Abstract: A 7-(5-amino-5-carboxyvaleramido)-7-methoxycephalosporin with amino and acid groups protected is reacted with PCl.sub.5 or other agent capable of forming an imino halide; the resulting imino halide is thereafter reacted under essentially non-aqueous conditions with a primary loweralkanol of C.sub.1 -C.sub.4 or with methan-d.sub.3 -ol, yielding nucleus bearing a 7-alkoxy group derived from the primary loweralkanol or methan-d.sub.3 -ol. In situ acylation of the nucleus affords 7-acylamido-7-alkoxycephalosporins in good yield; these products can be deesterified to yield the corresponding acids, which exhibit antibacterial activity.