0 G? 3
．． 12 2.5 5.0 2.
0 012.5 5.0
5.0 4.5 016
3.12 2.0 4.5
2.0 012.5
5.0 5.0 4.5
01B! 5.12 3.0
4.5 2.5 012.
5 5.0 5.0 5
．． 0 020 3・12
2.0 4.5 2.0
012.5 5.0 5.0
4.5 024 3.124.55
．． 02+00 12.5 5.0 5.0
4.5 026 3.1
2 5.5 4.5 3.
0 012.5 5.0
5.0 5.0 0 Control compound

Claims (1)

[Claims] (1) Formula [1] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [1] (In the formula, X represents a halogen atom, cyano group, methyl group, trifluoromethyl group, ethyl group, ethynyl group, methoxy group, Y represents a hydrogen atom, a halogen atom, a cyano group, or a methyl group.However, when Y represents a halogen atom, a cyano group, or a methyl group, X represents a halogen atom, a cyano group, or a methyl group.X is also connected to Y. , 3,4-trimethylene group or 3,4-dioxymethylene group may form a ring.) A cyanohexanilide derivative represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] (In the formula, X represents a halogen atom, cyano group, methyl group, trifluoromethyl group, ethyl group, ethynyl group, or methoxy group, and Y represents a hydrogen atom or a halogen atom. , represents a cyano group, or a methyl group.However, when Y represents a halogen atom, a cyano group, or a methyl group, X represents a halogen atom, a cyano group, or a methyl group.X is also connected to Y, and represents a 3,4-trimethylene group or 3,4-dioxymethylene groups may form a ring.) A herbicide for rice fields, characterized by containing a cyanohexanilide derivative represented by the following as an active ingredient.