Record Details
Dihalocarbene reactions with steroid olefins
ScholarsArchive at Oregon State University
| Field | Value |
|---|---|
| Title | Dihalocarbene reactions with steroid olefins |
| Names |
Cornelia, Richard Hartman
(creator) Bond, F. Thomas (advisor) |
| Date Issued | 1968-03-29 (iso8601) |
| Note | Graduation date: 1968 |
| Abstract | Dihalocarbenes have been generated mainly by thermal decomposition of sodium trihaloacetate and phenyl (trihalomethyl)mercury, and give gem-dihalocyclopropyl adducts with various steroid olefins. A new procedure involving the use of sealed tubes makes possible the addition of dihalocarbenes to sterically hindered olefins. In this manner, 7-cholestenyl benzoate when treated with PhHgCC1₃ furnished a 50% yield of the 7α, 8α adduct. Under forcing conditions cholesteryl benzoate was found to undergo an insertion reaction with dichloro- and dibromocarbene to produce 7α-dihalomethyl-5-cholesteryl benzoate. This represents a stereospecific dihalocarbene reaction. Dichlorocarbene was found to add, however, to isolated 5, 6 olefins of increased nucleophilicity such as 6-methylcholesteryl acetate. The stereochemistry of the various dihalocyclopropyl adducts has been demonstrated by correlation with compounds of known configuration prepared via stereospecific Simmons -Smith reactions. Both 5α, 6α and 5β, 6β cyclopropyl analogs of cholesterol have been prepared along with other small, strained ring steroids. |
| Genre | Thesis/Dissertation |
| Topic | Steroids |
| Identifier | http://hdl.handle.net/1957/46587 |
