Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Patent
1998-02-26
1998-11-24
Geist, Gary
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
568451, 568909, 502 74, 502232, 502260, 502158, C07C 4550
Patent
active
058409939
DESCRIPTION:
BRIEF SUMMARY
This is the U.S. National stage Application of PCT/EP96/02394 filed Jun. 3, 1996 now WO97/00132 published Jan. 3, 1997.
The invention relates to water-soluble cobalt catalysts, a process for their preparation and their use as hydroformylation catalysts in a two-phase system comprising polyethylene glycol as polar phase.
Water-soluble catalysts offer great industrial advantages owing to the ease of separating off the catalyst with at the same time high selectivity of the catalyst as a result of the homogeneous reaction procedure. The reduced primary energy consumption resulting from the ease of separating off the catalyst together with the simultaneous reduction in amounts of undesired by-products achieved as a result of the high selectivity is leading to an increasing interest in two-phase catalysts.
There is therefore a need for further compounds of this type to be made available.
This object is achieved by means of cobalt carbonyl catalysts of the formula (I) ##STR2## where R is --CH(CH.sub.2 OCH.sub.2 CH.sub.3).sub.2 or --C.sub.2 H.sub.4 (OCH.sub.2 CH.sub.2).sub.n OY, with n=1 to 12 and Y=H or CH.sub.3.
The compounds of the invention are prepared by reacting compounds of the formula (II) with alcohols (ROH): ##STR3##
Here, X is OH or chlorine,
Compounds of the formula (II) are obtainable by the method of D. Seyferth, J. Organomet. Chem. 1979, 178, 227-247.
Compounds of the formula (I) display high conversion rates and chemoselectivities in the hydroformylation of olefins. Of particular interest is the reaction of olefins of the formula CH.sub.3 (CH.sub.2).sub.m CH.dbd.CH.sub.2 (m=2 to 9) in a two-phase system comprising polyethylene glycol as polar phase. It has here been found useful to work at temperatures of from 50.degree. to 150.degree. C., pressures of from 50 to 100 kPa and a concentration ratio of catalyst:substrate of from 1:20 to 1:1000.
EXAMPLE 1
0.574 g (1 mmol) of trichlorosilylmethylidynyl-tricobalt nonacarbonyl is 80.degree. C. for 24 hours under a CO atmosphere. The sediment is subsequently filtered off. The CO content is 13.75 g/l (determined by atomic absorption spectroscopy). The compound is in the form of a solution in polyethylene glycol 400 and has an intense violet color. It is completely miscible with water and is virtually immiscible with nonpolar solvents (hexane, pentane, etc.).
The IR spectrum of the solution shows the following bands in the carbonyl region: 1887 cm.sup.-1, 1979 cm.sup.-1, 1995 cm.sup.-1, 2029 cm.sup.-1, 2060 cm.sup.-1.
EXAMPLE 2
0.574 g (1 mmol) of trichlorosilylmethylidynyl-tricobalt nonacarbonyl is taken up in 10 ml of 1,3-diethoxy-2-propanol and heated to 60.degree. C. for 24 hours under a CO atmosphere. The excess alcohol is subsequently distilled off in a high vacuum. The compound is obtained in the form of a violet high-viscosity solution. The IR spectrum of the compound in nujol shows the following bands in the carbonyl region:
2037 cm.sup.-1, 2056 cm.sup.-1. The .sup.1 H-NMR spectrum shows three groups of signals at: 1.03 ppm (CH.sub.3,d,6H); 3.26 ppm (CH.sub.2,q,4H); 3.42 ppm (CH.sub.2,m,4H); 4.01 ppm (CH,m,1H) (measured in d.sub.6 -benzene). The .sup.29 Si-NMR spectrum shows a singlet at -53.8 ppm (measured in d.sub.8 -THF).
EXAMPLES 3 to 6
Use of the compound prepared under 1 for the hydroformylation of 1-hexene in polyethylene glycol 400:
The catalysis tests are carried out in a 100 ml laboratory autoclave. In a typical reaction, 2 ml of the polyethylene glycol solution which has been prepared by reaction of trichlorosilylmethylindynyl-tricobalt nonacarbonyl with polyethylene glycol 400 in the manner described (I) are initially charged and admixed with 2 ml of 1-hexene (16 mmol). The autoclave is then charged with 70 kPa of a mixture (1/1) of CO and H.sub.2. The reaction mixture is heated at 120.degree. C. for 18 hours while stirring. After the reaction, 4 ml of pentane are added to assist phase separation and the phases are separated. The upper nonpolar phase contains pentane and the reaction products which are determined gas-chromatogr
REFERENCES:
patent: 4045493 (1977-08-01), Trevillyan
Dietmar Seyferth et al, "Novel Silicon Compounds Containing The Nonacarbonyl Tricobaltcarbon Substituent", Journal of Organometallic Chemistry, 1979, pp. 227-247, XP002009593.
John Evans et al, "Generalised Cluster Anchoring to Oxide Supports", J.C.S. Chem. Comm., 1980, pp. 852-853, XP002009594.
Maurice M. Kreevoy et al, "A General, High Yield Route to Novel Silicon-Functional Silymethylidynetricobalt Nonacarbonyl Cluster Complexes", Journal of the American Chem. Soc., 1977, pp. 5209-5210, XP002009595.
Ritter Uwe
Roesky Herbert
Winkhofer Norbert
Geist Gary
Hoechst AG
Padmanabhan Seeni
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