The Change of Aromaticity along a Diels-Alder Reaction Path

• Published in: Organic Letters, vol. 5, num. 7, p. 1127-1130
• Publication date: 2003

Quinodimethanes are highly reactive toward dienophiles since Diels-Alder cycloaddn. results in an arom. product. D. functional-based 13C, 1H NMR, NICS, and MO-NICS calcns. indicate that the increase of arom. character of the developing benzenoid ring along the reaction path is esp. pronounced after the transition state is reached, even though the no. of pi orbitals decreases. The forming aliph. ring exhibits large ring current effects during the reaction. [on SciFinder (R)]

Keywords: Diels-Alder reaction enthalpy (assocd. with aromatization; the change of aromaticity along a Diels-Alder reaction path for quinodimethane dienophiles); NMR (chem. shift ; 13C ; 1H ; and NICS; the change of aromaticity along a Diels-Alder reaction path for quinodimethane dienophiles); Potential barrier; Potential energy surface; Transition state structure (for Diels-Alder reaction; the change of aromaticity along a Diels-Alder reaction path for quinodimethane dienophiles); Antiaromaticity (of spectator ring in reactant; the change of aromaticity along a Diels-Alder reaction path for quinodimethane dienophiles); Aromaticity; Diels-Alder reaction; Dienophiles (the change of aromaticity along a Diels-Alder reaction path for quinodimethane dienophiles); Quinonoid compounds Role: CPS (Chemical process) ; PEP (Physical ; engineering or chemical process) ; PRP (Properties) ; RCT (Reactant) ; PROC (Process) ; RACT (Reactant or reagent) (the change of aromaticity along a Diels-Alder reaction path for quinodimethane dienophiles); Molecular orbital (pi ; pi-aromaticity; the change of aromaticity along a Diels-Alder reaction path for quinodimethane dienophiles) ; Diels Alder quinodimethane aromaticity

Note:

CAN 138:337582

22-5

Physical Organic Chemistry

Department of Physical Chemistry,University of Geneva,Geneva,Switz.

Journal

1523-7060

written in English.

74-85-1 (Ethylene); 32796-95-5 (o-Quinodimethane) Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), RCT (Reactant), PROC (Process), RACT (Reactant or reagent) (the change of aromaticity along a Diels-Alder reaction path for quinodimethane dienophiles); 119-64-2 (1,2,3,4-Tetrahydronaphthalene) Role: FMU (Formation, unclassified), PRP (Properties), FORM (Formation, nonpreparative) (the change of aromaticity along a Diels-Alder reaction path for quinodimethane dienophiles)

Reference

• LCMD-ARTICLE-2003-003

Record created on 2007-10-22, modified on 2017-05-12