3-nitro-1-(triisopropylsilyl)pyrrole | 87630-39-5

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: 3-nitro-1-(triisopropylsilyl)pyrrole
• 英文别名: 3-Nitro-1-(triisopropylsilyl)-1H-pyrrole；(3-nitropyrrol-1-yl)-tri(propan-2-yl)silane
• CAS: 87630-39-5
• 化学式: C₁₃H₂₄N₂O₂Si
• 分子量: 268.431
• InChiKey: BXNWETYTUVISTF-UHFFFAOYSA-N

物化性质

• 熔点：
  52-54 °C(Solv: ethyl acetate (141-78-6); hexane (110-54-3))
• 沸点：
  299.7±13.0 °C(Predicted)
• 密度：
  1.01±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.42
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  50.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-nitro-1-(triisopropylsilyl)pyrrole 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 以100%的产率得到3-硝基吡咯
  参考文献：
  名称：

  β-取代的吡咯通过正三异丙基甲硅烷基吡咯的亲电取代。

  摘要：

  N-三异丙基甲硅烷基吡咯在C-3处经受主要或排他的动力学亲电取代，并且由此获得的化合物在与四丁基氟化铵进行甲硅烷基化后，以良好的总收率得到3-取代的吡咯。

  DOI：

  10.1016/s0040-4039(00)86011-6
• 作为产物：
  描述：

  1-(三异丙基甲硅烷基)吡咯 在 copper(II) nitrate 作用下， 以 乙酸酐 为溶剂， 反应 2.0h， 以80%的产率得到3-nitro-1-(triisopropylsilyl)pyrrole
  参考文献：
  名称：

  β-取代的吡咯通过正三异丙基甲硅烷基吡咯的亲电取代。

  摘要：

  N-三异丙基甲硅烷基吡咯在C-3处经受主要或排他的动力学亲电取代，并且由此获得的化合物在与四丁基氟化铵进行甲硅烷基化后，以良好的总收率得到3-取代的吡咯。

  DOI：

  10.1016/s0040-4039(00)86011-6

文献信息

• Synthesis, biological evaluation, and docking studies of various β‐substituted porphyrin conjugates embedded with N‐containing heterocycles
  作者：Ghada S. Masaret

  DOI：10.1002/jhet.4314

  日期：2021.9

  A new methodology for the synthesis of some new β-porphyrin heterocyclic compounds containing nitrogen derivatives 10, 12, 13, 15, 17, 19, 21, 22, 25, 27, and 29 was screened for their cytotoxic activities. Both elemental and spectral analyses were used to confirm the structures of new compounds. Compounds 22, 27, and 21 exhibited very strong activity against the HepG2 cell line. Investigation of the

  对于含氮衍生物一些新的β -卟啉的杂环化合物的合成的新方法10，12，13，15，17，19，21，22，25，27，和29中筛选它们的细胞毒性活性。元素和光谱分析都用于确认新化合物的结构。化合物22，27和21抵靠HepG2细胞表现出非常强的活性。卟啉22结合的研究 端粒酶的结合位点通过分子对接进行。
• Efficient synthesis of <i>N</i>-methyltetranitropyrrole: A stable, insensitive and high energy melt-castable material
  作者：Vikranth Thaltiri、Kurumurthy Chavva、B. Sathish Kumar、Pradeepta K. Panda

  DOI：10.1039/c9nj01227c

  日期：——

  1-Methyl-2,3,4,5-tetranitropyrrole, a potential high energy density material, first reported in 1979 in only 0.28% overall yield, has been synthesized efficiently (in more than 5% overall yield) by following two alternate routes from 1-(triisopropylsilyl)pyrrole and 1-methylpyrrole. Detailed characterization shows that it is stable up to 196 °C and possesses a density of 1.93 g cm−3. The corresponding

  1-甲基-2,3,4,5-四硝基吡咯是一种潜在的高能量密度材料，于1979年首次报道，其总收率仅为0.28％，它是通过以下两种替代方法有效合成的（总收率超过5％）由1-（三异丙基甲硅烷基）吡咯和1-甲基吡咯制得。详细的表征表明，它在高达196°C的温度下稳定，密度为1.93 g cm -3。相应的爆震速度和爆震压力分别为8950 ms -1和36.9 GPa。这些值比RDX略好一些，而其对冲击和摩擦的敏感度则比RDX低得多。此外，其熔点为100°C，进一步彰显了其在高能配方中作为可熔融浇铸材料的潜力。
• Alkylatlon orientation rules in conjugate addition of grignard reagents to nitropyrrole and nitrothiophene systems
  作者：Roberto Ballini、Giuseppe Bartoli、Marcella Bosco、Renato Dalpozzo、Enrico Marcantoni

  DOI：10.1016/s0040-4020(01)89831-8

  日期：——

  Conjugate addition of various Grignard reagents to 1-alkyl-2-nitropyrroles and to 2-nitrothiophene has been investigated. 1-Alkyl-2-nitropyrroles undergo alkylation at 3 and 5 positions with prevalence of the latter isomer. On the contrary, in 2-nitrothiophene system, formation of the 3-isomer prevails. In both systems, a bulkier Grignard reagent favours the 5-isomer formation. This trend can be reversed

  已经研究了将各种格氏试剂偶联到1-烷基-2-硝基吡咯和2-硝基噻吩上的方法。1-烷基-2-硝基吡咯在3和5位发生烷基化，后一种异构体普遍存在。相反，在2-硝基噻吩系统中，形成了3-异构体。在两种体系中，较大的格利雅试剂都有利于5-异构体的形成。这种趋势可以逆转，由2-硝基吡咯的1-取代基增加空间位阻。1-（三异丙基甲硅烷基）-3-硝基吡咯和3-硝基噻吩仅产生2-异构体。该反应允许通过一锅法而不是经典的多阶段反应来合成2-烷基-3-硝基噻吩和吡咯。
• N-(Triisopropylsilyl)pyrrole. A progenitor "par excellence" of 3-substituted pyrroles
  作者：Brian L. Bray、Peter H. Mathies、Reto Naef、Dennis R. Solas、Thomas T. Tidwell、Dean R. Artis、Joseph M. Muchowski

  DOI：10.1021/jo00313a019

  日期：1990.12

  A very effective strategy has been devised for the synthesis of 3-substituted pyrroles based on the use of the triisopropylsilyl (TIPS) moiety as a sterically demanding nitrogen substituent to obstruct the attack of electrophilic reagents at the alpha-positions. 1-(Triisopropylsilyl)pyrrole (1) undergoes highly preferential kinetic electrophilic substitution at the beta-position with a variety of electrophiles (Br+, I+, NO2+, RCO+, etc.) and fluoride ion induced desilylation of the products provides the corresponding 3-substituted pyrroles in good overall yields. Competitive trifluoroacetylation experiments demonstrate that substitution of TIPS-pyrrole at the alpha-positions is decelerated by a factor of > 10(4), vs pyrrole at the same sites, without affecting reactivity at the beta-positions. 1-(Triisopropylsilyl)-3-bromopyrrole (2) is readily converted into the 3-lithio compound 44 by bromine-lithium interchange with alkyllithium reagents. This previously unavailable, formal equivalent of 3-lithiopyrrole is itself an excellent source of a wide range of beta-substituted pyrroles, many of which would not be directly preparable from 1. TIPS-pyrrole can be 3,4-dihalogenated and these compounds undergo sequential halogen-metal interchange trapping reactions. This process is exemplified by an efficient, three-step synthesis of the antibiotic verrucarin E (63) from the dibromo compound 5.
• BRAY, BRIAN L.;MATHIES, PETER H.;NAEF, RETO;SOLAS, DENNIS R.;TIDWELL, THO+, J. ORG. CHEM., 55,(1990) N6, C. 6317-6328
  作者：BRAY, BRIAN L.、MATHIES, PETER H.、NAEF, RETO、SOLAS, DENNIS R.、TIDWELL, THO+

  DOI：——

  日期：——