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Ep 0409164 A2 Europaisches Patentamt European Patent Office © Publication number: 0 409 1 64 A2 Office europeen des brevets © EUROPEAN PATENT APPLICATION © Application number: 90113679.6 © Int. CI* C07D 501/36, C07D 498/053, A61K 31/545, A61K 31/535 @ Date of filing: 17.07.90 © Priority: 18.07.89 JP 186330/89 © Applicant: SHIONOGI SEIYAKU KABUSHIKI KAISHA trading under the name of © Date of publication of application: SHIONOGI & CO. LTD.TD. 23.01.91 Bulletin 91/04 1-8, Doshomachi 3-chome Chuo-ku Osaka 541 (JP) © Designated Contracting States: CH DE FR GB IT LI NL © Inventor: Onoue, Hiroshi 3-7-4, Takatsukadai, Kawai-cho Kitakatsuragi-gun, Nara(JP) Inventor: Minami, Kyoji 720-42, Oze-cho Ikoma-shi, Nara(JP) Inventor: Ishikura, Koji 2-11-4, Mimatsu Nara-shi, Nara(JP) © Representative: Vossius & Partnerner Siebertstrasse 4 P.O. Box 86 07 67 D-8000 Munchen 86(DE) © Phenacylpyridiniothiocephalosporins. © An antibacterial- 3-optionally protected-vic-dihydroxyaroyl-Iower alkyl-pyridiniothiomethyl cephalosporin de- rivative represented by the following formula (I): {© (wherein, t™ R1 is an amino group or acylamino; R2 is hydrogen or methoxy; R3 is hydrogen or a mono- or divalent q) substituent; R4 is optionally protected vic-dihydroxyaryl; R5 is straight or branched lower alkylene; R6 is O hydrogen, a carboxy-protecting group or a negative charge when combined with Y; X is oxygen, sulfur, or "@jf sulfinyl; and Y is an anion or a negative charge when combined with R6; and the dotted line shows the presence © or absence of a bond), and method of bacterial infection it, and synthetic methods thereof are provided. n a disinfecting treating using HI Xerox Copy Centre EP 0 409 164 A2 PHENACYLPYRIDINIOTHIOCEPHALOSPORINS The known cephalosporins having a pyridiniomethyl group at position 3 (e.g., cephaloridine) are strong anti-bacterials against Gram-positive bacteria. Recently, such compounds active against Gram-negative bacteria have attracted attention. However, these are insufficient in clinical antibacterial activity (e.g. against Pseudomonas spp.). 5 It is the object of the present invention to provide novel cephalosporins having superior antibacterial activity against aerobic and anaerobic Gram-positve and Gram-negative bacteria. This object has been achieved by the provision of the cephalosporins according to the invention having a specifically substituted pyridiniothiomethyl group. The present invention relates to novel 3-optionally protected vic-dihydroxyaroyl-lower alkyl- w pyridiniothiomethylcephalosporin derivatives represented by the following formula I: 75 (wherein, 20 R1 is amino or acylamino; R2 is hydrogen or methoxy; R3 is hydrogen or a mono- or divalent substituent; R* is optionally protected vic-dihydroxyaryl; R5 is straight or branched lower alkylene; 25 R6 is hydrogen, a carboxy protecting group, or a negative charge when combined with Y; X is oxygen, sulfur, or sulfinyl; Y is an anion or a negative charge when combined with R6, and the dotted line shows the presence or absence of a bond). The groups of compound ( I ) are explained as follows : 30 When R1 is acylamino, the acyl can be an aliphatic, alicyclic, or aromatic carboxylic acyl group including those forming an amide side chain of natural or synthetic penicillins and cephalosporins. Representative acyls are shown by the following formulas : R10R11-CO (wherein, R10 is hydrogen, or an aliphatic, aromatic, heterocyclic or alicyclic group, or a group forming a carbonic acyl together with R11CO : 35 R11 is a single bond, -RUCH2 (Ru is a single bond, oxygen, sulfur, or imino), >CH-R12, >C = R13, or the like divalent group ; R12 is optionally protected carboxy, cyano, hydroxy, amino, sulfo, mercapto, or the like; and R13 is oxo, thioxo, imino, hydroxyimino, optionally substituted alkoxyimino, aryloxyimino, alkylidene, or the like) 40 Preferably, R10 is C1 to C8 aliphatic group (e.g., optionally substituted alkyl, alkenyl, alkinyl), mon- ocyclic or polycyclic aromatic group (e.g., optionally substituted phenyl, naphthyl), monocyclic or polycyclic heterocyclic group (optionally substituted, five- or six-membered heterocyclyl optionally having up to 4 nitrogen, oxygen, and/or sulfur atom as hetero atom), mono- or poly-cyclic alicyclic group (optionally substituted, optionally having 1 or 2 double bond, 4 to 8 membered cycloalkyl), a group constituting C2 to 45 C9 carbonic acyl (e.g., alkoxy-, alkylthio-, aralkoxy-, aralkylthio-, aryioxy-, arylthio-, or heterocyclooxy- carbonyl) or the like. A part of polycyclic group may be a saturated ring. When R12 is protected, the protective group can be that aiming to avoid adverse change during the synthesis (e.g., ester, amide, halide, ether, anhydride) and that aiming to alter its physiological or pharmaceutical characteristics. so Representatives of the former are, when R12 is hydroxy, sulfhydryl, amino, or the like, C1 to C8 alkyl (e.g., methyl, ethyl, isopropyl, butyl, t-butyl, cyclopentyl), monocyclic heterocyclyl (e.g., tetrahydropyranyl, tetrahydrofuranyl), C2 to C9 alkenyl (forming enol ether, enamine), C3 to C10 alkyl or alkoxysilyl or stannyl (e.g., trimethylsilyi, triethyl silyl, dimethyl-t-butylsilyl, trimethylstannyl, dimethylmethoxysilyl), C1 to C15 @araikyl (e.g., trityl, substituted diphenylmethyl, phenacyl), C1 to C10 acyl (e.g., alkanoyl, alkenoyl, aroyl, carbonic acid acyl); when R12 is carboxy, sulfo, etc., an ester forming group (e.g., C1 to C8 alkyl, C7 to C20 2 EP 0 409 164A2 aralkyl, C5 to C12 aryl), amide forming group (e.g., amino, C1 to C8 alkyl amino, C2 to C8 dialkyl- hydrazinyl), salt forming group (e.g., alkali metal, alkaline earth metal, C2 to C10 amine), and the like removable without adverse effect on other part of the moleule. Preferable representatives of the latter are when R12 is carboxy or sulfo, a group removable in vivo (e.g., 5 salt, pharmaceutical^ active ester, amide); when R12 is hydroxy, sulfo, carbamoyl, sulfamoyl, C2 to C9 carbalkoxy, C8 to C15 carbaralkoxy, C1 to C8 alkanoyl, C8 to C15 aralkanoyl, C7 to C15 aroyl, monocyclic heterocyclocarbonyl, cyano, or the like; when R12 is amino, C1 to C8 alkylsulfonyl, monocyclic arylsulfonyl, C1 to C8 alkyloxoimidazolidinylcarbonyl, dioxopiperazinylcarbonyl, alkylureidocarbonyl, thioureidocarbonyl, and the like. io When R13 is alkoxyimino or alkylidene, it can be C1 to C8 saturated or unsaturated straight or cyclic group; or is mono- or poly-cyclic carbo- or hetero-cyclic aryloxyimino. Each can have a substituent (e.g., carboxy, esterified or amidated carboxy, hydroxy, C1 to C8 alkyl, C1 to C8 alkoxy). R10 to R13 can further have a substituent. When the acyl remains in the final objective compound, it has preferably up to 20C atoms. There is an optionally protected vic-dihydroxylated aroyl-lower alkyl- 75 pyridiniothiomethyl group at position 3 of this cephalosporin compound. This pyridinio ring may optionally have a substituent R3 (preferably e.g., halogen, cyano, C2 to C9 alkylene, C1 to C8 alkyl, C2 to C6 alkenyl, carboxy, C2 to C9 alkoxycarbonyl, C8 to C15 aralkoxycarbonyl, carbamoyl, nitro or a mono- or bi-cyclic heterocyclyl having optionally nitrogen, oxygen and/or sulfur as 1 to 4 hetero atoms ). The hydroxy groups of optionally protected vic-dihydroxylated aryl residue R* at position 3 of this 20 cephalosporin may optionally have a protecting group (e.g., alkali metal, alkaline earth metal, C1 to C8 acyl, C3 to C9 silyl, C7 to C15 aralkyl, C2 to C9 alkoxycarbonyl). Its aryl part R4 may optionally have a substituent (preferably e.g., halogen, nitro, cyano, carboxy, carbamoyl, C2 to C9 alkoxycarbonyl, C8 to C15 aralkoxycarbonyl, C1 to C8 alkyl, C2 to C9 alkenyl, monocyclic heterocyclothio). Representative examples of straight or branched lower alkylene R5 include C1 to C5, preferably C1 to 25 C3 alkylene. Most preferred alkylene (R5 are methylene (-CH2-) and ethylidene Carboxy protective group RG is useful for carboxy-protection, or for medically useful derivative formation. The said RG are known in the field of penicillin and cephalosporin chemistry as those capable of introducing or removing without adverse effect on other part of the molecule and having up to 19C (for reaction or medical purpose, e.g., that forming medical salt, pharmaceutically active ester forming group). Representative are these for reaction including an ester forming group, C1 to C8 alkyl (e.g., methyl, methoxymethyl, ethyl, ethoxymethyl, iodoethyl, propyl, isopropyl, butyl, isobutyl, ethoxyethyl, methyl- thioethyl, methane sulfonylethyl, trichloroethyl, t-butyl), C3 to C8 alkenyl (e.g., propenyl, allyl, prenyl, hexenyl, phenylpropenyl, dimethylhexenyl), C7 to C19 aralkyl (e.g., benzyl, methylbenzyl, dimethylbenzyl, methoxybenzyl, ethoxybenzyl, nitrobenzyl, aminobenzyl, diphenylmethyl, phenethyl, trityl, di-t-butylhydrox- ybenzyl, phthalidyl, phenacyl), C6 to C12 aryl (e.g., phenyl, tolyl, xylyl, diisopropylphenyl, trichlorophenyl, pentachlorophenyl, indanyl), C1 to C12 N-substituted amino (ester group with e.g., acetoneoxime, ac- etophenoneoxime, acetaldoxime, N-hydroxysuccinimide, N-hydroxyphthalidmide, or the like), C3 to C12 hydrocarbylsilyl (e.g., trimethylsilyl, dimethylmethoxysilyl, t-butyldimethylsilyl), C3 to C12 hydrocarbylstan- nyl (e.g., trimethylstannyl) or the like protective groups. The protecting group may optionally be substituted with a group as given below. As the carboxy protecting group is removed until the objective product, its structure has not improtant meaning, if protection is effective and wide range of equivalent group (e.g., amide, anhydride
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