The Oxidation of 4-(4-Formylphenoxy) Phthalonitrile to 4-(4-Carboxylphenoxy) Phthalonitrile at Ambient Conditions
Abstract
The substituted
phthalonitriles have been used to prepare soluble phthalocyanine species in
recent years. One of the most used phthalonitrile derivatives for the target
product is 4-nitrophthalonitrile. In this study 4-(4-formylphenoxy)
phthalonitrile was prepared as the substituted phthalonitrile derivative by the
nucleophilic substitution reaction of para-hydroxybenzaldehyde with 4-nitrophthalonitrile.
During the crystallization of the product by slow evaporation technique, it
readily self-oxidized to 4-(4-carboxylphenoxy) phthalonitrile at ambient
condition open to air. The crystal structure of the molecule was determined by
XRD technique. The molecule crystalizes at triclinic space group P-1 and the
unit cell parameters of crystal are a=6.3591 (10) Å, b=7.5464
(11) Å, c=13.819 (2) Å, α=88.434 (11)°, β=87.942 (12)°, γ=80.111
(12)° and Z=2. The crystal structure
has intermolecular O―H∙∙∙O, C―H∙∙∙N and C―H∙∙∙O hydrogen bonds. In addition to
these hydrogen bonds, C—N∙∙∙Cg and Cg∙∙∙Cg interactions are present between
molecules. In the crystal, intermolecular O―H∙∙∙O hydrogen bonds occur between
molecular units in a dimeric molecular form. Molecular structure, vibrational
frequencies and 1H and 13C NMR chemical shifts of the
target compound have been calculated by using B3LYP method with 6-311++G(d, p)
basis set, as well.
Keywords
Substituted phthalonitrile,Crystal structure,Oxidation,Theoretical calculation
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