ACTION OF POTASSIUM FLUORIDE ON 5-BENZENSULFONYL-5,10-DIHYDRO-10-TRIMETHYLSILYLINDENO[1,2-B]INDOLE - ATTEMPTED SYNTHESIS OF DIBENZO[B,F-1]AZAPENTALENE
ACTION OF POTASSIUM FLUORIDE ON 5-BENZENSULFONYL-5,10-DIHYDRO-10-TRIMETHYLSILYLINDENO[1,2-B]INDOLE - ATTEMPTED SYNTHESIS OF DIBENZO[B,F-1]AZAPENTALENE
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DOI：
10.1007/bf00808753
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发表时间：
1989-02-01
影响因子：
1.8
通讯作者：
ABRAHAM, T
中科院分区：
文献类型：
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作者：
ABRAHAM, T
采用温和和中性的实验条件，以最大限度地提高从前体中分离二苯并[B，f-1]氮杂环戊二烯（3）（一种预期表现出反芳族特征的化合物）的成功机会。因此，使5-苯磺酰基-5，10-二氢-10-三甲基甲硅烷基茚并[1，2-B]吲哚（7）与氟化钾在室温下反应。该反应的产物是复杂的，但主要产物被鉴定为5，5“，10，10”-四氢-10，10“-联茚并[1，2-B]亚吲哚基（15）。显然，由氟化钾作用于7而产生的阴离子8没有受到苯次磺酸根阴离子的直接消除。相反，推测是由于3的反芳香性，苯次磺酸根阴离子仅在一系列电子转移反应后被消除，得到15。此外，出乎意料地，二苯并[B，f-1]氮杂并环戊二烯二价阴离子（5）仅在10-碳上甲硅烷基化，而不是在氮上甲硅烷基化。实验数据表明，5的10-碳直接与氯三甲基硅烷化。
Mild and neutral experimental conditions were employed in order to maximize the chance of success in the isolation of dibenzo[b,f-l]azapentalene (3), a compound expected to exhibit antiaromatic character, from a precursor. Thus, 5-benzensulfonyl-5, 10-dihydro-10-trimethylsilylindeno[1,2-b]indole (7) was allowed to react with potassium fluoride at room temperature. The outcome of the reaction was complex, but the major product was identified as 5,5'',10,10''-tetrahydro-10,10''-biindeno[1,2-b]indolylidene (15). Apparently, the anion 8 that was generated by the action potassium fluoride on 7, did not suffer direct elimination of the benzensulfenate anion. Instead, presumably due to the antiaromacitity of 3, the benzensulfenate anion was eliminated only after a series of electron transfer reactions, resulting in 15. Also, unexpectedly, dibenzo[b,f-1]azapentalene dianion (5) was silylated exclusively at the 10-carbon in preference to silylation at nitrogen. Experimental data indicated that the 10-carbon of 5 was silylated directly with chlorotrimethylsilane.