ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
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.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19680510502
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