Mechanism of polymerization reaction of 4-[(n-butylsulfinyl)methyl]-4′-(chloromethyl)benzene

Sang Yong Pyun; Whan Gi Kim; Jin Hyun Jeong; Bong Rae Cho

doi:10.5012/bkcs.2008.29.12.2453

Mechanism of polymerization reaction of 4-[(n-butylsulfinyl)methyl]-4′-(chloromethyl)benzene

Sang Yong Pyun, Whan Gi Kim, Jin Hyun Jeong, Bong Rae Cho

Research output: Contribution to journal › Article › peer-review

2 Citations (Scopus)

Abstract

The polymerization reaction of 4-[(n-butylsulfinyl)methyl]-4′-(chloromethyl)benzene (1a) with t-BuONa in CH₂Cl₂/monomethylformamide (MMF) (4/6) was studied kinetically. The reaction proceeds in two steps; the formation of a p-quinodimethane intermediate (M) followed by the polymerization of M. Results of kinetic studies and H-D exchange experiments reveal that the 1,6-elimination proceeds by the (E1cb)_irr mechanism. The rate of the disappearance of M was increased by the carbanion and S₂O₈^2-, inhibited by TEMPO and unaltered by the addition of HCl. From these results, a free radical polymerization mechanism is proposed.

Original language	English
Pages (from-to)	2453-2458
Number of pages	6
Journal	Bulletin of the Korean Chemical Society
Volume	29
Issue number	12
DOIs	https://doi.org/10.5012/bkcs.2008.29.12.2453
Publication status	Published - 2008 Dec

Keywords

Elimination
Intermediate
Polymerization

ASJC Scopus subject areas

General Chemistry

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10.5012/bkcs.2008.29.12.2453

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title = "Mechanism of polymerization reaction of 4-[(n-butylsulfinyl)methyl]-4′-(chloromethyl)benzene",

abstract = "The polymerization reaction of 4-[(n-butylsulfinyl)methyl]-4′-(chloromethyl)benzene (1a) with t-BuONa in CH2Cl2/monomethylformamide (MMF) (4/6) was studied kinetically. The reaction proceeds in two steps; the formation of a p-quinodimethane intermediate (M) followed by the polymerization of M. Results of kinetic studies and H-D exchange experiments reveal that the 1,6-elimination proceeds by the (E1cb)irr mechanism. The rate of the disappearance of M was increased by the carbanion and S2O82-, inhibited by TEMPO and unaltered by the addition of HCl. From these results, a free radical polymerization mechanism is proposed.",

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T1 - Mechanism of polymerization reaction of 4-[(n-butylsulfinyl)methyl]-4′-(chloromethyl)benzene

AU - Pyun, Sang Yong

AU - Kim, Whan Gi

AU - Jeong, Jin Hyun

AU - Cho, Bong Rae

PY - 2008/12

Y1 - 2008/12

N2 - The polymerization reaction of 4-[(n-butylsulfinyl)methyl]-4′-(chloromethyl)benzene (1a) with t-BuONa in CH2Cl2/monomethylformamide (MMF) (4/6) was studied kinetically. The reaction proceeds in two steps; the formation of a p-quinodimethane intermediate (M) followed by the polymerization of M. Results of kinetic studies and H-D exchange experiments reveal that the 1,6-elimination proceeds by the (E1cb)irr mechanism. The rate of the disappearance of M was increased by the carbanion and S2O82-, inhibited by TEMPO and unaltered by the addition of HCl. From these results, a free radical polymerization mechanism is proposed.

AB - The polymerization reaction of 4-[(n-butylsulfinyl)methyl]-4′-(chloromethyl)benzene (1a) with t-BuONa in CH2Cl2/monomethylformamide (MMF) (4/6) was studied kinetically. The reaction proceeds in two steps; the formation of a p-quinodimethane intermediate (M) followed by the polymerization of M. Results of kinetic studies and H-D exchange experiments reveal that the 1,6-elimination proceeds by the (E1cb)irr mechanism. The rate of the disappearance of M was increased by the carbanion and S2O82-, inhibited by TEMPO and unaltered by the addition of HCl. From these results, a free radical polymerization mechanism is proposed.

KW - Elimination

KW - Intermediate

KW - Polymerization

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U2 - 10.5012/bkcs.2008.29.12.2453

DO - 10.5012/bkcs.2008.29.12.2453

M3 - Article

AN - SCOPUS:60149091840

SN - 0253-2964

VL - 29

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EP - 2458

JO - Bulletin of the Korean Chemical Society

JF - Bulletin of the Korean Chemical Society

IS - 12

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Mechanism of polymerization reaction of 4-[(n-butylsulfinyl)methyl]-4′-(chloromethyl)benzene

Abstract

Keywords

ASJC Scopus subject areas

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