Departamento de Química Inorgánica y Orgánica, Universidad de Jaén, 23071 Jaén, Spain.
Departamento de Química, Universidad Nacional de Colombia, Cuidad Universitaria, Carrera 30, No. 45-03, Edificio 451, Bogotá, Colombia.
Acta Crystallogr C Struct Chem. 2023 Jun 1;79(Pt 6):227-236. doi: 10.1107/S2053229623003728. Epub 2023 May 5.
A concise and versatile synthesis of 5-(arylmethylideneamino)-4-(1H-benzo[d]imidazol-1-yl)pyrimidines has been developed, starting from 4-(1H-benzo[d]imidazol-1-yl)pyrimidines, and we report here the synthesis and spectroscopic and structural characterization of three such products, along with those of two intermediates in the reaction pathway. The intermediates 4-[2-(4-chlorophenyl)-1H-benzo[d]imidazol-1-yl]-6-methoxypyrimidine-2,5-diamine, (II), and 4-[2-(4-bromophenyl)-1H-benzo[d]imidazol-1-yl]-6-methoxypyrimidine-2,5-diamine, (III), crystallize as the isostructural monohydrates CHClNO·HO and CHBrNO·HO, respectively, in which the components are linked into complex sheets by O-H...N and N-H...O hydrogen bonds. In the product (E)-4-methoxy-5-[(4-nitrobenzylidene)amino]-6-[2-(4-nitrophenyl)-1H-benzo[d]imidazol-1-yl]pyrimidin-2-amine, which crystallizes as a 1:1 solvate with dimethyl sulfoxide, CHNO·CHOS, (IV), inversion-related pairs of the pyrimidine component are linked by N-H...N hydrogen bonds to form cyclic centrosymmetric R(8) dimers to which pairs of solvent molecules are linked by N-H...O hydrogen bonds. (E)-4-Methoxy-5-[(4-methylbenzylidene)amino]-6-[2-(4-methylphenyl)-1H-benzo[d]imidazol-1-yl]pyrimidin-2-amine, CHNO, (V), crystallizes with Z' = 2 and the molecules are linked into a three-dimensional framework structure by a combination of N-H...N, C-H...N and C-H...π(arene) hydrogen bonds. The analogous product (E)-4-methoxy-5-[(4-chlorobenzylidene)amino]-6-[2-(4-methylphenyl)-1H-benzo[d]imidazol-1-yl]pyrimidin-2-amine, CHClNO, (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 pyrimidine molecules are linked by N-H...N hydrogen bonds to form a ribbon containing two types of centrosymmetric ring.
已开发出一种简洁且通用的 5-（芳基亚甲基氨基）-4-（1H-苯并[d]咪唑-1-基）嘧啶的合成方法，该方法以 4-（1H-苯并[d]咪唑-1-基）嘧啶为起始原料，我们在此报告了三种此类产物的合成以及光谱和结构表征，同时还报告了反应途径中两种中间体的合成。中间体 4-[2-（4-氯苯基）-1H-苯并[d]咪唑-1-基]-6-甲氧基嘧啶-2,5-二胺，（II）和 4-[2-（4-溴苯基）-1H-苯并[d]咪唑-1-基]-6-甲氧基嘧啶-2,5-二胺，（III）分别结晶为等结构的一水合物 CHClNO·HO 和 CHBrNO·HO，其中各组分通过 O-H···N 和 N-H···O 氢键连接成复杂的薄片。产物（E）-4-甲氧基-5-[(4-硝基苄基)氨基]-6-[2-(4-硝基苯基）-1H-苯并[d]咪唑-1-基]嘧啶-2-胺，（IV）以 1:1 的比例与二甲基亚砜形成溶剂化物 CHNO·CHOS，（IV）中嘧啶部分的反转相关对通过 N-H···N 氢键连接形成环状中心对称的 R(8)二聚体，而对溶剂分子则通过 N-H···O 氢键连接。（E）-4-甲氧基-5-[(4-甲基苄基)氨基]-6-[2-(4-甲基苯基）-1H-苯并[d]咪唑-1-基]嘧啶-2-胺，CHNO，（V）以 Z'=2 结晶，分子通过 N-H···N、C-H···N 和 C-H···π(芳烃)氢键的组合连接成三维框架结构。类似的产物（E）-4-甲氧基-5-[(4-氯苄基)氨基]-6-[2-(4-甲基苯基）-1H-苯并[d]咪唑-1-基]嘧啶-2-胺，CHClNO，（VI）从二甲基亚砜中以两种形式结晶：一种形式，记为（VIa），与（V）结构相同，另一种形式，记为（VIb），结晶为 Z'=1，但作为未知溶剂化物结晶，其中嘧啶分子通过 N-H···N 氢键连接形成包含两种类型中心对称环的带状物。
