Synthesis of 2,5-disubstituted thienosultines and their thermal reactions with dienophiles and nucleophiles

Wen Dar Liu, Chih Chin Chi, I. Feng Pai, An Tai Wu, Wen Sheng Chung

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

The 2,5-disubstituted thienosultines (5,7-disubstituted 1,4-dihydro-1H-3λ4-thieno[3,4-d][2,3]oxathiin-3-oxides) 5a-d were prepared from the corresponding dichlorides 4a-d with the commercially available Rongalite (sodium formaldehyde sulfoxylate) in 17-60% yields. When heated in the presence of electron-poor dienophiles, sultines 5a-d underwent elimination of SO2, and the resulting non-Kekulé biradicals 7a-d were intercepted as the 1:1 adducts 8-12 in good to excellent yields. The pyrolysis of sultines and sulfolenes with different concentrations of dienophiles revealed that either a preequilibrium between starting reagents and biradical species or Diels-Alder and retro-Diels-Alder reaction mechanisms may be involved; however, more work is necessary to establish the proposed mechanisms. Reaction of sultine 5b with nBuLi was found to undergo a nucleophilic ring-opening reaction to give sulfinyl alcohol 17 after H2O workup. When sultine 5a was heated in benzene in a sealed tube in the presence of methanol, methanol-d4, or 2-mercaptoethanol, the respective 1:1 trapping adducts 19-21 as well as the rearranged sulfolene 6a were isolated in similar amounts. The isolation of adducts 19-21 may be explained by the involvement of either biradical or ionic intermediates during the pyrolysis.

Original languageEnglish
Pages (from-to)9267-9275
Number of pages9
JournalJournal of Organic Chemistry
Volume67
Issue number26
DOIs
Publication statusPublished - 2002 Dec 27

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Nucleophiles
Oxathiins
Methanol
Pyrolysis
Mercaptoethanol
Benzene
Oxides
Formaldehyde
Sodium
Alcohols
Electrons
Hot Temperature
formaldehydesulfoxylate

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Cite this

Liu, Wen Dar ; Chi, Chih Chin ; Pai, I. Feng ; Wu, An Tai ; Chung, Wen Sheng. / Synthesis of 2,5-disubstituted thienosultines and their thermal reactions with dienophiles and nucleophiles. In: Journal of Organic Chemistry. 2002 ; Vol. 67, No. 26. pp. 9267-9275.
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abstract = "The 2,5-disubstituted thienosultines (5,7-disubstituted 1,4-dihydro-1H-3λ4-thieno[3,4-d][2,3]oxathiin-3-oxides) 5a-d were prepared from the corresponding dichlorides 4a-d with the commercially available Rongalite (sodium formaldehyde sulfoxylate) in 17-60{\%} yields. When heated in the presence of electron-poor dienophiles, sultines 5a-d underwent elimination of SO2, and the resulting non-Kekul{\'e} biradicals 7a-d were intercepted as the 1:1 adducts 8-12 in good to excellent yields. The pyrolysis of sultines and sulfolenes with different concentrations of dienophiles revealed that either a preequilibrium between starting reagents and biradical species or Diels-Alder and retro-Diels-Alder reaction mechanisms may be involved; however, more work is necessary to establish the proposed mechanisms. Reaction of sultine 5b with nBuLi was found to undergo a nucleophilic ring-opening reaction to give sulfinyl alcohol 17 after H2O workup. When sultine 5a was heated in benzene in a sealed tube in the presence of methanol, methanol-d4, or 2-mercaptoethanol, the respective 1:1 trapping adducts 19-21 as well as the rearranged sulfolene 6a were isolated in similar amounts. The isolation of adducts 19-21 may be explained by the involvement of either biradical or ionic intermediates during the pyrolysis.",
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Synthesis of 2,5-disubstituted thienosultines and their thermal reactions with dienophiles and nucleophiles. / Liu, Wen Dar; Chi, Chih Chin; Pai, I. Feng; Wu, An Tai; Chung, Wen Sheng.

In: Journal of Organic Chemistry, Vol. 67, No. 26, 27.12.2002, p. 9267-9275.

Research output: Contribution to journalArticle

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T1 - Synthesis of 2,5-disubstituted thienosultines and their thermal reactions with dienophiles and nucleophiles

AU - Liu, Wen Dar

AU - Chi, Chih Chin

AU - Pai, I. Feng

AU - Wu, An Tai

AU - Chung, Wen Sheng

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N2 - The 2,5-disubstituted thienosultines (5,7-disubstituted 1,4-dihydro-1H-3λ4-thieno[3,4-d][2,3]oxathiin-3-oxides) 5a-d were prepared from the corresponding dichlorides 4a-d with the commercially available Rongalite (sodium formaldehyde sulfoxylate) in 17-60% yields. When heated in the presence of electron-poor dienophiles, sultines 5a-d underwent elimination of SO2, and the resulting non-Kekulé biradicals 7a-d were intercepted as the 1:1 adducts 8-12 in good to excellent yields. The pyrolysis of sultines and sulfolenes with different concentrations of dienophiles revealed that either a preequilibrium between starting reagents and biradical species or Diels-Alder and retro-Diels-Alder reaction mechanisms may be involved; however, more work is necessary to establish the proposed mechanisms. Reaction of sultine 5b with nBuLi was found to undergo a nucleophilic ring-opening reaction to give sulfinyl alcohol 17 after H2O workup. When sultine 5a was heated in benzene in a sealed tube in the presence of methanol, methanol-d4, or 2-mercaptoethanol, the respective 1:1 trapping adducts 19-21 as well as the rearranged sulfolene 6a were isolated in similar amounts. The isolation of adducts 19-21 may be explained by the involvement of either biradical or ionic intermediates during the pyrolysis.

AB - The 2,5-disubstituted thienosultines (5,7-disubstituted 1,4-dihydro-1H-3λ4-thieno[3,4-d][2,3]oxathiin-3-oxides) 5a-d were prepared from the corresponding dichlorides 4a-d with the commercially available Rongalite (sodium formaldehyde sulfoxylate) in 17-60% yields. When heated in the presence of electron-poor dienophiles, sultines 5a-d underwent elimination of SO2, and the resulting non-Kekulé biradicals 7a-d were intercepted as the 1:1 adducts 8-12 in good to excellent yields. The pyrolysis of sultines and sulfolenes with different concentrations of dienophiles revealed that either a preequilibrium between starting reagents and biradical species or Diels-Alder and retro-Diels-Alder reaction mechanisms may be involved; however, more work is necessary to establish the proposed mechanisms. Reaction of sultine 5b with nBuLi was found to undergo a nucleophilic ring-opening reaction to give sulfinyl alcohol 17 after H2O workup. When sultine 5a was heated in benzene in a sealed tube in the presence of methanol, methanol-d4, or 2-mercaptoethanol, the respective 1:1 trapping adducts 19-21 as well as the rearranged sulfolene 6a were isolated in similar amounts. The isolation of adducts 19-21 may be explained by the involvement of either biradical or ionic intermediates during the pyrolysis.

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