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 of 9-(2-fluorobenzyl)-6-methylamino-9H-purine

Synthesis of 9-(2-fluorobenzyl)-6-methylamino-9H-purine ( 1 ) from nine different precursors is reported. Compound 1 was prepared by methylamination of 6-chloro-9-(2-fluorobenzyl)-9H-purine ( 4 ), by alkylation of 6-methylaminepurine ( 5 ) or form 9-(2-fluorobenzyl)-1-methyladeninium iodide ( 8 ) via the Dimroth rearrangement. Selective 2-step methylation of 6-aminopurine 6 was accomplished by hydride reduction of 6-formamidopurine 9 , 6-dimethylaminomethyleneaminopurine 10 or 6-phenylthiomethyl purine 11 to give 1. Compound 1 was also prepared by dethiation or reductive dechlorination of 2-methylthiopurine 16 or 8-chloropurine 19 , respectively, or by hydrolysis of 6-N-methylformamidopurine 12 , which was prepared from 6-dimethylaminopurine 13 by selective oxidation.     

The determination of 2,6-diamino-9-(2-hydroxyethoxymethyl)-9H-purine (A134U) and 2-amino-9-(2-hydroxyethoxymethyl)-9H-purine (A515U) in human plasma and urine by gas chromatography

Summary A novel, sensitive and selective automated method for the analysis of low concentrations of A134U and A515U in human plasma and urine has been developed. It involved extraction of the drugs (with an internal standard) from urine or plasma and conversion to trimethylsilyl derivatives. The trimethylsilylated extract was then chromatographed using a temperature programmed injection cycle on a gas chromatographic column packed with 5% OV17 on Chromosorb W-HP. Components were detected by an alkaline flame-ionisation detector. BASIC computation capability was utilised for both control of the autosampler and calculation of the results using a linear regression calibration of the standards used. Automation allowed 48 injections per 24 hours. Samples were routinely assayed in duplicate with a range of spiked standards and a control sample. The assay was linear for plasma and urine in the range 0.5–200 μM with no interference from acyclovir, known metabolites, endogenous compounds, or a specific inhibitor [erythro-9-(2-hydroxy-2-nonyl) adenine (EHNA)]. The method had a sensitivity of less than 0.5μM. It has been applied successfully to clinical studies. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984     

基于N-对甲氧苯基咔唑-2-乙烯基-8-羟基喹啉锌的白色和黄色有机电致发光器件的性能

通过研究新型荧光染料N-对甲氧苯基咔唑-2-乙烯基-8-羟基喹啉锌(MoBCzHQZn)的电致发光(EL)特性, 发现MoBCzHQZn具有较强的发光特性和空穴传输特性, 利用此特性制备了非掺杂型的有机电致白光器件和掺杂型的有机电致黄光器件. 白光器件的结构为ITO/2T-NATA(20 nm)/MoBCzHQZn(25 nm)/NPBX(13 nm)/BCP(8nm)/Alq3(34 nm)/LiF(0.5 nm)/Al, 器件在15 V电压下实现了白光发射, 色坐标为(0.3719, 0.3275), 最大发光亮度为3414 cd·m-2, 在14 V 电压下的最大发光效率为1.69 cd·A-1、黄光器件的结构为ITO/2T-NATA(20 nm)/CBP:6%Ir(ppy)3:10%MoBCzHQZn(25 nm)/TPBi:6%Ir(ppy)3(47 nm)/LiF(0.5 nm)/Al, 器件在15 V电压下实现了黄绿光发射, 色坐标为(0.3590, 0.5787), 最大发光亮度为11073 cd·m-2, 在9 V电压下的最大发光效率为2.51 cd·A-1.     

[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。     

基于N-乙基咔唑-2-乙烯基-8-羟基喹啉锌的黄绿色有机电致发光器件的性能

通过用一种既具有空穴传输特性又具有发光特性的新型荧光染料N-乙基咔唑-2-乙烯基-8-羟基喹啉锌((E)-2-(2-(9-ethyl-9H-carbazol-3-yl)vinyl) quinolato-zinc, CzHQZn)作为受主, 制备了结构为ITO/2T-NATA (30 nm)/CBP: 6%Ir(ppy)3:wCzHQZn(20 nm)/Alq3(50 nm)/LiF/Al(ITO: indium-tin oxide, 2T-NATA: 4,4',4'-{N,N-(2-naphthyl)-N-phenylamino}-triphenylamine, CBP: 4,4-N,N'-dicarbazole-biphenyl, Ir(ppy)3: factris (2-phenylpyridine) iridium, Alq3: tris(8-quinolinolato) aluminum; w 是CzHQZn 的质量分数)的黄绿色有机电致发光器件(OLEDs). 研究了掺杂体系在不同掺杂浓度(w=5%、10%、12%、15%)时的电致发光(EL)特性. 结果表明, CzHQZn 掺杂浓度为10%的器件在11 V 电压下实现了黄绿光发射, 色坐标为(0.4045, 0.5113), 最大发光亮度为16110 cd·m-2; 而在7 V电压下的最大发光效率为2.19 cd·A-1, 最大外量子效率为0.775%.     

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.     

2-[(9-苯基)-9H-3-咔唑基]-5-[(9-对甲苯基)-9H-3-咔唑基]吡啶的合成及其光谱性能

以咔唑和2,5-二溴吡啶为初始原料,经Ullmann反应、NBS亲电取代反应和Suzuki偶联等反应,合成了一种新型的磷光配体2-[(9-苯基)-9H-3-咔唑基]-5-[(9-对甲苯基)-9H-3-咔唑基]吡啶(5),其结构经1HNMR,ESI-MS及元素分析表征。研究了5在二氯甲烷中的荧光光谱和紫外吸收光谱。     

Synthesis of 10-(4-heptyloxyphenyl)-2-[2-methyl-2-(4-methylphenylsulfonyl)-1-oxopropyl)-9-oxothioxanthenium hexafluorophosphate(V)

Russian Journal of Organic Chemistry -     

3-Methyl-9-aryl(aralkyl)-2-aza-9-fluorenols

3-Methyl-9-phenyl(o-tolyl, benzyl)-2-aza-9-fluorenols were synthesized, and some of their transformations were examined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1087–1089, August, 1971.     

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。     

9-Methyl-3-(2-Pyrrolyl) carbazole

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, p. 1448, June, 1989.