JPS6030667B2 - Production method of dicyclohexyl disulfide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for economically producing dicyclohexyl disulfide by using chlorocyclohexane as a raw material.

Dicyclohexyl disulfide is a compound that is useful as a raw material for various additives indispensable for the production of rubber and plastics, as well as for various synthetic chemicals such as surfactants, dyes, concentrates, and pharmaceuticals. General methods for synthesizing aliphatic or aromatic disulfides include oxidizing thiols, reacting sodium disulfide with alkyl halides or allyl halides, and reacting sodium disulfide with alkyl sulfate ester salts or alkyl diazonium salts. [Organic Chemistry Handbook - Organic Synthetic Chemistry Association Shima (1979)]
.

A known method for obtaining dicyclohexyl disulfide, which is a hydrocarbon hydrocarbon, is a method in which cyclohexene and hydrogen sulfide are reacted at 15,000 ℃ in the presence of sulfur [J. Chem
．． SoC. , 1947, 1532 (1947)], a method for reacting cyclohexanol and antimony polysulfide in the presence of dioxane at 200 and 0 [Japan Chemical Journal, 72
, 372 (1951)], a method of reacting cyclohexanone and hydrogen sulfide at 900 to 100 p atm and 13,000 [J. Am. Chem. Soc. , 74, 3982 (1
952)], but all of them are under harsh conditions and have low yields. An object of the present invention is to provide an economical and industrially practical method for producing dicyclohexyl disulfide that is easy to operate, has a high yield, and is industrially practical.

As a result of intensive study by the present inventors to achieve this purpose,
The present invention has been achieved as follows.

That is, the present invention is a method for producing dicyclohexyl disulfide, which is characterized by reacting chlorocyclohexane with an alkali metal sulfide or a mixture containing the same in the presence of a solvent.

The raw material chlorocyclohexane is not particularly limited, and chlorocyclohexane synthesized by photo-salting reaction of cyclohexane is applicable.

As the other raw material, an alkali metal sulfide or a mixture containing an alkali metal sulfide is used. When using an alkali metal sulfide as a raw material, it is preferable to use an alkali metal disulfide such as sodium disulfide or potassium disulfide. These alkali metal disulfides are directly reacted with chlorocyclohexane, and the reaction proceeds, for example, as shown in the following formula.

When using a mixture containing an alkali metal sulfide as a raw material, it is preferable to use a mixture of an alkali metal monosulfide, such as sodium monosulfide or potassium monosulfide, and sulfur.

Of course, as a mixture containing an alkali metal sulfide, in addition to the alkali metal monosulfide and sulfur, alkali metal sulfur compounds such as sodium sulfate, sodium thiosulfate, and sodium sulfite may also be added, which do not harm the reaction. It is also possible to use mixtures containing small amounts of sulfur, etc., and mixtures containing alkali metal disulfides in addition to mixtures of alkali metal monosulfides and sulfur.

A reaction product containing an alkali metal disulfide as a main component is produced by the reaction between the alkali metal monosulfide and the iodine, and this reaction product reacts with chlorocyclohexane to form a product represented by the following formula, for example, Na2S+S→Na2. The reaction proceeds as expected.

When alkali metal monosulfide and sulfur are mixed at 40 to 80 qo, alkali metal disulfide is easily produced.

When using a mixture of alkali metal monosulfide and sulfur as a raw material, in order to increase the production efficiency of dicyclohexyl disulfide, it is necessary to It is desirable that the mixing ratio with sulfur is in the range of 0.5 to 1.1 mol per mol of alkali metal monosulfide.

When the mixing ratio is less than 0.5, the by-product of dicyclohexyl disulfide increases, and when it exceeds 1.1, impurities such as dicyclohexyl disulfide increase, resulting in a decrease in the production rate of dicyclohexyl disulfide.
In addition, as a reaction solvent for the reaction between alkali metal monosulfide and sulfur, water, methanol, ethanol, isopro/
Organic solvents such as ethanol, butanol, and ethylene glycol can be used, but a mixed solvent of methanol and water is most suitable. In this mixed solvent, the mixing ratio of methanol and water significantly affects the yield and quality of dicyclohexyl disulfide. In order to obtain dicyclohexyl disulfide most effectively, the mixing ratio is preferably in the range of 0.4 to 5.0 moles, particularly 0.5 to 3.0 moles, per 1.0 mole of water. A range of 0 moles gives good results. If the amount of methanol relative to water is more than 5.0 mol, the amount of dicyclohexyl disulfide will increase, which will lower the yield of the target product. On the other hand, 0.4 mol/
When the amount is less than mol, the amount of dicyclohexyl disulfide increases and the yield of the target product decreases. The quantitative relationship between chlorocyclohexane and alkali metal sulfide is a major factor governing the production rate of dicyclohexyl disulfide.

When using an alkali metal disulfide as a raw material, dicyclohexyl disulfide is used when the molar ratio of the alkali metal disulfide to chlorocyclohexane is between 1.0 and 3.0, preferably between 1.0 and 1.5. This is preferable because it gives good results on the id production rate. When a mixture containing an alkali metal sulfide is used as a raw material, the molar ratio of the alkali metal disulfide to chlorocyclohexane produced in the intermediate stage is similarly 1.0 to 3. Preferably 1.
It is desirable that it be within the range of 0 to 1.5. The reaction temperature of chlorocyclohexane and alkali metal disulfide is 40
The reaction time, which is preferably in the range of 0 to 80°C, is not particularly limited in the present invention, and the most appropriate time may be selected depending on the concentration of the active ingredient in the reaction system or the reaction temperature.

The reaction pressure can be normal pressure, increased pressure, or reduced pressure, but normal pressure is the most practical. The reaction solvent can be the same as that used in the reaction between the alkali metal monosulfide and sulfur, and most preferably a mixed solvent of methanol and water, especially a mixture of methanol and water per 1.0 mol of water. Te 0
．． 4 to 5.0 moles, and more preferably 0.5 to 3.0 moles, are preferably used for the same reasons as above. For example, when an alkali metal disulfide is used as a raw material, the reaction can be carried out by mixing chlorocyclohexane and the alkali metal disulfide.

On the other hand, when using a mixture of an alkali metal monosulfide and sulfur as a raw material, for example, the alkali metal monosulfide and sulfur are mixed in advance to react, and the reaction mixture and chlorocyclohexane are mixed into a mixture. It is preferable to make people react by worshiping them. Dicyclohexyl disulfide is thus produced. EXAMPLES The present invention will be specifically explained below with reference to Examples.

Examples 1 to 11 40 methanol (1.25 mol) was charged into a 200-meter four-necked flask equipped with a backflow condenser, thermometer, dropping funnel, and stirrer, and while stirring the liquid, N.
Sodium sulfide containing 16.5 parts of a2S and 10.8 parts of water (0.6 moles) and 4.7 parts of sulfur were added.

At this time, the molar ratio of methanol to 1 mole of water in the flask was 2.08. Heat the flask to bring the liquid temperature to 60
When the temperature was maintained at ~65°C and stirring was continued for 30 minutes, the liquid became a uniform layer.

This liquid was further stirred and heated until it refluxed, and 24.3% of chlorocyclohexane with a purity of 97.5% was added.
The mixture was added little by little from the dropping funnel. After the addition of chlorocyclohexane was completed, the reaction was continued for 7 hours while maintaining the reflux state. The temperature inside the flask was once brought to room temperature, the backflow condenser was replaced with a distillate condenser, and the flask was heated again to remove the entire amount of methanol.

After adding 50 parts of water to the residual liquid, the entire liquid amount in the flask was transferred to a separating funnel, and the aqueous layer was separated to obtain an oil layer of 19.6 parts. As a result of gas chromatogram analysis of the oil layer, the content of dicyclohexyl disulfide was 86.2%, and the yield from chlorocyclohexane was 84.5%. Details of the experimental results are shown in Table 1 (Example 1). Table INo. shows the results of experiments using the same equipment with different raw materials and solvents.
2~No. 13 (Examples 2 to 13). Ship ``Toto Boku Toi Mimi Mi Tom I'o ＼ Kose 0 Toshi Shout'' S Samimimi song is Tonfu Ha 0 Zazaza no Iku〈Kumi N).

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Claims (1)

[Claims] 1. A method for producing dicyclohexyl disulfide, which comprises reacting chlorocyclohexane with an alkali metal sulfide or a mixture containing the same in the presence of a solvent. 2. The method according to claim 1, wherein the alkali metal sulfide is an alkali metal disulfide. 3. The method according to claim 2, wherein the alkali metal disulfide is used in an amount of 1.0 to 3.0 mol per mol of chlorocyclohexane. 4. The method according to claim 1, wherein the mixture containing an alkali metal sulfide is an alkali metal monosulfide and sulfur. 5 0.5 sulfur per mole of alkali metal monosulfide
3. The method according to claim 3, wherein the amount is used in a range of from 1.1 mol to 1.1 mol. 6. The method according to claim 1, wherein the solvent is a mixed solvent of methanol and water. 7. The method according to claim 6, wherein methanol is used in an amount of 0.4 to 5.0 mol per mol of water.