2-(dinitromethyl)-4-methylanisole | 130379-13-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2-(dinitromethyl)-4-methylanisole
• 英文别名: 2-(dinitromethyl)-1-methoxy-4-methylbenzene
• CAS: 130379-13-4
• 化学式: C₉H₁₀N₂O₅
• 分子量: 226.189
• InChiKey: ZWGJCFRVSZZZMQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.56
• 重原子数：
  16.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  95.51
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  四硝基甲烷 生成 2-(dinitromethyl)-4-methylanisole
  参考文献：
  名称：

  MASLAK, PRZEMYSLAW;CHAPMAN, WILLIAM H. (JR), J. ORG. CHEM., 55,(1990) N6, C. 6334-6347

  摘要：

  DOI：

文献信息

• Photochemically generated ion and radical pairs. Self-destructive charge-transfer complexes
  作者：Przemyslaw Maslak、William H. Chapman

  DOI：10.1021/jo00313a021

  日期：1990.12

  Irradiation of CT complexes between 4-methoxy-4'-X-bicumenes, 1a-e (X = H, a; OMe, b; Me, c, CF3, d, CN, e) and tetranitromethane (2) results in efficient generation of radical and ion pairs (phi-almost-equal-to 0.20). The identity of the final products depends on the dynamics of these pairs, which in turn is dramatically influenced by substitution and solvent. In all cases, 2.- dissociates rapidly ( < 3 ps) into (NO2)C-3(-) (4-) and NO2.. In CH2Cl2, 1a.+ reacts with 4- (aromatic trinitromethylation) and undergoes C-C bond fragmentation before diffusional separation of fragments can occur. Thus, a tetrad of reactive intermediates (cumyl radical, NO2., p-methoxycumyl cation and 4-) are produced in a single solvent cage. The cumyl radical is oxidized by 2, and both cumyl cations undergo alpha-trinitromethylation. The cumyl cations undergo trinitromethylation in the original solvent cage which is kinetically equivalent to a contact ion pair (CIP). In CH3CN the fragmentation is accompanied by aromatic nitration (radical collapse). In this solvent, the p-methoxycumyl cations produced by cleavage reaction undergo trinitromethylation at the CIP stage, but cumyl cations produced by thermal oxidation of the cumyl radicals are trapped by 4- at the solvent-separated ion pair stage. In CH2Cl2, 1b-c.+ undergo exclusively fragmentation, completely within the solvent cage. The cleavage of 1d-e.+ is much slower, and the radical cations undergo instead aromatic trinitromethylations. The observed substituent effect on the rate of cleavage (p+ = -2.2) indicates significant charge transfer across the scissile bond in the transition state for this process. The products of these reactions are predominantly derived from ion annihilation. The radical coupling processes are limited to radical cation/radical collapse that lead to nitrated products.