ISSN:
0009-2940
Keywords:
Episulfones
;
Thiirane 1,1-dioxides
;
Alkenes
;
Sulfines
;
Sulfonylsulfene-amine S,N-adducts
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Secondary Reactions of Sulfenes from Sulfonyl Chlorides and Tertiary Amines, 2. - Formation of Episulfones, Sulfonylsulfene - Amine S.N-Adducts. and Chlorosulfines from Primary Sulfonyl Chlorides and Tertiary AminesThe reaction of primary sulfonyl chlorides 1b-m with the tertiary amine bases quinuclidine, DABCO, Me3N, Et3N, Bu3N, EtiPr2N, and 1,2,2,6,6-pentamethylpiperidine is studied in acetonitrile solution between - 40 and 80°C. The 2,3-dialkylthiirane 1,1-dioxides 4 (trans/cis 〉 1) and the alkenes 5 [(E)/(Z) 〉 1] are obtained in high yields with Et3N at - 40°C. The stereochemistry is influenced by the amine base B in the ring closure reaction and partially by epimerization of the episulfones 4. Hindered bases favor the cis, β-branched sulfonyl chlorides the trans isomer. Competing formation of the sulfonylsulfene-amine S,N-adducts 7 is only observed with quinuclidine, DABCO, and Me3N, which are also the most active amines in the epimerization of the cis-2,3-diarylthiirane 1,1-dioxides 4. Methanesulfonyl chloride (1a) yields the mesylsulfene-amine S,N-adducts 7a with Me3N and Et3N in MeCN, but thiirane 1,1-dioxide (4a) with EtiPr2N in MeCN or with Et3N in Et2O. Formation of chlorosulfines 10 is favored by higher temperature (T 〉 20°C), hindered amine bases and β-branched sulfonyl chlorides. Isolation of 10g and 10h in high yields shows that tert-alkylchlorosulfines are rather stable sulfines.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19901231010
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