JPS6067463A - Production of thiocarbamate derivative - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as a herbicide in high purity and yield, by reacting an alkylphenyl chlorothioformate with an aminopyridine derivative in the presence of a dehydrohalogenating reagent in a mixture of hexane with water as a solvent. CONSTITUTION:An alkylphenyl chlorothioformate of formula I (R1 is 2-5C alkyl) e.g. 3-tert-butylphenyl chlorothioformate, is reacted with an aminopyridine derivative of formula II (R2 is H, halogen, lower alkyl or lower alkoxy), e.g. 2- methyl-6-methylaminopyridine, in the presence of a dehydrohalogenating reagent, e.g. sodium carbonate or pyridine, in a mixed solvent of hexane and water (preferably 10-90% based on the hexane, water) to give the aimed thiocarbamate derivative of formula III, e.g. O-3-tert-butylphenyl-N-methyl-N-(6-methyl-2- pyridyl)thiocarbamate.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing thiocarbamate derivatives. More specifically, a thiocarbamate derivative is prepared by reacting an alkylphenylchlorothioformate with an aminopyridine (f34 form) in the presence of a dehydrohalogenating agent in a hexane-water mixed medium I'8. Regarding manufacturing methods.

The thiocarbamate derivative obtained by the production method of the present invention is a new compound that has not been described in any literature, and the usefulness of this compound and the production method have already been proposed in Kame Sho 57-156710.

A herbicide containing the compound of the present invention as an active ingredient exhibits extremely excellent herbicidal activity against many weeds including field weeds, and is suitable as a herbicide for paddy fields. It also has applicability as a herbicide for upland fields.

In addition, as a production method, we proposed a method in which an alkylphenylchlorothiopormate and an aminopyridine derivative are reacted in an organic bath medium in the presence of a dehydrohalogenation reagent.

The present inventors have further found that the compound of the present invention is industrially advantageous.
As a result of extensive tests and intensive studies on the method of dehydrogenation, we found that a high He discovered that it was possible to produce 94 thiocarbamates of high purity and developed this method.

That is, the present invention relates to alkylphenylchlorothiopolmates represented by general formula CI) 1-0) and general formula (II) (wherein R2 represents a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group, ) is reacted with a hexane-water mixture @ in a φ medium in the presence of a dehydrohalogenating agent (in the formula, R, , R2 are The present invention provides a method for producing a thiocarbamate derivative represented by the same formula.

Next, the method of implementing the present invention will be explained in more detail.

Add the aminobi+1 zine derivative* and the dehydrohalogenation reagent to the hexane-water mixed solvent. Then, alkylphenylchlorothioformate is added dropwise. Total amount of alkylphenylchlorothiopormate? After lowering ff1z, reaction'
Fi is heated to complete the reaction. After the reaction is completed, the mixture is allowed to stand still while hot and the hexane layer is separated.

The hexane layer is cooled and the thiocarbamate derivative precipitates out and is collected by filtration.

The aminopyridine derivative is equimolar to the alkylphenylchlorothiopormate, and the dehydrohalogenation reagent is approximately
Use a mole or more.

As the dehydrohalogenation test M11, alkali carbonates such as IJ carbonate and 11 um carbonate, and organic bases such as triethylamine, di2methylaniline, and pyridine can be used.

The amount of water in the hexane-water mixed solvent used in the reaction is 10 to 90 times the amount of hexane, and each mixing section uses 2 to 20 times the weight of the aminopyridine group conductor.

Although the reaction proceeds at room temperature, it is usually carried out at the boiling point of hexane and can be completed within 20 hours.

In this way, the target thiocarbamate derivative of this production method can be obtained with high purity and high yield.Next, the present invention will be explained in detail with reference to raw material preparation examples and examples. It is not limited to examples only.

Raw material preparation example 1 (3-tert-butylphenylchlorothioformate) 3-tert-butylphenol 64! i and 50 g of thiophosgene in chloroform 60' Omlt.
20 inches of sodium diluted water while maintaining the temperature at 0'C.
After adding 00 ml and stirring for 13 hours, the chloroform layer was separated, dried over calcium chloride, and distilled to a boiling point of 123-1.
3-tert-butylphenylchlorothioformate at 24 °C/4 mu Hll 71 g f <! f
,=.

Original cumulative analysis (as Co H+5CIJ OS) CHC
l'S Actual measurement 57.69 5.64 15.62 1
3.96 calculations (%) (57,76) (5,73)
(15,50) (14J12) Raw material preparation example 2 (4-tert-butylphenylchlorothioformy
g) Using the same method as in Raw Material Preparation Example 1, the boiling point was 103°C.
I, j9 (7) 4-tert-butylphenylchlorothioformate was obtained.

Raw material preparation example 3 (2-chloro-6-methylaminopyridine) 2.6-dichloropyridine 2J9 and 40% methylamino water bath W 6
0 ml was kept at 120°C in an autoclave and stirred for 5 hours. After the reaction was completed, the contents were taken out and the solids were collected by filtration. This solid was then recrystallized from n-hexane to obtain 2-chloro-6-methylaminopyridine 22.7 & having a melting point of 63.5-64.5°C.

Elemental analysis 11111 (as C6l-I7Cd N2) CHN CA Actual measurement (%) 50.41 4.99 19.73 2
4.87' calculation once (%) (50,54) (4,9
5) (19,64) (24,86) Raw materials rJ￥Y Example 4 (2-methoxy-6-methylaminopyridine) 2-chloro-6-methylaminopyridine 20g 1 water saponification sodium 11
1.5 g of WAM and 80 ml of methanol were kept at 170°C in an autoclave and stirred for 5 hours. After the reaction, the methanol was distilled off, and the ether extract of the remaining IL', L was dried with magnene WAM, L'l: 2. L-chill was distilled off. The residue was distilled under reduced pressure to give a boiling point of 118~b pyridine 15.6,! I got i+.

Elemental analysis If (C?HI.Nto) CI4
NO Actual side directness ('%) 60.75 7.22 20. :U5
11.68 calculation 1st shift (ch) (60,85) (7
, 30) (20, 27) (11, 58) Example j: (00 ml third flask!?:, 2-methyl-6
-Methylaminobi 1) gin 6.1g, sodium carbonate 5
．． Take 6 g, 1 xane, 25 ml % water, and stir at room temperature with a magnetic stirrer: (-
tert-butylphenylchlorothioformate 11.
4E was added dropwise over 20 minutes.

After the dropwise addition, the mixture was heated under reflux for 6 hours to complete the reaction.

When heated, separate the hexane layer and cool it to a melting point of 116-117.
．． Q -3-tert-butylphenyl''〈-methyl-N-(6-methyl-2-pyridyl)thiocarbamate (compound No. 1) at 5°C 14.2 Ji''il-
Collected by filtration.

The purity was 9 when analyzed by chromatography.
It was 9.3φ □ Direct elemental analysis (as C+ s N22 N20”)C
f(N Actual measurement -4(%) 68.46 6.99 9.00%'
#: 1st shift (ch) (68,75) (7,05) (
8,91) Examples 2 to 9 Into the same reaction apparatus as in Example 1, the aminobi-11-dine derivative, the dehydrohalokenation reagent, hexane, and water were taken, and alkylphenylchlorothiopolmate #K was added dropwise.11.
% conditions.

After the reaction was completed, a thiocarbamate derivative was obtained by the same reaction procedure as in Example 1. The results are shown in Table 1.

Further, the physical constants of the obtained compound are shown in Table 2.

Next, application examples of the compounds obtained by the production method of the present invention will be shown.

Application example: Weeding effect test under water-resistant conditions Paddy field soil was put into a porcelain pot with a diameter of 9 CnL, water was added, and the weed seeds were swept over the soil surface. , Japanese tit () were planted in duplicate at a depth of IC:Irt.The next day, the plants were flooded with water to a depth of 2 cm, and a hydrating agent containing 10% of each compound was diluted in 1 ml of water per pot. Dropwise treatment was carried out on the water surface. (Amount of test substance 125 & / 1
0 a) After that, Onkan C? We investigated the herbicidal effect and the influence of the water pail on 1st repair and 3rd time treatment of leftover liquid.

The evaluation was displayed on a 6-level scale, and the specific details are as follows. The results are shown in Table 3.

Displayed water No. 113h Harm weeding effect 5 Death 100% control (residual amount of weeds 0) 4 Destruction 8
0 control (residual amount 20chi) 3 Medium No 60% control is (
Residual grass 'pi 40 attacks) 2 Kosho 40 chi control (residual grass amount
60) Indication Paddy rice chemical damage Weeding effect 1 Very small section 20 control (Residual weeds section 80) 0 Harmless
(Residual weed amount 1 (Part 10) Schedule 3 Procedural Amendments March 9, 1982! Samurai 671 Office Secretariat Officer Kazuo Wakasugi 1 Incident Display 1982 Patent Application No. 176406 2 Invention Name: Method for producing thiocarbamate derivatives 6 Person who corrects sleeves 4 Amendment order Daily 6 Subject of amendment [Column for detailed explanation of the invention that is harmful to Mei 111] 7 Contents of amendment (1) Mei M, page 5, line 8 Correct "equivalent mole" to "equivalent amount".

Claims (1)

[Claims] (1) Alkylphenyl chlorothioformate represented by general formula (I) (in which R7 represents an alkyl group having 2 to 5 carbon atoms) and general formula (II) (in which R2 is a hydrogen atom or a halogen atom) , lower alkyl group and lower alkoxy group) are reacted in a hexane-water mixed hot medium in the presence of a dehydrohalogenation reagent. ) (wherein R1 and R2 are the same as before).