JPS58201753A - α-amino fatty acid anilide derivatives, their production methods and herbicides - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (X is H, 1-4C lower alkyl, lower alkoxy, halogen, etc.; Y is H, methyl, ethyl or halogen; R1 is 1-4C lower alkyl or lower alkoxy). EXAMPLE:alpha-(2,3-Dimethylanilino)-3'-ethyl-isobutylanilide. USE:Herbicide having strong herbicidal activity against the weeds in paddy field, especially Deccan grass and cyperaceous weeds and remarkable selectivity between those weeds and the paddy rice plant. PROCESS:The compound of formula I can be prepared by reacting the alpha-halogenofatty acid anilide derivative of formula II (Z is halogen; R1 is 1-4C lower alkyl or lower alkoxy) with the aromatic amine of formula III. The reaction is carried out in an organic solvent (e.g. benzene) preferably in the presence of a dehalogenating agent (e.g. TEA) at room temperature or if necessary under heating.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel α-amine fatty acid anilide derivative, a method for producing the same, and a herbicide containing the compound as an active ingredient.

More specifically, the present invention provides (wherein, X is a hydrogen atom, a C1 to C4 lower alkyl group,
Lower alkoxy group or halogen atom, Y is hydrogen atom, methyl group, ethyl group, or halogen atom, RI is C
Each represents a 1-C2 lower alkyl group or a lower alkoxy group. ) α-amino fatty acid anilide derivatives represented by (wherein, Z represents a rogen atom, and C represents a C1 to C4 lower alkyl group or lower alkoxy group, respectively).・It is characterized by reacting a rogen aliphatic anilide derivative with an aromatic amine represented by the general formula (in the formula, X and Y are the same as above) (in the formula, x, y, R,
has the same meaning as above. The present invention relates to a method for producing an α-amine fatty acid anilide derivative represented by the formula (2) and a herbicide characterized by containing the α-amine fatty acid anilide derivative represented by the general formula [, (2)] as an active ingredient.

The object of the present invention is to industrially advantageously obtain the compounds represented by the general formula [I] and to provide a simple and reliable agricultural chemical.

The present inventors have developed a number of novel α-
Studies on amine fatty acid ani-IJ derivatives revealed that the compound of the present invention represented by the general formula CI) has a herbicidal effect, and has a particularly strong effect on barnyard grass and paddy weeds of the Cyperaceae family. They discovered that there is a high degree of selectivity between weeds and rice seeds, and completed the present invention.

Up to now, various herbicides have been developed and used for paddy rice, especially herbicides used at the beginning of rice blight outbreak. The main ones are 2.4.6- ) IJ chlorophenyl-4-nitrophenyl ether (CNP
), 5-(4-chlorobenzyl)-N.

N-diethylthiol carbamate (benthiol), 2-chloro-21,61-diethyl-N-(butoxymethyl)acetanilide (butachlor), 2.
4-dichlorophenyl-41-nitro-3'-me)xyphenyl ether (X-52), etc., but these have been put to practical use based on their physiological selective activity between rice fields and the harmful annual weed weed of rice field It is not something that is offered to people. In other words, these conventional herbicides are applied by taking advantage of differences in drug resistance due to the different growth stages of wild grass and paddy rice, or because the roots of transplanted paddy rice are located below the chemical treatment layer due to the soil adsorption principle of the drugs. Application methods are based on physical selectivity, which takes advantage of the low absorption of drugs. Therefore, when such herbicides are used to control weeds, there is a risk that paddy rice seedlings will be damaged by the chemical in fields where young seedlings are transplanted or in direct sowing cultivation fields. Therefore, there is a strong demand in this field for the development of a compound that is highly safe, that is, has a physiological selective activity between wild grass and paddy rice.

However, no herbicide has yet been developed that has high interwing selectivity between rice and barnyard grass, which are plants of the same genus Poaceae, and is effective against weeds of the Cyperaceae family, such as Cyperus japonica, Cyperus japonica, and Cyperaceae. The present inventors synthesized various α-amino fatty acid anilide derivatives, conducted extensive research, and examined their herbicidal activity. Surprisingly, when these inventive compounds are used as a treatment agent for flooded soil, 1 , is harmless to rice at extremely high doses, and shows high safety not only for transplanted rice, standing rice, but also for directly sown rice, and is effective against weeds that are harmful to paddy fields, such as Novie, Cyperus japonica, and It is highly effective against weeds that are difficult to control conventionally, such as Japanese cypress and firefly.

It exhibits many excellent characteristics not found in conventional herbicides.

That is, α-halogeno fatty acid anilides represented by the general formula [■] prepared by the reaction of α-nologenoaliphatic norogenide with an aromatic amine and aromatic amines represented by the general formula It can be obtained by reaction in the presence of a dehalogenating agent.

The above reaction is carried out in an organic solvent, and the compound represented by general formula (II) is dissolved in a solvent such as benzene, toluene, xylene, 7-oxane, tetrahydrofuran, methylene chloride, chloroporum, methyl ethyl ketone, dimethyl sulfoxide, dimethyl formamide, etc. Then, add an equivalent amount or a slight excess of the corresponding aromatic amine, an organic base such as triethylamine, pyridine, or dimethylaniline as a dehalogenating agent, or an inorganic carbonate such as powdered potassium carbonate or sodium carbonate. , perform the reaction at room temperature or with heating if necessary. After the reaction is complete, remove amine salts and inorganic salts by filtration or washing with water.
By distilling off the solvent, an α-amine fatty acid anilide derivative represented by the general formula CI) can be obtained with good purity and high yield. The product can be further purified by recrystallization in organic solvents.

Below, α-amino fatty acid anilide 7- according to the present invention Typical synthetic examples of derivatives will be described.

Synthesis example-1α-(2,3-dimethylanilino)-3'-
Synthesis of ethyl-isobutylanilide m-Ethylaniline 121.29 (1, Omol) was dissolved in benzene 500-, pyridine 959 (1,2 mol) was added, and while stirring under water cooling, α-bromoisobutyl bromide 1
86.29 (1', Omol) was added dropwise.

After further stirring at room temperature for 1 hour, the precipitated crystals were filtered off, the filtrate was concentrated, and the resulting residue was recrystallized from benzene to give m, p, : 82.0 to 83.0°C. α-Bromo-31-ethyl-isobutylanilide 178'I
I got Q.

α-Bromo-3I-ethyl-isobutylanilide 27.
0 (Q, lQmol), potassium carbonate 27.69 (
0,20 blood ■), 2,3-dimethylaniline 14.79
A mixture of (0.12 mol) and methyl ethyl ketone 200- was heated under reflux for 3 hours with stirring. After cooling, the solid matter was filtered off, the filtrate was concentrated under reduced pressure, and the resulting residue was □
Recrystallized from Hensen m, p: 102. Fr-
105,0'C target compound 23.89 (yield 76.6
%) was obtained.

Synthesis of 8-methoxylisobutylanilide 123.2 g (1, Omol) of m-anisidine was dissolved in 350 i of acetone, and 76 g of potassium carbonate was dissolved. (0,5
5 mo+) was added, stirred under water cooling, and α-bromoisobutyl bromide 186.29 (1, Omol) was added.
was dripped. After further stirring at room temperature for 1 hour, the solid matter was filtered off, the filtrate was concentrated, and the resulting residue was recrystallized from benzene to give m, p, : 103.0°C to 105.0
α-bromo-31-methoxy-isobutylanilide 2069 was obtained. ' Do27.29 (0,lQmol), Toriechi/I/
7 mmy 15.09 ('0.15 mo'l) and 0
- Dissolve 12.19 (0,1Qmol) of ethylaniline in 50- of dimethylformamide, and dissolve 100- of ethylaniline while stirring.
Heated to ~130°C. After stirring for 3 hours, the reaction mixture was poured into 500-ml ice water and extracted with ethyl acetate. The extracted phase was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the resulting residue was recrystallized from benzene to give m and p.

:64.5-67.0°' (1) Target compound 24.29
(yield 77.3%).

Other compounds included in the general formula [I] (see Table 1) can also be synthesized according to either Synthesis Example 1 or 2.

The physical properties and the characteristic absorption of the infrared absorption spectrum of the compound represented by the general formula [■], which is a representative herbicidal active ingredient compound according to the present invention, obtained as described above are classified by compound number and described below. Although described in Table 1, the present invention is not limited only to these. In addition, the active ingredient compounds in the formulation examples and test examples are shown by compound numbers in Table 1.

For the compound of the present invention, the active ingredient compound represented by the above general formula (I) may be used as it is, but generally, depending on the purpose of use, it may be dissolved or dissolved in a suitable liquid carrier (for example, an organic solvent). Dispersed or mixed or adsorbed onto a suitable solid carrier (eg diluent, filler). At that time, various auxiliary agents (e.g. emulsifiers, stabilizers,
By appropriately adding a dispersing agent, suspending agent, spreading agent, wetting agent, penetrating agent), it can be used in various dosage forms such as emulsions, wettable powders, granules, and powders.

The content of the active ingredient of the herbicide of the present invention is 1 to 10 in the case of granules.
%, 20-80% for wettable powders, 10-50% for emulsions (
% by weight) is desirable. Next, formulation formulation examples of herbicides containing the compound of the present invention as an active ingredient will be shown, but the present invention is of course not limited to these.

Formulation Example 1 15 parts of granule compound, 72 parts of bentonite, 20 parts of talc, 2 parts of sodium dodecylbenzenesulfonate and 1 part of sodium ligninsulfonate were mixed, an appropriate amount of water was added, and the mixture was kneaded, using an extrusion granulator. and granulate using the usual method.
100 parts of granules were obtained.

Formulation Example 2 450 parts of a hydrating agent compound, 40 parts of diatomaceous earth and 10 parts of sodium dodecylbenzenesulfonate were mixed and ground to produce 100 parts of a hydrating agent.
I got the department.

Formulation example 3 85 parts of emulsion compound, Tsurupol 800 A (Toho Chemical @)
Product name: 10 parts of a mixture of a nonionic surfactant and an anionic surfactant) and 85 parts of benzene were mixed to obtain 100 parts of an emulsion.

In addition, the compound of the present invention aims to improve its efficacy as a herbicide,
It is also possible to use it in combination with other herbicides, and in some cases synergistic effects can be expected. Examples include 2,4-dichlorophenoxyacetic acid, 2-methyl-4-
Phenoxy-based herbicides such as chlorphenoxyacetic acid (including esters and salts), 2.4.6-) dichlor-41-
Nitro diphenyl ether, 2,4-dichloro-31-
Methoxy-41-nitrodiphenyl ether, 2-chloro-4-)13-lifluoromethyl-31-aryloxy-3-yl-41
Diphenyl ether herbicides such as lower nitrodiphenyl ether, 1-(2,2-dimethylbenzyl)-3-(4
-methylphenyl)urea, 5-(4-chlorobenzyl)
-N,N-diethylchlorca □-bamate, S
-ethyl-N,N-hexamethylenethiolcarbamate, 4-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazol-5-yl-P-toluenesulfonate, 1,3-dimethyl-4-(2 ,4-dichlorobenzoyl)5-zenasiloxypyrazole,3-(2,4-dichloro-5-isopropoxyphenyl)-s-Lt-butyl-1,3,4-oxadiazol-2(3H)one , α-(β-naphthoxy)propionanilide, etc., but are not limited to these.

Furthermore, the compound of the present invention can be used in combination with insecticides, nematicides, fungicides, plant growth regulators, fertilizers, etc., if necessary.

Next, the herbicidal effects of the compounds of the present invention will be explained using test examples.

14- Test example-1 Paddy field pre-emergence weeding test A15000 Fill a Wagner pot with paddy soil and remove Japanese millet, broad-leaved weeds (Japanese oak, azalea, Japanese azalea, etc.)
Seeds or tubers of Cyperus japonica, Cyperus japonica, Cyperus japonica, Firefly, and Helaomodaka were mixed into the soil surface layer 1cIIL, and the soil was flooded to a depth of 3CIn. Two paddy rice seedlings (2-3 leaf stage) that had been raised in advance were used as one plant, and the two plants were transplanted and grown in a greenhouse. Three days after transplanting paddy rice, at the beginning of weed emergence, a predetermined amount of the test compound was submerged in water using a hydrating powder similar to the method described in Formulation Example 2 above. Thirty days after the treatment, weed growth and chemical damage to paddy rice were investigated, and the results shown in Table 2 were obtained.

In this table, the degree of chemical damage to rice and the herbicidal effect on weeds are expressed by comparing the emergence or growth of rice or weeds with the air-dried type in the untreated area, and according to the evaluation criteria below.

Evaluation standard O vs. untreated area Survival rate shown by air dry weight ratio 90-1oo%
1 n n 60
~892'nu
30-593n
10～291 4 n n 5
,95*n
O ~ 4 Test Example-2 Medicinal/Harmful Test for Paddy Rice aA000 Wagner pots were filled with paddy soil, submerged in water to a depth of 3 m, and paddy rice seedlings (in which seedlings had been previously raised)
2-3 leaf stage) Soil surface layer 2-4crrL with 2 plants as one plant
The rice was transplanted (transplanted paddy rice) to a depth of . Another plant was fixed with its roots on the soil surface (placed rice), and germinated rice seeds were sown on the soil surface (directly sown paddy rice). Three days later, a predetermined amount of the test compound was submerged in water as a wettable powder according to the method described in Formulation Example 2. Thirty days after the chemical treatment, the degree of drug damage was investigated according to the method shown in Test Example-1, and the results shown in Table 3 were obtained.

19- *5-(4-Chlorbenzyl) -N,N-diethylthiol carbamate * *2.4.6-) IJ Chlor-41-nitrodiphenyl ether Patent applicant Mitsui Toatsu Chemical Co., Ltd. Procedures Amendment ( (Spontaneous) - June 2, 2015 Wakasugi Kazuo, Commissioner of the Japan Patent Office1, Indication of the case, Patent Application No. 81535 of 19812, Name of the invention: α-amino fatty acid anilide derivatives and their manufacturing process and herbicidal diarrhea 3. The person making the amendment 4 makes 10 amendments to [Detailed explanation of the invention column 1, specification, Table 1 on page 12] of the specification to be amended.

2. Similarly, Table 2 (reading) on page 19 is corrected as shown in Attachment 2.

3. Similarly, Table 3 (continued) on page 22 is amended as shown in Attachment 3.

4. Similarly, replace page 23 with Attachment 4.

Attachment 3 Table 3 (continued) Attachment 4 Table 3 (continued) *5-(4-Chlorbenzyl) -N,N-diethylthiol carbamate *2,4.6-) IJ Chlor-4-nitro Diphenyl ether patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] General formula (wherein, X is a hydrogen atom, a C1 to C4 lower alkyl group,
A lower alkoxy group or a halogen atom, Y is a hydrogen atom, methyl group, ethyl group, or a halogen atom, and C1 is a lower alkoxy group or a halogen atom.
-C4 lower alkyl group or lower alkoxy group, respectively. ) α-Amino fatty acid anilide derivative represented by: . 2. An α-halogen fatty acid anilide derivative represented by the general formula (in the formula, Z represents a halogen atom and the formula represents a C0 to C3 lower alkyl group or a lower alkoxy group, respectively) and the general formula ゛ (in the formula, X is a hydrogen atom, C, -04 lower alkyl group,
Y represents a hydrogen atom, a methyl group, an ethyl group, or a -rogen atom; ') A method for producing an α-amine fatty acid anilide derivative represented by the general formula (wherein, X, Y, and R have the same meanings as above). (In the formula, X is a hydrogen atom, C, lower alkyl group of C,
A lower alkoxy group or a halogen atom, Y is a hydrogen atom, a methyl group, an ethyl group, or a halogen atom, and C is a
Each represents a 1 to C4 lower alkyl group or a lower alkoxy group. A herbicide characterized by containing an α-amino fatty acid anilide derivative represented by ) as an active ingredient.