DE2513805A1 - METHOD FOR PRODUCING ORGANIC SULPHIDES - Google Patents

Description

PATENT LAWYERS PROF. DR. DR. J. REITSTÖTTER DR.-ING. WOLFRAM BUNTE DR. WERNER KINZEBACH

D-80OO MUNICH 4O, BAUERSTRASSE 22 FERNRUF (O88) 37 80 83 TELEX S218208 ISAR POSTAL ADDRESS! D-8OOO MUNICH 43. POST BOX 7ΘΟ

Munich, March 27, 1975 'M / 16 055

CHIMOSA CHIMICA ORGANICA S.p.A. 40044 Pontecchio Marconi, Italy

Process for the production of organic sulfides

The present invention relates to a new process for the preparation of organic sulfides of the formula (I)

RS _n -R-

where R and R ^{1 represent} alkyl groups with a linear or branched chain, which are the same or different from one another and contain 1 Ms 30 and preferably 6 to 18 carbon atoms and where η is an integer between 1 and 4, preferably between 1 and 2. These compounds are obtained by treating the alkyl chloride provided with the desired alkyl group with an alkali sulfide in

50984Q / 1119

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Μ / 16 055 %

an aqueous medium and in the presence of a catalyst. The reaction takes place at a temperature between 70 and 110 ° C. and preferably between 95 and 105 ^° C. at atmospheric pressure or at a pressure which is below this. The catalyst used consists of an organic quaternary salt of the general formula (R-, Rp R- * R ^ M) ⁺ X ", where M is a pentavalent ion of the type, P, N or another element of group VA of the periodic table of the elements and R- ,, Rp, R ^ and R. represent organic alkyl radicals with 1 to 30 and preferably with 1 to 18 carbon atoms, (in particular methyl, ethyl, propyl, lauryl), and / or aryl radicals of the benzene type, which with a covalent , stable bond to the M ion. Aryl radicals of the benzene type are preferably understood to mean the phenyl radical, the benzyl radical and the like. These radicals can either be the same or different from one another. X "is a halide anion (of the type Cl, Br, etc. ) or hydroxide (OH).

An example of these compounds is the Dilauryl-dimethyl-

ammonium chloride.

"Aryl" is understood to mean, preferably, optionally substituted

Phenyl, naphthyl and the like.

The percentage of catalyst used, based on the chloride, is between 1 and 10 % and the yield varies in proportion to the amount of catalyst and the reaction time. The advantages of this process over the previously proposed processes (oxidation of mercaptans, reaction of sodium sulfide and alkyl chloride in a water-alcohol medium and the like) are obvious: the reaction is quick and almost complete, it can be easily reproduced and carried out, it gives very high yields and odorless and colorless products. A few examples of the method according to the invention are described below for purposes of illustration; these examples are not limiting.

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Example di-n-octyl monosulfide

36 g of sodium sulfide with a titer of 60 % and 25 ml of water are vigorously stirred in a flask and heated ^{to 70 to 75 ° C.} 74 g of n-octyl chloride and 3 g of dilauryldimethylammonium chloride are then added over the course of 30 minutes. The temperature is increased to 100 to 105 ^° C. and is held at this level for a further two hours. Then water is added in order to dissolve the sodium chloride formed, and the aqueous phase underneath is discarded. The remaining phase is washed with water and the organic phase is separated off. The liquid n-octyl monosulfide is isolated by distillation.

Boiling point at atmospheric pressure: 147 to 150 ⁰ C.

Example di-n-octvl disulfide

Dissolve 59.5 g of sodium disulfide in 100 ml of water and heated with stirring to 90 ⁰ C. In the course of approximately 20 minutes at a temperature between 90 and 100 ⁰ C are added dropwise 124 g of n-octyl chloride and 5.5 g of ammonium chloride Dilauryldimethy1 admitted. The mixture is kept at 105 to 110 ^° C. for 2 to 3 hours, then water is added, the aqueous phase is discarded, the remaining phase is washed with water and the organic phase is separated off and distilled. In this way the liquid n-octyl disulfide is isolated. Boiling point at atmospheric pressure: 175 to 179 ⁰ C.

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M / 16 055

Example 3 Di-n-dodecyl monosulfide

204 g of n-dodecyl chloride, 85 g of sodium sulfide with a titer of 60 %, 40 ml of water and 8 g of dilauryldimethylammonium chloride are introduced into a flask with vigorous stirring and gently heated. An exothermic reaction takes place at approximately 50 to 60.degree. C., which increases the temperature of the reaction mixture to approximately 100.degree. This temperature is held for two more hours. Water is added in order to dissolve the sodium chloride formed and the lower aqueous phase is discarded. The remaining phase is washed with water and the organic phase is separated off and crystallized from acetone. A white, odorless product with a melting point of 39 ° C. is obtained.

Example 4 Di-n-dodecyl disulfide

A solution of 59.5 g of sodium disulfide is dissolved in 100 ml of water and the solution is heated ^{to 90 ° C. with stirring.} One gives 170 g of dodecyl chloride and 5.5 g of dilauryl dropwise to and maintaining the mixture under continued, "^, setztem stirring for 2 towards · 95 to 100 ⁰ C. Water is Z 'hours at a Temperatur..vor added and the aqueous Ph ^ e is vorworien The remaining phase is washed to n. i1 Waßiser and 1reir ::> l (U <* ■ <"Tg aiii..sehe Pha; ^o from it and kri · Μ --jllißjei't mifs / \ cot <ri. lj.;. ") mMM ο in wcoßer ;, foruohnoniii« product mil οίικ. · ;; · > k-Im ■ -1: point of

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M / 16 055

Example 5 Di-n-octadecyl monosulfide

144 g of octadecyl chloride, 3 g of dilauryldimethylammonium chloride, 42 g of sodium sulfide with a titer of 60 % and 20 ml of water are placed in a reaction basket. The mass is heated to 50 to 55 ° C. with vigorous stirring. An exothermic reaction takes place which increases the temperature of the reaction mixture to approximately 105 ^° C .; this temperature is kept at 105 to 110 ^° C. for two hours. Then water is added and the aqueous phase is discarded. The remaining phase is washed again with warm water and the organic phase is separated therefrom and crystallized from acetone. A white, odorless product with a melting point of 65 ^° C. is obtained.

example Di-ri-octadecyl disulfide

59.5 g of sodium disulfide are dissolved in 100 ml of water and heated ^{to 90 ° C. with stirring.} In the course of approximately 20 minutes at a temperature of 95 to 100 ⁰ C are added 240 g of n-octadecyl chloride and 8 g of dilauryl dimethyl ammonium chloride dropwise. The mixture is kept at 105 to 110 ^° C. for two to three hours, then water is added, the aqueous phase is separated off, the remaining phase is washed with water and the organic phase is separated off therefrom and crystallized from acetone. A white, odorless product with a melting point of 56 to 58 ^° C. is obtained.

509840 / Ti 19

Claims (8)

M / 16 055 claims 1. Process for the preparation of organic compounds of the formula (I): R- S _n - R. in which R and R 'represent alkyl groups with a saturated linear or branched chain, which are identical or different from one another and which contain 1 to 30 carbon atoms and in which η is an integer between 1 and 4, preferably between 1 and 2, characterized in that that the alkyl chloride containing the desired alkyl group is reacted with an alkali sulfide or polysulfide in an aqueous medium in the presence of a catalyst which consists of an organic quaternary salt which has the general formula (R ₁ R ₂ R, R ^ M) ⁺ X " has, wherein M represents a pentavalent ion of the type P, N or another element of group VA of the Periodic Table of the Elements and R ₁ , Rp, Rz and Rr represent organic alkyl radicals with 1 to 30 carbon atoms and / or aryl radicals which are represented by a stable covalent bond to the M ion ■ are bonded and where X "represents a halide ion or hydroxide. 2. The method according to claim 1, characterized in that R and R ¹ contain 6 to 18 carbon atoms. 3. The method according to claim 1, characterized in that R-,, Rp, R * and R, represent alkyl radicals 1 to 18 Contain carbon atoms. - 6 509840/1119 " M / 16 055 "1st 4. The method according to claim 1, characterized in that R- ,, Rp, R ^ and R »represent aryl radicals of the benzene type. 5. The method according to claim 1, characterized in that the catalyst used is dilauryldimethylammonium chloride
used. 6. The method according to claim 1, characterized in that that the alkyl chloride is n-octyl chloride. 7. The method according to claim 1, characterized in that the alkyl chloride is n-dodecyl chloride. 8. The method according to claim 1, characterized in that the alkyl chloride is n-octadecyl chloride. ORIGINAL INSPECTED ^f .. |; q Γ /, I! - 1 1 i ^