Hydrolysis catalyst and process
A process of hydrolyzing a monodentate, bidentate or tridentate phosphorus-based phosphite ester ligand or ligand blend for a transition metal catalyst comprising contacting the ligand or ligand blend with a hydrolysis catalyst of the formula (R 11 X 11 ) n P(OH) 3-n where n is 0, 1 or 2 wherein the ligand or ligand blend 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 ), (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 —K 24 —P(X 23 —R 23 )—(X 22 —R 22 ) or (iii) a monodentate phosphite ligand of formula (IV) P(X 1 —R 1 )(X 2 —R 2 )(X 3 —R 3 ) where each X is oxygen or a bond and each Y is an optionally substituted C6-C20 arylene, followed by separation of the ligand hydrolysis products.
1. A process for maintaining a pre-determined concentration ratio of a monodentate phosphorus ligand and a bidentate phosphorus ligand in a hydrocyanation reaction mixture, comprising:
i) monitoring the reaction mixture for excess monodentate phosphorus ligand relative to the pre-determined concentration ratio of monodentate phosphorus ligand and bidentate phosphorus ligand;
ii) contacting the reaction mixture with a hydrolysis catalyst to remove excess monodentate phosphorus ligand by selectively hydrolyzing a phosphite ester group of the monodentate phosphorus ligand in the presence of the bidentate phosphorus ligand to produce a hydrolysis product from the hydrolyzed monodentate phosphorus ligand; and
iii) separating the hydrolysis catalyst and the hydrolysis product from the reaction mixture by contacting the reaction mixture with a nonpolar solvent and a polar organic solvent to extract the hydrolysis catalyst and the hydrolysis product from the reaction mixture into the polar organic solvent;
wherein
the hydrolysis catalyst is
H 3 PO 3 ,
or a mixture thereof;
the monodentate phosphorus ligand has formula (IV)
P(X 1 R 1 )(X 2 R 2 )(X 3 R 3 ) (IV)
X 1 , X 2 and X 3 are each oxygen and R 1 , R 2 and R 3 is each phenyl, each of which is independently unsubstituted or is substituted with 1-4 substituents selected from the group consisting of (C1-C3)alkyl; or, optionally, any two of R 1 , R 2 , or R 3 are a biphenyl which is unsubstituted or substituted with 1-4 substituents selected from the group consisting of (C1-C3)alkyl, 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;
the bidentate phosphorus ligand has formula (X)
wherein each of R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 and R 48 is independently H or (C 1 -C 3 )alkyl, or, optionally, any two of R 41 and R 42 , R 42 and R 43 , or R 43 and R 44 are substituted to form, together, a cyclohexyl ring.
2. The process of claim 1 , wherein the hydrolysis catalyst is a hydrolysis product of at least one of the phosphorus-containing ligand of formula (IV) or (X) produced in the reaction mixture, or is added to the reaction mixture, or both.
3. The process of claim 1 , wherein the polar organic solvent and the nonpolar solvent form a top layer comprising the nonpolar solvent, the monodentate phosphorus ligand and the bidentate phosphorus ligand, and a bottom layer comprising the polar organic solvent, the hydrolysis catalyst and the hydrolysis product.
4. The process of claim 1 , wherein the nonpolar solvent comprises cyclohexane.
5. The process of claim 1 , wherein the polar organic solvent is a raffinate from the hydrocyanation reaction of butadiene, comprises adiponitrile, or both.
6. The process of claim 1 , wherein for the ligand of formula (X),
R 41 is methyl, ethyl, or isopropyl;
R 42 is H or methyl;
R 43 is H or (C1-C3)alkyl;
R 44 is H or methyl;
R 45 is methyl, ethyl, or isopropyl; and
R 46 , R 47 and R 48 are independently H or (C1-C3)alkyl.
7. The process of claim 1 , wherein the ligand of formula (X) is of formula (VII):
wherein R 17 is methyl, ethyl or iso-propyl, and R 18 and R 19 are independently H or methyl.
8. The process of claim 1 , wherein the ligand of formula (X) is of formula (XII)
wherein R 12 , R 13 , R 22 and R 23 are each independently an unsubstituted or a substituted monovalent aryl, and each of R Y3 —R Y13 is independently selected from the group consisting of hydrogen, (C1-C3) alkyl, or wherein two adjacent R Y3 —R Y10 groups together form a cyclohexyl ring.
9. The process of claim 8 , wherein R 12 , R 13 , R 22 , and R 23 are each independently phenyl substituted at a respective first ortho-position with a (C1-C3) alkyl, at a respective second ortho-position with hydrogen, and wherein respective meta- and para-positions of the R 12 , R 13 , R 22 , and R 23 phenyls can each independently be unsubstituted or be independently substituted with (C1-C3) alkyl;
R Y6 and R Y10 are independently (C1-C3) alkyl, and R Y3 , R Y4 , R Y5 , R Y7 , R Y8 , and R Y9 , are independently H or (C1-C3) alkyl, provided that at least one of R Y3 , R Y4 , or R Y5 , and at least one of R Y7 , R Y8 , or R Y9 , is (C1-C3) alkyl.
10. The process of claim 1 , wherein the ligand of formula (X) is of formula (V):
11. The process of claim 1 wherein the hydrolysis catalyst has the following formula (IA2):
or is of formula (IB2):
or is a mixture thereof.
12. The method of claim 1 , wherein the bidentate phosphorus ligand of formula (X) is formula (V),
and the monodentate phosphorus ligand of formula (IV) is formula (XIII)
or formula (XIV):
or a mixture thereof;
and the hydrolysis catalyst of formula (I)—is formula (IA2):
or of formula (IB2):
or a mixture thereof.
13. The process of claim 1 , wherein the reaction mixture further comprises cyclohexane, toluene, or a combination thereof.
14. The process of claim 1 , wherein the reaction mixture further comprises one or more nitriles.
15. The process of claim 14 , wherein the nitriles comprise at least one of 3-pentenenitrile and adiponitrile.