DOE Patents title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: 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 » before reacting with the organic compound or in the reaction mixture.

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


Group 6 anionic μ-hydride complexes [HM2(CO)10]− (M = Cr, Mo, W): New catalysts for hydrogenation and hydrosilylation
journal, February 1991


Ruthenium(II)-Catalyzed Asymmetric Transfer Hydrogenation of Ketones Using a Formic Acid−Triethylamine Mixture
journal, January 1996


Homogeneous hydrogenation of ketones using chromium hexacarbonyl as catalyst precursor in the presence of bases
journal, April 1985


Preferential hydrogenation of aldehydes and ketones.
journal, October 1995


Asymmetric Transfer Hydrogenation of Aromatic Ketones Catalyzed by Chiral Ruthenium(II) Complexes
journal, July 1995


Homogeneous Transfer Hydrogenation of Ketones Catalyzed by Molybdenum Complexes
journal, February 1977


Homogeneous asymmetric hydrogenation of functionalized ketones
journal, January 1988


Practical Enantioselective Hydrogenation of Aromatic Ketones
journal, March 1995


Anionic group 6 hydrides and carboxylates as homogeneous catalysts for reduction of aldehydes and ketones
journal, September 1986


Asymmetric hydrogenation of cycloalkanones catalyzed by BINAP-iridium(I)-aminophosphine systems
journal, April 1993


Hydride Transfer by Hydrido Transition-Metal Complexes. Ionic Hydrogenation of Aldehydes and Ketones, and Structural Characterization of an Alcohol Complex
journal, September 1992