KR800000224B1 - Process for the preparation of thiolcarbamates - Google Patents

Abstract

Thiolcarbamates =DI; R = lower alkoxy, benzyl, methylbenzyl, naphthyl, m = 3-6 integer, R1 =formula II (Y = halogen, alkyl, alkoxy, nitro, methylthio, CF3, n = 0-3 integer) =Euseful as herbicides, were prepd. by reaction of thiolcarbamate salt (III; M =alkali metal, quaternary amine) with halides (IV; X = O, S; Z=halogen) in inert solvent such as aceton, DMF, alcohol, cellosolve, ether, benzene, toluene, xylene, etc. at 0-100≰C for 1-20 hr.

Description

Method for preparing thiol carbamate derivative

The present invention is a general formula

(Y는 할로겐원자, 알킬기, 알콕시기, 니트르기, 메틸티오기, 또는 트리플루오로메틸기를 나타내며 n는 0-3이다), 벤질기, 메틸벤질기, 또는 나프틸기를 나타내며, X는 산소원자 또는 유황원자를 나타내며 m는 3-6의 정수이다]로 표시되는 탁윌한 제초성, 살균성, 살벽슬성의 작용을 갖는 신규한 화합물에 관한 것이다.[R is a lower alkyl group, R 'is a formula

(Y represents a halogen atom, an alkyl group, an alkoxy group, a nitrile group, a methylthio group, or a trifluoromethyl group, n is 0-3), a benzyl group, a methylbenzyl group, or a naphthyl group, and X represents an oxygen atom. Or a sulfur atom, m being an integer of 3-6.] Relates to a novel compound having an excellent herbicidal, bactericidal, and crooked action.

Moreover, this invention relates to the manufacturing method of the herbicidal, bactericidal, and wall-like compound which contains the component represented by the general formula of the said description as an active ingredient. The components of the present invention represented by the general formula described above are useful as herbicides, fungicides, and skin husks.

The compounds of the present invention as herbicides exhibit excellent herbicidal activity against various weeds by spraying on the surface of rice paddy or treating the soil with the present compounds.

Compounds of the present invention are, for example, Slender spikerush [Eleocharis acicularis Var. Roem], Scirpus juncpides, Cypressus sertinus (Cyperusserotinus), Eleocharis Kurokuwai, Monochoria Vaginalis, Rotola indica Koehne, Dopatrium junceum, Echinochloa crus- galli, Cyperus microiria [Digitariaadscendens], Goosegrass [Eleusine indica], Green foxtail [Satari viridiss] Sataria Viridis]], purple Nutsedge [Cyperus rotundus], Quack grass [Agropyron repens], Oxalis Martiuna, Chamsori (Rumex Japonicus), Chenopodium album, People Pig weed [Amaranthus retroflexus] Polygonum nodosum, Common Purslane [Portu-laca Oleraca], Annual Fleabane [Eli] High herbicidal effect against weeds such as [Erigeron annus].

When the compound of the present invention is used as a fungicide, the compound controls the occurrence of rice destruction (pyricuria oryzae), downy mildew, andanthracnose, and the like in rice and cucumber. It is useful to. In addition, the compound of the present invention is also effective as a flesh wall agent.

That is, not only mite parasites in animals such as Boophilus microplus, Haemaphysalis bispinosa, Amblyomaatestadinarium, but also citrus fruits, apples, Citrus red mite, damaging plants such as pears, leaves, cotton, eggplants, cucumbers, strawberries, roses, carnations, chrysanthemums, and Japanese cedar. [Panomychus citri Mcgregor] ], European red mite [Panonychus ulmi koch] Two spotted spider mite Tetranychus telarius Linne, Carminemite [ Tetranychus telarius Linne], Kanazawa Spider mite [Tetranychus Kanazawai Kishida] Sugi spider mite [Oli] Phytoparasitic mites such as Oligonychus hondoensis Ahara] Clover mite (Bryobia Praetiosa Koch) also exhibit crustal activity.

Moreover, the compounds of the present invention can be safely used in various fields because there is no venom in humans, animals, fish, and crustaceans. US Pat. Nos. 3,166,401, 3,225,078 and 3,284,184 to A.G. WEISS et al describe compounds of the general formula

(R is a phenyl group or a halogen-substituted phenyl group, Y is an oxygen atom or a sulfur atom, X and X 'are oxygen atoms or sulfur atoms, at least one of them is a sulfur atom, and R' and R "are lower alkyl groups, cycloalkyl groups, and aryl groups). , A chloroaryl group, a piperidinyl group containing a nitrogen atom, and the like.)

It has also been described that the compound production process and the compound are useful as herbicides.

However, the compounds of the present invention exhibit higher herbicidal activity against weeds and less toxicity against rice than the compounds described in the aforementioned patents. That is, the compound of the present invention is superior to the known compound for screening weeds and rice. Moreover, the compound of the present invention also has bactericidal action and flesh wall action as described above.

In particular, mites breed about 18 times a year with a life span of about 20 days, which increases the use of the skin moisturizer, which in practice is such a resistance, by imparting the mite resistance or immunity to the skin moisturizer. It is a problem to get rid of immunity.

Therefore, there has been a strong demand for the development of a creeper sludge that can be used without giving resistance to drugs at any stage of tick eggs, larvae, and adults. The compounds of the present invention can meet the above requirements and are particularly good at killing eggs and adults.

The compound of this invention represented by the said general formula is manufactured by the following method.

That is, according to the manufacturing example,

The compound of formula I is

The compound represented by formula II

Compound represented by formula III and

(단, Y는 할로겐원자, 알킬기, 알콕시기, 니트로기, 메밀티오기 또는 트리플루오로메틸기를, n는 0-3을 나타낸다)로 표시되는 기, 벤질기, 메틸벤질기, 또는 나프틸기, X는 산소원자 또는 유황 원자, m는 3-6의 정수를 나타낸다.)][Where R is a lower alkyl group, M is an alkali metal or quaternary amine, Z is a halogen element,

(Wherein Y represents a halogen atom, an alkyl group, an alkoxy group, a nitro group, a buckwheatthio group, or a trifluoromethyl group, n represents 0-3), a benzyl group, a methylbenzyl group, or a naphthyl group, X represents an oxygen atom or a sulfur atom, and m represents an integer of 3-6.)]

It is prepared by reacting at a temperature of about 0-100 ° C. for 1-20 hours in a solvent such as water, acetone, dimethylformamide, alcohol, cellsolve, ether, benzene, toluene, and xylene.

According to another manufacturing example of the present invention,

The compound of formula (I) is a compound of formula (IV),

The compound represented by Formula (V),

(단, Y는 할로겐원자, 알킬기, 알콕시기, 니트로기, 메틸티오기, 트리플루오로메틸기, n는 0-3의 정수를 나타낸다)로 표시되는 기, 벤질기, 메틸벤질기, 나프틸기, X는 산소원자 또는 유황 원자를 나타낸다.][Wherein R is a lower alkyl group, Z is a halogen atom, m represents an integer of 3-6, and R '

(Wherein Y represents a halogen atom, an alkyl group, an alkoxy group, a nitro group, a methylthio group, a trifluoromethyl group, n represents an integer of 0-3), a benzyl group, a methylbenzyl group, a naphthyl group, X represents an oxygen atom or a sulfur atom.]

Sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, water, acetone, dimethylformamide, alcohol, cellosolve, ether, benzene, toluene, xylene, etc. Sodium bicarbonate, triethylamine, pyridine and the like are prepared by reacting with a dehydrohalogenated reagent.

According to another embodiment of the present invention,

The desired compound of general formula I is a compound represented by formula VI,

Compound represented by formula V

(단 Y는 할로겐원자, 알킬기, 알콕시기, 니트로기, 메틸티오기, 또는 트리플루오로메틸기, n는 0-3의 정수를 나타낸다)로 표시되는 기, 벤질기, 메틸벤질기, 나프틸기를 나타내며 X는 산소원자 또는 유황원자를 나타낸다.]을 비용매 또는 벤젠, 톨루엔, n-헥산 같은 반응용매속에서 실온∼150℃까지의 온도로 5-20시간 촉매 비존재하 또는 벤조일옥사이드, 인산, 황산 등이나 자외선 같은 부가가속 촉매 존재하에 반응시킴으로써 제조된다.[Where R is a lower alkyl group, m is an integer of 3-6, and R 'is

(Wherein Y represents a halogen atom, an alkyl group, an alkoxy group, a nitro group, a methylthio group, or a trifluoromethyl group, n represents an integer of 0-3), a benzyl group, a methylbenzyl group, a naphthyl group X represents an oxygen atom or a sulfur atom.] Is a nonsolvent or a catalyst free of benzoyl oxide, phosphoric acid, benzoyl oxide, phosphoric acid, It is made by reacting in the presence of an accelerating catalyst such as sulfuric acid or ultraviolet rays.

Hereinafter, the preparation process of the compound of the general formula I will be described in more detail according to the following examples.

[Base product preparation example 1]

Preparation of Sodium N, N-Dimethylthio Carbamate: 2.0 g (0.05 mole) of sodium hydroxide was dissolved in 60 ml of water and the solution was cooled to 5 ° C., followed by 5.6 g (0.05 mole) of 40% aqueous dimethylamine solution. And stirred.

Then 1.41 iter (0.06 mole) and other carbonyl sulfide gas is blown stepwise into the solution for about 50 minutes. Thereafter, the temperature of the reaction mixture is raised to room temperature, and the reaction mixture is stirred for about 30 minutes to produce sodium -N, N-dimethylolcarbamate.

Example 1

Preparation of S-3- (3'-Methylphenoxy) propyl-N, N-dimethylthiol carbamate:

Prepared as base product manufacturing example 1

To sodium N, N-dimethylthiolcarmabate, 50 ml of a dimethylformamide solution in which 9.2 g (0.05 mole) of 3- (3'-methylphenoxy) propyl chloride is dissolved are added, and the mixture is 70 to 80 ° C. Stir for about 5 hours.

을 갖는 엷은 황색의 투명액체를 생산한다.After the reaction is completed, the reaction mixture is poured into water, the resulting oily substance is extracted as benzene, and the resulting benzene layer is collected, washed with water and dried over anhydrous sodium sulfate. The residue produced by concentrating the benzene solution was distilled off under reduced pressure to give 9.7 g (76.3% yield) of 138-139 ° C./0.02 mmHg boiling point and 1.5452.

Produces pale yellow transparent liquid with.

Example 2

Preparation of S-3- (phenoxy) propyl-N, N-dimethylthiolcarbamate:

을 갖는 10.1g(84.2%의 수율)의 황색투명한 액체를 얻었다.The procedure was the same as in Example 1 except that 10.8 g (0.05 mole) of 3- (phenoxy) propyl bromide was used instead of 3- (3'-methylphenoxy) propyl bromide at 130-133 ° C / 0.02 boiling point of mmHg and of 1.5515

10.1 g (84.2% yield) of a yellow transparent liquid was obtained.

Example 3

Preparation of S-3- (phenoxy) propyl-N, N-diethylthiolcarbamate:

를 갖는 오렌지 빛 점성액체 10.9g(81.3%의 수율)을 얻었다.Sodium-N, N-diethylthiolcarbamate was prepared in the same manner as in Preparation Example 1, except that 3.7 g (0.05 mole) of diethylamine was used instead of dimethylamine, and 10.8 g ( 0.05 mole) of 3-phenoxypropyl bromide was reacted in the same manner as in Example 1 to give a boiling point of 142-144 ° C / 0.02 mmHg and 1.5386.

An orange viscous liquid having 10.9 g (81.3% yield) was obtained.

Example 4

Preparation of S-3- (phenylthio) propyl-N, N-dimethylthiolcarbamate:

To sodium N, N-dimethylthiol carbamate prepared in Example 1, 50 ml of dimethylformamide solution containing 9.3 g (0.05 mole) of 3- (phenylthio) propyl chloride was added thereto. The mixture was stirred at 50-60 ° C. for about 3 hours.

After the reaction, the reaction product is poured into water and the resulting oily substance is extracted with benzene. The formed benzene layer is collected, washed with water and dried over anhydrous sodium sulfate.

을 갖는 11.3g(88.0% 수율)의 엷은 황색액체를 얻었다.The benzene solution was concentrated and the residue was distilled off under reduced pressure to obtain a boiling point of 130-132 占 폚 /0.06 mmHg and 1.5872.

A pale yellow liquid of 11.3 g (88.0% yield) was obtained.

Example 5

Preparation of S-3- (phenylthio) propyl-N, N-diethylthiolcarbamate:

을 갖는 11.7g(82.4%의 수율)의 엷은 황색투명 액체를 얻었다.3.7 g (0.05 mole) of diethylamine was used instead of dimethylamine. In addition, sodium N, N-diethylthiolcarbamate was produced in the same manner as in Example 1, and the sodium N, N-diethylthiol was produced. Carbamate was used in the same process as in Example 4, with a boiling point of 133-136 ° C./0.05 mmHg and 1.5700

11.7 g (82.4% yield) of a pale yellow transparent liquid was obtained.

Example 6

Preparation of S-3- (phenylylo) propyl-N, N-di-n-propylthiolcarbamate:

을 갖는 13.3g(85.3%의 수율)의 엷은 황색 투명 액체를 얻었다.Sodium N, N-di-n-propyltitol carbamate was prepared in the same manner as in Reference Preparation Example 1 except that 5.1 g (0.05 mole) of di-n-propylamine was used instead of dimethylamine. Carbamate was used in the same process as in Example 4, and the boiling point of 148-151 ° C./0.01 mmHg and 1.5472

13.3 g (85.3% yield) of a pale yellow transparent liquid was obtained.

Example 7

Preparation of S-3- (phenylthio) propyl-N, N-di-iso-propylthiolcarbamate:

을 갖는 12.2g(78.2% 수율)의 엷은 황색 투명액체를 얻었다.Except for using 5.1 g (0.05 mole) of di-iso-propylamine in place of dimethylamine, the carbamate produced in the same process as in Preparation Example 1 of the basic product was used in the same process as in Example 4, using 132-135 ° C. Of 1.5602 with boiling point of /0.005mmHg

12.2 g (78.2% yield) of a pale yellow transparent liquid was obtained.

Basic Product Preparation Example 2:

Preparation of S-3-Chloropropyl-N, N-dimethylthiolcarbamate:

After dissolving 2.0 g (0.05 mole) of sodium hydroxide in 60 ml of water and ice-cooling the solution, 5.6 g (0.05 mole) of 40% dimethylamine aqueous solution was added to the solution, followed by stirring and 1.4liters (0.06 mole) of Carbonylsulfide gas is blown into the solution stepwise for about 50 minutes.

The temperature of the reaction product is then raised to room temperature and the reaction product is stirred for 30 minutes.

Then, 20 ml of acetone solution in which 9.4 g (0.06 mole) of 1-bromo-3-chloropropane is dissolved is added to the reaction product, and the mixture is refluxed with stirring for 7 hours.

The reaction mixture obtained is cooled and the resulting oily layer is extracted with 100 ml of benzene. The resulting benzene layer is collected, washed with water, dried over powder and filtered.

The filtrate was concentrated, and the resulting residue was distilled under reduced pressure to have a boiling point of 1.5-80 ° C./0.3 mmHg and 1.5116. 7.7 g (85.0% yield) of a colorless transparent liquid were obtained.

Example 8

Preparation of S-3- (phenylthio) propyl-N, N-dimethylthiolcarbamate:

2.2 g (0.04 mole) of potassium hydroxide was dissolved in 100 ml of ethanol, and 4.4 g (0.04 mole) of thiophenol was added to the solution.

Then, 7.3 g (0.04 mole) of S-3-chloropropyl-N, N-dimethylthiocarbamate produced in Preparation Example 2 of the basic product was added dropwise stepwise to the mixture at room temperature, and the mixture was then added. Reflux with stirring for about 3 hours.

The reaction mixture is cooled, and then the precipitated potassium chloride is filtered off, and the ethanol solution obtained as a filtrate is concentrated.

The resulting residue is extracted with 150 ml of benzene and the benzene extract is washed with water and dried over anhydrous sodium sulfate.

을갖는 9.3g(91.2%의 수율)의 엷은 황색 투명액체를 생성했다.The benzene solution was then concentrated and the resulting residue was distilled off under reduced pressure to give a boiling point of 130-132 ° C./0.006 mmHg and 1.5872.

9.3 g (91.2% yield) of pale yellow clear liquid were obtained.

Example 9

Preparation of S-3- (phenylthio) propyl-N, N-thiethylthiolcarbamate:

을 갖는 10.3g(90.8%의 수율)의 엷은 황색투명액체를 얻었다.Example 8 except that 8.4 g (0.04 mole) of S-3-chloropropyl-N, N-diethylthiolcarbamate was used instead of S-3-chloropropyl-N, N-dimethylthiolcarbamate. In the same process, the boiling point of 133-136 ℃ / 0.005mmHg and 1.5700

10.3 g (yield 90.8%) of a pale yellow transparent liquid was obtained.

Example 10

Preparation of S-3- (4'-Chlorophenoxy) propyl-N, N-dimethylthiolcarbamate:

2.0 g (0.05 mole) of sodium hydroxide is dissolved in 5 ml of water, and 40 ml of dimethylformamide solution containing 6.5 g (0.05 mole) of 4-chlorophenol is added to the solution and stirred at room temperature for 30 minutes. It was.

Then, 20 ml of dimethylform in which 9.1 g (0.05 mole) of S-3-chloropropyl-N, N-dimethylthiolcarbamate produced in Example 2 of the basic product was dissolved in the mixture prepared as described above. The amide solution was added and the resulting mixture was stirred at 70-80 ° C. for 5 hours to allow reaction.

After cooling the reaction mixture, it is poured into water and the resulting oily product is extracted with benzene. The benzene extract is washed with water and dried over anhydrous sodium sulfate.

The benzene solution was concentrated and the resulting residue was distilled off under reduced pressure to yield 10.5 g (79.6%) of pale yellow transparent liquid having 148-150 ° C./0.02 mmHg (crystal melting point of 48.5-51 ° C.).

Example 11

Preparation of S-3- (2 ', 4'-dichlorophenoxy) propyl-N, N-dimethylthiolcarbamate:

을 갖는 9.7g(63.0%의 수율)의 엷은 황색 투명 액체를 얻었다.Except for using 8.2 g (0.05 mole) of 2.4-dichlorophenol instead of 4-chlorophenol, the same process as in Example 10 was carried out, with the boiling point of 166-170 ° C./0.015 mm Hg and 1.5663

9.7 g (63.0% yield) of a pale yellow transparent liquid was obtained.

Example 12

Preparation of S-3- (4'-Methylphenoxy) propyl-N, N-dimethylthiolcarbamate:

2.8 g (0.05 mole) of potassium hydroxide was dissolved in 100 ml of ethanol, 5.4 g (0.05 mole) of 4-methylphenol was added to the solution, and the mixture was stirred at room temperature for 30 minutes.

9.1 g (0.05 mole) of S-3-chloropropyl-N, N-tomethylthiolcarbamate are then added to the mixture and the resulting mixture is stirred under reflux for 5 hours to allow reaction.

After the reaction was completed, the precipitated potassium chloride was filtered off, and the resulting ethanol solution was concentrated.

을 갖는 9.0g(69.8%의 수율)의 엷은 황색투명액체를 얻었다.The residue was extracted with benzene, the benzene extract was washed with water, dried over anhydrous sodium sulfate and concentrated. The resulting residue was distilled off under reduced pressure, having a boiling point of 141-142 ° C./0.02 mmHg and a boiling point of 1.5458.

9.0 g (69.8% yield) of a pale yellow transparent liquid was obtained.

[Production Example 3 of Basic Product]

Preparation of S-allyl-N, N-dimethylthiolcarbamate:

After 2.0 g (0.05 mole) of sodium hydroxide was dissolved in 60 ml of water and the solution was ice cooled to 5 ° C., 5.6 g (0.05 mole) of 40% dimethylamine aqueous solution was added to the solution with stirring. 1.4 liters (0.06 mole) of carbonylsulfide gas was then slowly blown into the solution for about 50 minutes.

The reaction mixture was then stirred for 30 minutes to raise to room temperature. Thereafter, a 20 ml acetone solution in which 7.8 g (0.06 mole) of allyl boramide was dissolved was added to the reaction mixture, and the obtained mixture was refluxed with stirring for 7 hours.

을 갖는 6.0g(82.0%의 수율)의 무색투명한 액체를 얻었다.After cooling, the resulting oil layer was extracted with 100 ml of benzene, and the benzene extract was washed with water, dried as sodium sulfate powder, and filtered. The filtrate was concentrated, the residue was distilled off under reduced pressure, and the boiling point of 110-112 ° C./22 mmHg and 1.507

6.0 g (82.0% yield) of colorless transparent liquid was obtained.

Example 13

Preparation of S-3- (phenylthio) propyl-N, N-dimethylthiolcarbamate:

7.3 g (0.05 mole) of S-allyl-N, N-dimethylthiolcarbamate and 5.5 g (0.05 mole) of thiophenol mixture prepared in Example 3 were stirred at 100 to 110 ° C. for about 15 hours. .

After the reaction, 150 ml of benzene was added to the reaction mixture, washed with 3% aqueous sodium hydroxide solution, and then washed with water to dry the reaction mixture with anhydrous sodium sulfate.

을 갖는 4.8g(35%의 수율)의 엷은 황색 투명액체를 얻었다.The obtained benzene solution was concentrated, and the residue was distilled off under reduced pressure to obtain a boiling point of 130 to 132 DEG C / 0.006 mmHg and 1.5872.

4.8 g (35% yield) of a pale yellow transparent liquid was obtained.

Typical examples of the compounds of the present invention prepared by the process of the present invention including the above examples are listed below.

을 갖는엷은 황색 투명액체인 S-3-(페녹시)프로필-N,N-디메틸티올카르바메이트,Compound 1; of the boiling point of 130 ~ 133 ° C / 0.02mmHg and of 1.5515

S-3- (phenoxy) propyl-N, N-dimethylthiolcarbamate, which is a pale yellow transparent liquid having

을 갖는 오렌지색 점성액체인Compound 2; Of boiling point of 142 ~ 144 ℃ / 0.02mmHg and of 1.5386

Orange viscous liquid chain

S-3- (phenoxy) propyl-N, N-diethylthiolcarbamate,

을 갖는 오렌지색 점성액체인Compound 3; 152 to 154 ° C / 0.02mmHg with boiling point of 1.5290

Orange viscous liquid chain

S-3- (phenoxy) propyl-N, N-di-n-propylthiolcarbamate,

을 갖는 오렌지색 점성액체인Compound 4; 144 ~ 146 ℃ / 0.02mmHg of boiling point and 1.5290

Orange viscous liquid chain

S-3- (phenoxy) propyl-N, N-di-iso-propylthiolcarbamate,

Compound 5: A pale yellow transparent liquid (crystalline) having a melting point of 48.5 to 51 ° C.

S-3- (4'-chlorophenoxy) propyl-N, N-dimethylthiolcarbamate,

을 갖는 무색 투명 액체인Compound 6; 140-145 ° C / 0.02mmHg with boiling point and 1.5621

Colorless transparent liquid

S-3- (2'-chlorophenoxy) propyl-N, N-dimethylthiolcarbamate,

을 갖는 엷은 적색 투명액체인Compound 7: of boiling point and 1.5741 of 153 ~ 155 ℃ / 0.02mmHg

Pale red transparent liquid with

S-3- (4'-bromophenoxy) propyl-N, N-dimethylthiolcarbamate,

을 갖는 엷은 황색 투명액체인Compound 8: of 1.5458 with boiling point of 141-142 ° C / 0.02mmHg

Light yellow transparent liquid with

S-3- (4'-methylphenoxy) propyl-N, N-dimethylthiolcarbamate,

을 갖는 엷은 황색 투명액첸인Compound 9; of 138 ~ 139 ° C / 0.02mmHg with boiling point of 1.5452

Pale yellow transparent axyne with

S-3- (3'-methylphenoxy) propyl-N, N-dimethylthiolcarbamate,

Compound 10: a colorless transparent liquid having a boiling point of 135-137 ° C./0.01 mmHg and an N ²⁰ _D of 1.5485.

S-3- (2'-methylphenoxy) propyl-N, N-dimethylthiolcarbamate,

을 갖는 엷은 적색 투명액체인Compound 11; of boiling point of 1.5155 to 157 ° C / 0.05mmHg and of 1.5332

Pale red transparent liquid with

S-3- (4'-tert-butylphenoxy) propyl-N, N-dimethylthiolcarbamate,

을 갖는 엷은 황색 투명액체인Compound 12; of 166-170 ° C./0.015 mmHg with a boiling point of 1.5663

Light yellow transparent liquid with

S-3- (2 '-, 4'-diclophenoxy) propyl-N, N-dimethylthiolcarbamate,

Compound 13; pale yellow fine needle crystal with a melting point of 99 to 100 ° C.

S-3- (4'-nitrophenoxy) propyl-N, N-dimethylthiolcarbamate,

Compound 14; 162-165 ° C / pale yellow transparent liquid with a boiling point of 0.015 mmHg

S-5- (4'-methylthiolphenoxy) propyl-N, N-dimethylthiolcarbamate,

을 갖는 황색투명 액체인Compound 15; 182-188 ° C./0.02 mmHg with boiling point of 1.6018

Yellow transparent liquid with

S-3- (1-naphthoxy) propyl-N, N-dimethylthiolcarbamate,

Compound 16: pale brown crystal with a melting point of 86 to 88 ° C.

S-3- (2-naphthoxy) propyl-N, N-dimethylthiolcarbamate,

을 갖는 황색 액체인Compound 17; 1.5539 with boiling point of 154 ° C./0.01 mmHg

Yellow liquid with

S-3- (3'-methylbenzyloxy) propyl-N, N-dimethylthiolcarbamate,

을 갖는 무색액체인Compound 18; 1.5473 with boiling point of 155 ° C./0.02 mmHg

Colorless liquid with

S-4-phenoxybutyl-N, N-dimethylthiolcarbamate,

을 갖는 무색투명 액체인Compound 19; 1.5368 with boiling point of 145 ° C / 0.05mmHg

Colorless transparent liquid

S-5- (phenoxy) pentyl-N, N-dimethylthiolcarbamate,

Compound 20: A white tetragonal crystal having a melting point of 58 to 59 ° C.

S-6- (phenoxy) hexyl-N, N-dimethylthiolcarbamate,

을 갖는 무색 투명액체인Compound 21; 142-149 ° C./0.08 mmHg of boiling point and 1.5560

Colorless transparent liquid chain

S-4- (3'-chlorophenoxy) butyl-N, N-dimethylthiolcarbamate,

Compound 22: A white crystal having a melting point of 43 to 47 ° C.

S-4- (2 ', 4'-dichlorophenoxy) butyl-N, N-dimethylthiolcarbamate,

을 갖는 무색 투명액체인Compound 23; of 175-180 ° C./0.013 mmHg with a boiling point of 1.5670

Colorless transparent liquid chain

S-4- (2 ', 4', 6'-trichlorophenoxy) butyl-N, N-dimethylthiolcarbamate,

Compound 24: A colorless tetragonal crystal having a melting point of 55 to 56 ° C.

S-4- (3'-methyl-4'-chlorophenoxy) butyl-N, N-dimethylthiolcarbamate,

을 갖는 무색 액체인Compound 25; 1.5450 / Boiling point of 0.1mmHg and 1.5450

Colorless liquid with

S-4- (3'-methylphenoxy) butyl-N, N-dimethylthiolcarbamate,

을 갖는 무색 투명액체인Compound 26; 1.5368 with boiling point of 165-166 ° C./0.005 mmHg

Colorless transparent liquid chain

을 갖는 무색투명 액체인Compound 27; 175-181 ° C./0.015 mm Hg with boiling point of 1.5339

Colorless transparent liquid

S-4- (3'-methyl-4'-isopropylphenoxy) butyl-N, N-dimethylthiolcarbamate,

을 갖는 무색투명 액체인Compound 28; 130 to 135 ° C / 0.01 mmHg with boiling point of 1.5038

Colorless transparent liquid

S-4- (3'-trifluoromethylphenoxy) butyl-N, N-dimethylthiolcarbamate,

을 갖는 엷은 황색 투명 액체인Compound 29; 130872C / 0.006mmHg, Boiling point of 1.5872

Pale yellow transparent liquid with

S-3- (phenylthio) propyl-N, N-dimethylthiolcarbamate,

을 갖는 엷은 황색 투명 액체인Compound 30; 147805 and boiling point of 150 ° C / 0.008mmHg and 1.5805

Pale yellow transparent liquid with

S-3- (4'-methylphenylthio) propyl-N, N-dimethylthiolcarbamate,

을 갖는 엷은 투명 액체인Compound 31; 151715 ~ 154 ° C / 0.007mmHg with boiling point of 1.5715

Is a thin transparent liquid

S-3- (2'-isopropylphenylthio) propyl-N, N-dimethylthiolcarbamate,

을 갖는 엷은 황색 투명 액체인Compound 32; of 160936 and boiling point of 160 ~ 163 ° C / 0.007mmHg

Pale yellow transparent liquid with

S-3- (4'-chlorophenylthio) propyl-N, N-dimethylthiolcarbamate,

을 갖는 엷은 황색투명 액체인Compound 33; 133700 ~ 136 ° C / 0.005mmHg Boiling point and 1.5700

It is a pale yellow transparent liquid

S-3- (phenylthio) propyl-N, N-dimethylthiolcarbamate,

을 갖는 엷은 투명 액체인Compound 34: 148-151 ° C./0.01 mmHg with boiling point of 1.5472

Is a thin transparent liquid

S-3- (phenylthio) propyl-N, N-di-iso-propylthiolcarbamate,

을 갖는 엷은 투명 액체인Compound 35; 132-135 ℃ / 0.005mmHg, Boiling point and 1.5602

Is a thin transparent liquid

S-3- (phenylthio) propyl-N, N-di-n-propylthiolcarbamate,

을 갖는 황색투명 액체인Compound 36; 151 to 152 ° C / 0.02mmHg with boiling point of 1.5761

Yellow transparent liquid with

S-4- (phenylthio) butyl-N, N-dimethylthiolcarbamate,

을 갖는 무색투명 액체인Compound 37; 162-163 ° C./0.01 mmHg of boiling point and 1.5731

Colorless transparent liquid

S-5- (phenylthio) phenyl-N, N-dimethylthiolcarbamate,

을 갖는 무색투명 액체인Compound 38; 162-165 ℃ / 0.05mmHg of boiling point and 1.5652

Colorless transparent liquid

S-6- (phenylthio) hexyl-N, N-dimethylthiolcarbamate,

을 갖는 황색점성 액체인Compound 39; of 1.6145 with boiling point of 193 ~ 194 ° C / 0.008mmHg

Yellow viscous liquid with

S-4- (4'-thiomethylphenylthio) butyl-N, N-dimethylthiolcarbamate,

Compound 40: Yellow fine acicular crystal with melting point of 68-69 ° C.

S-4- (4'-nitrophenylthio) butyl-N, N-dimethylthiolcarbamate,

을 갖는 엷은 황색투명 액체인Compound 41; of 1.5735 with boiling point of 139.5 ° C./0.01 mmHg

It is a pale yellow transparent liquid

S-3- (benzylthio) propyl-N, N-dimethylthiolcarbamate,

을 갖는 황색투명 액체인Compound 42; Boiling point of 160 ~ 165 ° C / 0.01mmHg and 1.5490

Yellow transparent liquid with

S-4- (3'-methoxyphenoxy) butyl-N, N-dimethylthiolcarbamate,

When such a compound is used as a herbicide, a bactericide, a skin moisturizer, an emulsifier, a fine powder, a granule, a fine granule, an emulsion, a solution, or a hygroscopic powder, such a compound alone or preferably, Examples include talc, kaolin, clay, diatomaceous earth, silicon dioxide, mica, chalk, alcohols, ketones, cyclohexane, dimethylformamide, DMSO, toluene, xylene, petroleum solvents, polyoxyethylene, alkylaryl ethers, polyoxyethylene sorbbi It is prepared with adjuvants such as extenders, solvents, moisture absorbents, emulsifiers, penetrants, and dispersants such as tan monolaurate, alkylaryl sulfonate, lignin sulfonate, polyvinyl alcohol, and methyl cellulose.

The preparations or modifiers of the herbicides, fungicides or skin husks thus prepared are used for weeds, mites or mites as follows.

That is, when the drug is a solution, a solution containing 1-2000p.p.m of active ingredient is used in an amount of 10-500liters per 10 acres.

When the agent is an atomizer, use 0.5-5 kg per 10 acres of a spray containing 0.1-10% active ingredient. In addition, when a pharmaceutical agent is a granule, the same amount as the atomizer is used for the surface of the soil or the soil.

And the drug containing the compound of this invention is demonstrated in detail according to the biological experiment.

Pharmaceutical Example 1 Emulsion:

50 parts by weight of compound 1, 35 parts by weight of xylene, 12 parts by weight of polyoxyethylene alkylaryl aryl ether, and 3 parts by weight of calcium alkylbenzene sulfonate were uniformly mixed to prepare an emulsion of compound 1.

At the time of use, emulsion was diluted with water and sprayed.

Pharmaceutical Example 2: Hygroscopic Powder

20 parts by weight of compound 2, 35 parts by weight of diatomaceous earth, 5 parts of silicon dioxide, and 5 parts of sodium lignin sulfonate were uniformly mixed and ground to prepare a hygroscopic powder of compound 2.

At the time of use, the hygroscopic powder was diluted with water and sprayed.

Pharmaceutical Example 3: Defoamer:

3 parts by weight of compound 3, 47 parts of talc, 47 parts of clay, and 3 parts of silicon dioxide were uniformly mixed to prepare an atomizing agent containing compound 3. When used, used directly.

Pharmaceutical Example 4: Granules:

5 parts by weight of compound 4, 15 parts of bentonite, 47.5 parts of talc, 30 parts of clay, 2 parts of sodium lignin sulfonate and 0.5 parts of sodium dodecylbenzene sulfonate were uniformly mixed and pulverized, 25 parts of water were mixed and extruded. The mixture was granulated by granulator and dried to sieve the granules to produce granules containing compound 4. When used directly used.

[Experiment 1] Experiment on dissociated rice and paddyweed

Fill a 30 cm-diameter earthenware bowl with soil containing evenly the roots of the Slanders Speaker rush (Elcocharis Ashcuraris) and Skillus Jancoides, and then bowl the seeds of the houseyard and the seeds of Monocolia baginalis. 50 seeds were planted each.

Then, two kinds of rice (rice varieties; Geumnam wind) of two seasons were divided into five bowls per bowl, and each bowl was filled with a depth of 3 cm.

Then, when the weed of the house garden became one leaf, the predetermined amount of the oil agent manufactured by the process of the said chemical agent 1 was sprayed uniformly on the water surface.

After 14 days of tanning, the toxicity of the weeds and the plants was measured. The results are shown in Table 1.

TABLE 1

[Experiment 2] Rice Destruction Effectiveness Test

A biscuit-like bowl having 20 kinds of rice seedlings (rice varieties; Aiki Asahi) was transferred to a tentable, and the moisture absorbent powder prepared by the step in the above-mentioned medicine 2 was diluted with water and sprayed. The amount of 30 ml per bowl was sprayed by the sprayer of 0.5 kg / cm <^2> of pressure. After 3 days of using the hygroscopic powder solution, the rice destruction spores continuously corroded in the greenhouse, spore suspension having 20 rice destructions per spore viewed under a microscope (15 × 10) were sprayed with 5 ml of water per bowl. Corroded by

The vessel was then placed in a corrosion chamber for 24 hours at saturation humidity, 24 [deg.] C., and then transferred to a greenhouse to keep the vessel at high temperature to raise the damage of rice destruction spots. After 7 days of spore suspension corrosion, the number of pests was examined for about 10 leaves per bowl, from which the control values were calculated and the results are shown in Table 2.

In addition,% pest control is as follows.

Where (A) is the number of rice that has not been treated by rice destruction,

(B) is the number of rice that has become a pest of rice destruction.

TABLE 2

Experiment 3 Test of Salinity Effect on Citrus Red Mite

Two 15-year-old biscuit-shaped bowls were inoculated with two adult summer tangerines per bowl, inoculated with female adults of citrus red mites and placed in a greenhouse to lay 50-100 eggs per bowl. Adults were then removed and the emulsifier prepared in medicament 1 was diluted to any concentration and sprayed with 30 ml per bowl. Ten days after the emulsifier was used, the mortality was examined and the results are shown in Table 3.

TABLE 3

[Experiment 4] Experiment on citrus red mites resistant to organophosphorus compounds.

After inoculating adults with citrus red mite, which is about 10 times more resistant to organophosphorus compounds, inoculated into a summer citrus (Chinese citron) grown in a 15 cm diameter bowl in a greenhouse, 100 ticks per bowl When prepared, the emulsion prepared in the above-mentioned medicine 1 was diluted to a concentration of 500 p.pm and sprayed at 30 ml per bowl.

The number of living ticks was then counted over time, and the results are shown in Table 4.

TABLE 4

(I): Number of ticks before use.

(II): Number of ticks 4 days after use.

(III): number of ticks after 8 days of use.

(IV): Number of ticks after 16 days of use.

(V): Number of ticks after 32 days of use.

(VI): Number of ticks 64 days after use.

Inhibition 1: The emulsion which does not contain the active ingredient of this invention is used.

Suppression 2: No Treatment.

Claims (1)

Preparation of thiol carbamate derivative of general formula (III) characterized by reacting a thiol carbamate salt represented by the following general formula (I) and a halide represented by the following general formula (II) in an inert solvent Way.

In formulas (I), (II) and (III), R is a lower alkyl group; R 'is an expression

Group represented by (Y is a halogen atom, an alkyl group, an alkoxy group, a nitro group, a methylthio group, a trifluoromethyl group, n is an integer of 0-3), a benzyl group, a methyl benzyl group, a naphthyl group; M is an alkali metal or quaternary amine; X is an oxygen atom or a sulfur atom; Z is a halogen atom and m is an integer of 3-6.)