the compounds of the present invention ( i ) are prepared according to the following scheme : ## str3 ## in words relative to the above diagram , the starting material 1 [ r = benzyl ; benzyl - 6α - bromo - 6β -[ 1 - hydroxyethyl ] penicillinate ; f . di ninno , et al ., j . org . chem . 42 2960 ( 1977 )] in a solvent such as tetrahydrofuran , diethyl ether , dichloromethane , or the like is treated with a triorganophosphine such as triphenylphosphine , tri - n - butylphosphine , hexamethylphosphorous triamide or the like and an azodicarboxylate such as diethylazodiazodicarboxylate , dimethylazidodicarboxylate , di - t - butylazodicarboxylate , or the like at a temperature of from - 78 ° c . to 25 ° c . for from 0 . 5 to 48 hours to provide 2 , which upon reductive debromination in a solvent such as methanol , methanol - acetic acid , tetrahydrofuran or the like in the presence of a reducing agent such as zinc - silver couple , zinc - copper couple , tri - n - butyltin hydride , or the like at a temperature of from 0 ° c . for from 0 . 5 to 24 hours yields 3 . relative to structure 1 , 2 , and 3 , in the above diagram the radical r may be any conventional , readily removable carboxyl blocking group such as benzyl , p - nitrobenzyl , trichloroethyl , methyl , or the like . the de - blocking reaction is illustrated above , and discussed below . alternatively , r may be a pharmaceutically acceptable ester moiety , such as pivaloyloxymethyl , 3 - buten - 1 - yl , ( 2 - methylthio )- ethyl or the like . the de - blocking procedure may be accomplished by any of a variety of well - known procedures such as hydrolysis or hydrogenation . preferably the carboxyl blocking group r is removed by hydrogenation in a solvent such as a loweralkanol , for example , ethanol in the presence of a hydrogenation catalyst such as palladium , platinum or oxides thereof under 1 - 40 atmospheres of hydrogen at from 0 ° to 50 ° c . for from 1 to 10 hours . salts of the free acid are easily prepared by treatment of the free acid dissolved in an organic solvent such as ethyl acetate , acetone , chloroform , or the like with an equivalent amount of an inorganic base such as sodium bicarbonate , sodium hydroxide , calcium carbonate or the like , evaporating the organic solvent and lyophilizing the aqueous phase . the products of this invention ( i ) form a wide variety of pharmacologically acceptable salts with inorganic and organic bases ; these include , for example , metal salts derived from alkali metal or alkaline earth metal hydroxides , carbonates or bicarbonates and salts derived from primary , secondary or tertiary amines such as monoalkylamines , dialkylamines , trialkylamines , lower alkanolamines , di - loweralkanolamines , lower alkylenediamines , n , n - diaralkyl lower alkylenediamines , aralkylamines , amino substituted lower alkanols , n , n - di - lower alkylamino substituted lower alkanols , amino -, polyamino - and quanidino - substituted lower alkanoic acids and nitrogen containing heterocyclic amines . representative examples include salts derived from sodium hydroxide , sodium carbonate , sodium bicarbonate , potassium carbonate , potassium hydroxide , calcium carbonate , trimethylamine , triethylamine , piperidine , morpholine , quinine , lysine , protamine , arginine , procaine , ethanolamine , morphine , benzylamine , ethylenediamine , n , n &# 39 ;- dibenzylethylenediamine , diethanolamine , piperazine , dimethylaminoethanol , 2 - amino - 2 - methyl - 1 - propanol , theophylline , n - methylglucamine and the like . salts of the primary amine of i with pharmaceutically acceptable organic and inorganic acids are also the compounds of the present invention , i , and salts thereof are valuable antimicrobial substances which are active against various gram - positive and gram - negative pathogens . thus , the free acid and especially the salts thereof such as amine and metal salts , particularly the alkali metal and alkaline earth metal salts , are useful bactericides and can be used for removing susceptible pathogens from dental and medical equipment , for separating microorganisms , and for therapeutic use in humans and animals . for this latter purpose pharmacologically acceptable salts with inorganic and organic bases such as those known in the art and used for the administration of penicillins and cephalosporins can be utilized . for example , salts such as alkali metal and alkaline earth metal salts , and primary , secondary and tertiary amine salts can be used for this purpose . these salts can be combined with pharmaceutically acceptable liquid and solid vehicles to form suitable dosage unit forms such as pills , tablets , capsules suppositories , syrups , elixirs and the like which can be prepared in accordance with procedures well known in this art . the novel compounds are valuable antibiotics active against various gram - positive and gram - negative bacteria and , accordingly , find utility in human and veterinary medicine . the compounds of this invention can therefore be used as antibacterial drugs for treating infections caused by gram - positive or gram - negative bacteria , for example against staphylococcus aureus , escherichia coli , klebsiella , pneumoniae , bacillus subtilis , salmonella typhosa , pseudomonas and bacterium proteus . the antibacterials of the invention may further be utilized as additives to animal feedingstuffs , for preserving foodstuffs and as disinfectants . for example , they may be employed in aqueous compositions in concentrations ranging from 0 . 1 to 100 parts of antibiotic per million parts of solution in order to destroy and inhibit the growth of harmful bacteria on medical and dental equipment and as bactericides in industrial applications , for example in waterbased paints and in the white water of paper mills to inhibit the growth of harmful bacteria . the products of this invention may be used alone or in combination as an active ingredient in any one of a variety of pharmaceutical preparations . these antibiotics and their corresponding salts may be employed in capsule form or as tablets , powders or liquid solutions or as suspensions or elixirs . they may be administered orally , intravenously or intramuscularly . the compositions are preferably presented in a form suitable for absorption by the gastro - intestinal tract . tablets and capsules for oral administration may be in unit dose presentation form , and may contain conventional excipients such as binding agents , for example , syrup , acacia , gelatin , sorbitol , tragacanth , or polyvinylpyrrolidone ; fillers for example , lactose , sugar , maizestarch , calcium phosphate , sorbitol or glycine ; lubricants , for example , magnesium , stearate , talc , polyethylene glycol , silica ; disintegrants , for example , potato starch or acceptable wetting agents such as sodium lauryl sulphate . the tablets may be coated according to methods well known in the art . oral liquid preparations may be in the form of aqueous or oily suspension , solution , emulsions , syrups , elixirs , etc . or may be presented as a dry product , for reconstitution with water or other suitable vehicles before use . such liquid preparations may contain conventional additives such as suspending agents , for example , sorbitol syrup , methyl cellulose , glucose / sugar syrup , gelatin , hydroxyethylcellulose , carboxymethyl cellulose , aluminum stearate gel or hydrogenated edible oils , for example almond oil , fractionated coconut oil , oily esters , propylene glycol , or ethyl alcohol ; preservatives , for example methyl or propyl p - hydroxybenzoates or sorbic acid . suppositories will contain conventional suppository bases , e . g ., cocoa butter or other glyceride . compositions for injection may be presented in unit dose form in ampules , or in multidose containers with an added preservative . the compositions may take such forms as suspensions , solutions , or emulsions in oil or aqueous vehicles , and may contain formulatory agents such as suspending , stabilizing and / or dispersing agents . alternatively , the active ingredient may be in powder form for reconstitution with a suitable vehicle , e . g ., sterile , pyrogen - free water , before use . the compositions may also be prepared in suitable forms for absorption through the mucous membranes of the nose and throat or bronchial tissues and may conveniently take the form of powder or liquid sprays or inhalants , lozenges , throat paints , etc . for medication of the eyes or ears , the preparations may be presented as individual capsules , in liquid or semi - solid form , or may be used as drops etc . topical applications may be formulated in hydrophobic or hydrophilic bases as ointments , creams , lotions , paints , powders , etc . also , in addition to a carrier , the instant compositions may include other ingredients such as stabilizers , binders , antioxidants , preservatives , lubricators , suspending agents , viscosity agents or flavoring agents and the like . in addition , there may also be included in the composition other active ingredients to provide a broader spectrum of antibiotic activity . for veterinary medicine the composition may , for example , be formulated as an intromammary preparation in either long acting or quick - release bases . the dosage to be administered depends to a large extent upon the condition of the subject being treated and the weight of the host , the route and frequency of administration , the parenteral route being preferred for generalized infections and the oral route for intestinal infections . in general , a daily oral dosage consists of from about 15 to about 600 mg . of active ingredient per kg . of body weight of the subject in one or more applications per day . a preferred daily dosage for adult humans lies in the range of from about 80 to 120 mg of active ingredient per kg . of body weight . the instant compositions may be administered in several unit dosage forms as , for example , in solid or liquid orally ingestible dosage form . the compositions per unit dosage , whether liquid or solid may contain from 0 . 1 % to 99 % of active material , the preferred range being from about 10 - 60 %. the composition will generally contain from 15 mg . to about 1500 mg . of the active ingredient ; however , in general , it is preferable to employ a dosage amount in the range of from about 250 mg to 1000 mg . in parenteral administration the unit dosage is usually the pure compound in a slightly acidified sterile water solution or in the form of a soluble powder intended for solution . the following examples illustrate but do not limit the product , process , compositional or method of treatment aspects of the present invention . all temperatures are in ° c . to a stirred solution of 46 . 3 mg ( 0 . 1 mmol ) of benzyl - 6α - bromo - 6β -[ 1 - hydroxyethyl ] penicillanate and 78 mg ( 0 . 3 mmol ) triphenylphosphine in 5 ml . dry tetrahydrofuran at room temperature ( 25 ° c .) under a nitrogen atmosphere is added dropwise 36 μ1 ( 0 . 22 mmole ) of neat diethylazodicarboxylate . the resulting mixture is stirred for 20 minutes and evaporated under reduced pressure . the residue is purified by plate layer chromatography [ 3 developments φh -- chcl 3 ( 2 : 1 )] to give 13 . 8 mg ( 31 %) of 2 : ir ( chcl 3 ) 1770 and 1724 cm - 1 ; nmr ( cdcl 3 ); δ1 . 64 ( d , j = 7 hz , ch 3 ), 2 . 14 ( s , ch 3 ), 2 . 3 ( s , ch 3 ), 3 . 94 ( qd , j = 0 . 8 and 7 . 0 hz , h - 5 ), 5 . 21 ( abq , j = 12 hz , co 2 ch 2 ph ), 5 . 28 ( d , j = 0 . 8 hz , h - 1 ), and 7 . 39 ( s , arh ); mass spectrum m / e 397 , 395 ( m + ) [ calc . for c 17 h 18 no 3 sbr : 395 . 0188 ; found : 395 . 0187 ], 316 , 256 , 231 , 166 , 164 , 91 . to a stirred suspension of 53 mg . of zinc - silver couple in 0 . 4 ml methanol at room temperature is added in rapid succession 41 mg ( 0 . 7 mmol ) of glacial acetic acid and a solution of 85 mg ( 0 . 2 mmol ) of 2 in 0 . 5 ml methanol . the mixture is stirred under a nitrogen atmosphere for 1 . 5 hours and is then filtered . the filtrate is diluted with ethyl acetate and washed successively with dilute , aqueous hydrochloric acid , aqueous sodium bicarbonate , and saturated sodium chloride . the organic phase is dried with magnesium sulfate , filtered , and evaporated . purification by plate layer chromatography [ 2 developments chcl 3 ] provides 39 . 2 mg ( 60 %) of 3 : ir ( chcl 3 ) 1754 and 1718 cm - 1 ; nmr ( cdcl 3 ) δ1 . 64 ( d , j = 6 . 5 hz , ch 3 ), 2 . 17 ( s , ch 3 ), 2 . 28 ( s , ch 3 ), 3 . 84 ( m , schch 3 ), 3 . 96 ( app . t , j = 3 and 4 hz , h - 4 ), 5 . 12 ( dd , j = 1 . 5 and 4 hz , h - 1 ), 5 . 2 ( abq , j = 12 hz , co 2 ch 2 ph ), and 7 . 38 ( s , arh ); m / e 317 ( m + ). a mixture of 30 mg . 10 % pd / c , 2 ml methanol , 0 . 4 ml deionized water , and 0 . 2 ml . 0 . 1 n ph 7 phosphate buffer is hydrogenated at room temperature and 50 psi for 25 minutes . to the reduction mixture is added a solution of 20 mg ( 0 . 06 mmol ) of 3 in 0 . 6 ml methanol . the resulting mixture is hydrogenated at room temperature and 50 psi for 0 . 5 hour . the catalyst is removed by filtration through celite and washed with methanol . the filtrate is concentrated under reduced pressure and diluted with deionized water . the ph of the solution is adjusted to 9 . 0 with 0 . 2 m aqueous sodium bicarbonate and is thoroughly extracted with ethyl acetate . the aqueous phase is then acidified to ph 2 . 5 with 2 . 5 n aqueous hydrochloric acid and is thoroughly extracted with ethyl acetate . the combined extracts are dried ( mgso 4 ), filtered , and evaporated to provide free acid i . the free acid is converted to its sodium salt 4 by treating an acetone solution of i ( 5 mg ) with an equivalent weight of sodium bicarbonate dissolved in water , removing the acetone under reduced pressure , and lyophilizing the remaining aqueous phase . one such unit dosage form consists in mixing 120 mg . sodium 5α - methyl - 6 - thia - 2 - azabicyclo [ 2 . 2 . 0 ] hexane carboxylate with 20 mg . of lactose and 5 mg of magnesium stearate and plcing the 145 mg mixture into a no . 3 gelatin capsule . similarly , by employing more of the active ingredient and less lactone , other dosage forms can be put in no . 3 gelatin capsules and should it be necessary to mix more than 145 mg of ingredients together , larger capsules such as compressed tablets and pills can also be prepared . the following examples are illustrative of the preparation of pharmaceutical formulations : ______________________________________tablet per tablet______________________________________sodium - 5α - methyl - 6 - thia - 2 - azabicyclo -[ 2 . 2 . 0 ] hexane carboxylate 125 mgcornstarch , u . s . p . 6 mgdicalcium phosphate 192 mglactose , u . s . p . 190 mg______________________________________ the active ingredient is blended with the dicalcium phosphate , lactose and about half of the cornstarch . the mixture is then granulated with 15 % cornstarch paste ( 6 mg ) and rough - screened . it is dried at 45 ° c . and screened again through no . 16 screens . the remaining cornstarch and magnesium stearate , being the balance , is added and the mixture is compressed into tablets , approximately 0 . 5 inch in diameter each weighing 800 mg . ______________________________________parenteral solutionampoule : sodium 5α - methyl - 6 - thia - 2 - azabicyclo [ 2 . 2 . 0 ]- hexane carboxylate 500 mgdiluent : sterile water for injection 2 mlopthalmic solutionampoule : sodium 5α - methyl - 6 - thia - 2 - azabicyclo [ 2 . 2 . 0 ]- hexane carboxylate 100 mghydroxypropylmethyl cellulose 5 mgsterile water 1 mloptic solutionampoule : sodium 5α - methyl - 6 - thia - 2 - azabicyclo [ 2 . 2 . 0 ]- hexane carboxylate 100 mgbenzalkonium chloride 0 . 1 mgsterile water 1 mltopical ointmentsodium 5α - methyl - 6 - thia - 2 - azabicyclo [ 2 . 2 . 0 ]- hexane carboxylate 100 mgpolyethylene glycol 4000 u . s . p . 400 mgpolyethylene glycol 400 u . s . p . 1 . 0 gram______________________________________ the active ingredient in the above formulations may be administered alone or in combination with other biologically active ingredients as , for example , with other antibacterial agents such as lincomycin , a penicillin , streptomycin , novobiocin , gentamicin , neomycin , colistin and kanamycin , or with other therapeutic agents such as probenecid .