PL114521B1 - Process for preparing sulfoxides of 3-methylenocepham - Google Patents

Description

The subject of the invention is a process for the production of 3-methylenecepham sulfoxides, which are valuable intermediates in the synthesis of cephalic antibiotics. Penicillins, and recently also cephalosporins, are of interest due to their high degree of bactericidal activity and are widely used in the treatment of infectious diseases in humans. A number of studies have also been undertaken to modify these compounds, looking for even more active β-lactam antibiotics. Recently, R. R. Chauvette and P. AND. Pennington used 3-methylenecephams to prepare both 7-aminodezacetoxycephalosporanic acid and its biologically active Jbrun derivatives! of Organic Chemistry, 3S, 2994/19737, as well as the new 3-methoxy and 3-halo-cephene / Journal of the American Chemical Society, 96, 4986 / 1974A. In each of these cases, the intermediate 3- Methylene cephams from cephalosporic acid, first by treating cephalosporanic acid with nucleophilic sulfur derivatives such as thiourea, thiobenzoic acid, potassium xanthate or sodium thiosulphate followed by reduction of the corresponding 3-thiomethyl cephem derivatives with Raney nickel the formation of ethanol or zinc in a mixture of formic acid and dimethylfermamide. Due to the versatility of '3-methylenecephams as intermediates for the production of new antibiotics, alternative methods of producing such compounds from cheap and easy starting materials have been sought from femora. The method according to the invention It is a new process in which 3-methylenecepham sulfoxides of the general formula I as defined below are prepared by intramolecular ring closure in penicillin sulfoxide single-ring azetidinone-2-sulfinyl chlorides and sulfinyl acid derivatives, sulfinate esters, thiosuKynate esters, sulfinamides and sulfinmrides using Frie defa-Crafts catalysts or cation-forming agents by metathesis. Some of the azetidinesulfinic acid derivatives which are the starting compounds are novel compounds. The method of producing 3-methylenechamine sulfoxides of general formula I, according to the invention, consists in a cyclization reaction of a compound of general formula II carried out with the aid of a Lewis acid Frtelle-Crafts catalyst, such as a protic Bronsted acid, or a cation-forming agent by reaction. metathesis in an inert anhydrous organic solvent or by dissolving the compound of formula II in an organic Bronsted acidosis. In elevated formulas, * H is the group; protecting @ rupe (carboxyl), R / has the same meaning as R or is * hydrogen, Rt is an imide group of the weight 3, in which Ri is an alkenylene group 114 521114 521 3 o 2 - 4 carbon atoms, an alkylene group with 2 - 4 carbon atoms, a 1,2-phenylene group or a 1,2-cyclobexenylene group, or RA is an amide group of the formula R8G / O / NH-, where RS is hydrogen , an alkyl group with 1 to 3 carbon atoms, a chloro-methyl group, a 3- (2-chlorophenyl) -5-inethyl group, or a s-2-s-4-zolyl group / or R 8 is benzyloxy, β-nitrobenzyloxy, 2,2,2- -trichloroethoxy? J Ill-rzed. -butoxy or 4-methoxybenzyloxy, or R8 is R ", being a 1,4-cyclohexadienyl group, a phenyl group, optionally substituted with one or two substituents independently representing a halogen atom, a protected hydroxyl group, a nitro group, cyano, trifluoromethyl, alkyl 1 to 3 carbon atoms and alkoxy 1 to 4 carbon atoms, or R 8 is an aralkyl group of the formula R "- (0) m-CH 2 - in which R" is as defined above, and m is 0 or 1, or R8 is a substituted arylalkyl group of formula IV, where R '"is as defined above for R", and W is a protected hydroxyl group or a protected group. amino group, R4 can also represent an imide group of the formula where R "and m are as defined above, and R" 2 is an alkyl group with 1 to 3 carbon atoms, a haloalkyl group with 1 to 6 atoms. carbon, 1-3 carbon alkoxy or trichloroethoxy group, or RA is an imide group azolidinyl of the formula 6, in which R "is as defined above, and Y is an acetyl or nitroso group, X is a chlorine atom, a bromine atom, a group of the formula -OR4, in which R4 is a hydrogen atom, an alkyl group with 1-10 carbon atoms, arylalkyl group with 1-3 carbon atoms in the alkyl part, chloro-alkyl group with 1-6 carbon atoms, or X is also a group of formula -SR5, where R 'is an alkyl group of 1-6 carbon atoms, an aryl or arylalkyl group with 1-3 carbon atoms in the alkyl part, or X is a group of the formula -Ni / Re / R7, where R6 is hydrogen and R7 is hydrogen, the group R "as defined above meaning or also a group of the formula -NHR8, in which R8 is an amino carbonyl, alkylaminocarbonyl group, with 1-3 carbon atoms in the alkyl part, alkoxycarbonyl with 1-3 carbon atoms in the alkoxy part, alkylcarbonyl group with 1-3 carbon atoms of the alkyl or tosyl moiety, or wherein R6 is -COOR9 or -CORfl, and R7 is denotes a group of the formula -NHCOOR9 or of the formula -NHCORg, in which R9 is a C1-C6 alkyl group or a phenyl group, or where R1, R7 and the nitrogen atom to which they are attached together form an imide group of formula III in which R2 has the meaning given above, wherein if R8 is -COOR9 or -COR9 and R7 is -NHCOOR9 or -NHCORg then Rf is additionally a heteroarylmethyl group of formula B. "" CHt-, where R "" represents 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-thiazolyl or 5-4-isoxazolyl, with the restriction that when X is bromine, then R4 is only an imide group of formula 3; and when a double exchange cation forming agent or a Lewis acid is used, X is only chlorine or bromine; and if R is an acid removable carboxyl protecting group, the product is 3-methylene-4-carboxylic acid sulfoxide. The term "1-3 carbon atoms" denotes a methyl, ethyl, n-propyl or isopropyl group. The term "1-10 carbon atom alkyl" includes methyl, ethyl, propyl, isopropyl, cyclohexyl, and the first groups. -butyl, heptyl, octyl, isooctyl, decyl or menthyl. The term "1-6 carbon haloalkyl group" includes such groups as chloromethyl, gunmethyl, iodoethyl, 2-chloropropyl, 2-chlorocyclohexyl or 2-chlorobutyl. The term "aralkyl group" having 1 to 3 carbon atoms in the alkyl portion includes benzyl, 2-phenylmethyl, 2-phenylpropyl, 4-chlorobenzyl, naphthylmethyl or 3- (2-nitrophenyl) propyl groups. Examples of "alkoxycarbonyl groups having 1-3 carbon atoms in the alkoxy portion" are groups such as methoxycarbonyl, ethoxycarbonyl and isopropoxycarbonyl. Examples of "chloromethyl" groups are such groups as chloromethyl, bromomethyl or iodomethyl. The imide groups when R 2 is an alkenylene group with 2 to 4 carbon atoms are maleimide, 3-ethyl maleimide or 3,4-dimethyl maleimide. The imide groups when R is 1,2-cyclohexylene or 1,2-phenylene are 3,4,5,6-tetrahydrophthalimide or phthalimide groups, respectively. If R "is a substituted phenyl group then it may be a monosubstituted or disubstituted halophenyl group such as 4-chlorophenyl, 2,6- 40 -dichlorophenyl, 2,5-dichlorophenyl, 3,4-dichlorophenyl, 3-chlorophenyl, 3 -bromophenyl, 4-bromophenyl, 3,4-dibromophenyl, 3-chloro-4-fluorophenyl or 2-fluorophenyl, or a phenyl group with a protected hydroxyl substituent, such as 4-benzyloxy, 3-benzyloxyphenyl, 4-III-row -butoxyphenyl, 4-tetrahydro-pyranyloxyphenyl, 4- (4-nitrobenzyloxy) phenyl, 2-phenacyloxyphenyl, 4- benzhydroxyphenyl or 4-triphenylmethoxyphenyl; or a nitrophenyl group such as a 3-nitrophenyl or 4-nitrophenyl group, and also a cyanophenyl group, for example 4-cyanophenyl, and a phenyl group having one or two alkyl substituents, such as 4-methylphenyl, 2,4-55-dimethylphenyl , 2-ethylphenyl, 4-isopropylphenyl, 4-ethylphenyl or 3-n-propylphenyl, or also a phenyl group having one or two alkoxy substituents and for example 2,6-dimethoxyphenyl, 4-methoxyphenyl, '3-ethoxyphenyl, 4-isopropoxyphenyl, 4- III-order. -butoxyphenyl or 3-ethoxy-4-methoxyphenyl group. The substituent R "also denotes disubstituted phenyl groups in which the substituents may be different, for example, group 65 3-methyl-4-methoxyphenylpwa, 3-chloro-4-benzyl-114,521 5-xphenyl, 2-methoxy-4-bromophenyl. , 4-ethyl-2-methoxyphenyl, 3-chloro-4-nitrophenyl, 2-methyl-4-chlorophenyl and similar disubstituted phenyl groups with different substituents. The term "protected amino" refers to amino groups substituted with one of the commonly used amino-blocking groups, such as the III-order group. -butoxycarbonyl (t-BOC), benzyloxycarbonyl group, 4-methoxybenzyloxycarbonyl group, or 4-u-nitrobenzyloxycarbonyl, 2,2,2-trichloroethoxy carbonyl or 1-carbomethoxy-2-propenyl prepared from methyl acetoacetate. Also suitable are the protecting groups for the amino groups described in publication I. IN. Berton "Protective Groups in Organic Chemistry", J. F. IN. McOmie, Ed. Pleum Press, New York, 1973, Chapter 3; The term "protected hydroxy" refers to readily cleavable groups formed from the hydroxyl group such as formyloxy, chloroacetoxy, benzyloxy, benzhydryloxy, trityloxy, 4-nitrobenzyloxy, trimethylsilyloxy, phenaarexyloxy, and phenylaloxyloxy. -butoxy, methoxymethoxy or tetrahydropyranyloxy. This term also covers other groups that protect the hydroxyl functions, mentioned in publication C. B. Reese in the above-mentioned work "Protective Groups in Organic Chemistry", Chapter 3. The term "carboxyl protecting group" refers to groups commonly used to block or protect a carboxylic acid functional group in reactions involving other functional groups on the compound. Such groups protecting carboxylic functions are known for their ease of decomposition by hydrolysis or hydrogenation methods to the corresponding carboxylic acids. Examples of ester protecting groups for a carboxyl group are groups such as methyl, tertiary. -butyl, benzyl, 4-methoxybenzyl, C2-C6 alkanoyloxymethyl, 2-iodoethyl, 4-nitrobenzyl, diphenylmethyl (benzhydryl), phenacyl, 4-halophenacyl, dimethylallyl, 2,2,2-trichloroethyl trialkylsilyl with 1-3 carbon atoms in each alkyl group or succinimidomethyl group. Other groups protecting carboxyl functions, such as those described by E. Haslam's "Protective Groups in Organic Chemistry", Chapter 5, also 50 proved to be relevant. The nature of the ester-forming group is not critical. If the carboxyl group is protected in the starting azetidine-kinic acid derivative of formula II, an acid labile group such as 4-methoxybenzyl, benzhydryl, III order. -butyl or trialkylsilyl, then the product of the citization according to the invention is obtained in the form of 3-exomethylene eephaic acid sulphate. If the starting compound contains similar, acid-labile protecting groups of the H-droltsylate groups of the antennae, such groups are usually destroyed in the acidic conditions of the cyclization process. The removal of acid-labile protecting groups in the presence of acids under the process conditions of the invention is not a significant feature of the process of the invention. Protective groups are present in the azetidinone derivative starting material of the invention because of the need to protect its precursors, which are penicillin sulfoxides, during the production of azetidinone sulfinyl halides. Thus, the primary purpose of the protecting groups is to protect reactive functional groups during the preparation of the starting compounds. The nature of the protecting groups is not essential in the process of the invention. There is no significant reduction in the yield of the sulfoxide. of the exomethylene-cepham of the formula (I) using protective groups that can be removed by acids. In this case, the only difference is that the products are usually obtained as acids instead of their esters. In view of the further conversion of the exomethylenecepham sulfoxides of formula 1, it is preferable that the reactive functionalities of these products remain protected throughout the cyclization process of the present invention. Therefore, protective groups that are not cleavable by the action of acids are preferred. The preferred ester groups protecting the acidic carboxylic functions are, therefore, methyl, 2-iodoethyl, 4-nitrobenzyl, 4-halophenacyl and 2,2,2-trichloroethyl. In the above definitions, the groups protecting the hydroxyl, amino and carboxyl functions are not defined exhaustively. The purpose of such groups is to protect the functional groups during the preparation of the starting compounds. These groups are then removed in a further step of synthesis without disturbing the rest of the molecule. Many such protecting groups are well known and can be used in the method of the invention. Therefore, these protective groups are not novel. Examples of acylamino groups of the formula R8C / O / NH- include formamide, acetamide, propionamide, butyramide, 2-pentenoylamino, chloroacetamide, bromoacetamide or 5-tertiary. -butoxycarbonylamino-5-yl before. -butoxycarbonyl valeriamide. Examples of specific acylamino groups of the formula R5C / O / NHs are: benzamide, 2,6-dimethoxybenzamide, 4-chlorobenzamide, 4-methylbenzamide, 3,4-dichlorobenzamide, 4-cyanobenzamide, 3-bromobenzamide or 3- -nitrobenzamide. Examples of acylamino groups of the formula RsC / O / NH-, in which R * is a group of the formula R "/ 0 / mCH | -, and m is O.sub.s of the group: cyclohexadien-1,4-yl-acetamide, phenylacetamide, 4-chlorophenylacetamide, 3-methoxyphenylacetamide, 3-cyanophenylacetamide, 3-methylphenylacetamide, 4-bromophenylacetamide, 4-ethoxy-phenylacetamide, 4-nitrophenylacetamide or 3,4-dimetophenylacetamide group. When m is 1, suitable examples of 114 521 8 acylamino groups are: phenoxyacetamide, 4-cyanophenoxyacetamide, 4-chlorophenoxyacetamide, 3,4-dichlorophenoxyacetamide, 2-cVorophenoxyacetamide, 4-methoxyphenoxyacetamide, ethoxyphenoxyacetamide, 3,4-dimethylphenoxyacetamide, 4-isopropylphenoxyacetamide, 3-cyanophenoxyacetamide or the 3-nitrophenoxyacetamide group. Examples of acylamino groups when R s is a substituted arylalkyl group of the formula where W is a protected hydroxyl group are: 2-formyloxy-2-phenylacetamide, 2-benzyloxy-2- (4-methoxyphenyl) - acetamide, 2- (4-nitrobenzyloxy-2- (3-chlorophenyl) -acetamide, 2-chloroacetoxy-2- (4-methoxyphenyl) -acetamide, 2-benzyloxy-2-phenylacetamide, 2-trimethylsilyloxy -2- (4-chlorophenyl) -acetamide or 2-benzhydryloxy-2-phenylacetamido. Examples of such groups when W is a protected amino group are: 2- (4-nitrobenzyloxycarbonylamino) -2-phenylacetamide, 2V-2,2,2-trichloroethoxycarbonylamino / -2-phenylacetamide, 2-chloroacetamido-2- (cyclohexadien-1,4-yl-1) acetamide, 2- (4-methoxybenzyloxycarbonylamino) - -2- (4-methoxyphenyl) -acetamide, 2-benzhydryloxycarbonylamino-2-phenylacetamide or 2- (1- -) carbomethoxy-2-propenyl) amino-2-phenylacetamide. Examples of groups marked with the symbol Rt representing imide groups of formula 5 are: N-acetyl-N-phenylacetylamino, N-trichloroethoxycarbonyl-N-phenoxyacetylamino, N-propoxycarbonyl-N- (4-chlorophenoxy) -acetylamino- wa or N- (2-bromoacetyl) -N-phenoxyacetylamine. Examples of acylamino groups of formula R8C / O / NH-, in which R8 is a heteroarylmethyl group of formula R "" - CH2- are: 2-thienylacetamide, 3-thienylacetamide, 2-furylacetamide, 2-thiazolylacetamide of formula 8 or a 3- (2-chlorophenyl) -5-methylisoxalolyl-4-amide group of formula 9. Examples of the groups designated by RA representing the imidazolidinyl groups of the formula 6 are: 2,2-dimethyl-3-nitroso-5-keto-4-phenyl-imidazolidinyl-1,2,2-dimethyl-3-nitroso-5. -keto-4- (4-benzyloxyphenyl) -imidazolidinyl-1,2,2-dimethyl-3-acetyl-5-keto-4- (cyclohexadien- -1,4-yl-1- (1-imidazolidinyl-1) or 2,2-dimethyl-3-nitroso-5-keto-4-i (2-thienyl) -imidazolidinyl--1. ; In general, the process of the invention comprises the cyclization of the azetidinylstilphinic acid derivatives of the formula 2 obtained from penicillin sulfoxide using a Friedel-Crafts catalyst for intra-molecular reactions of the sulfinyl and olefin groups in the azetidinone ring. The internal alkylsulfinylation reaction can be considered analogous to the Friedel-Crafts acylation reaction, "in which the sulfinyl group -S (O) - replaces the -C (O) - carbonyl group and the product is a sulfoxide instead of a ketone. At least three cases of Friedel-Crafts sulfinylation reactions have been described in the literature. In particular, cuprous aromatic aryl sulfinyl hydrocarbons to give diaryl sulfoxides have been described in a number of works and J. Frenkiel, CR. Acad. Sci. , 199, 557 (1934); George A. Olch and Jun Nishimura, J. Org. Chem. 39, 5 1203 (1973); Irwin B. Douglass and Basil Said Farah, J. Org. Chem. , 23, 805/1958). In a similar reaction, alkyl or arylsulfenyl chlorides reacting with aromatic hydrocarbons in the presence of aluminum chloride as catalyst yields thioethers in good yield. (H. Britzinger and M. Langheck, Ber. , 86, 557 (1953i)). The reaction of chlorides of alkyl or arylsulfonic acids with aromatic compounds to give sulfones has been investigated in more detail, see for example George A. Olch, "Friedela-Craftsa Chemistry," John Wiley and Sons, Inc. , New York, N. Y. , 1973, pp. 122-123, 146, 507. There is hitherto no mention of an intramolecular alkylsulfinylation reaction of the type described below. Intramellular cyclization of carboxylic acids and their derivatives with Friedel-Crafts catalysts to form cyclic ketones, on the other hand, has been thoroughly described in the chemical literature, see for example William S. Johnson "Organic Reactions" Roger Adams et al. , Ed. 25 John Wiley and Sons, Inc. New York, N. Y. , 1944, chapter 4, pp. 130-177 and the above-mentioned "Friel-Craftsa Chemistry". It has now been found that conventional Friedel-Crafts acylation methods, including reaction conditions, solvents and catalysts, can be successfully applied to the intramolecular cyclization reaction of azetidinesulfinyl chlorides and their derivatives in general. The starting azetidinonesulfinyl halides in general formula 2 are represented in more detail by formula 7, wherein Hal is chlorine or bromine, and R and RA are as defined above. Azetidinone sulfinyl chlorides of formula 7 are prepared from the corresponding known penicillin sulfoxide esters by reacting these esters at elevated temperatures with positive halogen source reagents, preferably an N-haloimide, such as N-chlorosulfoxide. cinimide (NCSA) The conversion of 6-imidopenicillin sulfoxide esters to the corresponding sulfinyl chlorides with sulfuryl chloride is described in the literature (S. Kukolja and S. R. Lammert, Angew. Chem. 12, 67-68 / 1973 //. Typically, the starting sulfinyl chloride derivatives of general formula II are prepared by reacting a penicillin sulfoxide ester with about 1.1 equivalents of N-chlorosuccinimide in an anhydrous, inert organic solvent, preferably 1.1,2 - trichlorethane or toluene at a temperature of about 70 to 120 ° C, the preferred temperature depending primarily on the nature of the substituent at position 6. Transformation of 6-imidopenicillin sulfoxide. -asa? it is usually at a temperature of 70-100 ° C *. in 60 cities, slightly higher temperatures (XW9-120 ° C) in the production of sulfiUfcrlu chloride from 6-acylaminopenicillin sulfoxides3 | The 8% action at the preferred western temperature completely within 45-90 minutes Sulfinylkyl in the penicillin starting material of the preparation of sulfinyl chloride derivatives are known or readily available, many of them are used to produce cephem compounds. They are obtained from the known 6-acylamino- and 6-imido-phenicillinic acids by esterification and subsequent oxidation, usually with metachloroperbenzoic acid or sodium periodate. An example of the preparation of starting azetidinene sulfinyl chloride of the general formula II is the process for the preparation of 2-methyl-1- (2-chlorosulfinyl-4-keto-3-acetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester) described below. - lowy. A solution of 5 mmol of 6-acetamidopenicillanic acid 4-nitrobenzyl 1-oxide in 200 ml of toluene is refluxed and dried azeotropically by distilling approximately 20 ml of toluene from the mixture. After briefly cooling the mixture, about 5.5 mmol of N-chlorosuccinimide are added. The mixture is refluxed for 90 minutes, then the solution is cooled to room temperature and filtered. After evaporation of the filtrate under reduced pressure, 2-methyl-1- (2-chlorosulfinyl-4-keto-3-acetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester is obtained in the form of a flocky precipitate) . The nitidine sulfinyl chlorides thus obtained can be used directly in the cyclization process of the invention without purification. Often the Friedel Crafts catalyst reagent is added directly to the final azetidine sulfinium chloride reaction mixture. By analogy with the reaction of penicillin ester sulfoxides with N-chlorosuccinimide, which produces azetidinone sulfinyl chlorides, penicillin ester sulfoxides containing an imide group in position 6 can be reacted with N-bromosuccinimide (NBSi) in order to obtain the appropriate Of these azetidinonesulfinyl bromides. The reaction conditions for this conversion are identical to those used in the NCS process for producing sulfinyl chlorides described above. The azetidinonesulfinyl chlorides described above and the corresponding bromides show similar chemical reactivity with respect to the cyclizing agents described in detail below. The starting azetidinesulfinic acids of formula 10, where R and Rt are as defined above, are usually prepared from the corresponding sulfinyl chlorides by slurrying a solution of sulfinyl chloride in ethyl acetate with an aqueous solution of sodium bicarbonate in at room temperature for about one hour. The aqueous layer containing the sulfinic acid salt is separated, washed with ethyl acetate, stirred again with more ethyl acetate, and then acidified. The organic layer was separated, washed with brine, dried over anhydrous sodium sulfate and then evaporated to dryness under reduced pressure. The sulfinic acids isolated in this way are usually obtained in the form of colorless and amorphous solids. The following compounds are examples of starting sulfinic acids: 2-Methyl-1- (3-sulfin-4-keto-3-phenylacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester), 2,2,2-trichloroethyl ester 2-methyl-1- (2-sulfino-4-keto-3-acetamidoazetidinyl-1 / -2-propenecarboxylic acid, 2-methyl-W2-sulfino-4-keto-3- carboxylic acid, 2-iodoethyl ester) chloroacetamidazetidinyl-l / -2-propenecarboxylic acid, 2-methyl-W2-sulfine-4-oxo-3-phthalimidazetidinyl-l / -2-propenecarboxylic acid 4-methoxybenzyl ester, tertiary ester. 2-methyl-H-2-sulfino-4-keto-3- (2-bromoacetamido) -azetidinyl-1) - 2-propenecarboxylic acid, benzhydryl ester of 2-methyl-1 - {- 2- sulfin-4-keto-3- (4-chlorophenoxyacetamido) azetidinyl-1] -2-propenecarboxylic acid, 2-methyl-li [-2-sulfinyl-4-keto-3- carboxylic acid 4-nitrobenzyl ester (4-nitrobenzyloxycarbonylamino) azetidinyl-l-] - 2-propenecarboxylic acid, 2-methyl-l-H acid 2,2,2-trichloroethyl ester [2-sulfino-4-keto-3- (2,2-dimethyl-3) -nitroso-5-keto-4-phenyimidazolidinyl-1 / azetidinyl-1] -2-p-phenecarboxylic acid, 2-methyl-1 - [- 2-sulfino-4-keto-3-, 2-iodoethyl ester acetamidoazetidinyl-1] -2-propenecarboxylic acid, 2-methyl-1 - [- 2-sulfin-4-keto-3- (4-chlorobenzamido / acetidinyl-1} -2-propenecarboxylic acid 4-nitrobenzyl ester) . It has been found that other azetidine sulfinyl chloride derivatives, including sulfinanone esters, thiosulfinate esters, mixed carboxyl sulfonic anhydrides, and sulfinamide and sulfinimide derivatives, can be prepared from the corresponding sulfinic acids and from their sulfinyl chloride precursors. Such derivatives may be prepared by conventional methods used in the preparation of carboxylic acid derivatives, for example esters, thioesters, anhydrides, amides and imides from carboxylic acids and carboxylic acid chlorides. Some azetidine sulfinamide derivatives were prepared directly from penicillin sulfoxides (S. Terao, T. Matsuc, S. Tsushima, N. Matsumoto, T. Miyanaki and M. Miyamoto, J. Chem. Soc. (C /, 1304 (1972)). It has also been found that such derivatives can be cyclized to 3-methylenecepham sulfoxide derivatives by the method and conditions described below. Azetidinnesulfinic acid esters (sulfinates) of formula 11, in which R and B are as defined above, and R4 is an alkyl group with 1 to 10 carbon atoms, an aralkyl group with 1 to 10 carbon atoms in the alkyl or haloalkyl part, with 1 to 6 carbon atoms are prepared from the above-described azetidinone sulfinyl chloride derivatives, obtained from penicillin sulfoxide, by reaction of sulfinyl chloride with a suitable alkanes with 1 to 10 carbon atoms, arylalkanol with 1-3 carbon atoms in the alkanol or halogenated alcohol group with 1-6 carbon atoms. Typically, sulfinic acid esters are prepared by adding the appropriate alcohol directly to the reaction mixture in which azetidine sulfinyl chloride is formed from penicillin sulfoxide. The sulfinic acid ester of the product is then separated by conventional methods such as evaporation, crystallization or chromatographic separation. Examples of alcohols that can be used for the preparation of sulfinic acid esters are methanol, ethanol, isopropanol, cyclohexanol, 4-chlorocylohexanol, isobutanol, n-heptanol, menthol, benzyl alcohol, 2-phenylethanol, 3-phenylpropanol, alcohol 2 -chlorobenzyl, 4-methoxybenzyl alcohol, 2- (4-nitrophenyl) ethanol, 2-chloroethanol, 2-bromoethanol, 3-bromocyclohexanol, 4-chlorobutanol or 3-chloropropanol. Examples of azetidinonesulfinic acid esters are the following compounds: 2-methyl-1- (2-isobutoxysulfinyl-4-keto-3-acetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester, 2-methyl acid benzhydryl ester) -1 [2- (2-chloropropoxysulfinyl-4-keto-3-acetamidoazetidin-1] -2-propenecarboxylic acid, 2-methyl-1- H [2 ^ 2- bromoethoxysulfinyl (-4-keto-3- (2-formyloxy-2-phenylacetamido) azetidinyl-1] -2-propene carboxylic acid, 2-methyl-1- [2- (4-bromo) acid 2-iodoethyl ester mobenzyloxysulfinyi -4-keto-8-phthalimidazetidinyl-1] -2-propenecarboxylic acid, tertiary ester. 2-Methyl-1- (2-methoxy-sulfinyl-4-keto-3-benzyloxycarbonylamino-azetidinyl-1 / -2-propenecarboxylic acid, 4-chlorophenacyl ester) 2-methyl-1- [2- (2- - - phenylisopropoxysulfinyl (-4-keto-3- (2-chlorobenimido) -azetidinyl-1] -2-propenecarboxylic acid, 2-methyl-1 - [- 2-cyclohexyloxysulfinyl-4-keto-3-, 4-methoxybenzyl ester (2,2-dimethyl-3-nitroso-5-keto-4-phenyimidazolidinyl-1) azetidinyl-1] -2-propenecarboxylic acid, 2-methyl-1- [2- (3-phenyl) acid methyl ester - propoxysulfinyl) -4-keto-3- (4-chlorophenoxyacet-Tnido) azetidinyl-1] -2-propenecarboxylic acid. Azetidinone thiosulfinate esters of the formula (12), in which Rj and Rj are as defined above, and R5 is an alkyl group of 1-6 carbon atoms, an aryl group or an arylalkyl group of 1-3 carbon atoms in the alkyl portion are prepared from the above-discussed azetidinone sulfinyl chlorides by reaction with the appropriate alkylthiol having 1-6 carbon atoms, arylthiol or arylalkylthiol having 1-3 carbon atoms in the alkyl portion. I2 thiosulfinate esters are prepared and isolated by standard methods. Their preparation is analogous to that of carboxylic acid thioesters from carboxylic acid chlorides. Examples of thiols or meriraptans that can be used in the preparation of azetidinone-thiosulfinate esters are methanethiol, ethanethiol, propa-thiof-2, 2-meiylpropanethiol-2, cyclohexanethiol, pentanethiol-2, butaryothio thiophenol, 4-chlorothiophenol, 2-phenylethanbthiol and benzyl mercaptan. The following compounds are examples of azetidinone thiosulfinate efhthers: 2-Methyl-W2-methylthiosulfinyl-4-keto-3-formamidoazetidinyl-1 / -2-propenecarboxylic acid, 4-nitrobenzyl ester. 2-Methyl-1 - [- 2- (2-methyl-1-propanethiosulfinyl) -4-keto-3- (4-methoxybenzyloxycarbonylamino) azetidinyl-1] -2-propenecarboxylic acid 2-iodoethyl ester , 2-Methyl-1- H [2-i (1-hexanethiosulfinyl) -4-keto-3- (4-trifluoromethylbenzamido / azetidinyl-1] -2-propenecarboxylic acid ester), 2,2,2-trichlorethyl ester 2-Methyl-lf-2-benzylthiosulfinyl-4-keto-3- (4-methylphenoxyacetamino) azetidinyl-l] -2-propenecarboxylic acid benzhydryl and tertiary ester. 2-methyl-1- ([2-phenylthiosulfinyl-4-keto-3- (4-nitrobenzyloxycarbonylamino) azelidinyl-1] -2-propenecarboxylic acid -butyl. The sulfinamide and sulfinimide derivatives of azetidinene sulfinyl chlorides, prepared from penicillin sulfoxides, are included in the general formula where R and R x are as defined above, R 6 is hydrogen and R 7 is hydrogen, and R is as defined above "or a group of the formula -NHR8 in which R8 is an aminocarbonyl group, an alkylaminocarbonyl group with 1-3 carbon atoms in the alkyl part, an alkoxycarbonyl group with 1-3 carbon atoms in the alkoxy part, an alkylcarbonyl group with 1-3 carbon atoms in the alkyl portion or tosyl group, or R8, R7 and the nitrogen atom to which they are attached form an imide group of formula III in which R2 is as defined above. In general, azetidinone sulfinamides and sulfinimides are prepared from the corresponding sulfinyl chlorides in the same manner as carboxamides, and carboximides are prepared from carboxylic acid chlorides, i.e. by reacting the acid chloride with from about 1 to about 2 equivalents of the appropriate amine base. . Typically these reactions, like the preparation of sulfinic acid esters and thioesters described above, are carried out in an inert organic solvent such as benzene, toluene, methylene chloride, chloroform or ethyl acetate. The table below illustrates the particular bases used in the preparation of the various sulfinamides and sulfinimides of Formula 14. 1 x -S / 0 / NH2 -S / Ó / NHR "-S / O / NHNHC / O / NH, -S / O / NHNHC / O / NH / Cj Csalkyl / -S / O / NHNHCtfO / O / C ! - -Csalkyl / | -S / O / NHNHC / O / C ^ 1 -C8alkyl / formula 15 1 formula 17 Animation rule NH4C1 1 R "-NH2 H, NNHC / 0 / NH2 H ^ NNHC / O / NH / Ci - -C, alk}! / H2NNHC / 0/0 / C! - -C8alkyl / ANNHC / O / ^ - Cs alkyD and formula 16j formula 18A Succinimidosulfinylazetidine can be prepared according to Scheme 1. The penicillin ester sulfoxide of formula 19 is heated in dimethylformamide to about 105 ° C with excess N-trimethylsilylsuccinimide of formula 20 in the presence of acetic acid. The azetidinonesulfenimide of formula 21 so prepared is then oxidized with chloroperbenzoic acid to give the corresponding sulfinimide derivative of formula 22. The following compounds are examples of azetidine sulfinamides and sulfinimides: 2-Methyl-1- (2-phthalimidosulfinyl-4-keto-3-phenylacetamidoazetidine-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester), 2-iodoethyl ester 2-methyl-li [2- (4-chloroanilinesulfinyl) -4-keto-3-phenoxyacetamidoazetidinyl-1] -2-propenecarboxylic acid, 2-methyl-ln [-3-carbamylhydrazosulfinyl-4-acid benzhydryl ester -keto-3- (4-nitrobenzyloxy-carbonylamino) azetidinyl-1] -2-propenecarboxylic acid, 2-methyl-1- (2-ethylcarbonylhydrazsulfinyl-4-keto-3-formami-azetidinyl-) 1 / -2-propenecarboxylic acid ester III order 2-methyl-1 - [- 2-carboxyhydrazosulfinyl-4-keto-3- (2-formyloxy--2-phenylacetamido) azetidinyl-1] -2-propenecarboxylic acid, 2,2,2- ester -butyl 2-Methyl-1- (2-propionylhydrazsulfinyl) / 4-keto-3-phthalimido-azetidinyl-1 / -2-propenecarboxylic acid-3-methyl ester, 2-methyl-1- | [-2- / 4- tolylsulfonylhydrazsulfinyl) -4-keto-3- (2-chlorobenzamido) -azetidinyl-1] -2-propenecarboxylic acid, 2-methyl-1- (2-succinimide-4-keto-3) -4-methoxybenzyl ester -propinonoamidoazetidinyl-1 / -2-propenecarboxylic acid, 2-methyl-1 - [- 2- (4-methoxyanilinesulfinyl) -4-keto-3-phenoxyacetamazetidinyl-1] -2-propenecarboxylic acid 4-nitrobenzyl ester , 2-Methyl-1- (2-carbomethoxyhydrazosulfinyl-4-keto-3-chloroacetamidazetidinyl-1 / -2-propenecarboxylic acid, 2-iodoethyl ester, and 2-methyl- 2-methyl-trichloroethyl ester) 1- - [- 2-acetylhydrazsulfinyl-4-keto-3- (2-tertiary). butoxycarbonylamino-2-phenylacetamido (azetidinyl-1] -2-propenecarboxylic acid. In addition to the sulfinamides described above, other sulfinamides can also be used as starting materials in the cyclization reaction of the present invention. In particular azetidine sulfinamides of formula 23 or 24, where R and R 1 are as defined above, and R 9 is an alkyl group of 1-6 carbon atoms or a phenyl group, can be cyclized under acidic conditions to give the appropriate 3-methylenecepham sulfoxides. Such azetidinonesulfamides are known compounds [S. Terdo et al. / As above /]. These compounds are prepared directly from penicillin sulfoxides by reaction with azodicarboxylates or diacyldiimides. By employing somewhat milder reaction conditions (compared to the preparation of sulfinyl iialogens) for the preparation of these azetidinnesulfamides, a wider range of penicillin sulfoxides can be used as starting materials. Thus, R 1 in formula 23 or 24 can represent, in addition to the groups previously mentioned, also an amide group of the formula R "" CH 2 C / O / NH, where R "" represents a heterocyclic group, such as, for example, 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-thiazoyl or isoxazolyl. The following compounds are examples of starting sulfinamides directly prepared from penicillin sulfoxides and azodicarboxylates or diacyldiimides: 2-methyl-1- [- 2- (N, N'-dicarbo-III-order) 4-nitrobenzyl ester. -butoxyhydrazasulfinyl) -4-keto-3- (2-thienylacetamido) azetidinyl-1] -2-propenecarboxylic acid, 2-methyl-1- | [-2- / N, N'- - - 2-iodoethyl ester dibenzoylhydrazsulfinyl (-4-keto-3-phenoxyacetimidazetidinyl-1] -2-propenecarboxylic acid, 2-methyl-1- - [2-N, N'-dicarboethoxyhydrazosulfinyl) -4-keto, 2,2,2-trichloroethyl ester - -3-phenylacetamidoazetidinyl-1] -2-propenecarboxylic acid, 2-methyl-1- | [2- (N, N'- -dicaromethoxyhydrazsulfinyl) -4-keto-3 / -2-formyloxy- benzhydryl ester 2-phenylacetamido / -azetidinyl-1] -2-propenecarboxylic acid, and 2-methyl-1- [2- (N, N'-dicarbopropoxyhydrazsulfinyl) -4-keto-3-acetamidoazetidinyl-1] 4-chlorophenacyl ester] Of the -2-propenecarboxylic acid. The range of reagents suitable for inducing an intramolecular sulfinylation reaction in the process of the invention overlaps substantially with those capable of eliciting Friedel-Crafts acylation reactions. A detailed description of the Friedel-Crafts acylation reactions, related reactions and the catalysts used is given by George A. Alder in "Friedel-Crafts Chemistry", John Wiley and Sons, New York, N. Y. , 1973. Suitable reagents which may be used in the process of the present invention to induce the intramolecular cyclization of azitidine sulfinyl chlorides and bromides are conventional Friedel-Crafts catalyst type catalysts, such as Lewis acid catalysts, Bronsted acid catalysts, and bronsted acid catalysts. forming a cation in the metathesis reaction. The preferred Friedel-Crafts catalysts as Lewis acids are metal halides. Bronsted protic acid catalysts include acidic oxygenate compounds (especially acid oxides) called acid "chalcides" analogously to "halides" which are compounds of halogens. The protic Bronsted acid catalysts also include the fused Friedel-Crafts catalysts of the formula HMA4j6 discussed in more detail below, and the organic and inorganic Bronsted acids as such. The cyanations of azetidine sulfinic acids, their esters, thioesters, amides and imides are carried out with the aid of a Bronsted protic acid catalyst. Lewis acid catalysts are characterized by the presence of free ort) itaJu? which has a free pair of electrons from, for example, an oxygen, sulfur or halogen atom, or a pair of electrons in the n orbital of a Lewis base compound, forming a bond compatible. Examples of suitable metal halides as Leisa acid catalysts are aluminum chloride, tin chloride, tin bromide, zinc chloride, zinc bromide, antimony pentachloride, titanium tetrachloride, ferric chloride, gallium trichloride, zirconium tetrachloride, mercury trichloride. chromium and similar metal halides, showing catalytic activity in the Friedel-Crafts reaction. Preferred among these catalysts are tin chloride, zinc chloride, zinc bromide, zirconium tetrachloride and titanium tetrachloride, with tin chloride being the most preferred. The Bronstate protic acid catalysts differ from Lewis acid halide catalysts in that, in the case of a protic acid, the ability to accept electrons is due to the presence of a positively charged particle, namely a proton. Examples of suitable organic Bronsted protic catalysts are methanesulfonic acid, ethanesulfonic acid, trifluoroacetic acid, trichloroacetic acid, dichloroacetic acid and similar organic acid compounds. The inorganic Bronstate protic acid catalysts suitable for use in the process of the invention include sulfuric acid, phosphoric acid, polyphosphoric acid, perchloric acid, chlorosiphonic acid, fluorosulfonic acid, and similar protic catalyst acids. The preferred bronsted acid catalysts are methanesulfonic, trifluoroacetic, phosphoric, sulfuric and polyphosphoric acids. Solid oxides and sulfides are catalysts of the "chalcide" type. Olah stated in the above-mentioned work "Friedel-Crafts Chemistry" that in a Friedel-Crafts type acylation reaction, steels of acid chalcide type catalysts are the most advantageous for future applications. In the case of acid chalcides, acid oxides or mixed acid oxides are particularly preferred for the process according to the invention. Examples of acid oxides are aluminum oxide, silicon oxide, CrFOs, Pf05, TiO * Al2Os. CoO and A1208. MnO. Phosphorus pentoxide is most preferred. In general, dehydrated chalcides are inactive as catalysts in the Friedel-Crafts acylation reaction, but the addition of small amounts (about 1 to 5% by weight) of water activates these catalysts. The absorbed protons appear to be essential for the catalytic activity of acid chalcide catalysts. The effect of water suggests that the Bronsted acidity is caused by the catalytic activity of the acid chalcides. / F. E. Condon, "Catalyts", Vol. VI, pub. P. H. Emmet, Reinhold Publ. Corp. , New York, N. Y. / 1953 /, pp. 43 /. From the point of view of the process according to the invention, the acid chalcides are classified as Bronsted proton catalysts. Lewis acid metal halides in combination with a protic Bronsted acid catalyst may also be used as catalysts, as is sometimes used in Friedel-Crafts acylation reactions, the effective catalyst being a coupled Friedel-Crafts acid catalyst. HMA4.6. The activity of the Bronsted acid is believed to be responsible for the performance of such catalysts. Thus, the mixed catalysts used in the process according to the invention are classified as Bronsted type catalysts. Examples of coupled catalysts are HBF4, HAICI4, HAsF6 and HAlBr4. The reactants that form a reactive cation as a result of the metathesis reaction do not work in a strict sense catalytically, since they are usually consumed in the cation-forming process. Particularly anhydrous silver salts such as silver para-toluenesulfonate, silver perchlorate, silver phosphate, silver tetrafluoroborate, silver trifluoroacetate, and similar compounds are active "catalysts" in Friedel-Crafts-type cyclization, azetidinone sulfinyl halides, By the method according to the invention. The silver salts act as cationic forming substances in reaction with the halide compounds and do not act as acids. Thus, it is likely that the intermediate sulfin type cation is formed from sulfinyl chloride by cleavage of the chloride ion by the silver cation, and not by acid-base reactions, as is the case with the catalysts discussed above. The reaction precipitates an insoluble by-product, silver chloride. The most preferred cationicide in the process of the invention is silver p-toluenesulfonate. Cation-forming agents are only effective when azetine sulfinyl halides are used as starting materials. These reagents are not suitable for the cyclization of any of the other sulfinic acid derivatives. Ring closure of the other derivatives is achieved with protic Bronsted acid catalysts. Thus, in the process of the present invention, the cyclization of the starting azetidine sulfinyl halides may be carried out by reacting them with a Lewis acid metal halide catalyst, a Bronsted acid protic catalyst or a metatiform cation forming agent. The best yields of 3-methylenecepham sulfoxides from azetidine nesulfinyl chlorides, which are the most preferred starting materials for the process of the invention, are obtained by using metal halide Lewis acids as catalysts. A good sulfoxide yield, starting from the sulfinyl halide, may, however, also be achieved with the use of a Bronsted acid proton catalyst or cationic forming agents. The Lewis acid metal halide catalysts are most preferred in the process of the invention when azetidine sulfinyl chlorides and bromides are used as starting materials. Proton-type Bronsted acid catalysts are most preferred for standstill. as starting materials, azetidine and nosulfinic acids and the corresponding sulfinate esters, thiosulfinate esters, sulfinamides and sulfinimides. The cyclization reactions according to the invention are carried out in an environment of dry, inert organic solvents. The term "inert organic solvent" denotes an organic solvent which, under the conditions of the reaction, does not substantially react with the reactants or with the products formed. Since sulfinyl chloride or other acid halide substrates are used as starting material are easily hydrolyzed and react with other protic compounds, for example alcohols and amines, therefore moisture and the presence of other protic compounds in a reaction environment is excluded. Therefore, a dry aprotic organic solvent is most preferred. Trace water as found in industrially dried solvents may be tolerated, but it is generally most advantageous to operate the process according to the invention under completely anhydrous conditions. Suitable solvents are, for example, aromatic hydrocarbons, such as benzene, toluene, xylene, chlorobenzene, nitrobenzene or nitromzythylene, halogen derivatives of aliphatic hydrocarbons, such as chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane (ethylene chloride). , 1,1,2-trichlorethane, 1,1-dibromo-2-chloroethane, and other known solvents suitable for Friedel-Crafts type reactions, including carbon disulfide and nitromethane. The preferred solvents are aromatic hydrocarbons and halogen derivatives of aliphatic hydrocarbons. The most preferred aromatic hydrocarbons used as solvents are benzene and toluene. The most preferred solvents of the halogen derivatives of aliphatic hydrocarbons are methylene chloride, ethylene chloride and 1,1,2-trichloroethane. The temperature at which the process of the invention is carried out depends on the nature of the catalyst or cation-forming agent used. The temperature must be adequate to induce a ring closure in the starting material. It is well known that the various Friedel-Crafts reagents are effective in producing a given type of acylation at different temperatures. Moreover, "as is known, up to 50 Friedel-Crafts reagents belonging to one particular class are concerned. The process according to the invention can generally be carried out at a temperature of 5 to 150 ° C. Cyclization of both azetidinesulfinic acid derivatives and sulfinyl halides can be performed with a Bronsted acid protic catalyst in an inert organic solvent at a temperature of about 70 ° -115 ° C, usually at the reflux temperature of the reaction environment. in which the closure of the ring is performed. Alternatively, each of the azetidine sulfinyl derivatives described above may be cyclized to the corresponding exomethylenecharma sulfoxide by dissolving the compound in pure proponic Bronsted acid such as methane sulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, trichloroacetic acid, or dichloroacetic. The time required for ring closure under these conditions depends on the nature of the sulfinyl derivative, the nature of the acid used, and the reaction temperature. The cyclization of the azetidinnesulfinamide and sulfinimide derivatives requires 5 to 10 minutes. at room temperature, in methanesulfonic acid, while the cyclization of sulfinic acids, their esters and thioesters takes place usually after about 30 minutes. at room temperature. The ring closure of the azetidine sulfinyl halides is preferably carried out at a temperature of about 10 to about 115 ° C. More preferably, the reactions are carried out at a temperature of about 20 to about 85 ° C., the most preferred temperature depending primarily on the solubility and catalytic activity of the cyclizing agent used. When using protic Bronsted acid catalysts (including acid chalcides and compressed Friedel-Crafts acid catalysts) as catalysts for the cyclization of the sulfinyl halide derivative carried out in an inert organic solvent, the preferred reaction temperature is about 70 to about 115. ° C. Most preferably, the reactions are carried out at the reflux temperature of the reaction medium under a reflux condenser. However, the cyclization of 2-methyl-1- (2-chlorosulfinyl-4-oxo-3-phthalimidazetidinyl-1-propenecarboxylate) methyl ester was carried out in pure polyphosphoric acid at room temperature. The intramolecular sulfinylation reactions using a cation former are most preferably conducted at a temperature of about 20 to about 80 ° C and most preferably at room temperature. When the preferred catalyst for the cyclization of sulfinyl halides, which is a Lewis acid metal halide, is used, the preferred reaction temperature depends primarily on the nature of the metal halide used. Thus, when tin chloride, tin bromide or antimony pentachloride are used, which compounds are usually soluble in the solvents used in the process, the cyclization reactions are preferably carried out at a temperature of about 10 to about 40 ° C. the most preferred temperature for these catalysts is room temperature. On the other hand, when titanium tetrachloride is used - a liquid which is also soluble in most of the solvents used in the reaction - an elevated temperature of about 4 to about 100 ° C is favorable for the conversion. When other metal halides of the Lewis acid type are used as the catalyst, an elevated temperature of about 40 to about 115 ° C. is preferably used, with the most preferred temperature being about 40 to about 85 ° C. In the case of using tin chloride as a cyclizing agent in the environment of toluene, it is possible to isolate the intermediate complex compound of the tin chloride with a sulfinyl halide by filtration of the reaction mixture. This complex can be dried and stored, or it can be dissolved in ethyl acetate and washed sequentially with hydrochloric acid, water and brine to obtain the corresponding exomethylenecepham sulfoxide. To ensure that the cyclization of the sulfinyl halide is fully completed, at least a stoichiometric / mole per mole / amount of a Lewis acid-type Friedel-Crafts catalyst or a cation-forming agent should be used. The use of a lower mole amount of these reagents reduces the yield of 3-methylenecepham sulfoxide product of the reaction and leaves some of the sulfinyl chloride unreacted. In general, the amount of catalyst used ranges from slightly more than 1 equivalent to about 2 molar equivalents per mole of sulfinyl chloride. It is preferable to use about 1.1 equivalents of a metal halide of the Lewis acid type or a cation former for each mole of the starting azetidinosulfinyl halide. Although less than a stoichiometric amount of Friedel-Crafts catalyst of the Bronsted protene acid type per mole of sulfinyl chloride or other sulfinic acid derivative may be used to induce complete cyclization, it is common practice to use an equivalent or greater amount of such acid catalyst. As stated earlier, the cyclization reactions can also be carried out in pure protic acid; this method is preferable. The reaction time under the conditions described above is usually from about 5 minutes. up to about 5 hours it depends to some extent on the nature of the reagents used, the solvent used and the reaction temperature. Typically, the reaction is complete by contacting the reactants at a preferred temperature for about 45 to about 90 minutes. However, as stated previously, shorter reaction times may be used in some conditions. The reaction mixture can be easily monitored by comparative thin layer chromatography to determine the progress of the ring closure reaction. The mechanism of the reaction carried out according to the invention has not been entirely established, but it is highly probable that the intermediate stage of the sulfinium ion of formula 25, or its complex, will occur, in which the substituent in position 2 in the azetidinone ring will be there is a group of formula 26 or 27 (M = H + or a metal halide of Lewis acid character). The conversion of the intermediate ion of formula 25 The product of formula Ia is illustrated in Scheme 2- Closure of the ring of deuterated sulfinyl chloride of formula 2S prepared from 6-phthalimido-3O-methyl-3α-tri-deute methyl ester 1-oxide. - romethylpenamocarboxyl-3 method described by R. D. G. Colpera, Journal of the American Chemical Society, 92, 5010 (1970) in the presence of tin chloride, and thus made according to the invention, gives the 1-oxide of the methyl ester of 7-phthalimido-2,2-dimutero-3. 4-methylene-cephalocarboxylic acid of formula 29 according to Scheme 3. The yield of the products will depend on the nature of the reagents used, their relative amounts, and the reaction conditions discussed above. The products of the invention can be isolated and purified using conventional preparative methods. These methods include chromatographic separation, filtration, crystallization, and recrystallization. The most preferred side chains denoted by the symbol Rt in the formulas given above are the side chains of the present invention present in penicillins produced directly by fermentation, especially the phenylacetamide and phenoxyacetamid side chains. Such penicillins can be esterified and oxidized (not necessarily in this order) to the corresponding penicillin ester sulfoxides from which the sulfinyl chlorides intermediate or other starting materials used in the process of the invention can be prepared. The above-mentioned preferred side chains are also convenient from an economic point of view. Stock penicillins having such chains are readily available and relatively inexpensive. The benefits of the process according to the invention in the use of the sulfinyl intermediate derivatives described above, prepared from such penicillins, are readily apparent. Of course, penicillin sulfoxides having other known side chains can also be easily prepared by acylating 6-APA or 6-APA esters followed by oxidation and can be used in the process of the invention. The 3-methylenecepham sulfoxides which constitute the product of the process according to the invention are valuable intermediates for the production of compounds of the nature of antibiotics. The sulfoxides can be reduced by known methods, usually with phosphorus trichloride or tribromide in dimethylformamide, to give the corresponding 3-methylenephamide, which can be converted in high yield to the deacetoxycephalosporin of formula 30 by the action of triethylacetamine in dimethylformamide. (Robert R. Chauvette and Pamela A. Pennigton, J. Org. Chem. , 38, 2994 (1973)). The deacetoxy cephalosporin esters are converted into active antibiotics by cleavage of the ester functional group. The de-esterification can be carried out, depending on the nature of the protecting group, by any of a number of known methods, such as: the action of acids such as trifluorobetic acid, formic acid or hydrochloric acid; (2) action of zinc and an acid such as formic, acetic or hydrochloric acid or (3) hydrogenation in the presence of palladium, platinum, rhodium or compounds thereof in the form of a suspension or on carriers such as barium sulfate, carbon or alumina. Alternatively, the exorriethylene cephams can be used to prepare the novel cephalic antibiotics of formula 31 in which Y is, for example, chlorine, bromine or methoxy. Such chemical transformations of 3-exometh- 20 25 30 35 40 45 50 55 60 114 521 21 22 lenocepham compounds are described in the professional literature: Robert R. Chauvette and Pamela A. Pennington, Joermnal of the American Chemical Society 96, 4986 (1974). In general, exomethylenecepham derivatives are converted by low-temperature ozonolysis to 3-hydroxycephem derivatives which, in turn, by the action of diazomethane in a mixture of ethylene chloride and ethylene at room temperature, are converted to 3-methoxycephem derivatives. 3-halocephem derivatives are obtained from 3-hydroxycephemic esters by the action of halogenating agents such as thionyl chloride or phosphorus tribromide in dimethylformamide. The corresponding cephamic acids have a bactericidal effect. An example is given below to illustrate the method of the invention. In these examples, the nuclear magnetic resonance spectrum is denoted by the symbol MRI and the infrared spectrum by IR. Nuclear magnetic resonance spectra were obtained on a Varian Associates T-60 type spectrometer using tetramethylsilane as a standard. The chemical shift expressed in the values of 8 is given in parts per million (ppm) and the coupling constants (J) are expressed in cycles per second and are denoted by the symbol Hz. Example I. 7-phthalimido-3-methylenecephamocarboxylic acid-4-methyl ester-oxide. AND. Tin chloride. A mixture of 18.8 g (50 mmol) of 6-phthalimidopenicillanate sulfoxide and 6.7 g (50 mmol) of N chlorosuccinimide in 1 liter of dry carbon tetrachloride was heated to reflux for 70 minutes. The crude product was cooled to room temperature, filtered, washed with water (X500 ml) and dried (MgSO4). The solvent was then evaporated to dryness under reduced pressure. The NMR spectrum shows complete conversion to chloride - NMR (CDCl3: 8 1.97 (broad s, 3.), 3.86 (s, 3), 5.05 (wide, 21.5.2). d, 1, J = 2 Hz /, 5.77 (d, 1, J = 4 Hz), 5.9 (d, 1, J = 4 Hz) and 7.83 (m, 4). The sulfinyl chloride product was dissolved in 1 liter of dry CH 2 Cl 2 and 6 ml (50 mmol) of anhydrous tin chloride was added. The resulting solution was stirred for 45 min. and washed with 1N hydrochloric acid (2 × 200 ml) and dried (MgSO 4). Evaporation in vacuo yielded 18.4 g (98.4%) of a mixture of R- and S-sulfoxides in a ratio of about 3: 2 as shown by NMR (as light yellow foam). Part of this mixture (1.26 g) was chromatographed on silica gel using a mixture of chloroform and ethyl acetate as solvent. Fractions 6 to 10, containing pure R-sulfoxide (340 mg), were recrystallized from a mixture of methylene chloride and cyclohexane (mp 201-202 ° C. (1, NMR (CDCl 8)); 8 3.62 and 4.12 / ABq, 2, J = 14 Hz /, 3.85 / s, 3 /, 4.88 7d, 1, J = 4.5 /, 5.25 / broad s, 1 /, 5.58 (m, 2), 5.97 (d, 1, J = 4.5 Hz) and 7.84 (m, 4); mass spectrum m / e 374, 358, 346/298, 287, 239, 220; IR (KBr): 1780, 1745 '* and 1390 cm "V Elemental analysis: - Values calculated for C17H14N206S (374.37): C- -54.54, H-3.77, N-7.48, C- 25.64, S, 8.56%. - Experimentally determined values: C-54.41, H- -4.06, N-7.26, C-25.59 and S-8.41%. Fractions 11-18 contained a mixture of R- and S-sulfoxides, and fractions 19-35 gave 210 mg of pure S-sulfoxide which was recrystallized from a mixture of methylene chloride and cyclohexane; MRJ / CDC13 /: 8 3.63 / s, 2 /, 3.82 / s, 3 /, 4.90 / d, J = 4.5 Hz /, 5.32 / s, 1 /, 5.46 (broad s, 1), 5.64 (d, 1, J = 4.5 Hz), 5.77 (s, 1) and 7.74 (m, 4); mass spectrum m / e 374, 358, 346, 398, 287, 239, 200; IR (KBr): 1775, "1745, 1725, 1390, 1205, 1111, 1051, 730 and 715 cm" *. Elemental analysis: - Values calculated for C17H14N206S: C-54.54, H- -3.77, N, 7.48%. ! 15 - Values determined experimentally: C-54.33, H- -3.76, N-7.36%. B. Titanium tetrachloride. A solution of 0.41 g of 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phthalimido-azetidinyl-1 / -2-propenecarbo-2t) acid methyl ester and 0.12 ml of titanium tetrachloride in 30 ml of dry 1, 2-dichloroethane was heated to reflux for 30 minutes. The mixture was then cooled to room temperature, washed with 1N HCl and brine, and dried (MgSO 4). After evaporation to dryness, 0.34 g of 7-phthalimido-3-methylenecephamocarboxylic acid methyl ester 1-oxide was obtained. C. Aluminum chloride. A mixture of 0.41 g of 2-methyl-1- (2-chlorosulfinyl-4-keto-M -3-phthalimidazetidinyl-1 / -2-propenecarboxylic acid methyl ester) and 0.13 g of aluminum chloride was heated under reflux. reflux condenser in 30 ml of dry 1,2-dichloroethane. The mixture was then cooled to room temperature, washed with 1 N HCl and brine and dried (MgSO 4). After evaporation in vacuo to dryness, 0.35 g of 3-methylenecepham sulfoxide was obtained in the form of a yellow foam. D. Zinc bromide. A mixture of 0.41 g of 2-methyl-1- (2-chlorosulfinyl-4-keto-40 -3-phthalimidoazetidinyl-1 / -2-propenecarboxylic acid methyl ester) and 0.27 g of zinc bromide in 30 ml of dry methylene chloride was heated to reflux for 1 hour. The mixture was then cooled to room temperature, washed with In HCl and brine, and dried (MgSO 4). After evaporation in vacuo to dryness, a mixture of the R- and S-sulfoxides of 3-methylenecepham was obtained in the form of a yellow foam. E. Antimony pentachloride. A solution of 0.41 g of 2-methyl-1- (2-chlorosulfinyl-4-oxo-3-phthalimidoazetidinyl-1 / -2-propenecarboxylic acid methyl ester) and 0.12 ml of antimony pentachloride were stirred at temperature room for 60 minutes. The reaction mixture was washed with 1 N HCl S 5 and brine, dried (MgSO 4) and evaporated in vacuo to dryness to give the desired 3-methyleriocepham sulfoxide as a yellow foam. The spectrum of the NMR, which is the product of a mixture of sulfoxides, was difficult to read. To confirm the presence of cepham sulfoxide, the reaction product was dissolved in 3 ml of dimethylfhamamide and reacted with 0.09 ml of phosphorus trichloride. After vigorous stirring of the reactants at the temperature of ° C. for 30 minutes. the mixture was poured into water with ice. The yellow precipitate thus formed was separated by filtration and dried under vacuum. The NMR product spectrum (0.15 g) showed that it was 7-phthalimido-3-methylene-c-4-carboxylic acid methyl ester: MRJ (CDClS) 5 3.47, 3.96 (ABq, 2, J = 17 Hz, C2-H /, 3.87 / s, 3, C4-H /, 5.20 / d, 1, J = 4.5 Hz /, 5.80 / d, 1, J = 4.5 Hz / and 7.83 / m, 4 /. F. Mercury chloride. A mixture of 0.20 g of 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phthalimidoazetidinyl-1) -2-propenecarboxylic acid methyl ester and 0.14 g of mercuric chloride in 10 ml of dry the 1,2-dichloroethane was heated under reflux for 1 hour. The mixture was cooled to room temperature, washed with 1 N HCl, dried (MgSO 4) and evaporated to dryness to give 0.14 g of 3-methylenecepham sulfoxide as a mixture of the R- and S-sulfoxides isomers. G. Ferrous chloride. The same products were used as in F, except that 0.08 g of ferric chloride was used as the catalyst instead of mercury chloride. Comparative thin layer chromatography confirmed the conversion of sulfinyl chloride to 3-methylenecepham sulfoxide. H. Zirconium tetrachloride. The same operations as described under F were repeated, except that 0.12 g of zirconium tetrachloride was used as the catalyst in place of the mercuric chloride. Comparative thin layer chromatography confirmed the pure conversion of the sulfinyl chloride to 3-methylenecepham sulfoxide. The NMR spectrum of the product was identical to that of the product obtained according to point A. AND. Polyphosphoric acid. 2-Methyl-1- (2-chlorosulfinyl-4-keto-3-phthalimido-azetidinyl-1 / -2-propenecarboxylic acid methyl ester (0.20 g) was stirred in about 27 g of polyphosphoric acid over a period of 20 minutes. Ice-water and ethyl acetate (25 ml) were then added to the reaction mixture. The organic layer was separated and washed successively with water, aqueous sodium bicarbonate solution, and brine, dried (MgSO 4) and evaporated in vacuo to dryness to give 0.05 g of methyl-4-phthalimido-3-methyl-4-methyl-4-carboxylate-1-oxide. white foam. J. Sulphuric acid. A solution of 0.20 g of methyl-1- (2-chlorosulfinyl-4-keto-3-phthalimidazetidinyl-1 / -2-propenecarboxylic acid) and 2 drops of concentrated sulfuric acid in 10 ml of dry 1,2-di-diacid The chloroethane was heated to reflux for 1 hour. The reaction mixture was cooled, washed with brine, dried (V, and evaporated in vacuo to dryness to give 0.09 g of a colorless foam, the NMR spectrum of which showed it to be predominantly the target 3-methylenecepham sulfoxide). K. Methanesulfonic acid. The same method as described under J was used except that 0.03 ml of methanesulfonic acid was used as the catalyst instead of sulfuric acid. The product was identified by NMR spectroscopy as the desired 3-methylenecepham sulfoxide. L. Trifluoroacetic acid. A solution of 0.29 g of 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phthalimido-azetidinyl-1- (2-propenecarboxylic acid) methyl ester in 10 ml of trifluoroacetic acid was heated to reflux under reflux. period of 30 minutes and then evaporated to dryness under a vacuum. The residue was dissolved in 20 ml of ethyl acetate. The resulting solution was washed successively with aqueous sodium bicarbonate (3X), water and brine, dried (MgSO 4) and evaporated in vacuo to dryness to give 7-phthalimido-3-methylenecephamocarboxylic-4-methyl ester-1-oxide. 10 M. Silver p-toluenesulfonate. Silver p-toluenesulfonate (0.80 g) was added to a solution of 1.0 g of 2-methyl-1- (2-chlorosulfinyl-4-oxo-3-phthalimidoazetidinyl-1- (-2-propene) acid methyl ester) carboxylic acid in 75 ml of dry toluene. The entirety was stirred at room temperature for 2.5 hours. then filtered. The filtrate was evaporated to dryness in a vacuum and the residue was dissolved in 50 ml of ethyl acetate. The solution was washed and evaporated in a vacuum to dryness. The product 20 was identified by the MRJ method as 7-phthalimido-3-methylenecephamocarboxylic acid-4-methyl ester oxide. Example II. 7-phthalimino-2,2-dimero-3-methylenecephamocarboxylic acid, 4-methyl ester. A mixture of 3.76 g (10 mmol) of methyl ester 6 (3-phthalimidopentilate) sulfoxide 5 ml of deuterium oxide and 500 ml of dry carbon tetrachloride was refluxed for 3 hours. The layers were then separated and the organic layer was dried (MgSO 4). After evaporation to dryness under vacuum, 3.59 g of an amorphous white foam were obtained. The NMR spectrum showed that deuterium (H2) was excluded only to group 2, and only hydrogen (H1) remained in this group less than 29% (determined by alkalization). Mass spectrum analysis showed the following deuterium distribution in the 2α-methyl group: up to -5.8, dj-20.5%, d2-41.3%, d3-32.4% ± 2%. Colorless crystals, m.p. 148 ° -151 ° C., are obtained after recrystallization from a mixture of ethyl ether and acetone; mass spectrum m / e 379, 378, 377, 376, 361, 360, 359, 358, 302/301, 300, 299; IR (KBr): 1800, 1775, and 1725 cm -1; MRJ / CDC18 / 8 1.83 / s, 3 /, 3.85 / s, 45 3 /, 4.62 / s, 1 /, 4, 85 (d, 1, J = 4.5 Hz), 5.86 (d, 1, J = 4.5 Hz), 7.83 (m, 4). Elemental analysis: - Values calculated for C17H16N206S (376.387): C-54.25, H-4.28, N-7.44, 0-25.50, S-8.52%. 50 - Values determined experimentally: C-54.05, H- -4.28, N-7.26, 0-25.61, S-8.53%. A solution of 0.57 g (1.5 mmol) of 2β-fetyl-2α-trdeuteromethyl-6β-phthalimidopenicillanic acid methyl ester 1-oxide and 0.20 g (1.5 mmol) N-55-chlorosuccinimide was heated to reflux. under a reflux cooler for a period of 30 minutes. along with 25 ml of dry 1,1,2-trichloroethane. The reaction mixture was then cooled, washed with water (1.times.50 ml), brine (1.times.50 ml) and dried (MgSO4). The solvent was evaporated in vacuo to give 0.69 g of a mixture of R- and S-sulfinyl chlorides as a light yellow amorphous foam. This mixture was dissolved in 25 ml of dry methylene chloride, and 0.20 (1.7 mmol) of anhydrous tin chloride was added. The whole was mixed for 50 minutes. The product was washed with 1 N hydrochloric acid, dried (MgSO 4) and evaporated in vacuo to give 0.57 g of a mixture of R- and S-sulfoxides as a yellow foam. The material so obtained was dissolved in 4 ml of dry N, N-dimethylformamide, cooled in an ice bath, and then 0.14 ml (1.6 mmol) of phosphorus trichloride was added. After 35 min. the crude mixture was poured into an ice-water mixture and stirred. The resulting precipitate was separated by filtration and dried in vacuo. The yield was 0.38 g. The NMR spectrum showed only a slight signal from the C2 substituent (less than 10th theoretical amount by integration of the NMR spectrum), while the signal of the exomethylene group at the C8 position was normal, showing selective attachment of deuterium to the C2 position. Mass spectrum analysis showed the following deuterium distribution (H2) in the C2 position: down to -2.2%, d = 25.5%, d2-72.3% ± 2M. After recrystallization from a mixture of methylene chloride and cyclohexane, colorless crystals melting at 198-201 ° C. (decomposed) were obtained; mass spectrum m / e: 360,273,174; IR (KBr): 1770, 1740 and 1710 cm "1; MRJ (CDC1): 6 3.80 (s, 3), 5.32 (m, 3), 5.46 (d, 1, J = 4 . 5 Hz /, 5.67 (d, 1, J = 4.5 Hz), 7.83 (m, 4). Elemental analysis: Values calculated for C17H14N2O5S (358.372): C-56.98, H-3.94, N-7.82, 0-22.32, S-8.95%. - Values determined experimentally: C-56.96, H- -3.85, N-7.94%. Example III. 7-phenoxyacetamido-3-methylenecepamino-4-carboxylic acid 4-nitrobenzyl ester oxide. AND. Tin chloride. A mixture of 6.0 g (12 mmol) of 6-phenoxyacetamidopenicillanic acid 4-nitrobenzyl ester-1-oxide and 500 ml of dry toluene was heated under reflux for 10 minutes. using the Dean-Stark attachment to remove traces of water. Then 1.8 g of N-chlorosuccinimide was added and the mixture was heated under reflux for 90 minutes. then cooled to approximately 50 ° C. 1.8 ml of anhydrous tin chloride was added to the resulting sulfinyl chloride solution. The mixture was stirred at room temperature for 90 minutes, then 100 ml of water and 100 ml of ethyl acetate were added. The organic layer was separated and washed with (1 N HCl, aq. NaHCO 3, brine) and dried (MgSO 4). After evaporation to dryness in vacuo, a product was obtained which was crystallized from ethyl acetate to give 2.16 g (36%) of the title product. A sample of the product was recrystallized from a mixture of ethyl acetate and acetone to give large crystals (mp 200-201 ° C MRJ (CDCl):? 3.5 and 3.75 (ABq, 2, J = 14 Hz), 4.55 / s, 2 /, 4.83 / d, 1, J = 4.5 Hz /, 5.3 / s, 2 /, 5.33 / s, 1 /, 5.5 / s, 1 /, 5 , 78 (s, 1), 5.94 and 6.1 (q, 1, J = 4.5 Hz and 8.0 Hz), 6.9-8.3 (m, 9). Elemental analysis: - Values calculated for CMH21NtOeS (499.5): C-55.31, H-4.24, N-8.41, 0-25.62, S-6.42 * / o. - Experimentally determined values: C-55.06, H- -4.14, N-8.30, 0-25.62, S-6.26 »/ o. B. Zinc chloride. 2-Methyl-1- (2-chlorosulfinyl-4-keto-3-phenoxyacetimidazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester) was prepared by heating to reflux for 30 min. a solution of 1 g of 6-phenoxyacetamidopenicillanic acid 4-nitrobenzyl sulfoxide and 0.27 g of N-chlorosuccinimide in 40 ml of 1,1,2-trichloroethane. 0.27 g of zinc chloride was then added. The mixture was heated to reflux for a further 45 minutes. and, after cooling to room temperature, it is washed with 1N HCl (2 ×), dried (MgSO 4) and evaporated in vacuo. The NMR spectrum of the product indicated that it was 7-phenoxyacetamido-3-methylenecephamo-4-carboxylic acid 4-nitrobenzyl ester-1-oxide. C. Silver p-toluenesulfonate. A solution of 1 g of 6-phenoxy-acetamidopenicillanic acid 4-nitrobenzyl ester 1-oxide and 0.27 g of N-chlorosuccinimide in 10 ml of dry toluene was heated to reflux for 1 hour. Then 0.61 g of silver p-toluenesulfonate was added to the hot solution. Everything was mixed for 45 minutes. (the mixture cooled to room temperature). The reaction mixture was filtered, washed with water (2X) and brine, dried with MgS (V and evaporated in vacuo to dryness to give 0.43 g of 7-phenoxyacetamido-3-acid 4-nitrobenzyl ester-1-oxide. 4 methylenephamocarboxylate (with some impurities) in the form of a yellow foam. Example IV. 7-phthalimido-3-methylenecephamocarboxylic acid 4-nitrobenzyl ester 1-oxide. To a solution of 23.1 g of 2-methyl-1- (2-chlorosulfinyl-4-oxo-3-phthalimazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester) in 400 ml of dichloromethane at room temperature, 6 , 1 ml of anhydrous tin chloride. As the reaction progressed, the amount of precipitate formed was increasing. After 45 min. the reaction mixture was washed with 1 N sulfuric acid, water, sodium bicarbonate solution and brine. The organic layer was dried and evaporated in vacuo to dryness, yielding 16.72 g (78%) of the title product. The R- and S-sulfoxide isomers were separated by fractionated recrystallization from acetone and dichloromethane. R-sulfoxide was obtained in the form of colorless crystals, which softened at 155 ° C and was completely finished at 213 ° C: IR / CHCy 1970, 1780, 1738 and 1723 cm -1; mass spectrum m / e 495, 479, 367, 343: MRJ / CDC18 /: 8 3.58 and 4.10 / ABq, 2 J = 13 Hz /, 4.87 / d, 1, J = 4.5 Hz /, 5.33 / s /, 5, 57 (m, 2), 5.95 (d, 1.1, J = 4.5 Hz), 7.4-8.4 (m, 8, ArH). Elemental analysis: - Values calculated for C ^ H ^ NtOsS / 495.5 /: C- -55.76, H-3.46, N-8.48, 0-25.83, S-GAW: - Specified Values experimental: C-55.50, H- 3.45, N-8.65, C-25.17, S-6.32 * / e. S-sulfoxide is isolated as colorless crystals (mp 190-192 ° C): IR (suspension) 1780, 1775, 1741 and 1928 cm "*, MRJ / CDCy: & 3.5 and 3.7 / ABq, 2 J -15 Hz /, 4.9 / d, 1, J = 4.5 Hz /, 5.34 s, 2 /, 5.46 / m, 2 /, 5.6 / d, 1, J = 4, 5 15 20 25 30 35 40 45 50 55 60 114 521 27 28 Hz /, 5.8 / s, 1 /, 7.4-8.4 / m, 8 /. Elemental analysis: - Values calculated for C28H17N808S: C-55.76, H- -3.46, N-8.48, 0-25.83, S-6.47%. - Values determined experimentally: C-55.58, H- -3.62, N-8.25, 0-25.19, S-6.18%. Example V. 7-phenylacetamido-3-methylenecepam-4-carboxylic acid 2,2,2-trichloroethyl ester-1-oxide. A mixture of 1.0 g of 7-phenylacetamidopenicillanic acid 2,2,2-trichloroethyl ester 1-oxide, 0.5 g of N-chlorosuccinimide and 80 ml of dry toluene was heated to reflux for 90 minutes. then cooled and washed (water and brine). To the obtained sulfinyl chloride solution was added 0.28 ml of anhydrous tin chloride. Everything was mixed for 90 minutes. After washing (water and brine), the solvent was evaporated to dryness in a vacuum. The product crystallized from a mixture of ether and ethyl acetate gave the title compound in the form of colorless crystals, mp 187 ° -189 ° C .; MRJ / CDCI3 /: 8 3.5 and 3.81 / ABq, 2 J = 14 Hz /, 3.63 / s, 2 /, 4.8 / m, 2.49 / d, 1, J = 4.5 Hz /, 5.37 / s, 1 /, 5.5 / s, 1 /, 5.82 / s, 1 /, 5.9 and 6.07 / q, 1, J = 4.5 Hz and 10.0 Hz /. 7.0 (d, NH, J = 10 Hz), 7.33 (s, 5). Example VI. 7- (2,2-dimethyl-3-nitroso-5-keto-4-phenyl-imidazolidinyl-1 / -3-methylenecephamocarboxylic acid-4-methyl ester-1-oxide). A mixture of 0.896 g of N-nitrosohethacillin methyl ester sulfoxide and 0.536 g of N-chlorosuccinimide in 55 ml of dry benzene was heated to reflux under nitrogen for about 1 hour. The reaction mixture was cooled and a 5 ml sample of the mixture was taken and evaporated to dryness under reduced pressure. The NMR pattern of the residue thus obtained was consistent with the structure of the target sulfinyl chloride intermediate. The rest of the reaction mixture was cooled under nitrogen in an ice bath, and 0.33 ml of tin chloride was added. A light orange precipitate formed immediately. The whole was mixed for 2 hours. and 15 min. at room temperature, and then 5.5 ml of dimethylacetamide and 55 ml of ethyl acetate are added. The resulting solution was washed with water and brine, dried over CaSO 4, and evaporated in vacuo to dryness, yielding 1.3 g of a yellow oil. This process was dissolved in methylene chloride and applied to 4 plates used in preparative thin layer chramatography. These chromatograms were developed with a 1: 1 mixture of benzene and ethyl acetate. The presence of 2 essential bands was found, one of which, with a lower retention, was the compound mentioned in the title, 3-Methylene Cepham Sulfoxide / mixture of R- and SrSUJIg isomers; with acetonitrile: MRJ (CJCV β 6 gem-dimethyl), 3.73 (s, 3, COOCH3), 4.7-5.6 (m) and 7.3 (s, ArH). Example VII. 2-Methylp-Rl- (2-ulfinine-ketp-3-phthalimidazetidine-lorl, - 2-propeiiocaxboxylic acid 4-trinitrobenzyl ester). A solution of 49, T g / 0 * 1 mpla / 6-phthalimidopenicillanic acid 4-nitrobenzyl ester-1-oxide and N-chlorosuccinimide 13.4 g / 0.1 mol in 1.5 L 1,2-dichloroethane was heated to boiling under reflux for 70 min. After the reaction mixture was cooled, it was washed with water and brine, and dried (MgSO 4). The solvent was evaporated to dryness under reduced pressure, yielding 52. 0 g of azetidinesulfinyl chloride: MRJ (CDCy 8 1.97 (s, 3), 5.05 (s, 1), 5.4 (s, 2), 5.76 (d, 1, J = 5 Hz), 5.91 (d, 1, J = 5 Hz), 7.83 (m, 8.10 ArH). The sulfinyl chloride was converted to sulfinic acid by slurrying the product in ethyl acetate, to which was added 5% sodium bicarbonate solutions at room temperature with stirring for 2 hours. After acidification of the aqueous layer with hydrochloric acid in the presence of ethyl acetate, separation of the organic layer, drying (MgSO 4) and evaporation under reduced pressure, sulfinic acid was obtained in the form of a colorless foam: MRJ (CDCl3) 8 1.92 / s, 3 /, 4.88 / s, 1, J = 4.5 Hz /, 5.00 / s, 2 /, 5.18 / broad, 1 /, 5.38 / s, 2 /, 5.67 / d , 1.1, J = 4.5 Hz (and 7.5-8.3 (m, 9, ArH). Example VIII. 7-phenoxyacetamido-3-methyl-4-methyl-4-methyl ester-1-oxide. A mixture of 4.82 g / 10 mmol / 1-oxide of 6-phenoxyacetamidopenic acid 2,2,2-trichlorethyl ester, 150 ml of dry toluene and 2.0 µmol / N-chlorophthalimide was boiled under a chiller. manoeuvrable within 50 minutes. using the Dean-Stark attachment. A 5 ml sample was evaporated; the NMR spectrum of the residue showed complete conversion to sulfinyl chloride. The solution of sulfinyl chloride in toluene was cooled to about 40 ° C. and 1.4 ml of tin chloride was added. Everything was mixed for 60 minutes. and then washed sequentially with 1 N HCl aq. NaHCO 3 solution and brine, and then dried (HgSO 4). After the solvent was evaporated, 30 ml of chloroform were added to the residue and the insoluble phthalimide was filtered off. The filtrate was evaporated to dryness and the amorphous yellow product was dried under reduced pressure. Yield: 3.4 g and / 70% of the product mentioned in the title; MRJ 45 (CDC13): 8 3.56 and 3.80 (ABq, 2, J = 14 Hz), 4.48 (s, 2), 4.75 µm, 2, CH2CC18), 4.89 (d, 1, J = 4.5 Hz /, 5.33 / s, 1 /, 5.48 / s, 1 /, 5.78 / s, 1 / 5.9 and 6.07 /, 1, J = 4 (5 Hz), 6.8-7.4 (m, 5, ArH) and 8.1 (d, NH, J = 10 Hz). Example IX. 2-Methyl-50-l- (2-sulfino-4-oxo-3-phthalimido-azetidinyl-l- - 2-propenecarboxylic acid methyl ester. A mixture of 3.76 g of 6-phthalimidopenicillanic acid methyl ester sulfoxide and 1.4 g of N-chlorosuccinimide in 250 ml of dry (CaCl2) carbon tetrachloride was refluxed for 70 minutes. The mixture was cooled to room temperature, filtered, washed with water and brine, and dried (MgSO 4). After evaporation to dryness in vacuo, 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phthAmidoazetidinyl-1 / -2-propenecarboxylic acid methyl ester is obtained as a white foam) (see Example IA) . 2 drops of water were added to a solution of 0.25 g of sulfinyl chloride in 25 ml of chloroform. The mixture was refluxed for 30 minutes under reflux. , cooled, dried (MgSO 4) and evaporated to dryness in vacuo to give the title compound as a colorless foam: MRJ (CDCl3 (8 1.93) s, 5.3 -CH8), 3.80 (s) , 3), -COOCH3), 4.88-5.15 (m, 4, C3-H, CH, (3-lactam H), 5.70 (d, 1, J = 5.0 Hz perton) .Β-lactam /, 7.80 (m, 4, ArH). The sulfinyl chloride was also converted to the title sulfinic acid after standing at room temperature with access to air for 2 days. Example X. 7-phthalimido-3-methylenecephamocarboxylic acid-4-methyl ester oxide (from azetidinonesulfinic acid). AND. Phosphorus pentoxide. A solution of 0.10 g of 2-methyl-1- (2-sulfino-4-keto-3-phthalimidoazetidinyl-1 / -2-propenecarboxylic acid methyl ester) and 0.04 g of phosphorus pentoxide in 20 ml 1, 2-dichloroethane was stirred at room temperature for 1 hour. The thin-layer chromatogram of the reaction mixture indicated the presence of only trace amounts of methylcepham sulfoxide. The mixture was then boiled under reflux for 30 minutes. , cooled to room temperature and combined with 25 ml of ethyl acetate and 50 ml of brine. The organic layer was separated, washed with aqueous sodium hydrogen carbonate and brine, and dried (MgSO 4). 0.04 g of the title * compound was evaporated to dryness under a vacuum in the form of 30 white filly. B. Sulphuric acid. The same operations as described in Example I (J) were carried out with the difference that the starting compound was 0.20 g of 2, -methyl-1- (2-sulfinyl) acid methyl ester instead of the corresponding sulfinyl chloride derivative. 4-keto-3-phthalimidazetidinyl-l / -2-proenecarboxylic acid. 0.03 g of the title compound was obtained. C. Polyphosphoric acid. The same operations were carried out as in Example I (J), except that the starting compound was 0.20 g of 2-methyl-1- (2-methyl-1-2-acid) methyl ester instead of the corresponding sulfinyl chloride derivative. -sulfino-4-keto-3-phthalimidoazetidinyl-1 / -2-propenecarboxylic acid. The yield was 0.10 g of the title compound 45 D. Trifluoroacetic acid. The same operations were carried out as described in Example 1, except that 0.20 g of 2-methyl-1- (2-sulfinyl) acid methyl ester was used as starting material instead of the corresponding sulfinyl chloride derivative. finq-4-keto-3-phthalimidazetidinyl-l / -2-proenecarboxylic acid. The NMR spectrum of the obtained product indicated that it is mostly the compound mentioned in the title. Example XI. AND. 2-Methyl-142-chlorosulfinyl-4-keto-3- (N-phenoxyacetyl-N- (2,2,2-trichloroethoxycarbonyl) -aminoazetidinyl-1) -2- acid 4-nitrobenzyl ester propenecarboxylic acid. A mixture of 4.855 g / 10 mmol / 6-phenoxyacetami-3-90 to-2,2-dimethyl-penamocarboxylic acid 4-nitrobenzyl ester, 16.94 g (8 O mmol) 2,2,2-trichlorethyl chloroformate, 18 ml N, 0 - (bis-trimethylsilyl) -trifluoromethylacetamide and 20 ml of methylene chloride. The mixture was allowed to stand overnight at room temperature and then heated to reflux for 7 hours. and then left to stand overnight at room temperature. Heating of the mixture was continued for a further 6 hours. The mixture was then evaporated and the residue dissolved in benzene, the resulting solution added to a large excess of heptane. The insoluble material was filtered off, dissolved in benzene and chromatographed on silica gel using a mixture of benzene and ethyl acetate as eluent. 4.76 g (72%) of the product 6-i [N-phenoxyacetyl-N- (2,2,2-trichloroethoxycarbonyl) amino] -2,2-dimethyl-3-dimethyl-4-nitrobenzyl ester were obtained: MRJ / CDCIJ 8 4.41 7s, 3 /, 1.62 / s, 3 /, 4.61 / s, 1 /, 4.84 / d, 1, J = 12 Hz /, 4.99 / d, 1, J = 12 Hz /, 5.20 / s, 2 /, 5.30 and / s, 2 /, 5.66 / s, 2 /, 6.8-7.4 / m, 5 /, 7 , 53 (d, 2, J = 9 Hz), 7.22 (d, 2, J = 9 Hz). B. Production of sulfoxide. 2.54 g (3.84 mmol) of the above product was added to about 75 ml of acetone. The mixture was cooled to -70 ° C and excess ozone was introduced into the reaction mixture at a rate of about 1.17 mmol / min. within 9 min. during which time the reaction mixture became blue in color. The mixture was kept at -70 ° C for about 35 minutes. and then warmed to room temperature. The solvent was removed under reduced pressure to give 2.76 g of 6-N-phenoxyacetyl-N- (2,2,2-trichloroethoxycarbonyl) -amino-2,2-diethyl-3-carboxylic acid 4-nitrobenzyl ester-1-oxide. Spectrum of the MRJ 7CDC1S: 8 1.22 / s, 3 /, 162 / s, 3 /, 4.60 / s, 1 /, 4.78 / d, 1, J = 5 Hz /, 4.93 / s, 2 /, 5.26 / s, 2 /, 5.30 / s, 2 /, 5.93 / d, 1, J = 5 Hz /, 6.8-7.4 / m, 5 /, 7, 51 (d, 2, J = 9 Hz) and 8.20 (d, 2, J = 9 Hz). C. Preparation of sulfinyl chloride. To 40 ml of dry benzene were added 792 mg (about 1 mmol) of the product obtained above and 155 mg (about 1.2 mmol) of N-chlorosuccinimide. The resulting mixture was heated to reflux for 1 hour. The NMR spectrum of the reaction mixture indicated the presence of the title compound: MRJ / CDC1S / 8 1.92 / s, 3 /, 4.89 / s, 1 /, 4.96 / s, 2 /, 5.05 / s, 2 /, 5.23 / s, 2 /, 5.26 / s, 1 /, 5.34 / s, 2 /, 5.64 / d, 1, J = 5 Hz /, 5.95 / d, 1, J = 5 Hz /, 6.10 (d, 1, J = 6 Hz), 6.8-7.5 (m, 5), 7.56 (d, 2, J = 9 Hz) and 8 , 23 (d, 2, J = 9 Hz). D. Conversion to 7- [N-phenoxyacetyl-N- (2,2,2-trichloroethoxycarbonyl-amino] -3-methylenecephamocarboxylic acid-4-oxide) 1-oxide. 390 mg (1.5 mmol) of tin chloride was added to the ether reaction mixture (above), cooled to room temperature. The mixture was kept at room temperature for a continuous 75 minutes. , a. then 5 ml of methanol was added. An additional amount of benzene was then added and the whole was washed three times with a mixture of HCl and aqueous sodium chloride solution. The benzene layer was separated, dried over sodium sulfate and evaporated to dryness under reduced pressure. The residue was chromatographed on silica gel (15% of water), 114 521 31 32, where a mixture of benzene and ethyl acetate in a changed ratio was used as eluent, yielding 246 mg of exomethylenecylamine sulfoxide: MRJ (CDCl). 8 3.42 / d, 1, J = 13 Hz /, 3.98 / d, 1, J = 13 Hz /, 3.98 / d, 1, J = 13 Hz /, 4.64 / d, 1 , J = 5 Hz /, 4.94 / s, 2 /, 5.25 / s, 2 /, 5.30 / s, 2 /, 5.34 / s, 1 /, 5.47 / s, 1 /, 6.04 (d, 1, J = 5 Hz), 6.8-7.4 (m, 5), 7.55 (d, 2, J = 9 Hz) and 8.23 / d, 2 , J = 9 Hz /. Example XII. 7-phenoxyacetamido-3-methylenecepacetamido-3-methylenecepacarboxylic acid-1-oxide. To 200 ml of dry toluene were added 5.6 g (10 mmol) 1-oxides of 6-phenoxyacetamido-2,2-dimethylpenanecarboxylic acid 4-bromophenacyl ester and 5.2 g (50 mmol) of sodium bisulfite. The mixture was heated to reflux and 1.5 g / L mmol / N-chlorosyccinimide was added. The mixture was stirred and refluxed for 1 hour. and then cooled in an ice bath and 1.3 g / L mmol / of tin chloride was added. The mixture was stirred at room temperature for 2 hours and then poured into a mixture of ethyl acetate and water. The organic layer was separated and washed successively with 5% hydrochloric acid, 5% sodium bicarbonate solution and brine. The mixture was dried over magnesium sulfate and, after evaporation in vacuo to near dryness, 1.75 g (31%) of the title compound was obtained, which crystallized and was isolated. The NMR spectrum of the product was consistent with the structure of the compound mentioned in the title. Elemental Analysis: Values Calculated for C 16 HttN 2 SBr: C, 51.35, H, 3.77, N, 4.99, Br, 14.23%. - Values determined experimentally: C-51.03, H- -3.91, N-5.10, Br-14.46%. Example XIII. 7-phenoxyacetamido-3-methylenecepamocarboxylic acid 1- oxide. To 200 ml of dried toluene were added 4.95 g (10 mmoles) of 6-phenoxyacetamido-2,2-dimethyl-3-dimethyl-3-methoxybenzyl ester-1-oxide and sodium bisulfite 5.2 g (50 mmoles). The mixture was heated to reflux and 1.5 g / L mmol / N-chlorosuccinimide was added. The mixture was stirred and refluxed for 1 hour, then cooled in an ice bath, and 1.3 g (1) mmol of tin chloride was added. The mixture was stirred at room temperature for 2 hours and then poured into a mixture of ethyl acetate and water. The organic layer was separated and washed successively with 5% hydrochloric acid and brine. The organic layer was then extracted with 5% sodium bicarbonate solution. The extract was taken up with ethyl acetate and acidified to pH 2.5. The ethyl acetate layer was separated, washed with water, dried over magnesium sulfate and concentrated in vacuo to a low volume, from which 1.3 g / 35 W of the title compound crystallized. The analysis of the NMR spectrum of the product was consistent with the structure of the compound mentioned in the title. Elemental analysis: - Values calculated for C18H16N208S: C-52.74, H- -4.43, N-7.69Ve. - Experimentally determined values: C-52 99 H- -4.64, N-7.5lVo. '' Example XIV. AND. 2-Methyl-l, -2-chlorosulfinyl-4-keto-3-phenoxy-acetamido-azetidinyl-l / -2 acid benzhydryl ester. -propenecarboxylic acid. To 800 ml of dry toluene, 20 g of 6-phenoxyacetamide-2, 2-dimethyl-3-carboxylic acid benzhydryl 1-oxide were added. The mixtures were heated to boiling in the Dean-Stark trap system to azeotropically remove residual moisture. 12.2 g of N-chlorosuccinimide were added stepwise to the mixture and the reflux was continued for a further 1.5 to 5 hours. The product was analyzed by the NMR spectroscopy method, and the spectrum was consistent with the structure of the compound mentioned in the title: MRJ / CDCy 8 1.88 / s, 3 /, 4.53 / s, 2 /, 4.90 / s, 1 /, 5.14 / s, 2 /, 5.54 / d, 1, J = 4 Hz /, 6.24 / q, 1, J = 4 Hz and 8 Hz /, 6.95 / s, 20 1 /, 7.15-7.4 (m, 15) and 8.0 (d, 1, J = 8 Hz). B. Conversion to exomethylene cepham sulfoxide. In accordance with the method described in Example 13, the azetidinonesulfinyl chloride from A was cyclized with stannous chloride to give 7-phenoxyacetamido-3-methylenecephamocarboxylic-4-carboxylic acid-1-oxide. Example XV. AND. 2-Methyl-1-i [chlorosulfinyl-4-keto-3- (4-nitrobenzyloxycarbamido) azetidinyl-1] -2-propenecarboxylic acid 2,2,2-trichloroethyl ester. A mixture of 300 ml of 1,1,2-trichloroethane and 10.26 g of 6- (4-nitrobenzyloxycarbamido) -2,2-dimethyl-3-dimethyl-3-carboxylic acid k-oxide was prepared. The mixture was heated to reflux, removing about 75 ml of solvent to dry the reaction mixture. The mixture was then cooled and propylene oxide was added followed by 4 g of N-chlorosuccinimide. The temperature of the reaction mixture rose to 102 ° C., and the mixture was then refluxed for 2.5 hours. A sample of the reaction mixture was taken and its solvent was evaporated. The NMR spectrum of the residue was consistent with the structure of the compound presented in the title: MRJ (CDCy 8 1.94 (wide s, 3), 4.83 (s, 2), 5.25 (s, 2), 5.0 - 5.4 (m, 3), 6.2 (d, 1, J = 4 Hz), 7.55 (d, 2, J = 8 Hz) and 8.24 (d 2, J = 8 Hz). B. Conversion to 7- (4-nitrobenzyloxycarbamamide) -3-methylenecephamocarboxylic acid-1-oxide of the 2,2,2-trichloroethyl ester. An aliquot of about 1/3 of the reaction mixture from step A was evaporated and the residue was dissolved in 100 ml of dry methylene chloride. 5 ml of tin chloride was added to the resulting mixture. The mixture was worked up according to the method of Example XII to obtain 700 mg of 3-methylenechamine sulfoxide; MRJ / CDC1, / & 3.60, 3.88 / ABq, 2, J = 15 Hz /, 4.82 / s, 2 /, 4.94 / d, 1, J = 4.5 Hz /, 5 , 23 / s, 27, 5.40 / s, 1 /, 5.56 / s, 1 /, 5.83 / s, 1 /, 6.37 / d, 1, J = 10 Hz /, 7 , 46 (d, 2, J = 9 Hz) and 8.20 (d, 2, J = 9 Hz). Example XVI. AND. 2-Methyl-1- (2-chlorosulfinyl-4-keto-3-acetaminazetidinyl-1- (2-chlorosulfinyl-4-keto-3-acetidazetidinyl-1 / -2-propenecarboxylic acid) 4-nitrobenzyl ester. 30 35 40 45 50 114 521 33 34 Toluene (500 ml) was heated in a flask fitted with a Dean-Stark trap to azeotropically remove residual moisture. 1.0 g (2.4 mmol) of 6-acetamido-2,2-dimethyl-3-penamecarboxylic acid 4-nitrobenzyl ester-1-oxide was added to the thus dried toluene. The mixture was heated to reflux using a Dean-Stark trap to remove additional residual water. The mixture was then cooled and 400 mg (2.9 mmol) of N-chlorosuccinimide was added. It was heated to reflux for 1 hour. The reaction mixture was sampled and the solvent was removed. The product thus obtained had a NMR spectrum in accordance with the structure of the compound mentioned in the title: MRJ / CDC13 / 8 1.86 / broad s, 3 /, 2.04, 2.09 / 2s, 3 /, 4.80 / m, 1 / , 5.2 (m, 2), 5.28 (s, 2), 5.63 (m, 1), 6.05 (d, 1, J = 4 Hz) and 7.4-8.4) q, 4, ArH). B. Conversion to 7-acetamido-3-methylenecyphamocarboxylic acid 4-nitrobenzyl ester 1-oxide. The reaction mixture from step A was cooled in an ice bath and 1 ml of tin chloride was added. Everything was held for 2 hours. at room temperature and then evaporated in vacuo to dryness. The residue obtained is dissolved in ethyl acetate and the mixture with ethyl acetate is washed twice with a mixture of HCl and aqueous sodium chloride solution and twice with aqueous sodium chloride solution, dried over magnesium sulfate and evaporated to dryness in vacuo. The residue was dissolved in the minimum amount of ethyl acetate and, after standing overnight, the resulting crystals of 3-methylenecepham sulfoxide were separated: MRJ (CDC18 (8) 1.92 (s, 3), 3.80 (s, 2) wide. 5.00 / d, 1, J = 4 Hz /, 5.32 / s, 2 /, 5.45— —5.80 / m, 5 /, 7.60 / d, 2, J = 8 Hz / , 7.86 (d, 1, J = 9 Hz) and 8.20 (d, 2, J = 8 Hz). Example XVII. 7-phenoxyacetamido-3-methylenecepacetamido-3-methylenecepacarboxylic acid-4-nitrobenzyl ester-1-oxide (isolation of the complex compound). 750 ml of toluene was heated to reflux for 15 minutes using a Dean-Stark trap. 35 ml of propylene oxide, 25 g of 6-phenoxyacetimidopenicillanic acid 4-nitrobenzyl ester-1-oxide and 7.37 N-chlorosuccinimide were added to the dried toluene. The reaction mixture was heated to reflux at 100 ° C for 2 h. then 120 ml of toluene were distilled from the mixture. After cooling, 7.3 ml of tin chloride were added. Filtration of the reaction mixture yielded 17.1 g of an orange complex which was dissolved in ethyl acetate and washed with an aqueous solution of LCl and brine. The ethyl acetate solution was dried and evaporated in vacuo to dryness, yielding 6.9 g of the title compound. Example XVIII. AND. 2-Methyl-1- (2-bromosulfinyl-4-keto-3-phthalimido-azetidinyl-1 / -2-propenecarboxylic acid methyl ester). A mixture of 1.88 g of 6-phthalimidopenicillanic acid methyl 1-oxide and 890 mg of N-bromidefccinimide in 150 ml of carbon tetrachloride was heated to reflux for 80 minutes. The reaction mixture was cooled, washed with water and brine, dried over anhydrous MgSO 4, and evaporated to dryness in vacuo to give 1.82 g of the title compound: 5 MRJ (CDCy 8 1.98 (broad, 3/3). 82 / s, 3, COOCH "/, 5.0-5.35 / m, 3 /, 5.8-6.2 / m, 2, hydrogen (3-lactam) and 7.80 / wide, 4 , ArH /. B. Conversion to exomethylene cepham sulfoxide. The azetidinone sulfinyl bromide obtained above was dissolved in 20 ml of methylene chloride, and 0.6 ml of tin chloride was added to the solution. After 45 min. at room temperature, the reaction mixture was washed with water and brine, dried over anhydrous MgSO 4, and evaporated in vacuo to dryness to give 1.15 g of 7-phthalimido-3-methylenecepam-4-carboxylic acid methyl ester-1-oxide / a mixture of R sulfoxide isomers. - and SA For the main isomer: MRJ / CDCy 8 3.64, 4.20 / ABq, 2, J = 13.0 Hz, C2-H /, 3.84 / s, 3, COOCH8 /, 20 4.90 (d, 1, J = 4.0 Hz, 0-lactam hydrogen), 5.3-5.7 (m, 3), 5.96 / d, 1, J = 4.0 Hz, β-lactam hydrogen (and 7.84 (broad s, 4, ArH). Example XIX. AND. 2-Methyl-1- (2-isopropylthiosulfinyl-4-keto-3- 25-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester). To a solution of 10 g of 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid- »• -3) in 450 ml of toluene was added 1 9 ml of isopropyl mercaptan and 3.5 ml of propylene oxide. The mixture was allowed to stand at room temperature for several days and then evaporated to dryness in vacuo to give an oily residue which was chromatographed on a silica gel column using a mixture of toluene and ethyl acetate as the eluent. relationship. In total, 6.62 g of the product with the name given in the title were isolated: MRJ / CDC1, / 8 1.40 * • / d, 6, J = 6.0 Hz, SCH / CH8 / 2 /, 2.01 / s, 3 /, 3.35 / m, 1, SCH / CH8 / 2, 4.60 / s, 2, side-chain CH2 /, 5.1-5.3 / m, 3 /, 5.53 / s, 2, ester CH2 /, 6.20 (dd, 1, J = 4.5 and 10.0 Hz, β-lactam hydrogen), 6.9-8.3 (m, 9, ArH) and 8.6 (d) , 2, J = 10.0 Hz, NH). 45 B. Conversion to exomethylene cepham sulfoxide. The compound of step A was dissolved in 3.4 ml of methanesulfonic acid. After 30 min. the solution was poured into a separating funnel containing ethyl acetate and saturated sodium bicarbonate solution. The organic layer was separated, washed successively with aqueous sodium bicarbonate, water and brine (2X), and dried over anhydrous MgSO 4. The product was crystallized from ethyl acetate overnight. In total, 60 mg of 7-phenoxyacetamido-3-methylenecepam-4-carboxylic acid 4-nitrobenzyl ester-1-oxide were recovered. Example XX. AND. 2-Methyl-1- (2-III-tier) acid, 4-nitrobenzyl ester -butylthiosulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid. The same method as described in Example 19 was used, but instead of isopropyl mercaptan 2.4 ml of tert-butyl mercaptan was used. 85 As a result of the chromatographic separation, 4.69 g of the product with the name given in the title: MRJ / CDC13 / 8 1.43 / s, 9, III row was released. -butyl /, 2.0 l, (s, 3), 4.57 s, 2, side-chain -CH2 /, 5.0-5.4 (m, 5), 6.20 (dd, 1, J = 4 .0 and 11.0 Hz, hydrogen (3-lactam), 6.8-8.2 (m, 9, ArH) and 8.64 (d, 1: J = 11.0 Hz, NH). B. Conversion to exomethylene cepham sulfoxide. The compound of Step A (700 mg) was dissolved in 3.5 ml of methanesulfonic acid. Using the same operations as described in the second part of Example IX, 190 mg of 7-phenoxyacetamido-3-methyl- 4-carboxylic acid 4-nitrobenzyl ester-1-oxide were obtained. Example XXI. AND. 2-Methyl-1- (2-methoxysulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester). To a solution of 2-methyl-1- (2-chlorosulfinyl-4-oxo-3-phenoxyacetimazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester) obtained from 10 g of 4-nitrobenzyl acid 1-oxide 6-phenoxyacetamidopenicillate and 2.68 g of N-chlorosuccinimide, in 400 ml of toluene, 25 ml of dry methanol were added. The mixture was stirred at room temperature overnight and then washed successively with aqueous sodium bicarbonate (2.times.), Water, and brine (2.times.). After evaporation in vacuo to dryness, 10 g of impure product named in the title were obtained, which was purified by chromatography on acid washed silica gel using a variable ratio of toluene and ethyl acetate as eluent. The product was isolated as a mixture of (R- and S-sulfinates) isomers. For the basic isomer: MRJ (CDCy b 1.90 (s, 3), 3.74 (s, 3, -OCH8), 4.52 (s, 2, CH2 side chain), 4.8-5.3 µm, 5), 5.32 (s,% CH2 ester), 5.76 (dd, 1, J = 5.0 Hz and 9.0 Hz, β-lactam hydrogen and 6.8-8.2 (m), 9 , ArH /. B. Conversion to exomethylene cepham sulfoxide. From step A (590 mg) was dissolved in 2.0 ml of methanesulfonic acid. After 30 min. at room temperature, the mixture was treated as in the second part of Example 19, yielding 0.13 g (40%) of 7-phenoxyacetamido-3-methylenecephem-4-carboxylic acid-4-nitrobenzyl-1-oxide. Example XXII. AND. 2-Methyl-1- (2-methyloxysulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester). The same operations as described in Example 21 were carried out with the difference that 3.12 g (20 mmol) of menthol was used instead of methanol. The sulfinate ester product was isolated by chromatography on acid washed silica gel with a variable ratio mixture of tolun and ethyl acetate as eluent. The isolated product was a mixture of the R- and S-sulfinate isomers. For the main isomer: MRJ (CDCy 6 0.6-2.4 (m, 18, menthyl hydrogen), 1.86 (s, 3), 3.98 (broad, 1), 4.52 / s, 2, side-chain CH2 /, 4.72 (d, 1, J = 5, ti Hz, β-lactam hydrogen), 4.8-5.2 (m, 3), 5.36 (s, 2, ester CH3) , 5, ± 2 (dd, 1, J = 5.0 and 9.0 Hz, β-lactam hydrogen), 6.8-8.2 (m, 9, ArH7 and 7.85 (d, 1.) J = 9.0 Hz, -NH). B. Conversion to exomethylene cepham sulfoxide. The product of Step A (906 mg) was dissolved in 4.6 ml of methanesulfonic acid. After 30 min. at room temperature the reaction mixture was worked up according to the method given in the second. part of example XIX. The conversion of the substrate to 7-phenoxy-10-acetamido-3-methyl-4-methyl-4-carboxylic acid 4-nitrobenzyl ester-1-oxide was confirmed by thin layer chromatography and NMR spectroscopy. Example XXIII. AND. 2-Methyl-1- (2-anilinsulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester). To a solution of 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phenoxyacetimazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester) prepared from 10 g of 4-nitrobenzyl ester 1-oxide 6-phenoxyacetamidopenicillanic acid and 2.68 g of N-chlorosuccinimide, 3.6 ml of aniline in 400 ml of toluene were added. After 5 min. at room temperature, the reaction mixture was washed with water (2 ×) and brine, dried over anhydrous MgSO 4, and evaporated to dryness in vacuo to give the title product: MRJ (CDCy 8 1.96 (s, 3), 4.5). s, 2, side chain CHg /, 5.34 (s, 2, ester CH2), 5.0-5.3 (m, 3), 5.77 (dd, 1, J = 4.5 Hz 30 and 10 0.0 Hz, hydrogen (3-lactam) and 6.8-8.4 (m, 14, ArH). B. Conversion to exomethylene cepham sulfoxide. The product of Step A (2.07 g) was dissolved in 10 ml of methanesulfonic acid. After 30 min. the solution was poured slowly into a cold mixture of saturated aqueous sodium hydrogen carbonate solution and ethyl acetate. The ethyl acetate layers were separated, washed successively with aqueous sodium bicarbonate (2.times. Water (2.times.) And brine (2.times.), Dried over anhydrous MgSO4 and evaporated in vacuo to dryness. 7-phenoxyacetamido-3-methylenecephamocarboxylic acid 4-nitrobenzyl ester-1-oxide (373 mg, 21%) crystallized from the ethyl acetate solution as impure product. 45 tyl-1- (2-N-succinimidosulfinyl-4-keto-3-phenyl). Example XXIV. AND. 2-Methyl-1- (2-N-succinimide-sulfinyl-4-keto-3-phenylacetamidoazetidinyl-1- (2-N-succinimide) -sulfinyl-4-keto-3-phenylacetamidoazetidinyl-1 / -2-propenecarboxylic acid methyl ester. A solution of 2.55 g II mmol / 4-nitro 1-oxide, 5.6 ml / 34 mmol / N-trimethylsilylsuccinimide and 0.18 ml of acetic acid in 41 ml of dimethylacetamide was stirred for 3.5 at the temperature was poured into a cold mixture of 50 mL of ethyl acetate and 150 mL of water. The aqueous layer was extracted twice with ethyl acetate. The combined ethyl acetate extracts were washed with water, dried over anhydrous MgSO 4 and evaporated in vacuo to dryness to give 3.3 g of methyl 2-methyl-1- (2-N-succinimidothio-4-keto-3) acid methyl ester. -phenylacetami-doazetidinyl-1 / -2-propenokarya-oxyl. MRJ, (CDCy 5 1.84 / s, 3); 2 ^ / s, 4, succinimide / ,. 3.65 (s, 2, side chain CHj), 3.74 (s, 3, COOCH), at 4.66 (s, 1), 5.6-5.5 µm, 4, hydrogen. O-lactam and ole? 40 50 55 80 114 521 37 fin CH2 (7.26 (s, 5, ArH) and 7.58 (d, 1, J = 8.0 Hz, -NH). The sulfenimide obtained above was dissolved in 50 ml of methylene chloride at 0 ° C. and oxidized with 1.48 g of m-chloroperbenzoic acid. After 1 hour reaction at 0 ° C, the reaction mixture was washed with an aqueous saturated sodium bicarbonate solution, water, brine, dried over anhydrous MgSO 4, and evaporated in vacuo to dryness to give the title product: MRJ / CDClS / 8 1.86 / s, 3 / 2.60 (s, 4, succinimide hydrogen) 3.54 (s, 2, CH2 side chain), 3.78 (s, 3, COOCH8), 4.8-5.2 (m, 3) , 5.6-5.9 (m, 1, 0-lactam hydrogen), 6.04 (d, 1, J = 5.0 Hz, β-lactam hydrogen) and 7.3 (s, 5, ArH /. B. Conversion to exomethylene cepham sulfoxide. The compound of Step A (469 mg, 1 mmol) was dissolved in 2.3 ml of methanesulfonic acid. After 30 min. At room temperature, the solution was poured slowly into a mixture of saturated aqueous sodium hydrogen carbonate solution with ethyl acetate. The ethyl acetate layers were separated, washed successively with aqueous sodium bicarbonate solution, water and brine, dried over anhydrous MgSO 4 and evaporated to dryness in vacuo. The conversion of 7-phenylacetam-to-3-methylenecephamocarboxylic-4-acid methyl ester to 1-oxide was confirmed by comparative thin layer chromatography and NMR spectroscopy. Example XXV. AND. 2-Methyl-l-i [2- (N, N'-dicarboethoxyhydrazosulfino) -4-keto-3-phenoxyacetamidazetidinyl-l-2-propenecarboxylic acid 4-nitrobenzyl ester. A solution of 10 g of 6-phenoxyacetamidopenicillanic acid 4-nitrobenzyl ester 1-oxide in 300 ml of dry 1,1,2-trichlorethane was heated to reflux and dried using a Dean-Stark trap. After about 50 ml of solvent had been distilled off, the mixture was cooled and 6 ml of diethyl azodicarboxylate was added. The reaction mixture was boiled under reflux for 45 minutes. and then evaporated to dryness under a vacuum. The residue was triturated with hexane to remove excess diethyl nitricarboxylate. Further drying of the title compound resulted in a contaminated yellow resinous product which was not further purified prior to its conversion to exomethylene cepham sulfoxide: MRJ (CDCl 3) 8 1.40 (t, 3, J = 7 Hz, CH 2 CH 3). 1.95 (broad s, 3), 3.8-4.7 (m, 6), 5.0-5.6 (m, 5) and 6.7-8.4 (m, 9, ArH) . B. Conversion to exomethylene cepham sulfoxide. 1 g of the product from step A was dissolved in 20 ml of methanesulfonic acid. The mixture was stirred at room temperature for 20 minutes. and then poured into an aqueous sodium chloride solution. The aqueous solution was then extracted with 200 ml of ethyl acetate. The ethyl acetate extract was washed with an aqueous sodium bicarbonate solution, dried (MgSO 4) and evaporated in a vacuum to dryness. The residue was purified by preparative thin-layer chromatography using silica gel plates developed with a 90% mixture of ethyl acetate and benzene. 160 mg of 7-phenoxyacetamido-3-methylenecephamo-4-carboxylic acid-4-nitrobenzoate 1-oxide were thus isolated. Example XXVI. AND. 2-Methyl-1-i [2- / N, N'-dicarbo-tertiary acid 4-hitrobenzyl ester. butoxyhydrazsulfinyl) -4-keto-3-acetamidoazetidinyl-1] -2-propenecarboxylic acid. In accordance with the method described in Example XXV, 820 mg of 5-acetamidopenicillanic acid 4-nitrobenzyl ester-1-oxide were reacted with 465 mg of di-tertiary azodicarboxylate. butyl, receiving the product mentioned in the title: MRJ / CDC13 / 8 1.50 / s, 18, III row. butyl), 190 (broad s, 3), 2.00 (s, 3, CH3C (0 (NH-)), 5.40 (s, 2, ester CHj), 5.0-6.0 (m, 5) (and 7.6-8.4 (m, 4, ArH). 15 B. Conversion to exomethylene sulfoxide. The product from step A was dissolved in 15 ml of methanesulfonic acid and after 10 min. keeping at room temperature, poured into a saturated aqueous sodium chloride solution. The aqueous solution was extracted with ethyl acetate. The organic extract was washed with aqueous sodium hydrogen carbonate, dried (MgSO 4) and evaporated in vacuo to dryness. Chromatographic purification of the residue for 7-acetamido-3-methylenecepam-4-4-nitrobenzyl-4-nitrobenzyl ester 1-oxide: MRJ / CDCy 8 2.04 / s, 3, CH8C / Ó / -NH- /, 3.66 (broad s, 2, C2-H), 4.90 (d, 1, J = 4.0 Hz, C "-H), 5.26 / s, 3, C4- H + ester CHj /, 5.45, 5.74 (2s, 2, = CH2), 5.92 (dd, 1, J = 4.0 and 8.0 Hz, C7-H), 6.97 (d, 1, J = 8.0 Hz, -NH) and 7.4-8.4 (m, 4, ArH). Example XXVII. 7V2-thienylacetamido / -3-methylenecepam-4-carboxylic acid 2,2,2-trichlorethyl ester sulfoxide. A solution of 1 g of 6- (2-thienyl acetamidopenicylic acid 2,2,2-trichloroethyl ester 1-oxide) and 525 mg of di-tertiary azodicarboxylate. of butyl alcohol in 50 ml of 1,1,2-trichloroethane was refluxed for 45 min. The reaction mixture was then cooled and evaporated to dryness in vacuo. The residue thus obtained was dissolved in methanesulfonic acid and after 15 min. At room temperature, the acidic solution was poured into a saturated aqueous sodium chloride solution. The aqueous solution was extracted with ethyl acetate. The organic extract was washed with sodium bicarbonate solution, dried (MgSO 4) and evaporated in vacuo to dryness to give 72 mg (7%) of the title product: MRJ (CDC18 / 8 2.87) wide, 2, C2-H /, 3.75 / s, 2, side-chain CH2 /, 4.80 / s, 2, ester CH2 /, 5.28 / d, 1, J = 4.0 Hz, C6-H / , 5.46, 5.77 (-2a, 2, = CH2), 5.90 (dd, 1, J = 4.0 and 8.0 Hz, C7-H) and 6.8-7.3) m, 3, ArH /. 55 Example XXVIII. AND. 2-Methyl-l - ([2- (N, N'-dibenzoylhydrazosulfyl) -4-keto-3-phenoxyacetamidoazetidinyl-l] -2-propenecarboxylic acid 4-nitrobenzyl ester. According to the method described in Example XXV, as many as 10 g of 6'-phenoxyacetamidopenicillanic acid 4-nitrobenzophenic acid-1-oxide were reacted with 7.8 g of dibenzoylbidimide in dry 1,1,2-trichloroethane. B. Conversion to exomethylene-acefam sulfoxide. 1 g of the crude product of step A114 521 39 40 10 15 20 25 was dissolved in 20 ml of methanesulfonic acid. After 20 min. the mixture was poured into 300 ml of a saturated aqueous sodium chloride solution. The aqueous solution was extracted with 200 ml of ethyl acetate and the organic extract was washed with sodium bicarbonate solution, dried over MgSO 4 and evaporated to dryness in a vacuum. The 7-phenoxyacetamino-3-methylenecepham-4-carboxylic acid-4-nitrobenzyl ester-1-oxide (90 mg, 40%) was isolated by preparative thin-layer chromatography. Example XXIX. AND. 2-Methyl-1- (2-acetalohydrazosulfinyl-4-ke- to-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester). To a solution of 2-methyl-1- (2-chlorosulfinyl-4-oxo-3-phenoxyacetimazetidinyl-1,2-propenecarboxylic acid 4-nitrobenzyl ester) made from 50 g of 4-nitrobenzyl ester 1-oxide 6-phenoxyacetamidopenicillanic acid and 15 g of N-chlorosuccinimide in 1000 ml of 1,1,2-trichloroethane (14.8 g of acetylhydrazide were added at room temperature). Everything was mixed for 30 minutes. at room temperature and then the reaction mixture was washed three times with 500 ml of a saturated aqueous sodium chloride solution three times, dried with MgS (V, and evaporated in vacuo to dryness). The residue was dissolved in ethyl acetate. After storage in a freezer, 29.7 g (52%) of the compound mentioned in the title: MRJ (CDCl) (8 1.94), 6, CH 3 C (0 - + allyl CH 2) crystallized out of the solution. 4.65 (s, 2, side chain CH2, 4.9-5.4 (m, 5), 5.55 (s, 2, ester CH2) and 6.8-8.4 (m, 9, ArH) . B. Conversion to exomethylene sulfoxide. 2 g of the compound from Step A was dissolved in 20 ml of methanesulfonic acid. After 15 min. At room temperature, the acid solution was poured into a separating funnel containing 200 mL of ethyl acetate, 250 mL of saturated sodium chloride solution, and 250 mL of saturated sodium bicarbonate. The organic layer was separated, washed with sodium bicarbonate solution, dried (MgSO 4) and evaporated in vacuo to dryness. The residue was dissolved in the minimum amount of ethyl acetate, from which on standing, 879 mg (51%) of 7-phenoxyacetimino-3-methylenecephamocarboxylic-4-4-nitrobenzyl ester-1-oxide crystallized. Example XXX. AND. 2-Methyl-1- (2-carbomethoxyhydrazsulfin-4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester). According to the method given in Example XXIX, carbomethoxyhydrazide (4.5 g) was reacted with a sulfinyl chloride derivative obtained from 15 g of 6-phenoxyacetimopenicillanic acid 4-nitrobenzyl ester-1-oxide to obtain the yellow resin product mentioned in the title : MRJ / CDC13 / o 1.92 / wide s, 3 /, 3.66 / s, 3, COOCH, /, 4.56 / s, 2, side chain CHj /, 4.8-5.6 m, / m, 7, ester CH * O-lactam hydrogen, olefinic hydrogen (6.7-8.4 (m, 9, ArH). H. Conversion to exomethylene sulfoxide. The ring closure reaction was carried out in accordance with the method described in the second part of Example XXIX. The resulting mixture was boiled in the above-mentioned compound (640 mg) with methanesulphonic acid (10 ml) obtained 240 mg (45%) of 7-phenoxyacetamido-3-methylenecephamocarboxylic acid 4-nitrobenzyl ester 1-oxide. Example XXXI. AND. 2-Methyl-1- (2-tolylsulfonyl-hydrazsulfin-4-keto-3-phenoxyacetamidoazetidinyl-1- (2-tolylsulfonyl-hydrazsulfin-1-4-keto-3-phenoxyacetamidoazetidin-l / -2-propenecarboxylic acid) 4-nitrobenzyl ester. Following the general method described in Example XXIX, tosylhydrazide (18 g) was reacted with a sulfinyl chloride derivative obtained from 6-phenoxyacetamidopenicylate-4-nitrobenzyl-1-oxide to give the title product as a resin that never did not crystallize. B. In accordance with the method described in the second part of Example XXIX, the product of step A was cyclized with methanesulfonic acid (150 ml) to give 7.0 g (23%) of 7- nitrobenzyl ester-1-oxide. phenoxyacetamido-3-methylenecepamocarboxylic-4. Example XXXII. AND. 2-Methyl-1- (2-aminosulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester). A solution of 5 g of sodium cyanate in 100 ml of water was added to a solution of 5 g of 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phenoxyacetimidazetidinyl-1 / -2-propenecarboxylic acid-3-nitrobenzyl ester) in toluene. . After 1 hour After reaction at room temperature, the organic layer was separated, dried (MgS) and evaporated to dryness in vacuo to give a mixture of the title 6-phenoxyacetamidopenicillanic acid 4-nitrobenzyl sulfoxide compound. For the compound mentioned in the title, the NMR spectrum was as follows: MRJ (CDC18 / 8 1.96 / s, 3 /, 4.55 / s, 4, side chain CH2 + -S (OZNH2), 4.88 / d, 1, J = 4.5 Hz, hydrogen. | 3-lactam /, 5.0-5.5 / m, 5 /, 5.72 (dd, 1, J = 4.5 Hz and 9.0 Hz, hydrogen (3-lactam /, 7.74) d, 1, J = 9.0 Hz, -NH), 6.9-8.4 (m, 9, ArH). • Elemental analysis: - Values calculated for C, H, N, aS: C, 53.48, H- -4.68, N, 10.85, 0-24.78, S, 6.21%. - Experimentally determined values: C-53.69, H- -4.77, N-10.62, S-5.90%. B. Conversion to exomethylene sulfoxide. According to the method described in the second part of Example XXIX, the product of Step A was cyclized in methanesulfonic acid to give 7-phenoxy-acetamido-3-methylenecephamocarboxylic-4-carboxylic acid-1-oxide. ^ Example XXXIII. AND. 2-Methyl-li [2-chlorosulfinyl-4-keto-3- - (2-tertiary) acid, 2,2,2-trichloroethyl ester. -butoxycarbonylamino-2-phenylacimido (azetidinyl-1] -2-propenecarboxylic acid. A solution of 2.85 g (5 mmol) of 6- (1H'-order) 2,2,2-trichloroethyl ester-1-oxide. -butoxycarbonylamino-2-phenylacetamido (-2,2-dimethyl-penamocarboxylic-3) in 175 ml of toluene was dried azeotropically by distilling about 50 ml of toluene from the mixture. To the dried solution was added 0.685 g (5.5 mmol) of N-chlorosuccinimide. 41 114 521 42 under a reflux condenser for 70 minutes. After the mixture was cooled to room temperature, it was filtered and evaporated to dryness under reduced pressure to give the product (contaminated with dry imide). MRJ spectrum / CDC1S /: 8 1.40 / s, 9, IIIrd row. -butyl), 1.95 (s, 3, CH (CH 3) (RCH 3), 4.82 broad s, 2, CH 2 ester), 5.20 (m, 3, CH (CH)). CH2 + CHCOOCH2CCl8 (5.38 (d, 1, J = 4.5 Hz, C2-H azetidinone), 5.80 (m, 1); Cj-H azetidinone (and 7.34 (s, 5, ArH). B. Cyclization to exomethylene cepham. The product from stage IAl was dissolved in 100 ml of dry toluene and 1.0 ml of anhydrous tin chloride was added. The resulting solution was stirred for one hour, washed with brine, dried over magnesium sulfate and evaporated to dryness. The product was recrystallized from ethyl acetate to give 7- / 2-tertiary acid 2,2,2-trichloroethyl ester-1-oxide. butoxycarbonylammo-2-phenylacetamido -3-methylenecephamo-4. Example XXXIV. AND. 2-Methyl-ln [2-sulfino-4-keto-3- (2--III-order), 2,2,2-trichloro-ethyl ester. butoxycarbonylamino (-2-phenylacetami-) azetidinyl-1] -2-propenecarboxylic acid. The sulfinyl chloride prepared as described in Example XXXIII was dissolved in 50 ml of acetone and 160 ml of 1N HCl. The resulting solution was stirred at ice bath temperature for two hours. The mixture was then extracted with ethyl acetate. The organic extracts were combined, washed with brine and then extracted with aqueous sodium bicarbonate. The aqueous extracts were adjusted to a value of about 2 with In HCl. The acetate layer was separated, washed with brine, dried over anhydrous magnesium sulfate, and evaporated to dryness under reduced pressure to give 1.032 g of product. MRJ (CDC18) spectrum: 8 1.44 / s, 9, III-row, butyV, 1.94 / s, 3, CHC (CH3): CIV, 4.82 / s, 2, -CH2CC13 /, 5, 22 (m, 4, CHCOOCH 2 Cl 3 + CHCl (CH,): CH 2 + Ca-H azetidinone), 5.74 (dd, 1, J = 4.5 and 9.0 Hz, C3-H azetidinone), 7 , 34 (s, 5, ArH), 8.10 (broad s, 1.1-NH) and 9.0 (wide s, 1.1 SOOH). B. Cyclization to exomethylene cepham. A solution of 0.1 g of the product of step (A) and 0.04 h of phosphorus pentoxide in 20 ml of 1,2-dichloroethane was stirred for one hour at room temperature. The mixture was boiled under reflux for 30 minutes, cooled to room temperature, and combined with 25 ml of ethyl acetate and 50 ml of brine. The organic layer was separated, washed with brine, dried over magnesium sulfate and evaporated to dryness to give 7n / 2-tertiary acid 2,2,2-trichlorethyl ester-1-oxide. butoxycarbonylamino-2-phenylacetamido (-3-methylnicephamocarboxyol-4). Example XXXV. AND. 2-Methyl-1- [2-chlorosulfinyl-4-keto-3- (2-thienyl acetamido) azetidinyl-1] -2-propenecarboxylic acid, 2,2,2-trichloroethyl ester. A solution of 3.5 g of 6- (2-thienyl-acetamido) -2,2-dimethylpenamocarboxylic-3-ester 1-oxide in 350 ml of toluene was prepared and azeotropically dried by distillation from a mixture of 100 ml. toluene. After cooling, and g of N-chlorosuccinimide were added. The reaction mixture was refluxed for 50 minutes, cooled and filtered. 5 ml aliquots were evaporated to dryness under reduced pressure to give the product. Spectrum of MRJ / CDCy 8 1.87 / s, 3, CH / CH, /: CH2 /, 3.82 / s, 2, CH2 in the side chain /, 4.80 / ABq, 2 J = 13 Hz, -CH ^ CC1, // 5.18 (m, 3, -CH / CH,: CH2), 5.50 (d, 1, J = 4.5 Hz, C2-H azetidinone) and 6.05 / m, 1 , C8-H azetidinone /. 10 B. Cyclization to exomethylene cepham. 1.5 ml of anhydrous tin chloride were added to the remaining toluene sulfinyl chloride solution from step (A), and stirred for one hour. 250 ml of ethyl acetate was added, the resulting solution was washed with three 400 ml portions of brine, dried over anhydrous magnesium sulfate and evaporated to dryness under reduced pressure. The product obtained is dissolved in 30 ml of ethyl acetate. 350 mg of the crystallized 2q-2,2,2-trichloroethyl ester of 7- (2-thienyl acetamide) -3-methylene-4-carboxylic acid-1-oxide were separated. NMR spectrum / DMSOd-6 /: 5 3.38 / broad s, 2, C2-H /, 3.80 / s, 2, CH2 in the side chain /, 5.02 / s, 2, -CKJ2CIJ, 25 5 , 04 (d, 1, J = 4 Hz, C 1 -H), 5.4-5.8 (m, 4), 6.8-7.4 (m, 3, thienyl) and 8.16) d, I, J = 8 Hz, -NH). Patent claims 30 1. A process for the preparation of 3-methylene cepham sulfoxides of the general formula I, in which R 'represents a carboxyl protecting group, preferably a methyl group, H1-order. butyl, benzyl, 4-methoxybenzyl C2 -C6 alkanoyloxymethyl, 2-iodoethyl, 4-nitrobenzyl, diphenylmethyl, phenacyl, 4-halophenacyl, dimethylallyl, 2,2,2-trichlorethyl, tri-alkyl, 1-kilosilyl - 3 carbon atoms in each alkyl group or succinimidomethyl group, R 1 is an imide group of formula III in which R 2 is an alkenylene group with 2 to 4 carbon atoms, a 1,2-phenylene group or a 1,2-cyclohek- group. senylene or Ri represents an amide group of the formula R3C / O / NH-, in which R8 is hydrogen, an alkyl group of 1-3 carbon atoms, a halomethyl group, a 3- (2-chlorophenyl) group -methylisoxazolyl-4, benzyloxy, 4-nitrobenzyloxy, 2,2,2-trichloroethoxy, tertiary. -butoxy, 4-methoxybenzyloxy, the group R "being a 1,4-cyclohexadienyl group, or a phenyl group optionally substituted with one or two substituents representing independently a halogen atom, a nitro, cyano, trifluoromethyl, 1- alkyl group) 3 carbon atoms, 1-4 carbon alkoxy and a protected hydroxyl group, preferably formyloxy, chloroacetoxy, benzyloxy, benzhydryloxy, trityloxy, 4-nitrobenzyloxy, trimethylsilyloxy, phenacyloxy, before. butoxy, methoxymethoxy or tetrahydropyranyloxy, or Rj is an aralkyl group of the formula R "- / 0 / nT -CH2-, where R" is as defined above and m is 0 or 1, or Rj is a substituted group aralkyl of formula IV, in which R '"has the meaning given above for R", while W is a protected hydroxyl group, preferably formyloxy, chloroacetoxy, benzyloxy, benzhydryloxy, trityloxy, 4-nitrobenzyloxy, trimethylsilyloxy,. phenacyloxy, III-order. -butoxy, methoxyacetoxy or tetrahydropyranyloxy or W is a protected amino group in which the protecting group is preferably in the tertiary order. - -butoxycarbonyl, 4-methoxybenzyloxycarbonyl, 4-nitrobenzyloxycarbonyl, 2,2,2-trichlorethoxycarbonyl or 1-carbomethoxy-2-propenylpwa, or Rx is an imidazolidinyl group of the formula 6 where R " has the meaning given above, Y is an acetyl or nitroso group, characterized in that a compound of the general formula II, in which R x is as defined above, R is a carboxyl protecting group, preferably a methyl group, III-order. -Butyl, benzyl, 4-methoxybenzyloxy, C2— —C8 alkanoyloxymethyl, 2-iodoethyl, 4-nitrobenzyl, diphenylmethyl, phenacyl, 4-chloro-phenacyl, dimethylallyl, tri-alkylsilyl with 1 to 3 carbon atoms An alkyl group or a succinimidomethyl group, and X is a chlorine atom or a group of the formula -OR4 in which R4 is hydrogen, is cyclized with a Lewis acid Friedel-Crafts catalyst of the Bronsted acid type or a cation-forming agent in the metathesis reaction in an anhydrous inert organic solvent, with the limitations such that if a metathesis agent or a Lewis acid is used, X is only chlorine, if X is hydroxy, then cyclizations are are carried out with a Friedel-Crafts catalyst of the protic Bronsted acid type, whereby, if the reactions are carried out in the presence of a Friedel-Crafts catalyst of the acid type in Lewis or the protic Bronsted acid type, R is a group that is stable in a relatively acidic reaction medium, which protects the carboxyl function, such as, in particular, methyl, 2-iodoethyl, 4-nitrobenzyl, 2,2,2-trichlorethyl and 4- halophenacyl. 2. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-W2-chlorosulfinyl-4-oxo-3-phthalimidazetidinyl-1 / -2-propenecarboxylic acid methyl ester is reacted with tin chloride to give 1-oxide 7-phthalimido-3-methylenecephamocarbpxyl-4-methyl ester. 3. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-chlorosulfin-io-4-keto-3-phthalimidazetidinyl-1 / -2-propenocarbosyl) acid methyl ester is reacted with titanium tetrachloride 55 to give 1- 7-phthalimido-3-methylenecephamocarboxylic acid methyl ester oxide-4. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-J- (2-chlorosulfinyl-4-keto-3-phthalimidazetidinyl-1) -2-propenecarboxylic acid methyl ester is reacted with aluminum chloride to give 1- 7-phthalimide-3-methyl-4-ocephamocarboxylic acid methyl ester oxide. 85 44 5. The method according to p. The process of claim 1, wherein 2-methyl-1- (2-chlorosulfinyl-4-oxo-3-phthalimidazetidinyl-1 / -2-propenecarboxylic acid methyl ester is reacted with zinc bromide to give 1). - 7-phthalimido-3-methylenecephamocarboxylic acid methyl ester oxide. 6. The method according to p. 2. The process of claim 1, wherein 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phthalimidoazetidinyl-1 / -2-propenecarboxylic acid methyl ester with antimony pentachloride is obtained to give the 1-ester oxide) 7-phthalim- to-3-methylenecephamocarboxylic acid-4. 7. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-chlorosulfinyl-4-oxo-3-phthalimidazetidinyl-1 / -2-propenecarboxylic acid methyl ester is reacted with mercuric chloride to give 1). 7-phthalimido-3-methylenecephamocarboxylic acid methyl ester-4 oxide. 8. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-chlorosulfinyl-4-oxo-3-phthalimidazetidinyl-1 / -2-propenecarboxylic acid methyl ester is reacted with ferric chloride to give 1). -7-phthalimido-3-methylenecephamocarboxylic acid methyl ester oxide. 9. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phthalimidazetidinyl-1 / -2-propenecarboxylic acid methyl ester is reacted with zirconium tetrachloride to give 1-oxide) 7-phthalimido-3-methylenecephamocarboxylic acid methyl ester-4. 10. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phthalimidoazetidinyl-1 / -2-propene-2-carboxylic acid methyl ester is reacted with polyphosphoric acid to give 7-phthalimido-3-methylenecepam-4-carboxylic acid-1-oxide of the methyl ester. 11. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-chlorosulfinyl-4-oxo-3-phthalimidazetidinyl-1 / -2-propenecarboxylic acid methyl ester) is reacted with sulfuric acid to give 1 -7-phthalimido-3-methylenecephamocarboxylic acid methyl ester oxide. 12. The method according to p. The process of claim 1, wherein 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phthalimidoazetidinol-1 / -2-propenecarboxylic acid methyl ester is reacted with methanesulfonic acid to give 1). 7-phthalimido-3-methylenecepham-4-carboxylic acid methyl ester oxide. 13. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phthalimidoazetidinyl-1 / -2-propenecarboxylic acid methyl ester is reacted with trifluoroacetic acid to give 1). 7-phthalimido-3-methylenecephamocarboxylic-4-acid methyl ester oxide. 14. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phthalimidazetid-3-methyl-1 / -2-propenecar-114 521 45-carboxylic acid methyl ester is reacted with p-toluenesulfonate) silver to give 7-phthalimido-3-methyl-4-methyl-4-carboxylic acid 1-oxide. 15. The method according to p. A process as claimed in claim 1, characterized in that B, 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester) is reacted with tin chloride to give 1 - 7-phenoxyacetamido-3- 10-metifrenocephamocarboxylic acid-4-nitrobenzyl ester oxide. 16. The method according to p. 2. The process of claim 1, wherein 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester is reacted with zinc chloride to give 1). - 7-phenoxyacetamido-3-methylenecephamocarboxylic acid 4-nitrobenzyl ester oxide. 17. The method according to p. The process of claim 1, characterized in that 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester) is reacted with silver p-toluenesulfonate and obtained August 1 -oxide, 4-nitrobenzyl ester, 7-phenoxy-acetamido-3-methylene-4-carboxylic acid. y 25 18. The method according to p. The process of claim 1, wherein 2-methyl-1- (2-chlorosulfinyl-4-oxo-3-phthalimidazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester is reacted with tin chloride and 7-phthalimido-3-methylene-4-methylenzyl-1-oxide is obtained. 19. The method according to p. 2. The process of claim 1, wherein the 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phenylacetamidoazetidinyl-1 / -2-propenecarboxylic acid) 2,2,2-trichloroethyl ester is reacted with tin chloride to give 7-phenyl-acetamido-3-methylenecepam-4-carboxylic acid 1-oxide of the 2,2,2-trichlorethyl ester. twenty. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-1- [2-chlorosulfinyl-4-keto-3- (2,2-dimethyl-3-nitroso-5-keto-4-phenylimidazolidinyl) methyl ester -V-azetidinyl-1] -2-propenecarboxylic acid is reacted with tin chloride to give 7- (2,2-dimethyl-3-nitroso-5-keto-4- acid methyl ester-1-oxide). lenyl-imidazolidinyl-l / -3-methylenecephamocarboxylic-4. 21. The method according to p. The process of claim 1, wherein the 2-methyl-1- (2-50-chlorosulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid) 2,2,2-trichloroethyl ester is reacted with with stannous chloride to give 7-phenoxyacetamido-3-methylenecephamid-4-carboxylic acid 1-oxide of the 2,2,2-trichloroethyl ester. 55 22. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-sulfinyl-4-keto-3-phthalimido-azetidinyl-1- (-2-pfropenecarboxylic acid) methyl ester is reacted with phosphorus pentoxide to give 1- 7-phthalimido-3-methyleneephamocarboxylic acid methyl ester oxide 60. 28. The method according to p. 2. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-sulfino-4-ketb-4-phthalimidazetidinyl-1 / -2-propenecarboxylic acid methyl ester) is reacted with sulfuric acid to give 1-oxide 7-phthalimido-3-methylenecephamocarboxylic acid-4 methyl ester. 24. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-sulfino-4-keto-3-phthalimidazetidinyl-1 / * 2-propenecarboxylic acid methyl ester is reacted with polyphosphoric acid to give 1-ester oxide) 7-phthalimido-3-methylenecephamocarboxylic acid-4. 25. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-sulfino-4-ke- to-3-phthalimido azytidinyl-1 / -2-propenecarboxylic acid methyl ester) is reacted with trifluoroacetic acid to give 1 -7-phthalimido-3-methylenecephamocarboxylic acid methyl ester oxide. 26. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-brombphenacyl ester) is reacted with tin chloride to give 1- 7-phenoxyacetamido-3-methylenecepamocarboxylic acid 4-bromophenacyl ester oxide. 27. The method according to p. 2. The process of claim 1, wherein 2-methyl-1- {2-chlorosulfinyl-4-keto-3- (4-nitrobenzyloxycarbamide) -azetidinyl-1] -2-propenecarboxylic acid is subjected to After reaction with tin chloride, 7- (4-nitrobenzyloxycarbamido) -3-methylene-4-cephamocarboxylic acid 2-oxide of the 2,2,2-trichlorethyl ester is obtained. 28. The method according to p. 2. The process of claim 1, wherein the 2-methyl-1- (2-chlorosulfinyl-4-oxo-3-acetamidoazetidinyl-1 / -2-pro-carboxylic acid 4-nitrobenzyl ester) is reacted with tin chloride to give 7-acetamido-3-methylenepampamocarboxylic acid 4-nitrobenzyl ester-1-oxide. 29. A process for the preparation of 3-methylacepham sulfoxides of the general formula I, wherein R 'is a hydrogen atom or a carboxyl protecting group, preferably a methyl group, III-order. -butyl, benzyl, 4-methoxybenzyl, C2-C6 alkahoyloxymethyl, 2-iodoethyl, 4-nitrobenzyl, diphenylmethyl, phenacyl, 4-halophenacyl, dimethylalkyl, 2,2,2-trichloroethylsilyl carbon in each alkyl group or succinimidomethyl group, Ri is the imide group in the formula 3, wherein R2 is alkenylene with 2 to 4 carbon atoms, alkylene with 2 to 4 carbon atoms, 1,2-phenyl or 1,2-cyclohexenylene or R 1 represents an amide group of the formula R 8 C (O) NH-, where R represents a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, a halomethyl group, 2-chlorophenyl / -5-methylisoxazolyl-4, benzylxyl, 4-nittobenzyloxy, 2,2,2-trichloroethoxy-4, tertiary. butoxy, methoxybenzylxyl, the group R "being a 1,4-cyclohexadienyl group or a phenyl group optionally substituted with one or two substituents representing independently a halogen atom, a nitro, cyano, trifluoromethyl group, an alkyl group with 1 to 3 carbon atoms; carbon 1 r-4 ato 114 521 47 48 and a hydroxyl protecting group, preferably formyloxy, chloroacetoxy, benzyloxy, benzhydroxy, trityloxy, 4-nitrobenzyloxy, trimethylsilyloxy, phenacyloxy, 3rd order. butoxy, methoxyl or tetrahydropiranyloxy, or R8 is an arylalkyl group of formula R "- / 0 / m-CH2-, wherein R" is as defined above and m is 0 or 1, or R3 is a substituted arylalkyl group of formula 4, in which R '"is as defined above for R" and W is a protected hydroxyl group, preferably formyloxy, chloroacetoxy, benzyloxy, benzhydryloxy, trityloxy, 4-nitrobenzyloxy, trimethylsilyloxy, phenacyloxy, III-order. -butoxy, methoxymethoxy or tetrahydro-pyranyloxy, or a protected amino group, the protecting group of which is preferably a tertiary group. butoxycarbonyl, benzyloxycarbonyl, 4-methoxybenzyloxycarbonyl, 4-nitrobenzylcarbonyl, 2,2,2-trichlorethoxycarbonyl or 1-carbomethoxy-2-propenyl, Ri can also denote an imide group of formula 5, wherein R " have the meanings given above, and R2 'represents an alkyl group of 1-3 carbon atoms, a haloalkyl group of 1-6 carbon atoms, an alkoxy group of 1-3 carbon atoms or a trichloroethoxy, or Tli is an imidazolidinyl group of the formula VI. in which R "has the meaning as defined above and Y is an acetyl or nitro group, characterized in that the compound of the general formula (II) in which R 1 is as defined above, R is a carboxyl protecting group, preferably a methyl group, III -before -butyl, benzyl. 4-methoxybenzyl, C2-C8 alkanoyloxymethyl, 2-iodoethyl, 4-nitrobenzyl, diphenylmethyl, phenacyl, 4-halophenacyl, dimethylallyl, 2,2,2-trichlorethyl, trialkylsilyl with 1 to 3 carbon atoms an alkyl group or a succinimidimethyl group, and X represents a chlorine or bromine atom, a group of the formula -OR 4 in which R 4 is a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an arylalkyl group with 1 to 3 carbon atoms in of an alkyl moiety or a haloalkyl group of 1-6 carbon atoms, or X is a group of the formula -SRB, wherein R5 is an alkyl group of 1-6 carbon atoms, an aryl or an aralkyl group of 1-3 carbon atoms in the alkyl portion or X represents a group of the formula -N / Re / Ry where R 6 is a hydrogen atom and R 7 is a hydrogen atom, the group R "as defined above, or a group of the formula -NHR 8 in which R 8 is a group - nocarbonyl, alkylaminocarbonyl with 1-3 carbon atoms in the alkyl part, alkylcarbonyl with 1-3 carbon atoms in Alkoxy, alkoxycarbonyl with 1-3 carbon atoms in the alkoxy part or tosyl group, or R8 is -COOR or -COR9, and R7 is -NHCOOR9 or -NHCOR9 where in the formulas R9 represents an alkyl group with 1-6 carbon atoms or a phenyl group, or also R6, R7 and the nitrogen atom to which they are attached together form an imide group of formula III, wherein R2 has the meaning as defined above, where if R8 is a group of formula -COOR9 or -CORfl and R7 is a group of formula -NHCOOR9 or -NHCOR9 then R3 is additionally a heteroarylmethyl group of formula R "" CH2-, in which R "" is 2, -thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-thiazolyl or 5-isoxazolyl, cyclized with a Lewis acid Friedel-Crafts catalyst, a Bronsted protic acid type, or of a cation-forming agent by metathesis in an anhydrous neutral solvent or The compound of formula (II) is dissolved or dissolved in an organic Bronsted acid, with the restrictions that if X is bromine, R4 is only an imide of formula III if a metathesis agent or an acid is used Lewis, then X represents only a chlorine or bromine atom, if R is a group that can be removed by the action of acids protecting the carboxyl function, then the product is obtained in the form of a sulfoxide - 3-methyl-4-cepa-carboxylic acid and it must be satisfied one of the conditions where: a) if X i is a chlorine atom or a group of the formula -OR4 in which R4 is a hydrogen atom, the cyclizations are carried out in an inorganic Bronsted acid, such as sulfuric, phosphoric, polyphosphoric, perchloric acid , chlorosulfonic or fluorosulfonic or HBF4, HA1C14, HasF4, HalBr4, SnCl4, SnBr4, SbCl5 and TiCl4, b / R 'is hydrogen, c / R2. represents an alkylene group of 2 to 4 carbon atoms, and dV Ri represents a 2-tinylacetamide group or an imide group of the formula V, in which R "and m are as defined above, and R 2 'is an alkyl group of 1 to 3 carbon atoms. , a haloalkyl group of 1-6 carbon atoms, an alkoxy group of 1-3 carbon atoms or a trichlorethoxy group, or that e / X represents a bromine atom, a group of the formula -OR4, in which R4 is an alkyl group of 1-10 atoms carbon, an aralkyl group of 1-3 carbon atoms in the alkyl portion or a haloalkyl group of 1-6 carbon atoms, or X is a group of the formula -SR5, where R5 is an alkyl group of 1-6 carbon atoms, an aryl or aralkyl group with 1-3 carbon atoms in the alkyl part, or X is a group of formula -N / Ra / R7, where R8 is hydrogen and R7 is hydrogen, R "or as defined above, or a group of the formula -NHR8, in which R8 represents an aminocarbonyl group, an alkylamino-carbonyl group with 1-3 carbon atoms, in part al Alkyl, alkylcarbonyl group with 1-3 carbon atoms in the alkyl part, alkoxycarbonyl group with 1-3 carbon atoms in the alkoxy part or tosyl group, or R8 is a group of the formula -COOR9 or of the formula -COR9 or R7 represents a group of formula -NHCOR9, or of formula -NHCOR9, in which formulas R9 represents an alkyl group of 1-6 carbon atoms or a phenyl group, or also R8, R7 and the nitrogen atom to which they are attached form the group imide of formula 3, in which Rf is as defined above, where if R5 is a group of formula -COOR9 or of formula -COR9 and R7 is a group of formula -NHCOORg or of formula -NHCOR9, then R8 may additionally denote a heteroarylmethyl group of the formula R "" CH2-, in which R "" is a 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 3-thiazolyl group or a 5-isoxazolyl group. thirty. The method according to p. A process as claimed in 29, characterized in that 2-methyl-1- [2-chlorosulfinyl-4-keto-3- (N-phenoxyacetyl-N- (2,2,2-trichloroethoxycarbonyl) amino) azetidinyl 4-nitrobenzyl ester The -1] -2-propenecarboxylic acid is reacted with tin chloride to give 7- [N-phenoxyacetyl-N- (2,2,2-trichloroethoxycarbonyl) -amino] -3-4-nitrobenzyl ester-1-oxide. - methylenecephamocarboxylic-4. 31. The method according to p. A process as claimed in 29, characterized in that 2-methyl-1- (2-bromoculfinyl-4-oxo-3-phthalimidazetidinyl-1,2-propenecarboxylic acid methyl ester) is reacted with tin chloride to give 1- 7-phthalimido-3-methylenecephamocarboxylic acid methyl ester oxide. 32. The method according to p. 29, characterized in that 2-methyl-1- (2-isopropylthiosulfinyl-4-keto-3-phenoxyacetamido-azetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester is reacted with methanesulfonic acid) 7-phenoxyacetamido-3-methylenecepamocarboxylic acid-4-nitrobenzyl ester-1-oxide. 33. The method according to p. A process as claimed in 29, characterized in that 2-methyl-1- (2-IIT-pre) 4-nitrobenzyl ester. -butylsulfinyl-4-keto-3-phenoxyacetamide-azetidinyl-1 / -2-propenecarboxylic acid is reacted with methanesulfonic acid to give 7-phenoxyacetamido-3-methylenecephamocarboxylic acid-4-nitrobenzyl ester 1-oxide. 34. The method according to p. 29, characterized in that 2-methyl-1- (2-methoxysulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1/2-propenecarboxylic acid 4-nitrobenzyl ester) is reacted with methanesulfonic acid to give 1 7- -phenoxyacetamido-3-methylenecephamocarboxylic acid 4-nitrobenzyl ester oxide. 35. The method according to p. A process as claimed in 29, characterized in that 2-methyl-1- (2-methyloxysulfinyl-4-keto-3-phenoxyacetamidoazethidinyl-1 - 2-propenecarboxylic acid 4-nitrobenzyl ester) is reacted with methanesulfonic acid and 7-phenoxyacetamido-3-methylenecephamorocarboxylic-4-nitrobenzyl ester-1-oxide is obtained. 36. The method according to p. A process as claimed in 29, characterized in that the 2-methyl-1- (2-aniline-4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester) is reacted with methanesulfonic acid to give 1- - 7-phenoxy-acetamido-3-methylenecepamocarboxylic acid 4-nitrobenzyl ester oxide. 37. The method according to p. 29, characterized in that 2-methyl-1- (2-N-succinimosulfinyl-4-keto-3-phenylacetamidoazetidin-1) -2-propenecarboxylic acid methyl ester is reacted with methanesulfonic acid to give 1 - 7-phenylacetami- to-3-methylenecephamocarboxylic acid methyl ester oxide. And 38. The method according to p. A process as claimed in 29, characterized in that the 2-methyl-1- [2- (N, N'-dicarboethoxyhydrazsulfinyl) -4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester is reacted with methanesulfonic acid to give 7-phenoxyacetamido-3-methyl-4-cephamocarboxylic acid 4-nitrobenzyl ester-1-oxide. 39. The method according to p. A process as claimed in 29, characterized in that 2-methyl-1-i [2-15- (N6-dicarbo-tertiary acid 4-nitrobenzyl ester). -butoxyhydrazsulfinyl (-4-keto-3-acetamido-azetidinyl-1,2-propenecarboxylic acid) is reacted with methanesulfonic acid to give 7-acetamido-3-methylene acid 4-nitrobenzyl ester-1-oxide. 20 cephamocarboxylic-4. 40. The method according to p. A process as claimed in 29, characterized in that 2-methyl-1 [2- / N, N''dicarbo-III acid, 2,2,2-trichloroethyl ester. -before -butyloxyhydrazosulfinyl (-4-keto-3- (2-thienylacetamido) -azetidinyl-25 -l) -2-propenecarboxylic acid is reacted with methanesulfonic acid to give the 1-oxide of the 2,2,2-trichloroethyl ester 7- (2-thienylacetamido) -3-methylenecephamocarboxylic acid-4. 41. The method according to p. A process as claimed in 29, characterized in that 2-methyl-1-; [2- (N, N'-dibenzoylhydrazsulfinyl) -4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester it is reacted with methanesulfonic acid to give 7-phenoxyacetamido-3-methylenecepacetamido-3-methylenecepacarboxylic acid-1-oxide 4-nitrobenzyl ester. 42. The method according to p. A process as claimed in 29, characterized in that 2-methyl-1- (2-acetylhydrazsulfinyl-4-keto-3-phenoxyacetamino-azetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester) is reacted with methanesulfonic acid to give 7-phenoxyacetamido-3-methylenecephamocarboxylic acid-4-nitrobenzyl ester-1-oxide. 45 43. The method according to p. 29, characterized in that 2-methyl-1- (2-carbomethoxyhydrazosulfinyl-4-keto-3-phenoxy-acetamidoazetidinyl (2-2) propenecarboxylic acid 4-nitrobenzyl ester is reacted with methanesulfonic acid 50 to give 1 - 7-phenoxyacetamido-3-methylenecefamocarboxylic acid 4-nitrobenzyl ester oxide. 44. The method according to p. 29, characterized in that 2-methyl-1- (2- 55 -tolylsulfonylhydrazosulfinyl-4-keto-3-phenoxy-acetamidazetidinyl-1-2-propenecarboxylic acid) 4-nitrobenzyl ester is reacted with methanesulfonic acid to give 1 - 7-phenoxyacetamido-3-methylenecepamocarbo-4-xylic acid 4-nitrobenzyl ester oxide. 45. The method according to p. 29, characterized in that 2-methyl-1- (2-aminosulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1/2-propenecarboxylic acid 4-nitrobenzyl ester) is reacted with methanesulfonic acid to give ester114 521 51 4-nitrobenzyl acid of 7-phenoxyacetamido-3-methylenocephamocarboxylic acid-4. 46. The method according to p. 29, characterized in that the 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phenoxyacetamidoazatidinyl-1 / -2-propenecarboxylic acid 4-methoxybenzyl ester) is reacted with tin chloride to give 7-phenoxyacetamido-3-methylenecephamocarboxylic acid-1-oxide. 52 47. The method according to p. 29, characterized in that 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid benzhydryl ester) is reacted with tin chloride to give acid-1-oxide ¬ su 7-phenoxyacetamido-3-methylenecephamocarboxylic-4. R "- (0) mCH2C I! Formula 5 0 0 R, SHal COOR Formula 7 Formula 6 r --N a 9 S CH2CNH- Formula 8 0 Rr ySOR4 o * COOR Formula 77 0 li / Re COOR Formula 13 0 R / SOH COOR 0 SOR, R. ^ p ^ SSR5 COOR Formula 12 Rr 0 X COOR H / ztfr 74114 521 O o o -SNHNHS-OCH. HiNNHS-OLri, 0 Formula 15 -s-nCr2 o Formula 17 l 0 Formula 16 0 K + "NC) R2 o Formula W 0 MHCOOR9 ONHCOR9 r $ k COOR9 Rr S-NCOR9 COOR COOR Yvz '* r 23 r. u R 0 ii S J-Si (CHJ3 R Formula 20 * 0 CCOR 0 NY_ H0Ac7DMFa o / "" N COOR Formula 79 0 0 [o] R ^ S "COOR Formula 21 o Formula 22 COOR Formula 1 Formula 2L 0 COOR 7 / zcr, "T Wztfr 7o. Scheme 2 X n. v Ct / i; . . - u X = M ~ s = o Formula 27 0 0% <5w o o W, D Y Mi ND ód'j «Ah COOCHa COOCH3 H / healthy 25 Wzcr 29 Scheme 3 R 0 COOR!) HÓ-y COOH l4 / z ^ r 30 Wztfr ^ 7 PL

Claims (47)

Claims 1. A process for the preparation of 3-methylene cepham sulfoxides of general formula I, wherein R 'is a carboxyl protecting group, preferably a methyl group, H1-order. butyl, benzyl, 4-methoxybenzyl C2 -C6 alkanoyloxymethyl, 2-iodoethyl, 4-nitrobenzyl, diphenylmethyl, phenacyl, 4-halophenacyl, dimethylallyl, 2,2,2-trichlorethyl, tri-alkyl, 1-kilosilyl - 3 carbon atoms in each alkyl group or succinimidomethyl group, R 1 is an imide group of formula III in which R 2 is an alkenylene group with 2 to 4 carbon atoms, a 1,2-phenylene group or a 1,2-cyclohek- group. senylene or Ri represents an amide group of the formula R3C / O / NH-, in which R8 is hydrogen, an alkyl group of 1-3 carbon atoms, a halomethyl group, a 3- (2-chlorophenyl) group -methylisoxazolyl-4, benzyloxy, 4-nitrobenzyloxy, 2,2,2-trichloroethoxy, tertiary-butoxy, 4-methoxybenzyloxy, R "group being 1,4-cyclohexadienyl group, 50 or a phenyl group optionally substituted with one or two substituents which are independently halogen, nitro, cyano, trio ifluoromethyl, alkyl with 1-3 carbon atoms, alkoxy group with 1-4 carbon atoms and protected hydroxyl group, preferably formyloxy, chloroacetoxy, benzyloxy, benzhydryloxy, trityloxy, 4-nitrobenzyloxy, trimethylsyloxy, phenacyloxy, IH-order. butoxy, methoxymethoxy or tetrahydropyranyloxy, or Rj is an aralkyl group of the formula R "- / 0 / nT -CH2-, where R" is as defined above and m is 0 or 1, or Rj is a substituted group aralkyl of formula IV, in which R '"has the meaning given above for R", while W is a protected hydroxyl group, preferably formyloxy, chloroacetoxy, benzyloxy, benzhydryloxy, trityloxy, 4-nitrobenzyloxy, trimethylsilyloxy,. phenacyloxy, tertiary-butoxy, methoxyacetoxy or tetrahydro-piranyloxy or W is a protected amino group in which the protecting group is preferably tertiary-butoxycarbonyl, 4-methoxybenzyloxycarbonyl, 4-nitrobenzyloxycarbonyl, 2,2-trichloroethoxycarbonyl or 1-carbomethoxy-2-propenylpwa, or Rx is an imidazolidinyl group of formula 6 wherein R "is as defined above, Y is an acetyl or nitroso group, characterized in that a compound of general formula II in which R x has the meaning given above, R is a carboxyl protecting group, preferably a methyl group, a tertiary butyl group, benzyl, 4-methoxybenzyloxy, C2-C8 alkanoyloxymethyl, 2-iodoethyl, 4-nitrobenzyl, diphenylmethyl, phenacyl, 4-chloro-phenacyl, dimethylallyl, tri-alkylsilyl with 1-3 carbon atoms in each alkyl group or succinimidomethyl group, and X is a chlorine atom or a group of formula OR 4, wherein R 4 is hydrogen, is cyclized with a Lewis acid Friedel-Crafts catalyst, a protic Bronsted acid type, or a cation forming agent by metathesis in an anhydrous inert organic solvent, with such limitations as With the proviso that if a metathesis agent or a Lewis acid is used, then X represents only a chlorine atom, if X represents a hydroxyl group, the cyclization is carried out with a Friedel-Crafts catalyst of the protic Bronsted acid type. whereby, if the reactions are carried out in the presence of a Friedel-Crafts catalyst of the Lewis acid type or of the protic Bronsted acid type, then R is a group that is stable in a relatively acidic reaction environment for a carboxylic acid, such as, in particular, methyl, 2-iodoethyl, 4-nitrobenzyl, 2,2,2-trichlorethyl and 4-halophenacyl. 2. The method according to claim A process as claimed in claim 1, characterized in that 2-methyl-W2-chlorosulfinyl-4-oxo-3-phthalimidazetidinyl-1 / -2-propenecarboxylic acid methyl ester is reacted with tin chloride to give 1-oxide 7-phthalimido-3-methylenecephamocarbpxyl-4-methyl ester. 3. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-chlorosulfin-io-4-keto-3-phthalimidazetidinyl-1 / -2-propenocarbosyl) acid methyl ester is reacted with titanium tetrachloride 55 to give 1- 7-phthalimido-3-methylenecephamocarboxylic acid methyl ester oxide. A process as claimed in claim 1, characterized in that 2-methyl-J- (2-chlorosulfinyl-4-keto-3-phthalimidazetidinyl-1) -2-propenecarboxylic acid methyl ester is reacted with aluminum chloride to give 1- 7-phthalimide Q-3-methyl-ocephamocarboxylic acid methyl ester oxide 4. 85 44 5. The method according to p. The process of claim 1, wherein 2-methyl-1- (2-chlorosulfinyl-4-oxo-3-phthalimidazetidinyl-1 / -2-propenecarboxylic acid methyl ester is reacted with zinc bromide to give 1). - 7-phthalimido-3-methylenecephamocarboxylic acid methyl ester oxide. 6. The method according to p. 2. The process of claim 1, wherein 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phthalimidoazetidinyl-1 / -2-propenecarboxylic acid methyl ester with antimony pentachloride is obtained to give the 1-ester oxide) 7-phthalim- to-3-methylenecephamocarboxylic acid-4. 7. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-chlorosulfinyl-4-oxo-3-phthalimidazetidinyl-1 / -2-propenecarboxylic acid methyl ester is reacted with mercuric chloride to give 1). 7-phthalimido-3-methylenecephamocarboxylic acid methyl ester-4 oxide. 8. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-chlorosulfinyl-4-oxo-3-phthalimidazetidinyl-1 / -2-propenecarboxylic acid methyl ester is reacted with ferric chloride to give 1). -7-phthalimido-3-methylenecephamocarboxylic acid methyl ester oxide. 9. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phthalimidazetidinyl-1 / -2-propenecarboxylic acid methyl ester is reacted with zirconium tetrachloride to give 1-oxide) 7-phthalimido-3-methylenecephamocarboxylic acid methyl ester-4. 10. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phthalimidoazetidinyl-1 / -2-propene-2-carboxylic acid methyl ester is reacted with polyphosphoric acid to give 7-phthalimido-3-methylenecepam-4-carboxylic acid-1-oxide of the methyl ester. 11. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-chlorosulfinyl-4-oxo-3-phthalimidazetidinyl-1 / -2-propenecarboxylic acid methyl ester) is reacted with sulfuric acid to give 1 -7-phthalimido-3-methylenecephamocarboxylic acid methyl ester oxide. 12. The method according to p. The process of claim 1, wherein 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phthalimidoazetidinol-1 / -2-propenecarboxylic acid methyl ester is reacted with methanesulfonic acid to give 1). 7-phthalimido-3-methylenecepham-4-carboxylic acid methyl ester oxide. 13. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phthalimidoazetidinyl-1 / -2-propenecarboxylic acid methyl ester is reacted with trifluoroacetic acid to give 1). 7-phthalimido-3-methylenecephamocarboxylic-4-acid methyl ester oxide. 14. The method according to p. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phthalimidazetid-3-methyl-1 / -2-propenecar-114 521 45-carboxylic acid methyl ester is reacted with p-toluenesulfonate) silver to give 7-phthalimido-3-methyl-4-methyl-4-carboxylic acid 1-oxide. 15. The method according to p. A process as claimed in claim 1, characterized in that B, 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester) is reacted with tin chloride to give 1 - 7-phenoxyacetamido-3- 10-metifrenocephamocarboxylic acid-4-nitrobenzyl ester oxide. 16. The method according to p. 2. The process of claim 1, wherein 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester is reacted with zinc chloride to give 1). - 7-phenoxyacetamido-3-methylenecephamocarboxylic acid 4-nitrobenzyl ester oxide. 17. The method according to p. The process of claim 1, characterized in that 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester) is reacted with silver p-toluenesulfonate and obtained Aug 1-oxide, 4-nitrobenzyl ester, 7-phenoxy-acetamido-3-methylenecarboxylic acid-4.y 25 18. The method according to p. The process of claim 1, wherein 2-methyl-1- (2-chlorosulfinyl-4-oxo-3-phthalimidazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester is reacted with tin chloride and 7-phthalimido-3-methylene-4-methylenzyl-1-oxide is obtained. 19. The method according to claim 2. The process of claim 1, wherein the 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phenylacetamidoazetidinyl-1 / -2-propenecarboxylic acid) 2,2,2-trichloroethyl ester is reacted with tin chloride to give 7-phenyl-acetamido-3-methylenecepam-4-carboxylic acid 1-oxide of the 2,2,2-trichlorethyl ester. 20. The method according to claim A process as claimed in claim 1, characterized in that 2-methyl-1- [2-chlorosulfinyl-4-keto-3- (2,2-dimethyl-3-nitroso-5-keto-4-phenylimidazolidinyl) methyl ester -V-azetidinyl-1] -2-propenecarboxylic acid is reacted with tin chloride to give 7- (2,2-dimethyl-3-nitroso-5-keto-4- acid methyl ester-1-oxide). lenyl-imidazolidinyl-l / -3-methylenecephamocarboxylic-4. 21. The method according to p. The process of claim 1, wherein the 2-methyl-1- (2-50-chlorosulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid) 2,2,2-trichloroethyl ester is reacted with with stannous chloride to give 7-phenoxyacetamido-3-methylenecephamid-4-carboxylic acid 1-oxide of the 2,2,2-trichloroethyl ester. 55 22. The method according to claim A process as claimed in claim 1, characterized in that 2-methyl-1- (2-sulfinyl-4-keto-3-phthalimido-azetidinyl-1- (-2-pfropenecarboxylic acid) methyl ester is reacted with phosphorus pentoxide to give 1- 7-phthalimido-3-methyleneephamocarboxylic acid methyl ester oxide 60. 23. 28. The method according to claim 2. A process as claimed in claim 1, characterized in that 2-methyl-1- (2-sulfino-4-ketb-4-phthalimidazetidinyl-1 / -2-propenecarboxylic acid methyl ester) is reacted with sulfuric acid to give 1-oxide 7-phthalimido-3-methylenecephamocarboxylic acid-4 methyl ester. 24. The method according to claim A process as claimed in claim 1, characterized in that 2-methyl-1- (2-sulfino-4-keto-3-phthalimidazetidinyl-1 / * 2-propenecarboxylic acid methyl ester is reacted with polyphosphoric acid to give 1-ester oxide) 7-phthalimido-3-methylenecephamocarboxylic acid-4. 25. The method according to claim A process as claimed in claim 1, characterized in that 2-methyl-1- (2-sulfino-4-ke- to-3-phthalimido azytidinyl-1 / -2-propenecarboxylic acid methyl ester) is reacted with trifluoroacetic acid to give 1 -7-phthalimido-3-methylenecephamocarboxylic acid methyl ester oxide. 26. The method according to claim A process as claimed in claim 1, characterized in that 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-brombphenacyl ester) is reacted with tin chloride to give 1- 7-phenoxyacetamido-3-methylenecepamocarboxylic acid 4-bromophenacyl ester oxide. 27. The method according to claim 2. The process of claim 1, wherein 2-methyl-1- {2-chlorosulfinyl-4-keto-3- (4-nitrobenzyloxycarbamide) -azetidinyl-1] -2-propenecarboxylic acid is subjected to After reaction with tin chloride, 7- (4-nitrobenzyloxycarbamido) -3-methylene-4-cephamocarboxylic acid 2-oxide of the 2,2,2-trichlorethyl ester is obtained. 28. The method according to claim 2. The process of claim 1, wherein the 2-methyl-1- (2-chlorosulfinyl-4-oxo-3-acetamidoazetidinyl-1 / -2-pro-carboxylic acid 4-nitrobenzyl ester) is reacted with tin chloride to give 7-acetamido-3-methylenepampamocarboxylic acid 4-nitrobenzyl ester-1-oxide. 29. A process for the preparation of 3-methylacepham sulfoxides of general formula I, wherein R 'is a hydrogen atom or a carboxyl protecting group, preferably a methyl, tertiary-butyl, benzyl, 4-methoxybenzyl, C2-C6 alkyloxymethyl group, 2-iodoethyl, 4-nitrobenzyl, diphenylmethyl, phenacyl, 4-halophenacyl, dimethylalkyl, 2,2,2-trichlorethyl, trialkylsilyl with 1-3 carbon atoms in each alkyl group or succinimidomethyl group imide compound 3 in which R2 is an alkenylene group with 2 to 4 carbon atoms, an alkylene group with 2 to 4 carbon atoms, a 1,2-phenyl group or a 1,2-cyclohexenylene group, or Ri is an amino group A compound of the formula R8C (O) NH-, in which R is a hydrogen atom, an alkyl group of 1-3 carbon atoms, a halomethyl group, a 3- (2-chlorophenyl) -5-methylisoxazolyl-4 group, a group of benzylxyl, 4-nittobenzyloxy, 2,2,2-trichloroethoxyl, tert-butoxy, methoxybenzy loxyl, R "1,4-cyclohexadienyl, or a phenyl group optionally substituted with one or two substituents independently representing halogen, nitro, cyano, trifluoromethyl, alkyl of 1-3 carbon atoms; an alkoxy group of 1-4 ato-114 521 47 48 carbon and a hydroxyl protecting group, preferably formyloxy, chloroacetoxy, benzyloxy, benzhydroxy, trityloxy, 4-nitrobenzyloxy, trimethylsilyloxy, phenacyloxy, III-phenacetoxy. butoxy, methoxyl or tetrahydropyranyloxy, or R8 is an arylalkyl group of formula R "- / 0 / m-CH2-, wherein R" is as defined above and m is 0 or 1, or R3 is a substituted arylalkyl group of formula 4, in which R '"is as defined above for R" and W is a protected hydroxyl group, preferably formyloxy, chloroacetoxy, benzyloxy, benzhydryloxy, trityloxy, 4-nitrobenzyloxy, trimethylsilyloxy, phenacyloxy, tertiary butoxy, methoxymethoxy or tetrahydro pyranyloxy, or a protected amino group, the protecting group of which is preferably tertiary butoxycarbonyl, benzyloxycarbonyl, 4-methoxybenzyloxycarbonyl, 4-nitroben R 1 may also be an imide group of the formula 5, where R "and m have the meaning given above, and R 2 'is a group of 1-carbomethoxy-2-propenyl groups. pe alkyl with 1-3 carbon atoms, haloalkyl with 1-6 carbon atoms, alkoxy with 1-3 carbon atoms or trichloroethoxy, or Tli is an imidazolidinyl group of formula 6, where R "is as defined above and Y is acetyl or nitro group, characterized in that a compound of general formula II, in which R 1 is as defined above, R is a carboxyl protecting group, preferably a methyl, tertiarybutyl, benzyl group. 4-methoxybenzyl, C2-C8 alkanoyloxymethyl, 2-iodoethyl, 4-nitrobenzyl, diphenylmethyl, phenacyl, 4-halophenacyl, dimethylallyl, 2,2,2-trichlorethyl, trialkylsilyl with 1 to 3 carbon atoms an alkyl group or a succinimidimethyl group, and X represents a chlorine or bromine atom, a group of the formula -OR 4 in which R 4 is a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an arylalkyl group with 1 to 3 carbon atoms in of an alkyl moiety or a haloalkyl group of 1-6 carbon atoms, or X is a group of the formula -SRB, wherein R5 is an alkyl group of 1-6 carbon atoms, an aryl or an aralkyl group of 1-3 carbon atoms in the alkyl portion or X represents a group of the formula -N / Re / Ry where R 6 is a hydrogen atom and R 7 is a hydrogen atom, the group R "as defined above, or a group of the formula -NHR 8 in which R 8 is a group - nocarbonyl, alkylaminocarbonyl with 1-3 carbon atoms in the alkyl part, alkylcarbonyl with 1-3 carbon atoms in Alkoxy, alkoxycarbonyl with 1-3 carbon atoms in the alkoxy part or tosyl group, or R8 is -COOR or -COR9, and R7 is -NHCOOR9 or -NHCOR9 where in the formulas R9 represents an alkyl group with 1-6 carbon atoms or a phenyl group, or also R6, R7 and the nitrogen atom to which they are attached together form an imide group of formula III, wherein R2 has the meaning as defined above, where if R8 is a group of formula -COOR9 or -CORfl and R7 is a group of formula -NHCOOR9 or -NHCOR9 then R3 is additionally a heteroarylmethyl group of formula R "" CH2-, in which R "" is 2, -thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-thiazolyl or 5-isoxazolyl, cyclized with a Lewis acid Friedel-Crafts catalyst, a Bronsted protic acid type, or of a cation-forming agent by metathesis in an anhydrous neutral solvent or The compound of formula (II) is dissolved or dissolved in an organic Bronsted acid, with the restrictions that if X is bromine, R4 is only an imide of formula III if a metathesis agent or an acid is used Lewis, then X represents only a chlorine or bromine atom, if R is a group that can be removed by the action of acids protecting the carboxyl function, then the product is obtained in the form of a sulfoxide - 3-methyl-4-cepa-carboxylic acid and it must be satisfied one of the conditions where: a) if X i is a chlorine atom or a group of the formula -OR4 in which R4 is a hydrogen atom, the cyclizations are carried out in an inorganic Bronsted acid, such as sulfuric, phosphoric, polyphosphoric, perchloric acid , chlorosulfonic or fluorosulfonic or HBF4, HA1C14, HasF4, HalBr4, SnCl4, SnBr4, SbCl5 and TiCl4, b / R 'is hydrogen, c / R2. represents an alkylene group of 2 to 4 carbon atoms, and dV Ri represents a 2-tinylacetamide group or an imide group of the formula V, in which R "and m are as defined above, and R 2 'is an alkyl group of 1 to 3 carbon atoms. , a haloalkyl group of 1-6 carbon atoms, an alkoxy group of 1-3 carbon atoms or a trichlorethoxy group, or that e / X represents a bromine atom, a group of the formula -OR4, in which R4 is an alkyl group of 1-10 atoms carbon, an aralkyl group of 1-3 carbon atoms in the alkyl portion or a haloalkyl group of 1-6 carbon atoms, or X is a group of the formula -SR5, where R5 is an alkyl group of 1-6 carbon atoms, an aryl or aralkyl group with 1-3 carbon atoms in the alkyl part, or X is a group of formula -N / Ra / R7, where R8 is hydrogen and R7 is hydrogen, R "or as defined above, or a group of the formula -NHR8, in which R8 represents an aminocarbonyl group, an alkylamino-carbonyl group with 1-3 carbon atoms, in part al Alkyl, alkylcarbonyl group with 1-3 carbon atoms in the alkyl part, alkoxycarbonyl group with 1-3 carbon atoms in the alkoxy part or tosyl group, or R8 is a group of the formula -COOR9 or of the formula -COR9 or R7 represents a group of formula -NHCOR9, or of formula -NHCOR9, in which formulas R9 represents an alkyl group of 1-6 carbon atoms or a phenyl group, or also R8, R7 and the nitrogen atom to which they are attached form the group imide of formula 3, in which Rf is as defined above, where if R5 is a group of formula -COOR9 or of formula -COR9 and R7 is a group of formula -NHCOORg or of formula -NHCOR9, then R8 may additionally denote a heteroarylmethyl group of the formula R "" CH2-, in which R "" is a 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 3-thiazolyl group or a 5-isoxazolyl group. 30. The method according to claim A process as claimed in 29, characterized in that 2-methyl-1- [2-chlorosulfinyl-4-keto-3- (N-phenoxyacetyl-N- (2,2,2-trichloroethoxycarbonyl) amino) azetidinyl 4-nitrobenzyl ester The -1] -2-propenecarboxylic acid is reacted with tin chloride to give 7- [N-phenoxyacetyl-N- (2,2,2-trichloroethoxycarbonyl) -amino] -3-4-nitrobenzyl ester-1-oxide. - methylenecephamocarboxylic-4. 31. The method according to claim A process as claimed in 29, characterized in that 2-methyl-1- (2-bromoculfinyl-4-oxo-3-phthalimidazetidinyl-1,2-propenecarboxylic acid methyl ester) is reacted with tin chloride to give 1- 7-phthalimido-3-methylenecephamocarboxylic acid methyl ester oxide. 32. The method according to claim 29, characterized in that 2-methyl-1- (2-isopropylthiosulfinyl-4-keto-3-phenoxyacetamido-azetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester is reacted with methanesulfonic acid) 7-phenoxyacetamido-3-methylenecepamocarboxylic acid-4-nitrobenzyl ester-1-oxide. 33. The method according to claim 29, characterized in that 2-methyl-1- / 2-IIT-pre-butylsulfinyl-4-keto-3-phenoxyacetamidazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester is reacted with methanesulfonic acid to give 7-phenoxyacetamido-3-methylenecepam-4-carboxylic acid 4-nitrobenzyl ester-1-oxide. 34. The method according to claim 29, characterized in that 2-methyl-1- (2-methoxysulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1/2-propenecarboxylic acid 4-nitrobenzyl ester) is reacted with methanesulfonic acid to give 1 7- -phenoxyacetamido-3-methylenecephamocarboxylic acid 4-nitrobenzyl ester oxide. 35. The method according to claim A process as claimed in 29, characterized in that 2-methyl-1- (2-methyloxysulfinyl-4-keto-3-phenoxyacetamidoazethidinyl-1 - 2-propenecarboxylic acid 4-nitrobenzyl ester) is reacted with methanesulfonic acid and 7-phenoxyacetamido-3-methylenecephamorocarboxylic-4-nitrobenzyl ester-1-oxide is obtained. 36. The method according to claim A process as claimed in 29, characterized in that the 2-methyl-1- (2-aniline-4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester) is reacted with methanesulfonic acid to give 1- - 7-phenoxy-acetamido-3-methylenecepamocarboxylic acid 4-nitrobenzyl ester oxide. 37. The method according to claim 29, characterized in that 2-methyl-1- (2-N-succinimosulfinyl-4-keto-3-phenylacetamidoazetidin-1) -2-propenecarboxylic acid methyl ester is reacted with methanesulfonic acid to give 1 - 7-phenylacetami- to-3-methylenecephamocarboxylic acid methyl ester oxide. AND 38. The method according to claim A process as claimed in 29, characterized in that the 2-methyl-1- [2- (N, N'-dicarboethoxyhydrazsulfinyl) -4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester is reacted with methanesulfonic acid to give 7-phenoxyacetamido-3-methyl-4-cephamocarboxylic acid 4-nitrobenzyl ester-1-oxide. 39. The method according to claim 29. The process of claim 29, characterized in that 2-methyl-li [2-15- (N'-dicarbo-tertiary-butoxyhydrazsulfinyl) -4-keto-3-acetamidoazetidinyl-1 / -2- acid 4-nitrobenzyl ester The propenecarboxylic acid is reacted with methanesulfonic acid to give 7-acetamido-3-methylene-4-cephamocarboxylic acid 4-nitrobenzyl ester-1-oxide. 40. The method according to claim A process as claimed in 29, characterized in that 2-methyl-1 [2- (N, N'-dicarbo-tert-butyloxyhydrazosulfinyl) -4-keto-3- (2) -butyloxyhydrazosulfinyl acid 2,2,2-trichloroethyl ester -thienyl acetamido (-azetidinyl-25 -1) -2-propenecarboxylic acid is reacted with methanesulfonic acid to give 7- (2-thienyl acetamido) -3-methylenecephamocarboxylic acid 1-oxide of 2,2,2-trichlorethyl ester -4. 41. The method according to claim A process as claimed in 29, characterized in that 2-methyl-1-; [2- (N, N'-dibenzoylhydrazsulfinyl) -4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester it is reacted with methanesulfonic acid to give 7-phenoxyacetamido-3-methylenecepacetamido-3-methylenecepacarboxylic acid-1-oxide 4-nitrobenzyl ester. 42. The method according to claim A process as claimed in 29, characterized in that 2-methyl-1- (2-acetylhydrazsulfinyl-4-keto-3-phenoxyacetamino-azetidinyl-1 / -2-propenecarboxylic acid 4-nitrobenzyl ester) is reacted with methanesulfonic acid to give 7-phenoxyacetamido-3-methylenecephamocarboxylic acid-4-nitrobenzyl ester-1-oxide. 45 43. The method according to claim 29, characterized in that 2-methyl-1- (2-carbomethoxyhydrazosulfinyl-4-keto-3-phenoxy-acetamidoazetidinyl (2-2) propenecarboxylic acid 4-nitrobenzyl ester is reacted with methanesulfonic acid 50 to give 1 - 7-phenoxyacetamido-3-methylenecefamocarboxylic acid 4-nitrobenzyl ester oxide. 44. The method according to claim 29, characterized in that 2-methyl-1- (2- 55 -tolylsulfonylhydrazosulfinyl-4-keto-3-phenoxy-acetamidazetidinyl-1-2-propenecarboxylic acid) 4-nitrobenzyl ester is reacted with methanesulfonic acid to give 1 - 7-phenoxyacetamido-3-methylenecepamocarbo-4-xylic acid 4-nitrobenzyl ester oxide. 45. The method of 29, characterized in that 2-methyl-1- (2-aminosulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1/2-propenecarboxylic acid 4-nitrobenzyl ester) is reacted with methanesulfonic acid to give ester114 521 51 4-nitrobenzyl acid of 7-phenoxyacetamido-3-methylenocephamocarboxylic acid-4. 46. The method according to claim 29, characterized in that the 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phenoxyacetamidoazatidinyl-1 / -2-propenecarboxylic acid 4-methoxybenzyl ester) is reacted with tin chloride to give 7-phenoxyacetamido-3-methylenecephamocarboxylic acid-1-oxide. 52 47. The method according to claim 29, characterized in that 2-methyl-1- (2-chlorosulfinyl-4-keto-3-phenoxyacetamidoazetidinyl-1 / -2-propenecarboxylic acid benzhydryl ester) is reacted with tin chloride to give acid-1-oxide ¬ su 7-phenoxyacetamido-3-methylenecephamocarboxylic-4. R "- (0) mCH2C I! Formula 5 0 0 R, SHal COOR Formula 7 Formula 6 r --N a 9 S CH2CNH- Formula 8 0 Rr ySOR4 o * COOR Formula 77 0 li / Re COOR Formula 13 0 R / SOH COOR 0 SOR, R. ^ p ^ SSR5 COOR Formula 12 Rr 0 X COOR H / ztfr 74114 521 O oo -SNHNHS-OCH. HiNNHS-OLri, 0 Formula 15 -s-nCr2 o Formula 17 l 0 Formula 16 0 K + "NC) R2 o Formula W 0 MHCOOR9 ONHCOR9 r $ k COOR9 Rr S-NCOR9 COOR COOR Yvz '* r 23 r. U R 0 ii S J-Si (CHJ3 R Formula 20 * 0 CCOR 0 NY_ H0Ac7DMFa o /" " N COOR Formula 79 0 0 [o] R ^ S "COOR Formula 21 o Formula 22 COOR Formula 1 Formula 2L 0 COOR 7 / zcr," T Wztfr 7o. Scheme 2 X n. V Ct / i; ..- u X = M ~ s = o Formula 27 0 0% <5w oo W, DY Mi ND ód'j «Ah COOCHa COOCH3 H / healthy 25 Wzcr 29 Scheme 3 R 0 COOR!) HÓ-y COOH l4 / z ^ r 30 Wztfr ^ 7 PL