Recent advances in acid- and base-catalyzed organic synthesis in high-temperature liquid water

Abstract High-temperature (200– 350 ∘ C) liquid water (HTW) is a promising reaction medium for conducting acid- and base-catalyzed organic synthesis reactions in an environmentally responsible manner. This article provides a summary of recent advances made concerning acid- and base-catalyzed organic synthesis in HTW. One advance is demonstrating that rates of acid-catalyzed reactions conducted in HTW can be accelerated while maintaining the solvent benignity by using CO 2 as an additive. A second advance is showing that additional commercially significant chemical products can be synthesized in HTW without catalyst. A third advance is demonstrating that product selectivity can be controlled by process variables such as temperature, water density, and heat-up time. A fourth advance is the emergence of mechanistic insight regarding acid- and base-catalyzed reactions in HTW. For example, we discuss the possibility that protons or hydroxide ions resulting from the dissociation of water may not be responsible for the occurrence of some classically acid- or base-catalyzed reactions in HTW without catalyst.

[1]  A. Kruse,et al.  Acidity and basicity of metal oxide catalysts for formaldehyde reaction in supercritical water at 673 K , 2003 .

[2]  H. Vogel,et al.  The Dehydration of 1,4‐Butanediol to Tetrahydrofuran in Supercritical Water , 2001 .

[3]  C. Eckert,et al.  The catalytic opportunities of near-critical water: a benign medium for conventionally acid and base catalyzed condensations for organic synthesis , 2003 .

[4]  J. F. Connolly,et al.  Solubility of Hydrocarbons in Water Near the Critical Solution Temperatures. , 1966 .

[5]  M. Goto,et al.  Synthesis of 2-Amino-ε-caprolactam by Cyclodehydration of Lysine in Subcritical Water , 2004 .

[6]  R. Smith,et al.  Regioselectivity of phenol alkylation in supercritical water , 2002 .

[7]  Charles A. Eckert,et al.  Phase Equilibria for Binary Aqueous Systems from a Near-Critical Water Reaction Apparatus , 1998 .

[8]  P. Savage,et al.  Kinetics and Mechanism of Cyclohexanol Dehydration in High-Temperature Water , 2001 .

[9]  P. Savage,et al.  Kinetics of crossed aldol condensations in high-temperature water , 2004 .

[10]  W. L. Marshall,et al.  Ion Product of Water Substance, 0-1000 C, 1-10,000 Bars. New International Formulation and Its Background, , 1981 .

[11]  P. Savage,et al.  Kinetics and mechanism of p-isopropenylphenol synthesis via hydrothermal cleavage of bisphenol A. , 2004, The Journal of organic chemistry.

[12]  M. Arai,et al.  Innovations in chemical reaction processes using supercritical water: an environmental application to the production of ε-caprolactam , 2003 .

[13]  Phillip E. Savage,et al.  Organic Chemical Reactions in Supercritical Water. , 1999, Chemical reviews.

[14]  K. Arai,et al.  Ortho-Selective Alkylation of Phenol with 2-Propanol without Catalyst in Supercritical Water , 2002 .

[15]  P. Savage,et al.  Synthesis of p-isopropenylphenol in high-temperature water , 2004 .

[16]  M. Nagaoka,et al.  Ab initio study of noncatalytic Beckmann rearrangement and hydrolysis of cyclohexanone–oxime in subcritical and supercritical water using the polarizable continuum model , 2003 .

[17]  A. L. Powell,et al.  Mechanism of the Cannizzaro reaction , 1979 .

[18]  P. Anastas,et al.  Green Chemistry , 2018, Environmental Science.

[19]  M. Arai,et al.  Innovation in a chemical reaction process using a supercritical water microreaction system: environmentally friendly production of epsilon-caprolactam. , 2002, Chemical communications.

[20]  P. Savage,et al.  Acid-Catalyzed Reactions in Carbon Dioxide-Enriched High-Temperature Liquid Water , 2003 .

[21]  C. Eckert,et al.  Acylation of activated aromatics without added acid catalyst , 2000 .

[22]  Jun-ichi Yoshida,et al.  Evidence for a hydroxide ion catalyzed pathway in ester hydrolysis in supercritical water , 2002 .

[23]  M. Antal,et al.  Mechanism and temperature-dependent kinetics of the dehydration of tert-butyl alcohol in hot compressed liquid water , 1997 .

[24]  Akio Mitsutani.  Future possibilities of recently commercialized acid/base-catalyzed chemical processes , 2002 .

[25]  J. Tester,et al.  Experimental measurement of the rate of methyl tert-butyl ether hydrolysis in sub- and supercritical water , 2001 .

[26]  Reaction Kinetics of 2-Propanol Dehydration in Supercritical Water , 2002 .

[27]  C. Eckert,et al.  Tuning alkylation reactions with temperature in near‐critical water , 1998 .

[28]  J. Tester,et al.  Multiscale reaction pathway analysis of methyl tert-butyl ether hydrolysis under hydrothermal conditions , 2002 .