CA1296733C - Process for producing chiral glycine derivatives - Google Patents
Process for producing chiral glycine derivativesInfo
- Publication number
- CA1296733C CA1296733C CA000529668A CA529668A CA1296733C CA 1296733 C CA1296733 C CA 1296733C CA 000529668 A CA000529668 A CA 000529668A CA 529668 A CA529668 A CA 529668A CA 1296733 C CA1296733 C CA 1296733C
- Authority
- CA
- Canada
- Prior art keywords
- acid
- process according
- general formula
- group
- imidazolidin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/30—Oxygen or sulfur atoms
- C07D233/32—One oxygen atom
- C07D233/38—One oxygen atom with acyl radicals or hetero atoms directly attached to ring nitrogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pyrrole Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
By a simple enantiomer separation of 1,3-imidazolin-4-ones produced from glycine esters, primary alkyl amines and pivaldehyde and having the general formula (II), wherein R represents a straight-chain or branched C1 to C4 -alkyl group with a chiral acid, chiral glycine derivatives having the general formula
By a simple enantiomer separation of 1,3-imidazolin-4-ones produced from glycine esters, primary alkyl amines and pivaldehyde and having the general formula (II), wherein R represents a straight-chain or branched C1 to C4 -alkyl group with a chiral acid, chiral glycine derivatives having the general formula
Description
~Z9~733 The present invention relates to a process for pro-ducing ~R)- and (S)- 1,3-imldazolidin-4-ones.
Heretofore, the chiral 1,3-imidazolidin-4-one having the general formula I was accessible only by degradation reac-tions of 1,3-imidazolidin-ones in the 5-position which had been obtained by means by multistage syntheses starting from L- or M-methionine and L- or O-benzyl serine (D) Seebach, D.D.
Miller, S. Muller and T Weber, Helv. Chim. Heta 68, 949 (1985).
The present invention provldes a process for produc-ing compounds according to formula ~I) given hereinafter in which inexpensive achiral starting products can be used.
The present invention thus provides a process for producing (R)- and (S)- 1,3-imidazolidin-4-ones having the general formula Cl13 / N C~O
l-l3c-c-llc* 1 (1), c~3 N_ C1l2 ~ ~ R1 wherein * represents an asymmetry centre, R represents a straight-chain or branched Cl to C4 alkyl group and Rl repre-sents a phenyl or benzyl group, a phenyl-oxy or benzyl-oxy group, preferably the phenyl group or a phenyl group mono- or tri-substituted in any ring position by a Cl to C~-alkyl or alkoxy group in which a racemic 1,3-imidazolidln-4-one having the general formula Cl13 ~N C~
113C-C-IIC 1 (11), C113 \N ~C112 wherein R has the meaning defined above, ls converted by reac-tion with a chiral acid having the general formula '~ ' ~L29~i733 *R2 _ COO~I (IV), wherein *R2 represents a chiral radical into a diastereomeric salt pair of, for exampl0, (S)- acid/(S)-II and (S)-acid/(R)-II.
Fundamentally any compound known from the litera-ture, such as N-acetyl amino acids, Z-protected amino acids, pyroglutamic acid, tartaric acid, mallc acid, camphor-10-sulphonic acid, dibenzoyl tartaric acid and deoxy cholic acid can be used as chiral acids, but (R)- or (s)-mandelic acid and (-)-diacetone-2-ketogluonic are preferred.
This is carried out at temperatures from -30C to 25C from solutions of compounds according to ~ormula (II) in solvents, as for example, alcohols, particularly methanol or ethanol, mixtures of these alcohols with water, acetic ester or chlorinated hydrocarbons, particularly methylene chloride or chloroform.
- Acetone is particularly suitable.
The solvent is always so selected as a function of the compounds to be separated that the solubility differences between the two salt pairs are large. ~or example, the salt form (-)-diacetone-2-gluonic acid and (S)-II and the salt from (R)-mandelic acid (R)-II in ethanol show the greatest tendency to crystallize out relative to their antipodes.
On separating the two diastereomeric salt pairs by fractional crystallization, which is followed by recrystal-lization for purification, when required, the 1,3-imidazo-lidin-4-ones (R)-II or (S)-II are obtained by reacting the salts preferably suspended in a chlorinated hydrocarbon, par-ticularly methylene chloride or chloroform, wlth an aqueous solution of caustic soda or a caustic potash solution whose amount is slightly above~that required stoichiometrically.
Subsequently the (R) and (S)-1,3-imidazolldin-~-ones 1~6733 having the general formula (II) are reacted in a conventional manner, without isolation, with a compound having the general formula (IIIa) R - C (IIIa), \~l a ~
wherein Hal is chlorine or bromine or (IIIb) C ) 20 ( I I I b), wherein Rl has the meaning deflned above. in the presence of trlethyl amine, pyridine or caustic soda or potash solution to the (R)- and (S)-l,3-imidazolidin-~-ones having the general formula (I) (see D. Seebach, D.D. Miller, S. Muller and T.
Weber, Helv. Chim. Acta 68, 94~ (1985)1.
The corresponding other antipode can be obtained in an analogous manner by concentrating the crystallization mother liquor.
After repeated recrystallization and subsequent dry-ing at reduced pressure until constant weight is attained the crystalline (R)- and (S)-1,3-imidazolidin-4-ones having the formula (I) are thus obtained in good chemical yields and in optical yields of 98 to 99%. Up to 95% of the applied chiral acids having the general formula ~IV) can be recovered without detectable racemization. Therefore, on separating (R)-I and (S)-I the aqueous phase is acidified with mineral acids, such as sulphuric acid or hydrochloric acid, and extracted with a solvent that is not miscible with water, as for example, acetic ester.
The process according to the present lnvention pro-vides an excellent access to enantiomer-pure glycine deriva-tives having the general formula (I) from achiral start:lng ~91~733 products and, as described, for example, by D. Seebach et al.
in DE-OS 3 334 855 or in Helv. Chim. Acta 68, 949 ~1985), after diasteroselective single or repeated C~-alkylation and ring cleavage this process provides a favourable basis for the synthesis of branched and non-branched proteinogenic or non-proteinogenic (R)- and (S)-amino acids.
For carrylng out the process according to the pre-sent invention there is first produced in a conventional man-ner from a glycine amide having the general formula 1 ~ 2 1 -- C ~ t V ) wherein R has the meaning defined hereinbefore, and from pivaldehyde the racemic 1,3-imidazolidin-4-one having the general formula (II)( (R. Naef and D. Seebach, Helv. Chim.
Acta 68, 135 (1985)). An alternative production process is evident from the degradation of a side chain in the 5-posi-tion, starting from DL-amino acids such as methionine or O-benzyl serine as described by D. Seebach et al. in Helv. Chim.
20 Acta 68, 949 (1985).
The present invention will be described in greater detail by the following Examples:
a) Production of (R,S)-2-(t-butyl)-3-methyl-1,3-imidazolidin-4-one The suspension obtained by adding 125.6 g (l mole) of glycine methyl ester hydrochloride to ice-cooled 375 ml of ; 8 M ethanolic methyl amine was stirred for 15 hours at room temperature and concentrated under reduced pressure so as to form a viscous paste. Said paste was suspended three times 30 using 200 ml of methylene chloride each time and reconcen-~rated again. The residue was mixed with 1 litre of methylene chloride, 235 ml (1.5 moles) of pivaldehyde and 209 ml (1.5 ~9~33 moles) of triethyl amine and boiled for 10 hours on a water separator. On filtering, washing the residue with 500 ml of ether and concentrating the filtrate under reduced pressure a solution of the oil obtained was mixed in 300 ml of methanol with 600 ml of HCl-saturated methanol whille cooling with ice, stirred for 0.5 hour at 0C and 2 hours at room temperature and again concentrated by evaporation. ,A solution of the syrup in 800 ml of methylene chloride was washed with 670 ml of a 3 M solution of caustic soda while cooling with ice and 10concentrated to 107.5 g (69%) of crude (R,S)-2-(t-butyl)-3-methyl-1,3-imidazolidin-4-one, a yellowish oil which crystallized in the cold. (For analytics see R. NaeE and ~.
Seebach, Helv. Chim. Acta 68, 135 ~1985).
b) Enantiomer Separation of (RS)-2-(t-butyl)-3-methyl-1,3-imidazolidin-4-one ~; A mixture of 70 g (0.448 mole) of the (R,S)-2-(t-butyl)-3-methyl-1,3-imidazolidin-4-one and 70 g of (R)-~-)-mandelic acid was dissolved in boiling acetone. On cooling to room temperatures within 6 hours and further 15 hours at 5C
the precipltated crystal cake was filtered off. Upon drying, 54.5 g of a slightly yellow crystallizate of R-mandelic acid and (R)-2-t-(butyl3-3-methyl-1,3-imidazolidin-4-one was iso-lated.
c) Production of (S)-(+)-l-benzoyl-2-(t-butyl)-3-methyl-1,3-imidazolidln-4-one A suspension of the diastereomeric salt of (R)-(-)-mandelic acid and ~R)-2-~t-butyl)-3-methyl-(1,3-imidazolidin-4-one (54.5 g, 0.177 mole) obtained according to b) in 200 ml of methylene chloride was mixed with g2 ml of a 2 M solution of caustic soda and shaken. By extracting the water phase acidlfied with a 50% sul~huric acid with 300 ml of acetic ethyl ester up to 25.5 g of (R)-(-)-mandelic acid can be 5 _ ~96733 recovered.
The 1,3-imidazolidin-4-one remaining in the organic phase was benzoylated by adding 20.1 ml (0.173 mole) of ben-zoyl chloride and 195 ml of a 1 M solution of caustic soda while cooling with ice. The organic phase was separated, dried over magnesium sulphate and concentrated under reduced pressure.
45.8 g of yellow crystallizate with ~ c~ ]D = + 107 (c = 1, CH2C12) were obtained. :~
Crystallizing twice from ethanol, precipitating from methylene chloride with pentane and drying for 12 hours at 0.1 torr and 60C yielded 34.7 g ~60~) of (S)-~)-l-benzoyl-2-(t-butyl)-3--methyl-1,3-imidazolidin-4-one with [c~]D = ~ 127 (c 1, CH2C12 ) -By crystallizing a sample three times from an ethanol and subsequent sublimation (135C/0.01 torr) an ~D
of ~ 127.5C and a melting point of 143 to 144C were obtained.
The spectroscopic data correspond to those of the (R,S)-compound described by Seebach et al. in Helv. Chim. Acta 68, 949 (1985).
d) Production of (R)-(-)-benzoyl)-2-(t-butyl)-3-methyl-1,3-lmidazolidin-4-one The syrup remaining on concentrating the crystal-lization mother liquor obtained according to b) was taken up in 300 ml oE methylene chloride, whereupon - as described under c)- the mandelic acid was washed out first (140 ml of a 2 M solution of caustic soda~ and the 1,3-imidazolidin-4-one was then directly benzoylated in the organic phase (30 ml, (0.258 mole) of benzoyl chloride, 280 ml of a 1 M solution of caustic soda).
The crude crystal obtained on concentrating the ~29~733 organic phase under reduced pressure was recrystallized from 45 ml of ethanol.
33.6 g of crystals with [c~]D = --109 (c = l, CH~C12) were obtained.
Recrystallizing and drying - as described under c) -yielded 26.4 g (45%) of (R)~ benzoyl-2-(t-butyl)-3-methyl-1,3-imidazolidin-4-one with [c~]D = -126 (c = 1, CH2C~
~ 30
Heretofore, the chiral 1,3-imidazolidin-4-one having the general formula I was accessible only by degradation reac-tions of 1,3-imidazolidin-ones in the 5-position which had been obtained by means by multistage syntheses starting from L- or M-methionine and L- or O-benzyl serine (D) Seebach, D.D.
Miller, S. Muller and T Weber, Helv. Chim. Heta 68, 949 (1985).
The present invention provldes a process for produc-ing compounds according to formula ~I) given hereinafter in which inexpensive achiral starting products can be used.
The present invention thus provides a process for producing (R)- and (S)- 1,3-imidazolidin-4-ones having the general formula Cl13 / N C~O
l-l3c-c-llc* 1 (1), c~3 N_ C1l2 ~ ~ R1 wherein * represents an asymmetry centre, R represents a straight-chain or branched Cl to C4 alkyl group and Rl repre-sents a phenyl or benzyl group, a phenyl-oxy or benzyl-oxy group, preferably the phenyl group or a phenyl group mono- or tri-substituted in any ring position by a Cl to C~-alkyl or alkoxy group in which a racemic 1,3-imidazolidln-4-one having the general formula Cl13 ~N C~
113C-C-IIC 1 (11), C113 \N ~C112 wherein R has the meaning defined above, ls converted by reac-tion with a chiral acid having the general formula '~ ' ~L29~i733 *R2 _ COO~I (IV), wherein *R2 represents a chiral radical into a diastereomeric salt pair of, for exampl0, (S)- acid/(S)-II and (S)-acid/(R)-II.
Fundamentally any compound known from the litera-ture, such as N-acetyl amino acids, Z-protected amino acids, pyroglutamic acid, tartaric acid, mallc acid, camphor-10-sulphonic acid, dibenzoyl tartaric acid and deoxy cholic acid can be used as chiral acids, but (R)- or (s)-mandelic acid and (-)-diacetone-2-ketogluonic are preferred.
This is carried out at temperatures from -30C to 25C from solutions of compounds according to ~ormula (II) in solvents, as for example, alcohols, particularly methanol or ethanol, mixtures of these alcohols with water, acetic ester or chlorinated hydrocarbons, particularly methylene chloride or chloroform.
- Acetone is particularly suitable.
The solvent is always so selected as a function of the compounds to be separated that the solubility differences between the two salt pairs are large. ~or example, the salt form (-)-diacetone-2-gluonic acid and (S)-II and the salt from (R)-mandelic acid (R)-II in ethanol show the greatest tendency to crystallize out relative to their antipodes.
On separating the two diastereomeric salt pairs by fractional crystallization, which is followed by recrystal-lization for purification, when required, the 1,3-imidazo-lidin-4-ones (R)-II or (S)-II are obtained by reacting the salts preferably suspended in a chlorinated hydrocarbon, par-ticularly methylene chloride or chloroform, wlth an aqueous solution of caustic soda or a caustic potash solution whose amount is slightly above~that required stoichiometrically.
Subsequently the (R) and (S)-1,3-imidazolldin-~-ones 1~6733 having the general formula (II) are reacted in a conventional manner, without isolation, with a compound having the general formula (IIIa) R - C (IIIa), \~l a ~
wherein Hal is chlorine or bromine or (IIIb) C ) 20 ( I I I b), wherein Rl has the meaning deflned above. in the presence of trlethyl amine, pyridine or caustic soda or potash solution to the (R)- and (S)-l,3-imidazolidin-~-ones having the general formula (I) (see D. Seebach, D.D. Miller, S. Muller and T.
Weber, Helv. Chim. Acta 68, 94~ (1985)1.
The corresponding other antipode can be obtained in an analogous manner by concentrating the crystallization mother liquor.
After repeated recrystallization and subsequent dry-ing at reduced pressure until constant weight is attained the crystalline (R)- and (S)-1,3-imidazolidin-4-ones having the formula (I) are thus obtained in good chemical yields and in optical yields of 98 to 99%. Up to 95% of the applied chiral acids having the general formula ~IV) can be recovered without detectable racemization. Therefore, on separating (R)-I and (S)-I the aqueous phase is acidified with mineral acids, such as sulphuric acid or hydrochloric acid, and extracted with a solvent that is not miscible with water, as for example, acetic ester.
The process according to the present lnvention pro-vides an excellent access to enantiomer-pure glycine deriva-tives having the general formula (I) from achiral start:lng ~91~733 products and, as described, for example, by D. Seebach et al.
in DE-OS 3 334 855 or in Helv. Chim. Acta 68, 949 ~1985), after diasteroselective single or repeated C~-alkylation and ring cleavage this process provides a favourable basis for the synthesis of branched and non-branched proteinogenic or non-proteinogenic (R)- and (S)-amino acids.
For carrylng out the process according to the pre-sent invention there is first produced in a conventional man-ner from a glycine amide having the general formula 1 ~ 2 1 -- C ~ t V ) wherein R has the meaning defined hereinbefore, and from pivaldehyde the racemic 1,3-imidazolidin-4-one having the general formula (II)( (R. Naef and D. Seebach, Helv. Chim.
Acta 68, 135 (1985)). An alternative production process is evident from the degradation of a side chain in the 5-posi-tion, starting from DL-amino acids such as methionine or O-benzyl serine as described by D. Seebach et al. in Helv. Chim.
20 Acta 68, 949 (1985).
The present invention will be described in greater detail by the following Examples:
a) Production of (R,S)-2-(t-butyl)-3-methyl-1,3-imidazolidin-4-one The suspension obtained by adding 125.6 g (l mole) of glycine methyl ester hydrochloride to ice-cooled 375 ml of ; 8 M ethanolic methyl amine was stirred for 15 hours at room temperature and concentrated under reduced pressure so as to form a viscous paste. Said paste was suspended three times 30 using 200 ml of methylene chloride each time and reconcen-~rated again. The residue was mixed with 1 litre of methylene chloride, 235 ml (1.5 moles) of pivaldehyde and 209 ml (1.5 ~9~33 moles) of triethyl amine and boiled for 10 hours on a water separator. On filtering, washing the residue with 500 ml of ether and concentrating the filtrate under reduced pressure a solution of the oil obtained was mixed in 300 ml of methanol with 600 ml of HCl-saturated methanol whille cooling with ice, stirred for 0.5 hour at 0C and 2 hours at room temperature and again concentrated by evaporation. ,A solution of the syrup in 800 ml of methylene chloride was washed with 670 ml of a 3 M solution of caustic soda while cooling with ice and 10concentrated to 107.5 g (69%) of crude (R,S)-2-(t-butyl)-3-methyl-1,3-imidazolidin-4-one, a yellowish oil which crystallized in the cold. (For analytics see R. NaeE and ~.
Seebach, Helv. Chim. Acta 68, 135 ~1985).
b) Enantiomer Separation of (RS)-2-(t-butyl)-3-methyl-1,3-imidazolidin-4-one ~; A mixture of 70 g (0.448 mole) of the (R,S)-2-(t-butyl)-3-methyl-1,3-imidazolidin-4-one and 70 g of (R)-~-)-mandelic acid was dissolved in boiling acetone. On cooling to room temperatures within 6 hours and further 15 hours at 5C
the precipltated crystal cake was filtered off. Upon drying, 54.5 g of a slightly yellow crystallizate of R-mandelic acid and (R)-2-t-(butyl3-3-methyl-1,3-imidazolidin-4-one was iso-lated.
c) Production of (S)-(+)-l-benzoyl-2-(t-butyl)-3-methyl-1,3-imidazolidln-4-one A suspension of the diastereomeric salt of (R)-(-)-mandelic acid and ~R)-2-~t-butyl)-3-methyl-(1,3-imidazolidin-4-one (54.5 g, 0.177 mole) obtained according to b) in 200 ml of methylene chloride was mixed with g2 ml of a 2 M solution of caustic soda and shaken. By extracting the water phase acidlfied with a 50% sul~huric acid with 300 ml of acetic ethyl ester up to 25.5 g of (R)-(-)-mandelic acid can be 5 _ ~96733 recovered.
The 1,3-imidazolidin-4-one remaining in the organic phase was benzoylated by adding 20.1 ml (0.173 mole) of ben-zoyl chloride and 195 ml of a 1 M solution of caustic soda while cooling with ice. The organic phase was separated, dried over magnesium sulphate and concentrated under reduced pressure.
45.8 g of yellow crystallizate with ~ c~ ]D = + 107 (c = 1, CH2C12) were obtained. :~
Crystallizing twice from ethanol, precipitating from methylene chloride with pentane and drying for 12 hours at 0.1 torr and 60C yielded 34.7 g ~60~) of (S)-~)-l-benzoyl-2-(t-butyl)-3--methyl-1,3-imidazolidin-4-one with [c~]D = ~ 127 (c 1, CH2C12 ) -By crystallizing a sample three times from an ethanol and subsequent sublimation (135C/0.01 torr) an ~D
of ~ 127.5C and a melting point of 143 to 144C were obtained.
The spectroscopic data correspond to those of the (R,S)-compound described by Seebach et al. in Helv. Chim. Acta 68, 949 (1985).
d) Production of (R)-(-)-benzoyl)-2-(t-butyl)-3-methyl-1,3-lmidazolidin-4-one The syrup remaining on concentrating the crystal-lization mother liquor obtained according to b) was taken up in 300 ml oE methylene chloride, whereupon - as described under c)- the mandelic acid was washed out first (140 ml of a 2 M solution of caustic soda~ and the 1,3-imidazolidin-4-one was then directly benzoylated in the organic phase (30 ml, (0.258 mole) of benzoyl chloride, 280 ml of a 1 M solution of caustic soda).
The crude crystal obtained on concentrating the ~29~733 organic phase under reduced pressure was recrystallized from 45 ml of ethanol.
33.6 g of crystals with [c~]D = --109 (c = l, CH~C12) were obtained.
Recrystallizing and drying - as described under c) -yielded 26.4 g (45%) of (R)~ benzoyl-2-(t-butyl)-3-methyl-1,3-imidazolidin-4-one with [c~]D = -126 (c = 1, CH2C~
~ 30
Claims (10)
1. A process for producing enantiomer-pure (R)- and (S)-1,3-imidazolidin-4-ones having the general formula (I), wherein * represents an asymmetry centre, R represents a straight-chain C1 to C4-alkyl group and R1 a phenyl or benzyl group, a phenyl-oxy or benzyl-oxy group or a phenyl group mono- or tri-substituted in any ring position by a C1 to C4-alkyl or alkoxy group, in which a racemic 1,3-imidazolidin-4-one having the general formula (II), wherein R has the meaning defined above, is converted into a diastereomeric salt pair by reaction with a chiral acid, said salt pair is fractionated and crystallized, (R)-II and (S)-II
are isolated on dividing this salt pair and these compounds are reacted with an acid halide having the general formula (IIIa), wherein Hal is chlorine or bromine or with an anhydride having the general formula (IIIb), wherein R1 has the meaning defined above.
are isolated on dividing this salt pair and these compounds are reacted with an acid halide having the general formula (IIIa), wherein Hal is chlorine or bromine or with an anhydride having the general formula (IIIb), wherein R1 has the meaning defined above.
2. A process according to claim 1, in which (R,S)-2-(t-butyl)-3-methyl-1,3-imidazolidin-4-one is used.
3. A process according to claim 1 or 2, in which (R)- and (S)-mandelic acid is used as chiral acid.
4. A process according to claim 1 or 2, in which (-)-diacetone-2-ketogulonic acid is used as chiral acid.
5. A process according to claim 1, in which the chiral acid is selected from N-acetyl amino acids, Z-protected amino acids, pyroglutamic acid, tartaric acid, malic acid, camphor-10-sulphonic acid, dibenzoyl tartaric acid and deoxy cholic acid.
6. A process according to claim 1, in which the reaction with the chiral acid is effected at a temperature from -30°C to 25°C in a solvent.
7. A process according to claim 6, in which the solvent is an alcohol, a mixture of alcohol with water, a acetic ester or a chlorinated hydrocarbon.
8. A process according to claim 7, in which the chlorinated hydrocarbon solvent is methylene chloride or chlo-roform.
9. A process according to claim 6, in which the solvent is acetone.
10. A process according to claim 6, in which the crystallization is effected in a chlorinated hydrocarbon and reacting with an aqueous solution of caustic soda or potash.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19863604591 DE3604591A1 (en) | 1986-02-14 | 1986-02-14 | METHOD FOR PRODUCING CHIRAL GLYCINE DERIVATIVES |
| DEP3604591.8 | 1986-02-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1296733C true CA1296733C (en) | 1992-03-03 |
Family
ID=6294046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000529668A Expired - Lifetime CA1296733C (en) | 1986-02-14 | 1987-02-13 | Process for producing chiral glycine derivatives |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0237630B1 (en) |
| JP (1) | JPS62192362A (en) |
| AT (1) | ATE78250T1 (en) |
| CA (1) | CA1296733C (en) |
| DE (2) | DE3604591A1 (en) |
| ES (1) | ES2044832T3 (en) |
| GR (1) | GR3005294T3 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5138060A (en) * | 1991-01-03 | 1992-08-11 | Pfizer Inc. | Process and intermediates for preparing azabicyclo(2.2.2)octan-3-imines |
| DE4137663A1 (en) * | 1991-11-12 | 1993-05-13 | Degussa | METHOD FOR PRODUCING OPTICALLY ACTIVE 1,3-IMIDAZOLIDIN-4-ONE AND THE USE THEREOF |
| FR2831033B1 (en) | 2001-10-23 | 2004-03-12 | Oreal | DEVICE FOR PACKAGING AND / OR APPLYING A PRODUCT TO EYELASHES AND / OR EYEBROWS AND MAKE-UP METHOD |
| EP2093218A1 (en) | 2008-02-22 | 2009-08-26 | Ruggero Fariello | Arylalkyl substituted imidazolidinones |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3334855A1 (en) * | 1983-09-27 | 1985-04-11 | Degussa Ag, 6000 Frankfurt | METHOD FOR THE ENANTIOSELECTIVE PRODUCTION OF (ALPHA) -ALKYLATED, ACYCLIC (ALPHA) -AMINOCARBONIC ACIDS |
-
1986
- 1986-02-14 DE DE19863604591 patent/DE3604591A1/en not_active Withdrawn
- 1986-11-21 EP EP86116149A patent/EP0237630B1/en not_active Expired - Lifetime
- 1986-11-21 AT AT86116149T patent/ATE78250T1/en not_active IP Right Cessation
- 1986-11-21 ES ES86116149T patent/ES2044832T3/en not_active Expired - Lifetime
- 1986-11-21 DE DE8686116149T patent/DE3686049D1/en not_active Expired - Lifetime
-
1987
- 1987-02-02 JP JP62020614A patent/JPS62192362A/en active Pending
- 1987-02-13 CA CA000529668A patent/CA1296733C/en not_active Expired - Lifetime
-
1992
- 1992-07-29 GR GR920401625T patent/GR3005294T3/el unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0237630A3 (en) | 1989-11-15 |
| DE3686049D1 (en) | 1992-08-20 |
| ATE78250T1 (en) | 1992-08-15 |
| EP0237630A2 (en) | 1987-09-23 |
| ES2044832T3 (en) | 1994-01-16 |
| EP0237630B1 (en) | 1992-07-15 |
| GR3005294T3 (en) | 1993-05-24 |
| DE3604591A1 (en) | 1987-08-20 |
| JPS62192362A (en) | 1987-08-22 |
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