Nitrile hydration catalyzed by recyclable ruthenium complexes
View Patent ↗A method for hydrating a nitrile derivative to generate an amide derivative is provided. The method includes mixing the nitrile derivative with a ruthenium catalyst complex in an aqueous solution to form a mixture, and reacting the nitrile derivative with water in the aqueous solution and in the presence of the ruthenium catalyst complex to form a reacted mixture comprising the amide derivative. The ruthenium catalyst complex is represented by the following structural formula: RuX 2 (L) n , wherein X is an anionic ligand, L is a bifunctional phosphine ligand, and n is 3 or 4.
1. A method for hydrating a nitrile derivative to generate an amide derivative comprising:
mixing the nitrile derivative with a ruthenium catalyst complex in an aqueous solution to form a mixture, the ruthenium catalyst complex represented by the following structural formula:
RuX 2 (L) n ,
wherein X is an anionic ligand, L is a bifunctional phosphine ligand, and n is either 3 or 4; and
reacting the nitrile derivative with water in the aqueous solution and in the presence of the ruthenium catalyst complex to form a reacted mixture comprising the amide derivative.
2. The method of claim 1 , wherein the bifunctional phosphine ligand is selected from the group consisting of 1,3,5-triaza-7-phosphaadamantane (PTA) or derivatives thereof, P(CH 2 OH) 3 , P(CH 2 CH 2 CH 2 OH) 3 , triphenylphosphine trissulfonate (TPPTS), triphenylphosphine monosulfolate (TPPMS), P(CH 2 NH 2 ) 3 , P(CH 2 NH 3 Br) 3 , and P(CH 2 NH 3 Cl) 3 .
3. The method of claim 1 , wherein the bifunctional phosphine ligand is 1,3,5-triaza-7-phosphaadamantane (PTA) or a PTA derivative.
4. The method of claim 1 , wherein the anionic ligand is selected from the group consisting of Cl, Br, I, H, hydroxide, alkoxide, carboxylate, and combinations thereof.
5. The method of claim 1 , wherein the ruthenium catalyst complex is RuCl 2 (PTA) 4 , where PTA is 1,3,5-triaza-7-phosphaadamantane.
6. The method of claim 1 , wherein the aqueous solution is selected from the group consisting of water, a buffered aqueous solution, and a biphasic aqueous solution.
7. The method of claim 1 , wherein the aqueous solution has a pH greater than about 4.
8. The method of claim 1 , wherein the aqueous solution has a pH in a range from about 4 to about 10.
9. The method of claim 1 , further comprising heating the mixture to a temperature greater than 50° C.
10. The method of claim 1 , further comprising heating the mixture to a temperature in a range from about 50° C. to about 100° C.
11. The method of claim 1 , further comprising:
forming the ruthenium catalyst complex in situ by mixing a ruthenium compound with the bifunctional phosphine ligand in the aqueous solution.
12. The method of claim 11 , wherein the ruthenium compound is selected from the group consisting RuCl 3 , RuBr 3 , RuI 3 , RuF 3 , ruthenium (III) acetate, ruthenium (III) acetylacetonate; ruthenium phosphate, ruthenium nitrate, ruthenium sulfate, RuX 2 (PRR′R″) n , wherein X is selected from the group consisting of Cl, Br, I, H, hydroxide, alkoxide, carboxylate, and combinations thereof wherein R, R′, and R″ are independently selected from substituted or unsubstituted alkyl or aryls; and n is an integer equal to 3 or 4; and solvates and/or hydrates thereof.
13. The method of claim 11 , wherein the ruthenium compound is a halide salt.
14. The method of claim 11 , wherein a stoichiometric ratio between the ruthenium compound and the bifunctional phosphine ligand is in a range from about 1:1 to about 1:10.
15. The method of claim 14 , wherein the stoichiometric ratio is in the range from about 1:4 to about 1:6.
16. The method of claim 1 , wherein reacting the nitrile derivative with water in the aqueous solution and in the presence of the ruthenium catalyst complex is conducted in the presence of air to form the amide derivative.
17. The method of claim 1 , further comprising:
isolating the amide derivative from the reacted mixture.
18. The method of claim 17 , wherein isolating the amide derivative from the reacted mixture comprises:
lowering a temperature of the reacted mixture to induce precipitation of a solid form of the amide derivative; and
filtering the solid form of the amide derivative.
19. The method of claim 17 , wherein isolating the amide derivative from the reacted mixture comprises:
mixing an immiscible organic solvent with the aqueous solution to extract the amide derivative from the aqueous solution; and
separating the immiscible organic solvent containing the extracted amide derivative from the aqueous solution.
20. The method of claim 1 , further comprising recycling the ruthenium catalyst complex.