JPS6067464A - 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 ethanol as a solvent, and adding water to the reaction system. CONSTITUTION:An alkylphenyl chlorothioformate of formula I (R1 is 2-5C alkyl), e.g. 4-tert-butylphenyl chlorothioformate, is reacted with an aminopyridine derivative of formula II (R2 is H, halogen, lower alkyl or lower alkoxy), e.g. 2-methoxy-6-methylaminopyridine, in the presence of a dehydrohalogenating reagent, e.g. sodium carbonate or pyridine, in ethanol (which may contain water). Water in an amount to give about 30-60% concentration in the aqueous ethanol solution is added to the reaction system to afford the aimed thiocarbamate derivative of formula III, e.g. O-4-tert-butylphenyl-N-methyl-N-(6-methoxy-2-pyridyl) thiocarbamate.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing thiocarbamate derivatives. More specifically, the present invention relates to a novel method for producing thiocarbamate derivatives, which comprises reacting an alkylphenylchlorothioformate and an aminopyridine salt conductor in ethanol in the presence of a dehydrohalogenating agent. Although the thiocarbamate derivative obtained by this production method is a new compound that has not been described in any literature, the present inventors have disclosed the usefulness of this compound and the production method in Japanese Patent Application No. 57-156.
I have already proposed one in 7i0.

The weed killer containing the compound of the present invention as an active ingredient exhibits 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 further conducted various tests and intensively reviewed methods for industrially advantageously obtaining the compounds of the present invention, and as a result, alkylphenylchlorothiopormate and aminopyridine CJ
It has been shown that high purity thiocarbamate derivative 47 can be produced without purification by operations such as column chromatography and recrystallization by reacting the 4-isomer in ethanol in the presence of a dehydrohalogenation reagent and then adding water. Heading Completing the Invention.

That is, the non-invention is an alkylphenylchlorothiopolmate represented by the general formula (11) (in which R1 represents an alkyl group having 5 to 5 carbon atoms) and an alkyl phenylchlorothiopolmate represented by the general formula (11) (wherein L2 is a hydrogen atom, a halogen atom, a (representing a pure alkyl group or a lower alkoxy group. E
``1'L1'L method.

Add to ethanol (which may contain water).

Then, alkylphenylchlorothiopormate is added dropwise. Total amount of alkylphenylchlorothiopormate 71
After heating, a predetermined amount of water is added, and the reaction product, the thiocarbamate derivative, is precipitated. In addition, alkylphenylchlorothiopormate and aminopyridine m
Hydrogen chloride produced by the reaction with the 4-mer reacts with the dehydrohalogenation reagent to precipitate a salt (hereinafter referred to as J-Yuichijaku).

After the reaction is complete, the reaction mixture is filtered to collect the thiocarbamate derivative and salt. Next, the collected thiocarbamate derivative and salt are washed with water to remove the salt and obtain a still pure thiocarbamate derivative.

The aminopyridine derivative is used in a molar equivalent to the alkylphenylchlorothiopormate, and the dehydrohalogenation reagent is used in an equivalent or more amount.

Examples of the dehalogenated water test MIJ include alkali carbonates such as sodium 11ium carbonate and potassium carbonate, and organic bases such as triethylamine, dimethylaniline and pyridine.

Ethanol used as a vehicle may contain up to 50% water, and is used in a weight range 5 to 30 times the weight of the aminopyridine i)'i'A form.

The amount of water added after the reaction is closely related to the concentration of water in the ethanol used in the reaction, but if the concentration of water in the ethanol water bath after addition is less than 30%, high purity thiocarbamate is produced. The derivative has a low 1 ml anti-strain, and if it exceeds 60 cm, the purity of the thiocarbame-Fn font will decrease, so it is preferable to use an amount that makes the amount of 1 ml in the ethanol water bath solution 30 to 60%.

The reaction can be completed within 10 hours at room temperature.

In this way, the target thiocarbamate derivative of the present 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, but the present invention is not limited only to these examples.

Raw material preparation example 1 (3-tert-butylphenylchlorothiopolmate) 64.9 g of 3-tert-butylphenol and 50 g of thiophosgene were heated at 5 to 10°C in 600 ml of 1 coform.
While keeping the
0 I11/! After adding and stirring for 13 hours, the chloroform layer was dried with preparative calcium chloride and then distilled to give 123 points.
~124℃ 74mmHg 3-ter
t-Pythylphenylchlorothioforme l-71g
I got it.

Original system analysis box (Cn 1 (+3CA as OS) c l
(Cl S real 6 old direct (chi) 57.69 5.64 15;62
13.96% Calculation 1st shift (person in charge) 57.76 5.73
15.50 14.02 Raw material preparation example 2 (4-tert-butylphenyl lylorothioformate) Boiling point 103°C/8 by the same method as raw material preparation example 1
rnmf(g(7) 4-tert-butylphenyl rolothioformate was obtained.

Thick phase adjustment example 3 (2-old-6-methylaminobi-11dine) 2.6-
25g dichloropyridine and 40% methylamine water bath 6
0ml was kept at 120"C in an autoclave and stirred for 5 hours. After the reaction was completed, the inner tube was taken out and the solid was (
Collected by passing 1 clause. This solid was then recrystallized from 11-hexadiene to obtain 22.7 g'i of 2-chloro-6-methylaminobi-11dine with a melting point of 63.5-64.5°C. )CHN C6 Actual measurement 50.41 4.99 19.73 z
4.87it Sancho (Article) 50. fi4 4.95 1
9.64 24. Above 36 Raw material preparation example 4 (2-methquin-6-methylaminopyridine) 2-chloro-6-methylaminopyridine 20,! /, sodium hydroxide 11.5 g, methanol 8 Fl me f
The mixture was kept at 170°C in an autoclave and stirred for 5 hours. After the completion of 16 incubations, methanol was distilled off, and the ether extract of the residue was dried over magnenwam sulfate, and then the needles were distilled off. The residue was distilled under reduced pressure to a boiling point of 88-92℃/5 mmH/
/2-methoxy-6-methylaminopyridine i 5.
6g was obtained.

Elemental analysis 111', (, C7f (as +oNzO)
CHN O real d old (po (person in charge) 60.75 7.22 20.35
11f) 8 calculations (straight) 60.85 7.30
20.27 11.58 Example 1 300 m1! 2-methoxy-6-
Methylaminopyridine 6.9g, charcoal potash 6.9g.
9. 1 (Take 90ml of 1% aqueous ethanol-resistant liquid,
At room temperature 1 trowel mug While stirring with a non-stick stirrer, 4-
tert-butylphenylchlorothioformate 11
．． Submitted 49 in 20 minutes.

After addition, the mixture was stirred for an additional 2 hours to complete the reaction.

After the reaction is complete, add 80 ml of water and remove the contents from the flask.
4"//J8 and collected the solid by filtration. The solid was then washed with 150 me of water and 04-tert-butylphenyl N-methyl-+'J with a melting point of 87-88°C
--(6-medoxy 2-pyridyl) thiocyanocoumate (compound 1) 15.59 was obtained.

When 1.1 was analyzed by fast liquid chromatography, the purity of 1.1 was 99.0.

Elemental analysis [direct (as "+ s %2 N202 s) CHN Actual measurement (% > 65.55 6. (338,55 words 1st division (ch) 6.5.43' 6.71 8.41
3 Example 2 In a third flask of 300 rnl, 6.1 g of 2-methyl-6-methylaminopyridine, charcoal, 41 sodium 11 um 5
．． Take 6g of 3()chi, 120ml of aqueous ethanol, and stir at room temperature with a magnetic stirrer.
tert-butylphenylchlorothiopolmate 11
,．． 4 g was added dropwise over 3 () minutes.

? After the temperature was lowered by 1 yen, the mixture was further stirred for 2 hours to complete the reaction.

After the reaction was completed, 60 nl of water was added, the contents were taken out from the flask, and the same operation as in Example 1 was carried out.
+1-3-tert-butylphenyl N-methyl-N-(6-methyl-2-pyridyl) at 6-117.5°C
Thiocarbamate (compound 1NQ2)] 4. Og 1
;↑.

The purity was 9 when analyzed by sieve speed chromatography.
I was in charge of 8.9.

Elemental analysis 1 [(C+ 8 ''22 N2 oS TOLTE') CHN Actual measurement 1iiiI (crack) 68.46 6.99 9.0
0 words - 1 more, H direct (%) 68.75 7.05
8.91 Implementation i3'll Take the aminobi-11dine derivative, dehydrohalogenation reagent, and aqueous ethanol into the same reaction apparatus as in 1, add alkylphenylchlorothiopolmate dropwise, and react under the conditions shown in Table 1. Ta.

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 7 Weeding effect test under water injection conditions Paddy soil was placed in a porcelain pot with a diameter of 9 cTL, water was added, and after puddling, weed seeds were sown on the soil surface layer, and paddy rice seedlings (variety, Nipponbare) at the two-leaf stage were placed in a porcelain pot with a diameter of 9 cTL. Two plants were planted at a depth of . The next day, each compound ntrx was flooded with 2 crfL of water.
A hydrating powder containing 0% was diluted in 10 ml of water per pot and dropped onto the water surface. (Amount of sample drug 125, !i'/1O
a) Thereafter, the herbicidal effect and the effect on paddy rice were investigated 3 weeks after the pox treatment was carried out in a greenhouse.

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

Indication Paddy rice chemical damage Weeding Evening 11 Death 5 Withering 100% control (remaining grass (remaining)) 4 Severe damage
-80% control (residue II: ', 20%) 3 Medium Harm 6
0φ control (Residual grass ht4o section) 2 Small book 40% control (Remaining grass hanging 6 () Chu) ■ Small book 20% control (Remaining grass FA:
80%) 0 Harmless (] Fissure control (Residual grass amount 100φ) Table 3 Procedural amendment document March 9, 1980 q '1 Agency Director Kazuo Wakasugi 1 Matter P1 indication 1988 Special r+ application No. 176407 No. 2 Name of the invention Thiocarbatter 1 - Process for producing derivatives 6 Person making the amendment Relationship to the NJN case Patent applicant 4 Date of amendment order Initiation 6 Subject of amendment [1IvJJ7 of Detailed Description of the Invention in Book III? il
! Correct contents (1) Akira 10th store, page 5, line 4 [thiocarbamate M conductor] is corrected to read ``thiocarbamate derivative''.

Claims (1)

[Claims] (1) Alkylphenylchlorothioformate represented by the general formula (1) (in the formula indicates an alkyl group having 92 to 5 carbon atoms) and the general formula (II) (in the formula, 1 and 2 are aqueous atoms, The general formula (III ) (In the formula, R1 and E are the same as above.) A method for producing a thiocarbamate derivative represented by the following.