Stable ligand mixtures and processes for making same

Patent metadata

Field	Value
Publication number	US-9834505-B2
Application number	US-201314404068-A
Country	US
Kind code	B2
Filing date	May 24, 2013
Priority date	Jun 1, 2012
Publication date	Dec 5, 2017
Grant date	Dec 5, 2017

Abstract

A process of stabilizing a bidentate or tridentate phosphorus-based phosphite ester ligand or mixture thereof in a hydrocyanation reaction milieu comprising water, wherein the ligand or ligand mixture comprises one or more of (i) a bidentate biphosphite ligand of formula (III), (R 12 —X 12 ) (R 13 —X 13 ) P—X 14 —Y—X 24 —P(X 22 —R 22 ) (X 23 —R 23 ) or (ii) a tridentate triphosphite ligand of formula (IIIA) (R 12 —X 12 ) (R 13 —X 13 ) P—X 14 —Y—X 32 —P(X 34 —R 34 )—(X 33 —Y 2 —R 24 —P(X 23 —R 23 )—(X 22 —R 22 ) where each X is oxygen or a bond and each Y is an optionally substituted C6-C20 arylene group, comprising admixing the bidentate and/or tridentate with a stabilizing amount of one or more monodentate phosphite ligand of formula P(X 1 —R 1 )(X 2 —R 2 )(X 3 —R 3 ) where each X is oxygen or a bond, wherein the monodentate ligand has a rate of hydrolysis greater than the rate of hydrolysis of the bidentate or tridentate ligand in the presence of water in a hydrocyanation reaction milieu, and thereby preserve concentrations and proportions of the bidentate and/or tridentate ligand(s) in the ligand blend.

First claim

What is claimed is:

1. A process for stabilizing a phosphorus-based bidentate ligand of formula (III) or tridentate ligand of formula (IIIA) or a mixture thereof, in a hydrocyanation reaction milieu comprising at least 2500 ppm of water, the ligands having respective formulas:
a bidentate phosphorus-based ligand of formula (III)

 or,
a tridentate phosphorus-based ligand of formula (IIIA)

wherein for the ligand of formula (III), X 12 , X 13 , X 14 , X 22 , X 23 , and X 24 , each independently is oxygen or a bond, provided that at least one of X 12 , X 13 , X 14 , X 22 , X 23 , or X 24 is oxygen, and for the ligand of formula (IIIA), X 12 , X 13 , X 14 , X 22 , X 23 , X 24 , X 32 , X 33 , and X 34 , each independently is oxygen or a bond, provided that at least one of X 12 , X 13 , X 14 , X 22 , X 23 , X 24 , X 32 , X 33 , or X 34 is oxygen;
for the ligand of formula (III), R 12 , R 13 , R 22 , and R 23 , and for the ligand of formula (IIIA), R 12 , R 13 , R 22 , R 23 , and R 34 , each independently is (C1-C10)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(C1-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(C1-C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(C1-C10)alkyl of R 12 , R 13 , R 22 , R 23 , or R 34 , each ring thereof is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, (C6-C20)aryl, and (C6-C20)aryl(C1-C10)alkyl;

or, optionally, one or more of pairs R 12 and R 13 or R 22 and R 23 are mutually directly bonded, such that the R 12 X 12 and R 13 X 13 groups, or the R 22 X 22 and R 23 X 23 groups, or both together with the respective phosphorus atom to which each pair of groups is bonded, forms a respective ring;
for the ligand of formula (III) the group Y, and for the ligand of formula (IIIA), the groups Y 1 and Y 2 independently, is an (C6-C20)arylene group, wherein each ring thereof is independently unsubstituted or is independently substituted with 1-4 (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, (C6-C20)aryl, (C6-C20)aryl(C1-C10)alkyl, fluorine, chlorine, bromine, or (C1-C10)haloalkyl;
the process comprising admixing with the bidentate and/or the tridentate ligand a stabilizing amount of one or more monodentate phosphorus-based ligand of formula (IV)
P(X 1 R 1 )(X 2 R 2 )(X 3 R 3 )  (IV)

wherein X 1 , X 2 and X 3 are each independently oxygen or a single bond, provided that at least one of X 1 , X 2 , or X 3 is an oxygen; and R 1 , R 2 and R 3 is each independently (C1-C10)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(C1-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(C1-C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(C1-C10)alkyl of R 1 , R 2 , or R 3 each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, (C6-C20)aryl, and (C6-C20)aryl(C1-C10)alkyl; or, optionally, any two of R 1 , R 2 , or R 3 are directly bonded to each other such that any pair of R 1 X 1 , R 2 X 2 , and R 3 X 3 groups, together with the phosphorus atom to which they are bonded, forms a ring;
wherein a molar ratio of the ligand of formula (IV) that is admixed to the ligand of formula (III) or formula (IIIA) or mixture thereof, is at least 0.01:1;
wherein the monodentate ligand of formula (IV) has a rate of hydrolysis greater than a rate of hydrolysis of a bidentate ligand of formula (III) or a tridentate ligand of formula (IIIA) or a mixture thereof, in the presence of water in a hydrocyanation reaction milieu optionally further comprising an organic component, under conditions of concentration, temperature, and time sufficient to bring about hydrolysis of the monodentate ligand of formula (IV).

2. The process of claim 1 , wherein the one or more monodentate ligand of formula (IV) is produced as a byproduct in a synthetic process for the production of the bidentate ligand of Formula (III) or the tridentate ligand of formula (IIIA) or both.

3. The process of claim 1 wherein the monodentate ligand of formula (IV) is a ligand of formula (XIII):

or a ligand of formula (XIV):

or a mixture thereof.

4. The process of claim 1 , wherein a molar ratio of the ligand of formula (IV) that is admixed to the ligand of formula (ill) or formula (IIIA) or mixture thereof, is at least 0.01, and, optionally, is no greater than 2.

5. The process of claim 1 wherein the one or more monodentate ligand of formula (IV) is each independently of formula (IVA)

wherein each R is methyl and each n is independently 0, 1, or 2.

6. The process of claim 1 , wherein the ligand of formula (IV) is of formula (XIII) or (XIV).

7. The process of claim 6 , wherein a mixture of the ligands of formula (XIII) and of formula (XIV) are admixed.

8. The process of claim 1 , wherein R 1 , R 2 , R 3 , R 12 , R 13 , R 22 , R 23 or R 34 is each an independently selected (C6-C20)aryl group, wherein each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, (C6-C20)aryl and (C6-C20)aryl(C1-C10)alkyl, or wherein any one or more pair of R 1 and R 2 , or R 12 and R 13 , or R 22 and R 23 , is directly mutually bonded such that any mutually bonded pair, together with the respective X 1 , X 2 , X 12 , X 13 , X 22 or X 23 groups and the phosphorus atom to which they are bonded, forms a ring.

9. The process of claim 1 , wherein each independently selected R 1 , R 2 , R 3 , R 12 , R 13 , R 22 , R 23 or R 34 is a group of formula (II)

wherein a wavy line indicates a point of attachment; and wherein R 45 is independently selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, and (C6-C20)aryl, and each of R 48 , R 47 and R 48 is independently selected from the group consisting of H, (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, and (C6-C20)aryl.

10. The process of claim 1 wherein Y, or independently selected Y 1 or Y 2 , is a (C6-C20)arylene group, whe

Assignees

• Invista North America Sarl

Inventors

• Aki Sudhir
• Tenn Iii William J
• Vos Thomas E

Classifications

• C07F15/04

  Nickel compounds · CPC title

• C07F9/65744

  condensed with carbocyclic or heterocyclic rings or ring systems · CPC title

• C07F9/4006

  Esters of acyclic acids which can have further substituents on alkyl · CPC title

• C07F9/145 Primary

  with hydroxyaryl compounds · CPC title

• C07C253/30 Primary

  by reactions not involving the formation of cyano groups · CPC title