Regioselective Ring-Emitting Esterification on Azacyclohexane Quaternary Salts: A DFT and Synthetic Study for Covalent Fixation of Electrostatic Polymer Self-Assemblies

A regioselective nucleophilic esterification upon six-membered, thus considered unstrained, azacyclohexane quaternary salts has been disclosed by DFT calculations using a model compound and subsequent experimental studies of nucleophilic substitution on N-phenyl-3,3-dimethylpiperidinium salt groups...

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Bibliographic Details
Published in:	Journal of organic chemistry 2013-04, Vol.78 (7), p.3086-3094
Main Authors:	Kimura, Akihiro, Takahashi, Shinnosuke, Kawauchi, Susumu, Yamamoto, Takuya, Tezuka, Yasuyuki
Format:	Article
Language:	eng
Subjects:	Aza Compounds - chemistry Cyclohexanes - chemistry Esters - chemical synthesis Esters - chemistry Molecular Structure Polymers - chemical synthesis Polymers - chemistry Quantum Theory Salts - chemistry Static Electricity Stereoisomerism
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Summary:	A regioselective nucleophilic esterification upon six-membered, thus considered unstrained, azacyclohexane quaternary salts has been disclosed by DFT calculations using a model compound and subsequent experimental studies of nucleophilic substitution on N-phenyl-3,3-dimethylpiperidinium salt groups at the polymer chain ends by carboxylate anions. An exclusive ring-emitting esterification was proposed theoretically and confirmed experimentally to produce a simple ester group, in contrast to less robust amino-ester linkages through an alternative ring-opening process with strained five-membered ammonium salts. This reaction was subsequently applied to a prototypical process of an electrostatic self-assembly and covalent fixation (ESA-CF) technique to produce a ring polymer having simple ester linking units.
ISSN:	0022-3263 1520-6904