Process for the separation of enantiomers and enantiopure reagent
AssigneeSolvay (Societe Anonyme)
InventorsThierry Delplanche, Roland Callens
Life of this patent
Estimating the term…
Abstract
Process for the separation of enantiomers comprising at least one free functional group, in which process a reagent based on an enantiopure amino acid is reacted in basic medium with a mixture comprising enantiometers.
Claims24
A reagent of formula
A reagent comprising a 2- and/or 4-substituted phenyloxy carbonyl group bonded to at least one amino group of an enantiopure amino acid and said enantiopure amino acid further contains at least one carboxyl group and said enantiopure amino acid is selected from the group consisting of phenylalanine, (1-naphthyl)-alanine, (2-naphthyl)-alanine, (2-indolyl)alanine and (3-indolyl)-alanine;
- wherein said substituent at the 2 and/or 4 position of said substituted phenyloxy carbonyl group is selected from the group consisting of groups having a negative inductive effect and groups having a negative resonance effect;
- and said carboxyl group in the amino acid is bonded to (a) or (b), wherein
- (a) is a substituent comprising at least one ether bond, and is a substituent comprising a chromophore selected from aromatic systems substituted in the 2 or 4 position by a substituent having a negative inductive effect and a negative resonance effect, (2-anthraquinoyl)methyl, and (9-(9H-fluorenylmethyl)) groups.
A reagent corresponding to the general formula (I)
- in which Z1 and/or Z2=NO2, R1=phenyl, α- or β-indolyl, 1-naphthyl or 2-naphthyl, R2=Me, Et, C3-C6 alkyl or C3-C6 cycloalkyl, and x represents an integer from 1 to 5.
A reagent comprising at least one chromophore, corresponding to the general formula (II)
- in which Z1 and/or Z2=NO2, R1=phenyl, α- or β-indolyl, 1-naphthyl or 2-naphthyl and Y corresponds to any one of the formulae (III to V),
- the carbon by which Y is bonded to the oxygen of the carboxyl group of the enantiopure amino acid being marked by *.
A reagent corresponding to the general formula (VI)
- in which Z1 and/or Z2=NO2 or F, R1=phenyl, α- or β-indolyl, 1-naphthyl or 2-naphthyl, R2=Me, Et, C3-C6 alkyl or C3-C6 cycloalkyl, and x represents an integer from 1 to 5.
A reagent comprising a 2- and/or 4-substituted phenyloxy thiocarbonyl group bonded to at least one amino group of an enantiopure amino acid and said enantiopure amino acid further contains at least one carboxyl group and said enantiopure amino acid is selected from the group consisting of alanine, valine, norvaline, leucine, norleucine, isoleucine, serine, isoserine, homoserine, threonine, allothreonine, methionine, ethionine, glutamic acid, aspartic acid, asparagine, cysteine, cystine, phenylalanine, tyrosine, tryptophane, lysine, arginine, histidine, ornithine, glutamine, citrulline, (1-naphthyl)alanine, (2-naphthyl)alanine, homophenylalanine, (4-chlorophenyl)alanine, (4-fluorophenyl)alanine, (3-pyridyl)alanine, phenylglycine, diaminopimelicacid (2,6-diaminoheptaine-1, 7-dioic acid), 2-aminobutyric acid, 2-aninotetraline-2-carboxylic acid, erythro-β-methylphenylalanine, threo-β-methylphenylalanine, (2-methoxyphenyl)alanine, 1-amino-5-hydroxyindan-2-carboxylic acid, 2-aminoheptane-1, 7-dioic acid, (2,6-dimethyl-4-hydroxyphenyl)alanine, erythro-β-methyltyrosine and threo-β-methyltyrosine;
- wherein said substituent at the 2 and/or 4 position of said substituted phenyloxy thiocarbonyl group is selected from the group consisting of groups having a negative inductive effect and groups having a negative resonance effect;
- and said carboxyl group in the amino acid is bonded to (a) or (b), wherein
- (a) is a substituent comprising at least one ether bond, and
- (b) is a substituent comprising a chromophore selected from aromatic systems substituted in the 2 or 4 position by a substituent having a negative inductive effect and a negative resonance effect, (2-anthraquinoyl)methyl, and (9-(9H-fluorenylmethyl)) groups.
A reagent comprising a 2- and/or 4-substituted phenyloxy carbonyl group bonded to at least one amino group of an enantiopure amino acid and, said enantiopure amino acid further contains at least one carboxyl group and said enantiopure amino acid is selected from the group consisting of alanine, valine, norvaline, leucine, norleucine, isoleucine, serine, isoserine, homoserine, threonine, allothreonine, methionine, ethionine, glutamnic acid, aspartic acid, asparagine, cysteine, cystine, phenylalanine, tyrosine, tryptophane, lysine, arginine, histidine, ornithine, glutamine, citrulline, (1-naphthyl)alanine, (2-naphthyl)alanine, homophenylalanine, (4-chlorophenyl)alanine, (4-fluorophenyl)alanine, (3-pyridyl)alanine, phenylglycine, diaminopimelicacid (2,6-diaminoheptaine-1,7-dioic acid), 2-aminobutyric acid, 2-aminotetraline-2-carboxylic acid, erythro-β-methylphenylalanine, threo-β-methylphenylalanine, (2-methoxyphenyl)alanine, 1-amino-5-hydroxyindan-2-carboxylic acid, 2-aminoheptane-1, 7-dioic acid, (2,6-dimethyl-4-hydroxyphenyl)alanine, erythro-β-methyltyrosine and threo-β-methyltyrosine;
- wherein said substituent at the 2 and/or 4 position of said substituted phenyloxy carbonyl group is selected from the group consisting of groups having a negative inductive effect and groups having a negative resonance effect;
- and said carboxyl group in the amino acid is bonded to (a) or (b), wherein
- (a) is a substituent comprising at least one ether bond, and is a substituent comprising at least one chromophore, correspond to the general formula (VII)
- in which Z1 and/or Z2=NO2, R1=phenyl, α- or β-indolyl, 1-naphthyl or 2-naphthyl and Y correspond to any one of the formulae (III to V),
- the carbon by which Y is bonded to the oxygen of the carboxyl group of the enantiopure amino acid being marked by *.
Dependencies are inferred from the claim text.