Cyclopropanation of substituted alkenes

Patent metadata

Field	Value
Publication number	US-10584080-B2
Application number	US-201916264818-A
Country	US
Kind code	B2
Filing date	Feb 1, 2019
Priority date	Dec 12, 2017
Publication date	Mar 10, 2020
Grant date	Mar 10, 2020

Abstract

Disclosed is a cyclopropanation process comprising the step of reacting an alkene compound having at least one carbon-carbon double bond with at least one dihaloalkane. The reaction is carried out in the presence of (i) particulate metal Zn, (ii) catalytically effective amount of particulate metal Cu or a salt thereof, (iii) at least one haloalkylsilane, and (iv) at least one solvent.

First claim

What is claimed is:

1. A cyclopropanation process comprising the step of reacting an alkene compound having at least one carbon-carbon double bond with at least one dihaloalkane in the presence of (i) particulate metal Zn, (ii) catalytically effective amount of particulate metal Cu, (iii) at least one haloalkylsilane, and (iv) at least one solvent; thereby producing a cyclopropane derivative of said compound, wherein said at least one dihaloalkane is chlorobromomethane.

2. The cyclopropanation process according to claim 1 , wherein said alkene compound has at least two carbon-carbon double bonds.

3. The cyclopropanation process according to claim 1 , wherein said particulate metal Zn has particle size of less than 10 μm.

4. The cyclopropanation process according to claim 1 , wherein said particulate metal Cu has particle size of less than 50 μm.

5. The cyclopropanation process according to claim 1 , wherein said haloalkylsilane is chlorotrialkyl silane.

6. The cyclopropanation process according to claim 5 , wherein said chlorotrialkyl silane is selected from the group consisting of chlorotrimethylsilane, chlorotriethylsilane, chlorotributylsilane, chlorotriisobutylsilane, chlorotrihexylsilane, and any combinations thereof.

7. The cyclopropanation process according to claim 1 , wherein said at least one solvent is an ether solvent.

8. The cyclopropanation process according to claim 7 , wherein said at least one ether solvent is selected from diethyl ether, 1,2-dimethoxyethane (DME), methyl tert-butyl ether, (MTBE), tetrahydrofuran (THF), cyclopentyl methyl ether (CPME) and any combinations thereof.

9. The cyclopropanation process according to claim 7 , wherein said at least one solvent further comprises dichloromethane.

10. The cyclopropanation process according to claim 9 , wherein said solvent is a mixture of cyclopentyl methyl ether and dichloromethane having a ratio of between 1:5 to 10:1.

11. The cyclopropanation process according to claim 1 , wherein when said alkene compound comprises one double bond, said particulate metal Zn is added in an amount of 1-10 molar equivalents relative to said alkene compound.

12. The cyclopropanation process according to claim 1 , wherein said particulate metal Cu is presented in an amount of 0.1 to 1 wt % of said particulate metal Zn.

13. The cyclopropanation process according to claim 1 , having a yield of between about 50% to about 95%.

14. A method of manufacturing a flavor or fragrance ingredient, comprising the cyclopropanation process according to claim 1 .

Assignees

• Int Flavors & Fragrances Inc

Inventors

• Gara Mohamad
• Becker Yigal

Classifications

• A23L27/203

  Alicyclic compounds · CPC title

• C07C45/69

  by addition to carbon-to-carbon double or triple bonds · CPC title

• C11B9/003

  the ring containing less than six carbon atoms · CPC title

• B01J23/80

  with zinc, cadmium or mercury · CPC title

• C11B9/0057

  Spiro compounds · CPC title