Sage Journals: Discover world-class research

Abstract

A theoretical study of the kinetics and mechanism of the intramolecular cycloaddition of 1,2,3-triazolo-1,4-benzoxazine was performed using DFT methods at the B3LYP level of theory with 6-311++G(d,p) basis set at 298.15 K and 310.15 K. Equilibrium molecular geometries and harmonic vibrational frequencies of the reactant, transition state and product were calculated. The solvent effect on the kinetic and thermodynamic parameters of the reaction were investigated. The calculated rate constants and activation thermodynamic parameters showed good agreement with experimental results. These calculations indicated that the reaction proceeds through a synchronous concerted mechanism.

Keywords

DFT kinetics activation energy 1,3-dipolar cycloaddition

References

Huisgen

, Grashey

, and Sauer

(1964) The chemistry of alkenes, Interscience, New York.

Pérez

, Domingo

L.R.

, Aurell

M.J.

, and Contreras

(2003) Tetrahedron, 59, 3117.

Huisgen

(1984) 1,3-Dipolar cycloadditions chemistry. Wiley, New York.

Huisgen

, Fisera

, Giera

, and Sustmann

(1995) J. Am. Chem. Soc., 117, 9671.

Scheiner

(1965) J. Org. Chem., 30, 7.

Torssel

K.B.G.

(1988) Nitrile oxides, nitrones, and nitronates in organic synthesis. VCH, New York.

Easton

C. J.

, Hughes

C.M.M.

, Savage

G. P.

, and Simpson

G.V.

(1994) Adv. Heterocycl. Chem., 60, 261.

Frisch

M.J.

(2003) Gaussian, Inc., Pittsburgh PA.

Becke

A.D.

(1988) Phys. Rev. A., 38, 3098.

10.

Lee

, Yang

, and Parr

R.G.

(1988) Phys. Rev. B., 371, 785.

11.

Petersson

G.A.

, and Al-Laham

M.A.

(1991) J. Chem. Phys., 94, 6081.

12.

Petersson

G.A.

, Bennett

, Tensfeldt

T. G.

, Al-Laham

M.A.

, Shirley

W.A.

, and Mantzaris

(1988) J. Chem. Phys., 89, 2193.

13.

Peng

, Ayala

P.Y.

, Schlegel

H.B.

, and Frisch

M.J.

(1996) J. Comp. Chem., 17, 49.

14.

Peng

, and Schlegel

H.B.

(1994) Israel J. Chem., 33, 449.

15.

Gonzalez

, and Schlegel

H.B.

(1990) J. Phys. Chem., 94, 5523.

16.

Gonzalez

, and Schlegel

H.B.

(1989) J. Chem. Phys., 90, 2154.

17.

Reed

A.E.

, Curtiss

L.A.

, and Weinhold

(1988) Chem. Rev., 88, 899.

18.

Carpenter

J.E.

, and Weinhold

(1988) J. Mol. Struct.: THEOCHEM, 169, 41.

19.

Barone

, and Cossi

(1998) J. Phys. Chem. A., 102, 1995.

20.

Glasstone

, Laidler

K.J.

, and Eyring

(1941) The theory of rate processes. McGraw-Hill, New York.

21.

Laidler

K.J.

(1969) Theories of chemical reaction rates. McGraw-Hill, New York.

22.

Pauling

(1947) J. Am. Chem. Soc., 9, 542.

23.

Garanti

, and Zecchi

(1979) J. Chem. Soc., Perkin Trans 2, 1176.

A DFT study on the effect of functional groups on the formation kinetics of 1,2,3-triazolo-1,4-benzoxazine via intramolecular 1,3-dipolar cycloaddition

Abstract

Keywords

References