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Solid-State Reaction of Poly(1,6-di-N-carbazolyl-2,4-hexadiyne) with Electrophiles

Yesinowski, James P. and Eckert, Hellmut and Sandman, Eckert and Velazquez, Christopher S. (1987) Solid-State Reaction of Poly(1,6-di-N-carbazolyl-2,4-hexadiyne) with Electrophiles. In: Crystallographically Ordered Polymers. ACS Symposium Series. No.337. American Chemical Society , Washington, DC, pp. 230-252. ISBN 9780841210233. https://resolver.caltech.edu/CaltechAUTHORS:20180405-071624085

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Abstract

^(13)C cross-polarization/magic angle spinning (CP-MAS) NMR at 50.36 MHz reveals that the reaction of the crystalline polymer poly-N-dicarbazolyl-2,4-hexadiyne (poly-DCH) with the electrophilic reagents liquid bromine, gaseous chlorine, and nitric acid fumes results in the formation of covalent bonds in the polymer. Spectra have been obtained both of the products formed as well as of model compounds, and factors influencing the quantitative interpretation of peak intensities have been taken into consideration. The observed disappearance of peaks from carbon atoms either bonded to or adjacent to bromine atoms is due to a dipolar interaction not averaged to zero by magic-angle spinning. The NMR results show that the initial anisotropic reaction is a selective attack of the bromine at the 3,6 positions of the aromatic rings of the carbazole moiety, resulting in a polymer with four Br/repeat unit. At higher bromination levels electrophilic addition to the multiple bonds in the backbone occurs. Other evidence suggests that the triple bond may react preferentially, resulting in formation of a mixed polyacetylene for products of composition poly-DCH(Br_(6.0)). The reaction of poly-DCH with nitric acid fumes appears to result in substitution at the 3,6 positions of the carbazole ring. In contrast, exposure of poly-DCH to chlorine gas most likely effects both electrophilic substitution and addition in the carbazole sidechains.


Item Type:Book Section
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/bk-1987-0337.ch018DOIArticle
https://pubs.acs.org/doi/abs/10.1021/bk-1987-0337.ch018PublisherArticle
Additional Information:© 1987 American Chemical Society. Received August 21, 1986. Published in print 26 March 1987. The NMR data were obtained at the Southern California Regional NMR Facility, supported by NSF grant CHE84-40137.
Funders:
Funding AgencyGrant Number
NSFCHE84-40137
Series Name:ACS Symposium Series
Issue or Number:337
Record Number:CaltechAUTHORS:20180405-071624085
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180405-071624085
Official Citation:Solid-State Reaction of Poly(1,6-di-N-carbazolyl-2,4-hexadiyne) with Electrophiles James P. Yesinowski, Hellmut Eckert, Eckert Sandman, and Christopher S. Velazquez Crystallographically Ordered Polymers. March 26, 1987 , 230-252 DOI:10.1021/bk-1987-0337.ch018
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:85626
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:05 Apr 2018 21:05
Last Modified:03 Oct 2019 19:33

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