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首页> 外文期刊>Bulletin of the Chemical Society of Japan >Preparation and Conformational Analysis of 6,10-Diethyl [1,2,3] trithiolo-[4,5-h] benzopentathiepin Monoxides: Isolation and Optical Properties of Chiral Benzopentathiepin Derivatives
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Preparation and Conformational Analysis of 6,10-Diethyl [1,2,3] trithiolo-[4,5-h] benzopentathiepin Monoxides: Isolation and Optical Properties of Chiral Benzopentathiepin Derivatives

机译：6,10-二乙基的制备和构象分析[1,2,3]甲基噻吩（Thezopentathiepin一氧化铁）：手性脑脑观蛋白衍生物的分离和光学性质

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摘要

6,10-Diethyl [1,2,3] trithiolo [4,5-h] benzopentathiepin (1) was oxidized by mCPBA in dichloromethane to produce the corresponding four monoxides. The structures of the monoxides 2,3,4, and 5 were determined by X-ray crystallography to be 6,10-diethyl [1,2,3] trithiolo [4,5-h] benzopentathiepin 8-oxides (1,2,3-trithiole 2-oxides) for 2 and 3, and 6,10-diethyl [1,2,3] trithiolo [4,5-h] benzopentathiepin 7-oxides (1,2,3-trithiole 1-oxides) for 4 and 5, respectively. Compound 2 and 3 are isomers with respect to the conformation of the 1,2,3,4,5-pentathiepin ring, and 4 and 5 are also the conformational isomers. These compound pair members, 2 and 3, and 4 and 5, were found to isomerize each other by inversion of the pentathiepin ring. The compound pair members, 2 and 3, and 4 and 5, were found to isomerized each other by inversion of the pentathiepin ring. The activation parameters of the isomerization, DELTAG_(298)~(not =), DELTAH~(not =), and DELTAS~(not =), were determined by ~1H NMR spectroscopy. Because of the slow inversion of the pentathiepin ring, isolation of unsymmetrically substituted benzopentathiepin as a chiral molecule is possible. Asymmetric oxidation of 1 was performed by a Sharpless reagent [1/Ti(O~iPr)_4/R,R-DET/t-BuOOH = 1:2:4:4] to produce optically active monoxides 4a and 5a. The configuration of 4a and 5a was confirmed as R configuration on the sulfinyl sulfur atom, respectively. The specific rotation and the circular dichroism spectra of 4a and 5a were measured in chloroform; such data are apparently affected by the conformation of the pentathiepin ring.
机译：通过MCPBA在二氯甲烷中氧化6,10-二乙基[1,2,3]甲基吡喃[4,5-H]苯并戊脂蛋白（1）以产生相应的四种一氧化物。通过X射线晶体学法测定一氧化物2,3,4和5的结构，为6,10-二乙基[4,5-H]苯并戊脂蛋白8-氧化物（1,2 2和3的3-三苯孔2-氧化物），和6,10-二乙基三酮[4,5-H]肠道素7-氧化物（1,2,3-三甲基1-氧化物）分别为4和5。化合物2和3是相对于1,2,3,4,5-戊硫代蛋白环的构象的异构体，4和5也是构象异构体。将这些化合物对构件，2和3和4和5发现通过Pentathiepin环的反转来彼此异构化。将复合对构件，2和3和4和5发现通过偏心环的反转来彼此异构化。通过〜1H NMR光谱法测定异构化的激活参数，deltag_（298）〜（not =），deltah〜（not =）和deltas〜（not =）。由于近肠蛋白环的慢反演，可能是不对称取代的苯并肠道素作为手性分子的分离。通过不合理的试剂[1 / Ti（O〜IPR）_4 / R，R-DET / T-BuOOH = 1：2：4：4]进行不对称氧化，以产生光学活性的一氧化铁4a和5a。在磺基硫原子上分别证实了4A和5A的构造。在氯仿中测量4A和5A的具体旋转和圆形二色性光谱;这种数据显然受到偏见环的构象的影响。

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    Takeshi Kimura; Masayuki Hanazawa; Kazuhiko Tsujimura; Tatsuya Takahashi; Satoshi Ogawa; Ryu Sato; Yasushi Kawai; Ernst Horn; Takayoshi Fujii;

  • 作者单位

    Center for Instrumental Analysis Iwate University Morioka 020-8551;

    Department of Chemical Engineering Faculty of Engineering Iwate University Morioka 020-8551;

    Department of Chemical Engineering Faculty of Engineering Iwate University Morioka 020-8551;

    Department of Chemical Engineering Faculty of Engineering Iwate University Morioka 020-8551;

    Department of Chemical Engineering Faculty of Engineering Iwate University Morioka 020-8551;

    Department of Chemical Engineering Faculty of Engineering Iwate University Morioka 020-8551;

    Institute for Chemical Research Kyoto University Uji 611-0011;

    Tsukuba Advanced Research Alliance Center University of Tsukuba Tsukuba 305-8577;

    Department of Material Systems Engineering and Life Science Faculty of Engineering Toyama University Toyama 930-8555;

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  • 正文语种 eng
  • 中图分类 化学;化学工业;
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