Resolution/racemization of aminolactam compounds
AssigneeAllied Chemical Corporation
InventorsStylianos Sifniades, William J. Boyle, Jr., Jan F. Van Peppen
Life of this patent
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Abstract
Resolution of .alpha.-amino-.epsilon.-caprolactam with simultaneous racemization of the undesired .alpha.-aminocaprolactam enantiomer is effected by preferentially crystallizing the L- (or D-) .alpha.-amino-caprolactam compound in the presence of a racemization catalyst. In a narrower embodiment racemization of .alpha.-amino-.epsilon.-caprolactam is effected by alternate routes of forming a coordinately saturated aminolactam-metal complex and reacting with a strong base or reacting a mixture of an aminolactam salt and aminolactam free base with a chelating carbonyl compound and a metal ion or reacting a mixture of an aminolactam salt and aminolactam free base in the presence of a salen derivative complex.
Claims21
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, .beta.-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.sub.1 is hydrogen or methyl and R.sub.2 through R.sub.5 are hydrogen, nitro, halogen, cyano or carboxylic substituents, and a metal ion selected from the group consisting of Fe.sup.2.sup.+, Fe.sup.3.sup.+, Al.sup.3.sup.+, Cu.sup.2.sup.+, Co.sup.2.sup.+, Zn.sup.2.sup.+ and Ni.sup.2 .sup.+, and maintaining said solution at a temperature of below 120.degree.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.
A method for the racemization of the D- or L-enantiomer of .alpha.-amino-.epsilon.-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.
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.
A process for the optical purification of optically impure .alpha.-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.
A continous process for effecting transformation of racemic .alpha.-amino-.epsilon.-caprolactam to the desired enantiomer of .alpha.-amino-.epsilon.-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.degree.C. by contacting it with a solution of a strong acid, and separating the resulting optically active .alpha.-amino-.epsilon.-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).
An aminocaprolactam Schiff base of the formula ##SPC5##
- wherein R.sub.1 is hydrogen or methyl and R.sub.2 through R.sub.5 are hydrogen, nitro, halogen, cyano or carboxylic substituents.
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.sub.1 is hydrogen or methyl and R.sub.2 through R.sub.5 are hydrogen, nitro, halogen, cyano or carboxylic substituents, and a metal ion selected from the group consisting of Fe.sup.2.sup.+, Fe.sup.3.sup.+, Al.sup.3.sup.+, Cu.sup.2.sup.+, Co.sup.2.sup.+, Zn.sup.2.sup.+ and Ni.sup.2.sup.+ in a common inert solvent at the temperature range of 45.degree. to 120.degree.C.
Dependencies are inferred from the claim text.