5 research outputs found
Conversion of 3-amino-4-arylamino-1H-isochromen-1-ones to 1-arylisochromeno[3,4-d][1,2,3]triazol-5(1H)-ones : synthesis, spectroscopic characterization and the structures of four products and one ring-opened derivative
The authors thank 'Centro de InstrumentaciĂłn CientĂfico-TĂ©cnica of Universidad de JaĂ©n' for data collection. The authors thank Universidad de Ciencias Aplicadas y Ambientales (UDCA), Universidad Nacional de Colombia, the ConsejerĂa de InnovaciĂłn, Ciencia y Empresa (Junta de AndalucĂa, Spain) and the Universidad de JaĂ©n for financial support.An efficient synthesis of 1-arylÂisochromeno[3,4-d][1,2,3]triazol-5(1H)-ones, involving the diazoÂtization of 3-amino-4-arylÂamino-1H-isochromen-1-ones in weakly acidic solution, has been developed and the spectroscopic characterization and crystal structures of four examples are reported. The molÂecules of 1-phenylÂisochromeno[3,4-d][1,2,3]triazol-5(1H)-one, C15H9N3O2, (I), are linked into sheets by a combination of C—Hâ‹ŻN and C—Hâ‹ŻO hydrogen bonds, while the structures of 1-(2-methylÂphenÂyl)isochromeno[3,4-d][1,2,3]triazol-5(1H)-one, C16H11N3O2, (II), and 1-(3-chloroÂphenÂyl)isochromeno[3,4-d][1,2,3]triazol-5(1H)-one, C15H8ClN3O2, (III), each contain just one hydrogen bond which links the molÂecules into simple chains, which are further linked into sheets by Ď€-stacking interÂactions in (II) but not in (III). In the structure of 1-(4-chloroÂphenÂyl)isochromeno[3,4-d][1,2,3]triazol-5(1H)-one, (IV), isomeric with (III), a combination of C—Hâ‹ŻO and C—Hâ‹ŻĎ€(arene) hydrogen bonds links the molÂecules into sheets. When comÂpound (II) was exposed to a strong acid in methanol, quÂantiÂtative conversion occurred to give the ring-opened transesterification product methyl 2-[4-hyÂdroxy-1-(2-methylÂphenÂyl)-1H-1,2,3-triazol-5-yl]benzoate, C17H15N3O3, (V), where the molÂecules are linked by paired O—Hâ‹ŻO hydrogen bonds to form centrosymmetric dimers.Publisher PDFPeer reviewe
Synthesis of 5-(arylmethylideneamino)-4-(1<i>H</i>-benzo[<i>d</i>]imidazol-1-yl)pyrimidine hybrids:synthetic sequence and the molecular and supramolecular structures of two intermediates and three final products
Funding: Funding for this research was provided by: Spanish Ministerio de Ciencia, InnovacĂon, y Universidades (R&D project No. RTI2018-098560-B-C22), co-financed by the FEDER funds of the European Union.A concise and versatile synthesis of 5-(arylÂmethylÂideneÂamino)-4-(1H-benzo[d]imidazol-1-yl)pyÂrimiÂdines has been developed, starting from 4-(1H-benzo[d]imidazol-1-yl)pyÂrimiÂdines, and we report here the synthesis and spectroscopic and structural characterization of three such products, along with those of two interÂmediates in the reaction pathway. The interÂmediates 4-[2-(4-chloroÂphenÂyl)-1H-benzo[d]imidazol-1-yl]-6-methÂoxyÂpyÂrimiÂdine-2,5-diÂamine, (II), and 4-[2-(4-bromoÂphenÂyl)-1H-benzo[d]imidazol-1-yl]-6-methÂoxyÂpyÂrimiÂdine-2,5-diÂamine, (III), crystallize as the isostructural monohydrates C18H15ClN5O·H2O and C18H15BrN5O·H2O, respectively, in which the components are linked into complex sheets by O—H...N and N—H...O hydroÂgen bonds. In the product (E)-4-methÂoxy-5-[(4-nitroÂbenzylÂidene)amino]-6-[2-(4-nitroÂphenÂyl)-1H-benzo[d]imidazol-1-yl]pyrimidin-2-amine, which crystallizes as a 1:1 solvate with dimethyl sulfoxide, C25H18N8O5·C2H6OS, (IV), inversion-related pairs of the pyÂrimiÂdine component are linked by N—H...N hydroÂgen bonds to form cyclic centrosymmetric R22(8) dimers to which pairs of solvent molÂecules are linked by N—H...O hydroÂgen bonds. (E)-4-MethÂoxy-5-[(4-methylÂbenzylÂidene)amino]-6-[2-(4-methylÂphenÂyl)-1H-benzo[d]imidazol-1-yl]pyrimidin-2-amine, C27H24N6O, (V), crystallizes with Z′ = 2 and the molÂecules are linked into a three-dimensional framework structure by a combination of N—H...N, C—H...N and C—H...Ď€(arene) hydroÂgen bonds. The analogous product (E)-4-methÂoxy-5-[(4-chloroÂbenzylÂidene)amino]-6-[2-(4-methylÂphenÂyl)-1H-benzo[d]imidazol-1-yl]pyrimidin-2-amine, C26H21ClN6O, (VI), crystallizes from dimethyl sulfoxide in two forms: one, denoted (VIa), is isostructural with (V), and the other, denoted (VIb), crystallizes with Z′ = 1, but as an unknown solvate in which the pyÂrimiÂdine molÂecules are linked by N—H...N hydroÂgen bonds to form a ribbon containing two types of centrosymmetric ring.Publisher PDFPeer reviewe
A concise and efficient synthesis of amino-substituted (1H-benzo[d]imidazol-1-yl)pyrimidine hybrids: Synthetic sequence and the molecular and supramolecular structures of six examples
A concise and efficient synthesis of a series of amino-substituted benzimidazole-pyrimidine hybrids has been developed, starting from the readily available N 4-(2-aminophenyl)-6-methoxy-5-nitrosopyrimidine-2,4-diamine. In each of N 5-benzyl-6-methoxy-4-(2-phenyl-1H-benzo[d]imidazol-1-yl)pyrimidine-2,5-diamine, C25H22N6O, (I), 6-methoxy-N 5-(4-methoxybenzyl)-4-[2-(4-methoxyphenyl)-1H-benzo[d]imidazol-1-yl]pyrimidine-2,5-diamine, C27H26N6O3, (III), 6-methoxy-N 5-(4-nitrobenzyl)-4-[2-(4-nitrophenyl)-1H-benzo[d]imidazol-1-yl]pyrimidine-2,5-diamine, C25H20N8O5, (IV), the molecules are linked into three-dimensional framework structures, using different combinations of N-H⋯N, N-H⋯O, C-H⋯O, C-H⋯N and C-H⋯π hydrogen bonds in each case. Oxidative cleavage of 6-methoxy-N 5-(4-methylbenzyl)-4-[2-(4-methylphenyl)-1H-benzo[d]imidazol-1-yl]pyrimidine-2,5-diamine, (II), with diiodine gave 6-methoxy-4-[2-(4-methylphenyl)-1H-benzo[d]imidazol-1-yl]pyrimidine-2,5-diamine, which crystallized as a monohydrate, C19H18N6O·H2O, (V), and reaction of (V) with trifluoroacetic acid gave two isomeric products, namely N-{5-amino-6-methoxy-6-[2-(4-methylphenyl)-1H-benzo[d]imidazol-1-yl]pyrimidin-2-yl}-2,2,2-trifluoroacetamide, which crystallized as an ethyl acetate monosolvate, C21H17F3N6O2·C4H8O2, (VI), and N-{2-amino-6-methoxy-4-[2-(4-methylphenyl)-1H-benzo[d]imidazol-1-yl]pyrimidin-5-yl}-2,2,2-trifluoroacetamide, which crystallized as a methanol monosolvate, C21H17F3N6O2·CH4O, (VIIa). For each of (V), (VI) and (VIIa), the supramolecular assembly is two-dimensional, based on different combinations of O-H⋯N, N-H⋯O, N-H⋯N, C-H⋯O and C-H⋯π hydrogen bonds in each case. Comparisons are made with some related structures
Synthesis of new 1,2-diaryl[2]benzopyrano[3,4-d]imidazol-5(1H)-one derivatives mediated by ceric ammonium nitrate
A concise synthesis of a highly substituted 6-(1H-benzimidazol-1-yl)-5-nitrosopyrimidin-2- amine: Synthetic sequence and the molecular and supramolecular structures of one product and two intermediates
A concise and efficient synthesis of 6-benzimidazolyl-5-nitrosopyrimidines has been developed using Schiff base-type intermediates derived from N4-(2-aminophenyl)-6-methoxy-5-nitrosopyrimidine-2,4-diamine. 6-Methoxy-N4-{2-[(4-methylbenzylidene)amino]phenyl}-5-nitrosopyrimidine-2,4-diamine, (I), and N4-{2-[(ethoxymethylidene)amino]phenyl}-6-methoxy-5-nitrosopyrimidine-2,4-diamine, (III), both crystallize from dimethyl sulfoxide solution as the 1:1 solvates C19H18N6O2·C2H6OS, (Ia), and C14H16N6O3·C2H6OS, (IIIa), respectively. The interatomic distances in these intermediates indicate significant electronic polarization within the substituted pyrimidine system. In each of (Ia) and (IIIa), intermolecular N-H…O hydrogen bonds generate centrosymmetric four-molecule aggregates. Oxidative ring closure of intermediate (I), effected using ammonium hexanitratocerate(IV), produced 4-methoxy-6-[2-(4-methylphenyl-1H-benzimidazol-1-yl]-5-nitrosopyrimidin-2-amine, C19H16N6O2, (II) [Cobo et al. (2018). Private communication (CCDC 1830889). CCDC, Cambridge, England], where the extent of electronic polarization is much less than in (Ia) and (IIIa). A combination of N–H…N and C–H…O hydrogen bonds links the molecules of (II) into complex sheets