US3989685A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Process for making a 2'-halopenicillin
Assignee: Shionogi and Co Ltd
•
Filing: 1973-06-21
•
Granted: 1976-11-02
•
Expires: 1993-06-21
Abstract
Abstract A 2'-halopenicillin compound is prepared from a penicillin-1-oxide compound by the action of an acid halide in the presence of a base. The product on heating rearranges to a 3-halo-3-methylcepham compound which itself gives a 3-methyl-3-cephem compound on further heating. A 2'-halopenicillin compound gives a 3-methyl-3-cephem compound on heating. The 2'-halopenicillin compounds, 3-halo-3-methylcepham compound and 3-methyl-3-cephem compounds are antibacterials which are also useful as intermediates for the synthesis of other penicillins and cephalosporins.
Inventors
- 👤 Hiroshi Tanida
- 👤 Teruji Tsuji
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-27 08:24
CPC Classifications
C; C07; C07D; C07D499/00
Claims Analysis
Total Claims: 8
Claim 1
Independent Claim
305 words
A process for the preparation of a 2'-halopenicillin compound of the following formula: ##SPC16## wherein A=N is a substituted amino selected from the group consisting of phenoxyacetamido, phenylacetamido, thienylacetamido, phenylglycylamino, phenylglycylamino substituted by alkanoyl or alkoxycarbonyl having up to 12 carbon atoms on its amino group, 2-ketopinoylamino, norbornanecarbonylamino, benzamido, 3-phenyl-5-methylisoxazole-4-carbonamido, alkoxycarbonamido having up to 12 carbon atoms, haloalkoxycarbonamido having up to 12 carbon atoms, o-nitrophenylsulfenylamino, benzylideneamino, hydroxybenzylideneamino, phthalimido, 2,2-dimethyl-4-phenyl-5-oxoimidazolidin-1-yl, 2,2-dimethyl-3-nitroso-4-phenyl-5-oxoimidazolidin-1-yl, and tritylamino; B is a member selected from the group consisting of alkoxy having 1 to 12 carbon atoms, haloalkoxy having 1 to 12 carbon atoms, phenacyloxy, halophenacyloxy, methoxymethoxy, alkanoyloxymethoxy having up to 12 carbon atoms, benzyloxy, benzyloxy substituted by nitro, alkoxy having up to 12 carbon atoms or halo, benzhydryloxy, benzalamino-oxy, hydroxy, sodio-oxy, potassio-oxy, trimethylsilyloxy, trimethyltin-oxy, and triethylammonium-oxy; and Hal is fluorine, chlorine, bromine or iodine, by the reaction of a penicillin-1-oxide compound of the following formula: ##SPC17## wherein A and B are as defined above, with an acid halide selected from the group consisting of alkanoyl halides having 1 to 12 carbon atoms, chloroacetyl chloride, oxalyl halide, crotonyl halide, ethynylacetyl halide, phenylacetyl halide, thiopheneacetyl halide, benzoyl halide, benzoyl halide substituted by nitro, methoxy, alkyl having 1 to 12 carbon atoms or halogen, naphthoyl halide, thienoyl halide, nicotinoyl halide, quinolinecarbonyl halide, alkanesulfonyl halide having up to 12 carbon atoms, benzenesulfonyl halide, benzenesulfonyl halide substituted by alkyl having 1 to 12 carbon atoms, methoxy, nitro or halo, naphthalenesulfonyl halide, quinoline-8-sulfonyl halide, 1,3,4-thiadiazolylsulfonyl halide, alkyl haloformate having up to 12 carbon atoms, and phenyl haloformate, in the presence of a base selected from the group consisting of dialkylamine or trialkylamine having up to 12 carbon atoms, N-methylpiperidine, N-methylmorpholine, N-ethylpyrrolidine, N,N-dimethylbenzylamine, pyridine, picoline, lutidine, quinoline, isoquinoline, N,N-dimethylaniline, urea, thiourea, guanidine, and N-lower alkylurea having up to 12 carbon atoms, at a temperature of from 70°C to 130°C.
Claim 2
Dependent Claim
305 words
A process for the preparation of a 2'-halopenicillin compound of the following formula: ##SPC16## wherein A=N is a substituted amino selected from the group consisting of phenoxyacetamido, phenylacetamido, thienylacetamido, phenylglycylamino, phenylglycylamino substituted by alkanoyl or alkoxycarbonyl having up to 12 carbon atoms on its amino group, 2-ketopinoylamino, norbornanecarbonylamino, benzamido, 3-phenyl-5-methylisoxazole-4-carbonamido, alkoxycarbonamido having up to 12 carbon atoms, haloalkoxycarbonamido having up to 12 carbon atoms, o-nitrophenylsulfenylamino, benzylideneamino, hydroxybenzylideneamino, phthalimido, 2,2-dimethyl-4-phenyl-5-oxoimidazolidin-1-yl, 2,2-dimethyl-3-nitroso-4-phenyl-5-oxoimidazolidin-1-yl, and tritylamino; B is a member selected from the group consisting of alkoxy having 1 to 12 carbon atoms, haloalkoxy having 1 to 12 carbon atoms, phenacyloxy, halophenacyloxy, methoxymethoxy, alkanoyloxymethoxy having up to 12 carbon atoms, benzyloxy, benzyloxy substituted by nitro, alkoxy having up to 12 carbon atoms or halo, benzhydryloxy, benzalamino-oxy, hydroxy, sodio-oxy, potassio-oxy, trimethylsilyloxy, trimethyltin-oxy, and triethylammonium-oxy; and Hal is fluorine, chlorine, bromine or iodine, by the reaction of a penicillin-1-oxide compound of the following formula: ##SPC17## wherein A and B are as defined above, with an acid halide selected from the group consisting of alkanoyl halides having 1 to 12 carbon atoms, chloroacetyl chloride, oxalyl halide, crotonyl halide, ethynylacetyl halide, phenylacetyl halide, thiopheneacetyl halide, benzoyl halide, benzoyl halide substituted by nitro, methoxy, alkyl having 1 to 12 carbon atoms or halogen, naphthoyl halide, thienoyl halide, nicotinoyl halide, quinolinecarbonyl halide, alkanesulfonyl halide having up to 12 carbon atoms, benzenesulfonyl halide, benzenesulfonyl halide substituted by alkyl having 1 to 12 carbon atoms, methoxy, nitro or halo, naphthalenesulfonyl halide, quinoline-8-sulfonyl halide, 1,3,4-thiadiazolylsulfonyl halide, alkyl haloformate having up to 12 carbon atoms, and phenyl haloformate, in the presence of a base selected from the group consisting of dialkylamine or trialkylamine having up to 12 carbon atoms, N-methylpiperidine, N-methylmorpholine, N-ethylpyrrolidine, N,N-dimethylbenzylamine, pyridine, picoline, lutidine, quinoline, isoquinoline, N,N-dimethylaniline, urea, thiourea, guanidine, and N-lower alkylurea having up to 12 carbon atoms, at a temperature of from 70°C to 130°C.
Claim 3
Dependent Claim
36 words
A process according to claim 1, wherein the acid halide is acetyl chloride, propionyl chloride, pivaloyl chloride, oxalyl chloride, benzoyl fluoride, benzoyl chloride, benzoyl bromide, p-nitrobenzoyl chloride, p-anisoyl chloride, toluene-p-sulfonyl chloride, methanesulfonyl chloride, or ethyl chloroformate.
Claim 4
Dependent Claim
16 words
A process according to claim 1, wherein the base is pyridine, picoline, lutidine, triethylamine, or trimethylamine.
Claim 5
Dependent Claim
22 words
A process according to claim 1, wherein the reaction is carried out at a temperature in the range from 80°C to 120°C.
Claim 6
Dependent Claim
32 words
A process according to claim 1, wherein one to ten mole equivalents, or one to two mole equivalents of the acid halide are used for one mole equivalent of the penicillin-1-oxide compound.
Claim 7
Dependent Claim
22 words
A process according to claim 1, wherein the reaction is carried out in a solvent selected from benzene, toluene, dioxane, and N,N-dimethylformamide.
Claim 8
Dependent Claim
31 words
A process according to claim 1, wherein the acid halide and the base are initially mixed to form an onium salt adduct, which is used in place of the two reagents.
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) | 1979-11-02 | 1980-05-03 | 1980-11-02 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1983-11-02 | 1984-05-03 | 1984-11-02 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1987-11-02 | 1988-05-03 | 1988-11-02 | $7700.00 | Window Closed / Lapsed |