GB1424374A - Chemical products - Google Patents
Chemical productsInfo
- Publication number
- GB1424374A GB1424374A GB2999673A GB2999673A GB1424374A GB 1424374 A GB1424374 A GB 1424374A GB 2999673 A GB2999673 A GB 2999673A GB 2999673 A GB2999673 A GB 2999673A GB 1424374 A GB1424374 A GB 1424374A
- Authority
- GB
- United Kingdom
- Prior art keywords
- amino
- compound
- acid
- base
- cephalosporanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 carbamoyloxy, N- substituted carbamoyloxy Chemical group 0.000 abstract 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract 6
- 239000002585 base Substances 0.000 abstract 5
- 150000001875 compounds Chemical class 0.000 abstract 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract 3
- 239000002253 acid Substances 0.000 abstract 3
- 125000003545 alkoxy group Chemical group 0.000 abstract 3
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 abstract 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 abstract 2
- 125000000217 alkyl group Chemical group 0.000 abstract 2
- 150000001412 amines Chemical class 0.000 abstract 2
- 239000000010 aprotic solvent Substances 0.000 abstract 2
- 125000003118 aryl group Chemical group 0.000 abstract 2
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 abstract 2
- 238000000034 method Methods 0.000 abstract 2
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical group [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 abstract 2
- 239000002904 solvent Substances 0.000 abstract 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract 2
- 125000006000 trichloroethyl group Chemical group 0.000 abstract 2
- FIZKXIDCBLKSRI-UHFFFAOYSA-N (2,4-dinitrophenyl)hydrazine;4-methylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1.NNC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O FIZKXIDCBLKSRI-UHFFFAOYSA-N 0.000 abstract 1
- PPNCOQHHSGMKGI-UHFFFAOYSA-N 1-cyclononyldiazonane Chemical compound C1CCCCCCCC1N1NCCCCCCC1 PPNCOQHHSGMKGI-UHFFFAOYSA-N 0.000 abstract 1
- HORQAOAYAYGIBM-UHFFFAOYSA-N 2,4-dinitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HORQAOAYAYGIBM-UHFFFAOYSA-N 0.000 abstract 1
- 229930186147 Cephalosporin Natural products 0.000 abstract 1
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 abstract 1
- 125000004423 acyloxy group Chemical group 0.000 abstract 1
- 150000001299 aldehydes Chemical class 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract 1
- 125000003180 beta-lactone group Chemical group 0.000 abstract 1
- 230000000903 blocking effect Effects 0.000 abstract 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 229940124587 cephalosporin Drugs 0.000 abstract 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 abstract 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 abstract 1
- 125000001475 halogen functional group Chemical group 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000012442 inert solvent Substances 0.000 abstract 1
- 150000002576 ketones Chemical class 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 125000000962 organic group Chemical group 0.000 abstract 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/568—Four-membered rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Cephalosporin Compounds (AREA)
Abstract
1424374 Epimerizing 7α-amino-3-cephem compounds MERCK & CO Inc 25 June 1973 [30 June 1972 16 April 1973] 29996/73 Heading C2C A process for epimerizing a 7α-amino cephalosporin wherein R 1 is a blocking group and R<SP>1</SP> is hydrogen, C 1-5 alkanoyloxy, carbamoyloxy, N- substituted carbamoyloxy, halo, C 1-5 alkoxy, C 1-5 alkoxy C 1-5 alkoxy, benzyloxy or substituted benzyloxy comprises reacting (a) the compound above with an aldehyde or ketone to yield compound IV wherein R<SP>2</SP> is alkyl or aryl, R<SP>3</SP> is H, alkyl or aryl, (b) reacting the latter compound with a strong base at -200‹ to + 20‹ C. in the presence of an aprotic solvent followed by the addition of excess acid to neutralize the base; (c) recovering the compound III and (d) reacting this compound with acid in the optional presence of an amine and recovering the 7#-aminocephalosporin. Step (a) may be suitably carried out using p-nitrobenzaldehyde, in the presence of methylene chloride solvent. A suitable solvent for step (b) is tetrahydrofuran; additionally a dipolar aprotic solvent such as dimethylformamide may be present. The base used in step (b) is preferably an organo alkali compound such as phenyl- or butyl-lithium. The acid used in step (b) is preferably a carboxylic acid such as acetic acid. Step (d) may suitably be carried out in the presence of 2,4- dinitrophenylhydrazine and p-toluene sulphonic acid. A modification of the above process comprises reacting the compound of Formula IV with a base that will not attack the betalactone ring in the presence of an inert solvent to obtain a product of Formula III. The base may be an amine, and the reaction may take place between -150‹ and 50‹ C. There is exemplified (1) the treatment of one of the following:- p-methoxybenzyl dl-7α amino cephalosporanate, p-methoxybenzyl dl-7α amino-3-methyl cephalosporanate, trichloroethyl dl-7α-amino-3-methyl decephalosporonate, benzhydryl dl-7α-amino-3-carbamoyloxy decephalosporanate, benzyl dl-7α-amino-3- chloromethyl decephalosporanate and trichloro ethyl dl-7α-amino cephalosporanate (a) with p-nitro benzaldehyde so as to form the p-nitrobenzylideneamino derivative which (b) is dissolved in tetrahydrofuran and reacted with phenyl lithium and acetic acid to epimerize the α- into the #-form and (c) the #-form is treated with 2,4 - dinitrophenylhydrazine p - toluene sulphonic acid to form the parent #-compound, e.g. p - methoxybenzyl dl-7# amino cephalosporanate; (2) in place of step (b), the p-nitrobenzylideneamino derivative may be epimerized by treatment in methylene chloride with diazabicyclononane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US26785872A | 1972-06-30 | 1972-06-30 | |
| US35054373A | 1973-04-16 | 1973-04-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1424374A true GB1424374A (en) | 1976-02-11 |
Family
ID=26952699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB2999673A Expired GB1424374A (en) | 1972-06-30 | 1973-06-25 | Chemical products |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS4949985A (en) |
| CH (1) | CH602757A5 (en) |
| DE (1) | DE2333322A1 (en) |
| ES (1) | ES416094A1 (en) |
| FR (1) | FR2198949B1 (en) |
| GB (1) | GB1424374A (en) |
| NL (1) | NL7308292A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1200543A (en) * | 1981-12-21 | 1986-02-11 | Eli Lilly And Company | 7-epi-3-exomethylenecepham derivatives |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1366682A (en) * | 1971-04-30 | 1974-09-11 | Merck & Co Inc | Process to prepare antibiotic intermediates |
-
1973
- 1973-06-14 NL NL7308292A patent/NL7308292A/xx not_active Application Discontinuation
- 1973-06-20 ES ES416094A patent/ES416094A1/en not_active Expired
- 1973-06-25 GB GB2999673A patent/GB1424374A/en not_active Expired
- 1973-06-26 FR FR7323229A patent/FR2198949B1/fr not_active Expired
- 1973-06-29 DE DE19732333322 patent/DE2333322A1/en active Pending
- 1973-06-29 JP JP48072982A patent/JPS4949985A/ja active Pending
- 1973-06-29 CH CH957173A patent/CH602757A5/xx not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| CH602757A5 (en) | 1978-07-31 |
| FR2198949B1 (en) | 1978-07-21 |
| NL7308292A (en) | 1974-01-02 |
| FR2198949A1 (en) | 1974-04-05 |
| ES416094A1 (en) | 1976-06-16 |
| DE2333322A1 (en) | 1974-01-10 |
| JPS4949985A (en) | 1974-05-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| PCNP | Patent ceased through non-payment of renewal fee |