Efficient catalyst for the formation of polyaryl hydrocarbons suitable as precursors for polydentate organophosphorus catalyst ligands

Patent metadata

Field	Value
Publication number	US-9975833-B2
Application number	US-201615253316-A
Country	US
Kind code	B2
Filing date	Aug 31, 2016
Priority date	Aug 31, 2016
Publication date	May 22, 2018
Grant date	May 22, 2018

Abstract

The disclosure relates to the efficient preparation of aromatic hydrocarbons useful as intermediates for di-, tri-, tetra- and poly-dentate organophosphorus ligands having value in particular as hydroformylation catalysts. The use of triarylphosphine halide catalysts have been found to be more efficient in forming these intermediates by the use of excess triarylphosphine in an amount beyond what is required to form a coordination complex.

First claim

I claim:

1. A method of preparing aromatic hydrocarbons for use as precursors for catalyst ligands, the method comprising:
providing a nickel based catalyst solution;
providing a polyhalogenated aromatic hydrocarbon comprising at least two reactive halogen groups on its ring;
combining the nickel based catalyst solution and polyhalogentated aromatic hydrocarbon to form a mixture; and
adding a Grignard reactant to the mixture to form an aromatic hydrocarbon as a precursor for the preparation of catalyst ligands, wherein the nickel based catalyst solution is prepared by the reaction of a nickel source with a triarylphosphine and the yield of aromatic hydrocarbon is 84% or higher
wherein the method is illustrated by the following general reaction:

wherein,
R=CH3; aryl; alkylaryl; alkyl; alkyl or aryl ether; H; thioether, or perfluoroalkyl
R′=CH3; aryl; alkylaryl; alkyl; alkyl or aryl ether; H; thioether, or perfluoroalkyl
X=reactive halogen groups
R′″=R, R′ and/or X
n=0 to 4
P=Phosphorous atom
Aryl3P=Triarylphosphine
Ar=Grignard aromatic moiety
/=and/or
Halo2=chloride or bromide
nickel source=(TPP)2Ni(II)X2; or anhydrous Ni (II) chloride or bromide
TPP=triphenylphosphine.

2. The method of claim 1 wherein the triarylphosphine is triphenylphosphine.

3. The method of claim 1 , wherein a mole ratio of triarylphosphine/Ni is comprised of a range from about 2.2/1 up to about 100/1.

4. The method of claim 1 , wherein the mole ratio of triarylphosphine/Ni is comprised of a range from about 10/1 up to about 100/1.

5. The method of claim 1 , wherein the mole ratio of triarylphosphine/Ni is about 5/1 up to about 10/1.

6. The method of claim 1 , wherein the triarylphosphine is tri(orthotolyl)phosphine, tri(p-methylphenyl)phosphine, diphenyl(o-tolyl)phosphine, diphenyl(p-methylphenyl)phosphine, or di-o-tolylyl(phenyl)phosphine.

7. The method of claim 1 , further comprising adding coupling co-solvent to the mixture of the nickel based catalyst solution and polyhalogentated aromatic hydrocarbon to facilitate coupling of the mixture with the Grignard reactant.

8. The method of claim 7 , wherein the coupling co-solvent is diethyl ether.

9. The method of claim 7 , wherein the coupling co-solvent is tetrahydrofurane.

10. The method of claim 1 , wherein the Grignard reactant is prepared by reacting a bromo or chloro aromatic hydrocarbon with magnesium metal in a solvent.

11. The method of claim 10 , wherein the solvent comprises diethyl ether, tetrahydrofurane, di-n-propyl ether, di-n-butyl ether or 1,4-dioxane.

12. The method of claim 1 , wherein the mole ratio of Ni/Grignard aromatic moiety is comprised of a range from about 1/10 up to about 1/1000.

13. The method of claim 12 , wherein the mole ratio of Ni/Grignard aromatic moiety is comprised of a range from about 1/100 up to about 1/200.

14. The method of claim 1 , wherein the Grignard reactant is added to the mixture in an anaerobic environment free of moisture.

15. The method of claim 1 , wherein the Grignard reactant is added to the mixture in a temperature range of from about 0 degrees Celsius to about 100 degrees Celsius.

16. The method of claim 15 , wherein the Grignard reactant is added to the mixture in a temperature range of from about 25 degrees Celsius to about 65 degrees Celsius.

17. The method of claim 1 , illustrated by the following specific reaction:

18. The method of claim 1 , illustrated by the following specific reaction:

19. The method of claim 1 , illustrated by the following specific reaction:

20. The method of claim 1 , illustrated by the following specific reaction:

21. The method of claim 1 , illustrated by the following specific reaction:

22. The method of claim 1 , illustrated by the following specific reaction:

23. The method of claim 1 , illustrated by the following specific reaction:

Assignees

• Eastman Chem Co

Inventors

• Devon Thomas James

Classifications

• C07C1/326

  the hetero-atom being a magnesium atom · CPC title

• C07C2531/22

  Organic complexes · CPC title

• C07C41/30 Primary

  by increasing the number of carbon atoms, e.g. by oligomerisation · CPC title

• C07C2523/755

  Nickel · CPC title