JPS6041648A - Alpha,alpha-dimethylphenylacetic acid anilide derivative, its preparation, and herbicide containing it - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (Y is lower alkoxy, halogen, with the proviso that Cl is omitted; X is lower alkyl, lower alkoxy, or halogen,; n is 0-2). EXAMPLE:alpha,alpha-Dimethyl-o-methoxyphenylacetic acid-m-ethylanilide. USE:A herbicide. Showing improved activity espectially against weeds in paddy rice plants. Although it is a slow-acting herbicide, this herbicide has improved residual effect, and low toxicity. PREPARATION:An alpha,alpha-dimethylphenylacetic acid derivative shown by the formula II or its reactive derivative is reacted with an aniline derivative shown by the formula III in a solvent such as benzene, methanol, etc. at 0 deg.C- the reflux temperature of the solvent preferably at 20-40 deg.C for 1-10hr to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides that the general formula (in the formula) 'is an IPA-class sylcoki/-J, l, or/.
Roken j1 bar J' / Kodashi I; j, c; Q 1
3 Excluding Takeshi), N, (]゛, Ishi class " Ru Kirno old, low, and Arkogi/) Old or no\ Roken!))! Finish, +1i', 10~2 (ri integer , ``λ・) units of 1 or 2 are fb'd 'n ゛・
−7 different and better] A shi・3XI j
A α,α-dimethylphenyl i'l'l t9 but'nyrito 1, ・Udera (・, its production IJ&; KoJshi as an active ingredient 1) 2j Go 1゛(Stone regardless of agent).

Phenylhydromonyl acid bunylide 1. There are already many stripes l, I
I +') is/9゛, 1 worried removal -, 7, the agent was developed 14.7? 8', J Chemical Abstracts No. 85 (1976) 62766t (above, 41' phenyl-111 acid anilide derivatives in which the α-carbon atom has been monofisted with a methyl group, that is, a plant of hydroatronoxic acid anilide) A research report on the harmful activity of isopropylphenyl 11'1 acid phenoxyoxime is described in Chemical Abstracts Vol. 48 (1954) 8193k).
-dimethylphenyl drunkenness [ll! The preparation of 2anilides has been described. However, until now, no information has been reported regarding the activity of C-carbon atoms (C-carbon atom is methyl, Il (di-substituted phenylated)l/oxacid anilide visiting body glue).

Misfire 1] Nagisa also attempted various modifications of this family of compounds (7) and attempted to create a new herbicide from melon.

Conclusion 9.4. α-dimethylphenylchocolate resistant anilide was visited by A.J8 crops in the Mizuin area. It accelerates the action and suppressing action on mid-sized fish, has a slow effect but has excellent residual effect, and is also effective against fish 3.1"iIf
It has been found that various improvement effects can be brought about, such as +71c.

The compound of formula 1 is suitable for pre-emergence flooded soil treatment and growing season flooded soil treatment of wholesale W1. , power ((harmed 1
? ,) Z)) 5, Nohie, Mizuriki-＼・Tsuri, Tar,
・Excellent off-killing effect and growth method against Japanese snails etc.
Shown for li production. In addition, the compound of the present invention (:) 1 was found to have a lower yield in rice and a lower yield in Japanese cypress than compared with the compound used as a control in the fruit test and test.
Shoulder(:' 1jiI, j;,fi was found to have a remarkable effect on J.

The compound of formula ■ has the general formula alK.

ct represented by (in the formula, Y has the meaning of "il")
, α-dimethylphenyl 1″1″11 visit 11・Also;
:),・Which reactivity 1. Mino! It can be produced by reacting the 7-isomer with an aniline derivative represented by the general formula (wherein X and n have the above-mentioned meanings).

This reaction is preferably carried out in a solvent in the presence of a suitable reaction aid. Examples of solvents include aromatic hydrocarbons such as benzene, toluene, and xylene, ethers such as diepyl ether, tetrahydrofuran, and dioxane, alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, methylene chloride, chloroform, Halogenated hydrocarbons such as carbon tetrachloride are used.

Examples of reaction aids used include phosphorus pentachloride, phosphorus trichloride, thionyl chloride, sodium hydroxide, potassium hydroxide, sodium bicarbonate, triethylamine, pyridine, tripropylamine, N,N-dimethylaniline, and the like.

In the reaction, it is advantageous to use the compounds of formula (1) and formula (2) in equimolar amounts. The reaction temperature is 0°C to the reflux temperature of the solvent, preferably 20 to 40°C.
It ends in 0 hours. The product can be isolated and purified by recrystallization, vacuum distillation, etc. Examples of solvents used for recrystallization include benzene, toluene, methyl alcohol, ethyl alcohol, chloroporm, 11-hexane, and ethyl acetate.

If necessary, by a conventional method using an auxiliary agent, for example, an aqueous phase agent,
It is used in formulations such as emulsions, granules, and powders. Other appropriate additives, fertilizer 1, pesticides such as herbicides, insecticides,
A bactericide or the like may also be added.

Examples of solid carriers include clay, talc, kaolin,
Liquid carriers include evabenzene, xylene, kerosene, alcohol, dimethylbormamide, etc., or mixtures thereof. Also drug dispersion,)
Surfactants such as sodium lauryl sulfate, alkyldimethylbenzylammonium chloride, polyoxyethylene alkylaryl ether, and polyoxyethylene are used as auxiliary agents to improve properties such as cloudiness, wetting, emulsification, adhesion, and fixation.

Polymer compounds such as polyvinyl alcohol, sodium alginate, etc. are used.

The above drugs generally contain 0.5 to 95% active ingredient by weight.
, preferably in a proportion of 1 to 90%. The content of the active ingredient varies depending on the dosage form, but for example, it is 1 to 15% in the case of granules and powders, and 10 to 80% in the case of wettable powders.
, and in the case of an emulsion, it is preferably 1 to 50%.

The amount of the herbicide of the present invention to be used depends on the dosage form, weather conditions, timing of use,
Although it varies depending on the soil conditions, the type of target weed, etc., the amount of active ingredient per are is usually o, s ~ 50. ! 7,
Preferably i is ~30.9.

Synthesis Example 1 (Compound No. 4) Benzene 5o7nC1 in a 100 me four-loop flask
)! 0.50 g of J-1-1-ruamine and 0.60 g of m-ethylaniline are added, and while cooling and stirring in water, α,α-dimethyl-〇-methoxyphenylacetic acid] is stirred. After the reaction is completed, the reaction solution is washed with water to remove the hydrochloride of I-ethylamine, the benzene layer is dried over anhydrous sodium sulfate, and the solvent is distilled off under reduced pressure. The residue was developed by column chromatography using 7 liters (developing solvent: rl-hexane/acetone-4/1).
'l'j produces a white solid α,α-dimethyl-O-
1.35 ml of methoxyphenyl-ethylanilide, Sl', is obtained.

Yield 90.9%, melting point 86-84°C0IR Direct ν
nujol a++, 2 3370 (NH),
165511aX (C=O) Elemental analysis value: C,, I (CHN as □302N Theoretical value ('%・) 76.83 7,80 4.72 Actual value (N6) 76.78 7.82 4.70 Synthesis Example 2 (Compound No. 16) 100 me four-fold benzea in a flask 50
me.

α, α-7 Methyl-〇-fluorophenyl choic acid 091β
and m ~ 067 g of normal propylaniline was added, cooled in ice water, and while stirring, dicyclohexylcarbodiimide 1.03,! Drip 7. After stirring, stir overnight at room temperature. After the reaction is complete, the reaction solution i+71a
L, excluding synchhexylcarbodiimide with added water, N+'? Concentrate the mixture under reduced pressure to remove the solvent. The residue was purified by silica gel column chromatography (developing solvent = 11-hegisan/ethyl citrate 28/2) and further recrystallized from l'l-hexane to obtain a white solid α,α-dimethyl- 0-Fluorophenyl l'l'f acid-m-n-propylanide is obtained. Yield 73.8%, melting point 61
~62℃.

1 knife (I direct νnujol Cn,, , ro 300 (
N-+ (), +1'l n
H to I Theoretical value (!A) 76.26 7,35 4.67 Actual 1
111 (Ili (%) 76, 0 7.32 4.6
5 Synthesis Example 6 (Compound No. 18)
me.

Add 0-chloroaniline 0.64.9 and triethylamine o, so, p, and add α, α while stirring at room temperature.
-dimethyl-l)-fluoronoenyl chloride 1
．． Go down 009 one mountain. After the addition, the reaction solution was stirred at room temperature for 6 hours.After the reaction, the reaction solution was washed with water and the acid salt was removed, and the benzene layer was diluted with anhydrous sulfuric acid. '7. After rubbing,
The solvent is removed under reduced pressure. Residue? silica gel color,
Developed by chromatography (extraction 1 solvent: 11-
Hexane/ethyl indicate Nisder - 20/i) When purified, α is a colorless transparent liquid.

α-Dimethyl-Y)-fluorophenyl chloranilide is obtained at t 2 0,9. Yield 82-2”A
- n D 165 44.

[R 1f4 v ” 111'cm-': 3
4 7 0 (N--H), 1700 (cmo) aX Elemental analysis value: C, oH,, CH as NOPCI
N Theoretical value (%) 65,89 5.14 4.80 Actual i1
jl ldirect (・ba.) 65.80 5,21 4.8
The following compounds are obtained in the same manner as in 2.

Table 1 Formulation Example 1 (Granules) Compound of the Invention (4g4)' 5 parts Sodium dodecylbenzenesulfonate 2 parts Sodium lauryl sulfate 1 part Talc 20 parts Bentonite 72 parts The above ingredients were mixed, and an appropriate amount of water was added. The mixture is kneaded, granulated through a granulator, dried, and sized to obtain granules.

Formulation example 2 (granules) Bentonite 20 parts Clay 76 parts Sodium lignin sulfonate 6 parts Alkylbenzenesulfonic acid sorter 1 part The above ingredients were mixed and kneaded with water, then granulated through a granulator, dried, and sized. Make a squid-like object. Granules are obtained by impregnating 95 parts of the granules with 5 parts of the compound of the present invention (cup 16). However, if the uninvented compound is in solid form, it is dissolved in an appropriate amount of an organic solvent and impregnated.

Formulation example 6 (emulsion) Compound of the present invention (j!M16) 30 parts xylene 60 parts The above components are mixed and dissolved to obtain an emulsion.

Formulation example 4 (hydrating powder) Compound of the present invention (A19) 50 parts Polyvinyl alcohol 2 parts Diatom ± 45 parts The ingredients are mixed and ground to obtain a wettable powder.

Test Example 1 Fill a 115,000 are pot with paddy soil, transplant paddy rice at the two-leaf stage, sow seeds of Novieum, Cyperus japonica, and Hokurui, plant tubers of Cyperus japonica, and fill the pot with water to a depth of 3 cm. I watered it. Six days after the germination of the weeds, flooded soil was treated using a predetermined amount of the hydrating powder produced in Formulation Example 4. Six weeks after chemical treatment, paddy rice and each d,
The degree of phytotoxicity and herbicidal efficacy of grasses was examined16. The results are shown in Table 2. In addition to the compounds of the present invention, the following compounds were used for comparison in the test.

C1-1゜ The phytotoxicity of rice (the basic rings are as shown below).

-2 Harmless 12 Minor harm 22 Minor harm Do1: Used 111: Excerpt Table 2 Test Example 2 A 1150 [10 are pot was filled with paddy soil and flooded to a water depth of 1 crn. Twenty-eighth days after the flood, 20 types of hydrating powder were prepared according to Formulation Example (4), and a week later, the wild plants were extracted and the dry weight of the above-ground parts was adjusted. The results are shown in Table 6.

In the test, the compound of the present invention was used for 4 days, and the following compound was used due to its relative softness.

(Refer to Special Publication No. 39-1699) CH,,Cl-1゜ (Refer to Special Publication No. 56-46455) Table 6

Claims (1)

[Claims] 1. General 2 (in the formula, Y is a lower alkoxy group or a halogen atom (excluding a chlorine atom), X is a lower alkyl group, a lower alkoxy group, or a halogen atom, +1 is 0 to 2 Indicates an integer of n
If is 2, the individual Xs may be the same or different)
An α,α-dimethylphenylchoic acid-resistant nilide derivative represented by: 2. α, α- represented by the general formula (in the formula, Y has the meaning below)
Dimethylphenylformic acid derivative or its reactive core,
A compound of the general formula (where Y is a lower alkoxy group, a halocarbon atom (however, excluding a chlorine atom), or a lower alkyl group (excluding a chlorine atom), or a lower alkyl group (,
＼ class alkoxy group or 1・kei/″-roken atom, 11 (represents an integer from 0 to 2, 11 is an individual number of 2) ζ may be the same or different from 10) old,ruα,α−
Notylphenyl IYl acid anilide derivative; %
'/) Manufacture υ,. 3 -'General formula (in the formula)'it lower alkoxy group or...rEken atom (excluding chlorine atom), or lower alyal group, lower alkokene group, or rogen atom, +1 is 0 to 2 (an integer , and the platforms with II of 2 are individually α) S is l, which may be the same or I, LLl, /:,, ) is represented by 1 α, α-dumealphenyl 1'ii acid Anilide”
J'A','X I4I: What does Igf-4 contain as an active ingredient? 1. ! Herbicide with 1' symptom.