1-Phenylthieno[3,4-d]borepin: a new 10 .pi. electron system isoelectronic with azulene
1-Phenylthieno[3,4-d]borepin: a new 10 .pi. electron system isoelectronic with azulene
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1-Phenylthieno[3,4-d]borepin：新的 10 .pi。
DOI：
10.1021/ja00030a052
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发表时间：
1992
影响因子：
15
通讯作者：
A. Imamura
中科院分区：
文献类型：
--
作者：
Y. Sugihara;T. Yagi;I. Murata;A. Imamura
3 （R= Ph）的合成；试剂和条件：(a) HC= C-Si (CH3) 3 (2.4 equiv), PdCl2 (Ph3P) 2 (0.04 equiv), Cul (0.04 equiv)，哌啶，回流，15h, 85%；(b) K2C03（0.4当量），MeOH，室温，3.5 h, 71%；(c) SnH2（«Bu） 2（1.1当量），KOH（0.5当量），18-crown-6（0.005当量），脱气苯，室温，2 h, 85%；(d) PhBCl2（3当量），脱气己烷，冰冷却，10分钟，40%。通过对1-甲基- 4,5 - propanborepine(1)和1-methylborepine(2)的光谱检查，分别通过硼原子进行环共轭。12 3 4这些判例的基础上,以及众所周知的事实是二价硫电子等效ethylenic双键,更换两个sp2-carbon原子的甘菊蓝三价硼和二价硫形成一个新家庭的分子,如thieno[3, 4 - 6、7 -害怕> ']dithiophenes(4)合成了Jeffries Gronowitz,勒的内在属性thienoborepine系统将由一个额外的大幅度摄动thieno anne-lation。1-苯基噻吩[3,4 -< f]硼甲碱（3，R= Ph）的合成和化学和物理性质的研究将为这一假设提供见解。我们合成的3，从3,4 -二溴噻吩(5)，3开始
" Synthesis of 3 (R= Ph); reagents and conditions:(a) HC= C-Si (CH3) 3 (2.4 equiv), PdCl2 (Ph3P) 2 (0.04 equiv), Cul (0.04 equiv), piperidine, reflux, 15 h, 85%;(b) K2C03 (0.4 equiv), MeOH, room temperature, 3.5 h, 71%;(c) SnH2 («Bu) 2 (1.1 equiv), KOH (0.5 equiv), 18-crown-6 (0.005 equiv), degassed benzene, room temperature, 2 h, 85%;(d) PhBCl2 (3 equiv), degassed hexane, ice-cooling, 10 min, 40%. cyclic conjugation through a boron atom on the basis of spec-troscopic examinations of 1-methyl-4, 5-propanoborepine (1) and 1-methylborepine (2), respectively.12 3 4 On the basis of these precedents, as well as the well-known fact that a divalent sulfur is electronically equivalent with an ethylenic double bond, replacement of two sp2-carbon atoms of azulene by a trivalent boron and a divalent sulfur forms a new family of molecules, such as thieno [3, 4-: 6, 7-¿>'] dithiophenes (4) synthesized by Jeffries and Gronowitz, le the intrinsic properties of the thienoborepine system would be substantially perturbed by an additional thieno anne-lation. The synthesis and examination of the chemical and physical properties of 1-phenylthieno [3, 4-< f] borepine (3, R= Ph) will provide insight into this assumption. Our synthesis of 3, starting from 3, 4-dibromothiophene (5), 3