Preparation of ketone containing cyclic compounds
View Patent ↗A method of preparing a polycyclic compound containing a ketone functionality comprising: reacting a mixture comprising a catalyst, a reactant compound and an amount of water greater than or equal to 3 weight percent (wt %) based on the weight of the reactant compound; wherein said catalyst comprises nickel and base and said reactant compound comprises at least two fused rings, A and B wherein ring A is a saturated ring or ring system having 5 to 7 cyclic carbons and substituted with a hydroxyl functionality and ring B is a non-aromatic unsaturated ring having 5 to 6 cyclic carbons; and converting the hydroxyl functionality of ring A to a ketone functionality and non-aromatic unsaturated ring B to a saturated ring.
1. A method of preparing a polycyclic compound containing a ketone functionality comprising:
reacting a mixture comprising a catalyst, a reactant compound and an amount of water greater than or equal to 3 weight percent based on the weight of the reactant compound; wherein said catalyst comprises nickel and base and said reactant compound comprises at least two fused rings, A and B wherein ring A is a saturated ring or ring system having 5 to 7 cyclic carbons and substituted with a hydroxyl functionality and ring B is a non-aromatic unsaturated ring having 5 to 6 cyclic carbons; and
converting the hydroxyl functionality of ring A to a ketone functionality and the non-aromatic unsaturated ring B to a saturated ring.
2. The method of claim 1 , wherein Ring A is a bicyclo ring system containing 7 cyclic carbons.
3. The method of claim 1 , wherein Ring A and Ring B together from a bicyclo ring system.
4. The method of claim 1 , wherein the method further comprises addition of hydrogen gas or hydrogen-containing gaseous mixture.
5. A method of claim 4 , wherein said hydrogen-containing gaseous mixture comprises nitrogen, ambient air, helium, argon or a combination of two or more of the foregoing.
6. The method of claim 1 wherein the mixture further comprises a solvent miscible with the reactant compound.
7. The method of claim 1 wherein ring A is substituted with one or more alkyl substituents having up to 4 carbons.
8. The method of claim 1 wherein ring B is substituted with one or more alkyl substituents having up to 4 carbons.
9. The method of claim 1 , wherein the reactant compound is selected from the group consisting of compounds of the formula:
10. A method of claim 1 , wherein the polycyclic cyclic compound containing a ketone functionality is selected from the group consisting of:
11. The method of claim 1 , wherein said catalyst comprising nickel is selected from the group consisting of Raney nickel, supported nickel catalysts, Ponder nickel catalysts, and nickel alloys.
12. The method of claim 11 , wherein said supported nickel catalyst is selected from the group consisting of nickel on silica and nickel/magnesium oxide supported on silica.
13. The method of claim 11 , wherein said nickel alloy is selected from the group consisting of aluminum-nickel alloy, nickel-vanadium alloy, magnesium-nickel alloy and copper-nickel alloy.
14. The method of claim 1 , wherein said catalyst comprising nickel is Raney nickel.
15. The method of claim 14 , wherein said catalyst is recycled.
16. The method of claim 1 , wherein said catalyst comprising nickel is nickel/magnesium oxide supported on silica wherein, the ratio of nickel to magnesium oxide is about 0.1:1 to about 0.5:1.
17. The method of claim 1 , wherein the amount of water is about 3% to about 10% based on the weight of said reactant compound on dry basis.
18. The method of claim 1 , wherein the reaction occurs at a temperature of about 170° C. to about 300° C.
19. The method of claim 1 , wherein said method is carried out in a batch mode.
20. The method of claim 19 , wherein said batch mode is carried out for about 1.5 to about 4 hours.
21. The method of claim 1 , wherein said method is carried out in a continuous mode.
22. The method of claim 21 , wherein said continuous mode is carried out at a weighted hourly space velocity of about 0.5 to about 2.0.
23. The method of claim 1 , wherein the catalyst is recycled.
24. A method of preparing a polycyclic compound containing a ketone functionality comprising:
reacting a mixture comprising a catalyst, a reactant compound and an amount of water greater than or equal to 3 weight percent based on the weight of the reactant compound; wherein said catalyst comprises water and base and said reactant compound comprises two fused rings, A and B wherein ring A is a saturated ring system having 5 cyclic carbons and substituted with a hydroxyl functionality and ring B is a non-aromatic unsaturated ring having 5 cyclic carbons; and
converting the hydroxyl functionality of ring A to a ketone functionality and the non-aromatic unsaturated ring B to a saturated ring.
25. A method of claim 24 wherein the reactant compound is
and the polycyclic compound containing a ketone functionality is,