Synthesis of corticosteroids from marine sources - Journal of the

J. Am. Chem. Soc. , 1973, 95 (2), pp 628–629. DOI: 10.1021/ja00783a076. Publication Date: January 1973. ACS Legacy Archive. Cite this:J. Am. Chem. S...
0 downloads 0 Views 260KB Size
628 RO.

+ HOR e [RO---H---OR] e ROH + .OR

It

intermediate or transition state

[HORln

It [ROHln

We infer that iminoxy radicals form hydrogen bonds more reluctantly than nitroxidesZO(or peroxy radicals21) from the observations that the a N value of 1 in isopentane is within 1 of its value in ethanol and that the visible spectra of 1 in cyclohexane and in ethanol are virtually identical. Substantial changes of these properties in nitroxides have been associated with the formation of hydrogen bond^.^^^^^ Reluctance to form a hydrogen-bonded intermediate probably explains the high activation energy and low rate constant for the 1 1-H reaction. The large value of KeqZ5’for the 1 2c-H system cannot be accounted for on this basis. We believe that it is due mainly to severe intramolecular repulsive interactions (principally Rl-R2 and R2-O) in the oxime 1-H that are lessened by a more relaxed geometry in 1. Evidence supporting this suggestion will be presented later. The present results appear to be relevant to the potential use of stable iminoxy radicals as spin l a b e l ~ ~ ~and .*5 in other studies of local molecular environment. 26-2?8 Acknowledgment. We gratefully acknowledge receipt of a generous sample of di-tert-butylketimine from Dr. H. D . Hartzler (Du Pont).

+

+

(16) J. A. Howard and I