Olefin hydroboration

Patent metadata

Field	Value
Publication number	US-9944661-B2
Application number	US-201615232442-A
Country	US
Kind code	B2
Filing date	Aug 9, 2016
Priority date	Aug 9, 2016
Publication date	Apr 17, 2018
Grant date	Apr 17, 2018

Abstract

A process comprising contacting a) an alkene, b) a hydrogen-boron bond containing compound, c) an α-diimine metal salt complex comprising an α-diimine iron salt complex or an α-diimine cobalt salt complex, and d) a group 1 metal borohydride under conditions suitable to form an alkylboron compound. A process comprising contacting a) an alkene, b) a hydrogen-boron bond containing compound, and c) an α-diimine metal salt complex comprising an α-diimine iron methylenetrihydrocarbylsilyl complex or an α-diimine cobalt methylenetrihydrocarbylsilyl complex, to form an alkyl-boron compound under conditions suitable to form an alkylboron compound. A process comprising contacting an alkene, a hydrogen-boron bond containing compound, and an α-diimine metal salt complex to form an alkyl-boron compound under conditions suitable to form an alkylboron compound.

First claim

What is claimed:

1. A process comprising contacting:
a) a linear internal alkene,
b) a hydrogen-boron bond containing compound,
c) an α-diimine metal salt complex comprising an α-diimine iron salt complex or an α-diimine cobalt salt complex, and
d) a group 1 metal borohydride to form a linear terminal alkylboron compound under conditions suitable to form the linear terminal alkylboron compound.

2. The process of claim 1 , wherein the α-diimine metal salt complex is an α-diimine iron halide complex or an α-diimine cobalt halide complex.

3. The process of claim 1 , wherein the α-diimine comprises:
i) an α-diimine group,
ii) a first imine nitrogen group comprising a C 1 to C 30 hydrocarbyl group attached to a first imine nitrogen atom of the α-diimine group, and
iii) a second imine nitrogen group comprising:
(1) a metal complexing group, and
(2) a linking group linking the metal complexing group to a second imine nitrogen atom of the α-diimine group.

4. The process of claim 1 , wherein the α-diimine metal salt complex has the structure

wherein
R 1 is a C 1 to C 30 hydrocarbyl group,
R 2 and R 3 independently are C 1 to C 30 hydrocarbyl groups and optionally R 2 and R 3 can be joined to form a ring or ring system,
L is a C 1 to C 10 hydrocarbylene group,
R 4 and R 5 independently are C 6 to C 30 aryl groups,
each X is a halide, and
p is 2 or 3.

5. The process of claim 1 , wherein a cobalt to boron molar ratio ranges from 0.001:1 to 0.05:1.

6. The process of claim 1 , wherein the linear terminal alkylboron compound is formed at a temperature of from 15 ° C. to 30° C.

7. The process of claim 1 , wherein the hydrogen-boron bond containing compound comprises borane, diborane, a borane-amine complex, a borane-phosphine complex, a borane-phosphite complex, a borane-ether complex, a borane-sulfide complex, a hydrogen borinic acid ester, a hydrogen boronic acid ester, a hydrogen monoaminoborane, a hydrogen diaminoborane, a hydrogen azaborolidine, a hydrogen diazaborlidine, or any combination thereof.

8. The process of claim 1 , wherein the hydrogen-boron bond containing compound comprises a hydrogen borinic acid ester, a hydrogen boronic acid ester, or combinations thereof.

9. The process of claim 1 , wherein the α-diimine metal salt complex comprises an α-diimine iron methylenetrihydrocarbylsilyl complex or an α-diimine cobalt methylenetrihydrocarbylsilyl complex.

10. The process of claim 9 , wherein the α-diimine comprises:
i) an α-diimine group,
ii) a first imine nitrogen group comprising a C 1 to C 30 hydrocarbyl group attached to a first imine nitrogen atom of the α-diimine group, and
iii) a second imine nitrogen group comprising:
(1) a metal complexing group, and
(2) a linking group linking the metal complexing group to a second imine nitrogen atom of the α-diimine group.

11. The process of claim 9 , wherein the α-diimine cobalt methylenetrihydrocarbylsilyl complex has the structure:

wherein
R 1 is a C 1 to C 30 hydrocarbyl group,
R 2 and R 3 independently are C 1 to C 30 hydrocarbyl groups and optionally R 2 and R 3 can be joined to form a ring or ring system,
L is a C 1 to C 10 hydrocarbylene group,
R 4 and R 5 independently are C 6 to C 30 aryl groups, and
each R 11 independently is a C 1 to C 5 hydrocarbyl group.

12. The process of claim 9 wherein a cobalt to boron molar ratio ranges from 0.001:1 to 0.05:1.

13. The process of claim 9 , wherein the linear terminal alkylboron compound is formed at a temperature of from 15 ° C. to 30 ° C.

14. The process of claim 9 , wherein the hydrogen-boron bond containing compound comprises horane, diborane, a borane-amine complex, a borane-phosphine complex, a borane-phosphite complex, a borane-ether complex, a borane-sulfide complex, a hydrogen borinic acid ester, a hydrogen boronic acid ester, a hydrogen monoaminoborane, a hydrogen diaminoborane, a hydrogen azaborolidine, a hydrogen diazaborlidine, or any combination thereof.

15. The process of claim 9 , wherein the hydrogen-boron bond containing compound comprises a hydrogen borinic acid ester, a hydrogen boronic acid ester, or combinations thereof.

16. The process of claim 1 , wherein the α-diimine comprises:
i) an α-diimine group derived from a C 4 to C 60 α-dione,
ii) a first imine nitrogen group comprising a C 1 to C 30 hydrocarbyl group attached to a first imine nitrogen atom of the α-diimine group, and
iii) a second imine nitrogen group comprising:
(1) a metal complexing group, and
(2) a linking group linking the metal complexing group to a second imine nitrogen atom of the α-diimine group.

17. The process of claim 9 , wherein the α-diimine comprises:
i) an α-diimine group derived from a C 4 to C 60 α-dione,
ii) a first imine nitrogen group comprising a C 1 to C 30 hydrocarbyl group attached to a first imine nitrogen atom of the α-diimine group, and
iii) a second imine nitrogen group comprising:
(1) a metal complexing group, and
(2) a linking group linking the metal complexing group to a second imine nitrogen atom of the α-diimine group.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Small Brooke L
• Schaefer Brian A
• Chirik Paul J

Classifications

• C07C1/321

  the hetero-atom being a non-metal atom · CPC title

• C07F5/027 Primary

  Organoboranes and organoborohydrides · CPC title

• B01J31/2295

  Cyclic compounds, e.g. cyclopentadienyls · CPC title

• B01J31/226

  Sulfur, e.g. thiocarbamates · CPC title

• B01J31/182

  comprising aliphatic or saturated rings · CPC title