US3941776A — Resolution/racemization of aminolactam compounds

Claim 1

Independent Claim 230 words

A process for effecting transformation of a D,L-aminocaprolactam compound selected from the group consisting of A. the D,L-aminocaprolactam complexes, (tris-aminocaprolactam)nickel (II) salts and (tris-aminocaprolactam)cobalt(II) salts, B. the D,L-aminocaprolactam salts of the acids hydrogen chloride, hydrogen bromide, β-naphthalenesulfonic acid and 2-naphthylamine-1-sulfonic acid, and C. the D,L-aminocaprolactam diasereomeric salts of the acids L-pyrrolidonecarboxylic acid, D-N-carbamoylvaline, L-N-p-nitrobenzoylglutamic acid, L-N-benzoylglutamic acid, L-N-p-toluylglutamic acid and L-N-p-chlorobenzoylglutamic acid, to the desired isomer of said aminocaprolactam compound which comprises a. forming a supersaturated feed solution of said D,L-aminocaprolactam compound in an inert solvent; said solution also containing D,L-aminocaprolactam, and a strong base when said D,L-aminocaprolactam compound is a complex, and, when said D,L-aminocaprolactam compound is a salt or diastereomeric salt, a compound of the formula I or II ##SPC4## wherein R 1 is hydrogen or methyl and R 2 through R 5 are hydrogen, nitro, halogen, cyano or carboxylic substituents, and a metal ion selected from the group consisting of Fe 2 + , Fe 3 + , Al 3 + , Cu 2 + , Co 2 + , Zn 2 + and Ni 2 + , and maintaining said solution at a temperature of below 120°C.; b. contacting said solution with seed crystals of the desired isomer of said aminocaprolactam compound, said contact being optional in the case that said aminocaprolactam compound is a diastereomeric salt; and c. removing the grown crystals of said compound.

Claim 2

Dependent Claim 230 words

A process for effecting transformation of a D,L-aminocaprolactam compound selected from the group consisting of A. the D,L-aminocaprolactam complexes, (tris-aminocaprolactam)nickel (II) salts and (tris-aminocaprolactam)cobalt(II) salts, B. the D,L-aminocaprolactam salts of the acids hydrogen chloride, hydrogen bromide, β-naphthalenesulfonic acid and 2-naphthylamine-1-sulfonic acid, and C. the D,L-aminocaprolactam diasereomeric salts of the acids L-pyrrolidonecarboxylic acid, D-N-carbamoylvaline, L-N-p-nitrobenzoylglutamic acid, L-N-benzoylglutamic acid, L-N-p-toluylglutamic acid and L-N-p-chlorobenzoylglutamic acid, to the desired isomer of said aminocaprolactam compound which comprises a. forming a supersaturated feed solution of said D,L-aminocaprolactam compound in an inert solvent; said solution also containing D,L-aminocaprolactam, and a strong base when said D,L-aminocaprolactam compound is a complex, and, when said D,L-aminocaprolactam compound is a salt or diastereomeric salt, a compound of the formula I or II ##SPC4## wherein R 1 is hydrogen or methyl and R 2 through R 5 are hydrogen, nitro, halogen, cyano or carboxylic substituents, and a metal ion selected from the group consisting of Fe 2 + , Fe 3 + , Al 3 + , Cu 2 + , Co 2 + , Zn 2 + and Ni 2 + , and maintaining said solution at a temperature of below 120°C.; b. contacting said solution with seed crystals of the desired isomer of said aminocaprolactam compound, said contact being optional in the case that said aminocaprolactam compound is a diastereomeric salt; and c. removing the grown crystals of said compound.

Claim 3

Dependent Claim 35 words

The process of claim 1 which is continuous and wherein said feed solution is introduced continuously and wherein grown crystals and solvent which is introduced as a part of said feed solution are removed continuously.

Claim 4

Dependent Claim 27 words

The process of claim 2 wherein seed crystals of the desired isomer are fed continuously to maintain optical purity of the crystals grown from said supersaturated solution.

Claim 5

Independent Claim 51 words

A method for the racemization of the D- or L-enantiomer of α-amino-ε-caprolactam comprising reacting the enantiomer with ions in the plus 2 valence state of nickel or cobalt, in a mol ratio ranging from at least 3.5:1 to about 20:1 in the presence of a catalytic amount of a strong base.

Claim 6

Independent Claim 51 words

A method for the racemization of the D- or L-enantiomer of α-amino-ε-caprolactam comprising reacting the enantiomer with ions in the plus 2 valence state of nickel or cobalt, in a mol ratio ranging from at least 3.5:1 to about 20:1 in the presence of a catalytic amount of a strong base.

Claim 7

Dependent Claim 26 words

The process of claim 4 wherein the mol ratio of the enantiomer to the metal ion is within the range of about 3.5:1 to about 10:1.

Claim 8

Dependent Claim 26 words

The process of claim 4 wherein the salt forming metal complex is a member of the group consisting of nickel (II) chloride and cobalt (II) chloride.

Claim 9

Dependent Claim 23 words

The process of claim 4 wherein the strong base is present in an amount of 1-100 mol % based on the metal ion.

Claim 10

Dependent Claim 32 words

The process of claim 4 wherein 1 to 3 mol of a member of the group consisting of ethylene diamine, sodium lysinate, 1,10-phenanthroline and ammonia are added per mol of metal ion.

Claim 11

Dependent Claim 21 words

The process of claim 4 wherein the base is a hydroxide or alkoxide of the metal ion employed in the complex.

Claim 12

Dependent Claim 18 words

The process of claim 4 wherein the reaction temperature is in the range of about 40° to 95°C.

Claim 13

Dependent Claim 35 words

The process of claim 9 wherein the metal hydroxide or alkoxide is obtained by treating an alcoholic or aqueous alcoholic solution of the metal ion with a strongly basic or weakly basic ion exchange resin.

Claim 14

Dependent Claim 86 words

A single stage process for effecting transformation of D,L-aminocaprolactam to the desired enantiomer of aminocaprolactam comprising contacting in an inert solvent said D,L-aminocaprolactam with ions in the plus 2 valence state of nickel or cobalt, in a mole ratio ranging from at least 3.5:1 to about 20:1, a catalytic amount of a strong base, and seed crystals of a complex of the desired enantiomer of aminocaprolactam with ions in the plus 2 valence state of nickel or cobalt, and removing the grown crystals of said complex.

Claim 15

Dependent Claim 86 words

A single stage process for effecting transformation of D,L-aminocaprolactam to the desired enantiomer of aminocaprolactam comprising contacting in an inert solvent said D,L-aminocaprolactam with ions in the plus 2 valence state of nickel or cobalt, in a mole ratio ranging from at least 3.5:1 to about 20:1, a catalytic amount of a strong base, and seed crystals of a complex of the desired enantiomer of aminocaprolactam with ions in the plus 2 valence state of nickel or cobalt, and removing the grown crystals of said complex.

Claim 16

Dependent Claim 25 words

The process of claim 12 wherein the mol ratio of the aminocaprolactam to metal ion is within the range of about 3.5:1 to about 10:1.

Claim 17

Dependent Claim 43 words

A process for the optical purification of optically impure α-aminocaprolactam nickel complex or cobalt complex comprising partially dissolving said impure complex in an alcohol or water, or mixtures thereof, and recovering the remaining undissolved crystals in a state of substantially improved optical purity.

Claim 18

Dependent Claim 43 words

A process for the optical purification of optically impure α-aminocaprolactam nickel complex or cobalt complex comprising partially dissolving said impure complex in an alcohol or water, or mixtures thereof, and recovering the remaining undissolved crystals in a state of substantially improved optical purity.

Claim 19

Dependent Claim 217 words

A continous process for effecting transformation of racemic α-amino-ε-caprolactam to the desired enantiomer of α-amino-ε-caprolactam comprising the steps of: a. forming a supersaturated solution of the racemic material with a complex forming metal ion in the plus 2 valence state of nickel or cobalt in amounts such that the mol ratio of said racemic material to the metal ion in the solution is in the range from about 3.5:1 to about 10:1, said solution containing also a strong base in amounts from 1 to 100 mol % with respect to the metal ion; b. contacting said solution with at least about 1% by weight preformed seeds of the desired enantiometer of said complex; c. separating the crystalline product of the desired enantiomer complex from the reaction mother liquor; d. partially dissolving the crystalline product from step (c) and recycling the remaining purified crystalline product as seed to step (b), decomposing the resulting solution at a temperature greater than about 0°C. by contacting it with a solution of a strong acid, and separating the resulting optically active α-amino-ε-caprolactam acid salt crystals from liquors containing primarily complex forming metal ions; e. treating the liquors from (d) with an ion exchange resin to eliminate excess acid and introducing the treated liquors which contain complex forming metal ion to step (a).

Claim 20

Dependent Claim 217 words

A continous process for effecting transformation of racemic α-amino-ε-caprolactam to the desired enantiomer of α-amino-ε-caprolactam comprising the steps of: a. forming a supersaturated solution of the racemic material with a complex forming metal ion in the plus 2 valence state of nickel or cobalt in amounts such that the mol ratio of said racemic material to the metal ion in the solution is in the range from about 3.5:1 to about 10:1, said solution containing also a strong base in amounts from 1 to 100 mol % with respect to the metal ion; b. contacting said solution with at least about 1% by weight preformed seeds of the desired enantiometer of said complex; c. separating the crystalline product of the desired enantiomer complex from the reaction mother liquor; d. partially dissolving the crystalline product from step (c) and recycling the remaining purified crystalline product as seed to step (b), decomposing the resulting solution at a temperature greater than about 0°C. by contacting it with a solution of a strong acid, and separating the resulting optically active α-amino-ε-caprolactam acid salt crystals from liquors containing primarily complex forming metal ions; e. treating the liquors from (d) with an ion exchange resin to eliminate excess acid and introducing the treated liquors which contain complex forming metal ion to step (a).

Claim 21

Dependent Claim 29 words

An aminocaprolactam Schiff base of the formula ##SPC5## wherein R 1 is hydrogen or methyl and R 2 through R 5 are hydrogen, nitro, halogen, cyano or carboxylic substituents.

Claim 22

Dependent Claim 29 words

An aminocaprolactam Schiff base of the formula ##SPC5## wherein R 1 is hydrogen or methyl and R 2 through R 5 are hydrogen, nitro, halogen, cyano or carboxylic substituents.

Claim 23

Dependent Claim 53 words

A complex selected from the group consisting of those formed by reacting the (a) Schiff bases of claim 16 and (b) metal salts of transition metals selected from the group consisting of Fe II , Fe III , Cu II , Zn II , Al III , Ni II and Co II .

Claim 24

Dependent Claim 11 words

The composition of claim 17 wherein the transition metai is iron.

Claim 25

Dependent Claim 23 words

The process of claim 12 wherein the nickel ion is provided by nickel (II) chloride and the cobalt ion by cobalt (II) chloride.

Claim 26

Dependent Claim 23 words

The process of claim 15 wherein the nickel ion is provided by nickel (II) chloride and the cobalt ion by cobalt (II) chloride.

Claim 27

Independent Claim 104 words

A method for the racemization of the D- or L-enantiomer of aminocaprolactam salts comprising reacting said salts in an inert solvent with D- or L-aminocaprolactam, a compound of formula I or II ##SPC6## wherein R 1 is hydrogen or methyl and R 2 through R 5 are hydrogen, nitro, halogen, cyano or carboxylic substituents, and a metal ion selected from the group consisting of Fe 2 + , Fe 3 + , Al 3 + , Cu 2 + , Co 2 + , Zn 2 + and Ni 2 + in a common inert solvent at the temperature range of 45° to 120°C.

Claim 28

Independent Claim 104 words

A method for the racemization of the D- or L-enantiomer of aminocaprolactam salts comprising reacting said salts in an inert solvent with D- or L-aminocaprolactam, a compound of formula I or II ##SPC6## wherein R 1 is hydrogen or methyl and R 2 through R 5 are hydrogen, nitro, halogen, cyano or carboxylic substituents, and a metal ion selected from the group consisting of Fe 2 + , Fe 3 + , Al 3 + , Cu 2 + , Co 2 + , Zn 2 + and Ni 2 + in a common inert solvent at the temperature range of 45° to 120°C.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1979-03-02	1979-09-01	1980-03-02	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1983-03-02	1983-09-01	1984-03-02	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1987-03-02	1987-09-01	1988-03-02	$7700.00	Window Closed / Lapsed

Resolution/racemization of aminolactam compounds

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