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Studies of some monocyclic and bicyclic arylacetonitriles
Author(s) -
Manimekalai A.,
Balamurugan A.
Publication year - 2011
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.2734
Subject(s) - chemistry , bicyclic molecule , cyclohexane conformation , group (periodic table) , stereochemistry , chemical shift , carbon 13 nmr , high resolution , crystal structure , proton nmr , nmr spectra database , computational chemistry , crystallography , spectral line , molecule , hydrogen bond , organic chemistry , remote sensing , geology , physics , astronomy
The high‐resolution 1 H, 13 C, 1 H 1 H COSY and 1 H 13 C COSY NMR spectra have been recorded in CDCl 3 for arylacetonitriles 1–12 and analyzed. The arylacetonitriles 3–7 exist in two isomeric forms E (methyl group is anti to cyano group) and Z (the methyl group is syn to cyano group) in solution. Normal chair conformation with equatorial orientations of phenyl rings at C‐2 and C‐6 for monocyclic nitriles 1 and 2, epimeric chair structure EC (axial configuration of methyl group at C‐3) for both the E and Z isomers of arylacetonitrile derivatives (3–7) and a distorted boat form, B 3 , for the N ‐acylacetonitrile derivatives (8–10) have been proposed based on NMR data. The bicyclic nitriles 11 and 12 exist in twin chair conformations in solution. DFT calculations and chemical shifts also support these conformations. Geometry optimizations for 1–12 were carried out according to density functional theory using B3LYP/6‐31G(d,p) basis set and for 1 and 8 the theoretical geometrical parameters have been compared with those of single crystal measurements. Copyright © 2011 John Wiley & Sons, Ltd.