1-苯基-3-甲基-4-(6-氢-4-氨基-5-硫杂-2,3-吡嗪)吡唑啉酮光致变色超分子化合物的合成、结构与性能  

Synthesis, Crystal Structure and Photochromism Properties of 1-Phenyl- 3-methyl-4-(6-hydro-4-amino-5-sulfo-2,3-pyrazine)-pyrazole-5-one

作　　者：刘浪[1] 贾殿赠[1] 郁开北[2] 

机构地区：[1]新疆大学应用化学研究所,乌鲁木齐830046 [2]中国科学院成都有机化学研究所,成都610041

出　　处：《化学学报》2002年第3期493-498,共6页Acta Chimica Sinica

基　　金：国家自然科学基金(No .2 986 10 0 2 )资助项目

摘　　要：通过 1 苯基 3 甲基 4 氯乙酰基 吡唑啉酮 5 (PMCP)和氨基硫脲 (TSC)缩合 ,形成了一种含NNS六元杂环的光致变色化合物 (PMCP TSC) .利用元素分析 ,MS ,1HNMR ,IR和UV光谱进行了表征 .通过紫外可见光谱对它的光致变色性质进行了研究 ,测出了光致变色反应的动力学常数 .并用X射线单晶衍射仪测定了PMCP TSC变色后的晶体结构 ,该晶体属单斜晶系 ,具有P2 1/c空间群 ,a =0 .10 5 10 (2 )nm ,b =0 .15 0 6 1(3)nm ,c =0 .99370 (10 )nm ,β =10 7.890 (10 )° ,V =1.496 9(4 )nm3 ,Z =4,Dc=1.417Mg/m3 ,μ =0 .2 32mm-1,F(0 0 0 ) =6 72 ,R =0 .0 334 ,wR =0 .0 896 .结构分析表明 :其光致变色现象是由于它在溶剂与光的共同作用下发生了从醇式到酮式的异构化 .同时该化合物经分子间氢键形成二聚体 ,又通过甲醇与本体分子之间的氢键使化合物形成具有三维网络结构的超分子化合物 .A novel photochromic compound (PMCP-TSC) containing NNS hexa-atomic heterocycle was obtained by the reaction of 1-phenyl-3-methyl-4-chloroacetyl-pyrazolone-5 with thiosemicarbazine. The compound has been characterized by elemental analysis, MS, 1 H NMR spectra, IR spectrum and X-ray single crystal diffraction. The photochromic properties and photochemical kinetics of PMCP-TSC have been studied by UV spectra under irradiation of 365 nm light. The crystal belongs to monoclinic system with space group P2 1/c. The unit cell parameters are a=0.105 10(2) nm, b=0.150 61(3) nm, c=0.993 70(10) nm, β=107.890(10) o, V=1.496 9(4) nm 3, Z=4, D c=1.417 Mg/m 3,μ=0.232 mm -1,F(000)=672, R=0.033 4, wR=0.089 6. The crystal structure analysis of photocolored product showed that the photochromic phenomenon was due to photoisomerization from enol form to keto form. Three types of hydrogen bonds \[N(1)...O(1), N(1)...O(2), O(1)...O(2)\] lead to the formation of supramolecular compound with three-dimensional network structure.

关 键 词：光致变色 吡唑啉酮 超分子化合物 合成 晶体结构 氨基硫脲 

分 类 号：O626[理学—有机化学]