7-Azaindole derivatives

A study is made of new synthetic routes, based on accessible 3-formyl-7-azaindoles, to 3-substituted 7-azaindole. 2-Phenyl-4-(1-phenyl-4-methyl-7-azaindolyl-3-rnethylene)-1, 3-oxazol-5-one is synthesized, and it is converted to 1-phenyl-4-methyl-7-azatryptophane, 1-phenyl-4-methyl-7-azaindolyl-3-acetic acid,1-phenyl-3-(,-dihydroxypropyl)-4-methyl-7-azaindole, and 1-phenyl-4-methyl-7-azaindolyl-3-pyrotartaric acid.For Part XVIII see [1].     

7-氮杂吲哚N-氧化物的区域选择性脱氧硫醚化反应

本文开发了一种3-硫代-7-氮杂吲哚衍生物的合成方法。研究发现,在30%的I2的催化作用下,磺酰肼和7-氮杂吲哚N-氧化物在正丁醇中110 °C条件下反应以53%-86%的产率得到硫醚化产物。该反应有较好的区域选择性和底物适应性。并具有反应时间较短,绿色环保和操作简便等优点。     

Synthesis and Antitumor Activity of a New 7-Azaindole Derivative

We designed and synthesized a 7-azaindole derivative（TH1082）, which was characterized by 1^H NMR and 13^C-NMR. We investigated its antitumor effects on human melanoma A375 cells, human liver cancer SMMC cells and human breast cancer MCF-7 cells in vitro via 3-（4,5-dimethyldiazol-2-yl）-2,5-diphenyl-tetrazolium bromide （MTT） assay and also explored the mechanism of antiproliferation of them. The results show that TH1082 significantly inhibited the proliferation of these cells to different extent. The IC50 values for A375 cells, SMMC cells and MCF-7 cells were 25.38, 48.70 and 76.94 μg/mL at 24 h, respectively. To observe cell morphological changes, acridine orange/ethidium bromide（AO/EB） staining and Hoechest33342/Pl staining were carried out. These results indicate that TH1082 could induced the apoptosis of A375 cells. The apoptotic rates were （9.5±2.09）%, （18.9±2.25）% and （39.5±2.02）%（5, 10 and 20 μg/mL） for A375, SMMC and MCF-7 cell lines, respectively. Further, we determined the activities of caspase-3 and caspase-9 in A375 cells treated with TH1082 at different concentrations（0, 5, 10 and 20 μg/mL） or Z-VAD-FMK（20 μmol/L）, a pan-caspase inhibitor for 24 h. The results show that TH1082 activated caspase-3 and caspase-9, and the activation could be blocked by Z-VAD-FMK. Taken together, these findings indicate that TH 1082 could inhibit the proliferation ofA375 cells via activating caspase-3 and caspase-9.     

7-氮杂吲哚衍生物分子基态和激发态性质的理论研究

用从头算HF和密度泛函B3LYP方法对7-氮杂吲哚衍生物1,3-二(N-7-氮杂吲哚基)苯、1,3,5 三(N-7-氮杂吲哚基)苯和4,4′-二(N-7-氮杂吲哚基)联苯进行全优化, 计算分子的电离势IP和电子亲和势EA等相关能量, 并用ZINDO和TDDFT方法计算吸收光谱, 用CIS优化三种化合物分子的S1激发态结构, 并分析其能量与发射光谱的关系, 计算溶剂中分子的吸收和发射光谱, 并与实验结果对照. 计算结果表明, 从7-氮杂吲哚到上述三种衍生物依次愈来愈容易接受空穴, 吸收和发射光谱红移.     

7—氮吲哚二体激发态双质子转移的量子化学研究

用AMl和INDO/CI方法研究了7-氮吲哚二体激发态双质子转移反应的位能面和机理,异构二体虽存在较强的分子内氢键,但基态时正常二体的能量仍比异构二体低,光照时正常二体可通过激发态质子转移变为异构二体,这是其荧光产生反常Stokes位移的原因。     

7-azaindole derivatives

A new method for synthesizing 5- and 7-azaindoles is given, -Chlorobutyronitrile and malonyl chloride give 2, 4, 6-trichloro-3-(ß-chloroethyl) pyridine, which is cyclized with ammonia to 4, 6-dichloro-7-azaindoline and 4, 6-dichloro-5-azaindoline. 6-Chloro derivatives of 7-azaindolines are not dehydrogenated by chlorainil, but 2, 3-dichloro-S, 6-dicyanobenzoquinone converts them to 6-chloro-7-azaindoles. It is shown that sodium in liquid ammonia is an effective means of dehydrogenating the 5-azaindoline to 5-azaindole. In this case, dehydrogenation of 4, 6-dichloro-7-azaindoline is followed by dehalogenation.For Part IX see [1].     

Quinoline-7-carboxylic acid derivatives

The preparation of 2-amino-5-chloroterephthalic acid and the synthesis from it of 1,2,3,4-tetrahydro-4-oxo-6-chloroquinoline-7-carboxylic acid are described.See [7] for communication III.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 235–237, February, 1971.     

Methoxy derivatives of 7-sulfodimethylamidoacridine

The 2-, 3-, and 4-methoxy derivatives of 4-sulfodimethylamidodiphenylamine-2-carboxylic acid were synthesized by the condensation of 2-chloro-5-sulfodimethylamidobenzoic acid with o-, m-, and p-anisidines, respectively. These acids were cyclized by the action of phosphorus oxychloride to the corresponding methoxy-substituted 7-sulfodimethylamido-9-chloroacridines. The 2-, 3-, and 4-methoxy derivatives of 7-sulfodimethylamido-9-acridone and 7-sulfodimethylamido-9-aminoacridine were obtained from the latter.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 115–117, January, 1971.     

Thiosemicarbazones of 7-azaisatin derivatives

A number of derivatives of 7-azaisatin with various substituents in the pyridine and pyrrole rings were synthesized by oxidation of the corresponding 7-azaindoles with chromic acid in acetic acid. 4-Azaindole is not oxidized to 4-azaisatin under these conditions. The -thiosemicarbazones of the 7-azaisatin derivatives were obtained.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 54–56, January, 1981.     

Synthesis of 7-substituted tetracycline derivatives

[formula: see text] The synthesis of 7-substituted tetracycline derivatives has been accomplished in high yield from 7-halotetracyclines by modified Suzuki and Stille coupling protocols. These novel derivatives may serve as a new class of tetracycline antibiotics effective against multi-antibiotic-resistant bacteria.     

Synthesis of 7-oxo- and 7-hydroxy- derivatives of stigmasterol

The phytosteroids 3ß-hydroxy-(24S)-stigmast-5, 22E-dien-7-one and (24S)-stigmasta-5, 22E-diene-3\, 7ß-diol have been synthesized from stigmasterol.     

A new route to 7-deazaguanine derivatives

The Synthesis of 2-amino-4,6-dichloro-5-(2,2-diethoxyethyl) pyrimidine $\text{7}$ has been performed in four steps starting from guanidine and diethylallylmalonate. $\text{7}$ is a new key intermediate for the synthesis of 7-alkyl-2-amino-3,4-dihydro-7H-pyrrolo [2,3-d] pyrimidin-4-ones.     

Synthesis of derivatives of 7-iodo-4-aminoquinolines

7-Iodo- and 7,8-diiodo-4-(3-dimethylaminopropylamino)quinolines and 7-iodo-4-(3) dipropyl-aminopropylamlno)- and 7-iodo-4-(3-diallylaminopropylamino)quinoline were obtained by the reaction of 7-iodo- and 7,8-diodo-4-chloroquinolines with the corresponding diamines. The catalytic hydrogenation of 7-iodo-4-(3-diallylaminopropylamino)quinoline at normal pressure leads to 7-iodo-4-(3-dipropylaminopropylamino)quinoline.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 972–975, July, 1980.     

Synthesis of amino acid derivatives of 7-methoxycarbonylneoflavones

A number of aminoacyl derivatives of 4-phenylcoumarin have been obtained by the condensation of N-hydroxysuccinimide esters of 7-(1-carboxyalkoxy)-4-phenylcoumarins with L-amino acids and their derivatives.Kiev Taras Shevchenko University, Chemical Faculty, 252033, Kiev, Ul. Vladimirskaya, 65, tel/fax 225 12 73. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 464–469, July–August, 1999.     

Absorption and fluorescence spectra of 7-aminocoumarin derivatives

The absorption and fluorescence spectra of twelve 7-aminocoumarin derivatives have been studied with methanol and chloroform as solvents. Electronic transitions to nπ^* states have been traced. The effect of different substituents on the nitrogen was easily observed in the fluorescence spectra. Fluorescence quantum yields and oscillator strengths were evaluated. The role of hydrogen bonding on emission maxima, quantum yields and photolytic dissociation were discussed.     

Acid-promoted multicomponent allylic amidation towards 7-acetamido tetrahydroindole derivatives

An acid-promoted multicomponent reaction for the direct C(sp³)N bond formation was achieved through intermolecular allylic amidation in a one-pot operation to synthesize 7-acetamido tetrahydroindole derivatives from simple and readily available arylglyoxal monohydrates, acetonitriles, and enamines of 5,5-dimethyl-1,3-cyclohexadione (dimedone) has been developed. Here acetonitrile acts both as solvent and reagent. These tetahydroindole derivatives are formed through domino condensation of the enamines and arylglyoxals followed by annulation and allylic amidation.