Organo-rhenium oxide cpds. - useful on oxide support materials, as catalysts for metathesis of olefin(s), esp. functional olefin(s)

摘要

Rhenium cpds. of formula (R')aRebOc (I) are claimed a=1-6; b=1-4; c=1-14; sum of a+b+c is as required for 5- to 7-valent Re, but c is not greater than 3.b; R1 = 1-9C alkyl, 5-10C cycloalky or 7-9C aralkyl; R1 can be at least partly fluorinated, the cpds. contain not more than 3 gps. with more than 6C atoms for each Re atom and there is at least one H atom on the C atom in the alpha-position; the following cpds. are not claimed as new; methylrhenium trioxisw MeReOa, Me6Re2O3 and pentamethyl cyclopentadienylrhenium trioxide C5Me5ReO3. Also claimed are: (a) a process for prodn. of metal-organic catalysts as above, by depositing the Re cpd. from soln. in an inert non-aq. solvent onto the support and removing the solvent, (b) a process for metathesis of olefins of formulaYCZ=CZ-(CX2)nR2 (with n = 1-28; X = H or F; Y = H or 1-10C alkyl; Z = H or 1-6C non-aromatic hydrocarbyl; R2 = H, alkyl, Hal, COOR3 or R4 (with R3, R4=1-15C, pref. 1-6C alkyl or Ph, opt. with 1-3 ring substits., or R4 = (R5)3Si with R5 = 1-5C, pref. 1-3C, alkyl) by reaction on oxide-supported (I); pref. olefin is a functionalised olefin or a cyclo-olefin; no activator is used; the support is Al2O3 or a mixt. thereof with SiO2, dried by ignition; catalyst contains methylrhenium trioxide as active substance; reaction is carried out at 0-60 (pref. 10-30) deg.C and atmos. pressure. USE/ADVANTAGE - (I) are good catalysts for the metathesis of olefins, partic. functional olefins, and do not require activators or cocatalysts (contrast prior-art Re oxide catalysts); they are produced e.g. by alkylation of Re2O7 with Me2Zn, without using toxic organotin cpds.