US4053468A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Process for preparing 7-oxo cephalosporins and 6-oxo penicillins
Assignee: GlaxoSmithKline LLC
•
Filing: 1976-02-25
•
Granted: 1977-10-11
•
Expires: 1996-02-25
Abstract
Abstract A process for preparing 7-oxo cephalosporins and 6-oxo penicillins by reaction of a 7-amino cephalosporin or 6-amino penicillin with a carbonyl-containing oxidizing agent is disclosed.
Inventors
- 👤 Kenneth G. Holden
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-25 17:26
CPC Classifications
C; C07; C07D; C07D499/00
Claims Analysis
Total Claims: 16
Claim 1
Independent Claim
154 words
A process for preparing a compound of the formula: ##STR3## R 1 is hydrogen or an easily removable conventional penicillin or cephalosporin ester protecting group; and R 2 is hydrogen, acetoxy or SHet where Het is a five or six membered heterocyclic ring containing carbon and one to four atoms selected from the group consisting of N, O and S, each such ring being unsubstituted or substituted with one or two groups selected from alkyl, alkoxyalkyl and trifluoromethyl, each alkyl or alkoxy group having from one to four carbon atoms, comprising reacting, in the presence of a non-hydroxylic solvent, a 7-amino cephalosporin or 6-amino penicillin of the formula: ##STR4## in which A, R 1 and R 2 are defined as above, with a carbonyl containing oxidizing agent selected from the group consisting of: mesitylglyoxal, 3-nitromesitylglyoxal, 3,5-dinitromesitylglyoxal, benzothiazole-2-carboxaldehyde, 6-nitrobenzothiazole-2-carboxaldehyde, 3,5-di-i-propyl-1,2-benzoquinone, 3-methyl-5-i-propyl-1,2-benzoquinone, tetrachloro-1,2-benzoquinone tetrabromo-1,2-benzoquinone, 2,6-di-t-butyl-1,4-benzoquinone and 3,5-di-t-butyl-1,2-benzoquinone, said reaction being carried out with removal of water.
Claim 2
Dependent Claim
154 words
A process for preparing a compound of the formula: ##STR3## R 1 is hydrogen or an easily removable conventional penicillin or cephalosporin ester protecting group; and R 2 is hydrogen, acetoxy or SHet where Het is a five or six membered heterocyclic ring containing carbon and one to four atoms selected from the group consisting of N, O and S, each such ring being unsubstituted or substituted with one or two groups selected from alkyl, alkoxyalkyl and trifluoromethyl, each alkyl or alkoxy group having from one to four carbon atoms, comprising reacting, in the presence of a non-hydroxylic solvent, a 7-amino cephalosporin or 6-amino penicillin of the formula: ##STR4## in which A, R 1 and R 2 are defined as above, with a carbonyl containing oxidizing agent selected from the group consisting of: mesitylglyoxal, 3-nitromesitylglyoxal, 3,5-dinitromesitylglyoxal, benzothiazole-2-carboxaldehyde, 6-nitrobenzothiazole-2-carboxaldehyde, 3,5-di-i-propyl-1,2-benzoquinone, 3-methyl-5-i-propyl-1,2-benzoquinone, tetrachloro-1,2-benzoquinone tetrabromo-1,2-benzoquinone, 2,6-di-t-butyl-1,4-benzoquinone and 3,5-di-t-butyl-1,2-benzoquinone, said reaction being carried out with removal of water.
Claim 3
Dependent Claim
21 words
A process according to claim 1 in which R 1 is benzhydryl, t-butyl, 2,2,2-trichloroethyl, benzyl, benzyloxymethyl, p-nitrophenyl, p-methoxyphenyl, p-nitrobenzyl or p-methoxybenzyl.
Claim 4
Dependent Claim
29 words
A process according to claim 1 in which R 2 is hydrogen, acetoxy or SHet where Het is unsubstituted or methyl substituted 1,2,3-triazolyl, 1,2,4-triazolyl, 1,2,3,4-tetrazolyl, 1,3,4-oxadiazolyl, 1,3,4-thiadiazolyl or 1,2,4-thiadiazolyl.
Claim 5
Dependent Claim
31 words
A process according to claim 1 in which the reaction is carried out in tetrahydrofuran, dioxane, chloroform, methylene chloride, carbon tetrachloride, benzene, toluene, xylene, ethyl acetate, ether, acetonitrile, dimethylformamide or dimethylsulfoxide.
Claim 6
Dependent Claim
14 words
A process according to claim 4 in which the carbonyl-containing oxidizing agent is 3,5-di-t-butyl-1,2-benzoquinone.
Claim 7
Dependent Claim
24 words
A process according to claim 4 in which the 7-amino cephalosporin or 6-amino penicillin and the carbonyl-containing oxidizing agent are present in equimolar amounts.
Claim 8
Dependent Claim
20 words
A process according to claim 6 in which the reaction is carried out in the presence of a dehydrating agent.
Claim 9
Dependent Claim
18 words
A process according to claim 6 in which the reaction is carried out with azeotropic removal of water.
Claim 10
Dependent Claim
13 words
A process according to claim 6 in which the reaction is base catalyzed.
Claim 11
Dependent Claim
33 words
A process according to claim 7 in which the reaction is carried out at a temperature of from about 0° C. to about 190° C. for from about 1 to about 72 hours.
Claim 12
Dependent Claim
33 words
A process according to claim 10 in which the reaction is carried out at a temperature of from about 0° C. to about 25° C. for from about 12 to about 72 hours.
Claim 13
Dependent Claim
38 words
A process according to claim 11 for preparing 7-oxocephalosporanic acid t-butyl ester comprising reacting 7-aminocephalosporanic acid t-butyl ester with 3,5-di-t-butyl-1,2-benzoquinone in tetrahydrofuran in the presence of molecular sieves as a dehydrating agent at 4° C. for 12 hours.
Claim 14
Dependent Claim
38 words
A process according to claim 11 for preparing 7-oxodesacetoxycephalosporanic acid t-butyl ester comprising reacting 7-aminodesacetoxycephalosporanic acid t-butyl ester and 3,5-di-t-butyl-1,2-benzoquinone in tetrahydrofuran in the presence of molecular sieves as a dehydrating agent at 4° C. for 72 hours.
Claim 15
Dependent Claim
35 words
A process according to claim 11 for preparing 7-oxodesacetoxycephalosporanic acid comprising reacting 7-aminodesacetoxycephalosporanic acid and 3,5-di-t-butyl-1,2-benzoquinone in acetonitrile in the presence of anhydrous magnesium sulfate as a dehydrating agent at 4° C. for 20 hours.
Claim 16
Dependent Claim
38 words
A process according to claim 11 for preparing 6-oxopenicillanic acid benzyl ester comprising reacting 6-aminopenicillanic acid benzyl ester and 3,5-di-t-butyl-1,2-benzoquinone in tetrahydrofuran in the presence of molecular sieves as a dehydrating agent at 4° C. for 16 hours.
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) | 1980-10-10 | 1981-04-11 | 1981-10-11 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-10-10 | 1985-04-11 | 1985-10-11 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-10-10 | 1989-04-11 | 1989-10-11 | $7700.00 | Window Closed / Lapsed |