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Photochemistry of 1-and 2-Methyl-5-aminotetrazoles: structural effects on reaction pathways

2016-12Journal article Restricted access
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dc.contributor.authorIsmael, Amin
dc.contributor.authorFausto, R.
dc.contributor.authorCristiano, Maria Lurdes Santos
dc.date.accessioned2017-04-07T15:55:35Z
dc.date.available2017-04-07T15:55:35Z
dc.date.issued2016-12
dc.description.abstractThe influence of the position of the methyl substituent in 1- and 2-methyl-substituted 5-aminotetrazoles on the photochemistry of these molecules is evaluated. The two compounds were isolated in an argon matrix (15 K) and the matrix was subjected to in situ narrowband UV excitation at different wavelengths, which induce selectively photochemical transformations of different species (reactants and initially formed photoproducts). The progress of the reactions was followed by infrared spectroscopy, supported by quantum chemical calculations. It is shown that the photochemistries of the two isomers, 1-methyl-(1H)-tetrazole-5-amine (la) and 2-methyl-(2H)-tetrazole-5-amine (1b), although resulting in a common intermediate diazirine 3, which undergoes subsequent photoconversion into 1-amino-3-methylcarbodiimide (H2N-N=C=N-CH3), show marked differences: formation of the amino cyanamide 4 (H2N-N(CH3)-CE equivalent to N) is only observed from the photo cleavage of the isomer la, whereas formation of the nitrile imine 2 (H2N-C-=N+=N-CH3) is only obtained from photolysis of 1b. The exclusive formation of nitrile imine from the isomer lb points to the possibility that only the 2H-tetrazoles forms can give a direct access to nitrile imines, while observation of the amino cyanamide 4 represents a novel reaction pathway in the photochemistry of tetrazoles and seems to be characteristic of 1H-tetrazoles. The structural and vibrational characterization of both reactants and photoproducts has been undertaken.
dc.description.sponsorshipFEDER/COMPETE 2020-UE; POCI-01-0145-FEDER-016617
dc.identifier.doi10.1021/acs.joc.6b02023
dc.identifier.issn0022-3263
dc.identifier.otherAUT: MCR00716;
dc.identifier.urihttp://hdl.handle.net/10400.1/9171
dc.language.isoeng
dc.peerreviewedyes
dc.relation2014 - Incentive
dc.relationThe Birth of High-Energy Crystals from Isolated Molecules – The Unsuspected Parenthood of Rare Conformers
dc.relationSTRUCTURE AND REACTIVITY OF NOVEL TETRAZOLE-SACCHARINATES USEFUL AS MULTIDENTATE NITROGEN LIGANDS
dc.relation.isbasedonWOS:000389396400013
dc.titlePhotochemistry of 1-and 2-Methyl-5-aminotetrazoles: structural effects on reaction pathways
dc.typejournal article
dspace.entity.typePublication
oaire.awardTitle2014 - Incentive
oaire.awardTitleThe Birth of High-Energy Crystals from Isolated Molecules – The Unsuspected Parenthood of Rare Conformers
oaire.awardTitleSTRUCTURE AND REACTIVITY OF NOVEL TETRAZOLE-SACCHARINATES USEFUL AS MULTIDENTATE NITROGEN LIGANDS
oaire.awardURIinfo:eu-repo/grantAgreement/FCT/5876/UID%2FMulti%2F04326%2F2013/PT
oaire.awardURIinfo:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/Incentivo%2FQUI%2FUI0313%2F2014/PT
oaire.awardURIinfo:eu-repo/grantAgreement/FCT/3599-PPCDT/PTDC%2FMAR-BIO%2F4132%2F2014/PT
oaire.awardURIinfo:eu-repo/grantAgreement/FCT/9471 - RIDTI/PTDC%2FQEQ-QFI%2F3284%2F2014/PT
oaire.awardURIinfo:eu-repo/grantAgreement/FCT//SFRH%2FBD%2F90435%2F2012/PT
oaire.citation.endPage11663
oaire.citation.issue23
oaire.citation.startPage11656
oaire.citation.titleJournal of Organic Chemistry
oaire.citation.volume81
oaire.fundingStream5876
oaire.fundingStream6817 - DCRRNI ID
oaire.fundingStream3599-PPCDT
oaire.fundingStream9471 - RIDTI
person.familyNameIsmael
person.familyNameCristiano
person.givenNameAmin
person.givenNameMaria de Lurdes
person.identifier.ciencia-idE411-6006-5A01
person.identifier.orcid0000-0002-7346-5998
person.identifier.orcid0000-0002-9447-2855
person.identifier.ridA-8153-2013
person.identifier.ridG-2345-2012
person.identifier.scopus-author-id35203489500
person.identifier.scopus-author-id9238724800
project.funder.identifierhttp://doi.org/10.13039/501100001871
project.funder.identifierhttp://doi.org/10.13039/501100001871
project.funder.identifierhttp://doi.org/10.13039/501100001871
project.funder.identifierhttp://doi.org/10.13039/501100001871
project.funder.identifierhttp://doi.org/10.13039/501100001871
project.funder.nameFundação para a Ciência e a Tecnologia
project.funder.nameFundação para a Ciência e a Tecnologia
project.funder.nameFundação para a Ciência e a Tecnologia
project.funder.nameFundação para a Ciência e a Tecnologia
project.funder.nameFundação para a Ciência e a Tecnologia
rcaap.rightsrestrictedAccess
rcaap.typearticle
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