The ozonolysis of p-nitrobenzyl ester of 7-amino-3-methylenecephem-4-carboxylic acid (I) in CH2Cl2 gives the p-nitrobenzyl ester of 7-amino-3-hydroxy-3-cephem-4-carboxylic acid (II), which is then condensed with thiophene-2-acetyl chloride (A) in aqueous THF to afford p-nitrobenzyl ester of 7-(thiophene-2-acetamido)-3-hydroxy-3-cephem-4-carboxylic acid (III). The chlorination of (III) with SOCl2, PCl3, POCl3, (COCl)2 or COCl2 in DMF yields p-nitrobenzyl ester of 7-(thiophene-2-acetamido)-3-chloro-3-cephem-4-carboxylic acid (IV), which is then partially hydrolyzed with dry pyridine and PCl5 giving p-nitrobenzyl ester of 7-amino-3-chloro-3-cephem-4-carboxylic acid (V). This compound can be acylated easily to p-nitrobenzyl ester of 7-(D-alpha-phenylglycylamido)-3-chloro-3-cephem-4-carboxylic acid (VI), which is finally hydrogenolyzed with Zn and conc. HCl. An alternative way starting also from (V) is its hydrogenolysis with H2 over Pd/C in THF-MeOH giving the 7-amino-3-chloro-3-cephem-4-carboxylic acid (VII), which is then acylated as usual.