3-Pyridylnitrene, 2- and 4-pyrimidinylcarbenes, 3-quinolylnitrenes, and 4-quinazolinylcarbenes. Interconversion, ring expansion to diazacycloheptatetraenes, ring opening to nitrile ylides, and ring contraction to cyanopyrroles and cyanoindoles
Precursors of 3-pyridylnitrene and 2- and 4-pyrimidinylcarbenes all afford mixtures of 2- and 3-cyanopyrroles on flash vacuum thermolysis, but 3-cyanopyrroles are the first-formed products. 3-Quinolylnitrenes and 4-quinazolinylcarbenes similarly afford 3-cyanoindoles. 2-Pyrimidinylcarbenes rearrange...
| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2013-04-01
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| Series: | Beilstein Journal of Organic Chemistry |
| Subjects: | |
| Online Access: | https://doi.org/10.3762/bjoc.9.84 |
| _version_ | 1818954962436096000 |
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| author | Curt Wentrup Nguyen Mong Lan Adelheid Lukosch Pawel Bednarek David Kvaskoff |
| author_facet | Curt Wentrup Nguyen Mong Lan Adelheid Lukosch Pawel Bednarek David Kvaskoff |
| author_sort | Curt Wentrup |
| collection | DOAJ |
| description | Precursors of 3-pyridylnitrene and 2- and 4-pyrimidinylcarbenes all afford mixtures of 2- and 3-cyanopyrroles on flash vacuum thermolysis, but 3-cyanopyrroles are the first-formed products. 3-Quinolylnitrenes and 4-quinazolinylcarbenes similarly afford 3-cyanoindoles. 2-Pyrimidinylcarbenes rearrange to 3-pyridylnitrenes, but 4-pyrimidinylcarbenes and 4-quinazolinylcarbenes do not necessarily rearrange to the corresponding 3-pyridylnitrenes or 3-quinolylnitrenes. The ring contraction reactions are interpreted in terms of ring opening of either the nitrenes or the diazacycloheptatetraenes to nitrile ylides. |
| first_indexed | 2024-12-20T10:30:30Z |
| format | Article |
| id | doaj.art-93a5aff86a7a41acac08676647c21076 |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-12-20T10:30:30Z |
| publishDate | 2013-04-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-93a5aff86a7a41acac08676647c210762022-12-21T19:43:44ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972013-04-019174375310.3762/bjoc.9.841860-5397-9-843-Pyridylnitrene, 2- and 4-pyrimidinylcarbenes, 3-quinolylnitrenes, and 4-quinazolinylcarbenes. Interconversion, ring expansion to diazacycloheptatetraenes, ring opening to nitrile ylides, and ring contraction to cyanopyrroles and cyanoindolesCurt Wentrup0Nguyen Mong Lan1Adelheid Lukosch2Pawel Bednarek3David Kvaskoff4School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, Qld 4072, AustraliaInstitut de Chimie Organique, Université de Lausanne, CH-1009 Lausanne, SwitzerlandFachbereich Chemie der Universität Marburg, D-3550 Marburg, GermanySchool of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, Qld 4072, AustraliaSchool of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, Qld 4072, AustraliaPrecursors of 3-pyridylnitrene and 2- and 4-pyrimidinylcarbenes all afford mixtures of 2- and 3-cyanopyrroles on flash vacuum thermolysis, but 3-cyanopyrroles are the first-formed products. 3-Quinolylnitrenes and 4-quinazolinylcarbenes similarly afford 3-cyanoindoles. 2-Pyrimidinylcarbenes rearrange to 3-pyridylnitrenes, but 4-pyrimidinylcarbenes and 4-quinazolinylcarbenes do not necessarily rearrange to the corresponding 3-pyridylnitrenes or 3-quinolylnitrenes. The ring contraction reactions are interpreted in terms of ring opening of either the nitrenes or the diazacycloheptatetraenes to nitrile ylides.https://doi.org/10.3762/bjoc.9.84carbene-nitrene interconversiondiazepinesflash vacuum thermolysismatrix photochemistrynitrile ylidesreactive intermediates |
| spellingShingle | Curt Wentrup Nguyen Mong Lan Adelheid Lukosch Pawel Bednarek David Kvaskoff 3-Pyridylnitrene, 2- and 4-pyrimidinylcarbenes, 3-quinolylnitrenes, and 4-quinazolinylcarbenes. Interconversion, ring expansion to diazacycloheptatetraenes, ring opening to nitrile ylides, and ring contraction to cyanopyrroles and cyanoindoles Beilstein Journal of Organic Chemistry carbene-nitrene interconversion diazepines flash vacuum thermolysis matrix photochemistry nitrile ylides reactive intermediates |
| title | 3-Pyridylnitrene, 2- and 4-pyrimidinylcarbenes, 3-quinolylnitrenes, and 4-quinazolinylcarbenes. Interconversion, ring expansion to diazacycloheptatetraenes, ring opening to nitrile ylides, and ring contraction to cyanopyrroles and cyanoindoles |
| title_full | 3-Pyridylnitrene, 2- and 4-pyrimidinylcarbenes, 3-quinolylnitrenes, and 4-quinazolinylcarbenes. Interconversion, ring expansion to diazacycloheptatetraenes, ring opening to nitrile ylides, and ring contraction to cyanopyrroles and cyanoindoles |
| title_fullStr | 3-Pyridylnitrene, 2- and 4-pyrimidinylcarbenes, 3-quinolylnitrenes, and 4-quinazolinylcarbenes. Interconversion, ring expansion to diazacycloheptatetraenes, ring opening to nitrile ylides, and ring contraction to cyanopyrroles and cyanoindoles |
| title_full_unstemmed | 3-Pyridylnitrene, 2- and 4-pyrimidinylcarbenes, 3-quinolylnitrenes, and 4-quinazolinylcarbenes. Interconversion, ring expansion to diazacycloheptatetraenes, ring opening to nitrile ylides, and ring contraction to cyanopyrroles and cyanoindoles |
| title_short | 3-Pyridylnitrene, 2- and 4-pyrimidinylcarbenes, 3-quinolylnitrenes, and 4-quinazolinylcarbenes. Interconversion, ring expansion to diazacycloheptatetraenes, ring opening to nitrile ylides, and ring contraction to cyanopyrroles and cyanoindoles |
| title_sort | 3 pyridylnitrene 2 and 4 pyrimidinylcarbenes 3 quinolylnitrenes and 4 quinazolinylcarbenes interconversion ring expansion to diazacycloheptatetraenes ring opening to nitrile ylides and ring contraction to cyanopyrroles and cyanoindoles |
| topic | carbene-nitrene interconversion diazepines flash vacuum thermolysis matrix photochemistry nitrile ylides reactive intermediates |
| url | https://doi.org/10.3762/bjoc.9.84 |
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