Organic derivatives of rhenium oxides and their preparation...

C - Chemistry – Metallurgy – 07 – C

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260/708, 252/94,

C07C 21/14 (2006.01) B01J 31/12 (2006.01) C07C 6/04 (2006.01) C07C 17/00 (2006.01) C07C 43/15 (2006.01) C07C 67/333 (2006.01) C07C 67/475 (2006.01) C07F 13/00 (2006.01)

Patent

CA 1330566

Abstract: A compound of the general formula R1aRebOc, wherein a is an integer from 1 to 6, b is an integer from 1 to 4 and c is an integer from 1 to 14 and the sum of a, b and c conforms to the 5- to 7-valency of rhenium with the proviso that c does not exceed 3-b, and wherein R1 represents alkyl having from 1 to 9 carbon atoms, cycloalkyl having from 5 to 10 carbon atoms or aralkyl having from 7 to 9 carbon atoms and wherein R1 is unsubstituted or at least partially fluorinated, said compounds containing not more than three groups of more than 6 carbon atoms per rhenium atom and containing a hydrogen atom bound to the carbon atom in .alpha.-position to the rhenium atom, the methylrhenium oxides CH3ReO3 and (CH3)6Re2O3 and pentamethylcyclopentadienyl-rheniumtrioxide (?5-C5(CH3)5)ReO3 being excluded. The invention further relates to a catalytic composition for the metathesis of olefinic compounds comprising an oxidic carrier charged with a compound of the general formula R1aRebOc, wherein a is an integer from 1 to 6, b is an integer from 1 to 4 and c is an integer from 1 to 14 and the sum of a, b and c conforms to the 5- to 7-valency of rhenium with the proviso that c does not exceed 3?b, and wherein R1 represents alkyl having from 1 to 9 carbon atoms, cycloalkyl having from 5 to 10 carbon atoms or aralkyl having from 7 to 9 carbon atoms and wherein R1 is unsubstituted or at least partially fluorinated, said compounds containing not more than three groups of more than 6 carbon atoms per rhenium atom and containing a hydrogen atom bound to the carbon atom in a-position to the rhenium atom. The invention also relates to a process for the preparation of a metal organic catalyst as defined hereinbefore, which comprises charging the carrier with the rhenium compound from an anhydrous solvent inert towards the rhenium compounds, and subsequently removing the volatile compounds. The invention finally relates to a process for the metathesis of olefins which comprises reacting an olefin of the formula YCZ=CZ-(CX2)nR2 (II) wherein n an integer from 1 to 28, X represents H or F, Y represents H or alkyl having from 1 to 10 carbon atoms and Z represents H or a non-aromatic hydrocarbon group having from 1 to 6 carbon atoms and R2 being H, alkyl, halogen, COOR3 or R4, wherein R3 and R4 represent alkyl having from 1 to 15 carbon atoms or phenyl which is unsubstituted or contains from 1 to 3 substituents or wherein R4 is trialkylsilyl R5Si, wherein R5 represents alkyl having from 1 to 5 carbon atoms, at a catalyst comprising an oxidic carrier charged with a rhenium compound as defined hereinbefore.

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