There is described a process for the preparation of 3-disubstituted cepham-4-carboxylic acid derivatives of formula I ##STR1## wherein R" is 4-methoxybenzyl, X is the residue of a thioether and Z is a residue of a nucleophilic compound, such as 2-furoylthio, acetoxy or 1,2,5,6-tetrahydro-2-methyl-5,6-dioxo-1,2,4-triazin-3-ylthio, by reaction of a functional derivative of .alpha.-(2-chloroacetamido)thiazol-4-yl-.alpha.-methoxyiminoacetic acid with 7.beta.-amino-3-methylenecepham-4-carboxylic acid 4-methoxybenzyl ester, subsequent treatment of the obtained 4-methoxybenzyl 7.beta.-[.alpha.-(2-chloroacetamido)thiazol-4-yl-.alpha.-methoxyimino]acet amido-3-methylenecepham-4-carboxylate with a S-chloromercaptan of formula X--S--Cl, such as methanesulfenyl chloride, and final treatment of the corresponding 4-methoxybenzyl 7.beta.-[.alpha.-(2-chloroacetamido)thiazol-4-yl-.alpha.-methoxyimino]acet amido-3-thio-3-chloromethylcepham-4-carboxylate thus obtained of formula V ##STR2## wherein R" and X are as defined above, with a compound of formula M-Z, in which M is an alkaline metal or a hydrogen atom and Z is as defined above. These novel intermediates may be converted into the corresponding 3-cephem derivatives by oxidative cleavage of the mercaptan X--SH. By suitable deprotection, these 3-cephem derivatives afford cephalosporins such as ceftiofur, cefotaxime and ceftriaxone.