Kinetics and Mechanism of the Aminolysis of Aryl N-Allyl Thiocarbamates in Acetonitrile

The aminolysis reactions of phenyl N-benzyl thiocarbamate with benzylamines in acetonitrile at are investigated. The reactions are first order in both the amine and the substrate. Under amine excess, pseudo-first coefficient () are obtained, plot of vs free amine concentration are linear. The signs of ( and with respect to the sustituent in the substrate and large value indicate that the reactions proceed concerted mechanism. The normal kinetic isotope effects ( = 1.3 ~ 1.5) involving deuterated benzylamine nucleophiles suggest a hydrogen-bonded, four-centered-type transition state. The activation parameters, and , are consistent with this transition state structure.

[1]  H. Oh.  Nucleophilic Substitution Reactions of Aryl Dithiocyclohexanecarboxylates with Anilines in Acetonitrile , 2010 .

[2]  S. Hong,et al.  Kinetics and Mechanism of the Aminolysis of Thiophenyl Cyclohexanecarboxylates , 2009 .

[3]  J. Coetzee.  Ionic Reactions in Acetonitrile , 2007 .

[4]  K. S. Jeong,et al.  Kinetics and Mechanism of the Aminolysis of Aryl N-Cyclohexyl Thiocarbamates in Acetonitrile , 2007 .

[5]  Jie-Eun Park,et al.  Kinetics and mechanism of the aminolysis of aryl N-ethyl thiocarbamates in acetonitrile. , 2004, The Journal of organic chemistry.

[6]  Ikchoon Lee and Dae Dong Sung.  Theoretical and Physical Aspects of Stepwise Mechanisms in Acyl-Transfer Reactions , 2004 .

[7]  Jie-Eun Park,et al.  Nucleophilic Substitution Reactions of O-Aryl N-phenyl Thioncarbamates with Benzylamines in Acetonitrile , 2012 .

[8]  H. Lee,et al.  Nucleophilic substitution reactions of alpha-chloroacetanilides with benzylamines in dimethyl sulfoxide. , 2003, Organic & biomolecular chemistry.

[9]  Ikchoon Lee.  Natural bond orbital analysis of the intrinsic reaction barriers in nucleophilic displacements , 2003 .

[10]  E. Castro,et al.  Kinetics and mechanism of the aminolysis of methyl 4-nitrophenyl, methyl 2,4-dinitrophenyl, and phenyl 2,4-dinitrophenyl carbonates. , 2002, The Journal of organic chemistry.

[11]  H. Lee,et al.  Nucleophilic substitution reactions of aryl dithioacetates with pyridines in acetonitrile. , 2002, The Journal of organic chemistry.

[12]  E. Castro,et al.  Kinetic study of the phenolysis of bis(4-nitrophenyl) carbonate, bis(4-nitrophenyl) thionocarbonate, and methyl 4-nitrophenyl thionocarbonate. , 2001, The Journal of organic chemistry.

[13]  E. Castro,et al.  Concerted mechanisms of the reactions of 2,4,6-trinitrophenyl methyl carbonate and 2,4,6-trinitrophenyl acetate with secondary alicyclic amines. , 2001, The Journal of organic chemistry.

[14]  E. Castro,et al.  Concerted mechanisms of the reactions of methyl aryl carbonates with substituted phenoxide ions. , 2001, The Journal of organic chemistry.

[15]  E. Castro,et al.  Structure–reactivity correlations in the aminolysis of aryl chloroformates , 2001 .

[16]  Chang Kon Kim,et al.  Acyl-Transfer Mechanisms Involving Various Acyl Functional Groups: >XY with X = C, S, P and Y = O, S , 2000 .

[17]  H. Oh,et al.  Kinetics and Mechanism of the Aminolysis of O-Methyl S-Aryl Thiocarbonates in Acetonitrile , 2011 .

[18]  E. Castro.  Kinetics and Mechanisms of Reactions of Thiol, Thiono, and Dithio Analogues of Carboxylic Esters with Nucleophiles. , 1999, Chemical reviews.

[19]  E. Castro,et al.  Kinetics and Mechanism of the Reactions of Quinuclidines with Ethyl S-Aryl Thiolcarbonates. , 1999, The Journal of organic chemistry.

[20]  Chang Kon Kim,et al.  THEORETICAL STUDIES OF SOLVENT EFFECT ON THE BASICITY OF SUBSTITUTED PYRIDINES , 1999 .

[21]  E. Castro,et al.  Kinetics and Mechanism of the Aminolysis of Phenyl and 4-Nitrophenyl Chloroformates in Aqueous Solution. , 1999, The Journal of organic chemistry.

[22]  P. Millán,et al.  Kinetics and Mechanism of the Reactions of Anilines with Ethyl S-Aryl Thiocarbonates. , 1999, The Journal of organic chemistry.

[23]  H. Lee,et al.  Cross-Interaction Constants. A Mechanistic Tool , 1999 .

[24]  E. Castro,et al.  Concerted Mechanisms of the Reactions of Phenyl and 4-Nitrophenyl Chlorothionoformates with Substituted Phenoxide Ions. , 1998, The Journal of organic chemistry.

[25]  Ji-won Lee,et al.  Kinetics and mechanism of the aminolysis of ethyl aryl carbonates in acetonitrile , 1998 .

[26]  Ikchoon Lee,et al.  KINETICS AND MECHANISM OF THE AMINOLYSIS OF O-ETHYL S-ARYL DITHIOCARBONATES IN ACETONITRILE , 1998 .

[27]  H. Lee,et al.  Kinetics and mechanism of the aminolysis of p‐nitrophenyl N‐phenylcarbamates , 1997 .

[28]  So Young Woo,et al.  Kinetics and Mechanism of the Aminolysis of Phenyl Dithioacetates in Acetonitrile , 1997 .

[29]  Chang Kon Kim,et al.  Theoretical Studies of Structural Effects on the Mechanism of Acyl-Transfer Reactions1 , 1997 .

[30]  E. Castro,et al.  Kinetics and Mechanism of the Pyridinolysis of 2,4-Dinitrophenyl and 2,4,6-Trinitrophenyl O-Ethyl Dithiocarbonates. , 1997, The Journal of organic chemistry.

[31]  Ikchoon Lee.  SECONDARY KINETIC ISOTOPE EFFECTS INVOLVING DEUTERATED NUCLEOPHILES , 1995 .

[32]  E. Castro,et al.  Concerted mechanism of the aminolysis of 2,4,6‐trinitrophenyl o‐ethyl dithiocarbonate in aqueous ethanol , 1994 .

[33]  W. Jencks,et al.  Structure-reactivity correlations for reactions of substituted phenolate anions with acetate and formate esters , 1993 .

[34]  E. Castro,et al.  Kinetics and mechanism of the aminolysis of 2,4-dinitrophenyl and 2,4,6-trinitrophenyl O-ethyl dithiocarbonates , 1993 .

[35]  Ikchoon Lee.  Cross-interaction constants and transition-state structure in solution , 1992 .

[36]  Corwin Hansch,et al.  A survey of Hammett substituent constants and resonance and field parameters , 1991 .

[37]  E. Castro,et al.  Kinetics and mechanism of the reactions of 2,4-dinitrophenyl acetate with secondary alicyclic amines. Different nucleofugalities of alicyclic amines and pyridines from a tetrahedral intermediate , 1990 .

[38]  Ikchoon Lee.  Characterization of transition states for reactions in solution by cross-interaction constants , 1990 .

[39]  A. Luthra,et al.  Concerted acetyl group transfer between substituted phenolate ion nucleophiles: variation of transition-state structure as a function of substituent , 1989 .

[40]  L. Kiriazis,et al.  Reactions of N-heteroaromatic bases with nitrous acid. Part 9. Kinetics of the nitrosation of 1-methyl-3- and 1-methyl-4-methylaminopyridinium perchlorate in aqueous perchloric acid and 13C nuclear magnetic resonance spectra of 1-methyl-4-alkylamino-substituted pyridinium ions , 1989 .

[41]  Erwin Buncel,et al.  The reactivity selectivity principle: Should it ever be used? , 1987 .

[42]  H. Hassaneen,et al.  Kinetics and mechanism of aminolysis of carbamates , 1986 .

[43]  E. Castro,et al.  Nonlinear Broensted-type plot in the pyridinolysis of 2,4-dinitrophenyl benzoate in aqueous ethanol , 1985 .

[44]  W. Jencks,et al.  Reactions of pyridines and primary amines with N-phosphorylated pyridines , 1984 .

[45]  S. Yamabe,et al.  MOLECULAR ORBITAL STUDY ON THE GAS-PHASE NUCLEOPHILIC DISPLACEMENT ON ACYL CHLORIDES , 1983 .

[46]  E. Castro,et al.  Curved Broensted plot in pyridinolysis of 2,4-dinitrophenyl methyl carbonate. Comparison of leaving group abilities between pyridines and phenolates , 1977 .

[47]  W. Jencks,et al.  Ester aminolysis. Partitioning of the tetrahedral addition intermediate, T.+-., and the relative leaving ability of nitrogen and oxygen , 1977 .

[48]  W. Jencks,et al.  Ester aminolysis. Structure-reactivity relationships and the rate-determining step in the aminolysis of substituted diphenyl carbonates , 1977 .

[49]  A. Pross.  The Reactivity—Selectivity Principle and its Mechanistic Applications , 1977 .

[50]  M. Dewar,et al.  The PMO Theory of Organic Chemistry , 1975 .

[51]  W. Jencks,et al.  The mechanism of the aminolysis of acetate esters. , 1974, Journal of the American Chemical Society.

[52]  E. A. Guggenheim.  XLVI. On the determination of the velocity constant of a unimolecular reaction , 1926 .