Patent GB-1288132-A (GB)
IPC: B01J31/06
Filed: 1970-11-25
Abstract: 1288132 Dehydragenation catalysts INSTITUT FRANCAIS DU PETROLE DES CARBURANTS ET LUBRIFIANTS 25 Nov 1970 [26 Nov 1969] 56143/70 Heading B1E [Also in Division C2] A catalyst for use in the preparation of a ketone from a secondary alcohol is prepared by mixing a compound of a metal selected from metals of Groups IB, IIB, IVA, VA and VIIA and non-noble metals of Group VIII with either an organic derivative of boron containing at least one hydrogen-boron bond or an organic derivative of aluminium containing at least one hydrogen-aluminium or carbonaluminium bond, the catalyst being soluble in the reaction medium. The metal compound may be a compound of copper, zinc, titanium, zirconium, vanadium, chromium, molybdenum, tungsten, managanese, iron, cobalt or nickel and may be a hydride, halide, thiocyanate, 2-ethylhexanoate, stearate, naphthenate, alkoxide, acetylacetonate, sulphonate, for example camphosulphonate, or a cyclopentadienyl compound; the metal of the metal compound may be co-ordinated with an electron donor ligand selected from ethers, amines, phosphines, arsines and stibines. Exemplified metal componds are chromium stearate, managese stearate, cobalt-bis-tricyclohexylphosphine dibromide and iron, cobalt and nickel bromide, octoate, oleate, stearate and naphthenate. The organic derivatives of aluminium may be a compound having a formula selected from (a) AlR' 3  wherein each R' is a hydrogen atom or a hydrocarbon radical with the provisos that at least one R' is a hydrocarbon radical and that two R' moieties together may represent a group having the formula -A-Z-B- wherein A and B each is an alklene radical and Z is an oxygen atom, a sulphur atom, an alkylene group having from one to three carbon atoms or a NR' group wherein R' is as defined above, (b) AIR 2 OR wherein each R is a monovalent organic radical with the proviso that two R moieties together may represent a group having the formula -A-Z-B- wherein A, B and Z each is as defined above, (c) AlH n X 3-n  wherein n is 1 or 2 and the or each X is OR, NR 2 , NHR or SR, wherein R is as defined above, with the proviso that, when n is 1, the two X moieties together may represent a group having the formula -A-Z-B- wherein A, B and Z each is as defined above, and (d) Me[AlH m X' 4-m ] p  wherein Me is a metal of valency p selected from metals of Groups IA and IIA, m is 1, 2 or 3 and the or each X' is R, OR, NR 2 , NHR or SR, wherein R is as defined above, with the proviso that, when m is 1 or 2, two of the three or the two X moieties together may represent a group having the formula -A-Z-B- wherein A, B and Z each is as defined above. The Specification lists many such aluminium derivatives including compounds wherein Me is lithium or sodium. The organic derivative of boron may be an analogue of such an organic derivative of aluminium containing a hydrogenaluminium bond. The catalyst may be prepared and/or used in the presence of solvent for example selected from heavy paraffins, tetrahydronaphthalene and decahydronaphthalene. Examples relate to the preparation of catalysts, in the presence of either diethyleneglycol dimethylether or decahydronaphthalene, from cobalt stearate and NaAlH(O-tert-butyl) 3  (Examples 1 to 7), cobalt stearate and NaAlH 2 (O-tert-butyl) (O-tetrahydrofurfuryl) (Example 8), nickel stearate and NaAIH (OCH 3 ) 3  (Example 9), ferrous stearate and Al(iso-butyl) 3  (Example 10), cobalt octoate and Al(C 2 H 5 )OC 2 H 5  (Example 11) and cobalt octoate and NaAlH 2 (iso-butyl) 2  (Example 12).