JPS59141504A - Herbicide containing thiocarbamate derivative - Google Patents

Abstract

PURPOSE:A herbicide having sufficient herbicidal effect and high selectivity, containing a specific thiocarbamate derivative. CONSTITUTION:The titled herbicide containing a compound such as O-3-isopropylphenyl N-methyl-N-(3-methylphenyl)thiocarbamate shown by the formula (R1 and R2 are lower alkyl; X and Y are H, halogen, lower alkyl, lower alkoxy, or CF3) as an active ingredient. The herbicide shows extremely improved herbicidal activity against a number of weeds such as umbrella plant, Monochoria vaginalis Presl, bulrush, etc. including Echinochloa crus-galli Beauv. var. praticola Ohwi. in paddy fields especially under flooding, has substantially no damage on transplanted paddy-rice plants, etc., and exhibits improved selective herbicidal effect between gramineous weeds and broad-leaved weeds by soil treatment of plowed field.

Description

[Detailed description of the invention] The herbicide contained in the herbicide.

It has been well known that O-aryl N-arylthiocarbamate compounds have antibacterial and insecticidal effects as medicines. Furthermore, it is generally known that cybamate, theocarbamate and dithiocarbamate compounds have herbicidal activity. Furthermore, in Japanese Patent Application Laid-open No. 48-49925, a specific aryl N
- It is disclosed that aryl carbamate compounds can be used as herbicides. However, it is not known that O-aryl N-arylthiocarbamate compounds can be used as effective herbicides.

The present inventors completed the present invention as a result of extensive research in order to develop an N-arylthiocarbamate derivative having a sufficient herbicidal effect and a high degree of selectivity.

That is, the present invention is based on the general formula (1) (where Ro and R2 represent a lower alkyl group, and X and Y each represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, or a trifluoromethyl group. R1 and R1 and X and Y are the same or different from each other.

) A herbicide containing a thiocarbamate derivative represented by the following as an active ingredient is provided.

The herbicide containing the thiocarbamate derivative of the present invention as an active ingredient exhibits extremely excellent herbicidal activity against many weeds including field weeds, especially in flooded rice fields, and has virtually no effect on transplanted paddy rice. It is harmless and suitable as a herbicide for paddy fields. In addition, it showed excellent selective herbicidal effects on grass and broad-leaved weeds when treating upland soil, and was recognized to have applicability as a herbicide for upland.

The thiocarbamate derivative represented by the general formula (I) used in the herbicide of the present invention can be produced according to the following reaction formula.

(In the formula, R1 and R2 represent a lower alkyl group, and X and Y each represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, or a trifluoromethyl group. Same or different.

Hat represents a halogen atom. ) The above reaction usually proceeds at a reaction temperature of 0°C to 150°C in the presence of a dehydrohalogenating agent and in the presence or absence of a reaction solvent, and the reaction time ranges from several minutes to 48 hours. That's about it.

Examples of dehydrohalogenating agents include alkali hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth hydroxides such as calcium hydroxide, sodium carbonate, potassium carbonate,
Examples include alkali carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, metal hydrides such as sodium hydride, and tertiary amines such as triethylamine, dimethylaniline, and pyridine. In reaction formula (2),
The raw material aniline derivative can be used as a dehydrohalogenating agent.

As a reaction solvent, water, methanol, ethanol,
Alcohols such as isopropanol, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene, and xylene, ethers such as ethyl ether, tetrahydrofuran, and dioxane, chlorobenzene, chloroform, carbon tetrachloride, and dichloroethane. halogenated hydrocarbons such as, polar solvents such as dimethylformamide, dimethyl sulfoxide, etc. are used.

Next, the method for producing the active ingredient compound used in the herbicide of the present invention will be explained by giving specific synthesis examples.

[Synthesis Example 1] 0-3-isopropylphenyl'N-methyl-N-(
Process for producing 3-methylphenyl)thiocarbamate (compound A3) N-methyl-N-(3-methylphenyl)thiocarbamoyl chloride 2-009,5-isopropylphenol 1.569 and anhydrous potassium carbonate 1,389 Lamethyl ethyl ketone 50 - and heated under reflux for 15 hours. After cooling the reaction mixture to room temperature, it was poured into cold water and
The product was extracted with benzene. The benzene solution was washed successively with a 10% sodium hydroxide aqueous solution, water, and a saturated sodium chloride aqueous solution, dried over anhydrous magnesium sulfate, and then benzene was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel, benzene/hexane-1/1 (
0-3-isopropylphenyl (N-methyl-N-(3-methylphenyl) thiocarbamate) 2.32 g (yield 78%, oily) [Synthesis Example 2] Q-5 -tert-butylphenyl 11-,, N-
Method for producing methyl-N-phenylthiocarbamate (compound A4) 1.077 g of N-methylaniline and 1.687 g. of anhydrous potassium carbonate were added to 20 g of acetone, and while stirring at room temperature, 3-tert-butylphenyl chlorothio 2.299 g of formate was dissolved in 20 g of acetone and added. After stirring as it was for 30 minutes, the mixture was heated under reflux for 2 hours. After the reaction mixture was cooled to room temperature, it was poured into cold water.1.
The product was extracted with benzene. Benzene solution with dilute hydrochloric acid,
After washing with water and a saturated aqueous sodium chloride solution in this order and drying over anhydrous magnesium sulfate, benzene was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel).

benzene/hexane (1/1 (V/v) development) to give O-3-tert-butylphenyl, N-methyl-N
-7enylthiocarbamate 1.779 (yield 77%)
I got it. A part of this product was recrystallized from hexane to obtain colorless crystals with a melting point of 7&5-79''C.

Next, representative examples of the compound represented by the general formula (1) and their physical properties are shown in Table 1 below.

The herbicide of the present invention is prepared by mixing appropriate amounts of one or more of the compounds represented by the general formula (1) with an inert carrier, and is used as an irrigation agent or emulsion, which is a conventional agricultural chemical.

It is used in the form of granules, etc.

Talc, clay, diatomaceous earth as solid carriers.

Bentonite and the like are used, and as the liquid carrier, water, alcohol, benzene, kerosene, cyclohexane, cyclohexanone, dimethylformamide, mineral oil and the like are used.

Furthermore, surfactants and stabilizers may be added if necessary for formulation. The herbicide of the present invention may also be used in other agricultural chemicals, such as insecticides, used in the same field.

It can be applied in combination with fungicides, herbicides, growth regulators or fertilizers. In particular, it may be appropriate to add and mix other herbicides in order to reduce the spraying effort or to widen the range of grass species that can be effectively controlled.

Examples of herbicides that can be added include triazine herbicides such as atrazine, simazine, cymetrin, and promethrin, carbamate herbicides such as Ashlam, Bentocarb, and Molinate, and urea herbicides such as Linyron and Daimeron.
．． 4-D, McP.

MOFB, phenoxy herbicides such as nabroanilide, diphenyl ether threads such as nitrofen, chlornitro-7ene, chromethoxynil, etc. 1111. txacyacin,
Examples include heterocyclic herbicides such as virazolate and pentacine, and amide herbicides such as alachlor, butachlor and propanil. By skillfully combining one or more of these herbicides, it is possible to provide a mixture that is effective against many grass species.

Next, formulation examples of the herbicide of the present invention will be described.

In the formulation examples, "parts" are parts by weight.

[Formulation Example 1] (Irrigation agent) 1.10 parts of Compound A as a carrier material, 87.3 parts of Zikrite [trade name, manufactured by Kunimine Kogyo ■], and Neoperex as a surfactant [trade name, Kao Atlas ■g ]1.3
5 parts and 1.35 parts of Tsurupol 800A (trade name, manufactured by Toho Chemical Industries, Ltd.) were mixed and ground to obtain a 10% irrigation agent.

[Formulation Example 2] (Emulsion) 3.25 parts of Compound A were mixed and dissolved with 65 parts of benzene and 10 parts of Tsurpol 80OA as a surfactant to give a 25%
An emulsion was obtained.

[Formulation Example 3] (Granules) After pulverizing 10 parts of the compound &(S) with 50 parts of bentonite, 35 parts of Kunishite [trade name, manufactured by Kunimine Kogyo ■] and 5 parts of Tsurupol 80 mouth A as a surfactant,
10 parts of water was added thereto, stirred uniformly, extruded through a nodal hole with a diameter of CL7yam, dried, and then cut into pieces of 1 to 2 lengths to obtain 1 part tablets.

The herbicide of the present invention exhibits excellent herbicidal activity against various weeds and does not cause chemical damage to crops such as paddy rice, soybeans, and cotton, and is thus suitable as an active ingredient of a herbicide. In other words, the herbicide of the present invention has the ability to kill or stop the growth of weeds without causing any chemical damage to crops.
Alternatively, by significantly suppressing or delaying growth, growth competition with crops may be lost.

The amount of the herbicide of the present invention to be applied varies depending on the application situation, application time, application method, target grass species, etc., but generally the amount of active ingredient is 10 to 1009/10a, preferably 50 to 5009/10a. A range of 10 a is suitable.

The herbicide of the present invention is particularly effective against many weeds such as field weeds, Japanese grasshoppers, Japanese grasshoppers, Japanese fireweeds, and fireflies, especially in flooded rice fields.
It was observed that the herbicidal activity was extremely excellent at the amount of active ingredient a. On the other hand, it is extremely safe for young paddy rice seedlings, with no effects observed at all even at the active ingredient level of 10009/10a, and has extremely excellent properties as a herbicide for paddy fields.

Furthermore, when the herbicide of the present invention is used as a soil treatment agent after sowing general broad-leaved crops such as soybeans, which are upland crops, it does not cause any chemical damage to the crops and eliminates the problem of novia.

It was found that it can effectively control grass weeds such as grasshopper and foxtail grass, and has applicability as a herbicide for upland fields.

Next, the herbicidal effect of the herbicide of the present invention will be explained using test examples.

[Test Example 1] Weeding effect test under flooded conditions Paddy soil was placed in a porcelain pot with a diameter of 9α, water was added, and after plowing, weed seeds were sown on the surface layer of the soil, and paddy rice seedlings at the two-leaf stage (
Two plants of the cultivar Nipponbare) were planted at a depth of 1 ctn. The next day, the plants were flooded with water to a depth of 2 cm, and a predetermined amount of the water use agent of each herbicide of the present invention was diluted in 101111 bottles of water and dropped onto the water surface. After that, leave it in a greenhouse and treat it with chemical solution 6.
After a week, the weeding effect and the effect on paddy rice were investigated.

Although the evaluation Fi was displayed in 6 stages, the specific details are as follows. The results are shown in Tables 2 and 3.

Display Paddy rice chemical damage weeding effect 5 Death 100 tchi control (residual weed amount 0 tchi) 4 Severe damage 80 tchi control (remaining amount 20 tchi) 3 Nakayoshi
60-chi control (residual weed amount 40-chi) 2 small book
40% control (residual weed amount 60 cm) 1 small amount
20-chi control (residual weed amount 80-chi) 0 Harmless
0chi control (residual weed amount 100chi) Table 2 +
1) Table 2 (2) Table 2 (3) Table 3 [Test Example 2] Weeding effect test by surface treatment of field soil A porcelain bottle with a diameter of 12 cm) K Filled with field soil and sown several types of plant seeds. , covered with 1cIn soil. A predetermined amount of the hydrating powder of the herbicide of the present invention was diluted in 10 pots of water and sprayed onto the soil surface, then left in a greenhouse and watered at appropriate times. Three weeks after the chemical solution treatment, the herbicidal effect and the effect on soybeans and cotton were investigated. It was evaluated according to.

Table 4 ``[♀shi'' Procedural amendment dated April 15, 1980 Kazuo Wakasugi, Commissioner of the Patent Office 1 Indication of the case Patent application No. 14596 of 1988 2 Name of the invention Herbicide containing thiocarbamate derivatives 6. Person making the amendment Relationship with the case Patent applicant telephone number (585) 3311 4. Date of amendment order 6. Target of amendment “Detailed description of the invention column in the specification” 7. Contents of the amendment (1) Specification, 2 Page 3, line 3, "Antibacterial action and sterilization" is corrected to "Antibacterial action and sterilization."

In the same book, the first line from the bottom of page 6 is ``78%, oily)'' followed by ``obtained.'' When this substance was left at room temperature, it crystallized, so it was recrystallized with ethanol to form colorless crystals with a melting point of 48-495℃. (3) Same book, page 9, 4 rows in the table, mp('C) column for compound A5 "Oily" was added to 1'-4
Correct it to 8-49, 5J.

(4) In the same book, page 24, line 2, "Compound of the present invention in the table" is corrected to read "Compound of the present invention."

Procedural Amendment July 8, 1980 Kazuo Wakasugi, Commissioner of the Patent Office 1 Display of Case 1982 Patent Application No. 14596 2 Name of Invention Related Patent applicant telephone number (j5851 Roro 11 4. Date of amendment order 6. Subject of amendment “Detailed description of the invention column in the specification” 7. Contents of amendment (1) Specification, page 2, line 15 “N- "arylthiocarbamate" is corrected to "0-7 aryl N-arylthiocarbamate."

(2) In the same book, page 7, lines 7-8, [3-tert-7'tylphenyl chlorothioformate] is corrected to "0-3-tert-butylphenyl chlorothioformate."

(3) Same book, page 24, Table 3 "Compound part of the present invention" Correct it to "compound."

Claims (1)

[Claims] (1) General formula (I) (In the formula, R1 and horse represent a lower alkyl group, and X and Y each represent a hydrogen atom or a halogen atom. They represent a lower alkyl group, a lower alkoxy group, or a trifluoromethyl group. R1 and A herbicide characterized by containing a thiocarbamate derivative represented by R2 and X and Y are the same or different.) as an active ingredient.