Simple and convenient synthesis of esters from carboxylic acids and alkyl halides using tetrabutylammonium fluoride.

A simple and convenient method has been developed for the synthesis of esters from the corresponding carboxylic acids and alkyl halides by using a stoichiometric amount of tetrabutylammonium fluoride (Bu₄NF) as the base. The reaction of carboxylic acids and a Bu₄NF/THF solution in DMF or THF as the solvent generates carboxylate ions in situ. The carboxylate ions thus generated and accumulated are highly reactive. They are then allowed to react with alkyl halides as the electrophiles, and afford the corresponding esters in moderate to good yields. The reaction without Bu₄NF does not afford any product; therefore, Bu₄NF seems to play an important role as the base in these reactions. A bulky countercation such as the tetrabutylammonium cation seems to increase the reactivity of the carboxylate ions in the solution phase.

[1]  Jason R. Schmink,et al.  Pd-catalyzed aldehyde to ester conversion: a hydrogen transfer approach. , 2013, Organic letters.

[2]  Jing Wang,et al.  Palladium-catalyzed aerobic oxidative direct esterification of alcohols. , 2011, Angewandte Chemie.

[3]  K. Srinivasan,et al.  A Rapid and Facile Esterification of Na‐Carboxylates with Alkyl Halides Promoted by the Synergy of the Combined Use of DMSO and an Ionic Liquid under Ambient Conditions. , 2011 .

[4]  P. Dussault,et al.  Fragmentation of chloroperoxides: hypochlorite-mediated dehydration of hydroperoxyacetals to esters. , 2010, Tetrahedron letters.

[5]  T. Shono,et al.  Electroorganic Chemistry. Part 130. A Novel Trifluoromethylation of Aldehydes and Ketones Promoted by an Electrogenerated Base. , 2010 .

[6]  K. Doda,et al.  Esterification of Carboxylic Acids Catalyzed by in situ Generated Tetraalkylammonium Fluorides. , 2010 .

[7]  I. Özdemir,et al.  Ionic liquids as solvent for efficient esterification of carboxylic acids with alkyl halides , 2010, Turkish journal of chemistry.

[8]  A. Lei,et al.  Palladium‐Catalyzed Oxidative Carbonylation of Alkyl and Aryl Indium Reagents with CO under Mild Conditions. , 2008 .

[9]  L. Brinchi,et al.  An Effective Chemoselective Esterification of Hydroxybenzoic Acids in Ionic Liquid Promoted by KF. , 2006 .

[10]  A. Robertson,et al.  A mild esterification process in phosphonium salt ionic liquid , 2005 .

[11]  L. Brinchi,et al.  Efficient Esterification of Carboxylic Acids with Alkyl Halides Catalyzed by Fluoride Ions in Ionic Liquids. , 2003 .

[12]  Atta-ur-rahman,et al.  An Alternative Method for the Synthesis of γ-Lactones by Using Cesium Fluoride-Celite/Acetonitrile Combination , 2003 .

[13]  Atta-ur-rahman,et al.  An expedient esterification of aromatic carboxylic acids using sodium bromate and sodium hydrogen sulfite , 2003 .

[14]  B. Borhan,et al.  Facile oxidation of aldehydes to acids and esters with Oxone. , 2003, Organic letters.

[15]  L. Brinchi,et al.  Ionic liquids as reaction media for esterification of carboxylate sodium salts with alkyl halides , 2003 .

[16]  Z. Judeh,et al.  A facile and efficient nucleophilic displacement reaction at room temperature in ionic liquids , 2002 .

[17]  K. Maruoka,et al.  Facile Conversion of Trialkylsilyl Esters to Alkyl Esters Mediated by Tetrabutylammonium Fluoride Trihydrate. , 2001 .

[18]  K. Maruoka,et al.  Facile Conversion of Trialkylsilyl Esters to Alkyl Esters Mediated by Tetrabutylammonium Fluoride Trihydrate , 2001 .

[19]  Jong Chan Lee,et al.  An Improved Method for Preparation of Carboxylic Esters Using CsF-Celite/Alkyl Halide/Ch3Cn Combination , 1998 .

[20]  Jung Ill Lee,et al.  EFFICIENT IN SITU ESTERIFICATION OF CARBOXYLIC ACIDS USING CESIUM CARBONATE , 1996 .

[21]  Takuma Sato,et al.  CsF‐Promoted Esterification of Carboxylic Acids. A Practical Alternative to the Diazomethane Method and Direct Conversion of Organotin Carboxylates. , 1992 .

[22]  Tsuneo Sato,et al.  Cesium fluoride-promoted esterification of carboxylic acids. A practical alternative to the diazomethane method and direct conversion of organotin carboxylates , 1992 .

[23]  T. Shono,et al.  Electroorganic Chemistry. Part 103. Selective C-Alkylation of β-Diketones. , 1988 .

[24]  T. Shono,et al.  Electroreductive N-alkylation of amides, carbamates, and N-heterocycles. , 1986 .

[25]  H. Uyama,et al.  A novel base useful for synthesis of esters and macrolides , 1986 .

[26]  T. Shono,et al.  A novel electrogenerated base. Alkylation of methyl arylacetates at the .alpha.-methylene group , 1984 .

[27]  T. Shono,et al.  ELECTROORGANIC CHEMISTRY. 75. A NEW ELECTROGENERATED BASE. CONDENSATION OF CHLOROFORM WITH ALIPHATIC ALDEHYDES , 1984 .

[28]  E. Mohacsi.  A Convenient Preparation of Methyl Esters from Carboxylic Acids , 1982 .

[29]  J. Clark,et al.  HYDROGEN BONDING IN ORGANIC SYNTHESIS. PART 9. THE SULFENYLATION OF FLUORIDE-ACTIVATED β-DICARBONYLS , 1978 .

[30]  J. Clark,et al.  REACTIONS OF CARBOXYLIC ACIDS WITH DICHLORO- AND DIBROMO-ALKANES IN THE PRESENCE OF FLUORIDE IONS- EFFECT OF VERY STRONG HYDROGEN BONDING , 1977 .

[31]  J. Clark,et al.  HYDROGEN BONDING IN ORGANIC SYNTHESIS. V. POTASSIUM FLUORIDE IN CARBOXYLIC ACIDS AS AN ALTERNATIVE TO CROWN ETHER WITH ACID SALTS IN THE PREPARATION OF PHENACYL ESTERS , 1977 .

[32]  J. Clark,et al.  HYDROGEN BONDING IN ORGANIC SYNTHESIS, ENHANCED REACTIVITY OF AROMATIC COMPOUNDS CAPABLE OF HYDROGEN BONDING TO FLUORIDE , 1976 .

[33]  T. Shono,et al.  Electroorganic chemistry. 130. A novel trifluoromethylation of aldehydes and ketones promoted by an electrogenerated base , 1991 .

[34]  H. Uyama,et al.  Formation of a reasonably stabilized trichloromethyl anion by the reaction of chloroform with electrogenerated base, and its 1,4-addition to α,β-unsaturated carbonyl compounds☆ , 1990 .

[35]  R. Larock.  Comprehensive Organic Transformations , 1989 .

[36]  E. Haslam.  Recent developments in methods for the esterification and protection of the carboxyl group , 1980 .

[37]  J. Clark,et al.  Hydrogen bonding in organic synthesis. 3. Hydrogen bond assisted reactions of cyclic organic hydrogen bond electron acceptors with halogenoalkanes in the presence of potassium fluoride , 1977 .

[38]  J. Clark,et al.  Reactions of carboxylic acids with dichloro- and dibromo-alkanes in the presence of fluoride ions: effects of very strong hydrogen bonding , 1977 .

[39]  J. Clark,et al.  Hydrogen bonding in organic synthesis V: potassium fluoride in carboxylic acids as an alternative to crown ether with acid salts in the preparation of phenacyl esters , 1977 .