| dc.contributor.author |
McNeely, Kenneth H. |
en |
| dc.date.accessioned |
2009-04-17T16:01:51Z |
|
| dc.date.available |
2009-04-17T16:01:51Z |
|
| dc.date.created |
1960 |
en |
| dc.date.issued |
2009-04-17T16:01:51Z |
|
| dc.identifier.citation |
Source: Dissertation Abstracts International, Volume: 68-07, Section: B, page: 4472. |
en |
| dc.identifier.uri |
http://hdl.handle.net/10393/10778 |
|
| dc.description.abstract |
Woodward's synthesis of sempervirine has been used to prepare 18-methoxysempervirine and 18-benzyloxysempervirine. In each case, the appropriate 4-alkoxyxyxlohexanone was condensed with ethylformate in the presence of sodium methoxide, and then with 2-iodopropane in acetone solution containing potassium carbonate. The resulting 2-isopropoxymethylene-4-alkoxyxyxlohexanone was reacted with the di-lithium salt of harman to give, after acid hydrolysis, the sempervivrine derivative. Attempts to demethylate the methoxysempervirvine or its reduction product 18-methoxyalloyohimbane were unsuccessful. Hydrogenolysis of 18-benzyloxysempervirine in the presence of palladium gave 18-hydroxysempervirine, which on further reduction with Adams' catalyst gave 18-hydroxyalloyohimbane. The sterochemistry of the hydroxyl group was shown in two different ways. The alcohol was oxidized to alloyohimbane-18-one, and the reduction of the ketone with lithium tri tertiary-butoxyaluminum hydride returned the original alcohol. This reducing agent is known to give almost entirely the equatorial isomer. The nuclear magnetic resonsance spectrum of the acetate prepared from the 18-hydroxyalloyohimbane showed that the acetoxy group, and therefore the original hydroxyl group was equatorial. The compound was therefore 18-beta-hydroxyalloyohimbane. The oxidation of 18-beta-hydroxyalloyohimbane with mercuric acetate gave 3-dehydro-18-beta-hydroxyalloyohimbane (isolated as a perchlorate salt) and reduction of thos with zinc and aqueous acetic acid gave 18-hydroxyepialloyohimbane. The sterochemical assignment of this compound was confirmed by the nuclear magnetic spectrum of its' acetate. The 3,4,5-trimethoxybenzoate of 18-beta-epialloyohimbane was prepared for pharmacological testing. |
en |
| dc.format.extent |
113 p. |
en |
| dc.publisher |
University of Ottawa (Canada). |
en |
| dc.subject.classification |
Chemistry, Inorganic. |
en |
| dc.title |
Synthetic compounds related to reserpine. |
en |
| dc.type |
Ph.D.Thesis (Ph.D.)--University of Ottawa (Canada), 1960. |
en |
