A Dft Study of Solvent Effects on the Cycloaddition of Norbornadiene and 3,4

Abstract

A theoretical study of the kinetics and mechanism of the second-order inter-molecular cycloaddition of norbornadiene and 3,4-dihydroisoquinoline-N-oxide (nitrone) at 398.15 K was performed using the DFT method at the B3LYP level of theory with the 6–311++G(d,p) basis set. Equilibrium molecular geometries and harmonic vibrational frequencies of the reactants, transition state and product were calculated. The effect of solvents on the kinetic and thermodynamic parameters of the reaction were investigated.

The calculated rate constants and activation parameters showed very good agreement with experimental results, especially for ethanol as solvent. These calculations indicated that the reaction proceeds through a synchronous concerted mechanism.

Keywords

DFT kinetics activation energy 1,3–dipolar cycloaddition norbordiene 3,4–dihydroisoquinoline-N-oxide

References

Haque

M.S.

(1984) J. Chem. Educ., 61(6), 490.

Klicic

J.J.

, and Friesner

R.A.

(1999) J. Phys. Chem. A, 103, 1276.

Slater

A.F.G.

, Nobel

, Stefan

, Maellaro

, Bustamante

, Kimland

, and Orrenius

(1995) Biochem. J, 306, 771.

Chung

C.W.Y.

, and Toy

P.H.

(2004) Tetrahedron: Asymmetry, 15, 387.

Rosen

G.M.

, Tsai

, Barth

E.D.

, Dorey

, Casara

, Spedding

, and Halpern

H.J.

(2000) J. Org. Chem., 65, 4460.

Padwa

(ed.), (1984) 1,3-Dipolarcycloaddition Chemistry, Wiley Interscience, New York.

Gholami

M.R.

, and Yangheh

A.H.

(2001) Int. J. Chem. Kinet., 33, 118.

Elender

, Riebel

, Weber

, and Sauer

(2000) Tetrahedron, 56, 4261.

Boyle

L.W.

, Peagram

M.J.

, and Whitham

G.H.

(1971) J. Chem. Soc. (B), 1728.

10.

Frisch

M.J.

, Trucks

G.W.

, Schlegel

H.B.

(2003) Gaussian, Inc., Wallingford CT.

11.

Becke

A.D.

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

12.

Lee

, Yang

, and Parr

R.G.

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

13.

Delchev

V.B.

, and Nenkova

M.V.

(2008) Acta Chim. Slov., 55, 132.

14.

Peng

, Ayala

P.Y.

, Schlegel

H.B.

, and Frisch

M.J.

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

15.

Peng

, and Schlegel

H.B.

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

16.

Gonzalez

, and Schlegel

H.B.

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

17.

Gonzalez

, and Schlegel

H.B.

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

18.

Reed

A.E.

, Curtiss

L.A.

, and Weinhold

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

19.

Carpenter

J.E.

, and Weinhold

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

20.

Barone

, and Cossi

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

21.

Glasstone

, Laidler

K.J.

, and Eyring

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

22.

Laidler

K.J.

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

23.

Pauling

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

A Dft Study of Solvent Effects on the Cycloaddition of Norbornadiene and 3,4–Dihydroisoquinoline-N-Oxide

Abstract

Keywords

References