Abstract
Rubidium phosphate can be more conveniently obtained by extracting trace Rb+ from the salt lake brine. Rb3PO4 was found to be an excellent heterogeneous catalyst for transfer hydrogenation. Rb3PO4 lost 70% of its active sites after adsorbing water, but the remaining was not affected. The reductions of aldehydes and ketones, when promoted by Rb3PO4, were allowed at room temperature. The activities of substrates at room temperature followed a descending order of 2,6-dichlorobenzaldehyde>4-bromobenzaldehyde>benzaldehyde>acetophenone>anisaldehyde>butanone. A new catalytic cycle postulating a six-membered cyclic transition state for the reductions of aldehydes and ketones was proposed. These results exploited the catalytic usage of Rb3PO4 and worth in industrial application.
Similar content being viewed by others
References
STASTNA E, CERNY I, POUZAR V, CHODOUNSKA H. Stereoselectivity of sodium borohydride reduction of saturated steroidal ketones utilizing conditions of luche reduction [J]. Steroids, 2010, 75(10): 721–725.
WU Xiao-feng, XIAO Jian-liang. Aqueous-phase asymmetric transfer hydrogenation of ketones-A greener approach to chiral alcohols [J]. Cheminform, 2007, 38(42): 2449–2466.
NOYORI R, OHKUMA T. Asymmetric catalysis by architectural and functional molecular engineering: Practical chemo-and stereoselective hydrogenation of ketones [J]. Angewandte Chemie International Edition, 2001, 40(1): 40–73.
LOGES B, BODDIEN A, JUNGE H, BELLER M. Controlled generation of hydrogen from formic acid amine adducts at room temperature and application in H2/O2 fuel cells [J]. Angewandte Chemie International Edition, 2008, 47(21): 3962–3965.
IVANOV V A, BACHELIER J, AUDRY F, LAVALLEY J C. Study of the Meerwein—Pondorff—Verley reaction between ethanol and acetone on various metal oxides [J]. Journal of Molecular Catalysis, 1994, 91(1): 45–59.
CHA J S. Reactions for the reduction of organic functional groups using aluminum, boron, and other metal reagents: A review [J]. Organic Process Research & Development Journal, 2006, 10(5): 1032–1053.
VERMA P K, SHARMA U, KUMAR N, BALA M, KUMAR V, SINGH B. Nickel phthalocyanine assisted highly efficient and selective carbonyl reduction in polyethylene glycol-400 [J]. Catalysis Letters, 2012, 142(7): 907–913.
BLUM J, PRI-BAR I. Selective transfer hydrogenation of various unsaturated functions by polymethylhydrosiloxane in the presence of a recyclable rhodium catalyst [J]. Journal of Molecular Catalysis 1986, 27(2/3): 359–367.
MOECZNIKOWSKI J R, CRABTREE R H. Transfer hydrogenation reduction of ketones, aldehydes and imines using chelated iridium(III) N-heterocyclic bis-carbene complexes [J]. Polyhedron, 2004, 23(17): 2857–2872.
JIMENEZ S, LOPEZ J A, CIRIANO M A, TEJEL C, MARTINEZ A, SANCHEZ-DELGADO R A. Selective hydrogenation of cinnamaldehyde and other a,ß-unsaturated substrates catalyzed by rhodium and ruthenium complexes [J]. Organometallics, 2009, 28(11): 3193–3202.
HE Lin, NI Ji, WANG Lu-cun, YU Feng-jiao, CAO Yong, HE He-yong, FAN Kang-nian. Aqueous room-temperature goldcatalyzed chemoselective transfer hydrogenation of aldehydes [J]. Chemistry-A European Journal, 2009, 15(44): 11833–11836.
BACCHI A, BALORDI M, CAMMI R, ELVIRI L, PELIZZI C, PICHHIONO F, VERDOLINO V, GOUBITZ K, PE-SCHAR R, PELAGATTI P. Mechanistic insights into acetophenone transfer hydrogenation catalyzed by half-sandwich ruthenium(II) complexes containing 2-(Diphenylphosphanyl)aniline–A combined experimental and theoretical study [J]. European Journal of Inorganic Chemistry, 2008, 2008(28): 4462–4473.
BACKVALL J E. Transition metal hydrides as active intermediates in hydrogen transfer reactions [J]. Journal of Organometallic Chemistry, 2002, 652(1/2): 105–111.
POLSHETTIWAR V, VARMA R S. Revisiting the Meerwein–Ponndorf–Verley reduction: A sustainable protocol for transfer hydrogenation of aldehydes and ketones [J]. Green Chemistry, 2009, 11(9): 1313–1316.
OUALI A, MAJORAL J P, CAMINADE A M, TAILLEFER M. NaOH-promoted hydrogen transfer: Does NaOH or traces of transition metals catalyze the reaction? [J]. ChemCatChem, 2009, 1(4): 504–509.
LIU Shi-ming, LIU He-hui, HUANG Yun-jing, YANG We-jun. Solvent extraction of rubidium and cesium from salt lake brine with t-BAMBP–kerosene solution [J]. Transactions of Nonferrous Metals Society of China, 2015, 25(1): 329–334.
VORONIN V I, BERGER I F, PROSKURNINA N V, SHEPTYAKOV D V, GOSHCHITSKII B N, BURMAKIND E I, STROEV S S, SHEKHTMAN G S. Crystal structure of the low-temperature forms of cesium and rubidium orthophosphates [J]. Inorganic Materials, 2008, 44(6): 646–652.
ADAMS D L. New phenomena in the adsorption of alkali metals on Al surfaces [J]. Applied Physics A: Materials Science & Processing, 1996, 62(2): 123–142.
RADHAKRISHAN R, DO D M, JAENICKE S, SASSON Y, CHUAH G K. Potassium phosphate as a solid base catalyst for the catalytic transfer hydrogenation of aldehydes and ketones [J]. ACS Catalysis, 2011, 1(11): 1631–1636.
VORONIN V I, PONOSOV Y S, BERGER I F, PROSKURNINA N V, ZUBKOV V G, TYUTYUNNIK A P, BUSHMELEVA S N, BALAGUROV A M, SHEPTYAKOV D V, BURMAKIN E I,. SHEKHTMAN G S, VOVKOTRUB E G. Crystal structure of the low-temperature form of K3PO4 [J]. Inorganic Materials, 2006, 42(8): 908–913.
Author information
Authors and Affiliations
Corresponding author
Additional information
Foundation item: Project(21576074) supported by the National Natural Science Foundation of China
Rights and permissions
About this article
Cite this article
Huang, Yj., Yang, Wj., Qin, Mg. et al. Mild and highly efficient transfer hydrogenation of aldehyde and ketone catalyzed by rubidium phosphate. J. Cent. South Univ. 23, 1603–1610 (2016). https://doi.org/10.1007/s11771-016-3214-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11771-016-3214-x