US4207258A
Expired / Lapsed
US
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Process for the preparatin of α-6-deoxytetracyclines
Assignee: Glaxochem SpA
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Filing: 1977-02-28
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Granted: 1980-06-10
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Expires: 1997-02-28
Abstract
Abstract A process is provided for preparing alpha-6-deoxytetracyclines depicted by the formula: ##STR1## wherein Y is H, F, Cl, Br or I; and R is H, OH or --O--CO--(C 1-6 alkyl); which comprises: contacting a 6-demethyl-6-deoxy-6-methylene tetracycline or salt thereof having the formula ##STR2## in which Y and R are as given above, with hydrogen at a temperature of between 15° C. and 80° C. in the presence of a catalyst soluble in a polar solvent, said catalyst being a complex of rhodium with electron donor ligands of a tertiary phosphine selected from the group consisting of triphenylphosphine, tributylphosphine, triethylphosphine, diethylphenylphosphine and diphenylethylphosphine and said polar solvent being a mono- or polyhydric alcohol with from 1 to 4 carbon atoms, N,N-dimethylformamide, N,N-dimethylacetamide, dioxan, tetrahydrofuran, methoxyethanol, ethoxyethanol, acetonitrile or pyridine.
Inventors
- 👤 Renato Broggi
- 👤 Gino Cotti
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 23:37
CPC Classifications
C; C07; C07C; C07C233/00
Claims Analysis
Total Claims: 15
Claim 1
Independent Claim
127 words
A process for the preparation of alpha-6-deoxytetracyclines of the formula: ##STR7## wherein Y is H, F, Cl, Br or I; and R is H, OH or --O--CO--(C 1-6 alkyl); which comprises contacting a 6-demethyl-6-deoxy-6-methylene tetracycline or salt thereof having the formula ##STR8## in which Y and R are as indicated above, with hydrogen at a temperature of between 15° C. and 80° C. in the presence of a catalyst soluble in a polar solvent, said catalyst being a complex of rhodium with electron donor ligands of a tertiary phosphine selected from the group consisting of triphenylphosphine, tributylphosphine, triethylphosphine, diethylphenylphosphine and diphenylethylphosphine and said polar solvent being a mono- or polyhydric alcohol with from 1 to 4 carbon atoms, N,N-dimethylformamide, N,N-dimethylacetamide, dioxan, tetrahydrofuran, methoxyethanol, ethoxyethanol, acetonitrile or pyridine.
Claim 2
Dependent Claim
127 words
A process for the preparation of alpha-6-deoxytetracyclines of the formula: ##STR7## wherein Y is H, F, Cl, Br or I; and R is H, OH or --O--CO--(C 1-6 alkyl); which comprises contacting a 6-demethyl-6-deoxy-6-methylene tetracycline or salt thereof having the formula ##STR8## in which Y and R are as indicated above, with hydrogen at a temperature of between 15° C. and 80° C. in the presence of a catalyst soluble in a polar solvent, said catalyst being a complex of rhodium with electron donor ligands of a tertiary phosphine selected from the group consisting of triphenylphosphine, tributylphosphine, triethylphosphine, diethylphenylphosphine and diphenylethylphosphine and said polar solvent being a mono- or polyhydric alcohol with from 1 to 4 carbon atoms, N,N-dimethylformamide, N,N-dimethylacetamide, dioxan, tetrahydrofuran, methoxyethanol, ethoxyethanol, acetonitrile or pyridine.
Claim 3
Dependent Claim
60 words
The process according to claim 1, wherein said catalyst is RhCl(Ph 3 P) 3 , RhCl(Ph 3 P), the dimer Rh 2 Cl 2 (Ph 3 P) 4 , the hydride derivative RhHCl 2 (Ph 3 P) 3 , the dihydride derivative RhH 2 Cl(Ph 3 P) 3 , or a solvate obtained from said complex with said polar solvent.
Claim 4
Dependent Claim
34 words
The process according to claim 1, wherein said catalyst is prepared directly in the reaction medium by reacting 1 mole RhCl 3 or RhCl 3 .3H 2 O with 1 to 4 mole triphenylphosphine.
Claim 5
Dependent Claim
17 words
The process of claim 1 wherein said catalyst is prepared from a rhodium chloride and a triphenylphosphine.
Claim 6
Dependent Claim
29 words
The process of claim 1, wherein said catalyst is RhCl(Ph 3 P) 2 S wherein Ph is a phenyl group and S is a molecule of said polar solvent.
Claim 7
Dependent Claim
13 words
A process of claim 1, wherein said 6-demethyl-6-deoxy-6-methylenetetracycline is 6-deoxy-6-demethyl-6-methylene-5-hydroxytetracycline or salt thereof.
Claim 8
Dependent Claim
14 words
A process of claim 6, wherein said salt is the hydrochloride of said 6-deoxy-6-demethyl-6-methylene-5-hydroxytetracycline.
Claim 9
Dependent Claim
14 words
A process of claim 1 conducted at a pressure of 1 to 150 kg/cm.
Claim 10
Dependent Claim
14 words
The process of claim 1 wherein said polar solvent is N,N-dimethylacetamide, N,N-dimethylformamide or methanol.
Claim 11
Dependent Claim
11 words
The process of claim 9 wherein said polar solvent is N,N-dimethylacetamide.
Claim 12
Dependent Claim
11 words
The process of claim 9 wherein said polar solvent is N,N-dimethylformamide.
Claim 13
Dependent Claim
11 words
The process of claim 9 wherein said polar solvent is methanol.
Claim 14
Dependent Claim
86 words
A process for the homogeneous catalytic hydrogenation of tetracyclines which comprises the step of treating a tetracycline of the formula ##STR9## where R is H or OH with hydrogen in the presence of a catalyst of the formula Rh Cl (Ph 3 P) 3 where Ph is phenyl at temperatures of between 15° C. and 80° C. at hydrogen pressures of from 1 to 150 Kg/cm 2 in a polar solvent selected from C 1 -C 4 alcohols, N,N'-dimethylacetamide, dioxane, tetrahydrofuran, methoxyethanol, ethoxyethanol, acetonitrile, and pyridine.
Claim 15
Dependent Claim
86 words
A process for the homogeneous catalytic hydrogenation of tetracyclines which comprises the step of treating a tetracycline of the formula ##STR9## where R is H or OH with hydrogen in the presence of a catalyst of the formula Rh Cl (Ph 3 P) 3 where Ph is phenyl at temperatures of between 15° C. and 80° C. at hydrogen pressures of from 1 to 150 Kg/cm 2 in a polar solvent selected from C 1 -C 4 alcohols, N,N'-dimethylacetamide, dioxane, tetrahydrofuran, methoxyethanol, ethoxyethanol, acetonitrile, and pyridine.
References Cited (Backward Citations)
No citation records indexed.
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1983-06-10 | 1983-12-10 | 1984-06-10 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1987-06-10 | 1987-12-10 | 1988-06-10 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1991-06-10 | 1991-12-10 | 1992-06-10 | $7700.00 | Window Closed / Lapsed |