Method of preparing N-acryloyl-α-amino acids

Claim 2

A process for providing an N-acryloyl-α-amino acid comprising the steps: (i) reacting a ketone having alkyl, aryl, or arenyl groups, or combinations of these groups, said ketone having 3 to 53 carbon and heteroatoms which can include up to 7 N, S,and O heteroatoms, an ammonium salt, and an alkali metal cyanide, in water, to provide an aminonitrile, (ii) acryloylating the resulting aminonitrile with an acryloylating agent having the formula, ##STR9## wherein R 3 is hydrogen or methyl and Y is chloride, methacryloyloxy, or acryloyloxy, in aqueous media to provide an acrylaminodonitrile, and (iii) hydrolyzing the resulting acrylamidonitrile in aqueous acid to provide said N-acryloyl-α-amino acid.

Claim 3

A process for providing an N-acryloyl-α-amino acid having the formula ##STR10## wherein:

Claim 4

A process for providing an N-acryloyl-α-amino acid having the formula ##STR10## wherein:

Claim 5

R 1 and R 2 are independently an alkyl group of 1 to 14 carbon atoms, a cycloalkyl group of 3 to 14 carbon atoms, an aryl group of 5 to 12 ring atoms, an arenyl group of 6 to 26 carbon and heteroatoms, or R 1 and R 2 taken together with the carbon to which they are joined form a carbocyclic ring containing 4 to 12 ring atoms, with the proviso that only one of R 1 and R 2 can be aryl, and R 3 is hydrogen or methyl, said process comprising the steps: (i) reacting a ketone of the formula ##STR11## with ammonium salt, NH 4 X, and a metal cyanide, MCN, in water, to provide an aminonitrile, wherein R 1 and R 2 are as previously defined, X is chloride, bromide, nitrate, or sulfate, and M is sodium, potassium, or lithium, (ii) acryloylating the resulting aminonitrile with an acryloylating agent having the formula, ##STR12## wherein R 3 is as previously defined and Y is chloride, methacryloyloxy, or acryloyloxy, to provide an acrylamidonitrile, and (iii) hydrolyzing the resulting acrylamidonitrile in aqueous acid to provide said N-acryloyl-α-amino acid.

Claim 6

R 1 and R 2 are independently an alkyl group of 1 to 14 carbon atoms, a cycloalkyl group of 3 to 14 carbon atoms, an aryl group of 5 to 12 ring atoms, an arenyl group of 6 to 26 carbon and heteroatoms, or R 1 and R 2 taken together with the carbon to which they are joined form a carbocyclic ring containing 4 to 12 ring atoms, with the proviso that only one of R 1 and R 2 can be aryl, and R 3 is hydrogen or methyl, said process comprising the steps: (i) reacting a ketone of the formula ##STR11## with ammonium salt, NH 4 X, and a metal cyanide, MCN, in water, to provide an aminonitrile, wherein R 1 and R 2 are as previously defined, X is chloride, bromide, nitrate, or sulfate, and M is sodium, potassium, or lithium, (ii) acryloylating the resulting aminonitrile with an acryloylating agent having the formula, ##STR12## wherein R 3 is as previously defined and Y is chloride, methacryloyloxy, or acryloyloxy, to provide an acrylamidonitrile, and (iii) hydrolyzing the resulting acrylamidonitrile in aqueous acid to provide said N-acryloyl-α-amino acid.

Claim 7

The process according to claim 2 wherein the step of reacting said ketone, an ammonium salt, and metal cyanide further comprises as reactants ammonium hydroxide and a non-reactive, water miscible, organic co-solvent.

Claim 8

The process according to step 3 wherein said co-solvent is ethanol, isopropanol, N,N-dimethylformamide, dioxane, or N,N-dimethylacetamide.

Claim 9

The process according to step 3 wherein said co-solvent is ethanol, isopropanol, N,N-dimethylformamide, dioxane, or N,N-dimethylacetamide.

Claim 10

The process according to claim 2 wherein said reaction takes place in one vessel without isolation of intermediate compounds.

Claim 11

The process according to claim 2 wherein said ratio of ketone to metal cyanide is in the range of 1:1 to 1.5:1.

Claim 12

The process according to claim 2 wherein step (i) takes place at a temperature in the range of 10° to 80° C.

Claim 13

The process according to claim 2 wherein the acryloylation reaction of step (ii) takes place in the presence of sodium or potassium hydroxide.

Claim 14

The process according to claim 2 wherein step (ii) takes place at a temperature in the range of 0° to 15° C.

Claim 15

The process according to claim 2 wherein the aqueous acid of step (iii) is hydrochloric, sulfuric, phosphoric, or nitric acid.

Claim 16

The process according to claim 2 wherein said N-aryloyl-α-amino acid is formed in a yield of 50 percent or higher.

Claim 17

The process according to claim 2 wherein said N-acryloyl-α-amino acid is N-acryloylmethylalanine, N-acryloylethylalanine, N-methacryloylmethylalanine, 1-acrylamidocyclopentanecarboxylic acid, 1-acrylamidocyclohexanecarboxylic acid, 1-acrylamidocycloheptanecarboxylic acid, 2-acrylamido-2-ethylbutyric acid, and 2-acrylamido-2-phenylpropanoic acid.

Claim 18

The process according to claim 2 wherein said N-acryloyl-α-amino acid is isolated from the reaction mixture with a substantially water-insoluble organic solvent.

Claim 19

The process according to claim 13 wherein said organic solvent is ethyl acetate.

Claim 20

The process according to claim 2 wherein said N-acryloyl-α-amino acid is isolated by filtration.