5-tert-Butyl-1,2,4-Benzenetricarbonitrile | 132381-82-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 5-tert-Butyl-1,2,4-Benzenetricarbonitrile
• 英文别名: 5-tert-Butylbenzene-1,2,4-tricarbonitrile
• CAS: 132381-82-9
• 化学式: C₁₃H₁₁N₃
• 分子量: 209.25
• InChiKey: IJCHULPUWLBCND-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  71.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-叔-丁基-2-甲基-1,3-二氧戊环 、 5-tert-Butyl-1,2,4-Benzenetricarbonitrile 以 乙腈 为溶剂， 生成 1,2-乙二醇单乙酸酯 、 1,4-dicyano-2,5-bis(1,1-dimethylethyl)benzene 、 2,4-dicyano-1,5-bis(1,1-dimethylethyl)benzene
  参考文献：
  名称：

  Electron transfer photoinduced cleavage of acetals. A mild preparation of alkyl radicals

  摘要：

  Electron transfer from 2-alkyl- and 2,2-dialkyldioxolanes as well as from open-chain ketals to singlet excited benzene-1,2,4,5-tetracarbonitrile (TCNB) is followed by fragmentation of the donors radical cation to yield alkyl radicals and dialkoxy carbocations. The first species are trapped by TCNB to yield alkylbenzenetricarbonitriles (substitution of a second cyano group can be obtained sequentially) and in a minor path are reduced to alkanes, while the latter ones react with nucleophiles to give ortho acid derivatives. In view of the results of radical clock experiments, it is assumed that part of the process is a concerted (radical cation cleavage-addition to the aromatic) reaction, while another part involves the free-radical cation. On the other hand, intersystem crossing from the singlet radical ion pair to the triplet manifold causes cleavage of the acetal to the corresponding carbonyl derivative. This reaction offers a mild method for the preparation of alkyl radicals via C-C bond cleavage.

  DOI：

  10.1021/jo00037a020
• 作为产物：
  描述：

  1,2,4,5-四氰基苯 、 (t-butyl)trimethylstannane 在 马来酸二甲酯 作用下， 以 乙腈 为溶剂， 以36%的产率得到5-tert-Butyl-1,2,4-Benzenetricarbonitrile
  参考文献：
  名称：

  光诱导单电子转移产生的自由基使烯烃烷基化

  摘要：

  在几个供体的存在下1,2,4,5- benzenetetracarbonitrile（TCB）（一些2-照射吨丁基-1,3-二氧戊环，新戊酸，吨-butyltrimethylstannane，吨丁基二Ñ辛基醚）引线使供体自由基阳离子断裂，得到叔丁基。当在吸电子取代的烯烃的存在下进行辐照时，自由基被捕集，加合物自由基与TCB- •偶联。（然后整个过程是自由基烯烃偶联-芳族取代）或被还原（导致TCB光敏烯烃烷基化）。讨论了自由基前体结构和介质对这些新反应的影响。

  DOI：

  10.1016/0040-4020(94)00976-2

文献信息

• Novel alkylation of aromatic nitriles via photo-induced electron transfer of group 14 metal-carbon σ donors
  作者：Soichiro Kyushin、Yukihiro Masuda、Kazuhiro Matsushita、Yasuhiro Nakadaira、Mamoru Ohashi

  DOI：10.1016/s0040-4039(00)97074-6

  日期：——

  Photo-induced electron transfer reactions of tetraalkylsilanes, -germanes, and -stannanes with aromatic nitriles afforded alkylated products. The mechanism was investigated by use of a radical clock.

  四烷基硅烷，-锗烷和-锡烷与芳族腈的光诱导电子转移反应可得到烷基化产物。通过使用基本时钟来研究该机制。
• Electron-donating behaviour of aliphatic carboxylic acids in the photoreaction with 1,2,4,5-tetracyanobenzene
  作者：Kazuo Tsujimoto、Nobuhisa Nakao、Mamoru Ohashi

  DOI：10.1039/c39920000366

  日期：——

  Irradiation of an acetonitrile solution of 1,2,4,5-tetracyanobenzene with aliphatic carboxylic acids gives 2,4,5-tricyanoalkylbenzenes efficiently; electron transfer from the carboxylic acids to the excited tetracyanobenzene is essential.

  用脂肪族羧酸辐照 1,2,4,5-四氰基苯的乙腈溶液，可以高效地生成 2,4,5-三氰基烷基苯；电子从羧酸转移到激发的四氰基苯是必不可少的。
• Radicals through Photoinduced Electron Transfer. Addition to Olefin and Addition to Olefin-Aromatic Substitution Reactions
  作者：Mariella Mella、Maurizio Fagnoni、Angelo Albini

  DOI：10.1021/jo00098a019

  日期：1994.9

  The radical cations of 2,2-dialkyl- and 2-alkyl-2-aryl-1,3-dioxolanes, when generated in solution by photoinduced electron transfer to 1,2,4,5-benzenetetracarbonitrile (TCB), fragment to yield alkyl radicals. These are trapped by electron-withdrawing substituted alkenes (acrylonitrile, methyl acrylate, methyl vinyl ketone, as well as dimethyl maleate and fumarate). The radicals thus formed are either reduced by the TCB radical anion or add to it. In the first process (observed only with the diesters) the end result is reductive alkylation of the olefin, while the latter process results in an addition to the olefin-aromatic substitution reaction, The selectivity of the process is explained on the basis of steric hindrance, since the radicals react when still in the cage with the aromatic radical anion.
• Mella, Mariella; d'Alessandro, Nicola; Freccero, Mauro, Journal of the Chemical Society. Perkin transactions II, 1993, # 3, p. 515 - 519
  作者：Mella, Mariella、d'Alessandro, Nicola、Freccero, Mauro、Albini, Angelo

  DOI：——

  日期：——
• Fagnoni; Mella; Albini, Journal of the American Chemical Society, 1995, vol. 117, # 30, p. 7877 - 7880
  作者：Fagnoni、Mella、Albini

  DOI：——

  日期：——