Catalytic process for diene dimerization

Patent metadata

Field	Value
Publication number	US-10647631-B2
Application number	US-201615543025-A
Country	US
Kind code	B2
Filing date	Jan 11, 2016
Priority date	Jan 12, 2015
Publication date	May 12, 2020
Grant date	May 12, 2020

Abstract

The disclosure relates to a selective head-to-head dimerization of conjugated diene compounds by a catalytic process in a reaction medium without solvent or with solvent comprising hydrocarbons, in the presence of a specific additive of the phenol type.

First claim

The invention claimed is:

1. A process for the head-to-head dimerization of farnesene, the process comprising contacting the farnesene with a catalyst in the presence of a phenol compound and in the absence of a solvent, wherein said catalyst comprises a ligand selected from triphenyl phosphine, triethyl phosphine and tritolyl phosphine.

2. The process according to claim 1 , wherein the farnesene is beta-farnesene.

3. The process according to claim 1 , wherein the catalyst is a homogeneous catalyst.

4. The process according to claim 1 , wherein the catalyst is a heterogeneous catalyst.

5. The process according to claim 1 , wherein the phenol compound is selected from phenol, dimethylphenol, diethylphenol, mesitylphenol, 2,4,6-trimethylphenol, 2,6-di-tert-butyl-4-methylphenol, dichlorophenol, 2-hydroxybenzotrifluoride, o-methoxyphenol, diphenylphenol, o-cresol, hydroquinone, diisopropylphenol, or diterbutylphenol.

6. The process according to claim 1 , wherein the phenol compound is selected from phenol, dimethylphenol, mesitylphenol or 2,6-di-tert-butyl-4-methylphenol.

7. The process according to claim 1 , wherein the pKa of the phenol compound is higher than or equal to 9.9.

8. The process according to claim 1 , wherein the phenol compound represents from 0.2 to 8% by weight based on the total weight of the reaction medium.

9. The process according to claim 1 , wherein the phenol compound/catalyst molar ratio is lower than or equal to 1000.

10. The process according to claim 1 , wherein the catalyst is selected from palladium catalysts.

11. The process according to claim 1 , wherein the head-to-head dimer obtained represents at least 50% by weight of the reaction products.

12. The process according claim 1 , further comprising a hydrogenation step to obtain hydrogenated dimers.

13. The process according to claim 1 , wherein said catalyst is formed from a palladium precursor selected from [Pd(allyl)Cl] 2 , Pd(cod)Cl 2 , Pd 2 (dba) 3 , Pd(dba) 2 , Pd(dba), Pd(acac) 2 , or an equimolar mixture of Pd(dba) 3 and Pd 2 (dba) 3 .

14. A process for the head-to-head dimerization of myrcene, the process comprising contacting myrcene with a catalyst in the presence of a phenol compound and in the absence of solvent; wherein said catalyst comprises a ligand selected from the group consisting of triphenyl phosphine, triethyl phosphine and tritolyl phosphine.

15. The process according to claim 14 , wherein the phenol compound is selected from phenol, dimethylphenol, diethylphenol, mesitylphenol, 2,4,6-trimethylphenol, 2,6-di-tert-butyl-4-methylphenol, dichlorophenol, 2-hydroxybenzotrifluoride, o-methoxyphenol, diphenylphenol, o-cresol, hydroquinone, diisopropylphenol, or diterbutylphenol.

16. The process according to claim 14 , wherein the phenol compound is selected from phenol, dimethylphenol, mesitylphenol or 2,6-di-tert-butyl-4-methylphenol.

17. The process according to claim 14 , wherein the pKa of the phenol compound is higher than or equal to 9.9.

18. The process according to claim 14 , wherein the phenol compound represents from 0.2 to 8% by weight based on the total weight of the reaction medium.

19. The process according to claim 14 , wherein the phenol compound/catalyst molar ratio is lower than or equal to 1000.

20. The process according to claim 14 , wherein the catalyst is a palladium catalyst.

21. The process according to claim 14 , wherein the process generates reaction products comprising the head-to-head dimerization of myrcene, the head-to-head dimerization of myrcene being at least 50% by weight of the reaction products.

22. The process according claim 14 , further comprising a hydrogenation step, whereby hydrogenated dimers are obtained.

23. The process according to claim 14 , wherein the catalyst is formed from a palladium precursor selected from [Pd(allyl)Cl] 2 , Pd(cod)Cl 2 , Pd2(dba) 3 , Pd(dba) 2 , Pd(dba), Pd(acac) 2 , or an equimolar mixture of Pd(dba) 3 and Pd 2 (dba) 3 .

Assignees

• Total Marketing Services
• Centre Nat Rech Scient
• Univ Claude Bernard Lyon
• Ecole Superieure De Chimie Physique Electronique Lyon
• Total Raffinage Chimie

Inventors

• Rios Neyra Cesar
• Szeto Kai Chung
• Taoufik Mostafa

Classifications

• C07C5/03

  of non-aromatic carbon-to-carbon double bonds · CPC title

• C07C2531/22

  Organic complexes · CPC title

• C07C2521/18

  Carbon · CPC title

• C07C2523/44

  Palladium · CPC title

• C07C2/403 Primary

  Catalytic processes · CPC title