JPS6160640A - Acetylalkane derivative and herbicide containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R<1> is H, alkyl or alkynyl; R<2> is haloalkyl, phenyl, benzyl, 2,2-dialkylbenzyl, or their nucleus-substituted group with halogen; R<1> and R<2> may together with adjacent N from piperidino or morpholino). EXAMPLE:N-methyl N-phenylcarbamic acid 4-acetylnonyl ester. USE:Herbicide having especially excellent herbicidal activity against the weeds in paddy field. PREPARATION:The compound of formula I can be prepared by reacting 4- acetylnonyl alcohol with trichlorometyl chloroformate or phosgene, and reacting the resultant 4-acetylnonl chloroforate with the amine of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel acetyl alkane derivative and a herbicide containing the novel compound as an active ingredient, which has a high herbicidal effect, particularly against paddy field weeds.

Conventionally, various herbicides have been commercially available for use in rice cultivation, etc., but the current situation is that many of them cause chemical damage to rice crops depending on the conditions of application.

The present inventors conducted research to develop a useful herbicide that does not have the above drawbacks. 4-acetylnonanoic acid, which has traditionally had physiological activity against plants, has little activity under soil-mediated conditions and is not known as a herbicide.

As a result of investigation, it was discovered that an ester of N-substituted rubamic acid of 4-acetylnonyl alcohol exhibits an excellent herbicidal effect on paddy rice and the like without any phytotoxicity, and based on this knowledge, the present invention was completed.

That is, the present invention provides a compound having the general formula (wherein RL represents hydrogen, an alkyl group, or an alkenyl group, and R2 represents 2-), an ethyl group, a phenyl group, a phenyl group substituted with a halogen, or a benzyl group.

α, α-dialkylbenzyl group or halogen-α,
Indicates an α-dialkylbenzyl group. Or R', R
2 represents a piperidino group or a morpholino group containing adjacent nitrogen atoms. The present invention provides an acetyl alkane derivative represented by the formula (I), and also provides a herbicide containing the acetyl alkane derivative represented by the above general formula (I) as an active ingredient.

Acetyl alkane derivative 4 represented by the general formula (Il) of the present invention
Form B is a compound in which 4-acetylnonyl alcohol and N-substituted rubamic acid form an ester bond, and is a novel compound that has not been previously known. In the general formula (Il), R1 represents hydrogen, an alkyl group, or an alkenyl group as described above, and the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, or a propyl group; The group preferably has 2 to 6 carbon atoms.On the other hand, R2 is a 2-chloroethyl group, etc.
- phenyl group substituted with halogen such as haloethyl group, phenyl a, o-chlorophenyl group, benzyl group, 'α
, α,α-dialkylbenzyl groups such as α-dimethylbenzyl group (the special alkyl group has 1 to 4 carbon atoms),
Indicates halogeno-α, α-dialkylbenzyl groups such as 0-chloro-α, α-dimethylbenzyl group, and the like. Furthermore, R1 and R2 also represent a piperidino group or a morpholino group containing adjacent nitrogen atoms.

Compounds such as those described above are manufactured by various methods. M, 4-acetyl nonyl alcohol is reacted with trichloromethyl chloroformate or phosge/chloroformate to synthesize 4-acetyl nonyl chloroformate, which is expressed by the general formula % formula % (2) (in the formula R' , Rz is the same as in the case of general formula (I)).
An acetyl alkane derivative represented by I) is obtained.

Alternatively, 4-7 cetylnonyl alcohol can be reacted with incyanates represented by the general formula % (in which R2 is the same as in the general formula (I)). ) is obtained.

The acetyl alkane derivative represented by the general formula (1) produced in this manner can inhibit the germination and growth of weeds and can kill weeds.

The herbicide of the present invention is a novel compound of the general formula (
The active ingredient is an acetyl alkane derivative represented by Il, and this active ingredient derivative is usually mixed with a liquid carrier such as an organic solvent or a solid carrier such as fine mineral powder to form a wettable powder, emulsion, or powder. It can be formulated and used in the form of a single granule or the like. A surfactant may be added to impart emulsifying properties, dispersibility, spreading properties, etc. during formulation.

When the herbicide of the present invention is used in the form of a wettable powder, it usually contains 10 to 55% by weight of the above-mentioned compound of the present invention as an active ingredient, 40 to 88% by weight of a solid carrier, and 2 to 5% of a surfactant.
A composition may be prepared by blending the components in proportions of % by weight, and this may be used. In addition, when used in the form of an emulsion, 5% of the compound of the present invention is usually used as an active ingredient, and 35% of a solvent is used.
It may be prepared by blending the surfactant in a proportion of 75% by weight and 5 to 15% by weight of the surfactant. On the other hand, when used in the form of a powder, the active ingredients are usually 1 to 15% by weight of the compound of the present invention, 80 to 97% by weight of a solid carrier, and 2 to 5% by weight of a surfactant. Just prepare it. SamoK
When used in the form of granules, the active ingredient is 3 to 15% by weight of the compound of the present invention, and the solid carrier is 80 to 95% by weight.
and a surfactant in a proportion of 2 to 5% by weight.

Here, fine mineral powder is used as the solid carrier, and examples of the fine mineral powder include oxides such as diatomaceous earth and slaked lime, phosphates such as apatite, sulfates such as ceracola, talc, and pyroferrite. , clay, kaori/, bentonite, acid clay 1, white carbon, quartz powder, silica powder, etc. can be used.

In addition, organic solvents are used as solvents, specifically aromatic hydrocarbons such as xylene, toluene, benzene, etc.
Chlorinated carbon such as chlorotoluene, trichloromethane, trichlorethylene, alcohol such as cyclohexanol, amyl alcohol, ethylene glycol, isophorone, cyclohexanone, cyclohexenyl-7chlorohexyl?
Ketones such as /N, butyl cellosolve, dimethyl ether.

Examples include ethers such as methyl ethyl ether, esters such as inpropyl acetate, benzyl acetate, and methyl phthalate, amides such as dimethylformamide, and mixtures thereof.

Further, as the surfactant, any of anionic, nonionic, cationic, and amphoteric ionic types (amino acids, betaine, etc.) can be used.

As described above, the acetyl alkane derivative represented by the general formula (I), which is a novel compound of the present invention, has a high herbicidal effect,
It is extremely useful as a highly selective herbicide without phytotoxicity to crops, and can be widely used by mixing with other herbicides, growth regulators, pesticides such as insecticides, fungicides, fertilizers, etc.

As mentioned above, the herbicide of the present invention contains the acetyl alkane derivative represented by the general formula (I) as an active ingredient, but it is also effective to use other active ingredients in combination. Active ingredients that can be used in combination here include l-(α
, α-dimethylpenenyl)-3-(paratolyl)urea,
3-Inglovir-2゜1,3-benzothiadiazinone-(4)-2,2-dioxide, IPC, 2-rio
Herbicides such as o-2',5'-diethyl-N-(methoxymethyl)acetanilide and 2-methylthio-4,6-
Bisethylamino-1,3,5-triazine; triazine herbicides such as 2-chloro-4,6-bisethylamino-1,3,5-triazine, 2,4-dichlorophenoxyacetic acid and its methyl, Phenoxy herbicides such as ethyl or butyl esters, 2,4°6-)! J Chlorphenyl-4'-nitrophenyl ether; 2.4
- Nocyphenyl ether herbicides such as dichlorophenyl-4'-nitrophenyl ether, other urea herbicides,
Carbamate herbicides, uracil herbicides, thiol carbamate herbicides, phosphorus herbicides, aniline herbicides, acid anilide herbicides, pyrazole herbicides, and N
-methoxycarbonyl-N'-4-methylphenylcarpamoylethylinurea; inourea plant growth regulator such as 1-(410ruphenylcarbamoyl)-3-ethoxycarbonyl-2-methylinurea, naphthalene acetic acid Sodium: 1,2-di and above The herbicides of the present invention can be used in various forms and with various other ingredients.

Moreover, by treating the soil with the herbicide of the present invention at the early stage of transplanted paddy rice cultivation, it is safe for transplanted paddy rice and can effectively control grass weeds, Cyperaceae weeds, and broad-leaved weeds.

Next, the present invention will be explained in more detail using examples.

Example 1 2.7 mmol of 4-acetylnonyl alcohol was added to ben9
After 5mjK of the solution was dissolved, 165 mmol of trichloromethyl chloroformate and 2.7 mmol of triethylamine were added dropwise in this order while stirring at room temperature, and the mixture was stirred at room temperature for 24 hours. Next, 10% of ice water was added, and after stirring for 1 hour under water cooling, the organic layer was dissolved in 10% of a 5% aqueous hydrochloric acid solution. tt and 10 nt of saturated aqueous sodium chloride solution. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 4-acetylnonyl chloroformate 0.59F.

On the other hand, 18 mmol of N-methylaniline and 2.0 mmol of triethylamine were dissolved in 10 yt of acetone, and 101 n of an acetone solution of 2.0 mmol of chloroformic acid-4-acetylnonyl ester prepared above was dissolved under stirring at room temperature.
t was added dropwise over 10 minutes, and the mixture was heated under reflux for 165 hours. After distilling off the solvent under reduced pressure, 20-mL of ethyl acetate was added, and 5
% hydrochloric acid aqueous solution 10-1 saturated sodium chloride aqueous solution 10m
Washed with 1. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain N-substituted rubamic acid-4-
An acetyl nonyl ester derivative was obtained. This was purified by silica gel column chromatography. Yield is 82
It was Chi.

Product name 2N-methyl N-phenylcarbamic acid-4-
Acetyl nonyl ester di-oil Structural formula: Refractive index: 1.4555 (70°C) Elemental analysis: Carbon Hydrogen Nitrogen Calculated value 71.4% 9.2% 4.4% Measured value 71.6% 9. 3ch 4.0ch Characteristic absorption peak of infrared absorption spectrum 1710 cm-' Example 2 In Example I, N-methylaniline was replaced with N-
An N-substituted rubamic acid-4-acetyl nonyl ester derivative was obtained in the same manner as in Example 1 except that allylaniline was used. This was purified by silica gel column chromatography.

The yield was 78 cm.

Product name 2N-allyl N-phenylcarbamic acid-4-
Acetyl nonyl ester properties Shape: Oil Structural formula: % Formula % (70): Calculated value 73.0% 9.0cm 4.1cm Actual value 73゜0cm 8.8cm 4.0cm Infrared absorption spectrum Characteristic absorption peak of 1705 cm-' Example 3 In Example 1, instead of N-methylanili/,
Same as Example 1 except that Zylamine was used,
N-substituted carbami/acid-4-acetyl nonyl ester was obtained. This was purified by silica gel column chromatography. The yield was 88 cm.

Product name 2-N-benzylcarbamic acid-4-acetyl nonyl ester Properties Shape: Oil Structural formula: % Formula %) Calculated value 71.4% 9.2% 4.4% Measured value 71.3% 9,6 H 4.3 Characteristic absorption peaks of infrared absorption spectrum 3380 cm-', 1710 cm-' Example 4 In Example 1, N- was substituted for 1N-methylaniline.
N-substituted carbamic acid-4-acetyl nonyl ester was obtained in the same manner as in Example 1 except that methylbenzylamine was used. It was purified by strained t-silica gel column chromatography.

The yield was 89%.

Product name 2N-methylpe/dylcarbami/acid-4-7 cetyl nonyl ester Properties: Oil Structural formula: % Formula %): Carbon Hydrogen Nitrogen Calculated value 72.0% 9.4% 4.2% Actual value 71.8% 9.4% Characteristic absorption peak of 4.5 cm infrared absorption spectrum 1705 cm' Example 5 In Example 1, instead of N-methylaniline, K, α
, N-substituted carbamic acid 4-acetyl nonyl ester was obtained in the same manner as in Example 1, except that α-dimethylbenzylamine was used.

This was purified by silica gel column chromatography. The yield was 91%.

Product group: N-(α,α-dimethylbenzyl)carbamic acid-4-acetylnonyl ester. Structural formula: % Formula %): Characteristic absorption peak of infrared absorption spectrum 3360 cm-', 1710 cm-" Example 6 N-
Substituted rubamic acid-4-acetyl nonyl ester was obtained. This was purified by silica gel column chromatography. The yield was 93%.

Product name: N,N-pentamethylenecarno(myic acid-4
-7 Cetyl Nonyl Ester Properties Shape: Oil Structural formula: % Formula %): Characteristic absorption peak of infrared absorption spectrum 1705 cm-' Example 7 In Example 1, morpholine was used instead of N-methylaniline. Other than that, the same procedure as in Example 1 was carried out, and N
-Displacement force Rubamic acid-4-acetyl nonyl ester was obtained. This was purified by silica gel column chromatography. The yield was 91 cm.

Product group: N,N-ethyleneoxyethylenecarbamic acid-4-acetylnonyl ester di-oil Structural formula: %) Refractive index: 1.4490 (70'C) Elemental analysis: Carbon Hydrogen Nitrogen Calculated value 64.2% 9.8% 4.7cm Actual value 64.5cm 9.6cm 4.5cm Characteristic absorption peak of infrared absorption spectrum 1705crn-' Example 8 4-acetylnonyl alcohol 2.2 mmol KQ-chlorophenylisocyanate) 2.2. mmol and 1 drop of triethylamine were added and stirred for 30 minutes at 100'CK to obtain N-substituted carbamic acid-4-acetyl nonyl ester. This was purified by silica gel column chromatography. The yield was 74%.

Product Masterpiece N-(0-chlorophenyl)carbamine rR
-4-acetyl nonyl ester Properties Shape: Oil Structural formula: % formula %): Actual value 63.2 7.9 4.2% Characteristic absorption peak of infrared absorption spectrum 3360 cm-', 170 F; cm- 'Example 9 The same procedure as in Example 1 was carried out except that in Example 8, 2-chloroethyl incyanate was used instead of 0-chlorophenylinocyanate.

N-substituted rubamic acid-4-acetyl nonyl ester was obtained. This was purified by silica gel column chromatography. The yield was 76 cm.

Product name: N-(2-chloroethyl)cal (minic acid)
4-acetylnonyl ester Properties Shape: Oil Structural formula: % Formula % (70): Calculated value 57.6 9.0% 4.8 1 Measured value 58.0% 9.2% 4.4 Characteristic absorption peaks of external absorption spectrum: 3350 cm-', 1710 cm-' Example 1
0-18 and Comparative Example 1 (1) Preparation of herbicide 97 parts by weight of Merck (trade name Nidikryte) as a carrier, alkylaryl sulfonate (trade name: Neoberex, manufactured by Kao Atlas Co., Ltd.) as a surfactant. 1,5
Parts by weight and nonionic and anionic surfactants (trade name: Tsurupol 800 A, manufactured by Toho Chemical Industry Co., Ltd.)
1.5 parts by weight were uniformly ground and mixed to obtain a carrier for wettable powders.

A herbicide was obtained by uniformly pulverizing and mixing 90 parts by weight of this wettable powder carrier and 10 parts by weight of Compounds 1 to 9 obtained in Examples 1 to 9 or 4-acetylnonanoic acid.

(2) Biological test (flooded soil treatment test) 1/ Fill a porcelain pot with paddy soil, and spread the seeds of Japanese wildflower, Japanese cypress, and Kikashigusa evenly on the surface layer.-K1
After seeding and flooding to a depth of 2 cm, two-leaf stage paddy rice (
Two plants (variety Nihonbare) were transplanted.

Thereafter, when the weeds germinated, a predetermined amount of the diluted herbicide obtained in (1) above was uniformly dropped onto the water surface to treat the weeds, and then the pots were left in a greenhouse and watered at appropriate times.

Table 1 shows the results of investigating the herbicidal effect and paddy rice damage 20 days after the chemical solution treatment. The dosage in the table is indicated by the amount of active ingredient, and the paddy rice damage and herbicidal effects were measured in air-dried form and expressed as follows.

Degree of drug damage: Mizuishi Dakyou (anti-soldier) 0
100% 1 95-99% 2 90-94chi 3 80-89chi 4 60-79% 5 50-69chi Degree of weeding effect Rate of remaining weeds (ratio to untreated area) 0
100% 1 61-99chi 2 21-60chi 3 11-20chi 4 1-10% 5 0chi procedural amendment (voluntary) September 5, 1980

Claims (22)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1 represents hydrogen, an alkyl group, or an alkenyl group, and R^2 represents a 2-haloethyl group, phenyl group, or phenyl substituted with halogen. group, a benzyl group, an α,α-dialkylbenzyl group, or a halogeno-α,α-dialkylbenzyl group.Alternatively, R^1 and R^2 represent a piperidino group or a morpholino group containing adjacent nitrogen atoms.) Acetyl alkane derivative represented. (2) R^1 represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms, and R^2 is a 2-haloethyl group, a phenyl group, a phenyl group substituted with a halogen, or a benzyl group Alternatively, it represents an α,α-dialkylbenzyl group having an alkyl group having 1 to 4 carbon atoms, or R
The derivative according to claim 1, wherein ^1 and R^2 represent a piperidino group or a morpholino group containing adjacent nitrogen atoms. (3) Formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The derivative according to claim 1, which is represented by: (4) Formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The derivative according to claim 1, which is represented by: (5) Formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The derivative according to claim 1, which is represented by: (6) Formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The derivative according to claim 1, which is represented by: (7) Formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The derivative according to claim 1, which is represented by: (8) Formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The derivative according to claim 1, which is represented by: (9) Formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The derivative according to claim 1, which is represented by: (10) Formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The derivative according to claim 1, which is represented by: (11) Formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The derivative according to claim 1, which is represented by: (12) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1 represents hydrogen, an alkyl group, or an alkenyl group, and R^2 represents a 2-haloethyl group, phenyl group, or phenyl substituted with halogen. group, a benzyl group, an α,α-dialkylbenzyl group, or a halogeno-α,α-dialkylbenzyl group.Alternatively, R^1 and R^2 represent a piperidino group or a morpholino group containing adjacent nitrogen atoms.) A herbicide containing the following acetyl alkane derivative as an active ingredient. (13) R^1 represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms, and R^2 represents 2-
Represents α,α-dialkylbenzyl having a haloethyl group, phenyl group, halogen-substituted phenyl group, benzyl group, or alkyl group having 1 to 4 carbon atoms, or R
13. The herbicide according to claim 12, wherein ^1 and R^2 represent a piperidino group or a morpholino group containing adjacent nitrogen atoms. (14) The acetyl alkane derivative has the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The herbicide according to claim 12, which is represented by: (15) The acetyl alkane derivative has the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The herbicide according to claim 12, which is represented by: (16) The acetyl alkane derivative has the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The herbicide according to claim 12, which is represented by: (17) The acetyl alkane derivative has the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The herbicide according to claim 12, which is represented by: (18) The acetyl alkane derivative has the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The herbicide according to claim 12, which is represented by: (19) The acetyl alkane derivative has the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The herbicide according to claim 12, which is represented by: (20) The acetyl alkane derivative has the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The herbicide according to claim 12, which is represented by: (21) The acetyl alkane derivative has the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The herbicide according to claim 12, which is represented by: (22) The acetyl alkane derivative has the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The herbicide according to claim 12, which is represented by: