Process for preparing palladium complexes

Patent metadata

Field	Value
Publication number	US-10808000-B2
Application number	US-201716342309-A
Country	US
Kind code	B2
Filing date	Sep 21, 2017
Priority date	Oct 21, 2016
Publication date	Oct 20, 2020
Grant date	Oct 20, 2020

Abstract

The present invention provides a process for the preparation of a complex of formula (I): comprising the step of reacting Pd(diolefin)X2 or PdX2 and PR1R2R3 in a solvent to form the complex of formula (I), wherein the process is carried out in the absence of a base, the molar ratio of Pd(diolefin)X2:PR1R2R3 or PdX2:PR1R2R3 is greater than 1:1.1, up to about 1:2.5; each X is independently a halide; and R1, R2 and R3 are independently selected from the group consisting of tert-butyl and isopropyl.

First claim

The invention claimed is:

1. A process for preparing a complex of formula (I):

comprising the step of reacting Pd(diolefin)X 2 or PdX 2 and PR 1 R 2 R 3 in a solvent to form the complex of formula (I), wherein:
the process is carried out in the absence of a base,
the molar ratio of Pd(diolefin)X 2 :PR 1 R 2 R 3 or PdX 2 :PR 1 R 2 R 3 is in a range of from greater than 1:1.1 to about 1:2.5;
each X is independently a halide; and
R 1 , R 2 and R 3 are, independently, tert-butyl or iso-propyl.

2. The process of claim 1 , wherein the diolefin is a cyclic diolefin or two molecules of a monoolefin.

3. The process of claim 1 , wherein the solvent is a C 6-10 aromatic hydrocarbon.

4. The process of claim 1 , wherein the molar ratio of Pd(diolefin)X 2 :PR 1 R 2 R 3 or PdX 2 :PR 1 R 2 R 3 is about 1:1.5.

5. The process of claim 1 , further comprising the step of preparing a complex of formula (I′):

by independently exchanging one or more of X for X′,
wherein each X′ is a halide which is different than the corresponding group X in the complex of formula (I).

6. A process for preparing a complex of formula (I), comprising the step of reacting a compound of formula (II):

(a) with an alkali hydroxide; or
(b) with [PR 1 R 2 R 3 ] 2 Pd,

in a solvent to form the complex of formula (I), wherein
each X is independently a halide; and
R 1 , R 2 and R 3 are, independently, tert-butyl or iso-propyl.

7. The process of claim 6 , wherein the solvent is a straight-chain, branched or cyclic C 1-10 alkanol, a C 6-10 aromatic hydrocarbon, or a combination thereof.

8. The process of claim 6 , wherein the alkali hydroxide is potassium hydroxide or sodium hydroxide.

9. The process of claim 6 , wherein the molar ratio of the compound of formula (II): alkali hydroxide is about 1:3.

10. The process of claim 6 , wherein the molar ratio of the compound of formula (II): [PR 1 R 2 R 3 ] 2 Pd is about 1:2.

11. A compound of formula (II):

wherein:
each X is independently a halide, and
R 1 , R 2 and R 3 are, independently, tert-butyl or iso-propyl.

12. A process for preparing a compound of formula (II):

comprising the step of reacting Pd(diolefin)X 2 or PdX 2 with [X][XPR 1 R 2 R 3 ] in a solvent to form the complex of formula (II), wherein:
each X is independently a halide; and
R 1 , R 2 and R 3 are, independently, tert-butyl or iso-propyl.

13. The process of claim 12 , wherein the diolefin is a cyclic diolefin or two molecules of a monoolefin.

14. The process of claim 12 , wherein the solvent is a C 6-10 aromatic hydrocarbon, a C 2-10 ether, or a combination thereof.

15. The process of claim 14 , wherein the solvent is xylene, toluene, benzene, tetrahydrofuran, dioxane, or a combination thereof.

16. The process of claim 12 , wherein [X][XPR 1 R 2 R 3 ] is prepared by reacting PR 1 R 2 R 3 with X 2 in a solvent to form [X][XPR 1 R 2 R 3 ].

17. A process for preparing [PR 1 R 2 R 3 ] 2 Pd, comprising the step of reacting Pd(diolefin)X 2 or PdX 2 and PR 1 R 2 R 3 in a solvent, wherein:
the process is carried out in the absence of a base,
the molar ratio of Pd(diolefin)X 2 :PR 1 R 2 R 3 or PdX 2 :PR 1 R 2 R 3 is at least 1:3, and wherein:
each X is independently a halide; and
R 1 , R 2 and R 3 are, independently, tert-butyl or iso-propyl.

18. The process of claim 17 , wherein the diolefin is a cyclic diolefin or two molecules of a monoolefin.

19. The process of claim 17 , wherein the solvent is a C 6-10 aromatic hydrocarbon.

20. The process of claim 17 , wherein the molar ratio of Pd(diolefin)X 2 :PR 1 R 2 R 3 or PdX 2 :PR 1 R 2 R 3 is about 1:4.

Assignees

• Johnson Matthey Plc

Inventors

• Carole William
• Colacot Thomas
• Seechurn Carin
• Scrase Thomas

Classifications

• C07F9/52

  Halophosphines · CPC title

• C07F15/0066 Primary

  without a metal-carbon linkage · CPC title