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Theoretical investigation of the abnormal Reimer–Tiemann reaction

✍ Scribed by R. Castillo; V. Moliner; J. Andrés; M. Oliva; V. S. Safont; S. Bohm

Publisher
John Wiley and Sons
Year
1998
Tongue
English
Weight
361 KB
Volume
11
Category
Article
ISSN
0894-3230

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✦ Synopsis

The molecular mechanism for the pyrrole ring expansion to yield 3-chloropyridine, as a model of the abnormal Reimer-Tiemann rearrangement, was characterized theoretically in vacuo by means of the HF/6-31G* computational method. The electron correlation was estimated at the MP2/6-31G* level and by calculations based on density functional theory, B3LYP/6-31G* and B3LYP/6-31G*. Solvent effects of the diethyl ether and ethanol media were analyzed by using a polarizable continuum model. The stationary points were characterized with analytical gradient techniques in the gas phase and insolvents. The topology of the potential energy surfaces calculated at the MP2/6-31G* and B3LYP/6-31G* levels shows that the molecular mechanism corresponds to an inverted energy profile along one intermediate, associated with the addition of dichlorocarbene at the b-position of the pyrrole anion, and only one transition structure related to the ring expansion associated with the breaking and forming of Ca-Cb and C-Ca bonds, respectively, and the Cl À leaving process.

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