PROCEDURE FOR THE PRODUCTION OF NEW CEPHALOSPORINEN AND PENICILLINEN

The invention concerns a procedure for the production of a new connection of the general formula B R.C. CO.NH. /) IL! z N \ o# o \ l COOH q) I0 where R ftir hydrogen or one of the following groups stands: (i) Ru, whereby Ru a carbocyclischen aryl residue, for example a Phenyloder Naphthylrest; or a hetero-cyclic aryl residue, for example a 5oder 6gliedfigen hetero-cyclic remainder, which contains at least one Heteroatom, i.e. of S.N or O, for example a Thien-2-yl, a Tbien-8-yl, a Fmyl, Pyridyl, a 8oder 4-Isoxazolyloder a suhstituierte 3oder 4-Isoxazoly gmppe like a 3-Aryl-5-methylisoxazol-4-yl-gruppe, where the Arylgrnppe for instance Phenyl or Halogenpheny! is, or a Sydnongruppe; or a Cyeloalkylrest, for example a Cyelopentyloder Cyelohexylrest; or one of the remainders mentioned, snbstituiert through for example ever eirl or several: Ha! ogenatome, hydroxy groups, Niederalkyl, Nitro. Amino, Niederalkylamino, Di (down alkyl) - amino., Niederalkanoyl. Niederalkanoylamido, Niederalkoxy or Niederalkylthiogruppen; or a Cyeloalkadienylrest, for example Cyclohexadienylrest; or a nichtaromatisehe or mesoionisch an e group of b OD euter; (ü) Rn (CHz) mQn (CHz) p where has Ru the angeftthrte meaning, into for zero or a whole stands number from 1 to 4, n for zero or 1 and p f a whole number from 1 to 4, and further for S, O or NRz, where RZ represents hydrogen or a Alkyloder group of aryls, stands for Q; (iii) CuH2 n+I where for a whole number from 1 to stands for n, whereby the group geradkettig or can be branched out or by a Sauerstoffatorn or a sulfur atom or the group of NR in that RZ to (ii) eye-led meaning has. to be interrupted can or by cyanogen, Carboxy, Aikoxycarbonyl, Hydroxy or Carboxycarbonyl (HOOC, CO) or halogen to be substituted can; (iv) CnH2 n! 'where n stands ftir a whole number from 2 to 7, whereby the group geradkettig or can be branched out or by an oxygen atom or a Sehwefelatom or the group of NRz, in that RZ in (ii) eye-led meaning has, to be interrupted can; (v) CnH2 n_3, where n stands fflr a whole number from 2 to 7; and (vi) a Cyanogruppe, a Amidogruppe or a Niederalkoxycarbonylgruppe; weather RA hydrogen or the remainder of a carbonic acid, Rcco. with 1 to 20 C-flavours it means where RH ftir an A! iphatische, cyc! oaliphatische, araliphatic or aromatic group, for example an alkyl, a A1kenyloder Alkinylgruppe along to 6 C-atoms a Csbis CT-Cycloalkyl, Csbis c1 z-Aryluiederalky! - stands or for C6b s c1 z-ArylgTuppe, where further Rc more tlber a Sauerstoffatorn. a sulfur atom or a einelminogruppe connected with the CarbonylgTuppe is, for example for a CIbis q-Alkoxy, CIbis C6 - Alky! - thiooder C6bis c1 z-Arylniederalkoxygruppe stands, where furthermore Rc replaces for one of the groups before specified, by halogen such as fluorine, chlorine, bromine or iodine, or with Amino, substitniertes Amino, Nitro, CIbis C6 - Alky! ode C1bis C “- Alkoxy stands, or for RA a Carbamoylgruppe, a ThiocarbamoylgTuppe or one by C1bis Cs-Alky! or ha! ogenalky! substituted Carbamoyloder Thioearbamoylgrappe means; furthermore B ftlr WG or > S -- O stands and for Z a group, in which 1 or 2 C-atoms connects the Ringschwefelatom and the group of carboxyls basic C-atom, meant; as well as a not-toxic derivative, for example a salt, like the well iumoder potassium salt of such a connection. It is proceeded in such a way according to invention that one A) a connection of the general formula HN B oß! I 1 COOR (vii) where B and 7 have angeführteßedeuinng and g 1 hydrogen or a group of carboxyl blockings means, or a N-silyliertes derivative or a Sliureadditionssalz of such a connection. with acylation means condensed, which the fall of the general formula R.C. COOH II N ORa (vi) where R and RA have the stating eating interpretation, corresponds or to a Vorlliuferslture of the general formula R. CO. COOH, (via) where R has the aforementioned meaning, or the general formula R.D. COOH, (Vlb) where R for an activating group and D for - CHzoder - CHsteht correspond, according to which one attaches I COOH g egeb enenfalls B) one in the following of the angeftlhrten reactions: B) (i) transformation of a Vorl, 'luferverbindung for the desired group of R. Co COII N ORa 95 33 into this group by (A) conversion the Vorlilufergruppe R. CO. CO, like before aforementioned, containing connection with a connection of the general formula RaO. NHz where has RA the aforementioned meaning, (B) conversion the Vorl tufergruppeR. D. CO, like before aforementioned, containing connection with a Nitrosierungsmittel, e with salpetriger S, 'lure, Nitrosylchlorid or an organic Nitrosierungsmittel, like an alkyl, a CycloaIkyl, aryl or Aralkylnitrit, favourable-proves in presence of a base. (C) Ester splitting of a connection. into the RA the acyl radical of an organic carbonic acid means. to a connection. in the RA hydrogen, or (D) acylation of a connection means. in the RA hydrogen means, to a connection. into the RA the acyl radical of an organic Carbonsliure means, for example by Umseßung with a S turehalogenid, a symmetrical or a mixture anhydride. a ketene. an ecyl azide. a Carbodiimid. a Halogenameisens, 'more lureester or an isocyanate. favourable-proves in presence of a basic catalyst. like Trigthylamin. Dimethylanilin. Pyridin. Propylenc yd, magnesium oxide, calcium carbonate or calcium carbonate, and/or or an organic solvent, like a Halogenkohlenwasserstoffes, a cyclischen ether, a Nitrffs, a Halogenkohlenwasserstoffes or an ester, and vorteilhafterwetse at a temperature from -10 to 100°C, for example from 0 to 50°C; B) (it) Überfflhrung of a Ceph-2-em-verbindung of the general formula ('I) into the appropriate Ceph - 3ereisomere; B) (iii) AhReanmag of if necessary existing Carboxylblocktermagsgmppen; 13) (iv) treatment of a connection, in which B m&gt ftlr S; O stands, with a Reduküonsmittel for the production of a connection, in which B is located ftlr to S; and finally I 0 C) the looked for connection of the general formula (I) isolated, gewünschtenfalls after Überflihrung the same into one of their not-toxic derivatives, beispiehweise by conversion with a base, as Natriumoder Kalium-2thylhexanoa and zw. in form the syn isomers or as lsomerengemisch, which at least 75Plo favourable-proves, at least 9 o, the syn isomers contains. The new connections are usable as Antibiottka. I s is well well-known that Antibiottka of the Cepbalosporinund Penicillirttelhen 7B-Acylamidoceph-3-em -4-carbonsäure and/or öf - Acylamidopenam-3-carbousauren and their appropriate nicbttoxische derivatives, z. B. Salts, esters, Lactone (if these to be formed can), amides, hydrates or the appropriate Snlfoxyde are. In the Cephalosporirtteihe know these antibiotics different substituents in the 3-Stellung contained including unsubstituierte groups of methyls and groups of methyls, which are subsütuiert with a multiplicity of Snbstituenten, how they are in the literature beschriebea. In the Penteillinreihe can the substitution e.g. to mindestem one in accordance with Dtmethylgruppen take place. The new according to invention manufactured connections are characterised by that the Acylamidogruppe of the Cephalosporinoder Pentcillhaanttbtoükums a C - Hydroxyiminoaeylamidooder A-AcyloxyiminoaeyIamido-group is, whereby the connections are syn Isomexe or mixtures, in which the syn isomers form tiberwtegt and which contain 7ir/o D it preferably at least syn isomers. Berstellbaren the according to invention, new connections exhibit syn (cis) the isomers form, which concerns the Konfiguratton of the group of ORa with regard on the Carboxamidogrnppe. Preferably the isomers the mixtures contain at least 90% the syn isomers and no more than llyr/o the antt isomers. In the following the syn Konfigurafion is thus represented as follows: R .CO. NH-- N ORa wahtend the anü configuration to be as follows represented can: R.C.CO. NHII BI Rao these configurations become in accordance with the proposal of Ahmad WAD Spencer (Can.J.Chem., VOL. 89, 9, P. 1340) designated. The expression” ninht tox sch ", how it is applied to the derivatives of the new connections, umfaöt those derivatives, for example salts, which dosinglikes physiologically with the verabrdchten verlrttglich is. Salts, which can be made of according to invention received the connections, cover: a) Salts with anorganischeu bases, like Alka1/metallsalze, e.g. Nalfiumund of potassium salts, alkaline earth metal salts, e.g. calcium salts and salts with organic bases, e.g. Procain, Phenyläthylbenzylaminund Dibenzyl thylendiaminsalze, and b) S ateadd ttonssalze, e.g. with Chlorwasserstoffstture, hydrobromic acid, Schwefelstture, Salpetersttnre, phosphoric acid, p-Toluolsulfons/lure and methane sulfone acid. The salts can be present also in the form of Reshaaten, which are formed e.g. with a polystyrene resin, the Aminogrnppen, qnatem/RH Aminogrnppen or groups of sulfone sour contain, or which is formed with a resin, the groups of carboxyls enthttlt, e.g. Polyaerylsttureharz. The resin can be interlaced gewtlnschtenfalls, i.e. it can be a styrene/a Dtvlnylbenzol copolymer, which enthttlt the suitable groups. Additionally the derivatives in form of a Chelates with a heavy metal, like iron or copper, can be present. Producible the according to invention connections including the ntchttoxtschen/vate of these connections are characterized by their high antibacterial Wirknng against a multiplicity of grampositiver and gtamnegattver Ofganismen, which are connected against 15-Lactamasen with a particularly high stability, which is formed by different gramnegative organisms. Stability opposite B-Lactamasen can be evaluated compared with Cephaloridin, to which by definition a value of 1 can be awarded regarding the special organism. The Cephalosporinvesbinduugen, to which in the following is referred, becomes generally with Himicht on the Cepham (LAmer.Chem. Soc. 84, S.3400) designated. The expression “Cephem” concerns the Cephamgrundst uktur, which is provided with a double bond. The Pen [cillinverbindungen, to which in the following is referred, become generally regarding the Penam (L Amer. Chem. Soc. , P. 3293) designated. Erfindungsgemäl herstellbarenCephalospor [nverbindungen correspond the following a11gemeinen formula R-- R.C. CONH. -- -- “- N ORa 0 COOH (ii) where R, RA and B the before indicated meaning possess and an organic group means P, whereby auclä the not-toxic derivatives of these connections under it-fall. Those invention in accordance with tB producible penicillin connections correspond to the general formula R.C. CONH -- --/B of /CHs N -- -- \ ORa o [COOH (in) where R, RA and B possess the before indicated meaning, whereby also the nichttoxtschen derivatives of these connections are enclosed. In the formulas (II) and (III) the group of B has preferably the meaning 3. Furthermore the invention covers Cephalosporinund penicillin connections, which not-through-those-general formulas (IL) tmd (III) enclosure are, e.g. 28-Acetoxymethylpenicilline and 2-Methylund 2-Methylencephalosporine. Examples fttr groups of RA cover Alkanoyl, Alkenoylund Alkinoyl groups with bits to q carbon flavours, e.g. the acetyl group, the Propionylgruppe, the Butyrylgruppe, the Acrylylgruppe or the Crotonylgruppe, substituted groups of this kind, e.g. halogenierte groups (F, c1, Br or I) or Aminoderivateoder substituted Aminoderivate such groups, e.g. the chlorine acetyl group, the Dichloracetylgruppe or the B-Aminopropionylgruppe, Alkoxycarbonylgruppe with bits to 7 carbon atoms, e.g. the Äthoxycarbonylgruppe or the teert Butoxycarbonylgruppe, A1koxycarbonylgruppen, e.g. the 2, 2, 2-Trichlor substituted - ttthoxycarbenylgruppe, Alkylthiocarbonylgruppen with up to 7 Kohlemtoffatomen, and substituted derivatives of these groups, Aralkyloxycarbonylgruppen, e.g. the Benzhydryloxycarbonylgruppe or the Benzyloxycarbonylgruppe, Aroylgruppen with 7 to 13 carbon atoms, e.g. and Carbamoyloder Thiocarbamoylgruppen, substituted or unsubsütuierte the ßenzoylgmppe and substituted derivatives of such groups, e.g. the Nitrobenzoylgruppe e.g. nitrated i.e. connections, with those the group of RA of the formula (Rb) zN. COoder /ltb hN. C8-- corresponds, where Rb can be homogenous or different and a hydrogen atom or a substituent, how an alkyl group with I to 7 carbon atoms, e.g. a group of ethyls or a group of methyls or a substituted, e.g. halogenierte Alkylgmppe with 1 bit 7 carbon atoms, e.g. a Chlorttthylgruppe, or the group of Ru meant, whereby Ru exhibits in managing indicated meaning. Those managing in general form defined group of R can be ausgewtthlt from the following not necessarily vollsttindigen list: (I) hydrogen, (left) Ru where Ru an aryl (carbocyclisch or heterocycltsch), Cycloalkyl, substituted aryl, substituted ¢ycloalkyl, Cycloalkadienyl group or one not aromatically e od it mesoionische group (III) meant. Examples of these groups include: the phenylgruppe, the Naphthylgruppe, sn tituierte Phenyloder Naphthylgruppen, like e.g. by halogen atoms, e.g. Chloroder of bromine atoms, Hydroxygrnppen, low alkyl groups, e.g., groups of methyls, amino group, amino groups, low alkyl amino groups, e.g. methyl amino groups, Diniedr galkylaminogropperi, e.g. Dimethylaminogruppen, Niedrigalkanoylgruppen, e.g. Acetylgrappen, Niedrigalkanoylamidogruppen, low alkoxy groups, e.g. Methoxyoder Äthoxygruppen or Niedrigalkylthiogmppen, e.g. Methylthiogruppen, is substituiart; or 5oder 6gliedfigehetarocyclischeGruppea, which mindestem a Hetaroatom, like S, contains N or O, 4-1soxazolyl e.g. Thien-2-yl, Thien-3-yl, Fury1, Pyridyl, 8-oder, substituiette 3oder 4-1soxazolyl-Gruppen, e.g. the 3-Aryl-5-methylisoxazol-4-yl-Gruppe, whereby the group of aryls is a Phenylgruppe or a Halogenphenylgruppe; the Cyclohexylgrnppe, the Cyclopentylgruppe, the Sydnongruppe or a Cyclohexadienylgruppe. Rn (CHz) rnQ dCHz) p where possesses RU the meaning indicated above and m zero or a whole number from 1 to 4, n zero or 1, p a whole number from 1 to 4 and Q S, O or NRbedeuten, whereby RWassarstoffodar represents an organic group, e.g. an alkyl group, like group of methyls, or a group of aryls, like the Phenylgruppe. Examples ftir these groups are methyl, Äthytoder Butylgruppen, which are replaced with the different above under (II) indicated groups Ru, e.g. groups of benzyles and the accordingly substituted Benzylgrnppen. (iv) CnH2n+1 where n a whole number from I to 7 means. The group can geradkettig or branches out to be and gewtinschtenfalls by a Sauerstoffoder sulfur atom or the group NR be interrupted, where R means a hydrogen atom or an organic group, e.g. an alkyl group, like group of methyls, or a Arylgxuppe, like a Phenylgruppe; or the group can by a Cyanogruppo, a group of carboxyls, a Alkoxycarbonylgruppe, a hydroxy group or a Carboxycarbonylgruppe (HOOC. CO. ) or by a halogen atom substituted its. Examples of such groups include Hexyl, Heptyl, Butylthiomethyl, Cyanomethyl or groups of tri halogen methyls, (v) CnH2n-1 where n a whole number from 2 to 7 meant. The group can geradkettig or branches out to be and gewflmehtenfa! LS by a Sauerstoffoder sulfur atom or the group of NR interrupted its, where R means a hydrogen atom or an organic group, e.g. an alkyl group, like group of methyls, or a group of aryls, like the Phenylgruppe. An example of a such group is the Vinylgruppe or the Propenylgruppe. (VI) CnH2 n3 'where n a whole number from 2 to? represents. An example of a such group is the Äthinylgruppe. (VII) Different by carbon atoms connected orgamsche groups, including Cyanogrnppen, Amidogruppen and Ni edrigalkoxycarbonylgruppen. 3-Substituent P of the Cephalosporinverbindungen indicated above can be any organic group, whereby the characteristic characteristic of the invention is the kind of the 7-Substituenten. The group of P can be thus a satisfied or ungestittigte substituted or umubstituierte organic group with 1 to 20 carbon atoms. B evorzugte geslittigte organic groups includes lViethylund groups of ethyls; b evorzugte ungesttttigte organic groups closes Viny! - and Vinylgruppen of the general formula substituted J - CH = C R4, where R-S and P can be those homogenous or different, hydrogen atoms or one subsfi ierte or umubstituierte aliphatic group (e.g. an alkyl group, preferably an alkyl group with 1 to 6 carbon atoms, how a Methy! -, Ethyl, Isopropyloder n-Propylgruppe etc.), a cyclo-aliphatic group with 5 to 7 Kohlemtoffatomen (e.g. a Cyclopentyloder group of cyclohexyls), an araliphatic group with 7 to 10 carbon atoms (e.g. a group of benzyles or a Phenyl a ithylgruppe), an aromatic group with 6 to 12 carbon atoms (e.g. a Phenylgruppe or a Phenylgruppe), OI a group of power packs or a Niedrigalkoxycarbonylgruppe mean. If P represents a substituted group of methyls, she can by the following general formula --CH2Y to be defined, where Y represents an atom or a group, e.g. the remainder of a Nukleophils or a derivative of a Nukleophilrestes. Y can be ihlt thus e.g. from the large range of the nukleophilen substances ausgew, which are characterized by the fact that ste a nukleophiles nitrogen, carbon, a Schwefeloder oxygen atom exhibit and in with the Cephalosporinchemie concerned patent specifications and literature is descriptive. Examples of such nukleophiler connections include the following: Nitrogenous nukleophile connections. Examples ftir nukleophile nitrogen connections include tertiary aliphatic, aromatic, araliphatic and cyelische amines including tri alkyl amines, e.g. tri ethyl amine, Pyridinbasen, like Pyridin and Alkylpyridine; hetero-cyclic amines with more than einemH eteroatom, whereby at least one Heteroatom is nitrogen, like Pyrimidine, Purine, Pyridazine, Pyrazine, Pyrazole, Imidazole, Triazole and Thiazole. A preferential class for nukleophile nitrogen connections are the connections of the general formula where n zero or a whole number can be vonl to 5 and RD those, if n means a whole number from 2 to 5, homogenously or differently, an aliphatic group, e.g. a low alkyl group, as methyl, ethyl, n-Propyl, Isopropylgruppe etc.; a group of aryls, e.g. a Phenylgruppe, an araliphatic group, e.g. a Phenylniedrigalkylgruppe, like the group of benzyles, the Phenyl ithylgruppe etc. or a Alkoxymethylgruppe, e.g. a Methoxymethylgruppe, a Äthoxymethylgruppe, a n-Propoxymethylgruppe, a Isopropoxymethylgruppe etc.; or a Acyloxymethylgruppe, e.g. a Alkanoyloxymethylgruppe, like the Acetoxymethylgruppe, a Formylgmppe, a Carbamoylgruppe, a Acyloxygruppe, e.g. a Alkanoyloxygruppe, like the Acetoxygruppe; a veresterte Carboxylgmppe; an alkoxy group, e.g. a Methoxygruppe, a Äthoxygruppe, a n-Propoxygruppe, a Isopropoxygruppe etc.; a .äryloxygruppe, e.g. a Phenoxygruppe, a Aralkoxygruppe, e.g. a Benzyloxygruppe, a Alkylthiogruppe, e.g. a Methylthiogruppe, a Äthylthiogruppe, a Arylthiogruppe, a Aralkylthiogruppe, a Cyanogruppe, a Hydmxygruppe, a N-mono-low-alkylcarbamoylgmppe, e.g. a N-Methylcarbamoylgruppe, a N-Äthylcarbamoylgruppe etc.; a N, N-Diniedrigalkylcarbamoylgruppe, e.g. a N, N-Dimethylcarbamoylgruppe, a N, N-Diäthylcarbamoylgruppe etc.; a n (HydroxyniedrigaIkyl), carbamoylgruppe, e.g. a n (Hydroxymethyl) - carbamoylgruppe, a n (Hydroxyäthyl) - carbamoylgmppe etc. or a Carbamoylniedrigalkylgruppe, e.g. a Carbamoylmethylgruppe, a Carbamoyl ithylgruppe etc., means. A further preferential class of nukleophilen nitrogen connections are the azides, e.g. the alkali metal azides, like sodium azide. If the group of Y represents a derivative of a remainder of a nukleophilen connection, it knows an amino group or a Acylamidogruppe to be, connections, where Y represents an amino group, it can be received from the appropriate azide by reduction, e.g. by catalytic hydrogenation of the azide using a precious metal catalyst, like palladium or platinum. The amino group can be acyliert under education that according to EN 8-Acylaminomethylgruppe. The education of such connections can take place e.g. in accordance with any procedure, which is suitable for the acylation of a Aminocephalosporins, e.g. via shifting of the 3-Aminomethylverbindung with a S iurechlorid, a Säureanhydrid or a mixed Säureanhydrid or with an acid, those that desired acyl group corresponds, and another sour ones. The 3-Aminomethylverbindungen can be converted also with a substituted isocyanate or a Isothiocyahat under education by Harnstoffod it thiourea derivatives. Other connections, where Y represents a derivative of a Nukleophilrestes, can be received, by converting 3-Azidomethylverbindungen with a dipolarophilen connection. Preferential classes of ditolarophilen connections include acetyl niche, old-Hellenic and cyano dipolarophile connections. Those possess acetyl niche dipolarophile connections following e general formula 8 - Nr.3273qfi R C=C. RZ where RL and RZ, which can be homogenous or different, atoms or groups darstdlen. Generally it is preferential that the group of RI is eleklronegativ preferably also the group of RZ. Examples of such groups close Cyanogruppen, groups of the formula of the formula co2Rs coR (where R-S e.g. means a Ntedrigalkylgruppe, a group of aryls or a Niedrigaralkylgruppe) and groups of tri halogen methyls, e.g. group of tri fluorine methyls. I0 however can be electrosensitive the groups of Ri and preferably also the group of RZ, i.e. Alkoxyoder alkyl minogruppen to represent. The groups of RI and RZ can form gemeimam a ring system with the acetyleuischen group, which e.g. in a Arin the case is. If the groups of RI and RZ represent discrete atoms or groups, which are identical, the conversion with the Azidocephalosporin only one connection results in, while one illuminates generally a mixture that position isomers, if these groups are different. To ethyl niche dipolarophfle connections to the following general formula R-S R \ C=C/R-S correspond \ R-S 'where R-S, R6, R and R-S, which can be homogenous or different, mean atoms or groups, although the groups of R-S, R6, check valve and R-S can represent jeweüs Wassexstoffatome, are to say that ethylen reacts as such like acetylene only slowly with amino groups, the groups of I and R7 can form together a cyclfsche structure, e.g., a carbocyclische structure with the double bond, so that this is present in strained condition. Examples of old-Hellenic d/polamphiler connections, which contain strained double bonds, include Norb rnene, to-Cycloalkene and Acenaphthaltu. Further tithylenische dipolarophfle connections, which can ground used w, close connections D it formula R-S. R6. C=CR;. R8, where at least one of the groups of R-S, R6, R7 and R-S is a elektronegattve group. The groups of R-S and R7 can be thus identical eleki onegative groups, whereby the groups of R “and R-S can represent gewünschtenfalls other groups. The groups of R6 and RA know thus together a ring system bildeu. Examples of such dipolarophiler connections include Benzochfnon and kernsubstituterte Benzochinone and mark A IMIDe. Further all groups of R5, R-S, R7 and R-S can be identical elek¢ onegatlve groups. Elek¢ onegative groups, which can be used, include the connections groups specified dipolarophilen under the acetyl niches, and examples of such connections include thus Dicyanollthylen and Ni edri gmonound Di-alkoxy carbonyläth71en e. Gewümchtenfalls can be electricalpositive or several of the groups of R5, R6, R and R8. cyanoverbindungen, in particular those, which are activated by groups of electronegative, can as cyanc dipolarophfle connections serve. Examples of such dipolarophile connections include Niedrigalkoxycarbonylcyanide and Dicyan. Nukleophile Kohl enstoffverbind ungen. Attachment plays for nukleophile Kohlemtoffverbindungen " close inorganic cyanides, Pyrrole and substituferte Pyrrole, z. 13. Indole, connections, D e, e.g. Acetyleue and connections with t3-Diketongruppen, z.tL Aeetoessigsäureester and malonic acid esters and Cyelohexan l, result in stabilized anions 3-dione or Enamine, Inamine or Enole. The nukleophile carbon compound can lead thus to Cephalosporinverbindungen, which are characterized by it that they exhibit a substituent in the 3-Stellung, with which a Carbonylgrnppe over zwef carbon atoms are bound at the Cephalosporinkern. Such connections know thus as 3-Substituenten a group of the general formula 1 --CH2. C. CO. R4 exhibit, where R2 and R-S, which can be homogenous or different, hydrogen atoms, Cyanogruppen, Niedrigalkylgruppeu, e.g. methyl or Äthylgruppeu, Phenylgruppen, e.g. by halogen atoms, low alkyl groups, Niedr [, Nitrogmppen or Amtnogruppen, substituted Phenylgruppen, Niedrigalkylaminophenylgruppea, galkoxygruppen Niedrigalkoxycarbonytgruppen, mono or Di-aryln [, Niedrigalky edrigalkoxycarbonytgruppen [, Arylniedrigalkylgfuppen or Cycloalkylg carbonylgruppen uppea with 5 to 6 carbon atoms and R4 hydrogen, a NtedrigalkTlgruppe, e.g. a Methyloder Äthylgmppe, a Phenylgmppe, one e.g. by halogen atoms, low alkyl groups, low alkoxy groups, N [trogruppen or Aminog*uppen subsütuierte Phenylgruppe, a Niedrigalkylaminophenylgruppe, a A lniedrtgalkylgruppe or a Cycloalkylgruppe with 5 to 6 carbon atoms means. Nukleophile Schw efelverbindungen. Examples f nukleophile sulfur connections " close Thiohamstoff and aliphatic, aromatically, araliphatic, alicycltsch and hetemcyclisch substituted Thiohamstoffe, Dithiocarbamate, aromaüsche, aliphatic and cyclische Thioamide, e.g. Thioacetamid and Thiosemicarbazid, Thiosulfate, Thiole, Thiophenole, Thiostluren, e.g. Thiobenzoestlure or Thiopicolinsäure and Dithiosäuren eiu. Eiue preferential class of “nukleophflen sulfur connections” includes connections of the general formula RI.S (O) nH, where RI mean an aliphatic group, e.g. a low alkyl group, like a methyl, an ethyl, a n-Propylgruppe etc., a alicyclische group, e.g. a group of cyclohexyls, a Cyclopentylgruppe etc., an aromatic group, e.g. a Phenylgruppe, a Naphthylgruppe etc., an araliphatic group, e.g. a group of benzyles or a hetero-cyclic group and n zero, 1 or 2. A particularly preferred class of nukleophiler connections, which correspond to the general formula indicated above, are connections of the following general formula R “SH, where R “a aliphaüsche group, e.g. a low alkyl group, e.g. a methyl, a n-Propyloder group of ethyls of etc., an araliphatic group, e.g. eiuePhenylniedrigalkylgruppe, e.g. a B enzylgruppe, a Phenyllithylgruppe etc. or a substituted Phenylniedrfgalkylgruppe, a alicyclische group, e.g. a Cycloalkylgruppe, e.g. a Cyclopentyloder group of cyclohexyls, an aromatic group, e.g. a Phenylgruppe or a substituted Phenylgruppe or a 5oder gliedrige hetero-cyclic group, which at least one o, Noder S-atom entheilt, e.g. eineThiadiazolylgruppe, in particular the 5-Methyl-l, 3, 4 - - faiadiazol-2-yl-Gruppe, a Diazoly1, Triazolyl, Tetrazoly1, Thiazoly1, Thiatriazolyl, Oxazoly1, Oxadiazolyl, Benzimidazoly1, Benzoxazolyl, Triazolopyridyl, Purinyl, Pyridyl, Pyrimidyl group of etc. meant. Nukleophile SA uers toffvexb ind ung EN. Examples of nukleophile Sauerstoffverbindungen " include water, alcohols, e.g. Alkanole, like methanol, ethanol, Pmpanol and butanol and Niedrigalkancarbonstiuren, the expression nukleophile Sauerstoffverbindungen " enclosure thus connections of the following general formula RtOH, where the group of blanks a low alkyl group, e.g. a Melhyl, an ethyl, a n-Propyl, a Isopropyl, a n-butyl, a Isobutyl group of etc., a group of low alkenyls, e.g. an allyl group, a Niedrigalktnylgruppe, e.g. a Propinylgruppe, a Niedrigcycloalkylgruppe, e.g. a Cyclopentyloder group of cyclohexyls of etc., a Niedrigcycloalkylniedrigalkylgruppe, e.g. a Cyclopeatylmethylgruppe, a cyclohexyl/Ithylgruppe etc., a group of aryls, e.g. a Pheny [- or Naphthylgruppe, an aryl low alkyl group, e.g. a group of benzyles, a hetero-cyclic group, one hetero-cyclic low alkyl group, e.g. a Furfurylgruppe, means or a group of this kind, e.g. by one or more low alkoxy groups (Methoxygruppen, Äthoxygcuppen etc.), Niedrigalkylthfogruppen (Methylthiogruppen, Äthylthiogruppen etc.), Halogeuatome (chlorine, bromine, iodine vein F1uoratome), low alkyl groups (groups of methyls, groups of ethyls of etc.), Nitrogruppen, hydroxy groups, Acyloxygruppen, Carboxygruppen, Carbalkoxygruppen, Niedrigalkylcarbonylgruppen, groups of low alkyl sulphonyls, Niedrigalkoxysulfonylgruppen, amino groups, Low alkyl amino groups or ecyl amino groups substitutes t. In the case, since water is used as nukleophile connection, erhä! t one 8-Hydroxymethylcephalosporinverb ind ungen. These connections possess the following general formula R.C. CONCHA IL /s COOH (A) where R and RA the meanings indicated above possess. Connections of the general formula (A) and their not toxic derivatives possess antihakterielleWirkung and these connections can Mehabolite of the connections of the general formula (IV) be, where P represents a Acyloxymethylgruppe, connections of the I 0 general formula (A) can under education by derivatives be acyliert, which are characterized by that them groups de Formel S-CHe, O. CO. R9 or 8-CH2. O. CO. ZR9 exhibit, where Z O or S and R-S mean a Methylgrnppe or a group of organic, whose atomic weight sum at least] of 6 fuel element g, the group of B COod it l Z. CO-- can from a multiplicity of groups, which in L [teratur, to be selected and can up to carbon atoms are descriptive exhibit. The GruppeR9 can be thus a group of hydrocarbons or a group, one or more substituents, atoms or Suhsti [uentengruppen exhibits the group of R9 can thus from the following, not when complete enumerating zn rating list are selected: C) CnH2 n+1, where n means a whole number from 1 to 9, e.g. 2 to 4. The group can geradketlig or branches out to be and gew [Inschtenfalls by a Sauerstoffoder sulfur atom or a Iminogr ppe to be interrupted or by Cyano, Carboxy, AlkoxycaIbonyl, hydraulic XY, Carboxycarbonyl (HOOC. CO. ) - groups, halogen atoms, e.g. chlorine, Bromoder of iodine atoms or amino groups substituted its. Examples fflr these groups are ethyl, Propyl, Isopropyl, n-butyl, terL Butyloder sec. Butylgruppen. (IL) CnH2n_1 (III) where n a whole number from 2 to 7 meant. The group can geradkettig or branches out to be and gewümchtenfalls by a Sauerstoffoder sulfur atom or a Iminogruppe be interrupted. An example of a such group is the Vinyloder Propenylgruppe. Check valve (iv) where check valve means an alkyl group (carboeycliseh or heterocyelisch), a Cycloalkylgru PE, a substituted Arylgtuppe or a subsütuierte Cycloalkylgruppe. Examples of these groups are the Phenylgruppe, substituted Phenylgruppen, e.g. Hydroxyphenyl, Chlorphenyl, Fluorphenyl, Tolyl, Niirophenyl, Aminophenyl, Methoxyphenyl or Methylthiophenylgmppen; Thien-2-und -, Pyridyl, Cyelohexyl, Cyelopentyl, Sydnon, Naphthyl, substitnierteNaphthylGruppen, e.g. the 2-Äthoxynaphthylgmppe E-yl-gmppen. Check valve (CH2) m where check valve above the Zah whole under (Ili) indicated meaning possesses and m! from 1 to 4 means. Examples of this group close methyl, Äthy! - or Butylgruppen, which by above under (eyelid indicated special groups of check valves substituted are, in, e.g. the group of benzyles and the accordingly substituted groups of benzyles. Connections of the general formula (A) can be acyliert under education by derivatives, which are characterized by it, dafl it the group of AC o. CO. NH (C) mR exhibit, where R hydrogen or a halogen atom (c1, Br, J or F) and m a whole number from I to 4 bed your. An important class of Cephalosporinverbindungen are the connections, which exhibit a 3-CHzHal-Gruppe, where Hal a chlorine, a Bromoder represents iodine atom. Such connections are mainmaterial as Zwischenpmdukte for the production of active Cepha! osporinverbindungen of importance. Important available according to invention antibiotic connections are due to their broad spectrum of antibiotic Eigemchaften, which are connected with a stability opposite by a multiplicity of organisms formed B-Lactamasen. Connections of the following general formulas: Ru. C. CO, NH 11 /S N OH WHETHER 18 "" M [Bi (B) I COOH CHzOCO. CHs RU. CONCHA /S I CH2. O. GOR9 COOH (C) Ru. C. CONH 11 of /s \ O. CO.R COOH (D) and their not-toxic derivatives. In the formulas (B), (C) and (D) means Ru a Phenylgruppe, a Naphthylgruppe, a Thienylgruppe, one by ha! ogenatome, hydroxy groups, low alkyl groups, amino groups, low alkyl amino groups, Diniedrigalkylaminogruppen, Niedrigalkanoylgruppen, Niedrigalkanoylaminogruppen, low alkoxy groups, Niedrigalkylthiogmppen or Carbamoylgruppen substituted phenyl, Naphthyloder Thienylgruppe; R9 an alkyl group with 2 to 4 carbon atoms or group of one alkenyls with 2 to 4 carbon atoms, R an alkyl group with 1 to 4 carbon atoms, a chlorine alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, a Phenylgmppe, a Nitrophenylgruppe or a chlorine alkyl amino group with 1 to 4 carbon atoms. Further important available according to invention anfibiotische connections are the connections of the following general formula: Ru' CONH/S…. I COOH CHzSW (e) where Ru above with view to the connections of the general formulas (B), (C) and (D) indicated meaning possesses and W the Thiadiazolylgruppe, preferably the 5-Methyl-1, 3, 5-thiadiazol-2-yl-Gruppe, a Diazolylgruppe, a Triazolylgruppe, a Te azolylgruppe, a Thiazolylgruppe, a Thiatriazolylgruppe, a Oxazolylgruppe, a Oxadiazolylgruppe, a Benzimidazolylgruppe, a Benzoxazolylgruppe, - 12 - Nr.32q375 a Triazolopyridylgruppe, a Purinylgruppe, a Pyridylgruppe or a Pyrimidylgruppe means, as well as the ntchttoxischen derivatives of these connections. The connections of the general formula (e) possess a very strong effect against a multiplicity of gram posiüven and gram negative organisms, connected with a high stability opposite by a multiplicity of organisms formed t3-Lactamasen. A further substantial characteristic of these connections is their stability of gegentlber Saugetteresterasen. Further important available according to invention antibiotic connections are the connections of the following general formula Ru. C. CONH OH0 i CHzSR8 GOOH (F) 0 where Ru D Te above with regard to the connections of the general formulas (t), (C) and (D) indicated meaning and R-S an alkyl group with 1 to 4 carbon atoms possesses meant, as well as the nichttoxisehen derivatives of these connections. These connections represent broad spectrum antibiotics, which can be orally given. They possess also a stability more gegentlber by a multiplicity of organisms formed B-Lactamasen. A particularly preferred class for available according to invention antibiotic Cephalosporinverbindungen are the connections of the following general formula Rl° " “CONCHA _/S COOH (v) where the group of R*° a Phenylgruppe or the Thien-2-yl-Gruppe means, RA possesses preferably the meaning indicated above and represents hydrogen as well as and” a Acetoxy, Crotonyloxy, Isobutyryloxy, Methoxyoder 5-Methyl-1, 3,4-thiadiazol-2-ylthiogruppe means R the base salts of these connections, e.g. the well of iumoder potassium salts. Important connections, which fall into this class, include the following connections in form their syn isomers: 8A eetoxymethyl7 [3 (2-hydroxyimino2-phenylaeetamido) - eeph-3em-4-earbonsäure; 3Aeetoxymethyl '/8 [2hydrox) rimino-2 (thien2 yl) - acetamido] - C eph3 ere-4carbonsättte; 7B [2-Hydroxyimino2 (thien-2-yl) - aeetamido] - 3 (5-methyl-1, 3,4thiadiazol-2-yl] - thiomethyl eeph -3-em-4-carbonsaure and 7B ('2Hydroxyimino -2-phenylacetamido) - 3 (5methyl1, 3, 4thiadiazol-2-yl) - thtomethylceph3 ere -4earbonsaure, in particular in form of their Natriumoder Kaltumsalze. The four last mentioning connections represent broad spectrum antibiotics, those against a multiplicity of gram positive (pentefllin resistant and penicillin-sensitive trunk of Staph. aurem) and work gram negative organisms, as it is evident through in vitround in vivo Untersuehungen. Further the connections are particularly steady against 8-Lactamasen, which is formed by a multiplicity of gram positive and gram negative organisms. The salts producible of the according to invention connections can be manufactured in any usual way. For example the base salts can be received by shifting of the Penieillinoder ¢ephalosporinsaure with well iumoder Kalium-2-äthylhexanoat. In practice it is comfortable, an acylation means, the one the sour of the general formula R.c. COOH (vi) Jl N \ oRa corresponds, where R and RA possess the meanings indicated above, with a Aminoverbindung of the general formula H 2 N. to B.] Æ COOR z, (Vll) where Z and B possess the meanings indicated above and hydrogen atom or a group of carboxyl blockings, e.g. the remainder of a ester-forming alcohol (aliphatic or araliphatic) represents RI, a phenol, Silanols, Stannanols or sour, is condensed, how those condensation erwünschtenfalls in presence of a condensing means accomplished and on which one the group of RI separates if required. During the production of the Cephalosporinund can the Aminoverbindung of of the general formula (VII) penicfllinverbindungen the connections of of the general indicated above formulas (IL) and (IIl) enSsprecheu and by the following a11gemeinen formulas to be represented: ! OOR1 tTx) and/or. H2N /B /HS NJ CHs 0 --C OOR (vm) where g 1, B and P possess meanings indicated those above. Also a derivative of the Aminoverbindungen, like a salt, can be used e.g. a Tosylat. Connections, where the group of RA means a hydrogen atom, can be manufactured indirectly, and connections, where the group of RA does not represent a hydrogen atom, can be kept direct, if one as acylation means a S turehalogenid, in particular a sour chloride or - bromide, uses. During the production of a connection, where RA a Wass first off atom means, an additive, liche E0 stage necessarily in accordance with this V experiences, is with which the acyl group RA under formation of the Hydroxyiminoverb£ndung is removed. The acylation can at temperatures from -50 to +50°C, preferably at temperatures from -20 to +g0°c, e.g. at temperatures by for instance 0°C, to be dttrchgeftährt. The acylation means can be manufactured, by one dle sour ones of the general formula (VI). where the group of RA does not mean a hydrogen atom, with a Halogenierungsmittel, e.g. phosphorus pentachloride, Thionylchlorid od it Oxalylchlorid, converts. A cylierung can take place in aqueous or not-aqueous medium, and suitable media wasserigesKeton, like wasseriges Aeeton, an ester, e.g. ethyl acetate, or an amide, e.g. Dimethylacetamid, or a nitrile, e.g. a Aeetonitril, or mixtures of these materials includes. The acylation with a Sattrehalogenid can in presence of a connecting means, e.g. a tertiary amine (e.g. Trittthylamin or Dimethylani! in), a anorgauischen base (e.g. Kalziumearbonat or well umbiearbonat) or a Oxirans, whom bind hydrogen halide set free with the acylation reaction, white manages. The Oxiran is a vorzngsweise Nledrig l, 2-alkylenoxyd, e.g. ethylen oxide or propylene oxide. If one uses the connection of the general formula (VI) in form the free sour one and if gewttnschtenfalls RA hydrogen represents the group, suitable Kondemationsmittel closes N, NT-Dittthyl, Dipropyloder Diisopropylcarbodiimid, N, N f-Dicyclohexylcarbodiimid or N-ethyl-n r-7-dimethylaminopropYlearbodiimid, a suitable CarbonFlverbindung, e.g. Carbonyldiimidazol, or a Isoxazoliniumsalz, for the production of the new connections Carbodiimide, e.g. e.g. Nthyl-5-phenylisoxazolininm-3, - sulfonat or N-fat. Butyl-5-methylisoxazolinium-perehlorat. The condensation reaction erfolgtwtlnschenswe - terweise in a water-free reaction medium, e.g. in dichloromethane, dimethylformamide or Aeetonitxil, since itself then the Reaktäonsparameter, as let the temperature adjust, more genaner. Alternatively the acylation with another amide-forming derivative the ketenes Steure, like e.g. a symmetrical anhydride or a mixed anhydride, e.g. with Pivalinst ure or with a Halogeuameisensäureester, can take place e.g. a halogen formic acid low alkyl ester. The mixed or symmetrical anhydrides can be formed in situ. For example kanu a mixed anhydride using N-Äthoxycarbonyl-2tlthoxy-l, 2-dihydrochinolin manufactured feast EN. Mixed anhydride e know also with Phosphorstlureu (e.g. Phosphorstlum or more phosphorously accumulated), Schwefelstlure, or aliphatic or aromaüschen Gulonsäuren (e.g. p-Toluolsulfonstlure) to be formed. A further suitable Acylietungsmittel is an activated ester, e.g. a connection of the general formula R, C. CO.W 11 N (X). where W e.g. represents an azide, a Oxysuccinimid, Oxybenztfiazol, Pentachlorphenoxy or to p-Nitrophenoxygrnppe. One can also those according to invention erhtiltl/chen connections, where the group of RA represents a hydrogen atom, manufacture, by eiu Acylierungsmtttel, which corresponds to the acid of the general formula (VI) and where RA a hydrogen atom does not represent the group, but a group, which can be removed easily under education of the desired group =N, *OH, with a Aminoverbindung of the general formula (VII1) condensing. The group of RA is removed afterwards gewtluschtenfalls together with the separation of the GruppeRt. Examples of such separable groups of RA are e.g. acetyl groups, which exhibit gewtlnschtenfalls mindestem a elektronenanzlehende group at a-carbon atom, like tri chlorine acetyl, Dichloracetyl, mono chlorine acetyl, Triflnoracetyl, Difluoracetyl and Monofinoracetylgruppen; the Formylgruppe, the Benzhydryloxycarbonylgruppe, the Benzyloxycarbonylgruppe, which tert. Bntoxycaxbonylgruppe and the 2, 2, B-Trichlortlthoxycarbonylgruppe. The separation of such groups can take place e.g. under weakly basic conditions. So an acetyl group can e.g. entfemtwerden by treating with aqueous alkali. Halogenierte acetyl groups can to be removed with wässerigemBicarbonat and additionally be able the chlorine acetyl groups by use of a nukleophilen connection, like a thiourea, abgespalten to become. B enzhydry1oxycarbonylgfuppeu and tert. Butoxycarbonylgmppen can be separated using Trifluoressigstlure with or without anisole. The 2, 2, 2-Trichloräthoxycarbonylgrnppe kanu with the help of a Reduktionsmitte.h, like zinc/Essigstlute or zinc/Ameisenstiure, abgespalten becomes. It understands itself that, although the production of connections represents also easily split off-pleading groups of RA a suitable way to Hydroxyiminoverbindungen, also connections with such groups of RA erhälüiche according to invention connections is and desirable characteristics can exhibit. Alternatively can the connections of the general formula (I) to connections of the general formula O = C = N.B. oJ COOK (xi) where B, Z and Ri the meanings with exception of the Bedentnng, indicated above that d/e GtuppeR! a hydrogen atom represents, has, by shifting with a Stiure of the allgemetnen formula (VI) (where the Grnppe RA does not represent a hydrogen atom) and through arschHeßendes separating the groups g 1 and gewünschtenfalls RA manufactured feast (see e.g. the hoIllindische patent application No. 6808622 and the Belgian patent specification No. 760494). The conversion of the connection that allgemeinen'Formal (Nile) or (XI) can to-ends the HersteIlungsverfahrens to be accomplished, whereby the only additional rh actions exist groups of protection and further cleaning stages in dec splitting off D it. The connections of the general formula (I), where the group of RA represents a Acylgmppe, it can from the appropriate connections of the general formula (I), where the GrnppeRa represents a hydrogen atom and from esters of these connections (i.e. from connections, which exhibit COORI into the 4-Stellung a group, where g 1 possesses the meaning indicated above) by acylation to be received. The Acylterung can be caused in any suitable width, e.g. using one the SäureRaOH corresponding Stiurehalogeuids of a mixed or symmetrical anhydride, a ketene, an ecyl azide or a Carbodi mids (if the 4-Carboxygmppe is protected). Alternatively the Acy can! ternng with hats of a halogen formic acid ester, e.g. a Chlorameisemäureesters, like chlorine formic acid ethyl ester, take place, - 15 - Nr°327375 whereby one the carbonates receive, or can with the help of an isocyanate of the formula RbNco e.g. by 2-Chloräthylisocyanat take place, on which one receives the Carbamate, where ORa of the formula RbNHcO. O-- it corresponds where Rb possesses the meaning indicated above. D eAcy! ierung can e.g. by e [ne ßase, like tri ethyl amine, Diäthylanilin, Pyridin, propylene oxide, magnesium oxide, Natriumcarbonat or calcium carbonate to be catalyzed. The Acylierurzg can be durchgeflihrt in an organic solvent. Suitable solvents close halogenierte hydrocarbons, e.g. Methylenehlorid, cyelisehe ethers, e.g. Dioxan or Te ahydrofuran, Nitzile, e.g. Acetonämie, N trokohlenwasserstoffe, e.g. Nitromethan, ester, e.g. Äthyll0 acetate, or the Aeylierungsm [ttel even in. The acylation can at a temperature from -10 to +100°C, vorzugsweße at a temperature from 0 to 50°C, favourable-proves at a temperature from 0 to 30°C, to be caused. After the Acylterung is accomplished, the group of g 1 is separated if required. Ewünschtenfalls one knows G first a connection of the general formula R, CO. CO, NH B COOR z (xn) manufacture, where R, RZ, 13 and Z possess the meanings indicated above, and afterwards the connection of the formula (XII) with a connection of the formula RaO. NHz (where RA possesses the meaning indicated above) convert, on which one knows the group of R abtrennt° the reaction product before or after the separation of the GruppeR1 in synund anti-isomers is if required separated, one can the connections of the general formula (I), where the group of R manufactures an activating group, how a Cyanogruppe or a Pyridylgruppe is, by a one Nitrosier ng an including procedure. Thus the Acylamidogruppe knows exhibiting connection of the following formulas R. CHzCONHoder R. CH. CO. NH-- I COOH to be nitrosiert, by using e.g. salpetrige acid (in situ by shifting of an alkali metal oxide with a weak acid, e.g. acetic acid, to be set knows), Nitrosylchlorid or an organic Nttrosierungsmtttel, e.g. an alkyl, a Cycloalkyl, Aryloder Aralkylnitrit. If one eineVexbindung, the one group of the following formula R. CH. CO. NH-- l COOH contains, nittosiert, sports club CCIT a simultaneous Decarboxylierung. The separation synund anti-isomers can be necessary after the Nitrosiesungsreaktion. Gewtlnschtenfalls can take place a replacement of a group of P via an and ere preferential group, after the Acyliesung of the 7-Aminoverbindung took place. In particular, if the group of P is following a group that EN allgemeiuea formula, -- CHzY, where Y possesses the meaning indicated above, can be eingeftthrt the group of Y in accordance with procedures described in the literature. Thus connections, where Y represents a halogen atom, a group of ethers or a Thioäthergruppe, can be manufactured in accordance with the procedures, which into the Belgian Patent16 - NR, 8273q5 writings Nr.719qll, No. 719qi0, No. 734532 and Nr.734533 are descriptive. Connections, where Y represents the remainder of a nukleophilen connection, know l by shifting of a 3-Acetoxymethylcephalosporinverbindung with a nukleophilen connection, e.g. ridin or another manufactured Ami.n, as it brit in. Patent specification NR, 912541 is descriptive; a sulfur-binding, a nitrogen-binding “or an inorganic nukleophilen compound, as it brit tn. Patentschrfft No. 1.012.943 is descriptive more dner sulfur-binding nukleophilen connection, as e brit in. Patent specifications No. 1.059, 562, No. 1.101.423 and No. 1.206.305 is descriptive; or a nitrogen-binding nukleophilen connection, IE it in brit. Godfathers chrtften No. 1.030, 630, Nr.1, 082, 943 and No. 1, 082.962 are descriptive, to be manufactured. Connections, where the group of Y a derivative of a remainder of a nukleophilen connection, how a Aminooder of a Acylamidogruppe, darstdlt, which is abgeldtet of a Azidogruppe, and connections, where Y a Azidogruppe are meant and with a Dipolarophil is converted, can geml! in brit. Patentschrfften No. 1.057, 883 and No. I, 211, 694 descriptive procedures to be manufactured. Erfindungsgemllfl erhlflfliche connections, where Y represents the remainder of a nukleophilen connection, can be manufactured also by shifting of a 3-Halogenmethyl-cephalosporins with any of the nukleophilen connections described in the above literature places, whereby a derarüges procedure is descriptive in the Belgian patent specification No. q19'/11. If Y represents a hydroxy group, kanu the connection gemllB in brit. Patent specification No. 1.121.308 descriptive procedures to be manufactured. Connections, which exhibit a Vinylgruppe or a subsütuierte Vinylgruppe as substituents of the 3-Stellung, can be received in accordance with in the Belgian patent specification No. 761897 described procedures, if Y represents a halogen atom (a chlorine, a Bromoder iodine atom), can the Ceph-3-em-Ausgangsverbindungen by Halogenieren of a qB-Acylamido-3-methylceph-3-em-4-carbous of ureester lB oxide, followed by a reduction of the 1B-Oxydgruppe in the later process of the procedure be manufactured, as it chrift in the Belgian patent No. 755256 is descriptive. The appropriate Ceph-2-em-Verbindungen can be received gemliß in the published hollllndischen patent application No. 6902013 described procedures by shifting of a Ceph-2-em-3-methylverbindung with N-Bromsuccinimid under formation of the Geph-2-em-3-brommehhylverbindung. If Y represents a hydrogen atom, the connections can be manufactured geml a procedure, that in brit. Patent chrift No. 957, 569 is descriptive, or can of a Penicillinverbtndung gemli6 dern in the USA patent specification No. 3, 2 " 15, 626 and the Belgian patent specifications No. 74 " 1119 and No. 74 " 1120 descriptive procedures be made. Gephalosporinverbindnugen, which aufwdsen as substituents in the S-position a Acyloxymethylgruppe, can be manufactured by any suitable procedure, i.e. they can from a Cephalosporinverbindung, which does not exhibit a 3-CH2 Y-group, where Y represents a OH-group or the remainder of the Sllure H Y, the one pKa value of no more as 4, 0, preferably from no more than 3, 5 (certainly in Wasse with 25°G), exhibits, represents, to be manufactured. The group of Y can a chlorine, Bromoder iodine atom, a Formyloxygruppe or a Acetoxygruppe, which at least a deklronenanziehenden Subst [tuenten at a-Kohlemtoffatom exhibits, or a nuclearsubstituted Benzyloxygruppe to be, whereby the Kemsubstituent elekt onenanziehender substituent is, as it brit in. Patent specification No. 1.241.657 fuel element-wrote is and whereby the nukleophile Verdrlingungsreaktton for the introduction of the gewtluschten substituent to the 3-Stellung gemll6 dern in erwlihnten the above brit. Patentsehrift NL 1.241, 65q takes place. Alternatively can, if the group of Y represents a hydroxy group, which brit gewtlnschte 3-Acyloxymethyicephalosporin by Acyliemng gem&B in. Patent specification No. 1.141, 293 descriptive procedures to be received. In brit. Patent specification No. I, 141.293 is a procedure for the production of a AS-Cephalosporins, which exhibits a 8-Acyloxymethylsubstituenten, from which appropriate similar 3-Hy oxymethylverbindung descriptive, which consists of that one aralkyltert the 4-Carboxygruppe, which acyliert 3-Hydroxymethylgruppe of the geschtltzten connection and splits afterwards the Aralkylgruppe off. A cylierung gemli6 any suitable procedure can take place, e.g. using a Sliurechlorids, a Stlureanhydrids or a mixed Sliureanhydrids as acylation means, whereby one works preferably in presence of an organic base, like Pyridin, and the reaction in solution in an inert water-free solvent, durchftkhrt e.g. dichloromethane. Alternatively the acylation can take place in wtisserigen acetone/Nai iumbicarbonat solution. The preferential acylation means is the Sllurechlorid. The acylation reaction should be accomplished as fast as possible, since on the acylation conditions a relocation can enter a2-derivative, in particular if a Aroyloxygfuppe is eingefilhrt into the exocyclische group of groupgroups in the 3-Stellung. The being DNN gene of the general formula (VII) those can be used the formula (XI) ester as esters, be represented wllhrend. One can use also the free Aminosliure or a Stlureaddittonssalz of the free Aminosllure or an ester this sour one. Salts, which can be used, include Sllureaddifioussalze, with e.g. Chlorwasserstoffsllure, Bromwasserstoffsllure, Schwefelsliure, Salpetersllure, phosphorus ure, p-Toluolsulfons ure and methane sulfone ure. - 17 - Nr.32 375 the esters can with an alcohol, a phenol, a Silanol or a Stannanol with up to Kohl enstoffatomen to be manufactured, how these easily with a later stage of the Gesamtrea! ¢tion abgespalten will can. A vexestemde group, those the 4-Carboxylgruppe of a connection of the general formulas (VII), (XI) or (XII) ubstituiert, is preferably formed for a Pheuol, a Silanol, a Stannanol with (aliphatic or araliphatic) an alcohol, or sour ones, which abgespalten easily with a sp/tteren stage of the reaction become kömäen. Suitable esters include thus connections, which contain as Estergmppe a group in of the following list indicated groups, which is to represent however no group of all possible esters: lo q) COOCRaßRc where at least one of the groups of RA, Rb or RH a Elektrouen Donor is, e.g. a p-Methoxyphenylgruppe, 2.4, 6-TrimethyI phenylgruppe, a 9-Anthrylgruppe, a Methoxygrnppe, a Aeetoxygruppe or a Fur-2-yl-Gmppe. The remaining groups of RA, Rb and RH can be hydrogen atoms or organic substituents. Suitable groups of esters of this kind close the p-Methoxybenzyloxyearbonylgmppe and the 2; 4, 6-Trimethylbenzyloxycarbonylgrnppe. COOCRaRbRc where at least one of the groups of RA, Rb and Rc a eleklronenanziehende group, e.g. a Benzoyl, a p-Nitrophenyl, a 4-Pyridyl, a Triehlormethyl, a tri bromine methyl, an iodine methyl, a Cyanomethyl, Äthoxyearbonylme yl, aryl sulphonyl methyl, 2-Dimetbylsulfonium thy1, o-Nitrophenyloder Cyanogruppe is. The remaining groups of RA, Rb and RH can be hydrogen atoms or organic substituents. Suitable esters of this kind close Benzoylmethoxyearbonyl, p-Nitrobenzyloxycarbonyl, 4-Pyridylmethoxycarbonyl. 2, 2, 2-Trichlor/ithoxycarbonylund 2, 2, 2-Tribrom/lthoxycarbonylGruppen. ([[I) COOCRaRbRc where at least two of the groups of RA, Rb and RH groups of hydrocarbons, like alkyl groups, e.g. Methyloder groups of ethyls or Arylgmppen, e.g. Phenylgruppen, represent and the remaining groups of RA, Rb and Rc, if available, hydrogen atoms mean. Suitable esters of this kind close text. Butyloxycarbonyl, tert. Amyloxycarbonyl, Diphenylmethoxycarbonylund Tr [phenylmethoxycarbonyl groups. qv) CooR “, where the group of RD represents a Adamantyl, a 2-Benzyloxyphenyl, a 4-Methylthiophenyl, a Tetrahydrofur -2-yloder Tetrahydropyran-2-yl-Gruppe. (V) Silyloxycarbonylgruppen, which became to receive by shifting of a group of carboxyls with a Stlanolderivat. The Silanolderivat is be suitable-proves a HaIogensflan or a Silazan of the following formulas: R4 SiX; R4zSiXz; R4 SI. NR4z; R4aSi. NH. SiR4; R43Si. NH. COR4; R4sSi. N! l. CO. NH. Sißs; NHCONR4SiR “s; I C (OSiR4s) or NSiR where X a halogen atom and the different groups of R4, those-homogenously or differently to be can, hydrogen atoms or Alkylgrnppen, e.g. methyl, ethyl, n-Propyl, Isopropyl groups, groups of aryls, e.g. a Phenyl a uppe odex Aralkylgmppen, e.g. groups of benzyles, mean. Preferential Silanolderivate is e.g. Sflylehloride, like tri methyl chlorosilane or Dimethyldichlorsilan. The group of carboxyls can be repaired by any usual procedure, where Saureund are generally applicable e.g. base-catalyzed hydrolyses exactly the same as enzymatic catalyzing hydrolyses. However wtisserige mixtures can represent bad solvents for these connections and be able to do it to isomerizations, result Umlagemngen, Nebeareaktionen and general Abbaureaktioneu, so that only certain procedures are erwiluscht. Five suitable Entestexungsverfahren are the following: - 18 - NR, 327375 1st reactions with Lewis sour ones. Suitable Lewis s, 'turen, which can be converted with the Eistem, close Trifluoressigstture, ant-brick, hydrochloric acid into acetic acid ones, Zinkbmmid in benzene and wttsserige solutions or suspensions of QuecksflberllI) - connections in. The reaction with the Lewis S/lure can be facilitated by addition of a nukleophilen connection, like anisole. 2. Reduction. To Ftlr the reduction suitable systems send zinc/vinegar ure, Ztnk/Ameisenstture, zinc/low Alkoho! , Zinc/Pyridin, palladium on activated charcoal with hydrogen and sodium in liquid ammonia. 8. Attack by nukleophile V erbindungen. Suitable ones nukleophile connections are e.g. connections, which a nukleophiles Sauerstoffoder Schw contains efelatom, like alcohols, Mercaptane and water. 4. Oxydative procedure, e.g. those, which include the use of hydrogen peroxide and Essigsanre. 5. Irradiation. If one ethtllt at expiration of a manufacture sequence connections, where group of those corresponds to B of the following formula: S” 0 and one a connection received wants, where the group of B: S means; the transformation can in a 8nifid e.g. by reduction of the appropriate Acy! oxysulfoninmoder Alkyloxysulfonium salts, tnsitu e.g. with Acetylch! orid in companies! 1 of a Acetoxysulfoniumsalzes to be manufactured can, takes place, as the reduction is inmdithionit e.g. by Nat or accomplished by iodide ions, like e.g. in a solution by potassium iodide in solvents mixable with water, acetic acid, T etrahydrofuran, Dioxan, dimethylformamide or Dimethylacetamid. The reaction can take place at a temperature from -20 to +50°C. Alternatively the reduction of the 1-Su can! finylgruppe by Phosphortrich! orid or phosphorus tri bromide in solvents, like dichloromethane, dimethylformamide or Teirahydrofuran, preferably at a temperature from -20 to +50°C, to be managed. If the arising connection is a Ceph-2-ere-4-ester, the gewlimchte Geph-3-ern-Verbindung can be made by shifting of the first connection with a base. The sour one of the general formula (VI), which the acylation means corresponds, can be received, by one the Glyoxyls lure of the general formula R. CO. COOH where occupies R the meaning indicated above, or an ester of this connection with a connection of the general formula RaO. NI! z, where RA possesses the meaning indicated above, converts. The arising sour one or the ester received thereby can then e.g. by crystallization, chromatography or by Desfi! lalion EN synund anti-isomers to be gepennt, on which one accomplishes a hydrolysis of the ester if required. Alternatively the sour one of the general formula (X/I), where the group of RA means a hydrogen atom, can to be received, by forming an ester of the S/lure of the following general! R. CHzCOOH where possesses R the meaning indicated above, with an inorganic or organic Nitrosierungsmittel, e.g. an alkyl nitrite, as Isopropylnitrit or Nit converts osylchlorid in present eine¢ Silurer or base. It is preferential that one uses the Nitrosierungsmittel in a surplus, e.g. a molecular surplus. Subsequently, erforderliehenfalls the group of esters is separated. Synund anti-isomers ktirmen by suitable procedures to be differentiated, e.g. by their U1traviolettspektren, by dtinnsehichtchromatographische or papierchromatographische procedures or by their nuclearmagnetic resonance spectra. For example appears in password in DMSO D “the amide NH doublet of the connections of the general formula (I) with syn lsometen with a lower field, than it with that anü lsomeren the case is. These factors can be used for the monitoring of the Reakttonen. - 19 - Nr°327375 producible the according to invention antibakterieUen connections can be formulated in any way into a form suitable for the administration, by one in similar way as pray other antibiotics works. Therefore one places also pharmaceutical compositions, an antibacterial connection the de general formula (I) or a not-toxic derivative of these connections, e.g. a salt (like it one defines), contained and to use in the Humanoder veterinary medicine suitably are, ago. Such compositions can be manufactured in usual way with the help of any necessary pharmaceutical substrates or bonding agents. erfindungsgemäI the available antäbakteriellen connections can to be formulated to Injeküonszweeken and be able in EinheHsdosisform, in ampuls or in multiple dose containers with an added I0 preservative be present. The Zusammemetzungen can be present in the form of suspensions, solutions, emulsions, in oily or zaserigen substrates and can formulation means, how Suspendiermfttel, stabilizers and/or dispersing agents contain. Alternatively the active active substance in powder form can be present and with a suitable substrate, e.g. sterile, pyrogenfreiem water, before which use are mixed. The compositions can be present also in a form suitable for the absorption by the gastro-intestinal tract. Tablets or caps to the oral Verabreichang can be present and know in unit dose form usual substrates, like bonding agent, e.g. syrups, rubber arabicum, gel, Sorbit, Tragantgummi or Polyvinylpyrrolidon, fillers, e.g. lactose, sugar, Maisstlirke, calcium phosphate, Sorbit or glycine, lubricant, e.g. magnesium stearate, talcum powder, PL glycol, silicon dioxide, decomposition means, e.g. potato strength or compatible wetting agents, how well iumlaurylsulfat, contain. The tablets can be covered after well-known procedures. Liquid preparations orally which can be given can in form-aqueous or oily 3uspemionen, solutions, emulsions, syrups, Elixiere etc. be present or can in form of a dry product be acted, which is mixed before the Veraendung along water or another suitable substrate. Such liquid preparations can contain usual additives, like suspending means, e.g. of Sorbihirup, Methylcellnlose, glucose/Zuckersirup, gel, HydroxyäthylceUulose, Carboxymethylcellulose, Aluminiumstearat, gel or hydrogenated edible fats, emulsifying means, e.g. Lecithin, Sorbitanmonooleat or rubber arabicum, nichtwässerigeTrägexmaterial EN, which oil edible include can, e.g. almond oil, fraküoniertes coconut oil, oily esters, propylene glycol or ethyl alcohol, preservative, e.g. Methyloder Propyl p hydroxybenzoate or Sorbinsäure. Suppositorien contain usual Suppositorien base materials, zoß. Cocoa butter or other Glyzeride. The compositions can be manufactured in suitable form to the absorption by the Schleimhänte, the nose, the throat and the Bronchial fabric and can be suitable-prove in form of powdered or liquid spray means or inhalation means, Lutschtabletten, throat lacquers etc. to be present. For the treatment of the eyes and the ears the preparations in individual caps, liquid or in halfliquid form can be present or can as drops - sw. are used. Topi applications can be formulated with the help of hydrophober or hydrophilic bases than ointments, creams, lotions, lacquers, powder etc. For veterinary purposes the compositions can be formulated e.g. as intramammäre preparations, with either long duration of effect or fast release. The compositions can contain the active substance in quantities of 0,1% upward, preferably in quantities from 10 to 60 /o as a function of the administration way. If the compositions cover Einheihdosierungen, each unit contains preferably 50 to 500 mg de Wirkstoffes. The dosage for treatment is appropriate preferably in a range from 100 to 3000 mg, e.g. 1500 for mg arise ago tliglich, as a function of the way and the H tufigkeit the administration. Producible the according to invention connections can be given in combination with other therapeutic means, like Antibioüka, e.g. different Cephalosporinen, Penicillinen or Tetracyclinen. The following examples are to describe the invention further, without limiting it however. 2-Hydroxyiminoessigsäure and their derivatives. Production 1:2 - Hydroxyimino (thien-2-yl) - acetic acid (syn isomer), a cooled down solution of 0,884 g hydroxyl amine hydrochloride and 1, 08 g Natriumbicarbonat in 20 ml water was given to one on 0°C cooled down solution by 2, 0 g Thien B YL glyoxylsäure and 1, to 08 g Natriumbicarbonat in 20 ml water. After 2 days with 20°C the solution with ether was extracted, abgektlhlt and acidified with concentrated hydrochloric acid. The arising white solid (0, 564 g) and the Ffltrat was filtered off was then extracted well with ether. The united excerpts were washed, dried and restricted with salt solution. The firm arrears became with benzene rubbed and resulted in 1, 05 g (51 /o) of the Cxims (syn isomer), Fp. = 132°C. UV spectrum: Xmax ethanol), 284 Nm (“9 00); 1R-Spektrum: Vmax (Nujol), 2590 and lq06 (COzH) and 1655 cm " 1 (C--N); NMR Spektr, m: (DMSO-d6), -2, 5 to -0, 5 (broad multiplet; N-OH and COOH), 2.36 (Mulüplett; Thienyl-C-5 H) and 2, 82 (multiplet; Thienyl-C-3 H and - C-4 H) o - O - LRO/. 'l RST production 2:2 - Dichloracetoxyiminophenylessigsliure (syn isomer). To a mixture of 45 ml one gave dichloromethane and 10 ml Dichloracetylchlorid by portion under agitating in the process of approximately 15 min fi g 2-Hydroxyiminophenylessigs iure (syn isomer). The Reaküonsmischung solidified itself and wtihrend I h at ambient temperature after finished addition was gertlhrt. The reaction mixture became with Petrolgther (boiling point 40 to 60°C) verdtinnt, and the solid filters off washed with Petrollither several times, in order to remove the remaining sgurechlorid. The solid was geHocknet in the vacuum, whereby one 8, 0 g (96 o) 2-Dichloracetoxyirninophenylessigsgure (of syn isomer) received, Fp. = 1 " 15°C. IR spectrum: Vmax (CHBrs) 3470 and 1750 (- COzH), 17ö5 cm-1 (ester). NMR Spektrurn: “(CDCls) the values include: 2, 0 to 2, 7 (multiplet; aromatic protons), 3, 85 (singlet; - CH__Clz). Production 3:2 - Dichloracefoxyimino (thien-2-yl) - acetic acid (syn isomer). 38 g 2-Hydroxyimino (thien-2-yl) - acetic acid (syn isomer) were given to dry dichloromethane by portion with 20°C to an agitated solution by 70 ml Dichloracetylchlorid in 350 ml. Then during about 20 min agitating was continued, whereby faserförmige crystals formed. DieSuspemion was agitated during further 10 min and filtered off then. The solid was washed with dichloromethane and PE more oltither and resulted in 38, 5 g (61%) the Titelsliure. UV-Spektzum: kmax (ÄtOH) 262, 5 (“9,520), 291 Nm (“8,580). Production 4:2 Dichloracetoxyimino (4chlorphenyl) - acetic acid (syn isomer). To a solution of 1, 8 ml Dichloracetylchlorid one gave to 1, 5 g 2-Hydmxyimino (4-chlorphenyl) - essigsgure (anti-isomer) and agitated the suspension during 2h at ambient temperature. W, 'thrend this time separated the Hauptrnenge of the material. The solid was removed, combined washed with Petrolgther (boiling point 40 to 60o¢) and the washing waters and the filtrate, collected with 5°C over night left untouched and the arising solid and dried and resulted in 2, 0 g (85aß) the Titelsgure, Fp. = 80o¢. UV spectrum: Xmax (ÄtOH), 258 (12280). IR-Spekt over: Vmax (Nujol), 1774 (ester), 1750 and 1722 cm " 1 (CO2 H). Production 5:2 - Dichloracetoxyiminonaphth ll yl acetyl chloride (syn [someres). To a password of 0, 375 g 2-Hydroxyiminonaphth1 r-ylessigsaure (syn isomer) in 10 ml ethyl acetate one gave bei0°C to 0.2 mI Dichloracetylchlorid and agitated the solution during 30 min with 0°C, after the addition of 0, 36 g phosphorus pentachloride the mixture during 90 min with 0°C was agitated. The solvent became subsequently, at low temperature (about 5°C) veaxlampft and evaporated toluol with about 5°C of the arrears. The remaining oil was loosened in 5 ml ethyl acetate and used without further cleaning. H production 6:2 - etylchIorid (syn isomer), to a suspension of 0, 27ö g 2-Dichloracetoxyiminophenylessigsgure (syn isomer) in 10 ml Methylenchloriä one gave 0, 208 g phosphorus pentachloride to Dichloracetoxyiminophenylac and agitated the mixture during 1 h with Ranmtemperatur, whereby during this time the material separated. After the separation of the solvent under decreased pressure benzene of the arrears was evaporated and the arising thing was released oil in the vacuum from the solvent, whereby one 0.29 g (100%) 2-Dichloraeetoxyiminophenylacetylchlor [D (of syn isomer) received. IR spectrum: Umax (Fltlssigkeitsfilm) 1770 cm-1 (COCl and CO2 R), production 7:2 - Dichloraeetoxyimino (thien-2-yl) - acetyl chloride (syn isomer). A 0,3m-Lösung von Phosphorpentachlorid in 179 ml dichloromethane w'urde drop by drop in the process and on 0°C a cooled suspension of 16,7 g syn-2-Hydroxyimino-thien-2-yl-essigsgure in 340, agitated from min to, ml dry MethyIenchlor [D admitted. After 5 min was restricted the solution under decreased pressure and at low temperature. The oil received as arrears was abdestilliert azeotrop with benzene, solved in Äthylaeetat and used without further cleaning. Production 8:2 - Hydroxyiminonaphth-1 - yl-essigsgure (synund anti-isomers). To a solution of 4, 62 g one gave phenolphthalein to Hydroxylamfnhydmehlorid in 40 ml MefllanoI and then a methanolic well iummethylaflösung (about 5 /0 thread/VOL. ), until with a pink color the terminator point was reached. Then a Krfstall was added by Hydmxylaminhydrochlorid, in order to drive the pink color out, on which the solution was filtered, in order to remove sodium chloride. Then 10, 0 gNaphth l - yl - was added glyoxyls ure and the mixture was heated up wlihrend 30 min at the Rüekfluß. It was evaporated then to dry ones, adjusted with 50 ml water shifted and the pH value with 2n hydrochloric acid to i. The received 8uspemion v¢urde with Äthylaeetat extracts, on which the united ExHakte was washed, dried and evaporated with water, whereby one received a weak-yellow solid, which from benzene Petrolgther (boiling point 60 to 80°C) was recrystallized, whereby one 2, 7 g (25a] 0) 2-Hydroxyiminonaphth-1 r - yl-essigsgure (anü isomer) received, Fp. = 159°C. UV spectrum: - max (ÄtOH) 279 Nm (“5940). IR spectrum: Umax (Nujol) 3245 (OH), 1701, 1712 cm " i (C02 H), NMR Speklrum: “(DMSO D “) -8, 0 to -2, 2 (broad signal; OH), 1.8 to 2, 7 (Mulüplett; aromatic protons). The mother liquor of the recrystallization was evaporated dry ones, on which the solid (2.2 g) was treated with a slight surplus of a DiazomethanlOsung in ethers and on which one the yellow F rbung by addition of the raw 2-Hydzoxyiminonaphth1, - ylEssigsäure distant, the ether solution became with a satisfied Natriumbicarbonatlösung washed, getmcknet and evaporated and resulted in 2.3 g of a mixture synund of the anti-Methyl-2-hydroxyiminonaphth-1, - yl-acetates. The mixture (9 0 g) was solved in ethyl acetate and applied on eight diinnschfchtchromatographischen plates coated with Merck silica-gel (20 × cm). The plates became more ther with ether/Petrol (boiling point 40 to 60°C; 1/2) developed and the Hauptbestandtell, which exhibited the higher Rf-value, with ethyl acetate were eluiert, whereby one 0.75 g (a4qo) 2-Hydroxyiminonaphth-1, - yl-vinegar (syn isomer) kept more luremethylester, Fp. = 110 to lll°C. UV spectrum: Xmax (ÄtOH) 298, 5 Nm (“8150). IR-Spekt; over: Vmax (CHBr) 3550 (OH) and 1737 cm " (ester). NMR spectrum: r (CDC ½) the values include: 1, 9 to 2, 85 (multiplet; aromatic protons), 6, 16 (singlet: CHs). A solution of the ester (i, i0 g) in 15 ml in Nai iumhydroxyd I h was left untouched, washed then with ether, acidified with 2n hydrochloric acid and extracted with ethyl acetate. United excerpts with water washed, dried and evaporated and resulted in Feslsfoff, which with PE more oläther (boiling point 40 to 60°C) rubbed, were filetiert and dried, whereby one 0, 89 g (86 o) of the title acid (syn - isomer) received, Fp. = 111 to 112°C. UV-Spek over: Xmax (ÄtOH), 292 Nm (7400). IR-Spek over: Umax (Nujol), 2630 (OH), 1678 (COzH) cm " i. Production 9: Äthyl-thien-3-yl-glyoxylat. To a solution of n-butyl lithium in ether (265 valley) under violent agitating with -70°C a solution of 41 g 3-Bromthiophen into 50 ml ethers drop by drop during 30 min under a nitrogen atmosphere course-follows was agitated the received Außch] $1mmung 5 min with -70° and afterwards under violent agitating to a solution of I] 0 g Di, 'Ithyloxalat into 220 ml ethers followed, whereby the temperature w; lhrend under - q0°C one held for the addition. After D it addition knew D [e temperature of the solution to ambient temperature to rise and the reaction 3 h one agitated and one poured afterwards in 2n hydrochloric acid. The organic phase was separated and with 2; Itheri excerpts of the aqueous phase combines. The united excerpts wutden dried and evaporated under education of an oil, which was fractionated under decreased dirt. After distillation of the überschflssigen Di; One received 12 g (26a/o) of the title ester of the kp to Ithyloxalats with 63°C/0, 1 mm. ll0°C/0, 1 mm. IR spectrum: Y of max 1720 cm " I (ester). NMR spectrum: T (CDC ½) 1.43, 2.28, 2, 61 (Thienylprotonen), 5, 56 (quartet J 8 cycles per second; C_HzCH), 8, 58 (triplet; J 8 cycles per second; CHzC__Hs). Production 10: Thien3-ylglyoxylsäure. To a mixture of 10 g Thien-3-yl-glyoxylat and 50 m 2n sodium hydroxide sufficiently methanol was added, in order to produce a homogeneous solution, and the conversion became 1 h at ambient temperature stehengeIassen. The solution was extracted in water poured, with ether, acidified with 2n hydrochloric acid and extracted with ether. The united excerpts were dried and evaporated under education of an oil, which became to angerieben with benzene Petrol more ther. The received solid was filtered off and dried (7, 5 g; 88 /o). Fp. 63°C. IR-Spek over: Vmax CNujol) 3600 and 1702 cm-1 (CO2 H). NMR spectrum: r (DMSO-d6) the values include: 1,29, 2, 21, 2, 38 (Thien-3-yl-protonen). Production 11:2 - Hydroxyimino-2 (thien-3-yl) - acetic acids. To a gertthrten solution of 1, 15 g Hydmxylaminhydmchlorid in 15 mI methanol, which contained 2 drops phenolphthalein, a solution of Nat was geftigt iummethylat in methanol, so for a long time, until a pink FärB0 was reached bung. After the addition of a crystal Hydmxylaminhydrochlorid, in order to extinguish the pink colouring, the mixture was added to a solution of 2, 0 g Thien-3-yl-glyoxyls, 'ture in 10 ml methanol and 1 h under return flow was warmed up. Methanol was restricted on a small volume and the arrears were divided between ethyl acetate and water. The zaserige layer was luert on the pH 1 the anges ure with 2n of hydrogen chloride, 'and extracted with ethyl acetate. After the Tmcknen ethyl acetate was evaporated, whereby a white solid formed, which from isomers 2-Hydmxyimino-2 (thien-8-yl) - vinegar luren existed. UV spectrum: Xmax (ethanol) 254, 5 Nm (9,700). IR spectrum: Umax (CHBrs) 3540 (OH not bound), 3200 (OH bound) and 1750 cm " j (COOH). NMR Spek over: T (DMSO-d6) those-worth cover: 1, 78 [multiplet; Thienylprotonen (anti-isomer)], 2, 2 to 2, 7 (complex multiplet; Thienylprotonen). 22 - No. S273? b production 12:2 - Dlchloracetoxyimino-2 (thien-3-yl) - acetyl chloride (syn isomer). 1, 03 g of the 2-Hydroxyimino-2 (thien-3-yl) - essigslturemischung to a gerllhrten password of 1, 8 ml Dichloracetylchlorid in 10 ml dry dichloromethane were added by portion. After 30 min became a surplus of petroleum ether (kp. 40 to 60°C) to the conversion added and the ausgefliflte white solid was collected, with Petrolltther (kp. 40 to 60°C) washed and dried. One received 1, 6 g (94%) 2-Dichloracetoxyimino-2 (thien-3-yl) - essigsl ure (syn isomer), which was suspended in dry dichloromethane and gekflhlt with ice. To the suspension drop by drop one-freshly ereitete solution was added by 1 equivalent “phosphorus pentachloride in dry dichloromethane. After all components were in password, the solvent in the vacuum was removed at low temperature and the oil left was removed azeotrop with benzene, under education from 2-Dichloracetoxyimino-2 (thien-3-yl) - for acetyl chloride (syn) as pale-yellow oil, which was used directly. Herstellnng 13:2 - Hydroxyimino-2 (fur-2-yl) - acetic acids. To an agitated solution of 1, to 94 g hydroxyl amine hydrochloride in 30 ml methanol, which phenolphthalein contained 2 drops, a solution of Natriummelhylat in methanol one followed, so long, until a pink Fltrbung was reached. After the addition of a hydroxyl amine hydrochloride crystal to distance of the pink Ftirbung the mixture was added zn a solution by 3, 0 g F, r-2-yl-glyoxyls lure in 10 ml methanol and 1 h under Rtlcldluß considered. Methanol was evaporated on a small volume and divided between ethyl acetate and water. The aqueous layer was angesliuert with 2n Chlorwasserstoffsliure on pH 1 and extracted with ethyl acetate. After drying the solvent was collected evaporated under education of a yellow solid, with Petrollither (kp. 40 to co°c) was washed and dried, whereby itself 2, 7 g (81] 0) a tsomerengemisches of 2-Hydroxyimino-2 (fur-2-y!)- acetic acids resulted in. UV spectrum: Xmax (ethanol) 271, 5 Nm (“12,400). IR-3pektrum: Vmax (CHBrs) 3550 (OH), 1740 and 1705 cm " 1 (COzH). NlvIR spectrum: - (DMSO DS) cover the values: 2, 62 [Dublett; J 4 cycles per second, FuryI (anti-isomer) C 3-H], 2, 14 and 3, 32 (complex signals, remaining Furylprotonen). Production 14:2 - Dichloracetoxyimino-2 (fur-2-yl) - acetylchlcrid (syn). 1, 38 g of the 2-Hydroxyimino-2 (fur-2-yl) - acetic acid mixture were added by portion to a ice-cooled solution by 2, 8 ml Dichloracetylchlorid in 14 ml dry dichloromethane. After 15minüügem Rllhren formed a white precipitation. collected, successively with cold dry dichloromethane and Petrollither (kp. 40 to 60°C) was washed and dried, under formation of I, to 5 g (68a/o) 2-Dichloracetoxyimino-2 (fur-2-yl) - acetic acid (of syn isomer). To a ice-cooled agitated suspension of 1,5 g 2-Dichloracetoxyimino-2 (fur-2-yl) - essigslBure in ml dry dichloromethane was added drop by drop a freshly prepared solution of 1, 0 equivalents phosphorus pentachloride in dichloromethane. If the solution were complete, the solvent was evaporated at low temperature and azeotrop along benzene distills the zurückgebliebeneÖ1, whereby itself 2-Dichloracetoxyimino-2 (fur-2-yl) - acetyl chloride (syn isomer) as pale-yellow oil (that was used directly) resulted in. Example 1: a) - Acetoxymethyl-7ß (2-hydroxyimino-2-phenylacetamido) - ceph-8-em4 carbonic acid tert, more butyIester (syn isomer). To a password of 3,28 g 3-Acetoxymethyl-7/] - amino-ceph-3-em-4-carbonsl! ure tert. more butylester and 2, 48 g Dicyclohexylcarbodiimid in 60 ml methyl enchlorid and 20 ml dimethylformamide gave one tropfenw to ice under agitating with Raumiemperatur a solution of 1, 64 g 2-Hydroxyiminophenylessigsäure (syn tsomeres) (Ahmad and Spencer, Can.L chem. one, 39, P. 1340) in 20 ml dimethylformamide and rflhrte the mixture during 3 h at ambient temperature. After the Ffltration for the distance of Dicyclohexylharnstoff the solution was taken up, filtered evaporated, the arrears to 50 ml ethers and washed successively with gesltttigter Natriumbicarbonatlösung, 2n Chlorwasserstoffstiure and water. The excerpt was dried and evaporated and resulted in the title ester in form of a foam, which was dried in the vacuum. Yield! , 6 g; 33, 8%. IR spectrum: Vmax (CHBr) 3570 (OH), 1786 (B-lactam), 1740 and 1230 cm (OAc). NlvIR spectrum: - (CDCls) the values include: 2, 2 to 2, 7 (Mulüplett; aromatic protons), 7, 93 (Singulelt; CH3 CO), 8.46 (singlet; tert. Bntylester). b) 3-Acetoxymethyl-73 (2-hydroxyimino-2-phenylacetamido) - ceph-3-em-4-carbomlture (syn isomer), a solution of 1,45g 3-Acet0 xymeti1 yl-73 (2-hydr0 xyimino-2-phenytacetamido) - ceph-3-em-4-carbonsliure-tert, more butylester (syn isomer) in 25 ml TrifluoressigslBure were left untouched 10 min at ambient temperature. DieTrifluoressigslIure was then evaporated under decreased pressure and derRttckstand into 50 ml ethers drew and with more ges/ittigter more zaseriger well iumbicarbonatlösung was extracted. United the wltsserigen excerpts were addressed with 2n hydrochloric acid and extracted with Äthytacetat. The united excerpts were washed, dried and evaporated with water. The arrears solved in 5 mt again Äthytacetat and drop by drop under agitating to 500 ml Petrolttther (boiling point 40 to 60°C) given. DEK failed solid was filtered off and dried and resulted in 0, 515 g (42%) 3-Acetoxymethyl-7$ (2-hydroxyimino-2 - phenylacetamido) - ceph-3em-4-earbonstture (syn isomer). D + 56° (C 0, 5, DMSO). UV-Spekl over: k max (Ä H) 253 Nm (ₜ 26,600). IR-SpekIrum: max (Nujoi) 3380 (NH and OH), 1778 (15-Lactam), 1720 (COzH and Aeetat), 1666 and 1540 cm " z (CONH). NMR Spektrurn: r (DMSO DS) the values include: 0, 32 (Dublett, J 9 cycles per second; NH), 2, 15 to 2, 7 (multiplet; aromatic protons), 7, 8 (Stngulett; CHsCO). c) Calcium salt of the 8-Acetoxymethyl-71B (2-hydroxy [mino-2-phenylacetamido) - ceph-3-em-4-carbons ure (of syn lsomeres). To a solution of 0,5 g 3-Acetoxymethyl-715 (2-hydroxyiminoß-phenylaeetamido) - ceph-8-em-4-carbons ure äthylacetatsolvat (syn lsomeres) in 50 ml ethyl acetate gave mall a in a solution Natrium-2; Ithylhexanoat in 1 ml ethyl acetate. After agitating wlihrend 15 min at ambient temperature the solid was collected by filtration, washed dried with ethyl acetate and ether and resulted in 0, 85 g (82a/o) of the TitelNalziumsalzes. D + 980 (_c 1 DMSO). UV-Speklrtun: kmax (pH of 6, 0 phosphate buffers) 253, 5 Nm (ₜ 18400). IR-Spekl Nm: Umax (Nujol) 3280 (NH undOH), 1765 (15-Lactam), 1740 (OCOC), 1670 and 1550 cm " 1 (CO). NMR-3pektrnrn: r (DMSO dG) the values include: 0, 24 (, J 9 cycles per second gingulett; NH), 2, 28 to 2, 72 (aromatic protons), 7.99 (singlet, OCOCH). Example 2: a) 3Acetoxymethyl715 (2-dichloracetoxyimino-2-phenylacetamido) - ceph-8-em-4-carbonstture-tert. more butylester (syn lsomeres). To a solution of 3,28 g 3-Acetoxymethyl-TB-amino-ceph-3-em-4-carbonstture-tert. more butylester in ml ethyl acetate one gave drop by drop under-agitates a solution forwards! 2-Dichlcracetoxyimino-2-phenylacetylch! orid (syn lsomeres) ha of 25 ml ethyl acetate. The solution warmed up and it formed a precipitation. After 2 h L was filtered off nng, more nachdnander washed with 2n hydrochloric acid, dried and evaporated to water and gesttttigter Natrfumbicarbonatlösung and resulted in a yellow foam, which solidified itself when standing and which then with the rubbing with petroleum ether 4, 0 g (/o) 3-Acetoxymethyl-715 (2-dichloracetoxyimino-2-phenylacetam DO) - ceph-3-em-4-carb0nstture-tert, more butylester resulted in. IR spectrum: Umax (CHBrs), 8420 (NH), 1796 (15-Lactam), 1730 and 1230 (acetate), 1700 and 1512 cm " 1 (CONH). NMR Spek over: “(DMSO D) among other things. 2, i to 2, 5 (multiplet; aromatic protons), 2, 98 (Singalett; CHCIz), 7, 6 (singlet; CHsCO), 8, 5 (singlet; tert Buty! more ¢ster). b) 3-Acetoxymethyl-7/5 (2-hydroxyimino-2-phenylacetamido) - ceph-3-em-4-carbonstture (syn isomer). A solution of 3, 0 g 3-,% cetoxymethyl715 - (2dichloracetoxyimino-2phenylacetamido) - ceph3 em-4 - carhonsäure tert. in 25 ml Trifluoresigsäure 10 min became more butylester at ambient temperature standing close cups. The surplus Stture was removed under decreased pressure and benzene was evaporated from the arrears, which were then taken up with ethyl acetate and extracted with more ges/tttigter more wltsseriger well iumbicarbonatlösung. The aqueous phase was washed, acidified with ethyl acetate and extracted with ethyl acetate. The excerpts were combined, getroeknet, restricted on approximately 5 ml and given drop by drop to 200 ml Petrol/tther. The failed Festsloff was iert ahfil and dried and resulted in 1.9 g (8 o) 3-Acetoxymethy! - 7 - (2-hydroxyimino-2-pöenylacetamido) - ceph-8-em-4-carbomlture (synsomeres) in form of a white Feslstoffes. D+ 68 (_c 0,8DMSO). UV spectrum: Xmax (ÄtOH) 254 Nm (17600). IR spectrum: z, max (Nujol) 3880 (NH and OH), 1 ' /78 (15-Lactam), I720 (COzH and acetate). 1666 and 1540 cm " I (CONH). . “/.h}. IR. ÖZ 'NMR Spek over: r (DMSO-d6) among other things. 0, 82 (Dublctt J 9 cycles per second; NH the syn isomers), 1, 00 (DubletL J 9 cycles per second; NH the anfi isomers, which constitutes about 10% of the product), 2, 15 to 2, 7 (multiplet aromatic protons), 7, 8 (Singniett; CH3 CO). Example S: Sodium salt of the 3-Acctoxymethyl-qS [9-hydroxyimino-2 (thicn-2-yl) - acetamido] - ceph-3-em-4-carbonsllure (syn lsomeres). I0 a) 2-Dichloracetoxyimino-2 (thien-2-yl) - acetyl chloride (syn isomer). 27, 2 g phosphorus pentachloride were given to dichloromethane by portion in the process (ice bath) suspension cooled of about 20 min to a gertlhrten and by 37, 0 g 2-Dichloracetoxyimino-2 (thien-2-yl) - essigsliure (syn isomer) in o 370 ml. The mixture was gertlhrt during further 80 min with 0 C, whereby the entire solid dissolved. After the distance of the solvent under decreased pressure the benzene was evaporated with 20°C out demRückstaud and dasVerfahreu wiederholt'so dass one 2-Dichloracetoxyimino-9. - (thien-9. - yl) - acetyl chloride (syn isomer) in form of an oil received, which was used directly in the n tehsten stage. b) 3-Ac ctoxymethylq3 [2-dichloracetoxyimino-2 (th [en9 - yl) - acetamido] - ccph3 cm-4carbons urc - text. more butylester (syn isomers). 90 a solution of 9. - Dichloracctoxyimino (fllien-2-yl) - aeetylchlorid (syn isomer) in 300 ml ethyl acetate became an agitated solution of 4S g 3-Acetoxymethyl-7 B-aminoceph-3em-4-carbomäuretert. more butylester and 84 ml propylene oxide in 400 ml ethyl acetate with 9.0°C given. Anfllnglich failed a solid, which see however gradually dissolved. The temperature held by cooling and/or, Erw. 'trmen the solution between 9.0 and 30°C. After 4 h became the solution with 9n Chlorwasserstoffsllure, with ges; more tttigter well iumbicar95 bonafl0sung, water and salt solution washed, dried and under decreased pressure evaporated, so that one received the title ester in form of an oil, which directly in the next stage one used. c) 3-A cctoxymethyl713 [9dioMoraectoxyimino9. - (thien9. - yl) - AC etamido] - ceph3 ere-4carbonsänre (syn IsomereO. A solution of the 3-A C etoxymethyl7fl - dichlorac etoxyimino (ihren2-yl) - AC etamido] - C eph8 cm-4carbons ure tert, butylesters (syn isomer) in 9.0 ml anisole became mit100 ml Trifluoressigsllureb ehand ELT. After 5 min bci20°C wurdedic solution under vermind ertem Druckbei35°C restricted. Then becoming ethyl acetate of course etzt and the password again restricted, on which itself e [nF eststoffabschied. Then becoming ethyl acetate dr eimal from the Rtlckstand evaporated and the solid was collected and with ether washed, whereby one 8q g (5S%) the 8-Acetoxyme • yl7B [9. - dichloracetoxyimiuo-2 (thien-9. - yl) - acetamido] - ceph-3-em-4-carboml'iure (syn isomer) received. UV-Spek Nm: ) 'max (ethanol) 268 Nm (ₜ 14800). NMR Spekilum: r (DMSO-d6) among other things. -0,19 (Dublett, J 8 cycles per second; NH}, 3, 02 (singlet, CHC ½), 7, 94 (singlet, OCOCH). d) 3-Acet xymethy -7B [2-hydr xyimin -2 (hien-9-yl) - ace at the D] - ceph-8-em-4-carb m ure (synisomeres). 86, 1 g 3-Acetoxymcthyl '/B [9. - dichloracetoxyimino-9. - (thien-9. - yl) - acetamido] - ccph-3-em-4carbonsaure (syn isomer) were distributed between about 250 ml ethyl acetate and 200 ml satisfied Nakiumbicarbonaflösung. The layers were separated and the Äthylacctatlösung was extracted twice with Nairinmbicarbonatlösung. United the excerpts were washed with ethyl acetate and then with ethyl acetate b cover and carefully with konzenixierter hydrochloric acid acidified. The layers were separated and the w serige layer twice with ethyl acetate were extracted. The united excerpts were washed, gelxocknet with water and salt solution and evaporated under decreased pressure to a small volume (zkka 60 valley), that drop by drop too about! 500 ml gertlhrtem Petrol more ther (boiling point 40 to 60°C) was given. The received lederfarbene F eststoff was collected and resulted in 27, 5 g (95°] o) 3-Aeetoxymethyl-qB [2-hydroxyimino-9. - (thien9-yl) - acetamido] - ceph3 cm4 carbomllur ₜ (syn isomer). e) Natrinmsalz of the 3-Aeetoxymethyl-q3 [9-hydroxyimino (thien-2-yl) - acetamido] - ceph-3-em-4-carbons ure (syn isomer it). A solution of 19 6 g well inm-9. - äßylhexanoat in! 9.0 ml ethyl acetate became an agitated solution of 27, 3 g 3-Acetoxymethyl-qB [9-hydroxyimino-9. - (thien-9-yl) - acetamido] - ccph-8-em-4-carbonsllure (synIsomeres) given in 9q0 ml Äthylaeetat at a temperature of 90°C. The mixture was cooled down during 1 h on 0°C and the weak lederfarbene solid was filtered off, washed with ethyl acetate and ether and in the vacuum dried and resulted in 25.1 g (8 '/, 5°) of the title Natrinmmlzes. D + q8, 50 (__e 1, ii DMSO). - 25 - NR, 327375 l0 UVSpektrum: NWJRSpek2um' example 4: Xmax (pH of 6 buffers) 261 Nm (“15200), Xlnflexion 285 Nm (“10200). T (DzO) 2.41 (D, 5 cycles per second; Thienyl-C-3 H or - C-5 H), 2, 64 (D, J 4 cycles per second; Th [enyl-C-5 H or - C-3 H), 2, 84 (dd, J 4 and 5 cycles per second; Th£enyl-C-4 H), 4.12 (D, J 5 cycles per second; C-7 H), 4.78 (D, J 5 cycles per second C-6 H), 5, 08 and 5, 28 (2ds, branches of a quartet, J 12 cycles per second: C-8 CHz), 6, 33 and 6, 65 (2ds, branches of a quartet, J 18 cycles per second; C-2 CH2) and 7.91 (s; OCOCI). 7B- (2-Hydroxyimino - 2 - phenylacetamtdo) - 3 - (5methylI, 3, 4thiadiazol2 yl) - thtomethylceph3 cm -4carbonst! ure (syn isomer). a) 7 - Form amide -3 (5-methy -1 3 4-th ad az 1-2-y) - thi methy1-ce h - em-4-carb MC a ure solution of 24, 0 g q/5-Formamido-3-acetoxymethyl-ceph-3-em-4-carbonstlure and I0, 56 g 5-Methyl-1, 3, 4-thiadiazol-2-thiol into 600 ml lm phosphate buffers (pH 6.4) was erwarmt w/lhrend 4 7/2 h on 60°C. The password was abgekflhlt on 9,0°C and to the wltsserigen layer with phosphorus/tute was brought to a value of 2, on which the product with ethyl acetate was exlmhtert. The excerpt was washed, dried with NatrtumchIorid and restricted under decreased pressure to a small volume and given to gertlhrtem Petrol/more ther. The arising solid was collected and dried and resulted in 9, 36 g of the title connection. [“] D “98° (_C I DMSO). UV-Spek over: Xmax (pH buffer) 271 Nm (“11400). Nk4R-Spektrum: - Values (DzO + NaHCO3) among other things. 1,74 (s; CHO), 4.30 (D, J 4, 5 cycles per second; C-7 H), 4.88 (D, J 4, 5 cycles per second; C-6 H) and 7.25 (s; c). b) QB-Formam [do3 (5methyl1,3,4thiadiazol2-yl) - thiomethylc eph3 em-4carbons'lurediph enylmethyl esters. A solution of 8,5 g 7D-Formamido-3 (5-methyl1,3,4thiadiazol-2-yl) - thiomethyl-ceph-3em-4-carbons/äure in 300 ml tetrahydrofurane was treated with a surplus of a solution of Diphenyldiazomethan in 800 ml Petrol/tther and those mixture was held wtihrend for 16h bei20°C. Then some few drops of vinegar/iure were added and the solvents were removed under decreased pressure. The arising yellow syrup was loosened in ethyl acetate and washed with a Natriumbiearbonatlösung. 7, 5 g of a solid failed, which was dried in the vacuum. One rehearses (5, 77 g) of the damp solid in dichloromethane and the solution was solved was dried and recrystallized under vermiudettem pressure restricted, the arrears from methanol and resulted in 5, 08 g of the title ester, Fp. = 108° (Zets,), UV spectrum: X of max (ÄtOH) 268 Nm (“19, 400) ° NlviR spectrum: r (CDC1s + few DMSO-d6) among other things, 1.50 (D, J 9 cycles per second of” NH), 1, 72 (s; HCO), 6.30 (singlet; C-2 CHz) and 7, 31 (singlet; CI). c) 7B-Amino-3 (5-methyl-l, 3,4-thiadiazol-2-yl) - thiomethyl-ceph-3-em-4-carbons of ture diphenylmethyles terhydrochlorid. 1, 8 ml Phosphoroxychlor [D became drop by drop in the process and S cooled down agitated of 2 min on 0°C uspension from 4, 1 g 73 - Formamido8 (5methyl1, 3,4thiadiazol2 yl) - thiomethylceph3 em -4-carbom; ture more diphenylmethylester in dry methanol given. After 30 min was restricted the yellow l ung under decreased pressure. Then ethyl acetate was given to the Rflckstand and the received solid was collected and washed with ether and resulted in the dichloromethane. UV-Spek around " Xmax (Ä H) 266 Nm (e II 800). IR spectrum: Umax (Nujol) 2590 (NHs+), 17 /8 (B-lactam) and 1710 cm-z (ester). NMR spectrum: r (DMSO-d6) among other things. 0, 50 (broad m: N), 2, 3 to 2, 7 (m; Phenylprotonen), 3, 02 (s; CHPhz), 4, 66 + 4, 76 (m; C-7 H and C-6 H), 5.39 + 5, 69 (2ds, branches of a quartet, J 18 cycles per second: C-3 CH S), 6, 15 (singlet; C-2 CH2) and q, 36 (singlet, CH3). 26 - Nr.32737b d) 7 - Amino-3 (5-methyl-l, 3, 4-thiadiazol-2-yl) - thiomethyl-ceph-8em-4-carbons ure more diphenylmethylester. g 7B-Amino-3 (5-methy1-1, 8, 4thiadiazol-2-yl) - thiomethyl-ceph-3-em-4-carbonstlure-diphenylmethylester-hydrochlorid were geschtittelt with gesllttigterNatriumbicarbonatlOsung and Äthylaeetat. The layers were separated and wt sserige layer with ethyl acetate were extracted, the united Äthylacetatexi document with well iumbicarbonaüösung and salt solution washed again, getroeknet and under decreased pressure restricted. The arrears were recrystallized made of ethyl acetate/ether and resulted in 2.75 g of the free o title base, Fp. = 152 (Zers.). UV-Spek over: kmax (ÄtOH) 268 Nm (“9,000). I0 IR spectrum: Vmax (CHBr3) 8400 and 8885 (NH), 1772 (B-lactam), 1720 (ester). NMR spectrum: “(CDC ½) among other things 2, 50 - 2, 75 (m; Phenylprotonen), 3, 00 (s; CHPh2), 7, 81 (singlet; CHs) and 8, 22 (s; NHz). e) 7B (2Hydroxyimino-2-phenylacetamido) - 8 (5-methyl-l, 3,4-thiadiazol-2-yl) - thiomethyl-ceph-8 - em-4-carbonsäure (syn lsomeres). A Imolare I sung of 2-D chloracetoxyimino-2-phenylacetylchlorid (syn lsomeres) in 8, 8 ml ethyl acetate was given to thiomethylceph8 em-4carbons in the process a suspension agitated of 5 min with 20°C to by I, 78 g 7B-Amino-3 (5-methylI, 8, 4thiadiazol-2-yl) - äurediphenylm ethyl esters in 2 Oml Ä thylaceta t, which enülieit 0.9 ml propylene oxide. After most finishing addition was kept the solution wtihrend for I h and verdt then with ethyl acetate [nnt, washed with 2n hydrochloric acid, Natriumbicarbonaü6sung, water and salt solution. The dried solution was evaporated and resulted in 2, 76 g of a red foam. The foam (2, 6 g) was loosened in 5 ml anisole and treated with 20 ml Trifluoressigsllure. After 5 min was restricted the Lösnng under decreased pressure and the arrears were solved in ethyl acetate 28, the solution was washed with water and extracted then with Natriumbicarbonaflösung. The united zaserigen excerpts wind with Älhylacetat washed, with 2n Chlorwasserstoffstture angesliuert and with ethyl acetate extracted. The united excerpts were washed, dried with Salzlö¢ung and restricted under decreased Drnck on a small volume and given then drop by drop to about 500 ml to gerflhrtem petroleum ether, whereby one received I, 88 g of the Tttelsäure in form of ice of yellow solid. [“] D -79 ° (c1, 2 DMSO). UV spectrum: Xmax (pH of 6 buffers) 256 Nm (“19250). IR spectrum: Vmax (Nnjol) among other things 8650 to 2100 bound OH), 8250 (NH), 1769 (JB-lactam), 1660 + 1525 cm-1 (CONH), NMR spectrum: - (DMSO DS) 0.88 (D. [8 cycles per second; CDNH), 2, 2 to 2, 7 (m; Phenylprotonen), 4, 12 (dd, J 5 and 8 cycles per second; C-7 H), 4, 78 CD, I 5 cycles per second; c6 H), 5.48 + 5, 77 (2 DS, branches of a quartet, J 18 cycles per second; C-3 CHe), 6.17 + 6.41 (2 DS, branches of a quartet, J 18 cycles per second; C-2 CHz) and 7, S0 (; CHs). Fuel element plays 5 to 16: General procedures for the production of 7B (2-Hydmxyimtno-2-arylacetamido) - 8 (more subsfftuterter} - methylceph8 ein4 of carbon äur EN. (I) production of the 2-Dichloracetoxyiminoester-Zwisehenprodukte. Method A. To a solution tert. Butyloder Diphenylmethylesters of the qB-Amino-8 (it suhstituierte) - methyl ceph -3-em-4-carbomäure (1 equivalent) in ethyl acetate one gave drop by drop under Rfihren with Ranmtempemtur a solution of the 2-Dichlo suitable from i to 1.15 Äquivaletlten acetoxy [min CO2 aryl acetyl chloride (of synoder anti-isomers) in ethyl acetate the mixture became w] lhrend i to 2 h gerflhrt, on which the Hydmchlorid qB - Amino-8 (subsdtuierten) - mefllyl-ceph-8-em-4-carbonstlureesters ausfiei and by Filiation removes wulüe. The Fill; RK was washed successively with 2n hydrochloric acid, water, briefly with ges] Ittigter Natriumhydrogencarhonatlösung and Salzl0sung. The organic layer was dried and evaporated and resulted in the desired 2-Dichloracetoxyiminoester in form of a foam or an oil. Method B. To a solution tert. To Butyloder Diphenylmethylesters of the 7 - Amino-8 (more substituted) - methyl ceph -3-em-4-carbonsäure (1 equivalent) and 3 to 15 equivalents Propylenaxyd in ethyl acetate (in example 7 dichloromethane used) one gave drop by drop under agitating at ambient temperature an l ung of a 2-Dichloracetoxyimino-2-arylacetylchlorids (syn lsomeres) in ethyl acetate, suitable by I, 05 to 1, 25 equivalents. Agitating was continued, until the reaction had vollstllndig run off at ambient temperature (whereby the reaction through was pursued and generally 40 min to 2 h dünnschichtchromatographischeVerfahren needed). The reaction solution was regenerated then, as in method described A, and resulted in the ester desired. M ethod e C. A password from 1 to 1,1Äqu [2-Dichloracetoxyimino-2-arylacetylchlorid (syn lsom res) valenten were inÄthylacetat drop by drop at ambient temperature to a gertthrten8uspension of 1 equivalent of the p-Toluolsulfons of uresalzes the 7 - to [no-3-acyloxy-methyl-ceph-3-em-4-carbons; lure diphenylmethylesters and 8 to equivalents Propyleuoxyd in ethyl acetate given. After that-agitated protecting 9,0 min to 9th h was regenerated the arising solution, as under method described A, and resulted in the ester desired. Method D. The method D takes place like the method C, with the difference that the reaction takes place in a mixture of acetonitrile and Dimethylacetamid in place from ethyl acetate/propylene oxide. This concerns also the example 12. (II) splitting off of the Schutzgrnppe of the ester intermediate products. Method E. I5 those common the procedures A or B manufactured tert. Butyloder Diphenylmethyl-2-dichloracetoxyimino - esters were drawn into 7 to 15 ml Trifluoressigsäure/g esters and 5 to 10 min ambient temperature left untouched and then under decreased pressure restricted. The raw product was distilled in certain filling with benzene in form of a Azeotrops, in order to remove traces the trifluorine-acetic acid. The raw product was then taken up to ethyl acetate and extracted with a satisfied sodium hydrogencarbonate solution. The w of sseeigen excerpts were washed with ethyl acetate and addressed then with 9.n hydrogen chloride-sour and extracted then with %thylacetat. The organic layer was separated, dried and restricted on a small volume and then drop by drop to a large good-agitated volume Petrolgther (boiling point 40 to 60°C) given. The arising amorphous solid was collected and TM vacuum dried and resulted in the kind striven 76 - (2Hydroxyimino2 arylacetamido) - 3 - (substitute Te) - methylceph3 ere-4carbons: lure. M ethod e F. In accordance with the methods A bisD manufactured esters in 1 to 15 ml anisole per gram ester one solved and with 4 to 10 ml trifluorine-acetic acid per gram of esters at ambient temperature one treated. After 5 to 10 min was removed dfe Trffluoressigsäure by evaporation under vermind ehrtem pressure, on which the sour as under method E was descriptive isolated. (III) salts production of the p-Toluolsulfona the 7 - Amino-3-acyloxymethyl-ceph-3-em-4-carbons iure more diphenylmethylester, which were used inclusively as raw materials in the examples 11 to 14: a) 3-Pivaloyloxymethyl-TB (thien-2-yl) - acetamido-ceph-3em-4-carbonsäure-diphenylmethylester. A password of 2,4 ml Pyridin in 5 ml dry tetrahydrofurane became with 20°C an agitated LöS5 sung from 3, 12 g - Hydr xymethy - - (thien-9. - y) - acetamid - ceph - em-4 carb nsaure diphenylmethy esters and 7, 9 g Pivaloylchlorid in 150 ml dry T etrahydrofuran given. The solution was agitated, filtered off during 16 h with 9.0°C and restricted under decreased pressure. The arrears were washed in ethyl acetate gel t and successively with Natrtumbiearbonatlosung, 2n hydrochloric acid, Natriumbicarbonatlosung, water and Salzl0sung. The dried solution was restricted under decreased pressure and resulted in firm arrears, which became to rub with ether and 2, /g (75%) of the title ester resulted in. D +5, 1° (_c 1.4, CHCIs). UV-Spektrnm: Xinflexion (ethanol) 235 (! 4! 00), 257 (4 8 300) and 263 Nm (e 8,050). IR spectrum: Vmax (CHBrs) 1787 (B-lactam), 1722 (ester), 1680 and 1510 cm-1 (CONH). NMR spectrum: “(CDC13) among other things 8.81 [singlet; C (CH3) 3 3. In similar way were manufactured: b) 3-B enzoyloxymethyl7 (thien2-yl) - acetam [doceph3 em4 of carbon/iure diph enylmethyl esters. (8Sqo). UV spectrum: Xmax (ÄtOH) 223 Nm (28,600), X1nflexi0n 260 ({9800) and 278, 5 Nm (4 7300). IR spectrum: Vmax (CHBrs) 1795 (B-lactam), 1729 (ester), 1690 and 1516 cm-1 (CONH). NMR Spektram: r (CDCls) among other things 2, 3 to 3, 1 (aromatic protons), 6, 18 (singlet; Thienyl-C__Hz), 4, 62 + 5, 02 (2 Dubletts I 14 cycles per second, C-3 CH2 OCO). c) 3 - Crotonoy.loxymethyl TB (thien2-yl) - AC etamidoc eph3 em-4carbons/lure-d [phenylmethylester. (5 o), suffering +7,2° (C 0.8 CHCls). UV spectrum: XInflexion (methanol) 237, 5 Nm (4 14400) and 260 Nm (“8,000). IR spectrum: Umax (CHBrs) 1783 (8-Lactam), 1719 (ester), 1680 and 1510 cm-1 (CONH). NMR spectrum: r (CDCls) among other things 6.19 (5ingulett; Thienyl-C__H2), 8, 12 (dopl eltes Dublett, I 2 and q cycles per second; CH=CHC__H). 28 - NR, 327375 d) 3-Isobutyryloxymethyl? B (th [en-2-yl) - acetamido-ceph-3-em-4-carbomtture-diphenylmethylester. (? r/o), iclD +4° (C 0, 9 CHCls). UV spectrum: Xinflexion (ÄtOH) 235 (13400), 25? (“7900) and 261, 5 Nm (7,760). IR spectrum: Vmax (CHBrs) 1767 (8-Lactam), 1710 (ester), 1667 and 1500 " cm " l (CONH). NMR spectrum: - (CDC ½) among other things 6.19 (8ingulett; Thienyl CH), 8.89 [Dubletf, J 6, 5 cycles per second; (C__.Hs) zCH]. e) qB-Amino-3-pivaloyloxymethyl-ceph-8em-4-carbons ure diphenylmethylester p toluolsulfonatsalz. A password of 6,2 g phosphorus pentachloride in 80 ml methyl enchlorid became one up - I 0°G abgekihlten and gerilhrten password of 6, 0 g 3-Pivaloyloxymethyl-TB (thien-2-yl) - acetamido-ceph-3-em-4-carbonsteure-d [phenylmethylester and 9, 6 ml Pyridin in 80 ml dichloromethane given. After 30 min I00 were added ml to methanol with a such speed that the temperature fuel element [-10°C was held. Then one discharged those password on 20°C to erwtlrmen and ktkhlte themselves her after 3 h with 20°C on 0°C. Then] 40 ml 2n Chlorwasserstoffstlure were given to the violently gertthrten solution. After istflndigem agitating the dichloromethane layer was separated and washed, dried successively with 2n Chlorwasserstoffsliure, to Natriumbicarbonaflosung, water and salt solution and restricted under decreased pressure. The remaining resin was loosened in I0 ml Ä thylacetat and with a password of i, 89 g p-Toluolsulfomtlure-monohydrat in 10 ml ethyl acetate treated. The abgektlhlte password resulted in crystals, which were collected and washed with ethyl acetate, whereby one 4, 34 g (66 o) of the title salt received. iclD +5, 9° (C! , DM80). UV spectrum: kmax (ethanol) 261, 5 Nm (“? 700), Xlnflexion 267, 5 (“? 400) and 226, 5 Nm (“16,600). IR spectrum: Umax (CHBr) 2600 to 2800 (NI +), 1800 (- lactam) and 1? 31 cm " z (ester). NMR Spek rum: “(CDCIs) NO A. 2.20 + 2.98 (2 Dubletts, J 8 cycles per second; aromatic pro fonen Toluolsulfonat) and 8, 89 [3ingulett; C (CHs) s]. In tlhnlicher way the following connections were manufactured: f) P-Toluolsulfonstluresalz of the? B-Amino-3-benzoyloxymethyl-ceph-3-em-4-carbonstlure-diphenylmethylesters tn form of needles (qf o), D +9, 5° (_c 0.94 DMSO). UV spectrum: XmaX (Ähhanol) 221 (32200) and 262 over (9 I00). IR spectrum: Umax (Nujol) 2600 to 2800 (Nils+), 1804 (/3-Lactam) and 1730 cm " I (ester). NMR Spek urn: - (DMSO-d6) among other things. 4? 9 + 4, 99 (2 Dubletts, branches of a quartet, J 14 cycles per second; C-3 C_H2) and ù/? 0 (singlet CH3), g) p-Toluolsulfons uresalz the 7B-Amino-3-orotonoyloxymethyl-ceph-3-em-4-carbons ture diphenylmethylesters (54%), iclD +% 3° (C o, 89 DL? ISO). UV spectrum: Xmax (ethanol) 261, 5 Nm (8,000), Xinflexion 266 Nm (? 700), IR spectrum: Umax (CHBrs) 2600 to 2700 (NHs+), 1790 (- lactam), 1720 and 1221 cm " i (ester). NMR spectrum: - (CDCIs) among other things 2.20 + 2, 89 [2 Dubletts (of branches of a quartet), J 8 cycles per second; aromatic toluol psulfonatprotonen] and 8, 11 (double Dublett, f 6, 5 and 1, 5 cycles per second; CH=CH-C__Hs). h) P-Toluolsulfomäuresalz of the? B-Amino-3-isobutyryloxymethyl-ceph-3-em-4-carbonstlure-diphenylmethylesters (6f r/o), i) +5, 3° (c1, 21, DMSO). UV spectrum: kmax (ÄtOH) 262 Nm (8,000). IR-Spektzum: Umax (CHBr3)! 780 (B-lactam), 1718 cm " I (ester). NMR spectrum: - (CDCIs) among other things 2, 2! , 2, 99 (2 Dubletts I 8 cycles per second; P-Toluolsulfonat) and 8.91 [Dublett, I 6 cycles per second; (CHs) zCH]. Example 5: a) q B (2Dichloracetoxyimino2 phenylacetamido) - 3methylc eph3 ern-4carbonstiure " tert. butyIes (syn isomer) became more ter in form of a yellow foam (75°/o) gernliß method A manufactured. IR spectrum: Umax (CHBrs) 3400 (NH), 1732 (B-lactam), 1712 (ester), 1782 and 1693 cm-1 (CONH). NMR Spek zurn: - (DMSO-d6) among other things. 2! 5 to 2, 60 (Mulfiplett; aromatic protons), 3, 03 (singlet: CI-ICIs), 8, 03 (singlet; C-3 methyl), 8, 54 (singlet; tert. Butylester). - 29 - Nro327875 b) QA (2-Hydroxyimino-2-phenylacetamido) - 3-methyl-ceph-3-em-4-carbom ure (syn isomercs), which about 107o the anti-isomers contained, with a yield by 8890 in accordance with the method E one manufactured. .l IR-Spek over: Vmax (Nujol) 3270 (NH), 1760 (8-Lactam), 2600 and 1710 (CO2 H), 1670 and 1580 cm (CO). NMR spectrum! . r (DMSO-d6) among other things. 0,36 (Dublett, J 9 cycles per second: NH the syn isomers), 1, 15 (Dubtett, J 9 cycles per second; NH the anti-isomers), 2, 25 to 2, 65 (Multfplett; aromatic Pmtonen), 7, 92 (singlet; CI). Example 6: a) 78 (2-Dichloracetoxyfmino2 phenylacetamido) - 8-methyl-thiomethyl-ceph-8-em-4-carbom, 'iure - (syn isomer) in accordance with t of the method A in form of an oil, IR-3pektrum was kept more diphenylmethylester: Umax (CHBr3) 8500 (OH), 1790 (8-Lactam), 1726 (ester), 1696 and 1520 cm " (CONH). NMR spectrum: r (DMSO-d6) 2, 1 to 2, 8 (multiplet; ammaßsche protons), 8, 05 (singlet; Diphenylmethyle more ter), 4, 05 (quartet, j " 9 cycles per second and 4, 5 cycles per second; C-7 H), 4.85 (Dublett, J 4, 5 cycles per second; C-6 H), 6.45 (broad 3ingulett; C-2 and C-8 CH2), 8, 2 (singlet; SCH3). b) 78 (2-Hydmxyimino-9-phenylacetamido) - 8methylthiomethyl-ceph-8-em-4-carbons, 'lure (syn Isomercs) was received in accordance with the method E, D+47,5° (c1, DMSO). UV spectrum: kmax (pH of 6 phosphate buffers) 255 Nm (“18400). IR spectrum: Vmax (Nujol) 3270 (NH and OH), 1752 (8-Lactam), 1660 and 1518 cm-1 (CONH). NMR Spektmm: r (DMSO-d6) 0.35 (Dublett, J 9 cycles per second; NH), 2, 3 to 2, q (multiplet; aromatic Protogen), 4.15 (quartet, J 9 cycles per second and 4, 5 cycles per second; C-7 H), 4, 7 (Dublett' J 4, 5 cycles per second; C-6 H), 6, 85 (broad 3ingulett; C-2 and C-8 CHz), %98 (singlet; S-CH3). Example 7: a) (syn isomer) in form of a yellow foam in accordance with the method B one kept more enylmethylester to 78 - (2Dichloracetoxyimino-2phenylac etamido) - 8vinylceph3 ere-4carbomaure-diph. IR spectrum: Vmax (CHBr3) 8500 (OH), 3380 (NH), 1770 (B-lactam), 1720 (ester), 1685 and 15! 0 C m " 1 (CONH). NlvIR spectrum: r (CDC13) among other things 2.2 to 2,85 (multiplet; aromatic protons), 4,0 to 5, 0 (multiplet; C-6 H, C-7 H and Vinyl-CH2), 6.40 (broad 3ingulett C-2 CH2), b) 78 (2Hydmxyimino2-phenylacetamido) - 3-vinyl-ceph-3em-4-carbons ure (syn isomer) was received to D -72° in form bets of a solid (459o) in accordance with tB the method E, (_c O, 85, DMSO). UV spectrum: Xmax (pH of 6 buffers) 285 Nm (16400). - I IR spectrum: vmax (Nujol) 89,70 (NH and OH), 1754 (8-Lactam), 1710 (CO H), 1660 and 1520 cm (CONH). NMR spectrum: r (DM80-d6) u, A. 0,30 (Dublett, J 9 cycles per second; NH), 2, 3 to 2, 6 (multiplet; ammathche powers), 3, 03 (quartet, J 11 cycles per second and 18 cycles per second; CH=CH), 4,37 and 4, 66 (two Dubletts, J 11 cycles per second and 18 TC CH=CH2), 6, 08 and 6.41 (two Dubletts, branches of a quartet, J'18 cycles per second; C-2 CH2). Example 8: a) 8-AcetoxymefhylqS [2-dichloracetoxyimino-2 (thien-2-yl) - acetamido] - ceph-8-em-4-carbons lure tert, more buttester (syn isomer) in accordance with the method A in form of an oil was isolated and in accordance with lB the method F from the Sehutzgruppen released, so that one. b) 3-Acetoxymethyl-7B [2-hydroxFimino2 (thien-2-yl) - acetamido] - ceph-3-em-4-carbomtLure (synIsomeres) in form of an amorphous solid (0, 86 g) received. iclD +57 0 (_c 0, 8, DM8O). UV-Speklrum: kmax (ethanol) 268 Nm (“18900). 1R-Spektrum: Vmax (Nujol) 3280 (NH), 1772 (/3-Lactam), 1720 (acetate) and 1662 urjd 1530 cm " 1 (CO RD, NMR Spekt over: r (DMSO D “) among other things. 0,23 (Dublett, J 8 cycles per second; NH), 2.36 (double Dublett, J 1 and 5 cycles per second; Thieayl-C-5 H), 2, 82 (Mulüplett Thienyl-C-3 H and - C-4 H) and 7, 93 (singlet; OCOCH). Example 9: a) 3-Az domethy1-7 - (9-d CH racet XY mino-9.pheny1acetamido) - ceph - em-4-carbons ure-dipheny1methylester (syn lsomeres) became using the method B in form of an F of e$tstoffes (46°/o) received. UV-Speklrum: k of max (ÄtOH) 254 Nm (18,000). IR spectrum: Vmax (CHBr) 8420 (NH), 2128 (LV), 1800 (B-lactam). NMR Spekt over: T (CDCI) among other things 2.1 to 2.85 (multiplet; aromatic Pmtonea), 3, 79 (8ingulett CHCIz), the distance of the Schutzgfuppe in accordance with the method F resulted in: b) 3-Aztdomethyl-TB (2-hydroxytmino-2-phenylacetamido) - ceph-3-em-4-carbormäure (syn lsomeres; 8 o), la] D +70° {_c 0, 84, DMSO). UV spectrum: k of max (pH of 6 phosphate buffers) 253, 5 Nm (E 18,800), IR spectrum: Vmax (Nnjol) 3260 (lqH), 2096 (LV), 1762 (/- Laetam), 1650 and 1520 cm-i (CONH) o NMP. - SpektTum: r (DMSO D “) among other things. 0,80 (NH), 2, 3 to 2, 65 (aromatic Pmtonen), 5.57 and 6, 06 (two Dubletts, J 13 cycles per second; C-3 CHz). Example 10: a) 7B (2-Diehloraeetoxyimino2 phenylaeetamido) - 3-methoxymethyl-eeph-3-em-4-earbonsame-diphenylmethylester (syn isomer) was manufactured in form of a yellow Sehaumes (2.31 g, 94%) in accordance with, 'lB the method B, [“] D +24° (C 0, 8 DMSO). UV-Spek over: k of max (ÄtOH) 256 Nm (17800). IR-SpektTum: Vmax (Nujol) 1790 (B-lactam), 1725 (CO2 K), 1698 and 1520 cm-i (amide). NMR Spektmm: r (DMSO-d6) among other things. 2,40 to 2, 75 (multiplet; aromatic protons), 3, 75 (8ingulett; CHCI2), 6, 80 (Singu! ett; - OCI) and the distance of the group of protection in accordance with tB the method F resulted in: b) 7B (2-Hydroxyimiao-2-pheaylaeetamido) - 3-methoxymethyl-eeph-3-em-4-earbonsattre (syn isomer) in form of a solid (5 o), D +7 " P1, o'2, D SO). UV-Spek over: X of max (ÄtOH) 253 Nm (e 16,800). IR-Spek over: Nmax (N ol) 1785 (- lactam), 1730 (- COzH), 1678 and 1580 cm-i (amide). NMR Spek over: r (DMSO-d6) among other things. 0,35 (DublettJ 9 cycles per second; NH), 2, 3 to 2, 6 (Mulfiplett; aromatic Pmtonen), 4.14 (quartet J 9 cycles per second and 4, 5 cycles per second; C-7 H), 4.79 (doublet 4, 5 cycles per second; C-6 H), 6.80 (singlet; OCH3). Example II: a) 713 - (2Diehloraeetoxyimino2 phenylaeetamido) - 3pivaIoyIoxymethyleeph3 ere4 earbonstittr e-diphenylmethylestex (syn isomer) winds in accordance with the method ¢ in form of an oil received and directly in accordance with the method F from the Sehußgruppe one released and resulted in: b) 7/3 (2-Hydr xyimin -2-pheny A etamido) - 3-piva y xymethy - eph-3-em-4arbom tt e (syn isomer) in form of a yellow solid (74 o), IC] D +62° (_c i, DM80). UV spectrum: k of max (pH 6 phosphate) 253, 5 Nm (17200). IR spectrum: Vmax (Nujol) 3700 to 2200 (bound OH), 1771 (] 3-Lactam), 1710 (ester and carbonic acid), 1665 and 1526 cm " 1 (CONH). - 31 - No. 32q3q5 NMR spectrum: T (DMSO DS) among other things. 0, 84 (Dublett, 1 8 cycles per second NH), 2, 8bis 2, 65 (multiplet; aromatic protons) and 8, 82 [singlet; C (C1-Is) s]. Beispie! :! 2: a) The 3-Benz y xymethy 7B (2-dich racet xyimin -2he y acetam D) - ceph-3 em-4-carb nsaur - more diphenylmethylester in accordance with the method D one manufactured and one isolated than a mixture synund anfi isomers. The distance the $chutzgruppe of the mixture in accordance with the method F and the separation of the traces through pr parative Dünnschichtchromatographie on MerckSflikagel 254FPlatten using chloroform/methanol/acetic acid (90: 7: 5 VOL, - parts] as Elutiommittel resulted in as a more slowly running component: b) 3-Benzoyloxymethyl-TB (2-hydroxyimino-2-phenylacetamido) - ceph-3-em-4-carbomäure (syn Isofilet it), IC] D +54, 5° (C! , DMSO). UV spectrum: kmax (pH 6 phosphate) 236, 5 Nm (22,200), Xinf1exi0n 250 Nm (19,600). IR spectrum: Vmax (Nujol) 3680 to 2200 (bound OH): 1770 (B-Lactarn)! 710 (carbonic acid esters): 1680 and: 15: 15 cm " t (CONH). NMR Spek over: T 03MSO-d6) among other things. 0, 32 (Dublett, J 8 cycles per second; NH), 2, 00 to 2, 50 (lvlnltiplett; aromatic Profonen) and 6,] 6 and 6, 38 [2 Dubletts (of branches dne of quartet) J: 18 cycles per second: C-2 Ct-Iz]: wahtend the faster moving component appropriate anti-isomers resulted in (77 mg). UV spectrum: X of max (pH 6 phosphate) 233 Nm (“9,2,500), Xinflexion 255 Nm (15,000), IR spectrum: Vmax (Nujol) 1770 (B-lactam), 1700 (carbon-sour and ester),] 650 and 1520 cm: (CO: qH). Niv - spectrum: I " (DMSO-d6) among other things. : 1, 01 (Dublett, J 8 cycles per second; NH), 1.94 to 2, 50 (multiplet: aromatic Protogen) and 6, 14 and 6, 33 [2 Dubletts (of branches of a quartet),]: 18 cycles per second; C-2 CHz]. Example 13: 3-Cro tonoyloxymethyt TB (2-hydroxy [mino-2ph enylacetamido) - ceph3 ere-4carbonsäure (syn isomer) was manufactured with a yield of 6070 as amorphous solid by a combination of the methods C and F, whereby as intermediate product anfaulende esters without ldentifizierung one used. D +54° (C! , 0, DMSO). UV-Spek over: Xmax (pH 6 phosphate) 252 Nm (16700). 1R-Spek over: max (Nujol) 17q4 (B-lactam), 1710 (COzH), 1670 and 1530 cm': (CONH). NlviR spectrum: r (DMSO-d6) among other things. 0, 35 (Dublett, J 8 cycles per second NH), 2, 3 to 2, q (multiplet, aromatic Pmtonen), 3, 08 (double quartet, J 15 and 7 shark CH=C__.H-CHs), 4, 09 (Dublett J 15 and! Cycles per second; C_. _H=CH-CHs), 8.14 (double Düblett, I 7 and: 1 cycles per second; CH=CH-C_. Hs). Example: 14: a) The 73 (2-D CH acetoxyimin -2 pheny acetam d) 3s butyry xymethy - ceph - m-4-carb (syn lsomeres) was kept nsaure more diphenylmethylester to IC in accordance with the method C in form of a resin,] D +114° (c1, DMSO) o UV-8pek over: kmax (ÄtOH) 255 Nm (e: 12,300). IR spectrum: Vmax (CHBr) 3380 (NH), 1780 (3-Lactam), 1695 and 15:18 cm-1 (CONH). NMR spectrum: T (CDC13) among other things 2, 0 to 2, 9 (multiplex NH and amrnatfsche Pmtonen), 3, 74 (singlet; CHClz), 8.88 (Dublett, J 7 cycles per second; In accordance with Dtmethyl). The distance of the Schntzgruppe in accordance with the method F resulted in: b) the 7B (2 - - Iydroxyirn no-2-Pheny acetamid) - 3-is butyry xymethy - ceph-3 em-4-carb LV ure (synIsomeres) with a yield of 8W/o in form of a solid. la] D +52° (c1, 0, DMSO). UV spectrum: Xmax (ÄtOH) 253 Nm (“14100). IR spectrum: Vmax (Nujol) 3280 (NH): 1770 (- lactam): 1660 and! 520 cm': (amide), Nlv - spectrum: “(DMSO-d6) among other things. 0,33 (DublettJ 9 cycles per second; NH), 2, 3 to 2, 6 (multiplet; aromatic protons) and 8, 86 [Dublett J 7 cycles per second; C (CI) z]. Example 15: a) The 3-Ace xymethy 7B [2 (4 CH r heny) - 2-dich RA etuxyimin - A etamid]. eph 3 em 4r bons ure tert. - more butylester (syn isomer) in accordance with the method B in form of of a yellow Sehaumes was isolated and released in accordance with lB the method F from the group of protection, how one et b) the 3 A xymethyl 8 [2 (4hl r henyl) - 2-hydr xyimin acetamido] eph 3 em-4 carb LV ure (syn isomer) in a Gesamtausbeute of 16v/o, related to that? 8-Aminoester as solid, received] D +62° (C to IC! , 0, DMSO) o UV spectrum: Xmax (pH of 6 buffers) 258 Nm (20900) ° IR spectrum: Vmax (Nujol) 3280 (NH), 1 ' /70 (8-Lactam), 1660 and 1524 cm-l (CONH). NMR spectrum: - (DMSO DS) among other things. 0,33 (Dublett J 9 cycles per second; NH) and “/, 98 (SinguIett OCOCHs). Example 16: a) The 3 Acetoxymethy 78 (2 you racetoxyimin -2 naPhth 2t-y - acetamid) - ceph 3-em-4-carbonsllure-tert, (syn lsomeres) one kept more butylester in form of a solid with a yield from 70 o gemttg the method B. D +32° (_c 0, 75, DMSO). UV spectrum: Xmax (ÄtOH) 9th “/0 Nm (A 13,050), IR spectrum: Vmax (CHBr3) 3340 (OH), 3380 (NH), i” /84 (B-lactam), 1 ' /88 cm " I (OCOCI), NlV] R-spectrum: - (CDC ½) among other things 3, 68 (singlet; CHCIz), 7, 93 (SinguIett; OCOCHs), 8.46 rsingulett; C (CHs) s]. The distance the protection, group gemtiß the method F resulted in: b) 3-Acet xymethy -78 (2-hydr XY min -9. - naphtht y - A etamid) - ceph - em-4-carb MC ure (synIsomeres), (9Wo), [“] D +440 0, '/2, DMSO). UV spectrum: X of max (pH of 6 phosphate buffers) 260 Nm (II 850). IR spectrum: v max (Nujol) 1 ' /70 (8-Lactam), 1714 cm-z (OCOCHs). NlvIR spectrum: r (DMSO DS) U, ao 0, 22 (Dublett; J 9 cycles per second Nile), 1, 3 to 2, 5 (Multtplett; aromatic protons), '/, 94 (singlet; COCH3). Example 1 "/: '/3 [2-Hydroxyimino-2 (thien-2-yl) - acetamido] - 3 (5-methyl1, 3, 4thiadiazol-2-yl) - thiomethylcepb - 3em4 carbonic acid (syn isomer). A solution of 0,585 g 2-Dichloracetoxyimino-2 (thien-2-yl) - acetyl chloride in 5 ml ethyl acetate became with 20oc an agitated Suspemion of 1 g 73-Amino-3 (5-methyl-l, 3,4-thiadiazol-2-yl) - thiomethyl - ceph-3-em-4-carbonsäure-dtphenylmethylester in 10 ml ethyl acetate and 1 ml propylene oxide given. After min sees solved the entire solid had. The solution was washed with 2n hydrochloric acid, geslitügter Natriumbicarbonat ung, dried and restricted water and Salzl0sung and resulted in 1, to 567 g '/8 [2-Di¢hloracetoxyimino-2 (thien-2-yl) - acetamido] - 3 (5-methyl1, 3, 4thiadiazol2 yl) - thiomethyl - ceph-3-em-4-carbons; lme-diphenylmethylesters1 (syn isomer) in form of a solvated foam. UV spectrum: Xmax (ÄtOH) 267, 5 Nm (Ez 240). NMP. - Spectrum: r (CDCls) among other things 3, 00 (singlet; CHPhz), 3, 75 (singlet; CHClz) and '/, 35 (singlet; CH3). To a password of 1,387 g of the above ester in 2 ml anisole one gave tri fluorine to 8 with 20°C ml sigs iure. After 5 min was restricted the solution under decreased pressure and the arrears were solved in ethyl acetate. The L0sungsmittel was evaporated and the arrears were taken up again to ethyl acetate. The L0sung was then washed with water and extracted with Natriumbicarbonatlösung. United the excerpts were washed with Äthylaeetat, brought with concentrated Chlorwasserstoffstiure on a pH value of 1, 9 and washed, geixocknet with ethyl acetate extracted, the excerpt wtttde with water and salt solution and restricted under decreased pressure, whereby one received a foam. The rubbing with more ther resulted in 0, 50 g of the title connection in form of a lederfarbenen solid, D -84o (c1, DMSO). l0 UVSpekkum: IR spectrum: NMRSp ektr over: Xmax (pH of 6 buffers) 271.5 Nm (17600). Vmax (Nujol), 3250 (NH), 1 ' 780 (B-lactam), 2600 + 1 ' 710 (COzH) and 1674 + 1548 cm " I (CONI-I). r (DiMSO-d6) 0.24 (Dublett, J 8 cycles per second; NH), example 18: 2, 37 4, 12 4.76 5, 6.13 and 7, 29 and 2, 82 (Thienylprotonen), (double Dublett, J 5 and 8 cycles per second; C-7 H), (Dublett; J 5 cycles per second; C-6 H), and 5, 75 (2 Dubletts, branches of a quartet, J! 3 cycles per second; C-3 CHz), + 6.40 (2 Dubletts, branches of a quartet, J 18 cycles per second; C-2 CHz) (Singulet CHs). 3-Acetoxymethyl7B (2-hydroxyimino-2phenylacetamido) - ceph-3ere-4Carbonsäure (syn isomer). To an agitated solution of 2, 72 g 8-Acetoxymethyl? B-amino-ceph-3-em-4-earbons lure and 1, 85 g Natriumbicarbonat in 50 ml water and 50 ml acetone gave one drop by drop under RIlhren with 5°C in the process of 5 min a lung of 2-Dichloracetoxyimino-2-phenylacetylchlorid (syn isomer) in 5 m! Acetone. The Reaktiommischung was then gertlhrt 1 h at ambient temperature, on which the pH value amounted to 4, 0, became the acetone then under decreased pressure far away and those mixture with ethyl acetate extracts. The excerpts were washed with 2n hydrochloric acid and satisfied salt solution, dried and on about 5 ml eing¢ confine. The solution was cooled down protecting 15 min on -30°C, filtered and the solid washed with cold ethyl acetate and then dried with Petrol.*lther (boiling point 40 to 60°C) and resulted in 1, 2 g (23 /o) the title-sour in form of a Ethylacetat Solvats, Xmax (ÄtOH) 253 Nm (e 18400). Vmax (Nujol) 3260 (NH), 1760 (eating lactam), 1710 (acetate), 1650 and 1550 cm-1 (amide). r (DMSO-d6) among other things. 0, 38 (Dublett; J 9 cycles per second; NH), 2, 3 to 2, 65 (multiplet; ammaüsehe protons), 7, 96 (singlet; CHsCO). Example! 9: 3A cetoxymethyl7JB - (2-hyd oxyimino2 pH enylacetamido) - e eph3 ere4 carbon-sour (syn lsomeres). To a suspension of 4, 8 g 3-Acetoxymethyl-7-amino-eeph-3-em-4-carbom lure p toluolsulfons, 'turesalz in 25 ml acetonitrile/Dimethylacetamid mixture (6/1) one gave drop by drop unterRIlhren ambient temperature 5 ml a 3m solution of 2-Dichloracetoxyimino-2-phenylacetylchlorid (of syn isomer) in acetonitrile. The reaction mixture was then poured at ambient temperature agitated, until L was homogeneous sung, and into geslittigte zaserige Natriumbiearbonafl0sung. The solution was washed with ethyl acetate, acidified with 2n hydrogen chloride-sour to a pH value of 1,0 and extracted with ethyl acetate. The united excerpts were washed, dried with water and on a volume of about! 0 ml restricted. The concentrate became drop by drop more ither under violent agitating Petrol (boiling point 40 to 60°C) given. In this way one received a resin-like Fesistoff, which was gertthrt with 80 ml ethyl acetate, on which the solution was filtered and given drop by drop to 300 ml Petrol more ither. The failed solid was filtered off and dried and resulted in 1.47 g (29 o) of the Titelslture, [C D +57° (_c 0, 7 DMSO). UV spectrum: Xmax (ÄtOH) 253, 8 Nm (e 18800). Example 20: 7B (2-Hydroxyimino-2phenylaeetamido) - 3methylceph-3ere-4carbonsäure (syn isomer). A lung of 34, 8 mg hydroxyl amine hydrochloride in 5 ml dry methanol was neutralized with Natriummethylat in methanol up to the Umsehlagspunkt by phenolphthalein. This password became then a solution of 201 mg 7B-Phenylglyoxamido-3-methyl-deph-3-em-4-carbons ure tert. more butylester in 10 ml dry methanol given and the mixture w was gerllhrt, 'thrend 2 days at ambient temperature. The arrears received by evaporation in 20 mlÄthylacetat and those solution was washed with water, dried and evaporated and resulted in 220 mg of a yellow 8chaumes were drawn. Pr the tparative Dtinnschichtchromatographie over silicon dioxide plates, those with 20% (Vö!. /Vol. ) Ethyl acetate in benzene, resulted in 46 mg of the Amgangsmaterials, 22 mg 73 (2-Hydroxyimino-2-phenylacetamido) were developed - 8-methyl-ceph-3-em-4-carbons lure tert, more butylester (syn isomer) and 94 mg of a slowly running parliamentary group, which none - lactam ring contained. The ester desired (20 mg) was geschtlttelt with 1 ml Trifluore igs ure at ambient temperature wlihrend min and evaporated then, whereby one received 15 mg of the Titelsliure, which were identified by dünnsehichtchromatographische investigation procedures and by the NMR spectrum as an authentic sample. [C D + 64°. UV-Speki over: IR spectrum: NMR spectrum: - - Nr.327875 - (DMSO-d6) among other things 0, 38 (Dublett; J = 8 cycles per second, NH von syn Isomerem), 2, 25 to 2, 65 (Multiplexor Phenylprotonen) and 7, 96 (singlet; CHe). The output ester was manufactured as follows: 0, 87 g Phenylglyoxylchlorid became a solution of 0, 54 g 7 - Amino-3-methyl-ceph-3-em-4-carbonsäure-tert, more butylester in I0 ml ethyl acetate given and the solution increasing I, 5 h at ambient temperature agitated, to no A usgangsmaterial (thin section chrome auto+graphically) was more present. The reaction mixture was then diluted with ethyl acetate and successively with gesichtigter Natriumhydrogenca [bonatlösung, water and salt, solution washed. The Eindarnpfen of the dried organic layer resulted in 0, 80 g I0 of an oil, which crystallized slowly. The recrystallization from cyclohexane resulted in 0.49 g (620) 7B-Phenylglyoxarnido3 rnethylc eph8 ern-4carbonsäuretert. butyl it more ter, Fp. = 141 b iS 148°C. ] D +122 ° (C I, ethanol). IR-Spektrurn: Vrnax (CI-IBr3) 1781 cm " I (B-lactam). NMR spectrum: r (CDCIs) among other things 1.5 to i, 75 (ortho ammatische protons), 9., 0 to 9, 7 (aromatic protons), 7, 89 (Singule [t; CH3), 8.45 (singlet; tert. Butyl). Example 9.1: N- [7/3 (2-Hydroxyimino-2phenylacetam ido) - ceph8 ere8-ylme thyl] - (4carbamoylpyr idlnium) - 4carb9.0 oxylat (syn Isorneres). A solution of 500 mg 3-Acetoxymethyl-7/3 (9. - hydmxyirnino-9' phenylacetamido) - ceph-3-ern-4-carbons ure (syn Isorneres) and 500 mg ISO nicotine amide in 10 ml water was heated up during 1.5 h on 70°C. The solution was then diluted, filtered with water, to remove urn the Hauptrneuge of a dark unsolvable material and led across an ion exchanger a ule 0Bio-rad AG-l-X8 in the acetate form). The Eluat was examined 9,5 by electrophoresis bd a pH value of 1, 9, whereby it was stated that two components were present, which zuwanderten both in the direction of the cathode. The faster moving component corresponded to ISO nicotine amide, during which a slower mobility similarly of Cephalor [DIN had and which also with Jodplattnatreagens the expected purpurfarbene refreshment resulted in. The Eindarnpfen of the Eluats under verrnindertern a pressure at 35°C resulted in arrears, which with acetone rubbed and one filtered. The solid was washed with acetone and dried and resulted in! , t0 mg (9,5%) of the title connection. The material was homogeneous with electrophoresis at a pH value of 1, 9 and zuwanderte in the direction of the cathode. x] D -44° (_c 0, 72, DMSO). UV-Spekkum: Xrnax (Ä [OH) 251 over (13,000). IR spectrum: Vrnax (Nujol) 3330, 8150 (NH and OH), 1771 (B-lactam), 1680 and 1560 (CONH) and 88 1606 cm-1 (COz), NMR spectrum: r (DMSO-d6) among other things. 0, 37, I, 0 [two Dubletts (of branches of a Quastetts),] 7 cycles per second; it p-diSubstituiext Pyridinring]! , 15 and! , 76 (two spreads singlet; CONH2), 2, 3 to 2, 7 (multiplet; ammatischePmtoneu), 4.26 (IVlultiplett; C-7 H and C-3 CHz), 4.8 (lvlultiplett; C-6 H and C-8 CH2), 6.40 and 6.88 [two Dubletis (of branches of a quartet), J 18 cycles per second; C-2 CH2]. Example 22: N [TB (2-Hydroxyimino2-phenylacetarnido) - eeph-3-ern-3-yl-methyl] - pyridiniurn, 1-carboxylat (synIsomeres). A solution of 5, 0 g 8-Acetoxymethyl7/3 (9. - hydtoxyimino-2-pheaylacetamido) - ceph-8em-4-carbonsliure (syn lsomeres) and 4 rnl Pyridin in 100 ml water one heated up wllhrend 3 h under a Stickstoffatmosphtlre on 70Oc. The reaction mixture was then gektlhlt and more tlber an ion exchanger a ttle (AG ix-shame Acetafforrn) was led, whereby with water one eluiert. Parliamentary groups of I00 were collected rnl and those, which contained the product desired with electrophoresis, were combined and freezingdried and resulted in 0.75 g (14qo) n [TB (2-Hydroxyirnino-2-phenylacetamido) - ceph-3em-8-yl-methyl] - pyridtnium -4-carboxylat (syn lsomeres), talD -49, 5° (_c 0, 83, DMSO). UV spectrum: Xmax (pH of 6 phosphate buffers) 255 Nm (“20,500). IR-Spek over: Vrnax (Nujol) 1770 (B-lactam), 1660 and 1 50 cm-1 (CONH), NMR spectrum: r (DMSO-d6) among other things. 0,46, 1, 36 and 1, 80 (Pyridimingprotonen), 2, 3 to 2, 7 (Muitiplett; aromatic Pmkmen). Example 23: a) 7/3 (2-Dich racet xyimin - i. heny A etamido) - - (4 5-dimeth x carbony1-1 2 3-triaz 1-1-y1) - methyl-celtl-3ere-4carbomaure-diphenylmethylester (syn isomer). To a solution of 1, to 0 g up 3-Azidomethyl~7/3 (2-dichlorace¢oxyimino-2-phenylacetamido) ceph-8-em -4-carbons ure diphenylmethylest¢r in 40 ml Dioxan one gave 2, 5 g Acetylendicarbons, 'ture more dimethylester and heated the solution w, 'lhrend 4 h at the Rtlckiluß. The Reaktiommischung was then abgektthlt, the solvent under decreased pressure was removed and the arrears with Petrol more ther rubbed (boiling point 40 to 30°C). Received the e F eslstoff wurd e collected, well with P more carolather gewasch EN and g etrocknet and resulted in 1.2 g (98 /o) D it DMSO). Xmax (Ä [OH) 250, 5 over (“19900). Vmax (Nujol) 3380 (NH), 1790 (- lactam), 1390 and 1515 cm-1 (CONH). r (CDC ½) among other things 2, 4 to 2, 75 (multiplet; aromatic protons), 6, 09, 6, 21 (two of singlet; Methylester). b) 3 (4, 5 - Dimethoxycarbonyl1, 2, 8 - triazo1-l-y1) - methy1-78 (2-hydroxyimino-2-phenylacetamido) - - ceph8 ere4 carbousäme (syn lsomeres). To a lung of 1,0 g of the ester in 8 ml .4nisol, spoiled above, one gave 4 ml tri fluorine vinegar lure. After 10mintltigem standing at ambient temperature was evaporated the Reaktiommischung to dry ones and evaporated benzene in form of a Azeotrop from the Rtlckstand, which was then solved in ethyl acetate, extracted with Natriumbicarbonat10sang, on which one washed the united excerpts with ethyl acetate, emptied and with ethyl acetate e.xi ahierte. The united organic excerpts were dried and restricted on a volume by about ml. The concentrate became drop by drop under agitating PetroHither (boiling point 40 to 60°C) given, on which one filtered the precipitation off and trocknere, whereby one received 0, 5 g (75q0) of the title series, la] D +68° (C 0.7 DMSO). UV spectrum: kmax (pH phosphate buffer) 249 Nm (“22200). IR spectrum: Vmax (NT ol) 1790 (/3-Lactam), 1680 and 1540 cm "! (Amide). NlViR Spek Nm: r (DMSO DS) among other things. 0, 31 (Dublett J 8 cycles per second; NH) 2, 8 to 2, 7 (Mulffplett: aromatic protons), 4.21 and 4.48 (two Dubletis, I 15 cycles per second; C-8 C__I), 6, 07 and 6, 12 (singlet, Methylester). Example 24: 7/3- (2Hydroxyimino2 phenylacetamido) - 3-hydroxymethylceph3 em4 Carbonsäurenarrt umsalz (synIsomere). To 5.0 g 3-Acetoxymethyl-7 - (2-hydroxyimino-2-phenylacetamido) - one gave a sufficient quantity of gesllttigte Natriumbicarbonatlösung to ceph-3-em-4-carbons', lure (syn lsomeres), in order to bring the pH value on 7, 0, on which a dissolution entered. To this L sung one gave ml water and 85 g to 300 degreased wheat - and agitated the suspension germinated violently, w; lhrenddem one the pH value by h ufigeZugaben from 2n sodium hydroxide solution between 6, 7 and 6, 9 held. After the addition of about 6 ml the pH value remained kontant with 6,9. The mixture was then poured in 400 ml acetone, filtered over Kieselgur and evaporated the Filiert under decreased pressure, in order to remove the Acelon, on which one ierte the material again elber Kiesdgur fil. The filtrate was then washed with ethyl acetate and the pH value to a value of 2, 8 einge - places. The w Issexige phase with ethyl acetate was extracted and the excerpts were gerfihrt with about 800 ml water, on which one brought the pH value with 2n to sodium hydroxide on 7, 0. The phases were separated and the w sserige phase twice with ethyl acetate and once with ether washed, under decreased pressure were evaporated, in order to remove the remaining solvents, and then in this way one kept 1,5 g (31%) freezingdried the title, 'lure, la] D +93° (_c I, 0, DMSO). UV spectrum: kmax (pH of 6 phosphate buffers) 252 Nm (“12,800). IR spectrum: Vmax (Nujol) 17b0 (B-lactam), 1650 lind 1530 cm4 (amide). NMR spectrum: “r (DM80-d “) among other things. 2, 8bis 2, 6 (multiplet; aromatic protons), 5.72 and 6, 05 [two Duble (of branches of a quartet), I 18 cycles per second; CHzOH], 6.44 and 6, 68 [two Dubletts (of branches of a quartet), I 18 cycles per second; c-2 C J. Example 25: Natrtnmsalz of the 75 ['2-Hydmxyimino-2 (thien-2-yl) - ace¢amido] - 8-hydroxymelhyl-ceph-3-em-4-carbons ure (syn isomer). A lung of 2, 0 g of the sodium salt of the 3-Acetoxymethyl-73 [2-hydroxyimino-2 (thien-2-yl) - acetT i tel it gate, D +25° (C I, i UVSpektrum: IR-FR ektrum: NMRSpektrum: amido] - ceph-3-em-4-carbons lure (syn isomer) in 160ml water was erwlirmt to 37°C and shifted then with 15 g enffetteten wheat germs. The mixture became during 4 h fuel element [8 '/°C gerllhrt, whereby the pH value was held for a 2n Natdumhydroxydlösung between 6, 5 by addition of altogether 2, 3 ml and ö, 9. The mixture was poured in 200 ml acetone and floated then over Kieselgur. The “acetone was removed under decreased pressure and the aqueous solution was filtered again Elber Kieselgur, on which it was washed with ethyl acetate, covered with ethyl acetate and brought by vorsichüge addition Chlorwasserstoffsliure concentrated of on a pH value of 2,7. The layers were separated and extracted again diewtisserigeSchicht with ethyl acetate. The united excerpts were washed with water and the pH value was brought to a 2n by addition Na¢n iumhydroxydlösung on 7, 0. The organic layer was continued to wash with water and the combined more wtisser [ge solution was washed, degassed and freezingdried with ethyl acetate and ether, whereby one 1.48 g (79°/o) of the Titeloxims in form of of a brown solid received, D +76° (_c 0, 46, DMSO). UV spectrum: k of max (pH 6 phosphate) 261, 5 Nm (“10,600) ° XInflexion 284 Nm (“ö 500). IR spectrum: Vmax (Nujol) 1760 (8-Lactam), 1560 (CO [), 1650 and 1520 cm " I (CONH). NMR Spektmm: - (DzO) among other things 2.41, 2, 63 and 2.83 (Dublett, Dublett and/or Trip1ett, J 4 cycles per second; Thienylprotonen). Example 26: a) 7B (2-A cetoxyimino2 phenylacetamido) - 3acetoxymethylceph3 ere4 carbonsliure. To a solution of 8 ml acetyl chloride in 8 by portion ml dichloromethane gave one in the process of 10 min under violent attachment. Raurntemperatur 500 mg 3-Acetoxymethyl713 (2-hydroxyimino-2-phenylacetamido) - ceph-3-em-4-carbons, 'lure (syn lsomeres). A resin formed, too dern one for 8 ml ethyl acetate gave, in order to receive a solution. After agitating w, 'lhrend 2 h at ambient temperature the mixture became slowly under violent agitating 300 ml Petrol; more ither given. The precipitation was filtered off, washed well with Petro1, 'more ither, in 10 ml chloroform ge1 t and with Aktfvkohle more ger [lhrt and abfiltrfert. The filtrate was given drop by drop under Rllhren to 250 ml Petrol, 'Ither. The precipitation was filtered off and dried and resulted in 350 mg (62°I0) of the title series. NMR spectrum: - (DMSO DS) among other things. -0, 11 (Dublett, J 8 cycles per second; NH), 2, 2 to 2, 6 (multiplet; aromatic protons), 7, 76 (singlet; CHs. CO2 N=), 7.94 (Singule CICO). Signals with “0, 05 (Dublett, J 9 cycles per second; NH) and 7, 78 (singlet; CH3 COzN=) refer to the presence of approximately 30% the anü isomers. b) 78 (2-Acetoxyimino-2-phenylacetamklo) - 3-acetoxymethyl-ceph-3-em-4-carbons " lure (syn isomer) to a solution of 1, 5 ml Pyrfdin in 20 ml ethyl acetate gave one 0, 5 g 8-Acetoxymethyl-TJ3 (2-hydmxyimino-2-phenylacetamido) - ceph-3-em-4-carbonstiure (syn isomer) and treated gertihrteMischung drop by drop with a solution of 1, 0 ml acetyl chloride in 5 ml ethyl acetate, whereby one continued an agitating during further min. The mixture was then poured in water, which became ethyl acetate phase separated and with 2n hydrochloric acid and water washed and with ges, 'lttigter wlisseriger Natriumbicarbo - natlOsung extracted. The united zaserigen excerpts were acidified and extracted with ethyl acetate, on which one dried and on a volume of about 5 ml restricted the excerpts. The concentrate wurdedanu drop by drop under agitating to Pelzol more lther (250 valley) given. The amgeflillte solid was collected and more getrockner and resulted in 0, 32 g (58%) the Titelsliure, D+83° (C 0.8, DMSO). UV spectrum: Xmax (pH buffer) 258 Nm (e 20800). IR spectrum: Vmax (Nujol) 3270 (NH), 1780 (B-lactam), 1680 and 1546 cm " 1 (CONH). NMR spectrum: - (DMSO DS) among other things. -0, 10 (Dublett J 8 cycles per second; NH), * 2, 2 to 2, 6 (Mulüplett; aromatic protons)? , 78 (singlet; --bi. O. COCHs), 7, 94 (singlet; OCOCH3). Example 27: 3-Acetoxymethyl-TB (2-chloracetoxyimino-2-phenylacetam [DO) - ceph-3em-4-carbons ure (of syn isomer). To a L sung of 7 ml chlorine acetyl chloride in 7 ml ethyl acetate gave one unterRtlhren by portion 0.488 g 3-Acetoxymefhyl713 (2-hydroxyimino-2-phenylacetamido) - ceph3 ere-4carbonsäure (syn isomer) and left the received guild untouched during 2 h at ambient temperature. The solution became then under violent Rtlhren in 300 rnl Petroltither (boiling point 40 to 60°C) poured. The received Festsfoff was washed several times with PE ol more ther, filtered, again with Petrol more lther washed and dried and resulted in 0.453 g (79%) the Titelstiure in form of a yellow solid. [“: b +520 (_c 0, 87, DMSO). UV spectrum: X of max (pH of 6 phosphate buffers) 254 Nm (“16,700). IR-8pektrum: Vmax (CHBrs) 8421 (NH), 1791 (8-Lactam), 1699 and 1521 cm'I (CONH). “NMR $pektrum: r ('DMSO DS) among other things. -0,13 (Dublett, J 8 cycles per second, NH), 5.36 (singlet; CHzC), 7, 96 ($ingulett; OCOCI). Example 28: 3Acetoxymethyl7 - (2ithoxycarbonyloxy [mino-2-phenylacetamido) - ceph-8-em-4-carbonsaure (syn [some it). A solution of 0, 5 g 8-Acetoxymethyl-7/B (2-hydroxyimino-2-phenylacetamido) - ceph-8em-4-carbonsäure (syn lsomeres) in 20tal of gestlttigter Natfiumbicarbonaflösung was geschtlttelt briefly with a solution by 1 ml Chlorameisensgure more thylester in 10 ml ethyl acetate. The wtisserfge layer was separated and vibrated with a second solution from 1 ml Chlorameisensguregthylester in 10 ml ethyl acetate, on which it was separated, washed, acidified twice with ethyl acetate and extracted with ethyl acetate. The united w of serigen excerpts were dried and restricted on about 5 ml. The concentrate was given drop by drop under Rtihren to 200 ml Petroltither. The precipitation was filtered off and dried and resulted in 0.45 g ('/Wo) of the title acid, iclD +48° (C 0, 8, DMSO). UV spectrum: Xmax (pH of 6 phosphate buffers) 258 Nm (21,800). IR-Spekq over: Pmax (Nujol) 8270 (NH), 1 ' /76 (B-Lac%am), 167g ünd 1535 cm " i (CONH). NMR spectrum: T (DM80-d6) among other things, - 0, 13 (Dublett, 1 8 cycles per second; NH), 2, 2 to 2, 5 (multiplet; aromatic protons), 5, 68 (quartet, J 8 cycles per second; OCH_zCH3), 7.96 (8ingulett; OCOCH), 8, 70 (triplet, J 8 cycles per second; OCH2 CH3), example 29: a) 8-Acetoxymethyl7B (2-benzoyloxyimino2 phenylacetam ido) - C eph8 em-4carbonsäur e-more diphenylmethylester (syn lsomeres). Z of a lung of i, 0 g 8-Acetoxymethyl7B (2-hydroxyimino-2-phenylacetam ido) - to C untouched eph-3ere4 carbonstlure more d/phenylmethylester and 1.5 ml Pyrtdin in 30 ml ethyl acetate gave one 1.5 ml Benzoylchlortd and left the mixture during 1 h at ambient temperature. The solution was then washed with 50 ml 2n hydrogen chloride-expensive and to satisfied salt solution, dried over sodium sulfate and restricted on a volume of about 5 ml. The concentrate became drop by drop 350 ml Petrolt more ther (boiling point 40 bls 60°C) given and the ausgeftfllte solid was filtered off, washed dried with PetroIäther and resulted in I, 0 g (85%) of the title ester in form of of a yellow Fesistoffes, D+6,4° (C 0.94, DMSO). UV spectrum: kmax (ÄtOH) 259 Nm (e 26,700), IR-8pekl over: Ztmax (CHBr) 1780 (t - lactam), 1640 and 1522 cm-z (CONH). NMR spectrum: ¢ (DMSO-d6) among other things. -0, 27 (Dublett J 8 cycles per second; NH), 1, 8 to 2, 8 (multiplet; aromatic Umtonen), 8, 01 (singlet; OCOCI). b) 8-Acet xymethy1-7B (2-benzoy oxyim no-2-pheny1acetamido) - ceph - em-4-carbon äure (syn lsoneres). A L sung of 0,85 g 3-A cetoxym ethyl7/3 - (2-b enzoyloxyimino-2-phenylacetamido) - ceph8 ere4 carbonic acid D [(syn lsomeres) in 10 ml Trifluoresstgstlure, which shifts 0 with I0 drop anisole was, became more phenylmethylester wghread: I 0 min with Raumtempera tur left untouched and then under decreased pressure to dry ones evaporated. The arrears were solved in ethyl acetate and extracted with Natriumbicarbonaflösung. United the excerpts were addressed with 2n Chlorwasserstoffstlure and extracted with ethyl acetate. The united organic excerpts were washed, dried with salt solution, restricted on a volume by about i0 ml and given drop by drop under agitating to petroleum ether. The ausgeftfllte Fesistoff was filtered off and getroeknet and resulted in 0, 89 g (60%) the Titelsgure, D +81o (C 0, g4, DM80). UV spectrum: kmax (ÄK) H) 260 Nm (26,000). IR-8pektrum: Umax (Nujol) 3270 (NH), Iq84 cm-i (JB-lactam). NMR Speklium: r (DMSO-d6) among other things. - 0, 27 (Dublett J 8 cycles per second; NH), 1, 75 to 2, 6 (multiplet; aromatic protons), 7, 96 (singlet: OCOCI-- ). The Amgangsmaterial used in the stage a) was manufactured as follows: To dner password of 2,0 g 8-Acetoxymethyl-7B (2-hydrox.yoimino-2-phenylacetamido) - ceph-8-em-4-carbons ure (syn lsomeres) in 50 ml Te was held ahydrofuran, 37 G, gave one by portion a L ung from Diphenyldiazomethan in Petrol more ther (boiling point 60 to 80°C), until the purpurfarbene Flirbung w was maintained hrend I h, after the addition of acetic acid, in order to destroy the surplus D phenyldiazomethan, wound the solution to the Ttockne evaporated, in ethyl acetate-taken up, mitNatfiumbicarbonat and Salzl ung washed and dried and evaporated. The arrears became with Petroltither rubbed, on which one filtered off the received solid and dried, so that one 1.93 g (69%) 3-Acetoxymethyl - °/I3 (2-hydroxyimino-2-pheny1acetam D) - ceph-3-em-4-car onsäured pheny methy ester (syu lsomeres) erhie.lt, in] D +24° (_c 1, DMSO). UV-Spekkum: Xmax (ÄtOH) 258 Nm (16150). IR spectrum: Umax (CHBrs) 8610 (OH), 1796 cm-z (- lactam), NMR spectrum: - (DMSO DS) among other things. 0, 27 (Dublett, J 9 cycles per second; NH), 8, 03 (singlet; OCOCI). Example 30: a) 3.Acetoxymethy1ß [2 (4-nitrobenzoyloxyimino) - 2-phenylacetamido] - ceph-3-em-4-carbons; iure - diphenylmethyl esters (syn lsomeres). To a solution of 1,5 g 3-Acetoxymethyl-7 - (2-hydroxyimino-2-phenylacetamido) - to ceph-3-em-4-carbonstiure-diphenylmethylester (syn lsomeres) and 0, 5 ml Pyridin in 100 ml ethyl acetate gave one 0, 42 g 4-Ni obenzoylchlorid and agitated the received solution during I h at ambient temperature, then further portions (0, 042 g, 0.015 g and 0.20 g) of the Säu.rechlorids were added and dieReakfionsmischung w; it-end altogether 4 h at ambient temperature gertib.rt. Subsequently, the lung was washed, dried with 2n Chlorwasserstoffsliure and Salz15sung and restricted on a volume of about 5 ml, on which one the concentrate drop by drop under agitating to Petroltither (boiling point 40 to 60°C) gave. In this way one received a solid, which was filtered off and dried, on which one received I, 1 g (58%) of the title ester. UV-Spek over: Xm ax (ÄtOH) 263 Nm (29,000). IR-Spek over: Umax (CI-IBr3) 3400 (NH), I'/80 (B-lactam), 1395 and 1525 (NOz), 1687 and 1515 cm " i (CONH). NMR spectrum: T (CDC) among other things. 1, 70 and 2, 71 (two Dubletts, I 8 cycles per second; --NOz), 2, 1 to 2, 85 (multiplet, aromatic Pmtonen), 8, O3 (singlet; OCOCHs). b) 3-Acetoxymethyl-7B [2 (4niliobenzoyloxyimino) - 2-phenylacetamido] - ceph-3-em-4-carbonstture (syn isomer). A L sung of 1, 0 g 3-Acetoxymethyl-7 - [2 (4-ni obenzoyloxyimino) - 2-phenylacetamido] - ceph-3 - em-4carbonstiure-d [(syn isomer) in 10 ml Trifluoressigstiure one let w more phenylmethylester; it-end 10 min at ambient temperature stand. After the evaporation of tri fluorine acetic acid under decreased pressure wv in ethyl acetate solved and with gestittigter wtisseriger Naliiumbicarbonatlösung extracts the le arrears. During the Natriumbicarbonatextraktion a solid failed, separated, with water and washed with ethyl acetate and between ethyl acetate and 2n the Chlorwasserstoffsäurevexteiltwurde. The phases were separated and the upper layer was washed, geliocknet with water and restricted on a volume of about 10 ml, on which one under-agitates ¢ ieses concentrate drop by drop in 200 ml PelIo [ethers (simmer epunkt 40 to 60°C) gave. The amgefällte solid was affiliiert and dried and resulted in 0! 50 g (20%) 3-Acetoxymethyl-7t3 [2 (4-nitzobenzoyloxyimino) - 2-phenylacetamido] - ceph-3em-4-carbonsäure (syn isomer). D +17° (_c 0, 8 DMSO). UV-SpeklIum: kmax (ÄtOH) 266, 5 Nm (33,000). IR-Spektmm: Vmax (Nujol) 3270 (NH), lq80 (/3-Lactam), 1520 and 1338 (NO2), 1675 and 1520 cm " 1 (CONH), - 39 - NR, 327375 NMR spectrum: r {DMSO DS) among other things. 1, 58 and 1, 69 (two Dubletts J 8 cycles per second; p-substituted Phenyl), 2.1 to 2, 5 (multiplet; aromatic protons), 7, 79 (Singalett; OCOC). Example 31: 3 - A cetoxymethyl7 - (2tithylcarbamoyloxyimtno2 phenylac etam [DO) - C eph3 ern-4karbons äure (synIsomeres). To 5 ml ethyl isocyanate gave one to 0.9 g 3-Acetoxymethyl-7 - (2-hydroxyimino-2-phenylacetamido) - ceph -3-em-4-carbomttureäthylaceta¢solvat (syn isomer) and rllhrte the mixture during 1 h with Raumtemperatut. Then further two portions were added of 5 ml isocyanate in the process of 2 h, then one left the mixture untouched 1 h, poured her into 250 ml petroleum ethers (Siedepunkt40 to 60°C), sammelteden themselves resulting in precipitation, washed these well with petroleum ether and trocknere it, which became Fesistoff in ethyl acetate solved and with Natriumbicarbonatlösung extracted. The Natriumbicarbonatlösung was then washed with ethyl acetate, acidified with 2n hydrochloric acid and extracted with ethyl acetate. The united excerpts were dried and restricted, on which one gave the Kormentrat (about 5 valley) drop by drop under violent agitating to Petrol/ither. The formed precipitation was filtered off and dried and resulted in 0.4 g (4W/o) def title acid, [o D +500 (C 0, 85, DMSO). UV spectrum: Xmax (pH of 6 buffers) 257, 5 Nm (“9,1200). IR spectrum: max (Nujol) 1q82 (- lactam), 1675 and 1520 cm " 1 (CONH). NMR spectrum: r (DMSO dG) among other things. 0, 04 (Dublett J 8 cycles per second; NH), 2, 0 to 2, 6 (multiplet; aromatic Pmtouen), 6? to 7, 1 (multiplet; NHCHzCH3) and 8.89 (triplet, J 9 cycles per second; C C_Ha). Example 32: 3-Acetoxymethyl-TB [2 (2 - chloräth71) - carbamoyloxyimino-2-phenylacetamido] - ceph-3ere-4carbonsäure (syn isomer). To a solution of 1,0 g 8. Cetoxymethyl TB (2-hydroxyimino-2-phenylacetamido) - ceph - em-4-carbonstture-lithylacetat-solvat (syn isomer) in 21 ml dimethylformamide, dic 0.425 g tri ethyl amine contained, gave one 0.274 g 2-Chlortithylisocyanat and agitated the mixture during! h at ambient temperature. The Reakttonsmischung was then addressed nU t 2n hydrochloric acid and extracted with ethyl acetate. The Extzakte was combined and extracted with satisfied aqueous Natriumbiearbonaflö$uug. United the aqueous excerpts were addressed with 2n hydrochloric acid and extracted, dried, restricted with ethyl acetate and brought drop by drop under violent agitating into petroleum ethers. The precipitated solid was filtered off, in 10 ml ethyl acetate drew and drop by drop in 800 ml Petrol was more ither given. The precipitation was filtered off and getmcknet and resulted in 0, 76 g (74%) of the title acid. la] D +28° (c1, 0, DMSO). UVSpekfrum: k of max (pH 6 Phospha buffers) 257, 5 Nm (“20,780). 1R-Spektrum: Vmax (Nujol) 8270 (NH), 1780 (- lactam), 1660 and 1520 cm-1 (amide). NMR spectrum: r (DMSO dG) among other things. - 0, 10 (Dublett, J 8 cycles per second; NH), 6.2 to 6, 7 (multiplet; C-2 CH + - CHzCHzC1), 7, 95 (singlet; OCOCHs). Example 38: 6B (2-Hydroxyimino2 phenylacetamido) - 2, 2-dimethylpenam-Sa-carbomäure (syn LSO of meres). To a suspension of I, to 08 g up 6/B-Amino-9., 2-dimethylpenam-3a-carbonsäure in 25 ml chloroform gave one 2.49 g Hexamethyldisilazan and heated the mixture during 2 h at the Rttckfluß, on which a dissolution entered. The solvents were separated under decreased pressure, whereby mau 2, 2-Dimethyl-6iß-trimethylsilylaminopenam-3a-carbons; lure trimethylsilylestex in form of a solid received. The Fesistoff was solved in 20 ml dichloromethane and cooled down with 1, ml propylene oxide shifted 5, the solution on 0°C and tropfenw ice e with 2-Dichloracetoxyimino2 phenylacetyl chloride (A US I, 38 g 2-Dichloracetoxyimino2 phenylessig äure: syn lsomeres) in 20 ml dichloromethane in the process of 15 min under agitating treats. Then dieIXisuug further 2 h at ambient temperature one agitated. The solvents were extracted under decreased pressure below a temperature of 85°C evaporated, on which one the Rtlckstand to ethyl acetate took up, after the addition of 2 ml methanol the solution as fast as possible with eisgektlhlter Natriumbicarbonafltlsung and the united excerpts were washed with ethyl acetate and poured into an agitated mixture of ethyl acetate and 2n of hydrogen chloride, *lure. The organic phase was separated and combined with an ethyl acetate excerpt of the aqueous phase, on what one dried and evaporated the password with water wuseh, the Rilckstand became taken up to 5 ml ethyl acetate and drop by drop 200 ml Petro! more tither (they, I &, among other things l U I U depunkt 40 to 60°C) given. The ausgefilllte solid was filtered off and dried and resulted in 0, 84 g (4 o) 6B (2-Hydroxyimino-2-phenylacetamido) - 2, 2-dimethyl-penam-3 of z-carbon ure {syn lsomeres), [“] D +s10° (_c O, 9, DMSO). UV spectrum: max (ÄtOH) 251 Nm (e 9450). IR spectrum: u of max (Nujol) 3650 to 2300 (OH), 3280 (NH), 1758 (B-lactam), 1735 (CO2 H), 1650 and 1510 cm " 1 (CONH). Nlv - spectrum: “(DMSO D “) 0, 51 (Dublett, J 7 cycles per second; NH), 2, 2 to 2, 7 (multiplet; aromatic protons), 4.28 (quartet, J 4 cycles per second and 7 cycles per second; C-6 H), 4.40 (Dublett J 4Hz; C-5 H), 5, 27 (singlet; C-3 H), 8, 39 and 8, 48 (two of singlet; Groups of methyls). Example 34: B enzyl-2phenyl lthylammonium3 acetoxymethyl7B (2-hydroxy mino-2-phenylacetamido) - ceph8 ere - 4carboxylat (syn lsomeres). To a solution of 0, 084 g Natriumbicarbonat in 20 ml one gave 0, 507 g 3-Acetoxymethyl-7B - (B-hydroxyimino-2-phenylacetamido) - to water ceph-8em-4-earbons urethylacetatsolvat and treated the received solution with a solution of 0, 396 g Benzyl-2-phenyl Ithylammoniumacetat in 10 ml water. A white solid separated itself, which iert after 15mintitigem agitating abfil, with water was washed and dried, whereby one received 0, 2 g (82%) of the title salt. UV spectrum: k of max (pH 6 Phosphaipuffer) 254 Nm ({18,000). IR-Spekt umv max (Nujol) 1773 0B-Lactam), 1650 and 1550 cm-i (CONH). NM_R-Spektrum: “(DlviSO DS) among other things. 0, 4 (Dublee J 8 cycles per second; Nil one), 2, 3 to 2, 71 (Mulüplett; aromatic protons), 7, 99 (singlet; OCOCHs). Example 35: 2, 2-Dimethyl6 - [2-Hydroxyimino (thien-2-yl) - acetamido] - penam-3a-carbons ure (syn isomer). A L sung of 2, 2Dimethyl6/5trim ethylsilylaminopenam3 Œ - Carbonsäuretrimethylsflylester (made of 0,864 g of the appropriate amino acid) and I ml propylene oxide in 20 ml Dichlormethan were cooled on 0° and drop by drop with a L sung of 2-Dichloracetoxyimino (thien-2-yl) - acetyl chloride (syn isomer; made of 0, 753 g of the appropriate Silurer) in 12 ml Dichlormethan shifts. The received solution was held I h with 0° and evaporated afterwards to a small mass and divided between ethyl acetate and satisfied Natriumbicarbonaflösung. The zaserige phase was washed with ethyl acetate, addressed with 2n hydrochloric acid and extracted with ethyl acetate. The dried organic password was evaporated to a small mass and drop by drop to agitated Petrol more ther (kp. 40 to 60°C) added. The received precipitation was collected, washed and dried, whereby 0, 337 g (24 /0, related to the amine) resulted the TiteIs ure; iclD + 224° (C 0, 57, DMSO). UV spectrum: Xmax (pH of 6 buffers) 288 Nm (e 6400), XInflexion 270 Nm (“5,800). IR spectrum: Vmax (Nujol), 2600 and 1730 (GO H), 1776 (/B-lactam), 1670 and 1526 cm "! (CONH), NMR spectrum: “(D “- DMSO) the values cover. 0,44 (D, I 6 cycles per second; NH), 2.45 and 2, 9 (multiplet, aromatic protons), 5, 78 (s; c-3 H), 8.46 and 8, 55 (2 s; CHs groups). Example 36: 2, 2-Dimethyl6/3 [2-hydroxyimino-2 (thien-3-yl) - acetamido] - penam3acarbonsäure (syn isomer). To a geklihlten solution of 2,2-Dimethyl-6/3-trimethylsilylamtno-penam-8a-carbomtture-trimethylsilylester (made of 0,43 g 6f3-Amino-2, 2-dimethylpenam-3a-carbonstture and 2, 1 ml Hexamethyldisilazan) and 0, 53 ml propylene oxide in 10 ml dry dichloromethane became drop by drop under Rtlhren a password of 2,1 mMol 2-Dichloracetoxyimino-2 (thien-3-yl) - acetyl chloride (syn isomer) in dry Methylench! orid erased. After 1 h fuel element [20°C the Reaktiomgemisch was evaporated and the arrears in ethyl acetate gel t. The Äthylacetafl0sung was extracted with ice-cooled gestttügter Natriumbicarbonatl ung. United the wtisserigen phases were addressed with ga Chlorwasserstoffstiure on pH 1 and extracted with ethyl acetate. After drying the excerpts were restricted on a small volume, that with additive to a surplus of Petroltithex (kp. 40 to 60°) a white solid it resulted in which was filtered and dried, whereby 0, 32 g (44%) of the title connection resulted, [(z] D +220° (C 0, 9, Dioxan). 41 - No. 32? 375 UV-Spek over: k of max (pH of 6 buffers) 256 Nm (ₜ 9,100). IR-Spektrurh: Umax (Nujol) 3800 (NH), 1770 (iB-lactam), 1940 and 2600 (COOH) and 1660 and 1526 - i cm (CONH). NMR Spektrurn: r (DMSO D) the values cover 0.46 (D; J 8 cycles per second; NH), 2, 80, 2, 35, 2, 59 (m; Thieuylprotouen), 5, 66 (s; C-3 H), and 8, 35 and 8, 44 (2s; CHs groups). Example 37: 0 2, 2-Dimethyl6 - [2-hydroxyimino (fur-2-yl) - acetamido] - penam-3acarbonsäure (syn isomer). A solution of 2, 2Dimelhy! - 68trimethylsilylaminopenam3acarbonstiuretrimethyisilylester (made of 0, 648 g of the appropriate Arninostture) and 0, 75 rnl propylene oxide in 15 ml Dichlormethan were gektthlt on 0° and drop by drop with a solution von2-Dichloracetoxyimino (fur-2-yl) - acetyl chloride (syn Isorneres; made of 0, 579 more gder corresponding accumulated) transferred in 12 ml DichIormethan. The received solution was held 1 h with 0° and angedampft afterwards a small volume and between Äthy! - acetate and satisfied Natriumbfcarbonatlösung divided. The wttsserige phase was washed with ethyl acetate, acidified with 2n hydrochloric acid and extracted with ethyl acetate. The dried organic password was evaporated to a small quantity and drop by drop to agitated petroleum ether (kp. 40 to 60°) added. The received precipitation was collected, washed and dried, whereby 0, 56 g (5 o, related to which Amiu) of the title connection resulted, D +243° (C,0, 93, DMSO). UV-3pektrurn: kmax (pH of 6 buffers) 275 Nm (e 9,600). In-spectrum: Vmax (Nujol), 1778 C - lactam), 1740 and 2600 CCOzH), 16 ' 70 and 1528 cm " 1 (CONH). NMR spectrum: r (D “- DMSO) the values cover 0, 44 (D, J 6 cycles per second; NH), 2, 18 and 3, 84 (multiplets; aromatic protons), 5, 70 (s; c-3 H), 8, 36 and 8, 46 (2s; CH3 - Groups). Example 38: 3A cetoxyme thyl7B - [2hydroxy [rnino-2 (thien3-yl - acetamido] - ceph3 ere4 carbensaur e (syn isomer). To a ice-cold solution of 1, 59 g 3-Acetoxymethyl-TB-amino-ceph-3-em-4-carbomtiure-tert. more butylester and 3, 5 ml propylene oxide tn 15 rnl ethyl acetate was added under agitating 5, 3 ml one lm solution by 2-Dichloracetoxyamino-2 (thien-3-yl) - acetyIchlorid (syn isomer) in ethyl acetate. After 1 1/2 h with 20°C w the de solution washed with 2n i-IC1, satisfied Natriumbicarbonatlösung and saline solution. The orgauische layer was dried and evaporated, whereby itself 2, 8 g (100%) 3-Acetoxyrnethyl-TB [2-dtchloracetoxyimino-2 (thien-3-yl) - acetamido] - ceph-3-em-4-carbonsgure-tert, more butylester (syu isomer) than white foam resulted in, [C D +47, 0° (C 0, 9, DMSO), UV-Spek urn: kmax (ethanol) 253 Nm (“13900), IR spectrum: Vmax (CHBr) 3580 (OH), 3410 (NH), 1790 03-Lactam), 1728 (OCOCHs), 1720 (CO0 But) and 1700 and 1520 cm-1 (CONH) o NMR spectrum: r (CDC13) the values cover 2, 1! to 2, 7 (m; Thieuylprotouen), 7, 92 (s; OCOCHs), 8.48 (s; But). A solution of 2,7 g tert. Butylesters in 25 ml tri fluorine vinegar, 'lure was left untouched 15 min, on which she was evaporated and the arrears were azeotropabdestilliert rnitBenzol. The oil was loosened in ethyl acetate and extracted with gesllttigter NatriumbicarbonaflOsung. Dia. w serige password was acidified with 2n HCI on the pH-Wertl and extracted rnitÄthylacetat. The united organic phases were dried and evaporated on a small volume, which with the additive to one over-stir up from Petrol more ither (kp. 40 to 60°) a white solid resulted in, which was filtered and dried. One received 1, 5 g (60, 8°] o) 3-Acetoxymethyl7B - [2-hydmxyimmo-2 (thien-3-yl) - acetamido] - ceph3 ern-4carbonsäure (syn lsomeres), [C D +50, 5° (C 0, 88, DMSO). UV spectrum: kmax (phosphate buffer pH 6) 256, 5 Nm (18,350). IR spectrum: Vmax (Nujol) 3280 (NH and OH), 1770 (- lactam), 1726 (OCOCHs)! 662 and 1522 (CONH) cm-i. NMR spectrum: r (DMSO DS) the values cover 0, 86 (D; 1 8 cycles per second; - NH), 2, 3 to 2, 7 (m; Thienylprotonen), 4, 12 (dd; J8, 5Hz; TH), 4, 77 (D, 15 cycles per second; 6H), 7, 96 (s, OCOCHs). Beispie! 39: 3A cetoxymethyl7 - [2hydroxyim ino-2 (fur-2-yl) - AC etamido] - ceph8 ere4 of carbon/iure (syn lsomeres). To a ice-cold password of I, 76 g 8-Acetoxymethyl-q/3-am [no-ceph-8-em-4-carbons/lure-tert. more butylester and 4 ml propylene oxide in 15 ml ethyl acetate became under agitating 5.37 ml one lm solution of syn-2-Dichloracetoxyimino-2 (fur-2-yl) - acetytchlorid in ethyl acetate gefttgt. After 1 h with 20°C the solution was washed successively with 2n HC1, more ges/ittigter well xiumbicarbonatlösung and saline solution. The organic layer was dried and evaporated, whereby itself 8, 04 g (100a/o) save. Butylesters (syn isomer) in form of a yellow foam resulted in, D +66, 5° (e 0, 9, DMSO). UV spectrum: X of max (ethanol) 270 Nm (“16,700), IR-Speklzum: Vmax (CHBr), 3300 (NI--I), 1780 (B-lactam), 1726 (OCOCH3 and cootBu) and 1680 and 1530 cm-1 (CONH). NMR spectrum: T (CDC13) the values cover 2, 31, 2, 88 and 3, 39 (multiplet, Furylprotonen), 8, 76 (s; CHC ½), 7, 92 (s; OCOCHs), 8.48 (s; But). A L sung of 2, 94 g of the managing Acetoxymethy! - 7/3 [2-dichtoracetoxyimino-2 (fur-2-yl) - acetamido] - ceph-3-em-4-carbons/iure-tert, butyle ters (syn isomer) in 20 ml Tr [fluorine vinegar ure 15 min it was left untouched on what the solvent taken off and the arrears azeotrop with Benzo! one distilled. 95 the Ö! in ethyl acetate one solved and with satisfied Natriumbiearbonat! Ssung extracts. The w/isserige solution with 2n hydrogen chloride-sour to the pH value 1 one persisted and one extracted with ethyl acetate. The united organic phases were dried and evaporated on a small volume, that with additive to a surplus of PE more xol/ither (kp. 40 to 60°) a white solid formed, which was filtered and dried. One received 1, 68 g (76%) 3-Acetoxymethyt-7/3 - [2-hydroxyimino-2 (fur-9-yt) - acetamido] - ceph-3ere -4carbons/ture, in] D +69° (c1, 2, DMSO). UV spectrum: kmax (pH of 6 buffers) 269 Nm (“16,300). IR spectrum: V max (Nujol) 1782 (- lactam), 1728 (OCOCH3), 1720 and 2600 (- COOH) and 1680 and 153 cm (CONH). NMR spectrum: r (DMSO-d6) the values cover 0.33 (D, J 8 cycles per second; NH), 2, 19 and 3, 3 (2s; Fury! protons), 6.28 and 6, 52 (2 Dubletts, branches of a quartet, J 18 cycles per second; C-2 CHz) and 7, 95 (s; OCOCHs). Example 40: 3Ac etylthiomethyl7t - [2-hydroxyimino-2 (th/en-2-yl) - acetamido] - eeph-3em-4-carbons ure (syn isomer). 1, 08 g 3A cety! thiomethyl7/3am [noceph3 em-4-earbons ture diphenylmethylester hydrochloride ethyl acetate and 30 wutden ml aqueous Natriumbicarbonatlösung divided between 30 ml. Dte ethyl acetate layer was separated, with satisfied Natriumch! oridl sung washed, dried and filters. The remaining solution was treated with 2, 15 ml one lm password of 2-Dichloracetoxyimino-2 (thien-2-yl) - aeetylchlorid (syn isomer) in ethyl acetate and 0, 5 ml propylene oxide and agitated with 21°C 40 min, whereby a white precipitation appeared and see again Sste. The solution became successively with aqueous Natriumb [- carbonate solution, water and ges/ittigter sodium chlorine DL Ssung washed and dried. As a result of removing the draw means in the vacuum arose 1.42 g of a nearly white foam. This was solved in 2 ml Anisot and 8 ml Trifluoressigsliure were added. After 5 miu with 10°C the reagents in the vacuum were discharger-harvested and the received rubber-like mass between ethyl acetate and w, 'isseriger Natr [umbicarbonatlösung divided. The organic layer was extracted with Natriumbicarbonatlosung and the united aqueous layers were washed again with ethyl acetate, which became aqueous layer with 2n of hydrogen chloride/iure adjusted to the pH value 2, 0 and with ethyl acetate extracted. The excerpts were washed with ges/ittigter sodium chlorid solution, removed dried and the L0sungsmittel in the vacuum, whereby 0, 97 g of the title connection resulted as pale-brown foam, in] D -52° (c1, 04, DMSO). UV spectrum: Xmax (pH buffer) 26 Nm (“13400). IR spectrum: Vmax (Nujol) 2600, lq20 (C02 H); lq'lO (B-lactam), 1740 (SCOCHs), 1660 and 1520 cm! (CONH), NMR Spek cum: “(DMSO-d6) the values cover 0.30 (D, I 9; Nil one), 2.40, 2, 84 (m, Thien-2-yl), 7, 66 (s; SCORE). The ester used as raw material for the vomtehende acylation was manufactured as follows: a) 3Acetylthiornnethylq 8formamidoceph-3ern-4carbonsliur of e-diphenylmethyles ter18-oxyd, a solution of 5, 0 g 3-Brommethyl-7 - formamido-ceph-3-em-4-carbonsaure-diphenylmethylester-1/3 - oxide in 30 ml N, N-dimethylformamide was treated with 4, 0 ml Thioessigsliure and 1,4 rnl T” i/lthylamin and the Urnsetzung 1, 6 h with +19° was agitated, which became geIbe solution in 100 rnl water and 100 ml ethyl acetate poured and the received insoluble solid became collected, with ethyl acetate washed and in the vacuum over Phosphorpentoxyd getmcknet, whereby itself 9th 49,2 g (49%) 3-AcetylthiomethyI78-formarnido-ceph-3em -4-carbonsaure-diphenylmethylester-18-oxyd of the Fp. 198 to 199° (decomposition) resulted in, [A -60° (c1, 0, DMSO). UV spectrum: Xmax (Ä H) 273 Nm (10,800), IR-Spektrurn: Umax (CHBrs) 3430 (NH), 1803 (B-lactam), 1725 (COzR), 1695, 1505 (CONH), 1042 cm (S --> O). NMR Spektmm: 'r (DMSO D “) 1.66 (D, J 9; NH), I, 78 (s; CHO), 2, 59 (m, Phenyl), 3, Ol (s, C hO, 7, ö8 (s sc% b) 3-Acetylthfomethyl7 - forma m/doceph3 ere-4carbornttur e-diphenylmethyl esters. A gertlhrte solution of I, O0 g 3-Acetylthiomethyl-Tt3-formamido-ceph-3em-4-carbons ture diphenylrnethylester lB oxide in 15 ml dry N, N-Dfmethylformamid was cooled for auf-5°C and treated with 0, 67 g KaIiumjodtd and 0.315 g acetyl chloride. The brown solution was agitated 5 min with 0oc, afterwards min after distance of the ice bath. A solution of 0.60 g Natriurnmetabisulfit in 12 ml water was added and the yellow suspension was agitated 5 min with 20°C, afterwards in 200 ml water poured and rnlt Dichloräthan extracted. The united excerpts were washed with water, dried and the LOsungsrnittel TM vacuum removed, whereby itself 0, 92 g (94%) 3-Acetylthiomethyl-78-formamido-ceph-3-em - 4carbomaurediph more eaylmethylester in form of a pale-yellow powder resulted in, D -136° (C i, 0, DMSO). UV spectrum: Xmax 268 nrn (ÄtOH) (“8950). c) 3A eetylthiomethyl78 - aminoceph3 em4 Carbonsäured/ph of enylmethyles terhydmchlorid. An agitating solution of 0,505 g 3-Acetyltbiomethyl78-formamido-ceph-3em-4-carbonsllure-diphenylmethylester in 3 ml methanol/ether (1: 1) pray 0°C wtthrend 10min with 0,468 g Phosphoroxychlorid one shifted. The ice bath was removed and further 20 min was agitated, whereby a clear solution developed. The conversion was gektthlt auf0°C and it appeared a white laistalline Ausfttllung. 15 rnl ethers were added and the Ausf was filtered off tllung, washed with ether and dried in the vacuum, whereby itself 0.456 g (89%) 3-Acetylthiomethyl-78-amino-ceph-3-em-4-carbonsliure-diphenylrnethylester-hydrochlorid in form of white micro crystals of the Fp. 155 to 160°C (decomposition) resulted in, D -91° (C O, 83, DMSO). UV spectrum: - max (Ä tOH) 268 Nm (8,700). IR spectrum: u max (Nujol) 1770 (- lactam), 1720 (CC R), 1702 cm-i (SCOCHs). NlVIR spectrum: “(DMSO there) dteWerte cover 2, 60 (m; F), 3, 02 (s, CHPhz), 7, 66 (s, SCOCEs). Example 41: 3-Cr t n y xymethy -7 - [2-hydr XY m no-2 (thien-2-y) - acetarn DO] - cePh-3-em-4-ca bom ure (synIsomeres). 2, 15 ml a molecular solution of 2-Dichloracetoxyimino-2 (thien-2-yl) - acetyl chloride (syn lsomeres) in Äthylaeetat became a solution of 0, 938 g 7 - Amino-8-crotonoyloxymethy1-ceph-3-em-4-carbonstlure - more diphenylmethylester in 15 ml Äthylacetat' the 0, 6 rnl propylene oxide enthielt' erased. After 30 min became the password with 2n hydrochloric acid, Natfiumb [carbon AF solution, water and saline solution washed, getmckriet and concentrated to 1.575 g of a foam. A solution of 1,464 g of this foam in 2 ml anisole became with Trifluoressigstlure with 20°Cbehandelt. After 5 min was concentrated the guild. The oily arrears were solved in ethyl acetate and the solution was washed with water. The ethyl acetate solution became on it 3mal with diluted Natriumbicarbonaüösung extra44 - No. 3273 hiert. United the excerpts were washed with ethyl acetate and brought then with concentrated hydrogen chloride ture on the pH value 2. The solution was extracted with ethyl acetate and the excerpt was washed, dried with water and saline solution and concentrated to a foam. As a result of additive from Athylacetat to this foam arose crystals, which became filtered off and thylacetat'gewaschen with j. One received the Titeloxim,) to +60° (c1, DMSO). UV spectrum: kmax (pH of 6 phosphate buffers) 261 Nm (16270). IR-Spekt over: Ymax (Nujol), the spectrum covers 17 5 (8-Lactam), 1783 (tmges tttigter ester), 1658 and 1545 (CONH) and 960 cm " 1 (Iran CH=CH). NMR spectrum: r (DMSO DS) the values cover 0.26 (Dublett 8 cycles per second, NH), 2, 38 and 2, 83 (2 Mulüpletts; Thienylprotonen), 6.29 and 6.49 (Dubletts, J 18 cycles per second; C-2 cycles per second), 8, 13 (Dubletts J /und 1 cycles per second; - CH=CH-C_. Hs). Example 42: 7 B [2-Hydroxyimino-2 (thien-2-yl) - acetamido] - 3 - (1ph enyltetrazol5-ylthiomethy!)- C eph3 ere4 carbomaure (syn isomer s). A solution of 2-Dichloracetoxyimino-2 (thien-2-y!)- acetyl chloride (syn isomer) in Methylendichlorid (7 ml 15 /dgen a password, an about 3, 5 mMol) became during 5 min an agitated solution of 1,779 g 7B-Amino3 (1-phenyltetrazol-5-y! thiomethyl} - eeph-8em-4-carbonslture-diphenylmethylester “hydrochloride and 1.5 ml propylene oxide in 25 ml dry Methylendiehlorid added. After w the solution was washed, getroeknet to eiterem 20minütigemRühren b egg 23°C successively with gesänftigtem Natriumbiearbonatwasser and Koehsalzl0sung (in each case valley) and evaporated to 2, 62 g of a Sehaumes. A solution of this Sehaumes in I0 ml benzene became by chromatography at silicagel with benzene: Ethyl acetate (10: 1) as Eluiermittel cleaned. Associated parliamentary groups were united and evaporated in the vacuum to dry ones, how itself 1, 2 " 1 g 7/3 [2Hydroxyimino-2 (thien2-yl) - AC etamido] - 3 (1ph enyltetrazol5-y! - thiom ethyl) - C eph3 ere-4carbonsäure-diphenylmethylester in form of a foam formed. A solution of this foam in 5 ml tri fluorine vinegar tute and 1 ml anisole was held for 5 min with 28°C and the solvents were removed in the vacuum with 40°C. The Rflckstand was solved in 50 ml ethyl acetate, which solution with Natriumbicarbonatlösung extracted and which angesltuert alkaline excerpt with 100 ml ethyl acetate übersehiehtet and with 2n hydrogen chloride-stubborn on the pH " value 2. The organic phase was washed separated, with water and saline solution, evaporated more getrockner and to 750 mg of a foam. A password of this Sehaumes in ethyl acetate was gefttgt to Petrolather, whereby 469 mg (29%) resulted the Titelvetbindung as pale-yellow solid, la] D -51,4° (C 0.91, acetone). UV spectrum: kmax (pH of 6 phosphate buffers) 264 Nm (19,500), IR spectrum: Ymax (Nujol) 8320 (NH), 1784 (B-lactam), 1722 (CO2 I: I) and 1674 and 1580 cm-1 (CO). NlvlR spectrum: r (DM80-d6) 0.26 (NH, Dublett, J 8 cycles per second), 2, 81 (s; F), 4.18 (C 7-H, Doppeldublett, J 5 and 8 cycles per second), 4.82 (C 6-H, Dublett, J 5 cycles per second), 5.89 and 5, 79 (quartet, J 13 cycles per second: C-3 CHe) and 6.28 (s; C=2 CHe). With the managing acylation as Amgangsmaterial more verwendeteAminoester in similar way was manufactured as the Aminoester, how the 5-Mercapto-2-phenyl-l, described in example 46, 8,4-oxadiazo! by 5-Mercapto-l-phenylte azo! one replaced. 7 - Amino-8 (1-phenyltetrazol-5-ylthiomethyl) - ceph-3cm4 formed carbonslture diphenylmethyl it terhydrochlorid, for UV spectrum: kmax (ÄiDH) 251, 5 Nm (e 10,000). IR spectrum: Umax (CHBrs) 1782 (- lactam) and 1 20 cm " 1 (COB). NMR spectrum: r (DM80-ds) the values cover 2, 32 (pH-n), 4, 78 (C-6 H and C-7 H), 5, 32 and 5, 68 (C-3 CHz, quartet, J 14 cycles per second) and 6, RST (c-2 CHe). Example 43: 7B- [2-Hydroxyimino-2 (thien-2-yl) - acetamido] - 3 (Imethylte azol5-ylthiomethyl) - ceph-8em-4carbonsäure (syn lsomeres). A solution of 2-Dichloracetoxyimino-2 (thien-2-yl) - acetyl chloride (syn isomer) in dry lviethylenehlorid (6 ml one! 5% solution, about 3 mMol) min became a solution of 1, 24 g 7 - - Amino-3 during 5 (1-methyltetrazol-5-ylthiomethy!)- eeph-3-em-4-earbonsäure-diphenylmethylester and 0.8 ml propylene oxide in 20 ml Methylendichlorid erased. After 30mtntltigem agitating with 23°C was added w s of eriges Natriumbtcarbonat and the Zwdphasenmischung further 80 min was gertlhrt. The organic phase was washed, dried separated, with saline solution and evaporated to 2, 0 g of a 8chaumes. A password of this foam EN 20 ml benzene became by Chromatograph/e at silicagel with benzene: Äthyla6etat (5: I) as E1uiermittel cleaned. Associated parliamentary groups were united and evaporated in the vacuum, whereby itself 1, 68 g 7B [2-Hydroxyimino-2 (tbien-2-yl) - acetamido] - 3 (1-methyl tetrazol5-ylthiomethyl) - C eph3 ere-4carbonstture-diphenylmethylester inForm a foam resulted in. A password of this foam in 6 ml Trifluoressigstlure and 1,5 ml anisole was held for 5 min with 23°C and the solvents were removed with 40°C (2 mm). The Rilckstand was solved in 30 ml ethyl acetate and the solution with NatriumbicarbonaflSsung was extracted. The alkaline excerpt was over-laminated with ethyl acetate and angmäuert with 2n Chlorwassetstoffstiure to the pH value 2. The organic phase was separated, washed with water and saline solution and evaporated the solvent in the vacuum. The Rtlckstand was solved in acetone, the lung was treated with something activated charcoal and by a K [eselgurschicht fi1 iert. The filtrate was dried and evaporated to I, 085 g of a foam. A solution of this 8chaume in Äthyiacetat was cast in Petrolltther, whereby 852 mg (71%) resulted the Titelstture in form of a colorless amorphous Fesistoffes, [A -90° (C 0, 91, acetone). UV spectrum: Xmax (pH of 6 phosphate buffers) 267, 5 Nm (“18,000). IR spectrum: Vmax (Nujol) 8290 (NH), 1 ' 780 (B-lactam), 1720 (COzH) and 1670 and 1530 cm-i (CO). NMR Speki over: I " (DMSO-d6) the values cover 0.25 (NH, Dublett, J 8 cycles per second), 4, 14 (C-7 H, Doppeldublett, J 4, 5 and 8 cycles per second), 4, 79 (C-6 H, Dublett, 1 4, 5 cycles per second), 6, 08 (C). On lhnIiche way were harsh-placed: B eisptel 44: 7] - [2-Hydroxyimino2 - (fur2-yl) - acetamido] - 3 (1methyltetrazol-5-yl thiomethyl) - ceph-3-em-4-carbonstture (syn isomer), [A -102° (C 0.9, acetone). 90 UV spectrum: kmax (pH of 6 phosphate buffers), 2 3, 5 Nm (“20,700). -1 IR spectrum: Umax (Nujol) 8280 (NH), 1780 (- lactam), 1 ' /20 (COzH) and 16q4 and 1530 cm (CONH). NMR Spekttum: r (DMSO-d6) the values cover 0, 38 (NH, Dublett, J 8 cycles per second) and 95 6, 0 (C s). The output ester filr the Acyiierungen of the examples 43 and 44 was manufactured as follows: a) 3 (1-M ethyltetra ol5-ylthiomethyl) - 7/3 (2thienylacetamido) - ceph3 cm-4carbonsttur ediph more enylmethylester. A lung of 17, 505 g 3-Brommethyl-713 (2-thienylacetamtdo) - ceph - em-4-carbonstture-diphenylmethylester and 9.486 g 5-Mercapto-l-methylte razol in 250 ml dry tetrahydrofurane were gertibrt with 10°C and shifted wtthrend 5 min with a Lgsung by 4,16 ml Triathylamin in 50 ml dry tetrahydrofurane. The received Smpension was gertlhrt further 45 min (whereby the temperature could rise to for instance 20°C) and afterwards protecting 5 min to a gertlhrten mixture of 50 ml 2u hydrogen chloride-sour, 700 ml water, 700 ml Kochsalziösung and 1.5 i Äthyiacetat geftlgt. The organic phase was washed separated, with 2n hydrochloric acid, water and KochsalzlOsuug, treated with something Akttvkohle and by a layer from K [eselgur filtered. The filtrate was dried and evaporated to 20,6g of a foam. The foam in 200 ml hot methanol was drawn and cooled the solution, whereby 14, 392 g (77, 5%) of the ester resulted in the form of colorless panels. UV-Speklrum: kmax (ÄtOH) 264 Nm (“8,700). IR-Spekt; over: Vmax (CHBrs) 9420 (NH), 1780 (5-Lactam), 1710 (COzR) and 1680 and 1502 cm-1 (CONH). NMR Spekt; over: r (CDCls) the values cover 3.40 (NH, Dublett, J 9 cycles per second), (C-7 H, DoppeldubletL J 5 and 9 cycles per second), 5.02 (C-6 H, Dublett, J 5 cycles per second), 6.19 (CHs). b) 7 - A mino3 (1methyltetrazol5-ylthiomethyl) - C eph3 ere-4carbonsttur e-diphenylmethyl esters. A suspension of 416 mg phosphorus pentachloride in 10 ml dry Methylendichlorid was gertthrt with 23°C and a solution of 0, 16 ml Pyridin was added. The warm suspension was gertthrt 10 min and gektthlt on 0Oc and wtthrend 10 min with a Lgsung of 619 mg 3 (! - Methyltetrazol-5-ylthiomethyl) - TB - (2-thienylacetamido) - ceph-3-em-4-carbonsäure-diphenylmethylester in 15 ml dichloromethane treats. After further 45mintltigem agitating, whereby the temperature to 23°C rise konute, became the solution wlihrend 5 min an agitated and a geküblten (0°C) mixture of 5 ml methanol and 15 ml Methylendichlorid erased. The received solution was agitated further 10 min and washed with 20 ml in Chlorwässerstoffstture and gerflhrt 30 min with 50 ml gesttttigter Natriumbicarbonaüösung. The organic phase was separated and washed with 25 ml satisfied wtisseriger Natriumbicarbonatlösung and treated with something Aküvkohle. The mixture was filtered through eineKieselgurschicht and the filtrate was evaporated to 640mg of one gummiartigeu l Iasse, which became to angerieben with 20 ml ethers, whereby itself 403 mg 481, 5 /o) the amine in form one nearly wei EN of solid resulted in. UV spectrum: Xmax (CHC ½) 268, 5 Nm 4E 7,700). IR spectrum: Vmax (CHBrs) 3416 and 3350 4NI-I2), 1780 (eat Iactam) and I 20 cm-t (COzR). NMR Spektmm: r (CDC ½) the values cover 8, 00 and 8, 18 4C-6 H and C-7 H, two Dubletis, I 8 cycles per second), 6.14 (CHz) and 7, 89 (Nllz). Example 45: In a similar way as in example 43 the acylation of 73-Amino-3 (5-methyl-1, 8, 4-thiadiazolyl-2) resulted in - thiomethyl-ceph-3ere-4carbonsäure-diphenylmethylester with syn-2-Dichloracetoxyimino-2 (fur-2-yl) - - acetyl chloride and amchließende splitting off of the group of protection the syn isomers of the 7B [2-Hydroxyimino-2 - (fur-2-yl) - acetamido] - 3 (8-methyl-1, 3, 4-thiadiazol-2-yl) - thiomethyl-ceph-3ere-4carbonsäure, NMR Spek over: - (DMSO-d6) the values cover 0.36 (D, I 9 cycles per second, NE), 9 23, 3,39 (25, antiprotons), 4.19 (dd, I 5 and 9 cycles per second, C-7 H), 28 4.83 (D, I 5 cycles per second, C-6 H), 8.48, 8.90 (q, J 14Hz, C-8 CH2), 6.21, 6.44 (q, I 18Hz, C-2 cycles per second), 7th s3 (s, CHs). Example 46: 71B- [2-Hydroxyimino - 2 - (thien - 2-yl) - acetamido] - 8 (5-phenyI1, 3, 4oxadiazoI-2ylthiomethyl) - ceph - 3ere-4-earbonsättte (syn LSO more mer it). A solution erased by 2-Dichloracetoxyimino-2-4thien-2-yl) - acetylehlorid 4syn-Isomeres) in Methylendichlorid 47 ml a 15%tgen solution) wtttde during 5min to an agitated solution of 1,779 g 3-Amino-3 (5-phenyl1, 3, 4-oxadiazol-2-ylthiomethyl) - ceph-8em-4-carbom, “ture diphenylmethylester hydrochloride in 5 ml propylene oxide in 25 ml dry Methylendichlotid. After further 30minütigemRtlhren L was washed, dried ung with satisfied NatriumbicarbonatliSsung, water and saline solution (in each case 20 valley) and evaporated to 2, 84 g of a foam. A password of this foam in 10 ml benzene became by Chmmatographie outer silicagel with benzene: Ethyl acetate (10: 1) as Eluiermittel cleaned. Associated parliamentary groups were combined and in the vacuum to dry ones evaporated and the arrears with 25 ml ethers angerieben, whereby itself 870 mg 441%)” /iß [2-Hydroxyimino-2 (thien-2-yl) - acetamido] - 3 (8-phenyl-1, 8, 4-oxadiazol -2-ylthiomethyl> - ceph-3-em-4-carbonsäure-diphenylmethylester in form of colorless prisms resulted in. A suspension of 810 mg of this ester in a mixture of 3 ml tri fluorine acetic acid and 0, 8 ml Aniso! one geschtlttelt with 23°C, thus are enough, until the solid was drawn (about 10 min). The reagents were evaporated with 40oc (2 mm) and the arrears were solved in Äthylaeetat. The solution was extracted with aqueous Natriumbicarbonatlösung, the alkaline excerpt was flberschichtet with ethyl acetate and addressed with 2nChlorwasserstoffsaureauf the pH value 2. The organic phase was separated, washed with water and Kochsalzl0sung and evaporated the solvent in the vacuum. The arrears were solved in acetone, which filters solution treated with something activated charcoal and dumh a Kieselgurschicht. The Fillrat was dried and evaporated to 470 mg of a foam. A password of this foam poured in ethyl acetate in PE more oläther, whereby itself 410 mg 466%) the title connection in form of a colorless amorphous solid resulted in,] 3 -118° (c1, 08, acetone). UV-Speklrum: Xmax (pH of 6 phosphate buffers) 274 Nm (“28800). -1 IR spectrum: Vmax (Nujol) 3280 (NH), 1786 (T3 lactam), 1720 (COzH) and 1672 and I580 cm (CONH). NMR spectrum: r (DMSO-d6) the values cover 0.24 (NH, Dublett, 1 8 cycles per second), 4.15 (C-7 H, Doppeldublett, J 4, 5 and 8 cycles per second), 4.78 (C-6 H, Dublett, J 4, 5 cycles per second). The Aminoester used for those-managing acylation was manufactured as follows: 78A mino3 (5phenylI, 3,4oxad iazol2-ylthiomethyl) - ceph3 ere-4carbons Iturediphenylmethyl ester - hydrochloride. A solution of I 0, 07 g 3-Brommethyl-q8-formamido-eeph-3-em-4-carbomäure-18-oxyd-diphenylmethylester and 3.564 g 5-Mercap -2-phenyl-l, 3,4-oxadiazol in 250 ml dry N, N-Dim4thylformamid was agitated with 0°C and treated wtlhrend I0 min with a solution by 3,2 ml TritLthylamin in 20 ml N, N-dimethylformamide. The received solution was agitated further 2 1/2 h, whereby the temperature could rise to for instance 20°C; subsequently, the solvent pray 40°C in the vacuum evaporated. The arrears were divided between 250 ml Methylendichlorid and 150 ml water and the organic phase was separated, washed and dried with 2n hydrochloric acid, water and saline solution; the solvent became abgeI0 pulled, whereby itself 12, 076 g 78-Formamido-3 (5-phenyl-1, 3, 4-oxadiazol-2-ylthiomethyl) - ceph-3-em-4-carbonsllure-diphenylmethylester-18-oxyd in form of an orange Feslstoffes resulted in. A solution of this material in 250 ml dry Methylendichlorid was gerflhrt with -20°C and treated during I0 min with a solution of 5, q ml Phosphortlibromid in 25 ml dichloromethane. The received solution was agitated a further hour with -10 to -15°C and amchließend during 10min to a gertthrten and a gektlhlten (0°C) mixture of Methylendichlorid and gestittigter Natriumbicarbonadösung gefttgt. The Zweiphasemystem was agitated a further hour with for instance 23oc, which became organic phase separated, with geslittigt Natriumbicarbonatl0sung and Koehsalzlösung washed and with something activated charcoal treated. The suspension was evaporated filtered, the filtrate dried and in the vacuum, whereby itself i1,231 g 7/3-Formamido-3 (5-phenyl], 3, 4-oxadiazol-2-ylthiomethyl) - ceph-3em-4-carbonstiure-diphenylmethylester in form of a Scha mes resulted in. A suspension of this foam in a mixture of 100 ml methanol and] 00 ml ether was agitated with 0°C and treated wtihrend 20 min with 3, 4 ml Phosphoroxychlorid. After further hour agitating the suspension was poured into 200 ml ethers, whereby 8 resulted, qOq g (7T] o) of the title hydrochloride in form of a light brown solid. UV spectrum: Xmax (ÄtOH) 222 Nm (“21200). IR spectrum: Vmax (Nujol) 1790 (8-Lactam) and 1220 cm-1 (COzR). NIvIR spectrum: r (DMSO D “) the values cover 4.70 (C-6 H and C-7 H), 5.42 and 5, 65 (C-3 CH2 quartet I 13 cycles per second). Example 47: 3Ae etoxymethyl78 [2tlthoxycarbonyloxyimino - 2 - (thien2-yl) - acetamido] - ceph3 cm-4earbons ur e (syn isomer), to a solution of 0, 6 g Natrium-3-ac etoxymethyl78 - ['hydroxyimino-2 (thien-2-yl) - aeetam ido] - eeph -3-em-4-carboxylat (syn isomer) in 25 ml satisfied aqueous Natrtumbicarbonatlösung was added a password of 1, 5 ml Chlorameisens more uretlthylester in 20 ml ethyl acetate and the whole 1 min was violently vibrated. The Bicarhonatphase was separated and geschtlttelt with a second portion (1.0 ml) of Chlorametsenstiureäthylester in ml ethyl acetate. The Bicarboaatphase was washed, angestiuert separated, with ethyl acetate and extracted with ethyl acetate. The united excerpts were dried and concentrated on approximately 5 ml. The concentrate became more oläther under agitating 200 ml PE (kp. 40 to 60°C) dripped. The ausgeftlllte Fesistoff was filtered and dried; 0, 47 g of the title connection,] D +420 (C 0, 9, DMSO) resulted. UV spectrum: Xmax (pH of 6 phosphate buffers) 265 to (16,900). IR spectrum: max (Nujol) 3290 (NH), 1784 (B-lactam), 1740 (acetate), 1690 and 1550 cm " 1 (CONH) NMR Spek over: “(DMSO D “) the values cover -0, 16 (D; 1 9 cycles per second; NH), 2, 08, 2, 53, 2, 74 (three of quartet; Thienylprotonen), 5, 7o (q; I 8 cycles per second; - C__H2 C), q, 96 (s: OAc), 8, 72 (t; J 8 cycles per second; - CH CzC_.Hs). Example 48: 7 - [2-A cetoxyimino-2 (thien-2-yl) - acetamido] - 3aeetoxymethyl-eeph3 em-4-carbonst [ur e (of syn isomer). A solution of 0, 7 g Natrium-3-acetoxymethyl78 [2-hydroxyimino-2 (thien-2-yl) - acetamido] - ceph -3-em-4-carboxylat (syn isomer) in 20 ml water was gertlhrt with 50tal ethyl acetate and the pH value de wltsserigen layer with 2n hydrochloric acid was stopped to I. The ethyl acetate phase was combined, dried separated, with an ethyl acetate extraction the wasserigenPhase and evaporated under formation of an oil. The oil in 28 ml ethyl acetate one drew, which contained 2, 1 g Pyridin, and drop by drop under agitating at ambient temperature with a solution of! , 4 g acetyl chloride in 14 ml ethyl acetate shifts. After! 2mintltigem Rtlhren was poured the mixture in 2n hydrochloric acid, which extracts ethyl acetate layer separated, with water washed and with a gestttfigten wttssetigenNatriumbicarbonatlösung. The united excerpts were washed, headed for with ethyl acetate (2n of hydrogen chloride/lure) and 3mal with ethyl acetate extracts. - 48 - the Nr.32q875 combined organic excerpts was dried, on 5 ml concentrated and to 250 ml PetroI, 'more tther (kp. potted to 60°C). The amgefltllte solid was filtered and dried; one received 0, 5 g (68%) the TitelSff'ure, UV-8pek over: k of max (pH of 6 phosphate buffers) 265 Nm (15,500). IR spectrum: Umax (Nujo!) 32q0 (NH), lq80 (B-lactam), lq86 (acetate), 1680 and 1540 cm " z (CONH) NlvIR. - Spek over: “(DMSO D “) the values cover - 0, 15 (D; J 9 cycles per second; NH), 2, 08, 2, 54, 2, 78 (Thien-2-yl-pmtonen), q, q9 (s; AGAIN), I0 q, 94 (singlet, OCOCHs). Example 49: 3Aeetoxymethylq/3 [2 - (2-Chlor Ithylcarba moyloxyimino) - 2 - (thien2-y [) - acetamido] - ceph3 em-4-carbom ure (syn isomer it). A solution of 0,89 g Natr [um-3-acetoxymethyl-qB [2-hydroxyimino-2 (thien-2-yl) - acetamMo] - ceph -8-em-4-carboxylat (syn lsomeres) in II ml dimethylformamide, which contained 0, 22 g tri methyl amine, became m [t 0, 25 g 2-Chlor Ithylisocyanat treated. The solution was left untouched at ambient temperature 30 min and afterwards a further hour with 5°C. It became into cold (5°C) 2n hydrochloric acid poured, extracted and the united the excerpts with 2n hydrochloric acid and afterwards with water were washed to 8mal with ethyl acetate, extracted whereupon 3mal with more coldly (5oc) satisfied aqueous Nalxiumbicarbonatlösung. The united aqueous excerpts were washed, headed for with Äthylaeetat (2n of hydrogen chloride, 'iure) and rapidly with ethyl acetate extracts. The united excerpts were dried, concentrated on approximately 5 ml and the Konzenkat to 250 ml Petrol more lher (kp. 40bis 60°C) gelzopft. Ausgef llteFesi toff one filtered and one dried; one received D +38° (C O, 7, DMSO) to 0, 8 g (76a/o) of the title series, is]. UV-Spek over: X of max (pH of 6 phosphate buffers) 264 Nm (17200). IR spectrum: Viax (Nujol) Iq86 (B-lactam), 1784 (Aeetat), 1682 and 1508 cm " I (CONH), NMR Speklrum: I " (DMSO-d6) the values cover - 0, 12 (Dublett; 9 cycles per second; NH), 2, 12, 2, 56, 2, 74 (three quartet; Thienylpmtonen), q, 97 (s; OCOCH3). Example 50: N {QA - [2-Hydmxyimino2 (fur-2-yl) - ae etamido] - ceph3 ere8 ylmethyl} - 4 Icarbamoylpyrid inium4 - carboxylate (syu lsomeres). A solution of 2, 5 g 3-AeetoxymethylqB - [2-hydroxyimino (fur-2-yl) - acetamido] - eeph-3em-4-carborsäure and 2, 5 g ISO nicotine amide in water under nitrogen 3 1/2 h to 65 to q0°C was heated up, which became cooled mixture abw i by a column with AGIX8-Harz (Aeetafform) led and with water eluiert. Parliamentary groups were combined on the basis of the Elektrophoretogramme and gefriergetIocknet to a white powder, which was washed to the title connection well with acetone and under education by 0, 834 g (29%) was dried, is] D -61° (C 0, 84, DMSO). UV spectrum: X of max (pH of 6 buffers) 267, 5 Nm (19,500). IR-Speki over: Umsx (Nujol) 3840 (NH), lqq2 (B-lactam), 1680 and 1560 (CONH), 1608 cm-i (COz "). NlvIR Speklrum: I " (d6 - DMSC) the values cover 0.40, 1.26, 1, 50 and], 75 (Multipletls, aromatic leptons), 1.26 and 1, 75 (spreads singlet; CONH2), 4, 26 (Mulüplett C-7 H), 4.28 and 4, 77 (C-3 CHz), 4.88 (D, J 5 cycles per second, C-6 H). Example 51: 8A eetoxymethyl7/B [2hydroxyimino2 (pyrid4 yl) - AC etamido] - ce [Jh8 ere-4carbonsäure, tri fluorine vinegar uresalz (syn isomer). a) 3-Acetoxymethyl-TB (pyrid-4-ylacetamido) - ceph-3-em-4-carbons lure tert, ethyl esters. A suspension of 6,0 g pyrid-4-ylace Ichlorid hydrochloride in 50 ml ethyl acetate, which contained 12 ml Pmpylenoxyd, was gerflhrt, in ice geldlhlt and drop by drop with a solution of 5, 0 g 3-Acetoxymethyl -7B-amino-ceph-8-em-4-carbons, 'iure tert. more butylester in 50 ml ethyl acetate treats. The mixture was geriihrt h with 20°C and washed afterwards with ges/ttügter Natriumbicarbonatlösung and extracted with 2n Chlorwasserstoffstture. The zaserige excerpt was washed with ethyl acetate, neutralized with ges/ltügter Natriumbtcarbonatl0sung and extracted with ethyl acetate. The excerpt was washed with water, dried over Magnesinmsulfat and evaporated to small quantity, on which the crystallization began. The crystalline solid became good with Petroltither (kp. 40 to 60°C) washed and under education dried by 5,4 g (80a] o, related to the amine) of the title ester in form of a leather-colored powder. Some of 250 mg was recrystallized from ÄthYöacetat under education by 170 mg of white needles, IC] D+94 (C 0.9, DMSO). UVSpektrnm: X of max (ÄtOH) 256, 5 Nm (“9,900). IR spectrum: Vmax (CHBrs) 8412 (NE), 1784 (8-Lactam), 1736 (OAc), 1722 (CO2 R). 1690 and 1512 cm-1 (CONH), NMR spectrum: T (DS-DMSO) 0.81 (D, i 8 cycles per second; NH), 1.47 and 2, 68 (2d, J 5 cycles per second; aromatic protons), 4.27 (q, J 8 and 5 cycles per second; C-7 H), 4, 86 (D, J 5 cycles per second; C-6 H), 5, 01 and 5, 36 (2d, J 13 cycles per second; C-3 CH2), 6, 38 (s; CHzCONH), 6.39 (s; C-2 CH2), 7.96 (s; OCOCHa) and 8, 50 is; C (C]. b) 3-Acet xyme hy -7 - [2-hydr xyim n - (pyrid-4-y) - acetami] - cephem-4-carb LV ure more tert.butylester. A I/Ssung of 3, 0 g 3A cetoxymethyl76 - (pyrid4-ylacetamido) - ceph3 ere-4Carbonsäure etext. more butylester in 80 ml acetic acid was agitated, briefly on ice cooled and drop by drop during 3 to 4 min with a/. , Ssung of 1, 38 g Natriumnitrit in 10 ml water treats. The mixture was agitated 30 min with 20°C and afterwards with water diluted and with ethyl acetate extracted, the organic excerpt with gestitügter Natriumbicarbonaflösung and water washed and over Magnestumsulfat dried, by Eindampfenbis nearly to dry ones received one arrears, that in the minimum volume from acetone was drawn and to more ger {lhrtem Petrol more ther (kp. 40 to 60°C) dripped, the received Fes toffwurde was collected, washed with Pe9.5 trol more ither and dried under education by 2,9 g (91%) of the Titeloxims in form of a white powder, itself in the NMR Spekl over than a yn-/anti-mixture (80: 70) proved. 2, 5 g Oximgemi were atographiert on Sfliciumdioxydgel chrome and with methanol chloroform (I: 49) eluiert, whereby 1, 09 g (44 /0 of the mixture) of the title connection (anti-isomer) resulted. By further EIuiemng with Methano! /Chloroform (1: ) one kept a material, that drawn to 49 in acetone and to gertihrtem Petrowitzer (kp. 40 to 60oc) one geftlgt; one received 0 of the mixture) 3-Acetoxyme thyl78 - [2-hydroxytmtno (pyrid4 yl) - to 0, 81 g (32a] AC eta mido] - ceph3 ere4 carbonsaur etert. b nW1 it more ter (syn isomer), iclD +57° (C 1.11, DMSO). UV spectrum: Xmax (ÄtOH) 253, 5 Nm (17,600). IR spectrum: Vmax (Nujo!) 3220 (NH), 1784 (6-Lactam), 1744 (OAc), 1710 (COzR), 1640 and 1526 cm-1 (CONH). NlviR spectrum: r (d6 - DM80) -2.26 (s; NOH), 0, 27 (D, J 8 cycles per second; NH), 1, 33 and 2, 47 (2d, aromatic protons), 4, 04 (q, J 5 and 8 cycles per second; C-7 H), 4, 71 (D, J 5 cycles per second; C-6 H), 4.98 and 5.33 (2d, J 13 cycles per second: C-3 CI4z), 6.20 and 6, 53 (2d, J 18 cycles per second; G-2 CHz), 7.94 (s, OCOCHa), 4.5 8, 49 [% C (CH]. c) 0, 6 g syn tert. Butylesters in 15 ml tri fluorine vinegar ture were left to 15 min with 20°Cstehe and evaporated afterwards to dry ones. The Rtlckstand was treated with acetone and the I ungsmittel in the vacuum was removed, on which this procedure was repeated. The Rtlckstand in acetone became slow Petroltlther (kp. 40 to 60°C) added. The precipitation was collected and dried; one received Trifhroressigsanresalz of the 3Acetoxymethyl78 - [2-hydroxyamino-2 (pyrid-4-yl) - to 0, 66 g (99%) acetamido] - ceph3 em-4carbonsaure (syn Isomet it), icl] D +47, 5° (C 0.84, DMSO). UV spectrum: Xmax (pH of 6 buffers) 248, 5 Nm (“17,000). IR spectrum: Vmax (Nujol) 3250 (NH), 1772 (/3-Lactam), 1720 (OAc), 1660 (CFsCOa'), 1660 and 1530 cm " 1 (CONH). NMR-8pektrum: T (d6 - DMSO) 0, 16 (D, J 8 cycles per second; NH), 1.14 and 2, 20 (multiplet, aromatic protons), 4.06 (q, J 5 and 8 cycles per second; C-7 H), 4.71 (D, J 5 cycles per second; C-6 H), 4, 92 and 5, 24 (2d, I 13 cycles per second; C-CH2), 6, 25 and 6, 61 (2d, I 18 cycles per second; C-2 CH2), 7, 93 (s; OCOCHs).