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Umsetzungen des Cyclohex‐3‐en‐carbaldehyd‐ p ‐toluolsulfonylhydrazons
Author(s) -
Rey M.,
Begrich R.,
Kirmse W.,
Dreiding André S.
Publication year - 1968
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/hlca.19680510502
Subject(s) - chemistry , thermal decomposition , ene reaction , medicinal chemistry , bicyclic molecule , carbene , tributyltin hydride , bond cleavage , organic chemistry , catalysis
The vacuum thermolysis (80–90°) of the sodium salt of cyclohex‐3‐ene‐carbaldehyde p ‐toluenesulfonylhydrazone ( 1 ) in silicone oil gave diazomethyl‐cyclohex‐3‐ene ( 2 ). Pyrolytic and photolytic decomposition of this diazo compound 2 lead to methylenecyclohex‐3‐ene ( 5 ) and bicyclo [4.1.0]hept‐2‐ene ( 6 ) (about 3:1), while the CuCl catalyzed cleavage yielded only 5 . The postulated carbene mechanism should also apply under the direct aprotic decomposition conditions of the sodium salt of 1 in diglyme, where methylenecyclohex‐3‐ene and bicyclo[4.1.0]hept‐2‐ene (about 3:1) were formed besides small amounts of 1‐methylcyclohexa‐1, 3‐diene ( 9 ) and bicyclo [4.1.0]hept‐3‐ene ( 8 ). Under protic conditions (in ethylene‐glycol) methylenecyclohex‐3‐ene, 1‐methylcyclohexa‐1, 3‐diene and 1‐methylcyclohexa‐1, 4‐diene ( 14 ) were produced in a ratio of 1:1:1. The direct mild thermolysis of cyclohex‐3‐ene‐carbaldehyde p ‐toluenesulfonylhydrazone ( 1 ) in benzene solution afforded N‐( p ‐toluenesulfinyl)‐O‐( p ‐toluenesulfinyl)‐cyclohex‐3‐en‐yl‐α‐methanolamine ( 15 ) and di‐(cyclohex‐3‐en‐yl‐methyl)‐ammonium p ‐toluenesulfonate ( 16 ), the structures of which were supported by their nmr. spectra and by alkaline cleavage.