US4500458A
Expired / Lapsed
US
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Process for the preparation of α-6-deoxytetracyclines
Assignee: Plurichemie Anstalt
•
Filing: 1983-01-14
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Granted: 1985-02-19
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Expires: 2003-01-14
Abstract
Abstract An improved process for the preparation of α-6-deoxytetracyclines and more particularly to the stereo specific hydrogenation of the 6-methylene group of 6-deoxy-6-demethyl-6-methylene-5-hydroxytetracyline and of its 11a-halo-analog, is described in which the catalyst is the reaction product of a rhodium salt or a complex with a hydrazine or salt thereof.
Inventors
- 👤 Ivan Villax
- 👤 Philip R. Page
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 21:13
CPC Classifications
B; B01; B01J; B01J31/00; B01J31/26; B01J31/28; B01J31/16; B01J31/18; B01J31/1805; B01J31/24; B01J31/2404; B01J2231/00; B01J2231/60; B01J2231/64; B01J2231/641; B01J2231/645; B01J2531/00; B01J2531/80; B01J2531/82; B01J2531/822
Claims Analysis
Total Claims: 21
Claim 1
Independent Claim
71 words
A new improved homogeneous hydrogenation process to prepare α-6-deoxytetracyclines in high yield and purity from a 6-deoxy-6-demethyl-6-methylenetetracycline or salt thereof in the presence or absence of a tertiary phosphine or from a 11a-chloro-6-deoxy-6-demethyl-6-methylenetetracycline or a salt thereof in the presence of a tertiary phosphine by catalytic hydrogenation, characterised in that the catalyst is a tertiary phosphine-hydrazino-chlororhodium obtained by reacting a rhodium salt or a complex with a hydrazine or salt thereof.
Claim 2
Dependent Claim
71 words
A new improved homogeneous hydrogenation process to prepare α-6-deoxytetracyclines in high yield and purity from a 6-deoxy-6-demethyl-6-methylenetetracycline or salt thereof in the presence or absence of a tertiary phosphine or from a 11a-chloro-6-deoxy-6-demethyl-6-methylenetetracycline or a salt thereof in the presence of a tertiary phosphine by catalytic hydrogenation, characterised in that the catalyst is a tertiary phosphine-hydrazino-chlororhodium obtained by reacting a rhodium salt or a complex with a hydrazine or salt thereof.
Claim 3
Dependent Claim
32 words
Process according to claim 1, wherein for each part of substrate to be hydrogenated the amount of rhodium metal in the catalyst necessary to perform the hydrogenation is less than 0.0007 part.
Claim 4
Dependent Claim
22 words
Process according to claim 1 wherein the rhodium salt or complex is tris(triphenylphosphine)chlororhodium and the hydrazine or a salt thereof is hydrazine.
Claim 5
Dependent Claim
22 words
Process according to claim 1 wherein the rhodium salt or complex is tris(triphenylphosphine)chlororhodium and the hydrazine or salt thereof is phenyl hydrazine.
Claim 6
Dependent Claim
25 words
Process according to claim 1 wherein the rhodium salt or complex there of is rhodium trichloride trihydrate and the hydrazine or salt thereof is hydrazine.
Claim 7
Dependent Claim
19 words
Process according to claim 1 wherein the catalyst is the reaction product of rhodium trichloride trihydrate, triphenylphosphine and benzenesulphonylhdyrazine.
Claim 8
Dependent Claim
32 words
Process according to claim 1 wherein 6-deoxy-6-demethyl-6-methylene-tetracycline or salt thereof is hydrogenated in the presence of said catalyst and 0.01-0.06 mole of tertiary phosphine per mole of tertiary phosphine of said catalyst.
Claim 9
Dependent Claim
31 words
Process according to claim 7 wherein the tertiary phosphine in the catalyst and the additional tertiary phosphine in which the reaction is carried out in the presence of are the same.
Claim 10
Dependent Claim
37 words
Process according to claim 1 in which a 11a-chloro-6-deoxy-6-demethyl-6-methylenetetracycline or a salt thereof is hydrogenated in the presence of said catalyst and up to 1 mole of tertiary phosphine per mole of tertiary phosphine in said catalyst.
Claim 11
Dependent Claim
31 words
Process according to claim 9 wherein the tertiary phosphine in the catalyst and the additional tertiary phosphine in which the reaction is carried out in the presence of are the same.
Claim 12
Dependent Claim
12 words
Process according to claim 1 wherein 6-deoxy-6-demethyl-6-methylenetetracycline or salt thereof is hydrogenated.
Claim 13
Dependent Claim
28 words
Process according to claim 1, wherein the pure α-6-deoxytetracycline formed is recovered directly from the reaction mixture as crystalline p-toluenesulfonate by addition of an excess of p-toluenesulfonic acid.
Claim 14
Dependent Claim
28 words
Process according to claim 2, wherein the pure α6-deoxytetracycline formed is recovered directly from the reaction mixture as crystalline p-toluenesufonate by addition of an excess of p-toluenesulfonic acid.
Claim 15
Dependent Claim
28 words
Process according to claim 3, wherein the pure α6-deoxytetracycline formed is recovered directly from the reaction mixture as crystalline p-toluenesolufonate by addition of an excess of p-toluenesulfonic acid.
Claim 16
Dependent Claim
28 words
Process according to claim 4, wherein the pure α6-deoxytetracycline formed is recovered directly from the reaction mixture as crystalline p-toluenesulfonate by addition of an excess of p-toluenesulfonic acid.
Claim 17
Dependent Claim
28 words
Process according to claim 5, wherein the pure α6-deoxytetracycline formed is recovered directly from the reaction mixture as crystalline p-toluenesulfonate by addition of an excess of p-toluenesulfonic acid.
Claim 18
Dependent Claim
28 words
Process according to claim 6, wherein the pure α6-deoxytetracycline formed is recovered directly from the reaction mixture as crystalline p-toluenesulfonate by addition of an excess of p-toluenesulfonic acid.
Claim 19
Dependent Claim
28 words
Process according to claim 7, wherein the pure α6-deoxytetracycline formed is recovered directly from the reaction mixture as crystalline p-toluenesulfonate by addition of an excess of p-toluenesulfonic acid.
Claim 20
Dependent Claim
28 words
Process according to claim 8, wherein the pure α6-deoxytetracycline formed is recovered directly from the reaction mixture as crystalline p-toluenesulfonate by addition of an excess of p-toluenesulfonic acid.
Claim 21
Dependent Claim
28 words
Process according to claim 9, wherein the pure α6-deoxytetracycline formed is recovered directly from the reaction mixture as crystalline p-toluenesulfonate by addition of an excess of p-toluenesulfonic acid.
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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) | 1988-02-19 | 1988-08-20 | 1989-02-19 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1992-02-19 | 1992-08-20 | 1993-02-19 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1996-02-19 | 1996-08-20 | 1997-02-19 | $7700.00 | Window Closed / Lapsed |