ES405883A1 - Penicillin sulphoxides and their use in preparing delta3-7- substituted amino-descetoxy-cephalosporins - Google Patents

Abstract

Procedure for obtaining derivatives of Δ 3-7-acylamido-deacetoxycephalosporanic acid, of general formula **(See formula)** where R1 means an acylamido group and its salts, characterized in that a 6-acylamido-penicilanico acid sulfoxide of general formula **(See formula)** where R1 has the meaning defined above and Y means hydrogen or an alkali metal, with a halide of formula R2Hal, where R2 means an acid anhydride group of the following general formulas where R3, R31, R4, R41, R5, R51, R6 and R7 are the same or different and in each case signify halogen or R5 and R6 together represent oxygen or sulfur or R31, R41 or R51 signify a lower alkyl group and R7 signifies a lower alkyl group which may be substituted by one or more halogens, or a phenyl group and M1 means boron, aluminum, or phosphorus, M2 means germanium or tin and M3 means phosphorus or tungsten or R2 means a thionyl-, oxalyl anhydride group - or p-toluenesulfonyl; or R2 signifies hydrogen or an alkali or alkaline earth metal cation or a cation derived from an amine, and Hal signifies halogen, the general formula is transformed into an anhydride **(See formula)** where R1 has the meaning defined above and R21 means an acid anhydride group of the class indicated above for R2, where R3 and R7 to R31 to R51 have the meanings indicated above and furthermore a 6-acylamido-penicylanylsulfoxide-3-carbonyloxy group, such as the group linked in general formula IVb with R21 and this anhydride is heated in a dry, inert organic solvent to extend the ring from the penamic ring to a Δ 3-cephem ring with an anhydride acid, especially from the acidic group hydrobromic, hydrochloric acid, p-toluenesulfonic acid and concentrated sulfuric acid, hydroiodic acid, perchloric, periodic, nitric, chloric, iodic, selenic, substituted acetic acids, substituted sulfonic acids, naphthalene sulfonic acid, oxalic acid, picrinic acids and CH acids, and in general compounds containing cyano, nitro and/or methoxycarbonyl groups, in the presence of a silicon-containing compound, especially the N, O group -bis (trimethylsilyl) -acetamide, N, N-bis (trimethylsilyl) urea, hexamethyldisilazane, N, O-bis (trimethylsilyl) trifluoracetamide, N, N1-bis (trimethylsilyl) -carbodiimide, N-methyl-N-trimethylsilyl -acetamide and N-methyl-N-trimethylsilyltrifluoracetamide, at a maximum temperature of 160ºC and then the compound formed is hydrolyzed in situ and the Δ 3-7-acylamidodecetoxycephaloesporanic acid formed is isolated as such or in the form of a salt. (Machine-translation by Google Translate, not legally binding)