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Reactivity of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π‐Conjugated 2‐Azabutadienes and Unexpected 1,4‐Thiazine Formati...
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| Zeitschriftentitel: | European Journal of Organic Chemistry |
|---|---|
| Personen und Körperschaften: | , , , , , , |
| In: | European Journal of Organic Chemistry, 2006, 2006, 6, S. 1555-1562 |
| Format: | E-Article |
| Sprache: | Englisch |
| veröffentlicht: |
Wiley
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| Schlagwörter: |
| author_facet |
Jacquot‐Rousseau, Sandrine Schmitt, Gérard Khatyr, Abderrahim Knorr, Michael Kubicki, Marek M. Vigier, Estelle Blacque, Olivier Jacquot‐Rousseau, Sandrine Schmitt, Gérard Khatyr, Abderrahim Knorr, Michael Kubicki, Marek M. Vigier, Estelle Blacque, Olivier |
|---|---|
| author |
Jacquot‐Rousseau, Sandrine Schmitt, Gérard Khatyr, Abderrahim Knorr, Michael Kubicki, Marek M. Vigier, Estelle Blacque, Olivier |
| spellingShingle |
Jacquot‐Rousseau, Sandrine Schmitt, Gérard Khatyr, Abderrahim Knorr, Michael Kubicki, Marek M. Vigier, Estelle Blacque, Olivier European Journal of Organic Chemistry Reactivity of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π‐Conjugated 2‐Azabutadienes and Unexpected 1,4‐Thiazine Formation Organic Chemistry Physical and Theoretical Chemistry |
| author_sort |
jacquot‐rousseau, sandrine |
| spelling |
Jacquot‐Rousseau, Sandrine Schmitt, Gérard Khatyr, Abderrahim Knorr, Michael Kubicki, Marek M. Vigier, Estelle Blacque, Olivier 1434-193X 1099-0690 Wiley Organic Chemistry Physical and Theoretical Chemistry http://dx.doi.org/10.1002/ejoc.200500538 <jats:title>Abstract</jats:title><jats:p>Treatment of 4,4‐dichloro‐1,1‐diphenyl‐2‐azabuta‐1,3‐diene [Cl<jats:sub>2</jats:sub>C=C(H)‐N=CPh<jats:sub>2</jats:sub>] (<jats:bold>1</jats:bold>) with excess sodium isopropylthiolate or sodium thiophenolate in DMF yielded the 2‐azabutadiene derivatives (RS)<jats:sub>2</jats:sub>C=C(H)–N=CPh<jats:sub>2</jats:sub> (<jats:bold>2</jats:bold>) (<jats:bold>2a</jats:bold> R = <jats:italic>i</jats:italic>Pr; <jats:bold>2b</jats:bold> R = Ph). Nucleophilic attack of the sodium salt of ethyl thioglycolate on <jats:bold>1</jats:bold> afforded as the sole product the six‐membered heterocyclic compound ethyl 2‐ethoxycarbonylmethylthio‐5,5‐diphenyl‐5,6‐dihydro‐4<jats:italic>H</jats:italic>‐1,4‐thiazine‐6‐carboxylate (<jats:bold>5</jats:bold>). The reaction is initiated by substitution of the two vinyl‐bound chloro substituents to give {EtO(O=)CCH<jats:sub>2</jats:sub>S}<jats:sub>2</jats:sub>C=C(H)–N=CPh<jats:sub>2</jats:sub> (<jats:bold>2c</jats:bold>) as intermediate. A mechanism that accounts for the subsequent cyclisation reaction is proposed. The 2‐azabutadiene derivative (PhO)<jats:sub>2</jats:sub>C=C(H)–N=CPh<jats:sub>2</jats:sub> (<jats:bold>7</jats:bold>) was obtained by the reaction of <jats:bold>1</jats:bold> with sodium phenolate. The regioselectivity of the incoming nucleophile is roughly correlated with its hardness/softness in accord with Pearson’s HSAB principle. The molecular structures of <jats:bold>2a</jats:bold>,<jats:bold>b</jats:bold>, <jats:bold>5</jats:bold> and <jats:bold>7</jats:bold> were determined by single‐crystal X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)</jats:p> Reactivity of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π‐Conjugated 2‐Azabutadienes and Unexpected 1,4‐Thiazine Formation European Journal of Organic Chemistry |
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Wiley, 2006 |
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Wiley, 2006 |
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1434-193X 1099-0690 |
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1434-193X 1099-0690 |
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jacquotrousseau2006reactivityof44dichloro11diphenyl2azabutadienetowardsalkoxidesandthiolatessynthesisoffunctionalisedpconjugated2azabutadienesandunexpected14thiazineformation |
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2006 |
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Wiley |
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ai |
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European Journal of Organic Chemistry |
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49 |
| title |
Reactivity of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π‐Conjugated 2‐Azabutadienes and Unexpected 1,4‐Thiazine Formation |
| title_unstemmed |
Reactivity of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π‐Conjugated 2‐Azabutadienes and Unexpected 1,4‐Thiazine Formation |
| title_full |
Reactivity of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π‐Conjugated 2‐Azabutadienes and Unexpected 1,4‐Thiazine Formation |
| title_fullStr |
Reactivity of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π‐Conjugated 2‐Azabutadienes and Unexpected 1,4‐Thiazine Formation |
| title_full_unstemmed |
Reactivity of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π‐Conjugated 2‐Azabutadienes and Unexpected 1,4‐Thiazine Formation |
| title_short |
Reactivity of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π‐Conjugated 2‐Azabutadienes and Unexpected 1,4‐Thiazine Formation |
| title_sort |
reactivity of 4,4‐dichloro‐1,1‐diphenyl‐2‐azabutadiene towards alkoxides and thiolates: synthesis of functionalised π‐conjugated 2‐azabutadienes and unexpected 1,4‐thiazine formation |
| topic |
Organic Chemistry Physical and Theoretical Chemistry |
| url |
http://dx.doi.org/10.1002/ejoc.200500538 |
| publishDate |
2006 |
| physical |
1555-1562 |
| description |
<jats:title>Abstract</jats:title><jats:p>Treatment of 4,4‐dichloro‐1,1‐diphenyl‐2‐azabuta‐1,3‐diene [Cl<jats:sub>2</jats:sub>C=C(H)‐N=CPh<jats:sub>2</jats:sub>] (<jats:bold>1</jats:bold>) with excess sodium isopropylthiolate or sodium thiophenolate in DMF yielded the 2‐azabutadiene derivatives (RS)<jats:sub>2</jats:sub>C=C(H)–N=CPh<jats:sub>2</jats:sub> (<jats:bold>2</jats:bold>) (<jats:bold>2a</jats:bold> R = <jats:italic>i</jats:italic>Pr; <jats:bold>2b</jats:bold> R = Ph). Nucleophilic attack of the sodium salt of ethyl thioglycolate on <jats:bold>1</jats:bold> afforded as the sole product the six‐membered heterocyclic compound ethyl 2‐ethoxycarbonylmethylthio‐5,5‐diphenyl‐5,6‐dihydro‐4<jats:italic>H</jats:italic>‐1,4‐thiazine‐6‐carboxylate (<jats:bold>5</jats:bold>). The reaction is initiated by substitution of the two vinyl‐bound chloro substituents to give {EtO(O=)CCH<jats:sub>2</jats:sub>S}<jats:sub>2</jats:sub>C=C(H)–N=CPh<jats:sub>2</jats:sub> (<jats:bold>2c</jats:bold>) as intermediate. A mechanism that accounts for the subsequent cyclisation reaction is proposed. The 2‐azabutadiene derivative (PhO)<jats:sub>2</jats:sub>C=C(H)–N=CPh<jats:sub>2</jats:sub> (<jats:bold>7</jats:bold>) was obtained by the reaction of <jats:bold>1</jats:bold> with sodium phenolate. The regioselectivity of the incoming nucleophile is roughly correlated with its hardness/softness in accord with Pearson’s HSAB principle. The molecular structures of <jats:bold>2a</jats:bold>,<jats:bold>b</jats:bold>, <jats:bold>5</jats:bold> and <jats:bold>7</jats:bold> were determined by single‐crystal X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)</jats:p> |
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| author | Jacquot‐Rousseau, Sandrine, Schmitt, Gérard, Khatyr, Abderrahim, Knorr, Michael, Kubicki, Marek M., Vigier, Estelle, Blacque, Olivier |
| author_facet | Jacquot‐Rousseau, Sandrine, Schmitt, Gérard, Khatyr, Abderrahim, Knorr, Michael, Kubicki, Marek M., Vigier, Estelle, Blacque, Olivier, Jacquot‐Rousseau, Sandrine, Schmitt, Gérard, Khatyr, Abderrahim, Knorr, Michael, Kubicki, Marek M., Vigier, Estelle, Blacque, Olivier |
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| description | <jats:title>Abstract</jats:title><jats:p>Treatment of 4,4‐dichloro‐1,1‐diphenyl‐2‐azabuta‐1,3‐diene [Cl<jats:sub>2</jats:sub>C=C(H)‐N=CPh<jats:sub>2</jats:sub>] (<jats:bold>1</jats:bold>) with excess sodium isopropylthiolate or sodium thiophenolate in DMF yielded the 2‐azabutadiene derivatives (RS)<jats:sub>2</jats:sub>C=C(H)–N=CPh<jats:sub>2</jats:sub> (<jats:bold>2</jats:bold>) (<jats:bold>2a</jats:bold> R = <jats:italic>i</jats:italic>Pr; <jats:bold>2b</jats:bold> R = Ph). Nucleophilic attack of the sodium salt of ethyl thioglycolate on <jats:bold>1</jats:bold> afforded as the sole product the six‐membered heterocyclic compound ethyl 2‐ethoxycarbonylmethylthio‐5,5‐diphenyl‐5,6‐dihydro‐4<jats:italic>H</jats:italic>‐1,4‐thiazine‐6‐carboxylate (<jats:bold>5</jats:bold>). The reaction is initiated by substitution of the two vinyl‐bound chloro substituents to give {EtO(O=)CCH<jats:sub>2</jats:sub>S}<jats:sub>2</jats:sub>C=C(H)–N=CPh<jats:sub>2</jats:sub> (<jats:bold>2c</jats:bold>) as intermediate. A mechanism that accounts for the subsequent cyclisation reaction is proposed. The 2‐azabutadiene derivative (PhO)<jats:sub>2</jats:sub>C=C(H)–N=CPh<jats:sub>2</jats:sub> (<jats:bold>7</jats:bold>) was obtained by the reaction of <jats:bold>1</jats:bold> with sodium phenolate. The regioselectivity of the incoming nucleophile is roughly correlated with its hardness/softness in accord with Pearson’s HSAB principle. The molecular structures of <jats:bold>2a</jats:bold>,<jats:bold>b</jats:bold>, <jats:bold>5</jats:bold> and <jats:bold>7</jats:bold> were determined by single‐crystal X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)</jats:p> |
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| spelling | Jacquot‐Rousseau, Sandrine Schmitt, Gérard Khatyr, Abderrahim Knorr, Michael Kubicki, Marek M. Vigier, Estelle Blacque, Olivier 1434-193X 1099-0690 Wiley Organic Chemistry Physical and Theoretical Chemistry http://dx.doi.org/10.1002/ejoc.200500538 <jats:title>Abstract</jats:title><jats:p>Treatment of 4,4‐dichloro‐1,1‐diphenyl‐2‐azabuta‐1,3‐diene [Cl<jats:sub>2</jats:sub>C=C(H)‐N=CPh<jats:sub>2</jats:sub>] (<jats:bold>1</jats:bold>) with excess sodium isopropylthiolate or sodium thiophenolate in DMF yielded the 2‐azabutadiene derivatives (RS)<jats:sub>2</jats:sub>C=C(H)–N=CPh<jats:sub>2</jats:sub> (<jats:bold>2</jats:bold>) (<jats:bold>2a</jats:bold> R = <jats:italic>i</jats:italic>Pr; <jats:bold>2b</jats:bold> R = Ph). Nucleophilic attack of the sodium salt of ethyl thioglycolate on <jats:bold>1</jats:bold> afforded as the sole product the six‐membered heterocyclic compound ethyl 2‐ethoxycarbonylmethylthio‐5,5‐diphenyl‐5,6‐dihydro‐4<jats:italic>H</jats:italic>‐1,4‐thiazine‐6‐carboxylate (<jats:bold>5</jats:bold>). The reaction is initiated by substitution of the two vinyl‐bound chloro substituents to give {EtO(O=)CCH<jats:sub>2</jats:sub>S}<jats:sub>2</jats:sub>C=C(H)–N=CPh<jats:sub>2</jats:sub> (<jats:bold>2c</jats:bold>) as intermediate. A mechanism that accounts for the subsequent cyclisation reaction is proposed. The 2‐azabutadiene derivative (PhO)<jats:sub>2</jats:sub>C=C(H)–N=CPh<jats:sub>2</jats:sub> (<jats:bold>7</jats:bold>) was obtained by the reaction of <jats:bold>1</jats:bold> with sodium phenolate. The regioselectivity of the incoming nucleophile is roughly correlated with its hardness/softness in accord with Pearson’s HSAB principle. The molecular structures of <jats:bold>2a</jats:bold>,<jats:bold>b</jats:bold>, <jats:bold>5</jats:bold> and <jats:bold>7</jats:bold> were determined by single‐crystal X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)</jats:p> Reactivity of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π‐Conjugated 2‐Azabutadienes and Unexpected 1,4‐Thiazine Formation European Journal of Organic Chemistry |
| spellingShingle | Jacquot‐Rousseau, Sandrine, Schmitt, Gérard, Khatyr, Abderrahim, Knorr, Michael, Kubicki, Marek M., Vigier, Estelle, Blacque, Olivier, European Journal of Organic Chemistry, Reactivity of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π‐Conjugated 2‐Azabutadienes and Unexpected 1,4‐Thiazine Formation, Organic Chemistry, Physical and Theoretical Chemistry |
| title | Reactivity of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π‐Conjugated 2‐Azabutadienes and Unexpected 1,4‐Thiazine Formation |
| title_full | Reactivity of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π‐Conjugated 2‐Azabutadienes and Unexpected 1,4‐Thiazine Formation |
| title_fullStr | Reactivity of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π‐Conjugated 2‐Azabutadienes and Unexpected 1,4‐Thiazine Formation |
| title_full_unstemmed | Reactivity of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π‐Conjugated 2‐Azabutadienes and Unexpected 1,4‐Thiazine Formation |
| title_short | Reactivity of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π‐Conjugated 2‐Azabutadienes and Unexpected 1,4‐Thiazine Formation |
| title_sort | reactivity of 4,4‐dichloro‐1,1‐diphenyl‐2‐azabutadiene towards alkoxides and thiolates: synthesis of functionalised π‐conjugated 2‐azabutadienes and unexpected 1,4‐thiazine formation |
| title_unstemmed | Reactivity of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π‐Conjugated 2‐Azabutadienes and Unexpected 1,4‐Thiazine Formation |
| topic | Organic Chemistry, Physical and Theoretical Chemistry |
| url | http://dx.doi.org/10.1002/ejoc.200500538 |