JPS5867653A - Benzylamide derivative of phenoxyalkanoic acid and herbicide - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formulaI[X is lower alkyl, or Cl; (n) is 0, 1, 2 or 3; R1 is lower alkyl; R2 is H, lower alkyl or lower alkenyl; R3 is H or lower alkyl; Y is lower alkyl, Cl or lower alkoxyl; (m) is 0, 1 or 2]. EXAMPLE:N-benzyl-2-(3,5-dimethylphenoxy)-butyramide. USE:A herbicide, having improved herbicidal activity against the chlorosis action (yellowing or blanching), and exhibiting almost no phytotoxicity due to the auxin action. PROCESS:A compound expressed by formula II is reacted with a compound expressed by formula III in the presence of a suitable solvent, e.g. benzene, by adding a weak alkali, e.g. pyridine, to give the compound expressed by formulaI. The reaction is carried out at 50-130 deg.C for 1-10hr.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention is based on the general formula (wherein X represents a lower alkyl group or a chlorine atom, and n(dO1]-+ represents 2 or 3 + R1
represents a lower alkyl group; R2 represents a hydrogen atom, a lower alkyl group, or a lower alkenyl group; R3 represents a hydrogen atom or a lower alkyl group; Y represents a lower alkyl group, a chlorine atom, or a lower alkoxy group; 1m represents 0 .1 or 2. ).

Benzylamide derivatives of novel naphenoxyalkanoic acids,
The present invention also provides a herbicide containing this common benzylamide derivative of phenoxyalkanoic acid as an active ingredient.

Weeding and wound removal uses phenoxy compounds as active ingredients.

There are many products that have been proposed for a long time and are commercially available, such as 2.4-D (active ingredient 2.
4-dichlorophenoxyacetic acid), 2,4,-D
P (active ingredient 2-(2,4-dichlorophenoxylene)brohy).

(monic acid) MOPC active ingredient 2-methyl-4-chlorophenoxyacetic acid] or MOPCA C active ingredient N-(
2-chlorophenyl)-2-methyl-4-chlorophenoxyacetamide] and the like.

These conventionally known phenoxy herbicides generally have extremely superior herbicidal effects against a wide range of broad-leaved weeds compared to pond herbicides, but they do not cause division of grass crops due to their auxin action. They share the common characteristic of being associated with drug-induced harm such as inhibition and malformations.

The inventors aimed to find a compound among phenoxy compounds that has excellent herbicidal activity and is not harmful to crops, and synthesized various compounds of this family and searched for their plant activities. .

As a result, we succeeded in synthesizing a benzylamide derivative of phenoxyalkanoic acid, which is a new compound represented by the above-mentioned general formula (1) and has not been reported in the literature, and this derivative can be used in rice fields, fields, other arable land, and non-arable land. The present invention was completed based on the discovery that the present invention has the ability to selectively eliminate a wide range of weeds that occur without causing any chemical damage to two crops.

That is, the herbicide in this invention has an excellent herbicidal effect on not only broad-leaved weeds but also various other weeds due to its bleaching action.
There is almost no phytotoxicity to crops caused by the auxin action seen in conventionally known 72-noxy herbicides, and there is no toxicity to humans, livestock, fish, or shellfish, and there is no off-flavor.

The benzylamide derivative of phenoxyalkanoic acid in this invention can be synthesized, for example, by the following reaction (1) or (2).

(In formula 7f'L1)Xr Y* RIs R2,R
s, n and m have the same meanings as above. Z means a chlorine atom or a bromine atom. ) The above reactions (1) and (2) are carried out in the presence of a suitable solvent.

Addition of a weak alkali such as pyridine, triethylamine, sodium carbonate or potassium carbonate is preferably carried out. As the solvent 1 used in the reaction, benzene, toluene, xylene fx, etc. (D aromatic hydrocarbon,
Examples include ethers such as diethyl ether, tetrahydrofuran, and dioxane, and ketones such as methyl ethyl ketone and dimethyl ketone. Especially reaction (2)
Ethers or ketones are preferably used. The reaction temperature varies depending on the type of reagent and solvent used.
There is no particular limitation, but for one reaction (1), the temperature is 0°C to 30'C,
Reaction (2) is suitably carried out at a temperature of 50°C to 130°C.

Reaction time is approximately 1 to 10 hours. A specific synthesis example of the present invention will now be described.

Next, an example of its synthesis will be shown.

Synthesis Example 1 N-benzyl-2-(5,5-dimethylphenoxy)-
Synthesis of butyramide (compound number 3 in Table 1 below)
0 compound) Benzylamine 1.8 # (0,0'17 mol) Tobiridine 1.2 # (0,015 mol) in benzene 30
- 2-(3,5-dimethylphenoxy)-butyroyl chloride 3.0. y(0,
013 mol) was administered subcutaneously. After 5 hours of reaction, 1 reaction solution was mixed with water,
After sequentially washing with dilute hydrochloric acid, dilute caustic soda, and water, and dehydrating the benzene layer, the benzene was distilled off. The obtained crude crystals were recrystallized from n-hexane.

Colorless acicular N-benzyl-2- with a melting point of 93-94°C
(5,5-dimethylphenoxy)-butyramide 2.4
I got g.

Synthesis Example 2 Synthesis of N-(2-methylbenzyl)-2-(3,5-dichlorophenoxy)-butyramide (compound No. 116 in Table 1 below) 2-methylbenzylamine 1.5f (0, 012 mol) and triethylamine 1.
0# (0.01 mol) was dissolved in benzene 30-, and 2-(3,5-dichlorophenoxy) was dissolved under stirring at room temperature.
-butyroyl chloride 2.8 g (0.01 mol)
Benzene 20rn! , the solution was added dropwise. After 2 hours □ reaction, add 1 reaction solution to diluted hydrochloric acid.

After sequentially washing with dilute caustic soda and water and dehydrating the benzene layer, the benzene was distilled off.

The obtained crude crystals were recrystallized with ethanol, and the melting point was 135~
Colorless prismatic N-(z-L methylbenzyl)-2-(3,5-dichlorophenoxy)-butyramide 2.3f exhibiting a temperature of 1'37°C was obtained.

Synthesis Example 3 Synthesis of N-benzyl-2-(4-chloro-3-methylphenoxy)-valeramide (compound No. 54 in Table 1 below) N-benzyl-α-brombaleramyl' 3. ．． 5
g (0,013 mol) and 4-chloro-3-methylphenol 6,zg (o, o4o mol) were dissolved in 60 ml of acetone, and to this was added 6.9 g (0,05 mol) of anhydrous potassium carbonate.
0 mol) was added thereto, and the mixture was boiled and refluxed for 10 hours with stirring.

After cooling, the acetone is distilled off, and the residue is mixed with 10 ml of water.

m7! was added, and the precipitated oil was extracted with benzene. The benzene layer was washed with dilute hydrochloric acid, diluted caustic soda, and ice in this order, dehydrated, and then the benzene was distilled off. The residue was applied to a silica gel column to obtain N-hensyl-z-(4-chloro-3-methylphenoxy)-valeramide as a colorless oil.3. Obtained OIP.

When left at room temperature, it crystallized and exhibited a melting point of 75-78°C.

It was manufactured according to the above synthesis example. Examples of the novel benzylamide derivatives of phenoxyalkanoic acid in this invention are as follows:
Listed in Table 1.

In addition, the upper row of elemental analysis values in Table 1 shows theoretical values, and the lower row shows actual measured values.

Table 1 ζ Continuation of Table 1 Continuation of Table 1 Continuation of Table 1 Continuation of Table 1 Continuation of Table 1 (15) Continuation of Table 1 Continuation of Table 1 Continuation of Table 1 Continued from Table 1Continued from Table 1Continued from Table 1Continued from Table 1Continued from Table 1Continued from Table 1Continued from Table 1Continued from Table 1Continued from Table 11 Table continues in this invention. When the phenoxyalkanoic acid nopendylamide conductor is used as a herbicide, an inert solid carrier is used in accordance with the customary practice for agricultural chemical formulations.

Single tablet using liquid carrier and emulsifying dispersant.

It can be used in any dosage form such as powder, emulsion, water-soluble tablet, aerosol, smoke agent, etc. Examples of inert carriers include talc, clay, kaolin, diatomaceous powder, etc. Soil, calcium carbonate.

Potassium chlorate, saltpeter, wood flour, nitrocellulose.

Starch, benzene, xylene, n-hexane.

Examples include gum arabic, vinyl chloride, carbon dioxide, Freon, propane, and butane.

Further, auxiliary agents 1 for formulation, such as spreading agents, diluents, surfactants, solvents, etc., may be appropriately incorporated.

Plus fungicides, insecticides and pesticides, urea.

Ammonium sulfate, ammonium phosphorous, potassium salts and their planer fertilizer substances.

It can be used by appropriately mixing it with a soil conditioner.

Ru,.

Next, examples of the herbicide of this invention will be given. Note that each part in each example represents 1 part by weight.

Example 1 N-hensyl-2-(5,5-dimethylphenoxy)-
An emulsion was obtained by mixing and dissolving 50 parts of butyramide (compound No. 30), 40 parts of xylene, and 10 parts of Trupol 800 (surfactant, trade name).

Example 2 50 parts of N-(2-methylbenzyl)-2-(3,5-dichlorophenoxy)-butylamide (compound No. 116), 30 parts of kaolin, 15 parts of bentonite, 5 parts of sodium ligninsulfonate Mix and grind to make a hydrating agent□
I got it.

Example 3 7 parts of N-benzyl-2-(5-chloroenoxy)-butyramide (compound No. 67).

After mixing and pulverizing 60 parts of bentonite, 30 parts of talc, and 3 parts of sodium naphthalene sulfonate, an appropriate amount of water was added, kneaded, and granulated using a granulator to obtain one granule.

Next, the effects of the herbicide of the present invention will be specifically explained using experimental examples. In addition, the test compound number in each experimental example is the same as the compound number in Table 1.

Experimental Example 1 Soil Treatment Test A 1/9000 are pot was filled with paddy soil (diluvial soil), and the seeds of various weeds such as field weeds, broad-leaved weeds (kicanthus, azalea, and japonica), fireweed, and cypress were evenly distributed on the surface layer. The mixture was sown and 1. Urikawa tubers and paddy rice seedlings at the 3-leaf stage were transplanted.

Water was added to make it flooded at 3Ω. Then, three days later, at the beginning of the emergence of various weeds, a predetermined amount of diluted solutions of each wettable powder produced according to Example 2 was uniformly sprayed on the flooded surface. Four weeks after spraying, the herbicidal effects of each test compound were investigated. The results are shown in Table 2.

5: Complete withering 4: Great luck 3: Vital damage 2: Small damage 1: Slight damage O: Harmless (normal growth) In addition, the upper row of each column in Table 2 indicates the amount of active ingredient 50f.
/R, and the bottom row shows the results of an experiment conducted at 259/R.

Compounds in Table 2 Numbers for weeding effect on rice Placing Broadleaf grass weed Firefly cypress Urikawa 1 5 5 5
5 '30553 5
2 0555 5 2 0455 5 1 0555 5 2 30 5 5 5 '5 20 5
5 5 5 50553
5 3 05.5.5 5 30.553
5 1, · °°°° ” 01523 KO0 5 .5. 5 5
2045 4 5 10
555 5 4 8 0555 5 2 0 5 5 5 '5.
50 4 5 4 5
．． 3055 5 5
3Q 0 5 5 5 5
'21 5 5 5
5 21 0455 5 1 0 5 5 5 5
22 Table 2 continued Table 2 continued Table 2 continued Table 2 continued Table 2 continued Table 2 continued Table 2 continued Table 2 continued Experimental example 2 Upland soil treatment test 115,000 are The pots were completely filled with field soil (diluvial soil), seeds of corn, soybean, barnyard grass, crabgrass, clover, purslane, and whiteweed were sown, and after covering with soil, dilution of each irrigation agent produced according to Example 2 was carried out. A predetermined amount of the liquid was uniformly sprayed using a pressure sprayer. After the chemical treatment, the herbicidal effect of each test compound was investigated on the ridge for 3 weeks. The results are shown in Table 3. The criteria for the herbicidal effect in Table 3 are the same as in Experimental Example 1.

In addition, the upper row of each column in Table 3 indicates the amount of active ingredient 50t.
/R, and the bottom row shows the results of an experiment conducted at 25t/R.

From the experimental results shown in Table 3 and above, it was found that the herbicide of the present invention is highly safe for one crop and has excellent herbicidal effects against various weeds. It is recognized that it is a drug.

Patent Applicant Ube Industries Co., Ltd. Procedural Amendment July-0, 1982 Director-General of the Patent Office 1, Indication of Case Patent Application No. 166345-1982 2, Name of Invention Benzylamide derivatives of phenoxyalkanoic acids and herbicides 3. Relationship with the person making the amendment Patent applicant postal code 755 1-12-32 Nishihonmachi, Ube City, Yamaguchi Prefecture (020)
Ube Industries Co., Ltd. Tel: 03 (581) 3311 7 8 4. There is no order to correct the date of the correction order (voluntary correction).

5. There is no increase in the number of inventions due to amendment.

6. Subject of correction Detailed description of the invention in the specification 7. Contents of amendment (1) In the table following Table 1 on page 18 of the specification.

■ Physical property values rm, p of compound number 49.

111-113°C" to "m, p, 95-97°C."

■ Physical property values rm, p of compound number 51.

141-14°C" to "m, p, 115-117°C
” to.

■ Physical properties of compound number 52 “m, p.

97-99°C" to "m, p, 88-90°C."

■ Physical property values rm, p of compound number 56.

120-121°C" to "m, p, 113-11' 5
°C”.

Correct each.

Claims (2)

[Claims] (1), general formula (in formula 1, X represents a lower alkyl group or a chlorine atom, n represents 0, 1.2 or 3, Ro represents a lower alkyl group, R2 represents a hydrogen atom or a lower alkyl group) or a lower alkenyl group, R8 represents a hydrogen atom or a lower alkyl group, Y represents a lower alkyl group, a chlorine atom or a lower alkoxy group, and 8m represents 0, 1 or 2.)
It is expressed as Benzylamide derivative of phenoxyalkanoic acid. (2), general formula (in formula 2, X represents a lower alkyl group or a chlorine atom, n represents 0, 1.2 or 3 + R1 represents a lower alkyl group, R2 represents a hydrogen atom, a lower Represents an alkyl group or a lower alkenyl group, R8 represents a hydrogen atom, a chlorine atom, or a lower alkyl group. Y represents a lower alkyl group or a lower alkoxy group.
indicates 0, 1 or 2. ). A herbicide characterized by having a benzylamide derivative of phenoxyalkanoic acid as the entire active ingredient.