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.     

Synthesis of C-nucleoside isosteres of 9-(2-hydroxyethoxymethyl)guanine (acyclovir)

Syntheses of 2-amino-7-(2-hydroxyethoxymethyl)imidazo[5,1-f]-1,2,4-triazin-4(3H)-one ( 2 ) and 6-amino-3-(2-hydroxyethoxymethyl)-1,2,4-triazolo[3,4-f]-1,2,4-triazin-8(7H)-one ( 3 ), novel isosteres of the antiviral agent acyclovir, are reported.     

Crystal structure of 6-benzylamino-9-[2-tetrahydropyranyl]-9H-purine.

C17H19O2N5 is monoclinic, P2(1)/n. Unit-cell dimensions at 293 K are a = 10.802(1), b = 24.085(2), c = 12.933(1)A, beta = 106.119(6) degrees, V = 3232.4(6)A3, Dx = 1.271 g/cm3, and Z = 8. The R value is 0.068 for 3017 observed reflections. There are two independent molecules in the asymmetric unit, denoted by A and B. In A, the dihedral angle between the adenine moiety and the phenyl ring is 73.2(3)degrees [in B, the angle is 83.9(2)degrees]. For A, the tetrahydropyranyl ring adopts a half-chair conformation [for B, chair conformation]. The packing in the crystal is entirely due to van der Waals forces.     

Acyclic analogs of pyrimidine nucleosides. Synthesis of 1-(2-hydroxyethoxymethyl)- and 1-(4-hydroxybutyl)-5-amino derivatives of uracil

With the objective of discovering new antiviral agents based on acyclic analogs of pyrimidine nucleosides, we have synthesized 1-(2-hydroxyethoxymethyl)- and 1-(4-hydroxybutyl) derivatives of uracil having various aromatic and heterocyclic amino-containing substituents in the 5 position of the pyrimidine ring.Scientific-Research Institute of Pharmacology, Volgograd Medical Academy, Volgograd 400066, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 971–978, July, 1998.     

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.     

Synthesis and anticonvulsant activity of 3H-imidazo[4,5-c]-pyridazine, 1H-imidazo[4,5-d]pyridazine and 1H-benzimidazole analogues of 9-(2-fluorobenzyl)-6-methylamino-9H-purine

The 3H-imidazo[4,5-c]pyridazine, 1H-imidazo[4,5-d]pyridazine, and 1H-benzimidazole analogues of the potent anticonvulsant purine 9-(2-fluorobenzyl)-6-methylamino-9H-purine (1, 78U79) were synthesized and tested for anticonvulsant activity. The 3H-imidazo[4,5-c]pyridazines 8 and 9 were prepared in five stages from 3,4,5-trichloropyridazine (2) . The 1H-imidazolo[4,5-d]pyridazine 15 was synthesized in four stages from 5-[(benzyloxy)methyl]-1,5-dihydro-4H-imidazo[4,5-d] pyridazin-4-one (10a) . The benz-imidazole analogues 18 and 20 were prepared from 2,6-dinitroaniline in three stages. These compounds were one-tenth or less as active as 1 in protecting rats against maximal electroshock-induced seizures.     

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.     

[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-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.     

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。     

Facile Synthesis of Some 3-(Benzimidazol-2-yl)- and 3,6-Di(Benzimidazol-2-yl)-9-ethyl-9H-carbazoles

A simple and efficient synthesis of novel 3-(benzimidazol-2-yl)- and 3,6-di(benzimidazol-2-yl)-9-ethyl-9H-carbazoles is described. The synthetic approach for the preparation of 2-substituted benzimidazoles 4–8 and bis-benzimidazoles 9–12 was achieved by the condensation of carbazole-3-carbaldehyde 2 and carbazole-3,6-dicarbaldehyde 3 with o-phenyldiamines in dimethylformamide or dimethylsulfoxide in moderate to excellent yield. The identities of synthesized compounds were confirmed using ¹H NMR, ¹³C NMR, infrared (IR), and high-resolution mass spectrometry (HRMS).