含(1-芳乙酰胺基-2-叔胺基)乙烷结构的六氢-1H-1，4- 二氮卓类新化合物的合 成(Ⅱ)

设计并合成了2-[1-(4-(N-苯基-N-丙酰基)氨基)哌啶基]甲基-六氢-1H-1,4-二氮卓7.由3经还原、氯取代、胺取代、胺脱苄反应得到了7.7经单酰化反应得到了8.8经酰化反应后得到了11个带有(1-芳乙酰胺基-2-叔氨基)乙烷结构的六氢-1H-1,4-二氮卓类目标化合物(9a～9g,10a～10d)。     

含(1-芳乙酰胺基-2-叔胺基)乙烷结构的六氢-1H-1，4- 二氮卓类新化合物的合 成(Ⅱ)

设计并合成了2-[1-(4-(N-苯基-N-丙酰基)氨基)哌啶基]甲基-六氢-1H-1,4-二氮卓7.由3经还原、氯取代、胺取代、胺脱苄反应得到了7.7经单酰化反应得到了8.8经酰化反应后得到了11个带有(1-芳乙酰胺基-2-叔氨基)乙烷结构的六氢-1H-1,4-二氮卓类目标化合物(9a～9g,10a～10d)。     

5-取代氨基-12-取代苯并[c]菲啶衍生物的合成、晶体结构及生物活性

为了寻找新的高活性农药, 利用2-甲基苯甲腈与不同的醛反应, 再通过2,3-二氯-5,6-二氰基-1,4-苯醌(DDQ)脱氢或NaH和CH3I氮甲基化, 合成了3个系列共18个5-取代氨基-12-取代苯并[c]菲啶衍生物, 其中15个是未见文献报道的化合物. 它们的结构均经1H NMR, 13C NMR, IR和高分辨质谱表征; 用X射线衍射测定了化合物5-氨基-12-(4-二乙氨基苯基)-11,12-2H-苯并[c]菲啶盐酸盐(3c)的晶体结构. 初步的生物活性测试结果表明, 部分化合物具有一定的杀菌活性和促进黄瓜子叶生根活性.     

新颖3,4-二氢-苯并[b]氧杂棘-5(2H)-酮类化合物的合成以及蛋白酪氨酸激酶抑制活性研究

通过合成得到了一系列新颖的苯并[b]氧杂棘-5(2H)-酮类化合物单晶,结构经~1HNMR,~(13)CNMR和HREIMS确证,E-7-[(2,5-二羟基苯基)甲亚基]氨基-3,4-二氢-苯并[b]氧杂棘-5(2H)-酮(8k)和E-7-[(2,3,4-三羟基苯基)亚基]氨基-3,4-二氢-苯并[b]氧杂棘-5-(2H)-酮(8n)的结构经单晶X衍射方法进一步确证.系统测试了化合物对蛋白酪氨酸激酶(PTKs),如ErbB1,ErbB2,c-Met,ALK,FGFR1,RET和KDR等的抑制活性,结果表明含有邻苯二酚片段的化合物对蛋白酪氨酸激酶具有显著的抑制活性,其中E-7-[(3,4-二羟基苯基)甲亚基]氨基-3,4-二氢-苯并[b]氧杂棘-5(2H)-酮(8i)对ErbB1和ErbB2的IC50分别为1.0和0.33μmol/L,8n对RET的IC_(50)为0.7μmol/L,7-[(3,4-二羟基苯基)甲基]氨基-2,3,4,5-四氢-苯并[b]氧杂棘-5-醇(10b)对ErbB2的IC_(50)为1.02μmol/L.     

1,3,4-噁二唑键联二芳基乙烯化合物的合成及性质

将1,3,4-噁二唑基团引入二芳基乙烯分子中, 合成了2种新的二芳基乙烯类光致变色化合物1-氰基-2-(2H-5-苯基-1,3,4-噁二唑)-1,2-二(2,4,5-三甲基-3-噻吩)乙烯(3)和1,4-二{[1-氰基-2-(2H-5-苯基-1,3,4-噁二唑)-1,2-二(2,4,5-三甲基-3-噻吩)乙烯]-1,3,4-噁二唑}苯(4). 通过IR, NMR, MS和元素分析对化合物进行了结构表征, 并研究了其UV-Vis吸收、荧光发射、动力学特性和抗疲劳性质. 实验结果表明, 化合物[STHZ]3[STBZ]和[STHZ]4[STBZ]具有良好的光致变色性质, 光致变色闭环反应为零级反应, 开环反应为一级反应.     

Y型三苯胺生色分子的二阶极化率

通过Knoevenagel反应合成了3个Y型三苯胺生色分子N,N-二{4-[2-(2-苯并噻唑基)乙烯基]苯基}苯胺(BBtVPA)、N,N-二{4-[1-(2-苯并噻唑基)-1,3-丁二烯-4-基]苯基}苯胺(BBtBPA)和N,N-二{4-[1-(2-二氰基甲叉-3-氰基-5,5-二甲基-2,5-二氢-4-呋喃基)-1,3-丁二烯-4-基]苯基}苯胺(BCfBPA), 以及4个一维偶极分子4-[2-(2-苯丙噻唑基)乙烯基]-N,N-二苯基苯胺(BtVPA)、1-(2-苯并噻唑基)-4-[4-(N,N-二苯基)氨基]苯基-1,3-丁二烯(BtAPB)、1-[(2-二氰基甲叉-3-氰基-5,5-二甲基-2,5-二氢)-4-呋喃基]-4-[4-(N,N-二苯基氨基)]苯基-1,3-丁二烯(CfAPB)和4-[2-(2-二氰基甲叉-3-氰基-5,5-二甲基-2,5-二氢呋喃-4-基)乙烯基]-N,N-二苯基苯胺(CfVPA). 测定了生色分子的紫外吸收和荧光性质, 在二氯甲烷中, Y型分子BBtVPA, BBtBPA和BCfBPA的最大吸收波长分别为425, 443和613 nm, 比偶极分子红移了约30 nm, Y型分子BBtVPA和BBtBPA的最大荧光发射峰分别位于516和558 nm, 比偶极分子稍有红移. 根据双能级模型理论, 用溶致变色法测定了生色分子的二阶非线性极化率(β), Y型分子BBtVPA, BBtBPA和BCfBPA的β0分别为40×10-30, 64×10-30和238×10-30 esu, 比相应的偶极分子分别提高了0.9~2.8倍. 结果表明, 提高吸电子基团强度, 增大共轭体系有助于获得更大的β值.     

含(1-芳乙酰胺基-2-叔胺基)乙烷结构的六氢-1H-1,4-二氮革类新化合物的合成(Ⅱ)

设计并合成了2-[1-(4-(N-苯基-N-丙酰基)氨基)哌啶基]甲基-六氢-1H-1,4-二氮 7.由3经还原、氯取代、胺取代、胺脱苄反应得到了7.7经单酰化反应得到了8.8经酰化反应后得到了11个带有(1-芳乙酰胺基-2-叔氨基)乙烷结构的六氢-1H-1,4-二氮类目标化合物(9a～9g,10a～10d).     

含1,2,3-三氮唑结构的1,5-苯并硫氮杂[艹卓]的合成及其抑真菌活性

设计合成了三类含1,2,3-三氮唑结构的1,5-苯并硫氮杂[艹卓]化合物3-(1H-1,2,3-三氮唑)-4-芳基-2,5-二氢-1,5-苯并硫氮杂[艹卓](5a^5f)、3-(2H-1,2,3-三氮唑)-4-芳基-2,3-二氢-1,5-苯并硫氮杂[艹卓](6a^6f)和3-(1H-1,2,3-三氮唑)-4-芳基-2,3,4,5-四氢-1,5-苯并硫氮杂[艹卓](7a^7f).研究了中间体及目标产物的合成条件,分离出其中两个副产物并进行了结构确定.目标产物的抑真菌活性测试表明,化合物5a^5f对真菌具有良好的抑制作用,对新生隐球菌的抑制效果尤为突出.初步抑真菌构效关系研究表明, 1H-1,2,3-三氮唑环和C=C双键是化合物5a^5f抑真菌活性的关键官能团.     

敏化染料分子长径比对太阳能电池性能的影响

采用同一系列但分子长径比不同的3种染料:2-氰基-3-[2-[4-{2-[4-N,N-二(4-甲基苯基)氨基苯基]乙烯基}-苯基氨基)-嘧啶-5-取代基]-丙烯酸(MTPA-Pyc)、2-氰基-3-(4-{2-[4-N,N-二(4-甲基苯基)氨基苯基]乙烯基}-苯基)-丙烯酸(MTPAcc)和2-氰基-3-[4-N,N-二(4-甲基苯基)氨基苯基]-丙烯酸(MTPAc),研究了在不同吸附溶剂中3种染料分子在Ti O2上的吸附量和聚集态,探讨了敏化染料分子长径比对染料敏化太阳电池性能的影响.结果表明,MTPAcc具有最合适的分子长径比,其在Ti O2表面的吸附量及应用的光电性能最高;吸附溶剂的极性增大有利于提高染料的吸附量,但也会影响染料分子的聚集态.当以四氢呋喃为吸附溶剂时,MTPAcc在Ti O2表面的吸附量大且不发生聚集,对应的敏化太阳能电池器件在所有结果中表现最好,在490 nm处的单色光光电转化效率(IPCE)极值达到84%,总光电转化效率(η)达到5.72%.     

含二氮杂萘砌块化合物的荧光性能构效关系研究及应用

通过文献方法合成了具有较好平面共轭结构和较高电子云密度的5-氨基-2-芳基-3H-色烯[4,3,2-de][1,6]并二氮杂萘-4-腈(4)和5-氨基-2-芳基-3H-喹啉[4,3,2-de][1,6]并二氮杂萘-4-腈(6),研究了稠合环数、荧光助色团数量以及取代基类型对产物发光性能的影响,探索了其结构与发光性能之间的关系.在发光性能构效关系指导下初步探究了化合物4对9种金属离子的识别,并从产物中筛选得到了具有进一步研究价值的、具开发为有机荧光材料潜质的产物.     

Synthèses de 1,2,4-triazolo[4,3-d][1,4]diazépines et de 1,2,4-oxadiazolo[4,5-d][1,4]diazépines par cycloaddition dipolaire-1,3

We report here a one-step synthesis of the 4,5,6,7-tetrahydro-1H- 1,2,4,-triazolo[4,3-d][1,4]diazepine, 4-6, and 1,2,4-oxadiazolo[4,5-d][1,4]-diazepine, 7-10, by 1,3-dipolar cycloaddition of nitrile imines and nitrile oxides with 2,3-dihydro-H-1,4-diazepine, 1. In all cases these cycloaddition are peri- and regioselectives (the C ? N bond is sole affected) and occures with high yields. Structure and conformations of cycloadducts have been assigned by means of nmr analysis     

Synthesis and some heterocyclization reactions of new diethyl (1,1-difluoro-3,3-dicyano-2-trifluoromethylallyl)phosphonate and ethyl 3,3-dicyano-2-[(diethoxyphosphoryl)difluoromethyl]acrylate

A new CF₂X-analogue of 1,1-bis(trifluoromethyl)-2,2-dicyanoethylene (X = P(O)(OEt)₂), diethyl (1,1-difluoro-3,3-dicyano-2-trifluoromethylallyl)phosphonate, has been synthesized from diethoxyphosphoryl pentafluoroacetone 1. A similar phosphoryl analogue of ethyl 3,3-dicyano-2-trifluoromethylacrylate, ethyl 3,3-dicyano-2-[(diethoxyphosphoryl)difluoromethyl]acrylate, has been obtained from ethyl 3-(diethoxyphosphoryl)-3,3-difluoro-2-oxopropionate 2. By heterocyclization of these new ethylenes with 3-methyl-2-pyrazoline-5-ones, 3(5)-aminopyrazoles, dimedone, 2-aminopyridines, 1-aryl-3-methyl-5-aminopyrazoles, 1,3,3-trimethylisoquinolines, as well as by condensation with anilines and ketones, the difluoromethylphosphonate-substituted derivatives of 1,4-dihydropyrano[2,3-c]pyrazole, 4,5-dihydropyrazolo[1,5-a]pyrimidine, 5,6,7,8-tetrahydro-4H-chromene, 2H-pyrido[1,2-a]pyrimidine, 4,7-dihydro-1H-pyrazolo[3,4-b]pyridine, 1,4-dihydropyridine, 4,5,6,7-tetrahydro-1H-[1]pyrindine, 1,4,5,6,7,8-hexahydroquinoline, and 6,7-dihydro-2H-pyrido[2,1-a]isoquinoline have been obtained in one stage.     

Quinazolincs and 1,4-benzodiazepines. LXXXVI. The synthesis of imidazothienodiazepines and imidazopyrazolodiazepines

The thieno[3,2-e][1,4]diazepin-2-one ( 1a ), the thieno[2,3-e] [ 1,4] diazepin-2-one ( 1b ), the pyrazolo[3,4-e][1,4]diazepin-2-one ( 1c ) and a chloro analog of 1b , compound 1d , were each converted to derivatives of the novel tricyclic ring systems 4H-imidazo[1,5-a]thieno[2,3-f] [1,4]-diazepine, 4Himidazo[1,5a]thieno[2,3f][1,4]diazepine and 4H-imidazo[ 1,5-a]pyrazolo[4,3-f]-[1,4]diazepine. Depending on the substituents desired on the imidazo ring, two different synthetic pathways were employed.     

Promoted colorimetric response of spirooxazine derivative: a simple assay for sensitive mercury(II) detection

Research on Chemical Intermediates - A spirooxazine derivative 1,3-dihydro-1,3,3-trimethyl-spiro[2-H-indole-2-2′-[2H-1,4] oxazino [2,3-f] [1, 10] phenanthroline] (compound 1) was explored as...     

Benzofused tricycles based on 2-quinoxalinol

This paper describes our recent efforts to synthesize novel compound scaffolds integrating 2-quinoxalinol with privileged structures of 1,3-dihydro-benzoimidazol-2-one, 1,3-dihydro-benzoimidazole-2-thione, 3-hydroxy-1H-quinoxalin-2-one, 2H-benzo[1,4]oxazin-3-ol, 2H-benzo[1,4]thiazin-3-ol, and 1,3,4,5-tetrahydro-benzo[1,4]diazepin-2-one, respectively. Eight novel benzofused tricycles and their substituent diversity points were developed. These include pyrazino[2,3-g]quinoxaline-2,8-diol (I), 3-hydroxy-6,8,9,10-tetrahydro-1,4,6,10-tetraaza-cyclohepta[b]naphthalen-7-one (II), 6-hydroxy-4H-1-oxa-4,5,8-triaza-anthracen-3-one (III), 6-hydroxy-4H-1-thia-4,5,8-triaza-anthracen-3-one (IV), 6-hydroxy-1,1-dioxo-1,4-dihydro-2H-1lambda(6)-thia-4,5,8-triaza-anthracen-3-one (V), 6-hydroxy-1,3-dihydro-imidazo[4,5-g]quinoxalin-2-one (VI), 6-hydroxy-1,3-dihydro-imidazo[4,5-g]quinoxaline-2-thione (VII), and 7-hydroxy-1,4-dihydro-pyrazino[2,3-g]quinoxaline-2,3-dione (VIII). This strategy of integrating two benzofused privileged structures into one molecule may provide a greater chance for the discovery of novel lead compounds.     

二氰基乙烯基并三噻吩的光谱行为

本文设计合成了两种二氰基乙烯基并三噻吩化合物,即2-二氰基乙烯基二噻吩并[3,2-b:2’,3-’d]噻吩(DCTT)与2-二氰基乙烯基二噻吩并[2,3-b:3’,2-’d]噻吩(DCST).研究了介质极性对吸收与发射光谱行为的影响,考察了化合物的分子结构与其发光能力的关系.溶剂效应显示化合物DCST随介质的极性增加,分子内电荷转移态(ICT)的荧光发射峰位红移现象更为明显,展示出较大的Stokes位移.化合物DCTT随介质的极性增加,发光行为表现出负的溶致变色效应,与"能级邻近效应"有关.溶剂效应说明了DCTT分子中并三噻吩部分给出电子的能力较弱,而DCST分子中的并三噻吩部分给出电子的能力较强,是导致二者ICT态的发光能力的差异的主要原因.     

Electrochemical and spectral properties of thienylene-polyparaphenylenevinylene derivative stereoisomers

Four new compounds: 1,4-dimetoxy-2,5-bis[2-(tien-2-yl)ethenyl]benzene), 1,4-dietoxy-2,5-bis[2-(tien-2-yl)ethenyl]benzene), 1,4-isopropyloxy-2,5-bis[2-(tien-2-yl)ethenyl]benzene) and 1,4-dietoksy-2,5-bis[2-(5-methylthiophen-2-yl)ethenyl]benzene are synthesized. Three steroisomers ZZ, EZ and EE are isolated from the reaction mixture for the first two of them. Third compound is fully converted to the most stable EE form. Polymerization of all isomers leads to identical polymeric product. Mechanism of polymerization is recognized by using model molecule with methyl substituents blocking α-, α′-sites. All seven stereoisomers have photoluminescent properties. Detailed spectral and electrochemical studies reveal isomerization phenomena during oxidation or at light exposure. Published in Russian in Elektrekhimiya, 2006, Vol. 42, No. 12, pp. 1401–1408. Based on the report delivered at the 8th International Frumkin Symposium “Kinetics of the Electrode Processes.” October 18–22, 2005, Moscow. The text was submitted by the authors in English.     

Synthesis of Fluoroalkylated Heterocycles via the Reaction of 3-(1-Hydropolyfluoroalkenyl)-1-oxo-2,4,1-benzoxazines with Dinucleophilic Reagents

The reaction of 3-(1-hydropolyfluoroalkenyl)-1-oxo-2,4,1-benzoxazines 1 with some dinucleophiles was inves-tigated.7-Fluoroalkyl-2,3-dihydro-1,4-diazepine[1,2-d]quinazolin-11-ones 2,2-fluoroalkylisoxazolo[3,2-b]quin-azolin-9-ones 3 and 2-fluoroalkylbenzoimidazoles 4 were obtained from the reaction of 1 with 1,2-diaminoethane,hydroxylamine hydrochloride and 1,2-diaminobenzene respectively.     

大环配体过渡金属配合物——Ⅵ.四(对-二硫杂环己烯)四氮杂卟啉钒(Ⅳ)、锰(Ⅱ)和钼(Ⅴ)配合物的合成与表征

d过渡金属含硫四氮杂卟啉配合物,是一类新型功能性配合物,因其具有比金属卟啉、金属酞菁更为优异的光电和催化特性,故近十多年来颇受重视。我们对该类金属配合物及其自由配体的合成、性质和某些功能,正在进行广泛和深入的研究。本文简要报道标题配合物的合成、元素分析,红外光谱、电子光谱和电子顺磁共振谱的表征。