DE1912729A1 - Process for the production of sulfoxides - Google Patents

Description

The invention relates to a method for the production of sulfoxides by oxidation of sulfides in the presence of a sensitizer and a non-polar solvent under the action of light.

It is from Houben-Weyl, Methods of Organic Chemistry, Volume 9, Pages 211 ff (1955) known, sulfides with hydrogen peroxide, peracids, Chromic acid, nitric acid, dinitrogen tetroxide, hypochlorite, iodosobenzene, halogen, potassium permanganate, ozone or to oxidize to sulfoxides by anodic oxidation at the lowest possible temperatures. These methods result in the Production of relatively simple sulfoxides mostly in good yields. However, if the molecule also contains other, easily oxidizable groups, the yield is considerably reduced as a result of side reactions Dimensions.

The conversion of sulfides into the corresponding sulfoxides has also been carried out by oxidation with atmospheric oxygen (N. Kharasch "Organic Sulfur Compounds", pages 229 to 247, Pergamon Press London 196I). The yield of sulfoxide can not exceed 50% of theory for reasons of reaction mechanics; in fact, only yields of up to 20 % are usually described.

Likewise, the oxidation under the action of light in the presence of a sensitizer (photosensitization) was already in the. Case of methionine in aqueous solution (Archives of Biochemistry and Biophysics, Volume 33, Pages 90 ff. (1951)) and of dialkyl and alkylaryl thioethers in alcoholic solution (Angewandte Chemie, Volume 7 * », page 510 (1962)) described. The high selectivity of such reactions is lost, however, if one of the polar solvents (alcohols or alcohol-water mixtures) _; changes to non-polar solvents (dissertation by GH Krauch, University of Qöttingen, 1960). In the reaction solutions, * 655/68 - 2 - *

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Sulphoxides only in small amounts, but instead, in considerable amounts Scope of peroxides can be detected. Since the sulphides are usually produced in a reaction mixture with hydrocarbons, especially the starting olefins, they must first be removed separated from the mixture, then taken up in an alcohol and subjected to photosensitized autoxidation.

It has now been found that sulfoxides of the general formula can be obtained

R ₂ -SR ₁ -X. I _1:. ,,, = -

in the R. means an aliphatic radical, Rp an aliphatic, cycloaliphatic ^ araliphatic or aromatic radical called and X represents a hydroxyl group or an amino group Sulphides by reaction with an oxidizing agent under the action of light in the presence of a photosensitizer and egg, Solvent advantageously obtained when sulfides of the general .; a formula ·. ■: -., .- ■■■ .- =

. R ₂ -SR ₁ -X II, ■

in which R ₁ , R ₂ and X have the aforementioned meaning, is reacted in the presence of a non-polar solvent.

The reaction can be carried out in the case of the use of dodecylß-hydroxyethyl sulfide and oxygen by the following formulas: represent:

- (CH ₂ J ₁₁ -S-CH ₂ -GH ₂ -OH- + 2

Compared to the known processes, the process according to the invention on einfächerem and more economically übex * rs "seeing a larger number of Sui foxideti 'in gnt & f yield and oparation.' Ttrcf & tL · the use * vöft ühpöia'f en solvents and Hydroxy - ■ b between ÄmiiiGälky Is ul t i den al k "Alis gäniga st οff en one obtains the corresponding end product ^;" in ^ Ufreiia ^ OKVria'Kbfter "" Yield "öhrib" - ""

'■ * "' OZ 26 066

substantial formation "of by-products. Those involved in manufacture of the sulfide, '2.' "BY by reaction of mercaptans with QC-olefins, resulting reaction mixtures, which often have even larger proportions Containing non-polar starting olefin can be used directly as a starting gene of the method according to the invention and thus can be used economically.

Preferred starting materials of the general formula II and correspondingly preferred end materials I are those in whose formula R _{1 is} an alkyl radical or an alkenyl radical with in each case 1 or 2 to 18, preferably 1 or 2 to 12, in particular 1 or 2 to M carbon atoms, R_ denotes an alkyl radical or an alkenyl radical with in each case 1 or 2 to 18, preferably 1 or 2 to 12, carbon atoms, a cyeloalkyl radical with 5 to 7 carbon atoms, an araikyir radical with 7 to 12 carbon atoms or denotes a phenyl radical and X denotes a Hydroxyl group or an amino group. The radicals mentioned can still through under the reaction conditions are inert groups and / or atoms, such as hydroxyl *, amino-j cyano, alkoxy, alky! Amino, dialkylamino groups each having 1 to 4 carbon atoms, _s halogen atoms, e.g., B. Ghlaratomej substituted be. The alkyl and / or alkenyl radicals can still be in the carbon chains through the groups -CO-NH- or -CO-O- be ünterbrödhen.

It can e.g. B. the following sulfides are used as starting materials-II: dodecyl, isobutyl, cyclohexyl, benzyl, phenyl § p-hydroxyphenyl, vinyl, ß-cyanoethyl, (^ Hydroxyhexy1-, stearyl, lauryl-jf Stearic acid amidoethyl, acetatoethyl, p-aminobenzyl, ß-ethoxypropyl, ß-hydroxyethyl sulfide; analogous ß-hydroxy-n-hexyl, W-Hydroxylaury 1-, ^ -hydroxy-ß-dimethy 1-propyl, "^" - Aminoallyl-, ß-Äfltino-tert-butyl-, ß-Aminoäthy! -Sulfide instead of the ß-HydroxyäthyIgülfide mentioned.

Oxidizing agents, e.g. B. those already listed in the prior art. Preferred oxidizing agents are oxygen or corresponding mixtures with inert gases, z. B * air. The reaction with the starting materials can be carried out in stoichiometric Amounts or with the oxidizing agent in excess, e.g.

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in a ratio of 0.5 to 15, in particular 0.5 to ¹ J mol of oxidizing agent per 1 mol of starting material II. In the case of oxygen or air, preference is given to using 0.5 to 15 *, in particular 0.5 to 1.5 mol of oxygen per 1 mol of starting material II, expediently in the form of the cycle gas.

The oxidation is carried out under the action of light (photo-oxidation) and in the presence of a photosensitizer. Suitable light sources are those with strong radiation in the visible and especially in the ultraviolet range, ζ. Β. Mercury vapor, high pressure, medium pressure and low pressure lamps, xenon high pressure, carbon arc, fluorescence, argon incandescent, flood light, Jupiter, surface cold light, filament or sodium vapor lamps and also sunlight. For better light utilization, the light sources are preferably located in Tauchschäehten within the reaction mixture, in special cases, for. B. when irradiated with sunlight, the reaction mixture is irradiated from the outside. A3.5 Photosensitizers are advantageously Rose Bengal, PtilQxin, porphins such as zinc tetraphenylporphine, protoporphyrin, or haematoporphyrin, methylene blue, rubrene, chlorophyll, dinaphthylenethiophene, eosin, fluorescein , Benzil, benzopyrene, erythrosine, riboflavin, triphenylene, anthracenes are also all in the book by K. Gollniek, "Advances in Phptoehemig ^ ry" (John Wiley, NY 1968), Volume 6, Chapter C, in particular pages lft , 15, 2ή, 28, 3 ^, ^ O listed photo sensitizers are suitable. With regard to the term photo-sensitizer, please refer to Chapter C.

As a rule, those sensitizers are selected that are in the solvents used in the reaction are readily soluble. The sensitizers are usually used in an amount of 0.001 to 1, preferably from 0.05 to 0.1 Gew.Jf, based on the Solvent"

The reaction is carried out in the presence of a non-polar solvent carried out. Non-polar solvents are those with a dielectric constant below 23 »5j especially below * Understood. Regarding the concept of polarity in solvents

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will be on Houben-Weyl, Methods of Organic Chemistry, Volume 1/1, Pages 285 ff (1958) and Landolt-Börnstein, 6th edition, Volume II, Part 6, (Electrical Properties I) pages 449 ff., 559 ff

Suitable solvents are e.g. B. those in Table 14 (Houben-Weyl, loc. Cit. Page 286) behind aniline. The following solvents can be used: aromatic hydrocarbons such as benzene, toluene, xylene; cycloaliphatic hydrocarbons such as cyclohexane: decalin, tetralin; Alkanes such as n-decane, n-hexane, 2,2,4-trimethylpentane, n-octane, pentane; Esters such as butyl acetate, ethyl acetate; Chlorinated hydrocarbons such as chloroform, ethylene chloride, carbon tetrachloride; and in particular unsaturated, aliphatic hydrocarbons, preferably C-olefins, which each have a hydrogen atom on both carbon atoms of the double bond, such as 6-hexene, 1-octene, 1-dodecene, 1-tridecene, 1-octadecene. The non-polar solvent is used in de _; c. _r Rege 1 in an amount from 10 to 95%, preferably from 75 to 90% by weight, based on starting material II. In a particularly advantageous embodiment, the solvent used is the olefin used to prepare the starting sulfide II by reacting mercaptan with (-olefins (patent. ... ..... (Patent application P 15 68 098.5)) '.

In such cases, the reaction mixture of sulphide production, with a corresponding excess of olefin over that for sulfide production stoichiometrically necessary amount, without separation of the sulfide II directly as starting material for the process serve the invention. Preferred olefins, which are used in this context as starting materials for the preparation of the sulfides II and at the same time serve as the solvent of the process are, for. B. hexene, octene, decene, dodecene, tridecene, hexadecene, octadecene.

The response is in general; at a temperature between - 20 and 150 ⁰ C, preferably between 0 and 1OQ ⁰ C, under atmospheric ode.r. carried out under pressure, continuously or batchwise. , »Embodiments of the implementation are z. B. the following: A mixture of starting material M, photosensitizer, unpolarp, fti ^: Losginge; * · agent and oxidizing agent is for 20 minutes until ■ ·· ££ '- "Siprääeit.-depending on the amount of" sulfide under the action vjon light beli am · .. ^; ft reaction temperature held. Instead of the starting material £ 1 ^ £ φιπι &

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also the reaction mixture used for its preparation, such as was described above, with an excess of C-C olefin in question. In the case of oxygen or air as the oxidizing agent, the gas is expediently passed continuously through the circulating gas Reaction mixture. Then the end product is in the usual way, for. B. * by filtration, if necessary after concentrating the mixture Removal of the solvent, separated and recrystallized sation from a suitable solvent, e.g. B. ethanol, ethyl acetate, methanol, acetone, ethylene chloride, purified.

The compounds which can be prepared by the process of the invention are surfactants, oxidation inhibitors, fragrances and flavorings and valuable starting materials for the production of surfactants, fragrances, oxidation inhibitors, dyes, solvents and pesticides. With regard to the use, reference is made to the publications mentioned and Ullmanns Encyklopadie der technical chemistry, volume 16, pages 528 ff; U.S. Patent 2,859,248, Belgian Patent 590,265 and French Patent 1 260 789 referenced.

The parts given in the following examples are parts by weight.

Examples

The procedure is for those listed in the table below Examples the following: The starting sulfide II is combined with the sensitizer (e.g. Rose Bengale) dissolved in the specified solvent. The solution is then placed in a diving lamp assembly made of glass with inner jacket cooling by water with a high pressure mercury torch Philips. HPK 125 W passing through of 3.2 parts of oxygen (consumed oxygen is continuously replenished) exposed. The oxygen is circulated through the Out reaction mixture and registered its consumption. If no more oxygen is absorbed, the exposure is canceled. the Sulphoxides I of Examples 1, 3-6, 10-13, I5-I8 already fall

00984072100

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During the reaction from the solutions are removed by filtration or suction separated from the solvent and by recrystallization the filter material thus obtained with z. B. Purified methanol. The end products I of Examples 2, 7-9 and 11} remain dissolved and are isolated by fractional distillation after the photo-oxidation has ended.

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Tabel

Ex. Starting sulfide II Jemp ..
C. Consumption Parts Sensitizer ■ No. R ₁ Xs-CH ₂ -CH ₂ -OH Parts 35 oxygen
in pieces , 1 HO (CH ₂ Jg-SR ₁ X 80 25th 6.8 0.5 Rose Bengal .-, 2 CH ₂ = CH-SR ₁ X 20th 25th 2.8 0.1 Rose Bengal '}: 3 NC-CH ₂ -CH ₂ -SR ₁ X 30th 40 2.9 0.3 Rose Bengal 4 ^s ΛΤΤ / ΛΤΤ \ O T5 V 25th 40 1.5 0.2 Rose Bengal 5 50 60 3.1 0.5 Rose Bengal O
(O 6th ^ CXJ Δ. 100 20th 5.2 0.5 Rose Bengal 00
© 7th CH ₃ -SR ₁ X 18.5 20th 3.3 0.2 Phloxin CH-CHo "S-R ^ X 20th 25th 3.0 0.1 Rose Bengal 9 CH ₂ = CH-CH ₂ -SR ₁ X 100 25th 14.0 0.5 Rose Bengal σ>
© 10 CH -, - (CHp) ~ -S-R, .X 100 40 8.2 0.5 Rose Bengal 11th nti ^ f ην \ _C_R γ
νπ, -ν, VyIi ₂ ; i ι · ⁰ *> ι ^Λ 120 40 6.4 0.5 Rose Bengal 12th CH ₃ - (CH ₂ J ₁₁ -SR ₁ X 12.5 25th 0.7 0.1 Rose Bengal 13th CH ₃ - (CH ₂ J ₇ -S ^ ₁ X 40 25th 2.0 0.2 Rose Bengal 14th / hY-s-r χ 16 1.6 0.1 Protoporphyrin

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0.1 phloxin

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Ex. End product I No. Part names

Parts solvent

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2 3

5 6 7 8

10 11 12 13 14 15 16

17 18

51 ω-hydroxyhexyl-ß-hydroxy-ethyl-70/71 sulfoxide

120 butyl acetate

19th Vinyl-ß-hydroxyethyl sulfoxide (1.5262) 180 Tetrahydrofuran 25th ß-cyano-ethyl-ß-hydroxy-ethyl-
sulfoxide 80/82 300 chloroform 17th Dodecy l-ß.-hydroxy-ethyl-sulfoxide 70/71 175 Ethyl acetate 33 Dodecy1-ß-hydroxy-ethyl-sulfoxide 70/71 ISO Cyclohexane 70 Hexadecy1-ß-hydroxy-ethyl-sulfoxide 81/82 ISO Chloroforia 21.5 Methy1-ß-hydroxy-ethyl-sulfoxide Ci * 5073) 181 Ethyl acetate.; 24 Ethyl-ß-hydroxy-ethyl-sulfoxide d, 4868} 180 acetone 105 Ally1-ß-hydroxy-ethyl-sulfoxide 0.5152) 100 Ethyl acetate 70 Octy1-ß-hydroxy-ethyl-sulfoxide 47/48 155 Ethylene chloride 103 Dodecy1-ß-hydroxy-ethyl-sulfoxide 70/71 ⁵ : ;; * 17O _o toluene 7.5 Dodecy1-ß-hydroxy-ethyl-sulfoxide 70/71 Ethyl acetate 32 Octy1-ß-hydroxy-ethyl-sulfoxide 47/48 ■ '[ 160 1 Octene 17th Cyclohexy1-ß-hydroxy-ethyl-sulfoxide Q- , 5230) ' 18Q ^: - Dioxane 4 29 Pheny1-ß-hydroxy-ethyl-sulfoxide 88/89 - , 166 Acetone ] l 32 ß-Hydroxy-äthy1-ß'-amino ^ äthy1-
sulfoxide 98 / IOÖ 160 '■' acetone 16 ■ Dodecy1-ß-amino-ethyl-sulfoxide 219/20 ' . "175- ' Acetone ₃ 10 Benzvl-ß-amino-ethyl-sulfoxide 210 " ^! 180 Dioxane

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Claims (1)

. • -μ '-. ·· '«.-' ■ O.Z. 26 066 Patent claim A method for preparing sulfoxides of the general formula ■ 0 u R ₂ -SR ₁ -XI, in which R _{1 is} an aliphatic radical, R _{2 is} an aliphatic, cycloaliphatic ,; araliphatic or aromatic radical and X stands for a hydroxyl group or an amino group, from sulfides by reaction with an oxidizing agent under the action of light in the presence of a photosensitizer and a solvent, characterized in that sulfides of the general formula R ₂ -SR ₁ -X II » in which R ₁ , Rp and X have the aforementioned meanings, reacted in the presence of a non-polar solvent. Badische Anilin- & Soda-Fabrik AG 009840/2160