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US4415504A
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p-Hydroxyphenylglycine.α-phenylethanesulfonate, process for production thereof and utilization thereof in resolution of p-hydroxyphenylglycine
Assignee: Tanabe Pharma Corp
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Filing: 1982-09-09
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Granted: 1983-11-15
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Expires: 2002-09-09
Abstract
Abstract p-Hydroxyphenylglycine. alpha -phenylethanesulfonate which is useful for the production of optically active p-hydroxyphenylglycine and optically active alpha -phenylethanesulfonic acid is disclosed. p-Hydroxyphenylglycine. alpha -phenylethanesulfonate is produced by either reacting DL-p-hydroxyphenylglycine with optically active alpha -phenylethanesulfonic acid or reacting (+/-)- alpha -phentylethanesulfonic acid with optically active p-hydroxyphenylglycine to form two diastereomers of DL-p-hydroxyphenylglycine optically active alpha -phenylethanesulfonate or optically active p-hydroxyphenylglycine (+/-)- alpha -phenylethanesulfonate, and isolating one diastereomer according to the difference between solubilities of the diastereomers, optionally, combining selective crystallization of one diastereomer and epimerization of another diastereomer in the case of reaction of DL-p-hydroxyphenylglycine and optically active alpha -phenylethanesulfonic acid. This reaction is utilized in the resolution of p-hydroxyphenylglycine or alpha -phenylethanesulfonic acid by deacidifying the resulting diastereomer.
Inventors
- 👤 Ichiro Chibata
- 👤 Shigeki Yamada
- 👤 Chikara Hongo
- 👤 Ryuzo Yoshioka
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 21:24
CPC Classifications
C; C07; C07C; C07C229/00; C07C229/02; C07C229/34; C07C229/36; C07C227/00; C07C227/30; C07C227/34; C07C303/00; C07C303/42; C07C303/44; C07C309/00; C07C309/01; C07C309/02; C07C309/24; C07B; C07B2200/00; C07B2200/07; Y; Y02; Y02P; Y02P20/00; Y02P20/50; Y02P20/582
Claims Analysis
Total Claims: 37
Claim 1
Independent Claim
1 words
p-Hydroxyphenylglycine.α-phenylethanesulfonate.
Claim 2
Dependent Claim
1 words
p-Hydroxyphenylglycine.α-phenylethanesulfonate.
Claim 3
Dependent Claim
10 words
The compound according to claim 1 being DL-p-hydroxyphenylglycine.optically active α-phenylethanesulfonate.
Claim 4
Dependent Claim
10 words
The compound according to claim 1 being optically active p-hydroxyphenylglycine.(±)-α-phenylethanesulfonate.
Claim 5
Dependent Claim
8 words
The compound according to claim 1 being D-p-hydroxyphenylglycine.(+)-α-phenylethanesulfonate.
Claim 6
Dependent Claim
8 words
The compound according to claim 1 being L-p-hydroxyphenylglycine.(-)-α-phenylethanesulfonate.
Claim 7
Dependent Claim
60 words
A process for producing the optically active p-hydroxyphenylglycine.optically active α-phenylethanesulfonate which comprises reacting DL-p-hydroxyphenylglycine with optically active α-phenylethanesulfonic acid to form two diastereomers of the optically active p-hydroxyphenylglycine.optically active α-phenylethanesulfonate one of which being the easily soluble diastereomer and the other of which being the slightly soluble diastereomer, crystallizing the slightly soluble diastereomer and collecting the crystallized slightly soluble diastereomer.
Claim 8
Dependent Claim
60 words
A process for producing the optically active p-hydroxyphenylglycine.optically active α-phenylethanesulfonate which comprises reacting DL-p-hydroxyphenylglycine with optically active α-phenylethanesulfonic acid to form two diastereomers of the optically active p-hydroxyphenylglycine.optically active α-phenylethanesulfonate one of which being the easily soluble diastereomer and the other of which being the slightly soluble diastereomer, crystallizing the slightly soluble diastereomer and collecting the crystallized slightly soluble diastereomer.
Claim 9
Dependent Claim
25 words
A process according to claim 6, wherein crystallization of the slightly soluble diastereomer is effected under a condition for epimerization of the easily soluble diastereomer.
Claim 10
Dependent Claim
26 words
A process according to claim 6 or 7, wherein optically active α-phenylethanesulfonic acid is used in a molar ratio to DL-p-hydroxyphenylglycine of about 0.5 or more.
Claim 11
Dependent Claim
24 words
A process according to claim 8, wherein optically active α-phenylethanesulfonic acid is used in a molar ratio to DL-p-hydroxyphenylglycine of about 0.8 to 1.1.
Claim 12
Dependent Claim
23 words
A process according to claim 7, wherein the epimerization is effected in the presence of water with heating at 80° to 160° C.
Claim 13
Dependent Claim
24 words
A process according to claim 7, wherein the epimerization is effected in the presence of a aliphatic acid and an aliphatic or aromatic aldehyde.
Claim 14
Dependent Claim
18 words
A process according to claim 11, wherein the aliphatic acid is that having 1 to 5 carbon atoms.
Claim 15
Dependent Claim
14 words
A process according to claim 12, wherein the aliphatic acid is glacial acetic acid.
Claim 16
Dependent Claim
21 words
A process according to claim 11, wherein the aliphatic acid is present in a concentration of 50 W/V % or more.
Claim 17
Dependent Claim
30 words
A process according to claim 11, wherein the aldehyde is a member selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, n-butylaldehyde, i-butylaldehyde, acrolein, benzaldehyde, salicylaldehyde, hydroxybenzaldehyde, nitrobenzaldehyde and anisaldehyde.
Claim 18
Dependent Claim
13 words
A process according to claim 15, wherein the aldehyde is salicylaldehyde or n-butylaldehyde.
Claim 19
Dependent Claim
23 words
A process according to claim 15, the aldehyde is used in a molar ratio to DL-p-hydroxyphenylglycine.optically active α-phenylethanesulfonic acid of 0.01 to 0.2.
Claim 20
Dependent Claim
19 words
A process according to claim 7, wherein the epimerization is effected in the presence of a free amino acid.
Claim 21
Dependent Claim
27 words
A process according to claim 18, wherein the free amino acid is used in a molar ratio to optically active α-phenylethanesulfonic acid of about 0.02 to 0.2.
Claim 22
Dependent Claim
32 words
A process according to claim 6, wherein the reaction is carried out in an aqueous solvent and collection of the diastereomer is effected according to the difference between solubilities of two diastereomers.
Claim 23
Dependent Claim
30 words
A process according to claim 20, wherein the solvent is a member selected from the group consisting of water, methanol, ethanol, acetone, acetic acid, propionic acid and a mixture thereof.
Claim 24
Dependent Claim
49 words
A process for producing optically active p-hydroxyphenylglycine which comprises reacting DL-p-hydroxyphenylglycine with optically active α-phenylethanesulfonic acid to form two diastereormers of the optically active p-hydroxyphenylglycine.optically active α-phenylethane sulfonate, epimerizing the easily soluble diastereomer, collecting the crystallized slightly soluble diastereomer and converting the slightly soluble diastereomer into optically active p-hydroxyphenylglycine.
Claim 25
Dependent Claim
49 words
A process for producing optically active p-hydroxyphenylglycine which comprises reacting DL-p-hydroxyphenylglycine with optically active α-phenylethanesulfonic acid to form two diastereormers of the optically active p-hydroxyphenylglycine.optically active α-phenylethane sulfonate, epimerizing the easily soluble diastereomer, collecting the crystallized slightly soluble diastereomer and converting the slightly soluble diastereomer into optically active p-hydroxyphenylglycine.
Claim 26
Independent Claim
33 words
A method for resolving DL-p-hydroxyphenylglycine which comprises reacting DL-p-hydroxyphenylglycine with optically active α-phenylethanesulfonic acid to form two diastereomers of DL-p-hydroxyphenylglycine.optically active α-phenylethanesulfonate collecting one diastereomer and converting the diastereomer into optically active p-hydroxyphenylglycine.
Claim 27
Independent Claim
33 words
A method for resolving DL-p-hydroxyphenylglycine which comprises reacting DL-p-hydroxyphenylglycine with optically active α-phenylethanesulfonic acid to form two diastereomers of DL-p-hydroxyphenylglycine.optically active α-phenylethanesulfonate collecting one diastereomer and converting the diastereomer into optically active p-hydroxyphenylglycine.
Claim 28
Dependent Claim
32 words
A method according to claim 23, wherein the reaction is carried out in an aqueous solvent and collection of the diastereomer is effected according to the difference between solubilities of two diastereomers.
Claim 29
Dependent Claim
30 words
A method according to claim 24, wherein the solvent is a member selected from the group consisting of water, methanol, ethanol, acetone, acetic acid, propionic acid and a mixture thereof.
Claim 30
Dependent Claim
25 words
A method according to claim 24, wherein optically active α-phenylethanesulfonic acid is used in a molar ratio of to DL-p-hydroxyphenylglycine of about 0.5 or more.
Claim 31
Dependent Claim
15 words
A method according to claim 26, wherein the molar ratio is about 0.8 to 1.1.
Claim 32
Independent Claim
30 words
A method for resolving (±)-α-phenylethanesulfonic acid which comprises reacting (±)-α-phenylethanesulfonic acid with optically active p-hydroxyphenylglycine to form two diastereomers of optically active p-hydroxyphenylglycine.(±)-α-phenylethanesulfonate, collecting one diastereomer and deacidifying the diastereomer.
Claim 33
Independent Claim
30 words
A method for resolving (±)-α-phenylethanesulfonic acid which comprises reacting (±)-α-phenylethanesulfonic acid with optically active p-hydroxyphenylglycine to form two diastereomers of optically active p-hydroxyphenylglycine.(±)-α-phenylethanesulfonate, collecting one diastereomer and deacidifying the diastereomer.
Claim 34
Dependent Claim
32 words
A method according to claim 28, wherein the reaction is carried out in an aqueous solvent and collection of the diastereomer is effected according to the difference between solubilities of two diastereomers.
Claim 35
Dependent Claim
30 words
A method according to claim 29, wherein the solvent is a member selected from the group consisting of water, methanol, ethanol, acetone, acetic acid, propionic acid and a mixture thereof.
Claim 36
Dependent Claim
24 words
A method according to claim 29, wherein optically active p-hydroxyphenylglycine is used in a molar ratio to (±)-α-phenylethanesulfonic acid of about 0.5 or more.
Claim 37
Dependent Claim
15 words
A method according to claim 31, wherein the molar ratio is about 0.8 to 1.1.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-11-14 | 1987-05-16 | 1987-11-15 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-11-14 | 1991-05-16 | 1991-11-15 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-11-14 | 1995-05-16 | 1995-11-15 | $7700.00 | Window Closed / Lapsed |