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Reactions of Thioketones with Dichlorocarbene
Author(s) -
Mlostoń Grzegorz,
Romański Jaroslaw,
Swia¸tek Anna,
Heimgartner Heinz
Publication year - 1999
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/(sici)1522-2675(19990609)82:6<946::aid-hlca946>3.0.co;2-p
Subject(s) - chemistry , dichlorocarbene , catalysis , reagent , benzene , boiling , derivative (finance) , naphthalene , medicinal chemistry , ammonium chloride , flue gas desulfurization , organic chemistry , financial economics , economics
The reactions of sterically crowded cycloalkanethiones of type 2 with CHCl 3 /NaOH under phase‐transfer catalysis (PTC) with benzyl(triethyl)ammonium chloride (TEBA) as catalyst afforded the corresponding `gem.‐dichlorothiiranes' of type 3 in good yields ( cf. Scheme 2 and Table ). The desulfurization, which, in some cases, occurred spontaneously, led to (dichloromethylidene)cycloalkanes of type 4 . Similar results were obtained using Seyferth' s reagent in boiling benzene. In the case of 2,2,6,6‐tetramethylcyclohexanethione, reaction under PTC conditions after 3 h yielded only the corresponding dichloromethylidene derivative; on the other hand, workup after 1 h gave (2,2,6,6‐tetramethylcyclohexylidene)methanethione (thioketene 9 ; Scheme 5 ).