HU193691B - Process for production of organic sulphids and oligosulphids - Google Patents

Abstract

Suphides and oligo-suphides of formula I are prepd. by alkylation with alkyl-halides or alkenyl-halides of general formula II in the presence as catalyst of 0.01-2.0 wt. % based on organic halogenide of an amine of general formula III and/or of carbionic surfactants of general formula IV, V or VI. The resulting prods. are sepd. in the known way on the basis of density differences. - In the formulas R1 and R1' are alkyl, iso-alkyl or 2-12C alkenyl, R2, R3 and R4 are each 2-8C alkyl or alkenyl, R5 is alkyl or iso-alkyl with 6-18 C, R6 is alkyl or alkenyl with 8-22 C, n is 1, 2, 3 or 4, m is an integer between 2 and 40. X is chlorine, bromine or iodine.

Description

The present invention relates to a process for the preparation of organic sulfides and oligosulfides.

The method alkyl of the general formula (I), izoalkil-, alkenyl sulfides and S ₂ -S ₄ oligoszulfidok containing sulfur - in which R 5 ¹ and R ¹ 'represents a C2-12 alkyl, izoalkil- 3-6 n is 1, 2, 3 or 4.

These compounds are important intermediates in various chemical syntheses and are components of some of their aromatic compositions (e.g. diallyl, dipropyl mono-, di- and trisulfide).

The known synthesis methods mainly describe the preparation of mono-disulfides. Syntheses are most often based on organo-sulfur-containing compounds, in particular mercaptans, or by reduction of sulfones to obtain the desired compounds. ( E.g.

No. 1,194,841 U.S. Patent No. 1,230,018; and Nos. 1,230,788. Disclosure documents in the Federal Republic of Germany, No. 921,352. French, No. 117,836 and 334,977. U.S. Patents).

Methods for the preparation of disulfides from other sulfur-containing compounds (thioic acid esters, sulfonic acids, sulfinic acids) are also known (Houben-Weil, Methoden d Organischen Chemie, Vol. 9, p. 59).

However, these processes have not been commercialized because the starting compounds are difficult to access and the β ₀ synthesis method is complicated.

A procedure has also been described (Rev. Trav.

Chim. 32.68.1963) in which metal sodium and elemental sulfur are dissolved in liquid ammonia followed by addition of an alkyl halide. 35 The method requiring very expensive equipment is also not widespread.

Alkali sulfides and disulfides may also be alkylated with organic halides to provide the corresponding organic sulfides. Syntheses are carried out primarily in the presence of an intermediate 40 solvents, mostly alcohol (Houben-Weil, cited in Vol. 9, p. 65).

The Hungarian patent specification No. 166,880 the alkylation solve without intermediary solvent or disulfides alkáliszulfidok the aqueous solution ⁵ present in the heterogeneous phase C ₂ -C ₅ alkyl being treating or alkenyl halides. The applicability of the process is limited by the fact that the difference in weight between the two liquid phases does not exceed 0,15 g / cm ³ and is not applicable to the synthesis of compounds containing more than 2 sulfur atoms with carbon numbers greater than 6.

The process described in German Patent Publication No. 2,020,051 discloses a mixture of aliphatic di- and trisulfides by reacting an aliphatic thiosulfate with an alkali metal sulfide. However, the product obtained is not pure and therefore has limited use.

According to another known process (British Patent No. 1,460.559) and heterocyclic aromatic sulfides and disulfides in the gas phase, or from 180 to 230 ° C in an inert solvent at a temperature of 430 to 600 ⁶ 5 ° C produced the appropriate organic halide and kénhidrogénből. Due to the high temperature required, the method is difficult to implement in industry.

In the presence of a quaternary phosphonium compound, dialkyl sulfides are prepared from alkyl halides and sodium sulfide according to Org. Synth. 58. p 154. Method described in 1978.

The process described is difficult to apply on an industrial scale. The purity of the product is unsatisfactory, further purification steps are required to obtain a pure final product.

The aim is to develop a method which provides the target compounds with simple means, good yields of technical size and good quality.

It has now been found that the oligosulfides of formula I, wherein R ¹ and R ¹ 'are andrn, can be prepared in good yield and quality when an aqueous solution of alkali metal sulfides or S ₂ -S ₄ oligosulfides of general formula II is obtained. with organic halides of the formula wherein R ¹ is as defined above, X is Cl, Br, J - tertiary amines of formula III wherein R ² , R ³ and R ⁴ are C 2 -C 8 alkyl or alkenyl - and / or (IV), (V), (VI) - wherein R ⁵ is C 8 -C 12 alkyl, isoalkyl, R ⁶ is C 12 -C 18 alkyl or alkenyl, m is 4 to 30 integers - non-ionic in the presence of surfactants without the use of an organic solvent.

It is particularly advantageous to use as a catalyst a mixture of the amine (III) and the surfactant (IV) - (VI).

The alkali metal sulfide used in the reaction is preferably sodium or potassium sulfide. Preferably, the inorganic oligosulfides are prepared in the reaction mixture by adding elemental sulfur to the aqueous solution of the monosulfides. The concentration of the aqueous solution may be varied within the range of 2 to 50% by weight. It is advantageous to use water for dissolution so that the resulting effluent is present in a concentration of 20 to 25% by weight with respect to the alkali metal halide. In this case, the difference in specific gravity between the product and the wastewater makes it easy to separate the phases.

A preferred amount of the organic halide of formula (II) is 95-100 mol% based on the inorganic sulfide content. In excess of the stoichiometric amount, the excess contaminates the product, which requires an additional purification step.

The process comprises stirring an aqueous solution containing an inorganic sulfide or oligosulfide, a biphasic liquid mixture containing a catalyst and an organic halide, at a temperature between room temperature and the boiling point of the organic halide, but not more than 80 ° C. The reaction is slightly exothermic, so the temperature increases as the reaction progresses. Indirect cooling and the cross-219369.1 beat intensity of regulation is preferably kept in a 40 ^Q 45 C temperature.

The progress of the reaction can be monitored by examining the composition of the organic phase, e.g. by checking the specific gravity, refractive index or chromatography. If the amount of organic halide does not exceed the stoichiometric ratio, the total amount is reacted and the starting material does not contaminate the product.

The product formed is insoluble in the aqueous phase and can be separated by specific gravity. The yield is almost theoretical and the purity of the product is satisfactory for most purposes or can be further purified by distillation or steam distillation if desired.

The method is very generally applicable to the preparation of compounds of formula (I). Whether the quality of the alkyl halide or the amount and quality of the catalyst can be selected within the given range, the course of the reaction and the quality of the product are well controlled. However, without a catalyst, the reaction takes a long time, yields are poorer and the product is more polluted.

The process is illustrated by the following examples, but is not limited to the examples.

Example 1

Preparation of diethyl disulfide

In a 1 liter round-bottomed flask equipped with stirring, addition funnel and reflux condenser, dissolve 250 g of sodium sulfide nonahydrate (Na ₂ .9H ₂ O, 1.01 mol) in 100 cm ^{3 of} water and add 33.4 g of elemental sulfur (1.04 mol). and stir until completely dissolved. While stirring, a mixture of 0.2 g of trihexylamine and 218 g (2.0 mol) of ethyl bromide was added dropwise to the solution at 35 ° C. Stirring was continued until then; while the total amount of ethyl bromide reacts (30-40 minutes).

The phases are separated. The organic phase / diethyl disulfide (120 g - 98%), purity 95%. (GLC analysis).

Example 2

Preparation of diethyl disulfide

Example 1 was followed alive, but no catalyst was used. The reaction requires 2 hours with vigorous stirring and refluxing. The yield of diethyl disulfide was 90 g 74% and purity 90%.

Compared to Example 1, the yield is worse and the product is more impure.

Example 3

Preparation of diethyl trisulfide

In the apparatus of Example 1, 210 g of potassium sulfide pentahydrate (K ₂ S. ₅ H ₂ O; 1.05 mol) was dissolved in 200 cm ^{3 of} water, stirred with 67.3 g of elemental sulfur (2.1 mol) until completely dissolved. To the solution was added 0.1 g of Tween 80 emulsifier (polyoxyethylene) sorbitan monooleate (m = 20) and 218 g of ethyl bromide (2.0 moles) were added dropwise as in Example 1.

The yield of diethyl trisulphide was 140 g, 97% and purity (by GLC analysis) 95%. 1-2% of diethyl disulphide and tetrasulphide.

Example 4

Preparation of dipropyl sulfide

In the apparatus of Example 1, 250 g of sodium sulfide nonahydrate (Na ₂ S. ₉ H ₂ O; 1.04 mole) was dissolved in 150 cm ^{3 of} water, and 0.4 g of trioctylamine was added while maintaining 406 g of n- propyl bromide (2.0 mol) was added dropwise to the solution. In the following, the procedure of Example 1 is followed. The required reaction time is 30 to 40 minutes.

The yield of dipropyl sulfide was 117 g (98%), purity (by GLC) 97-98%

Example 5 (Comparative)

Preparation of dipropyl sulfide

Example 4 was followed but no catalyst was used. The reaction is complete within 3 hours.

The yield of the product was 102 g (85%) and purity (by GLC analysis) 88%.

Example 6

Preparation of dipropyl disulfide

The procedure was as in Example 4, but 33.4 g of elemental sulfur (1.04 mol) were dissolved in the sodium sulfide solution and 0.1 g of trihexylamine was used as catalyst.

The yield of dipropyl disulfide was 146 g (97%) and purity (GLC) 96%.

1-2% dipropyl mono- and trisulfide contaminated.

Example 7

Preparation of dipropyl trisulfide

The same procedure as in Example 6 was used, but the amount of dissolved elemental sulfur was 66.8 g (2.08 mol) and the catalyst was 0.4 g of nonylphenol polyglycol ether Cm = 30, Renex 688 emulsifier.

The yield of dipropyl trisulfide was 185 g (96%) and purity 95%.

Example 8

Preparation of dipropyl tetrasulfide

The procedure is as in Example 6, but the amount of dissolved elemental sulfur is 100, Og (3.12 mol) and the catalyst is 0.1 g tributylamine and 0.1 g cetyl polyglycol ether (m = 16 G). 3816 emulsifier).

The yield of dipropyl tetrasulfide was 206 g (96%) and purity 93% (by HPLC).

Example 9

Preparation of diallyl sulfide

Example 4 was repeated, but 153 g of allyl chloride were reacted.

The yield of diallyl sulfide was 112 g (98%) and purity 97% (GLC method).

-3193691

Example 10

Preparation of disalyl disulfide

Example 6 was repeated except that 242 g of allyl bromide were reacted.

The yield of diallyl disulfide was 142 g (97%) and purity 95%.

Example 11

Preparation of disalyl disulfide

Example 10 was used, but no catalyst was used. The reaction time is one hour.

The resulting diallyl disulfide was dark brown in a yield of 126 g (85%) and purity 87%.

Compared to Example 10, the yield is poorer and the product is more impure.

Example 12

Preparation of disalyl disulfide

Example 7 was used, but 153 g of allyl chloride (2.0 moles) were recovered.

The yield of diallyl trisulphide was 171 g (96%) and purity 93%.

Example 13

Preparation of di-n-butylsulfide

In the same manner as in Example 4, 0.05 g of tributylamine was used as the catalyst and 185 g of n-butyl chloride (2.0 mol) were reacted.

The yield of di-n-butyl sulfide was 142 g (97%) and purity 97%.

Example 14

Preparation of di-n-butyl disulfide

Example 6 was carried out using 0.05 g of trihexylamine and 0.1 g of nonylphenyl polyglycol ether (m = 30, Renex 650 emulsifier) as catalyst and 274 g of n-butyl bromide (2 g). (0 mol).

The yield of di-n-butyl disulfide was 172 g (96%) and purity 95.5%.

Example 15

Preparation of di-tert-butylsulfide

In the same manner as in Example 4, 0.5 g of Tween 60 (polyoxyethylene) sorbitan monopalmitate (emulsifier and 185 g of tert-butyl chloride, m = 20) were used as catalyst.

The yield of di-tert-butylsulfide was 140 g (96%) and its purity was 96%.

Example 16

Preparation of dioctyl sulfide

In the same manner as in Example 4, 0.2 g of triethylamine was used as the catalyst and 386 g of n-octyl bromide (2.0 mol) were reacted.

The yield of the resulting dioctyl sulfide was 248 g (96%) and purity 96% (HPLC method).

Example 17

Preparation of diethyl trisulfide

In the same manner as in Example 3, 311.9 g of ethyl iodide (2.0 moles) were reacted using 0.1 g of ethyldiisopropylamine and 0.05 g of octylphenol polyglycol ether (m = 6; Renex 756 emulsifier) as catalyst. .

The yield and product quality are the same as in Example 3

Example 18

Preparation of diallyl tetrasulfide

The procedure was as in Example 12, but the amount of dissolved elemental sulfur was 100.0 g (3.12 moles) and the catalyst was 0.1 g of dioctyl ethylamine and 0.1 g of P0'-hydroxyethylene sorbitan monolaurate. m = 4; Tween 21 emulsifier).

The yield of diallyl tetrasulfide was 202 g (96%) and purity 94% (HPLC method).

Example 19

Preparation of dipropyl disulfide

Example 6 was carried out, but the catalyst was 0.1 g tridecyl polyglycol cholesterol (m = 6; Renex 36 emulsifier).

The yield and product quality are the same as in Example 6.

Example 20

Preparation of dipropyl disulfide

Example 6 was carried out using a mixture of 0.05 g monylphenol polyglycol ether (m = 30; Renex 650 emulsifier) and 0.05 g triethylamine as catalyst.

The yield and product quality are the same as in Example 6.

Example 21

Preparation of dipropyl disulfide

Example 6, but using 0.1 g of dodecylphenol polyglycol ether (m = 20).

The yield and product quality are the same as in Example 6.

Claims (4)

A process for the preparation of the organic sulfides and oligosulfides of the formula I in the formula R ¹ and R ¹ 'are the same and form a straight or branched alkyl group of 2 to 12 carbon atoms or a C 3 to C 6 alkenyl group, n being 1, 2, 3 or 4, for the preparation of an aqueous solution of Alkylation at 100 ° C with alkyl halides of formula II or alkenyl halides wherein R 'is as defined above and X is Cl, Br, J, characterized in that 0.01 to 20% by weight, based on the amount of organic halide of formula (III), of formula (I), wherein R, R ³ , and R * are the same or different from C 2 to C 8 alkyl or alkenyl, and / or (IV), ( V), (VI) of formula: - wherein R ⁵ represents a C 8-12 linear or branched alkyl group having 12 to 18 R® is a lower alkyl or alkenyl group, m is -4193691 4 to 30 integer nonionic surfactants are used and the resulting products are separated on the basis of their specific gravity in a manner known per se. 2. A process according to claim 1, wherein the catalyst is a mixture of the compounds of the formulas III and IV. 3. The process according to claim 1, wherein the catalyst is a mixture of the compounds of formula (III) and (V). 4. A process according to claim 1 wherein the catalyst is a mixture of compounds of formula III and VI.