UV-induced photochemistry of matrix-isolated 1-phenyl-4-allyl-tetrazolone
Autor(a) principal: | |
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Data de Publicação: | 2007 |
Outros Autores: | , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10316/17938 https://doi.org/10.1039/B703961A |
Resumo: | The photochemistry and molecular structure of 1-phenyl-4-allyl-tetrazolone (PAT) was studied by FT-IR matrix isolation spectroscopy and DFT(B3LYP)/6-311++G(d,p) calculations. The spectrum of matrix-isolated PAT monomers agrees well with the sum spectrum of three conformers predicted theoretically. UV irradiation (λ > 235 nm) of matrix-isolated PAT induces three types of photofragmentation: (1) production of phenylazide and allyl-isocyanate, with phenylazide then losing N2 to yield 1-aza-1,2,4,6-cycloheptatetraene; (2) formation of phenyl-isocyanate and allylazide; (3) N2 elimination leading to formation of 1-allyl-2-phenyldiaziridin-3-one; this compound partially reacts further to form 1-allyl-1H-benzoimidazol-2(3H)-one. The observed photochemistry of the matrix-isolated PAT is distinct from the preferred photochemical fragmentation in solution, where 3,4-dihydro-3-phenylpyrimidin-2(1H)-one is produced as the primary photoproduct. |
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UV-induced photochemistry of matrix-isolated 1-phenyl-4-allyl-tetrazoloneThe photochemistry and molecular structure of 1-phenyl-4-allyl-tetrazolone (PAT) was studied by FT-IR matrix isolation spectroscopy and DFT(B3LYP)/6-311++G(d,p) calculations. The spectrum of matrix-isolated PAT monomers agrees well with the sum spectrum of three conformers predicted theoretically. UV irradiation (λ > 235 nm) of matrix-isolated PAT induces three types of photofragmentation: (1) production of phenylazide and allyl-isocyanate, with phenylazide then losing N2 to yield 1-aza-1,2,4,6-cycloheptatetraene; (2) formation of phenyl-isocyanate and allylazide; (3) N2 elimination leading to formation of 1-allyl-2-phenyldiaziridin-3-one; this compound partially reacts further to form 1-allyl-1H-benzoimidazol-2(3H)-one. The observed photochemistry of the matrix-isolated PAT is distinct from the preferred photochemical fragmentation in solution, where 3,4-dihydro-3-phenylpyrimidin-2(1H)-one is produced as the primary photoproduct.The Royal Society of Chemistry2007-07info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10316/17938http://hdl.handle.net/10316/17938https://doi.org/10.1039/B703961AengFrija, L. M. T.Reva, I. D.Gómez-Zavaglia, A.Cristiano, M. L. S.Fausto, R.info:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2021-08-30T11:19:08Zoai:estudogeral.uc.pt:10316/17938Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:01:45.522444Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
UV-induced photochemistry of matrix-isolated 1-phenyl-4-allyl-tetrazolone |
title |
UV-induced photochemistry of matrix-isolated 1-phenyl-4-allyl-tetrazolone |
spellingShingle |
UV-induced photochemistry of matrix-isolated 1-phenyl-4-allyl-tetrazolone Frija, L. M. T. |
title_short |
UV-induced photochemistry of matrix-isolated 1-phenyl-4-allyl-tetrazolone |
title_full |
UV-induced photochemistry of matrix-isolated 1-phenyl-4-allyl-tetrazolone |
title_fullStr |
UV-induced photochemistry of matrix-isolated 1-phenyl-4-allyl-tetrazolone |
title_full_unstemmed |
UV-induced photochemistry of matrix-isolated 1-phenyl-4-allyl-tetrazolone |
title_sort |
UV-induced photochemistry of matrix-isolated 1-phenyl-4-allyl-tetrazolone |
author |
Frija, L. M. T. |
author_facet |
Frija, L. M. T. Reva, I. D. Gómez-Zavaglia, A. Cristiano, M. L. S. Fausto, R. |
author_role |
author |
author2 |
Reva, I. D. Gómez-Zavaglia, A. Cristiano, M. L. S. Fausto, R. |
author2_role |
author author author author |
dc.contributor.author.fl_str_mv |
Frija, L. M. T. Reva, I. D. Gómez-Zavaglia, A. Cristiano, M. L. S. Fausto, R. |
description |
The photochemistry and molecular structure of 1-phenyl-4-allyl-tetrazolone (PAT) was studied by FT-IR matrix isolation spectroscopy and DFT(B3LYP)/6-311++G(d,p) calculations. The spectrum of matrix-isolated PAT monomers agrees well with the sum spectrum of three conformers predicted theoretically. UV irradiation (λ > 235 nm) of matrix-isolated PAT induces three types of photofragmentation: (1) production of phenylazide and allyl-isocyanate, with phenylazide then losing N2 to yield 1-aza-1,2,4,6-cycloheptatetraene; (2) formation of phenyl-isocyanate and allylazide; (3) N2 elimination leading to formation of 1-allyl-2-phenyldiaziridin-3-one; this compound partially reacts further to form 1-allyl-1H-benzoimidazol-2(3H)-one. The observed photochemistry of the matrix-isolated PAT is distinct from the preferred photochemical fragmentation in solution, where 3,4-dihydro-3-phenylpyrimidin-2(1H)-one is produced as the primary photoproduct. |
publishDate |
2007 |
dc.date.none.fl_str_mv |
2007-07 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://hdl.handle.net/10316/17938 http://hdl.handle.net/10316/17938 https://doi.org/10.1039/B703961A |
url |
http://hdl.handle.net/10316/17938 https://doi.org/10.1039/B703961A |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
The Royal Society of Chemistry |
publisher.none.fl_str_mv |
The Royal Society of Chemistry |
dc.source.none.fl_str_mv |
reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
instname_str |
Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
instacron_str |
RCAAP |
institution |
RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
collection |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository.name.fl_str_mv |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
repository.mail.fl_str_mv |
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1799133907949453312 |