Process for the selective preparation of z-isomers of...

C - Chemistry – Metallurgy – 07 – D

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C07D 501/04 (2006.01) C07D 501/00 (2006.01) C07D 501/18 (2006.01) C07D 501/24 (2006.01) C07F 7/10 (2006.01)

Patent

CA 2294178

There can be produced, at a high selectivity and in a high yield, the Z-isomer of a 7-N-unsubstituted or substituted- amino-3-[2-(4-substituted or unsubstituted-thiazol-5-yl) vinyl]-3-cephem-4-carboxylic acid or an ester thereof having the general formula (IV) Image wherein R1 denotes a hydrogen atom, a mono-valent amino- protecting group or a 2-(2-N-protected or unprotected aminothiazol-4-yl)- 2-alkoxyiminoacetyl group, R2 denotes a hydrogen atom, or R1 and R2 as taken together mean one di- valent amino-protecting group, R3 denotes a hydrogen atom, pivaloyloxymethyl group or a carboxyl-protecting group and R8 denotes an alkyl group and so on, by a process comprising reacting a 7-N-unsubstituted or substituted-amino-3-[(tri- substituted-phosphoranylidene) methyl]-3-cephem-4- carboxylic acid or an ester thereof having the general formula (I) Image wherein R1 , R2 and R3 each have the same meanings as defined above, and R4 denotes a lower alkyl group or an aryl group, 49 with a 4-substituted or unsubstituted-thiazol-5-carbaldehyde in a mixed solvent consisting of a mixture of one or more chlorinated hydrocarbon solvent(s) with one or more lower alkanol(s) at a low temperature of +5°C or below. According to the processes of this invention, the production of such E-isomer of the compound (IV) that is of lower antibacterial activity than that of the Z-isomer can be suppressed remarkedly. Further, the Z-isomer of a high purity can be produced efficiently in a facile way.

L'invention concerne des Z-isomères de composés représentés par la formule générale (IV). Dans ladite formule, R<1> est 2-(2-aminothiazole protégé en N-4-yl)-2-alcoxyiminoacétyle ou similaire; R<2> est hydrogène ou similaire; R<3> est hydrogène, un groupe inhibant carboxyle ou similaire; et R<8> est alkyle ou similaire. On peut élaborer les produits considérés à des niveaux élevés de sélectivité et de rendement en faisant réagir un composé de formule générale (I), où R<1>, R<2> et R<3> sont tels que définis ci-dessus et où R<4> est aryle ou similaire, avec un thiazole-5-carbaldéhyde substitué ou non en 4, dans un solvant mixte comprenant un chlorocarbure et un alcanol inférieur, à une température égale ou inférieure à +5 DEG C.

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