The synthesis of naphthosultine and benzodisultines and their pyrolysis with dienophiles: Studies on o-naphthoquinodimethane and bis-o-quinodimethane

An-Tai Wu, Wen Dar Liu, Wen Sheng Chung

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

Sealed tube reactions of the naphthosultine 8 with a series of electron-deficient dienophiles (fumaronitrile, N-phenylmaleimide, dimethyl fumarate, and dimethyl acetylenedicarboxylate) in toluene at 180 °C gave corresponding 1:1 cycloadducts 11-14 in various amounts along with rearranged naphthosulfolene 7 in 67-95% yields. The reaction of 1,2,4,5-tetra(bromomethyl) benzene with Rongalite (sodium formaldehyde sulfoxylate) and tetrabuty lammonium bromide in DMF gave benzodisultines 17 and 18 in a combined yield of 56%. Sealed tube reactions of benzodisultines 17 and 18 with a series of dienophiles in xylene at 200 °C gave corresponding 1:1 and 1:2 cycloadducts 20-27. The results suggested that thermal extrusion of sulfur dioxide from these sultines led to either o-naphthoquinodimethane 6 (from 8) or bis-o-quinodimethane 19 (from 17 and 18); subsequent trapping of these reactive intermediates by dienophiles and SO2 gave various 1:1 and 1:2 Diels-Alder adducts in modest to excellent yields.

Original languageEnglish
Pages (from-to)77-82
Number of pages6
JournalJournal of the Chinese Chemical Society
Volume49
Issue number1
DOIs
Publication statusPublished - 2002 Jan 1

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Sulfur Dioxide
Xylenes
Toluene
Benzene
Bromides
Formaldehyde
Extrusion
Pyrolysis
Sodium
Electrons
N-phenylmaleimide
Hot Temperature
acetylenedicarboxylic acid dimethyl ester
formaldehydesulfoxylate
fumaronitrile
Dimethyl Fumarate

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

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title = "The synthesis of naphthosultine and benzodisultines and their pyrolysis with dienophiles: Studies on o-naphthoquinodimethane and bis-o-quinodimethane",
abstract = "Sealed tube reactions of the naphthosultine 8 with a series of electron-deficient dienophiles (fumaronitrile, N-phenylmaleimide, dimethyl fumarate, and dimethyl acetylenedicarboxylate) in toluene at 180 °C gave corresponding 1:1 cycloadducts 11-14 in various amounts along with rearranged naphthosulfolene 7 in 67-95{\%} yields. The reaction of 1,2,4,5-tetra(bromomethyl) benzene with Rongalite (sodium formaldehyde sulfoxylate) and tetrabuty lammonium bromide in DMF gave benzodisultines 17 and 18 in a combined yield of 56{\%}. Sealed tube reactions of benzodisultines 17 and 18 with a series of dienophiles in xylene at 200 °C gave corresponding 1:1 and 1:2 cycloadducts 20-27. The results suggested that thermal extrusion of sulfur dioxide from these sultines led to either o-naphthoquinodimethane 6 (from 8) or bis-o-quinodimethane 19 (from 17 and 18); subsequent trapping of these reactive intermediates by dienophiles and SO2 gave various 1:1 and 1:2 Diels-Alder adducts in modest to excellent yields.",
author = "An-Tai Wu and Liu, {Wen Dar} and Chung, {Wen Sheng}",
year = "2002",
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T1 - The synthesis of naphthosultine and benzodisultines and their pyrolysis with dienophiles

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AU - Liu, Wen Dar

AU - Chung, Wen Sheng

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N2 - Sealed tube reactions of the naphthosultine 8 with a series of electron-deficient dienophiles (fumaronitrile, N-phenylmaleimide, dimethyl fumarate, and dimethyl acetylenedicarboxylate) in toluene at 180 °C gave corresponding 1:1 cycloadducts 11-14 in various amounts along with rearranged naphthosulfolene 7 in 67-95% yields. The reaction of 1,2,4,5-tetra(bromomethyl) benzene with Rongalite (sodium formaldehyde sulfoxylate) and tetrabuty lammonium bromide in DMF gave benzodisultines 17 and 18 in a combined yield of 56%. Sealed tube reactions of benzodisultines 17 and 18 with a series of dienophiles in xylene at 200 °C gave corresponding 1:1 and 1:2 cycloadducts 20-27. The results suggested that thermal extrusion of sulfur dioxide from these sultines led to either o-naphthoquinodimethane 6 (from 8) or bis-o-quinodimethane 19 (from 17 and 18); subsequent trapping of these reactive intermediates by dienophiles and SO2 gave various 1:1 and 1:2 Diels-Alder adducts in modest to excellent yields.

AB - Sealed tube reactions of the naphthosultine 8 with a series of electron-deficient dienophiles (fumaronitrile, N-phenylmaleimide, dimethyl fumarate, and dimethyl acetylenedicarboxylate) in toluene at 180 °C gave corresponding 1:1 cycloadducts 11-14 in various amounts along with rearranged naphthosulfolene 7 in 67-95% yields. The reaction of 1,2,4,5-tetra(bromomethyl) benzene with Rongalite (sodium formaldehyde sulfoxylate) and tetrabuty lammonium bromide in DMF gave benzodisultines 17 and 18 in a combined yield of 56%. Sealed tube reactions of benzodisultines 17 and 18 with a series of dienophiles in xylene at 200 °C gave corresponding 1:1 and 1:2 cycloadducts 20-27. The results suggested that thermal extrusion of sulfur dioxide from these sultines led to either o-naphthoquinodimethane 6 (from 8) or bis-o-quinodimethane 19 (from 17 and 18); subsequent trapping of these reactive intermediates by dienophiles and SO2 gave various 1:1 and 1:2 Diels-Alder adducts in modest to excellent yields.

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