Monitoring the hydrogen bond net configuration and the dimensionality of aniline and phenyloxamate by adding 1H-pyrazole and isoxazole as substituents for molecular self-recognition

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dc.creatorWillian Xerxes Coelho Oliveira
dc.creatorWallace Doti do Pim
dc.creatorCarlos Basílio Pinheiro
dc.creatorYves Journaux
dc.creatorMiguel Julve
dc.creatorCynthia Lopes Martins Pereira
dc.date.accessioned2023-02-02T18:19:31Z
dc.date.accessioned2025-09-09T00:51:32Z
dc.date.available2023-02-02T18:19:31Z
dc.date.issued2019
dc.description.sponsorshipCNPq - Conselho Nacional de Desenvolvimento Científico e Tecnológico
dc.description.sponsorshipFAPEMIG - Fundação de Amparo à Pesquisa do Estado de Minas Gerais
dc.description.sponsorshipCAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
dc.description.sponsorshipOutra Agência
dc.identifier.doihttps://doi.org/10.1039/C9CE00215D
dc.identifier.issn1466-8033
dc.identifier.urihttps://hdl.handle.net/1843/49485
dc.languageeng
dc.publisherUniversidade Federal de Minas Gerais
dc.relation.ispartofCrystEngComm
dc.rightsAcesso Restrito
dc.subjectCristalografia
dc.subjectReconhecimento molecular
dc.subjectLigação de hidrogênio
dc.subjectAnilina
dc.subject.otherCrystal engineering
dc.subject.otherOxamic acid
dc.subject.otherHydrogen bond
dc.subject.otherAniline
dc.subject.otherPhenyloxamate
dc.subject.otherPyrazole
dc.subject.otherIsoxazole
dc.titleMonitoring the hydrogen bond net configuration and the dimensionality of aniline and phenyloxamate by adding 1H-pyrazole and isoxazole as substituents for molecular self-recognition
dc.typeArtigo de periódico
local.citation.epage2833
local.citation.issue17
local.citation.spage2818
local.citation.volume21
local.description.resumoThis work describes the synthesis and characterization of a new class of oxamic acid derivatives containing pyrazole and isoxazole as substituents to investigate their ability to form hydrogen bonds aiming at applying them in crystal engineering and molecular self-recognition. In this respect, we report a new synthesis of 2-(4-nitrophenyl)-1,3-propanedial (1) in high yield using SOCl2 as a chlorinating agent. The new oxamic esters 4-(1H-pyrazol-4-yl)phenylene-N-(ethyloxamate) (2d) and 4-(1,2-oxazol-4-yl)phenylene-N-(ethyloxamate) (3d) were prepared from 1. The synthetic route consists of the cyclisation of 1 either with hydrazine to afford 4-(-aminophenyl)-1H-pyrazole (2a) or with hydroxylamine to obtain the isoxazole-based molecule 4-(4-nitrophenyl)-1,2-oxazole (3a). The reduction of 2a and 3a was carried out in an acidic/tin solution to yield 4-(4-ammoniophenyl)-1H-pyrazol-2-ium trichlorostannate(II) chloride monohydrate (2b) and 4-(4-ammoniophenyl)-1,2-oxazole hexachlorostannate(IV) (3b). Basic extraction of 3b provided 4-(4-aminophenyl)-1,2-oxazole (3c). The reduction of 2a to 4-(4-aminophenyl)-1H-pyrazole (2c) was achieved by means of hydrazine associated with supported palladium on carbon. The condensation of 2c and 3c with ethyl chlorooxoacetate delivers oxamic esters 2d and 3d. In n-tetrabutylammonium hydroxide solution 2d is fully hydrolyzed, obtaining the n-tetrabutylammonium salt of 4-(1H-pyrazole-4-yl)phenylene-N-oxamate as a hemihydrate (2e). The low stability of isoxazole molecules in basic solutions was proved by crystallizing the n-tetrabutylammonium salt of 1-cyano-1-(4-nitrophenyl)-2-oxoethanide (3f) (obtained by cleavage of 3d with n-Bu4NOH) and preparing its conjugated acid 2-(4-nitrophenyl-3-oxopropanenitrile (3e). The structures of 2b, 3b, 3d and 2e were solved by single crystal X-ray diffraction techniques. The analysis of their crystal packing reveals hydrogen bond features compatible for all compounds as well as some differences depending on the pH of the crystallization solution and the presence or absence of the oxamate group due to the increase of hydrogen bond donors and acceptors.
local.identifier.orcidhttps://orcid.org/0000-0003-0722-5352
local.identifier.orcidhttps://orcid.org/0000-0002-0281-9592
local.identifier.orcidhttps://orcid.org/0000-0002-8674-1779
local.identifier.orcidhttps://orcid.org/0000-0003-1587-5718
local.identifier.orcidhttps://orcid.org/0000-0001-9006-8268
local.identifier.orcidhttps://orcid.org/0000-0002-3799-8092
local.publisher.countryBrasil
local.publisher.departmentICX - DEPARTAMENTO DE FÍSICA
local.publisher.departmentICX - DEPARTAMENTO DE QUÍMICA
local.publisher.initialsUFMG
local.url.externahttps://pubs.rsc.org/en/content/articlelanding/2019/CE/C9CE00215D

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