JPH0710829B2 - Method for producing benzyl mercaptan derivative - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel process for producing a benzylmercaptan derivative. INDUSTRIAL APPLICABILITY The benzyl mercaptan derivative of the present invention is useful as an intermediate of active ingredient compounds of agricultural chemicals, especially insecticides, acaricides, nematicides and fungicides.

(Prior Art) As a method for producing a benzyl mercaptan derivative, U.S. Pat.No. 2,456,588 describes a method of obtaining benzyl mercaptan by reacting benzyl chloride and sodium hydrosulfide with water as a solvent. ing. However, the inventors of the present invention conducted additional tests on this method and found that the yield was about 30%.

On the other hand, in this method, it is described that the addition of hydroquinone, potassium cyanide, bis (2-chloroethyl) ether, glycerol, etc. has the effect of improving the yield. In addition, when the above substances were added, it was found that the yield was rather reduced as compared with the case where the above substances were not added.

[Problems to be solved by the invention]

There is a demand for an industrially advantageous method for producing a benzyl mercaptan derivative, and in particular, a method for obtaining it in a high yield.

[Means for solving problems]

The present invention relates to a novel method for producing a benzylmercaptan derivative, and more specifically, the present invention relates to the following formula (I): In the method for producing a benzyl mercaptan derivative represented by the following formula (II): A method for producing a benzyl mercaptan derivative, which comprises reacting a benzyl halide derivative represented by and an alkali hydrosulfide in a mixed solvent of water and a water-insoluble organic solvent in the presence of a phase transfer catalyst ( Hereinafter referred to as Method A) and a benzyl halide derivative represented by the above formula (II),
A method for producing a benzyl mercaptan derivative characterized by reacting with alkali hydrosulfide in a water-soluble organic solvent (hereinafter referred to as method B), and addition of a specific acid catalyst during method A or method B And a method for producing a benzyl mercaptan derivative.

[In the above formula, Z represents a halogen atom, R represents a hydrogen atom or a lower alkyl group, X represents a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkyl group having 1 to 6 carbon atoms. An alkoxy group having 3 to 6 carbon atoms, an alkenyloxy group having 3 to 6 carbon atoms, a lower haloalkyl group, a cycloalkyl group having 3 to 6 carbon atoms, a halogen atom, (However, Y represents a halogen atom, a lower alkyl group or a lower haloalkyl group, m represents an integer of 0 or 1 to 3, and when m is 2 or 3, Y may be the same or different from each other.) Trimethylsilyl group, n
Represents an integer of 1 to 3. When n is 2 or 3, X may be the same or different from each other. ].

According to the method of the present invention, the yield of the target benzyl mercaptan derivative is at least 70% or more, and in some cases,
It can be performed with a high yield of 90% or more. Next, the methods A and B of the present invention will be specifically described.

Method A The method A found by the present inventors is shown as a reaction formula as follows.

[In the reaction formula, Z, R, X, and n have the same meanings as described above. In the above reaction formula, as the sodium hydrosulfide, any of commercially available solid hydrates or aqueous solutions can be similarly used.

As the non-water-soluble organic solvent, aromatic hydrocarbons represented by benzene, toluene, xylene, etc., aliphatic hydrocarbons represented by pentane, hexane, heptane, ethyl formate, methyl acetate, ethyl acetate, etc. Examples thereof include esters such as esters, carbon tetrachloride, 1,2-dichloroethane, halogenated hydrocarbons such as methyl chloroform, and ethers such as diethyl ether, tetrahydrofuran, and diisopropyl ether. Among these, aromatic hydrocarbons, esters and halogenated hydrocarbons are particularly preferable.

As the phase transfer catalyst, a quaternary ammonium salt represented by tetra-n-butylammonium bromide, tetra-n-butylammonium hydrogensulfate, triethylbenzylammonium chloride, tetra-n-butylammonium hydroxide, tetra, etc. Examples include phosphonium salts represented by -n-butylphosphonium bromide. Among these, particularly preferred are tetra-n-butylammonium bromide, tetra-n-butylammonium hydrogensulfide and the like. The amount added is 0.1 mol% or more, preferably 0.5 to 10 mol%, based on the raw material benzyl halide derivative.
It is practical to set to.

The reaction temperature can be around 0 ° C to 150 ° C, but especially 1
Around 0 ° C to 100 ° C is preferable.

Further, in order to improve the yield, it is preferable to add an acid catalyst in the above production method. Examples of the acid catalyst include fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid and tartaric acid, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and boric acid, methanesulfonic acid and benzenesulfone. Acid, P-
Examples thereof include sulfonic acids typified by toluenesulfonic acid, inorganic salts typified by ammonium sulfate, ammonium hydrogen sulfate, ammonium nitrate, and the like, and aliphatics and inorganic acids are particularly excellent. The addition amount is preferably 1 mol% or more, and particularly 5 to 50 mol% is practical for the starting benzyl halide derivative.

Method B The method B found by the present inventors is shown below by a reaction formula.

[In the reaction formula, Z, R, X, and n have the same meanings as described above. In the above reaction formula, sodium hydrosulfide can be used in the same manner as any of commercially available solid hydrates and aqueous solutions, but it is preferable to use an aqueous solution.

Examples of the water-soluble solvent include lower alcohols represented by methanol, ethanol, propanol, etc., ketones represented by acetone, methyl ethyl ketone, diisobutyl ketone, etc., nitriles represented by acetonitrile, propionitrile, etc., N, N -Amids such as dimethylformamide and N, N-dimethylacetamide, and oxides such as dimethyl sulfoxide and oxirane. Among these, alcohols, ketones,
All of the nitriles are excellent solvents.

Since this method B is a homogeneous reaction, the reaction proceeds rapidly, and the reaction temperature sufficiently proceeds even at room temperature. Practically 0 ℃ ~
Around 100 ° C is preferable.

In method B as well, as in method A, the yield is improved by adding an acid catalyst. The type of acid catalyst that can be used is the same as in Method A.

The method of the present invention has an advantage that the target substance can be obtained with a high yield and an easy operation as compared with the conventional method.

Next, the method of the present invention will be described with reference to specific examples.

However, the present invention is not limited to these examples.

Example 1 Preparation of 4-tert-butyl benzyl mercaptan Paratertiary butyl benzyl chloride (hereinafter abbreviated as TBC) 18.3 g (0.1 mol), toluene 100 g, tetrabutyl animonium bromide 0.5 g, in a 300 ml four-neck reaction flask. Charge 1.8 g (0.03 mol) of acetic acid, warm to 50 ° C, and then, with stirring, add 31.7 g (0.1%) of a 23% aqueous sodium hydrosulfide solution with stirring.
3 mol) was added dropwise in 30 minutes.

Stirring was continued for another 30 minutes at 50 ° C. to complete the reaction.

After cooling and returning to room temperature, liquid separation was performed, and the toluene layer was washed with water,
By concentrating, 18.0 g (purity 93%) of pale yellow liquid of the target 4-tert-butylbenzyl mercaptan (abbreviated as TBSH hereinafter) was obtained with a yield of 92%.

In addition, by distilling the crude TBSH obtained by the scale-up of this example, a high purity (purity of 90 to 92 ° C / 4 mmHg (purity
99%) TBSH was obtained.

Example 2 Preparation of 4-tert-butyl benzyl mercaptan A 300 ml four-neck reaction flask was charged with 18.3 g (0.1 mol) of TBC, 100 g of toluene, and 0.5 g of tetrabutylanimium bromide, heated to 50 ° C., and then stirred. To the above, 31.7 g (0.13 mol) of 23% sodium hydrosulfide aqueous solution was added dropwise over 30 minutes. 30 more
The stirring was continued at 50 ° C. for 50 minutes to complete the reaction.

After cooling and returning to room temperature, the layers were separated, and the obtained toluene layer was washed with water and quantified by an internal standard analysis method of gas chromatography. As a result, the yield of the target TBSH was 71%.

Examples 3 to 14 Except for changing the conditions such as the acid catalyst, the phase transfer catalyst and the reaction time in Example 1, the same operation was performed. First result
Shown in the table.

In Table 1, TBC 18.3g (0.1mol), 23% sodium hydrosulfide aqueous solution 31.7g (0.13mol), toluene 100g, reaction temperature 50 ° C
The reaction conditions were as follows.

The yield (%) of TBSH was calculated by quantitative analysis by gas chromatography.

Examples 15 to 24 In Example 1, the solvent, the phase transfer catalyst, the acid catalyst, the temperature,
Except for changing the time etc., the same operation was performed. The results are shown in Table 2.

In Table 2, the reaction conditions are TBC 18.3 g (0.1 mol), 23
% Sodium hydrosulfide aqueous solution 31.7 g, solvent 100 g each.

The yield (%) of TBSH was calculated by quantitative analysis by gas chromatography.

Examples 25 to 34 The same operation as in Example 1 was carried out except that the raw material benzyl halide derivative was replaced. The results are shown in Table 3.

In Table 3, the reaction conditions are: raw material (0.1 mol), 23% sodium hydrosulfide 31.7g, toluene 100g reaction temperature 50 ° C, reaction time 1h
I went with r.

The analysis of the products was performed by the quantitative analysis method of liquid chromatography, and the yield (%) of each product was calculated.

Comparative Example 1 (additional test described in US Pat. No. 2,456,588) A 200 ml four-neck reaction flask was charged with 44.1 g of benzyl chloride, 50 g of hydrous sodium hydrosulfide (NaSH purity about 70%), and 40 g of water and refluxed for 8 hours. After the reaction was completed, it was cooled and extracted with toluene. The toluene solution was washed with water and then quantified by gas chromatography. As a result, the target benzyl mercaptan yield was 31%.

Comparative Examples 2 to 5 The procedure of Example 1 was repeated, except that the acetic acid was replaced by the additive described in US Pat. No. 2,456,588. The results are shown in Table 4.

As is clear from the results in Table 4, as compared with the production method of the present invention (Example 2; yield 71%) in which the above additives are not added at all,
In each case, the yield is low.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C07C 323/16 323/22 // C07B 61/00 300

Claims (4)

[Claims] 1. The following formula (I): In the method for producing a benzyl mercaptan derivative represented by the following formula (II): A method for producing a benzyl mercaptan derivative, which comprises reacting the benzyl halide derivative represented by and an alkali hydrosulfide in a mixed solvent of water and a water-insoluble organic solvent in the presence of a phase transfer catalyst. [In the above formula, Z represents a halogen atom, R represents a hydrogen atom or a lower alkyl group, X represents a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkyl group having 1 to 6 carbon atoms. An alkoxy group having 3 to 6 carbon atoms, an alkenyloxy group having 3 to 6 carbon atoms, a lower haloalkyl group, a cycloalkyl group having 3 to 6 carbon atoms, a halogen atom, (However, Y represents a halogen atom, a lower alkyl group or a lower haloalkyl group, m represents an integer of 0 or 1 to 3, and when m is 2 or 3, Y may be the same or different from each other.) Trimethylsilyl group, n
Represents an integer of 1 to 3. When n is 2 or 3, X may be the same or different from each other. ]. 2. The following formula (I): In the method for producing a benzyl mercaptan derivative represented by the following formula (II): A method for producing a benzylmercapto derivative, which comprises reacting the benzyl halide derivative represented by and an alkali hydrosulfide in a water-soluble organic solvent. [In the above formula, Z represents a halogen atom, R represents a hydrogen atom or a lower alkyl group, X represents a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkyl group having 1 to 6 carbon atoms. An alkoxy group having 3 to 6 carbon atoms, an alkenyloxy group having 3 to 6 carbon atoms, a lower haloalkyl group, a cycloalkyl group having 3 to 6 carbon atoms, a halogen atom, (However, Y represents a halogen atom, a lower alkyl group or a lower haloalkyl group, m represents an integer of 0 or 1 to 3, and when m is 2 or 3, Y may be the same or different from each other.) Trimethylsilyl group, n
Represents an integer of 1 to 3. When n is 2 or 3, X may be the same or different from each other. ]. 3. The production method according to claim 1 or 2, wherein an acid catalyst is added during the reaction in the claim 1 or 2. 4. The benzyl halide derivative is paratertiary butyl benzyl halide.
The manufacturing method described in the item.