Chemoselective hydrogenation of terpenes with cyclopropane groups

Patent metadata

Field	Value
Publication number	US-12152003-B1
Application number	US-202318128520-A
Country	US
Kind code	B1
Filing date	Mar 30, 2023
Priority date	Mar 31, 2022
Publication date	Nov 26, 2024
Grant date	Nov 26, 2024

Abstract

The present invention provides a novel method for chemoselectively hydrogenating cyclic monoterpene precursors with reduced PtO 2 at low temperatures, to yield products in which the alkene groups are saturated while the cyclopropane rings from the parent hydrocarbons are conserved.

First claim

The invention claimed is:

1. A method for the chemoselective hydrogenation of cycloalkene, comprising
obtaining a cycloalkene having at least one alkene group and at least one cyclopropane group; and,
hydrogenating the cycloalkene with a catalyst;
controlling the degree of hydrogenation through temperature;
wherein the at least one alkene group is saturated and the at least one cyclopropane group is conserved.

2. The method of claim 1 , further comprising purifying the hydrogenated cycloalkene by filtration, washing, and distillation.

3. The method of claim 1 , wherein the cycloalkene is a monoterpene (C10), a sesquiterpene (C15), a diterpene (C20), a heavier oligomer, or combinations thereof.

4. The method of claim 3 , wherein the cycloalkene is sabinene, thujene, 3-carene, 2-carene, thujopsene, or combinations thereof.

5. The method of claim 1 wherein controlling the degree of hydrogenation further comprises catalyst selection.

6. The method of claim 5 , wherein the catalyst is a heterogenous catalyst.

7. The method of claim 5 , wherein the catalyst is a platinum-based hydrogenation catalyst.

8. The method of claim 5 , wherein the catalyst is a Pd-based hydrogenation catalyst.

9. The method of claim 5 , wherein the catalyst is about 0.0001 to about 1 mol %.

10. The method of claim 1 , wherein the hydrogenation is conducted at or below ambient temperature.

11. The method of claim 1 , wherein the hydrogenation is conducted at between about −80° C. to about 50° C.

12. The method of claim 1 , wherein the hydrogenation is conducted at low pressure between about 1 to about 100 psi.

13. The method of claim 1 wherein a carboxylic acid is added as a co-solvent.

14. The method of claim 13 wherein the carboxylic acid as added in about a 1:5 to about a 1:10 ratio of carboxylic acid:cycloalkane.

15. The method of claim 13 wherein the carboxylic acid is acetic acid.

16. A fuel blend comprising jet fuel and the hydrogenated cycloalkene produced by the method of claim 1 .

Assignees

• Us Navy

Inventors

• Harvey Benjamin G
• Woodroffe Joseanne Dee

Classifications

• B01J23/42

  Platinum · CPC title

• C07C2601/18

  with a ring being at least seven-membered · CPC title

• C07C2601/08

  the ring being saturated · CPC title

• C07C5/13

  with simultaneous isomerisation · CPC title

• C07C2602/18

  the ring system containing six carbon atoms · CPC title