Catalytic ionic hydrogenation of ketones using tungsten or molybdenum catalysts with increased lifetimes
Abstract
The present invention is a process for the catalytic hydrogenation of ketones and aldehydes to alcohols at low temperatures and pressures using organometallic molybdenum and tungsten complexes and the catalyst used in the process. The reactants include a functional group which is selected from groups represented by the formulas R*(C.dbd.O)R' and R*(C.dbd.O)H, wherein R* and R' are selected from hydrogen or any alkyl or aryl group. The process includes reacting the organic compound in the presence of hydrogen and a catalyst to form a reaction mixture. The catalyst is prepared by reacting Ph.sub.3 C.sup.+ A.sup.- with a metal hydride. A.sup.- represents an anion and can be BF.sub.4.sup.-, PF.sub.6.sup.-, CF.sub.3 SO.sub.3.sup.- or Bar'.sub.4.sup.-, wherein Ar'=3,5-bis(trifluoromethyl)phenyl. The metal hydride is represented by the formula: HM(CO).sub.2 [.eta..sup.5 :.eta..sup.1 --C.sub.5 H.sub.4 (XH.sub.2).sub.n PR.sub.2 ] wherein M represents a molybdenum (Mo) atom or a tungsten (W) atom; X is a carbon atom, a silicon atom or a combination of carbon (C) and silicon (Si) atoms; n is any positive integer; R represents two hydrocarbon groups selected from H, an aryl group and an alkyl group, wherein both R groups can be the same or different. The metal hydride is reacted with Ph.sub.3 C.sup.+ A.sup.- eithermore »
- Inventors:
- Issue Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1174475
- Patent Number(s):
- 6613923
- Application Number:
- 09/552,212
- Assignee:
- Brookhaven Science Associates, LLC (Upton, NY)
- Patent Classifications (CPCs):
-
C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07C - ACYCLIC OR CARBOCYCLIC COMPOUNDS
- DOE Contract Number:
- AC02-98CH10886
- Resource Type:
- Patent
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Bullock, R. Morris, Kimmich, Barbara F. M., Fagan, Paul J., and Hauptman, Elisabeth. Catalytic ionic hydrogenation of ketones using tungsten or molybdenum catalysts with increased lifetimes. United States: N. p., 2003.
Web.
Bullock, R. Morris, Kimmich, Barbara F. M., Fagan, Paul J., & Hauptman, Elisabeth. Catalytic ionic hydrogenation of ketones using tungsten or molybdenum catalysts with increased lifetimes. United States.
Bullock, R. Morris, Kimmich, Barbara F. M., Fagan, Paul J., and Hauptman, Elisabeth. Tue .
"Catalytic ionic hydrogenation of ketones using tungsten or molybdenum catalysts with increased lifetimes". United States. https://www.osti.gov/servlets/purl/1174475.
@article{osti_1174475,
title = {Catalytic ionic hydrogenation of ketones using tungsten or molybdenum catalysts with increased lifetimes},
author = {Bullock, R. Morris and Kimmich, Barbara F. M. and Fagan, Paul J. and Hauptman, Elisabeth},
abstractNote = {The present invention is a process for the catalytic hydrogenation of ketones and aldehydes to alcohols at low temperatures and pressures using organometallic molybdenum and tungsten complexes and the catalyst used in the process. The reactants include a functional group which is selected from groups represented by the formulas R*(C.dbd.O)R' and R*(C.dbd.O)H, wherein R* and R' are selected from hydrogen or any alkyl or aryl group. The process includes reacting the organic compound in the presence of hydrogen and a catalyst to form a reaction mixture. The catalyst is prepared by reacting Ph.sub.3 C.sup.+ A.sup.- with a metal hydride. A.sup.- represents an anion and can be BF.sub.4.sup.-, PF.sub.6.sup.-, CF.sub.3 SO.sub.3.sup.- or Bar'.sub.4.sup.-, wherein Ar'=3,5-bis(trifluoromethyl)phenyl. The metal hydride is represented by the formula: HM(CO).sub.2 [.eta..sup.5 :.eta..sup.1 --C.sub.5 H.sub.4 (XH.sub.2).sub.n PR.sub.2 ] wherein M represents a molybdenum (Mo) atom or a tungsten (W) atom; X is a carbon atom, a silicon atom or a combination of carbon (C) and silicon (Si) atoms; n is any positive integer; R represents two hydrocarbon groups selected from H, an aryl group and an alkyl group, wherein both R groups can be the same or different. The metal hydride is reacted with Ph.sub.3 C.sup.+ A.sup.- either before reacting with the organic compound or in the reaction mixture.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {2003},
month = {9}
}
Works referenced in this record:
Effective Catalysts for Transfer Hydrogenation of Ketones and Imines by Propan-2-ol : Ruthenium-Hydride or Ruthenium-Dihydride Complexes
journal, March 1997
- Mizushima, Eiichiro; Yamaguchi, Motowo; Yamagishi, Takamichi
- Chemistry Letters, Vol. 26, Issue 3
Group 6 anionic μ-hydride complexes [HM2(CO)10]− (M = Cr, Mo, W): New catalysts for hydrogenation and hydrosilylation
journal, February 1991
- Fuchikami, Takamasa; Ubukata, Yumiko; Tanaka, Yasutaka
- Tetrahedron Letters, Vol. 32, Issue 9
Ruthenium(II)-Catalyzed Asymmetric Transfer Hydrogenation of Ketones Using a Formic Acid−Triethylamine Mixture
journal, January 1996
- Fujii, Akio; Hashiguchi, Shohei; Uematsu, Nobuyuki
- Journal of the American Chemical Society, Vol. 118, Issue 10
Homogeneous hydrogenation of ketones using chromium hexacarbonyl as catalyst precursor in the presence of bases
journal, April 1985
- Markó, László; Nagy-Magos, Zsuzsa
- Journal of Organometallic Chemistry, Vol. 285, Issue 1-3
Preferential hydrogenation of aldehydes and ketones.
journal, October 1995
- Ohkuma, Takeshi; Ooka, Hirohito; Ikariya, Takao
- Journal of the American Chemical Society, Vol. 117, Issue 41
Asymmetric Transfer Hydrogenation of Aromatic Ketones Catalyzed by Chiral Ruthenium(II) Complexes
journal, July 1995
- Hashiguchi, Shohei; Fujii, Akio; Takehara, Jun
- Journal of the American Chemical Society, Vol. 117, Issue 28
Homogeneous Transfer Hydrogenation of Ketones Catalyzed by Molybdenum Complexes
journal, February 1977
- Tatsumi, Takashi; Kizawa, Kazutoshi; Tominaga, Hiroo
- Chemistry Letters, Vol. 6, Issue 2
Homogeneous asymmetric hydrogenation of functionalized ketones
journal, January 1988
- Kitamura, Masato.; Ohkuma, Takeshi.; Inoue, Shinichi.
- Journal of the American Chemical Society, Vol. 110, Issue 2
Practical Enantioselective Hydrogenation of Aromatic Ketones
journal, March 1995
- Ohkuma, Takeshi; Ooka, Hirohito; Hashiguchi, Shohei
- Journal of the American Chemical Society, Vol. 117, Issue 9
Anionic group 6 hydrides and carboxylates as homogeneous catalysts for reduction of aldehydes and ketones
journal, September 1986
- Tooley, Patricia A.; Ovalles, Cesar.; Kao, S. C.
- Journal of the American Chemical Society, Vol. 108, Issue 18
Asymmetric hydrogenation of cycloalkanones catalyzed by BINAP-iridium(I)-aminophosphine systems
journal, April 1993
- Zhang, Xiaoyong; Taketomi, Takanao; Yoshizumi, Takashi
- Journal of the American Chemical Society, Vol. 115, Issue 8
Hydride Transfer by Hydrido Transition-Metal Complexes. Ionic Hydrogenation of Aldehydes and Ketones, and Structural Characterization of an Alcohol Complex
journal, September 1992
- Song, Jeong-Sup; Szalda, David J.; Bullock, R. Morris
- Angewandte Chemie International Edition in English, Vol. 31, Issue 9