Westerhuis, Eggo

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It is known that asymmetric disulphides can be formed from aromatic sulphenic chlorides and mercaptans. In the work described in this thesis an analogous reaction has been carried out with trichloromethanesulphenic chloride, whereby only the chlorine atom attached to the sulphur atom proved to be reactive. ... Zie: Summary

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   University of GroningenTrichloormethaansulfeenchloride met mercaptanen, sulfinaten en olefinen.Westerhuis, EggoIMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite fromit. Please check the document version below.Document VersionPublisher's PDF, also known as Version of recordPublication date:1950Link to publication in University of Groningen/UMCG research databaseCitation for published version (APA):Westerhuis, E. (1950). Trichloormethaansulfeenchloride met mercaptanen, sulfinaten en olefinen. s.n.CopyrightOther than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of theauthor(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).The publication may also be distributed here under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license.More information can be found on the University of Groningen website: https://www.rug.nl/library/open-access/self-archiving-pure/taverne-amendment.Take-down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediatelyand investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons thenumber of authors shown on this cover page is limited to 10 maximum.Download date: 21-06-2022X. SUMMARY.It is known that asymmetric disulphides can be formed fromaromatic sulphenic chlorides and mercaptans. In the work describedin this thesis an analogous reaction has been carried out withtrichloromethanesulphenic chloride, whereby only the chlorine atomattached to the sulphur atom proved to be reactive. The followingreaction has been shown to take place:CCl3SCl + RSH -+ CCI3SSR + HCIIn this manner disulphides have been prepared in which Rrepresents an aliphatic, alicyclic or aromatic group. With fewexceptions all products are liquids, fuming when exposed to the air.Trichloromethanesulphenic hloride reacts with aromatic sulphi-nates, forming trichloromethyl arylthiolsulphonates:CClsSCl * RSOsNa + CCI3SSOzR * NaClThe chlorine analysis of these compounds could be carried outby titration after decomposition by sodium methylate.The reaction of trichloromethanesulphenic chloride with aliphaticsodium mercaptides yielded chiefly disulphides RSSR and a smallquantity of hexa-alkylthio-dimethyldisulphides : (RS) 3CSSC (SR) a.Since a sulphenic chloride RSCI and a sodium mercaptide R'SNaalways give two symmetric disulphides RSSR and R'SSR', theresults reported are not unexpected. These new compounds are,with one exception, liquids, which can be purified by high vacuumdistillation. Hexa-tert.butylthio-dimethyldisulphide is a colourless,crystalline compound, volatile with steam.Trichloromethanesulphenic hloride and aromatic mercaptidesyield not only disulphides RSSR, but also large quantities ot hexa-arylthio-dimethyltrisulphides (RS)3CSSSC(SR)s. The latter com-pounds exhibit a bright yellow colour. To explain the formationof these trisulphides, we can first postulate the intermediateformation of sulphur by the alcoholate present in the alcoholicsolution of the mercaptide r):CCIBSCI + 4 C2HsONa -+ C(OC2Hs)4 f    NaCl f  SThe disulphide originally formed (RS)BCSSC(SR)s can probably1) Tieckelmann and Post, J. Org. Chemistry 13,265 (1948).62split into free radicals, which may then add to the sulphur atom.S(RS)BCSSC(SR)3 -+  2  (RS)3CS'  - r  (RS)BCSSSC(SR)gThe oxidation of the trisulphides with hydrogen peroxide inacetic acid gave trithiopercarbonic diaryl esters:Reduction of the m-tolyl ester with lithium aluminium hydridegave methyl alcohol, methyl mercaptan, hydrogen sulphide andm-tolyl mercaptan. Thus it is evident that an oxygen and a sulphuratom (not belonging to a thioaryl group) are attached to thecentral carbon atom.In a number of cases it was possible to add trichloromethane-sulphenic chloride to unsaturated compounds, e.g. cyclohexene,styrene, phenylacetylene, diallyl, allyl chloride and isobutenylchloride. In some of the reactions irradiation with U.V. light wasrequired. Several of the addition products formed azeotropic mix-tures with trichloromethanesulphenic hloride. In the case of theaddition to allyl chloride it was proved that the reaction takesplace in the same manner as with aromatic sulphenic chlorides: thechlorine atom adds to the least hydrogenated carbon atom of thedouble bond, thus:CH2 :CHCH2CI+CCI3SCI + CCI3SCH2CHCICHzCI,SRoc(SSR

Trichloormethaansulfeenchloride met mercaptanen, sulfinaten en olefinen.

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Trichloormethaansulfeenchloride met mercaptanen, sulfinaten en olefinen.

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