Synthesis and optical behaviors of 2-(9-phenanthrenyl)-, 2-(9-anthryl)-, and 2-(1-pyrenyl)-1-alkylimidazole homologues

Eight 2-(9-phenanthrenyl)-, 2-(9-anthryl)- and 2-(1-pyrenyl)-1-alkyl-benzimidazole compounds, three 2-(9-anthryl)-1-alkylphenanthroimidazole compounds and five 4,5-diphenyl-1-alkyl-2-(9-anthryl)imidazole compounds were synthesized by alkylation reactions of the corresponding benzimidazole, phenanthroimidazole or imidazole compounds. 2-(10-Bromo-9-anthryl)-1-alkyl-benzimidazole compounds were prepared by bromination reaction of 2-(9-anthryl)-1-alkylbenzimidazole compounds. All the synthesized compounds were characterized by elemental analysis, ¹H NMR, ¹³C NMR, MS or HRMS; their absorption coefficients (), maximum absorption λ_amax, fluorescence emission maximum λ_em, Stokes shifts and fluorescence quantum yields (Φ_F) in ethyl acetate were determined; their fluorescent lifetimes (T₁ and T₂) were measured in ethyl acetate and in solid state, respectively. The crystal structure of 2-(9-anthryl)-1-n-butyl-4,5-diphenylimidazole (12a) was determined to be triclinic, space group P-1 types, using single crystal X-ray crystallography technique. The results showed that these compounds exhibited moderate fluorescence-emission abilities and higher solubility in most organic solvents than their corresponding starting materials. The relationships between the optical behaviors and structures for these compounds were discussed.     

Photochemical Properties of 1-(9-Phehanthryl)-2-(2-Quinolyl)ethylene

Spectral and photochemical properties of 1-(9-phehanthryl)-2-(2-quinolyl)ethylene (9Ph2QE) in neutral and protonated forms have been investigated. It has been found that both isomers of 9Ph2QE are photoactive. The quantum yield of trans–cis photoisomerization (? _tc = 0.47) in the neutral form is typical of the diabatic photoisomerization; on passing to the protonated form, ? _tc increases up to 0.70. Thus, the double annelation of the 2-styrylquinoline phenyl group to form 9Ph2QE makes it possible to conserve the α-effect, which consists in an increase in the quantum yield to ? _tc > 0.5 on passing from the neutral to protonated form, whereas the effect disappears for other types of annelation (naphthylquinolylethylenes, 1-(9-anthryl)-2-(2-quinolyl)ethylene).     

Photochemical properties of 1-(9-Anthryl)-2-(2-Quinolyl)ethylene

Spectral and photochemical properties of 1-(9-anthryl)-2-(2-quinolyl)ethylene (9A2QE) in neutral and protonated forms have been studied experimentally and by quantum-chemical methods. It has been found that the quantum yield of trans-cis photoisomerization (φ_tc) has values of φ_tc < 0.5 typical of the diabatic photoisomerization for both forms of 9A2QE. A comparison of this data with the results of the study of other aza-diarylethylenes containing the 2-styrylquinoline (2SQ) moiety has led to the general conclusion that the increase in the π-system in 2SQ upon fusion of the benzene rings results in the disappearance of the α-effect, which lies in the fact that the quantum yield increases upon going from the neutral to protonated form up to the values φ_tc > 0.5, which exceeds the limiting value for the diabatic photoisomerization.     

Synthesis, Crystal Structure and Theoretical Studies of (E)-1-((9-(2-(2-methoxyethoxy)ethyl)-9H-carbazol-3-yl)methylene)thiosemicarbazide

A novel thiosemicarbazide derivative, (E)-1-(9-(2-(2-methoxyethoxy)ethyl)-9H-carbazol-3-yl) methylene)-thiosemicarbazide (CMT), was synthesized and structurally characterized by IR, 1H-NMR, EI-MS and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 14.769(5), b = 8.279(5), c = 17.166(5) , β = 114.391(5)°, V = 1911.6(14) 3, Z = 4, F(000) = 784, Dc = 1.287 g/m3, Mr = 370.47, μ = 0.190 mm-1, the final R = 0.0390 and wR = 0.1358 for 1446 observed reflections with Ⅰ > 2σ(Ⅰ). The UV-vis absorption spectra of CMT were explained based on quantum chemical calculations, using time dependent density functional theory (TD-DFT) at the B3LYP/6-31G (d) level.     

1-(2′-triethylsilylethyl)-, 1-(2′-triethylsilylvinyl)-, and 1′-(2′-triethylsilylethynyl)-silatranes

Conclusions The reaction of 2-triethylsilyl-substituted ethyl-, vinyl-, and ethynyltrialkoxysilanes with triethanolamine gave 1-substituted silatranes possessing neurotropic activity.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2611–2613, November, 1984.     

Synthesis and properties of 1-(2-bromoethyl)-, 1-(2-alkoxyethyl)- and 1-(2-dialkylaminoethyl)2-alkylpyrroles

The reaction of 3-chloropropenyl alkyl ketones or 2,3-dichloropropyl alkyl ketones with 2-substituted ethylamine derivatives leads to the formation of the hitherto unknown 1-(2-R-ethyl)-2-alkylpyrroles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1047–1049, August, 1990.     

[Z]-2-(芳基锡基)-1-(9-芴醇)乙烯的合成、结构与性质

用三苯基氢化锡,三对甲苯基氢化锡作为锡氢化试剂与9-乙炔基-9-芴醇进行反应,合成了2个有机锡化合物:[Z]-2-(三苯基锡基)-1-(9-芴醇)乙烯(1)和[Z]-2-(三对甲苯基锡基)-1-(9-芴醇)乙烯(2)。化合物1和2分别与ICl,Br~2,I~2反应,得到6个有机锡一卤化物,6个有机锡二卤化物和2个有机锡混合卤化物(3-16)。有机锡一碘化物7,13和有机锡二碘化物8,14与KOH乙醇溶液反应,分别得到相应的有机锡氢氧化物17,18和有机锡氧化物19,20。有机锡二碘化物8,14分别与含氮双齿配体1,10-邻菲罗啉(Phen),2,2'-联吡啶(Bipy),8-羟基喹啉(Oxin)反应,得到6个相应的配合物21-26。26个新化合物通过元素分析,锡含量测定,IR,^1HNMR测定对其结构进行了表征。同时测定了化合物2的晶体结构,晶体属单斜晶系,空间群P2~1/c。化合物2是以Sn原子为中心扭曲的四面体构型。     

制备2-O-[1(R)-(9-次夹氧蒽基)-2-羟基乙基]丙三醇的新方法

以肌苷为底物,用两种性质相反的聚合物支载的高碘酸根离子和硼氢要离子一锅法合成了２－Ｏ－「１（Ｒ）－（９－次夹氧蒽基）－２－羟基乙基」丙三醇。该法具有操作简便,反应条件温和,缩短合成中线,无须分离中间体、产率较高等特点。