Tandem transfer hydrogenation and oligomerization for hydrocarbon production

Patent metadata

Field	Value
Publication number	US-9944572-B2
Application number	US-201715596255-A
Country	US
Kind code	B2
Filing date	May 16, 2017
Priority date	Jan 17, 2013
Publication date	Apr 17, 2018
Grant date	Apr 17, 2018

Abstract

A method for coupling an alkane with an alkene using a hydrogen transfer catalyst and an alkene dimerization catalyst to form one or more higher molecular weight hydrocarbons.

First claim

The invention claimed is:

1. A method of coupling a n-alkane reactant with a n-alkene reactant so as to form one or more branched alkene products in a single tandem process, comprising:
coupling a n-alkane reactant with a n-alkene reactant in the presence of a catalyst comprising: (i) a hydrogen transfer catalyst and (ii) an alkene dimerization catalyst so as to generate one or more branched alkene products, wherein the molecular weight of the one or more branched alkene products is greater than the molecular weight of the n-alkane reactant and greater than the molecular weight of the n-alkene reactant;
wherein the hydrogen transfer catalyst is a pincer complex catalyst, and
wherein the alkene dimerization catalyst is a tantalum catalyst that is selective for the formation of dimer products comprising a structure of Formula II:

wherein,
Z is either 1 or 2;
n is an integer from 1 to 5;
each Y is independently selected from the group consisting of D, H, optionally substituted C 1 -C 6 alkyl, silane, and C 1 -C 4 alkylsilane;
Y 1 is selected from the group consisting of H, D, halo, ═S, ═O, PMe 3 , and ═C(H)(CMe 3 );
Y 2 is selected from the group consisting of H, D, halo, ═S, ═O, and PMe 3 , or Y 2 is absent;
R 2 is selected from the group consisting of H, aryl, optionally substituted C 15 alkyl, and optionally substituted C 1 -C 15 hetero-alkyl; and
R 3 is selected from the group consisting of H, aryl, optionally substituted C 15 alkyl, and optionally substituted C 1 -C 15 hetero-alkyl,
wherein the one or more branched alkene products comprise one or more carbon atoms from both the n-alkane reactant and the n-alkene reactant.

2. The method of claim 1 , wherein the alkene dimerization catalyst comprises a structure of Formula II(a):

wherein,
R 2 is selected from the group consisting of aryl, optionally substituted C 1 -C 15 alkyl, and optionally substituted C 1 -C 15 hetero-alkyl.

3. The method of claim 1 , wherein the hydrogen transfer catalyst is immobilized on a solid support, wherein the coupling is carried out in a solvent, and wherein the method further comprises the step of separating free hydrogen transfer catalyst from the solvent.

4. The method of claim 1 , wherein the n-alkane reactant is a C 5 -C 10 n-alkane.

5. The method of claim 1 , wherein the n-alkene reactant is a C 5 -C 10 n-alkene.

6. The method of claim 1 , wherein the method further comprises hydrogenating or reducing the one or more branched alkene products to produce one or more branched alkane products.

7. A method for coupling a first n-alkane reactant with a second n-alkane reactant to form one or more branched alkene products, comprising:
coupling the first n-alkane reactant with the second n-alkane reactant using styrene as a sacrificial hydrogen acceptor in the presence of a catalyst comprising: (i) a hydrogen transfer catalyst and (ii) an alkene dimerization catalyst so as to generate one or more branched alkene products, wherein the molecular weight of the one or more branched alkene products is greater than the molecular weight of the first n-alkane reactant and greater than the molecular weight of the second n-alkane reactant;
wherein the hydrogen transfer catalyst is a pincer complex catalyst, and
wherein the alkene dimerization catalyst is a tantalum catalyst that is selective for the formation of dimer products comprising a structure of Formula II,

wherein:
Z is either 1 or 2;
n is an integer from 1 to 5;
each Y is independently selected from the group consisting of D, H, optionally substituted C 1 -C 6 alkyl, silane, and C 1 -C 4 alkylsilane;
Y 1 is selected from the group consisting of H, D, halo, ═S, ═O, PMe 3 , and ═C(H)(CMe 3 );
Y 2 is selected from the group consisting of H, D, halo, ═S, ═O, PMe 3 , or Y 2 is absent;
R 2 is selected from the group consisting of H, aryl, optionally substituted C 15 alkyl, and optionally substituted C 1 -C 15 hetero-alkyl; and
R 3 is selected from the group consisting of H, aryl, optionally substituted C 15 alkyl, and optionally substituted C 1 -C 15 hetero-alkyl,
wherein the one or more branched alkene products comprise carbon atoms from both the first n-alkane reactant and the second n-alkane reactant.

8. The method of claim 7 , wherein the alkene dimerization catalyst comprises a structure of Formula II(a):

wherein,
R 2 is a phenyl.

9. The method of claim 7 , wherein the first n-alkane reactant and the second n-alkane reactant are C 5 -C 10 n-alkanes.

10. The method of claim 7 , wherein the method further comprises hydrogenating or reducing the one or more branched alkene products to produce one or more branched alkane products.

11. A method of coupling a n-alkane reactant with a n-alkene reactant so as to form one or more branched alkene products in a single tandem process, comprising:
coupling a n-alkane reactant with a n-alkene reactant in the presence of a catalyst comprising: (i) a hydrogen transfer catalyst and (ii) an alkene dimerization catalyst so as to generate one or more branched alkene products, wherein the molecular weight of the one or more branched alkene products is greater than the molecular weight of the n-alkane reactant and greater than the molecular weight of the n-alkene reactant;
wherein the alkene dimerization catalyst is a tantalum catalyst that is selective for the formation of dimer products, and
wherein the hydrogen transfer catalyst is an iridium pincer complex catalyst comprising the structure of Formula I:

wherein,
each R is independently a H or a C 1 -C 30 hydrocarbyl radical;
each R 1 is independently a C 1 -C 30 hydrocarbyl radical; and
each X is independently an O or CH 2 ,
wherein the one or more branched alkene products comprise one or more carbon atoms from both the n-alkane reactant and the n-alkene reactant.

12. The method of claim 11 , wherein the iridium pincer complex catalyst comprises a structure of Formula I(a):

13. The method of claim 11 , wherein the hydrogen transfer catalyst is immobilized on a solid support, wherein the coupling is carried out in a solvent, and wherein the method further comprises the step of separating free hydrogen transfer catalyst from the solvent.

14. The method of claim 11 , wherein the n-alkane reactant is a C 5 -C 10 n-alkane.

15. The method of claim 11 , wherein the n-alkene reactant is a C 5 -C 10 n-alkene.

16. A method for coupling a first n-alkane reactant with a second n-alkane reactant to form one or more branched alkene products, comprising:
coupling the first n-alkane reactant with the second n-alkane reactant using styrene as a sacrificial hydrogen acceptor in the presence of a catalyst comprising: (i) a hydrogen transfer catalyst and (ii) an alkene dimerization catalyst so as to generate one or more branched alkene products, wherein the molecular weight of the one or more branched alkene products is greater than the molecular weight of the first n-alkane reactant an

Assignees

• California Inst Of Techn

Inventors

• Leitch David
• Labinger Jay A
• Bercaw John E
• Lam Yan Choi

Classifications

• C07C15/12

  Polycyclic non-condensed hydrocarbons · CPC title

• C07C2/58 Primary

  Catalytic processes · CPC title

• C07C2/74 Primary

  by addition with simultaneous hydrogenation · CPC title

• C07C2531/28

  of the platinum group metals, iron group metals or copper · CPC title

• C07C2531/24

  Phosphines · CPC title