Claims
- 1. A process for the preparation of 2,9-dioxatricyclo[4,3,1,0.sup.3,7 ]decane of the general Formula I: ##STR33## wherein one of R.sub.1 and R.sub.2 is hydrogen and the other is a hydroxy, acyloxy or carbamyloxy or R.sub.1 and R.sub.2 together denote oxygen comprising:
- (a) reacting didrovaltratum or an extract containing didrovaltratum with halogen hydride to obtain 8-hydroxy-3-halomethyl-4-acetoxy-10-methylene-2,9-dioxatricyclo[4,3,1,0.sup.3,7 ]decane;
- (b) oxidizing the product of (a) to give the lactone of said product;
- (c) converting said lactone with hydrogen on palladium/charcoal to give 1-halomethyl-4-methyl-7-acetoxy-2-oxa-bicyclo[3,2,1]oct-3-en-8-carboxylic acid;
- (d) reducing the product of (c) with a metal hydride to give the primary alcohol of said product;
- (e) converting the product of (d) into 10-halo-10-methyl-3-halomethyl-4-acetoxy-2,9-dioxatricyclo[4,3,1,0.sup.3,7 ]decane through oxidative cyclization by means of a halogen in a halogenated hydrocarbon;
- (f) splitting off the halogens with hydrogen on Raney nickel in the presence of a strong base, while simultaneously hydrolyzing the ester to obtain 3,10-dimethyl-4-.beta.-hydroxy-2,9-dioxatricyclo[4,3,1,0.sup.3,7 ]decane; and
- (g) converting the product of (f) into the acyloxy or carbamyloxy compound by treating with a compound selected from the group consisting of carboxylic anhydride, carboxylic acid chloride, alkyl isocyanate and a carbamic acid ester.
- 2. The process of claim 1 wherein didrovaltratum is reacted in step a with halogen hydride in glacial acetic acid.
- 3. The process of claim 1 wherein step a comprises reacting didrovaltratum or an extract containing didrovaltratum with halogen hydride in alcohol followed by the splitting of the ether bond by means of nitric acid in acetic acid.
- 4. The process of claim 3 wherein the ether bond of 4-acetoxy-3-iodomethyl-10-methylene-8-alkoxy-2,9-dioxatricyclo[4,3,1,0.sup.3,7 ]decane is split to obtain the 8-hydroxy compound.
- 5. The process of claim 1 wherein step b comprises oxidizing the product of step a with chromic acid to give said lactone.
- 6. The process of claim 1 wherein the product oxidized in step b is 4-acetoxy-8-hydroxy-3-iodomethyl-10-methylene-2,9-dioxatricyclo[4,3,1,0.sup.3,7 ]decane.
- 7. The process of claim 1 wherein the lactone converted in step c is 4-acetoxy-3-iodomethyl-10-methylene-8-oxo-2,9-dioxatricyclo[4,3,1,0.sup.3,7 ]decane.
- 8. The process of claim 1 wherein the product reduced in step d is 1-iodomethyl-4-methyl-7-acetoxy-2-oxa-bicyclo[3,2,1]oct-3-en-8-carboxylic acid.
- 9. The process of claim 1 wherein the product converted in step e is 1-iodomethyl-4-methyl-7-acetoxy-8-hydroxymethyl-2-oxa-bicyclo[3,2,1]oct-3-ene (Formula V).
- 10. The process of claim 1 wherein the product from which halogens are split off in step f is the 4-acetoxy-3-iodomethyl-10-methyl-10-halo-2,9-dioxatricyclo[4,3,1,0.sup.3,7 ]decanes of the general Formula VI, in which X is iodine or bromine.
- 11. The process of claim 1 wherein step f includes oxidation of the 4-hydroxy group of 3,10-dimethyl-4.beta.-hydroxy-2,9-dioxatricyclo[4,3,1,0.sup.3,7 ]decane into 3,10-dimethyl-2,9-dioxatricyclo[4,3,1,0.sup.3,7 ]decan-4-one followed by reduction of said decanone with a metal hydride to give 3,10-dimethyl-4-.alpha.-hydroxy-2,9-dioxatricyclo[4,3,1,0.sup.3,7 ]decane.
Priority Claims (1)
Number |
Date |
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2547205 |
Oct 1975 |
DEX |
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Parent Case Info
This application is a division of application of Ser. No. 884,854, filed Mar. 9, 1978, now U.S. Pat. No. 4,189,437, which is a division of Ser. No. 732,791, filed Oct. 15, 1976, now U.S. Pat. No. 4,089,971.
US Referenced Citations (9)
Foreign Referenced Citations (1)
Number |
Date |
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759840 |
May 1971 |
BEX |
Divisions (2)
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Number |
Date |
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Parent |
884854 |
Mar 1978 |
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Parent |
732791 |
Oct 1976 |
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