Method for preparing 7-substituted cephalosporins and 6-substituted penicillins by replacement of sulfur-containing groups

A process for the preparation of compounds of the formula:

• ##STR119## wherein R.sub.1 is selected from the group consisting of phthalimido, benzalimino, substituted benzalimino, ##STR120## wherein R.sub.10 is selected from the group consisting of phenyl, substituted phenyl, 1,4-cyclohexadienyl, phenoxy, substituted phenoxy, thienyl, furyl, phenylthio and substituted phenylthio, ##STR121## wherein R.sub.11 is selected from the group consisting of phenyl, substituted phenyl, and 1,4-cyclohexadienyl, and ##STR122## wherein R.sub.12 is selected from the group consisting of lower alkyl, phenyl and substituted phenyl, and wherein said benzalimino, phenyl, phenoxy, or phenylthio substituent is one or two members selected from the group consisting of lower alkyl, lower alkoxy, nitro, chloro, fluoro and trifluoromethyl;
• R.sub.3 is selected from the group consisting of hydrogen, t-butyl, trichloroethyl, trimethylsilyl, p-methoxybenzyl, and a cation selected from the group consisting of Na.sup.+, Ca.sup.++, Li.sup.+, K.sup.+, NH.sub.4.sup.+, and (C.sub.2 H.sub.5).sub.3 NH.sup.+ ;
• R.sub.4 is selected from the group consisting of methyl, acetoxymethyl, and carbamoyloxymethyl;
• and R.sub.5 is selected from the group consisting of lower alkoxy, phenoxy, benzoyloxy, lower alkanoyloxy, amino, lower alkylamino, lower dialkylamino, and azido;
• which comprises reacting a compound of the formula ##STR123## wherein R.sub.2 is selected from the group consisting of lower alkyl, phenyl, phenyl-lower alkyl and substituted phenyl or phenyl-lower alkyl wherein said phenyl substituent is one or two members selected from the group consisting of lower alkyl, lower alkoxy, nitro, chloro, fluoro, and trifluoromethyl;
• with a compound selected from the group consisting of a lower alkyl alcohol, phenol, lower alkanoic acid or its heavy metal salt, sodium azide, potassium azide, ammonia, lower alkylamine, and lower dialkylamine at a temperature of from about -10.degree. C to about 110.degree. C in the presence of an effective catalytic amount of a catalyst selected from the group consisting of mercuric acetate, mercuric chloride, dimethoxy mercury, thallium acetate, silver tetrafluoroborate, silver acetate, lead acetate, silver nitrate, and silver perchlorate.

A process for the preparation of compounds of the formula:

• ##STR124## wherein R.sub.1 is selected from the group consisting of phthalimido, benzalimino, substituted benzalimino, ##STR125## wherein R.sub.10 is selected from the group consisting of phenyl, substituted phenyl, 1,4-cyclohexadienyl, phenoxy, substituted phenoxy, thienyl, furyl, phenylthio and substituted phenylthio, ##STR126## wherein R.sub.11 is selected from the group consisting of phenyl, substituted phenyl, and 1,4-cyclohexadienyl, and ##STR127## wherein R.sub.12 is selected from the group consisting of lower alkyl, phenyl and substituted phenyl, and wherein said benzalimino, phenyl, phenoxy, or phenylthio substituent is one or two members selected from the group consisting of lower alkyl, lower alkoxy, nitro, chloro, fluoro and trifluoromethyl;
• R.sub.3 is selected from the group consisting of hydrogen, t-butyl, trichloroethyl, trimethylsilyl, p-methoxybenzyl, and a cation selected from the group consisting of Na.sup.+, Ca.sup.++, Li.sup.+, K.sup.+, NH.sub.4.sup.+, and (C.sub.2 H.sub.5).sub.3 NH.sup.+ ;
• R.sub.5 is selected from the group consisting of lower alkoxy, phenoxy, benzoyloxy, lower alkanoyloxy, amino, lower alkylamino, lower dialkylamino, and azido;
• which comprises reacting a compound of the formula:
• ##STR128## wherein R.sub.2 is selected from the group consisting of lower alkyl, phenyl, phenyl-lower alkyl and substituted phenyl or phenyl-lower alkyl wherein said phenyl substituent is one or two members selected from the group consisting of lower alkyl, lower alkoxy, nitro, chloro, fluoro, and trifluoromethyl;
• with a compound selected from the group consisting of a lower alkyl alcohol, phenol, lower alkanoic acid or its heavy metal salt, sodium azide, potassium azide, ammonia, lower alkylamine, and lower dialkylamine at a temperature of from about -10.degree. C to about 110.degree. C in the presence of an effective catalytic amount of a catalyst selected from the group consisting of mercuric acetate, mercuric chloride, dimethoxy mercury, thallium acetate, silver tetrafluoroborate, silver acetate, lead acetate, silver nitrate, and silver perchlorate.