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Synthetic Applications of Nitropyridine Derivatives
Norwegian University of Science and Technology, Faculty of Natural Sciences and Technology, Department of Chemistry.
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The present work represents a continuation of the investigation of the chemistry of nitropyridine derivatives, based on the methodology for nitration of pyridines developed by Professor Jan M. Bakke and co-workers at NTNU. Nitropyridines have been utilized as substrates for the formation of novel bis- and tris-heterocyclic compounds, and new synthetic routes to fused heterocycles have been developed.

Several new β-carboline analogues and fused azacinnolines have been prepared based on a Suzuki coupling and subsequent cyclization approuch. The formation of 4-isocyanobut-2-enenitrile and 3-cyanopyrrole products by ring opening and ring contraction of 3-pyridyl nitrenes, respectively, is reported. 7-Azacinnolin-4(1H)-one has been prepared and tautomery investigated by NMR. The general ability of appropriate pyridyl compunds to undergo Friedländer condensation to give different 1,7-naphthyridines has been demonstrated. Bis-heterocyclic products have been prepared from methyl/allylpyridylketones fromed by Weinreb tranformations, and a method has been developed to allow for the preperation of reactive pure pyridylvinylketones to be used in further reactions, such as Diels-Alder cycloaddition reactions.

Place, publisher, year, edition, pages
NTNU, 2010.
Series
Doctoral theses at NTNU, ISSN 1503-8181 ; 2010:238
Identifiers
URN: urn:nbn:no:ntnu:diva-12220ISBN: 978-82-471-2468-0 (printed ver.)ISBN: 978-82-471-2469-7 (electronic ver.)OAI: oai:DiVA.org:ntnu-12220DiVA: diva2:403869
Public defence
2010-12-03, 00:00
Available from: 2011-03-15 Created: 2011-03-15 Last updated: 2011-03-15Bibliographically approved
List of papers
1. Preparation of new pyrido[3,4-b]thienopyrroles and pyrido[4,3-e]-thienopyridazines
Open this publication in new window or tab >>Preparation of new pyrido[3,4-b]thienopyrroles and pyrido[4,3-e]-thienopyridazines
2008 (English)In: Tetrahedron, ISSN 0040-4020, E-ISSN 1464-5416, Vol. 64, no 32, 7626-7632 p.Article in journal (Refereed) Published
Abstract [en]

Two new types of pyrido-fused tris-heterocycles (1a,b and 2a,b) have been prepared from 3-amino-pyridine in five/six steps. A synthetic strategy for the preparation of the novel pyrido[3,4-b]thieno[2,3-and 3,2-d]pyrroles (1a,b) and pyrido[4,3-a]thieno[2,3- and 3,2-c]pyridazines (2a,b) has been studied. The Suzuki cross coupling of the appropriate 2- and 3-thienoboronic acids (3,4) and 4-bromo-3-pyridylpivaloylamide (9) afforded the biaryl coupling products (10,11) in high yields (85%). Diazotization of the hydrolysed (2-thienyl)-coupling product (12) and azide substitution gave the 3-azido-4-(2-thienyl)pyridine intermediate (72%,14). 3-Azido-4-(3-thienyl)pyridine (15) was prepared by exchanging the previous order of reactions. The desired a-carboline thiophene analogues (la,b) were obtained via the nitrene by thermal decomposition of the azido precursors (14,15). By optimising conditions for intramolecular diazocoupling, the corresponding pyridazine products (72-83%, 2a,b) were afforded. (C) 2008 Elsevier Ltd. All rights reserved.

Place, publisher, year, edition, pages
Elsevier, 2008
Keyword
pyrido[3, 4-b]thieno[2, 3-d]pyrrole, pyrido[3, 4-b]thieno[3, 2-d]pyrrole, pyrido]4, 3-e]thieno[2, 3-c]pyridazine, pyrido[4, 3-e]thieno[3, 2-c]pyridazine, Suzuki cross coupling, diazotization, diazocoupling, azide, nitrene, thermal decomposition
Identifiers
urn:nbn:no:ntnu:diva-11940 (URN)10.1016/j.tet.2008.05.062 (DOI)000257912200022 ()
Note

The article is reprinted with kind permission from Elsevier, sciencedirect.com

Available from: 2011-02-02 Created: 2011-02-02 Last updated: 2012-09-07Bibliographically approved
2. Preparation of novel pyridine-fused tris-heterocycles; pyrido[4,3-e]pyrrolo-/pyrido[4,3-e]furano[2,3-c]pyridazines and pyrido[3,4-b]pyrrolo[3,2-d]pyrrole
Open this publication in new window or tab >>Preparation of novel pyridine-fused tris-heterocycles; pyrido[4,3-e]pyrrolo-/pyrido[4,3-e]furano[2,3-c]pyridazines and pyrido[3,4-b]pyrrolo[3,2-d]pyrrole
2008 (English)In: Tetrahedron, ISSN 0040-4020, E-ISSN 1464-5416, Vol. 64, no 49, 11180-11184 p.Article in journal (Refereed) Published
Abstract [en]

Three novel pyrido-fused tris-heterocycles have been prepared based on a Suzuki coupling and subsequent cyclisation approach. Pyriclo[4,3-e]pyrrolo[2,3-c]pyridazine (3b, 77%) and pyrido[4,3-e]furano[2,3-c]pyridazine (5b, 76%) were obtained by intramolecular diazocoupling. Successful diazocoupling of furan (5b) is thus reported for the first time by NOBF4 generation of the diazonium intermediate. N-TIPS-pyrido[3,4-b]pyrrolo[3,2-d]pyrrole (TIPS-4b) was synthesised by thermal cyclisation of pyridyl nitrene in considerably higher yield (71%) than previously experienced from similar cyclisations, due to TIPS-activation. (C) 2008 Elsevier Ltd. All rights reserved.

Place, publisher, year, edition, pages
Elsevier, 2008
Keyword
Pyrido[4, 3-e]pyrrolo[2, 3-c]pyridazine, Pyrido[4, 3-e]furano[2, 3-c]pyridazine, N-TIPS-pyrido[3, 4-b]pyrrolo[3, 2-d]pyrrole, Diazotisation, Diazocoupling, Azide thermal decomposition, 4-(3-Furanyl)pyridin-3-amine, 4-(3-Pyrrolyl)pyridin-3-amine
Identifiers
urn:nbn:no:ntnu:diva-11941 (URN)10.1016/j.tet.2008.09.051 (DOI)000261416900029 ()
Note
The article is reprinted with kind permission from Elsevier, sciencedirect.comAvailable from: 2011-02-02 Created: 2011-02-02 Last updated: 2011-03-15Bibliographically approved
3. Formation of new 4-isocyanobut-2-enenitriles by thermal ring cleavage of 3-pyridyl azides
Open this publication in new window or tab >>Formation of new 4-isocyanobut-2-enenitriles by thermal ring cleavage of 3-pyridyl azides
2009 (English)In: Tetrahedron, ISSN 0040-4020, E-ISSN 1464-5416, Vol. 65, no 18, 3668-3672 p.Article in journal (Refereed) Published
Abstract [en]

A new thermal ring cleavage of 3-pyridyl nitrenes for the formation of 4-isocyanobut-2-enenitrile products is reported. Thermolysis of 4-(thien-3-yl)-3-pyridyl azide 1 and 3-azido-4-(1-TIPS-1H-pyrrol-3-yl)pyridine 5 afforded two new isonitrile-nitrile products by ring cleavage; 4-isocyano-2-(thiophen-3-yl)but-2-enenitrile (3, 27%) and 4-isocyano-2-(1-TIPS-1H-pyrrol-3-yl)but-2-enenitrile (7, 20%), in addition to our previously reported pyrido[3,4-b]thienopyrrole (2, 29%) and pyrido[3,4-b]pyrrolo[3,2-d]pyrrole (6, 71%) products. Minor amounts of 2-(thien-3-yl)-1H-pyrrole-3-carbonitrile (4, 6%), formed by ring contraction, were also isolated after thermolysis of azide 1. Isonitriles 3 and 7 underwent degradation into amine 3b and formamide 7a by acidic hydrolysis. The nature and chemistry of compounds 3, 4 and 7 were investigated. (C) 2009 Elsevier Ltd. All rights reserved.

Place, publisher, year, edition, pages
Elsevier, 2009
Keyword
3-Pyridylazide, 3-Pyridyl nitrene, Thermolysis, 4-Isocyano-2-(thiophen-3-yl)but-2-enenitrile, 4-Isocyano-2-(1-TIPS-1H-pyrrol-3-yl)but-2-enenitrile, 2-(Thien-3-yl)-1H-pyrrole-3-carbonitrile
Identifiers
urn:nbn:no:ntnu:diva-11942 (URN)10.1016/j.tet.2009.02.072 (DOI)000265264400016 ()
Note
The article is reprinted with kind permission from Elsevier, sciencedirect.comAvailable from: 2011-02-02 Created: 2011-02-02 Last updated: 2011-03-15Bibliographically approved
4. 8H-6-Azathieno[2,3-b]indole
Open this publication in new window or tab >>8H-6-Azathieno[2,3-b]indole
2010 (English)In: Acta Crystallographica Section E: Structure Reports Online, ISSN 1600-5368, E-ISSN 1600-5368, CCDC 778181- p.Article in journal (Refereed) Accepted
Identifiers
urn:nbn:no:ntnu:diva-11946 (URN)
Available from: 2011-02-02 Created: 2011-02-02 Last updated: 2011-03-15Bibliographically approved
5. 7-azathieno[3,2-c]cinnoline
Open this publication in new window or tab >>7-azathieno[3,2-c]cinnoline
2007 (English)In: Acta Crystallographica Section E: Structure Reports Online, ISSN 1600-5368, E-ISSN 1600-5368, Vol. 63, O3290-U4201 p.Article in journal (Refereed) Published
Abstract [en]

The title compound, also known as pyrido[4,3-e] thieno[3,2-c]pyridazine, C9H5N3S, was crystallized from ethyl acetate. The molecule is planar and the N = N bond is 1.304 (3) angstrom compared with 1.306 (2) angstrom for the regio-isomer 7-azathieno[ 2,3-c]cinnoline and also in good agreement with similar compounds.

Identifiers
urn:nbn:no:ntnu:diva-11943 (URN)10.1107/S1600536807029947 (DOI)000248149900405 ()
Available from: 2011-02-02 Created: 2011-02-02 Last updated: 2011-03-15Bibliographically approved
6. 7-Azathieno[2,3-c] cinnoline
Open this publication in new window or tab >>7-Azathieno[2,3-c] cinnoline
2007 (English)In: Acta Crystallographica Section E: Structure Reports Online, ISSN 1600-5368, E-ISSN 1600-5368, Vol. 63, O3896-U3816 p.Article in journal (Refereed) Published
Abstract [en]

The title compound (systematic name: pyrido[4,3-e]thieno[ 2,3-c]pyridazine), C9H5N3S, consists of three fused heterocyclic rings. The molecule is planar and the N = N bond length of 1.302 (2) A is in good agreement with values observed in similar compounds. The molecules show pi-pi stacking interactions, forming molecular stacks along the b axis with interplanar distances of 3.39 (2) and 3.49 ( 2) A. The C-H groups of the thiophene ring are involved in C-H center dot center dot center dot N interactions, joining molecules into two-dimensional sheets parallel to (011).

Identifiers
urn:nbn:no:ntnu:diva-11944 (URN)10.1107/S1600536807041335 (DOI)000249759900363 ()
Available from: 2011-02-02 Created: 2011-02-02 Last updated: 2011-03-15Bibliographically approved
7. 7-Azacinnolin-4(1H)-one preparation and NMR studies of tautomery
Open this publication in new window or tab >>7-Azacinnolin-4(1H)-one preparation and NMR studies of tautomery
2010 (English)In: Journal of Heterocyclic Chemistry, ISSN 0022-152X, Vol. 48, no 3, 737-741 p.Article in journal (Refereed) Accepted
Identifiers
urn:nbn:no:ntnu:diva-11947 (URN)10.1002/jhet.580 (DOI)
Note

The definitive version is available at www3.interscience.wiley.com

Available from: 2011-02-02 Created: 2011-02-02 Last updated: 2012-09-07Bibliographically approved
8. Synthesis of novel 1,7-naphthyridines
Open this publication in new window or tab >>Synthesis of novel 1,7-naphthyridines
2010 (English)In: Journal of Heterocyclic Chemistry, ISSN 0022-152X, Vol. 48, no 6, 1383-1387 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:no:ntnu:diva-11948 (URN)10.1002/jhet.657 (DOI)
Note

The definitive version is available at www3.interscience.wiley.com

Available from: 2011-02-02 Created: 2011-02-02 Last updated: 2012-09-06Bibliographically approved
9. Studies on reactive pyridylketones formed by Weinreb transformations
Open this publication in new window or tab >>Studies on reactive pyridylketones formed by Weinreb transformations
(English)Manuscript (preprint) (Other academic)
Identifiers
urn:nbn:no:ntnu:diva-11949 (URN)
Note
If accecpted The definitive version will be available at www3.interscience.wiley.comAvailable from: 2011-02-02 Created: 2011-02-02 Last updated: 2011-03-15Bibliographically approved

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