SECONDARY HYDROGEN ISOTOPE EFFECTS. VI. ACETOLYSIS RATE OF CYCLOPENTYL- 3,3,4,4-d$sub 4$ TOSYLATE

Journal Article · Tue Jan 01 04:00:00 EST 1963 · Croatica Chemica Acta (Yugoslavia)

OSTI ID:4676235

Borcis, S

The synthesis of cyclopentyl-3,3,4,4-d/sub 4/-toluenesulfonate is described. The acetolysis rate constant of this compound at 50.00 was determined. With the help of the IBM 7090 computer a kinetic isotope effect (k/sub H//k/sub D/ ) of about 0.95 was found to occur. This small rate increase is interpreted as possibly due to the +I effect of deuterium. (auth) Fifteen mono- or poly- deuterated analogs of 5 alpha androstan-11-one were synthesized with the label occurring in positions 1, 2, 3, 4, 5, 6, 8, 9, 12, and 17 and their mass spectra determined. As a result, it was possible to assign plausible representations to the principal mass spectral fragments and to examine the occurrence of hydrogen transfer reactions. These were found to be remarkably diverse and complicated, mechanisms being postulated for many of the fragmentation-cum-transfer processes. In the course of the synthetic work, it was possible to study in detail the enolization of 11-keto steroids, the ease of hydrogen abstraction proceeding in the order 9 alpha > 12 alpha >> 12 BETA . (auth)

• Research Organization: Inst. "Ruder Boskovic," Zagreb
• NSA Number: NSA-17-030568
• OSTI ID: 4676235
• Journal Information: Croatica Chemica Acta (Yugoslavia), Journal Name: Croatica Chemica Acta (Yugoslavia) Vol. Vol: 35; ISSN CCACA
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

ACETOLYSIS
ACETYL RADICALS
CHEMISTRY
COMPUTERS
CYCLOALKANES
DECOMPOSITION
DEUTERIUM
HYDROGEN
ISOTOPE EFFECTS
SULFONIC ACIDS
TOLUENE