4-chloro-2-(trinitromethyl)anisole | 110175-20-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 4-chloro-2-(trinitromethyl)anisole
• 英文别名: 2-trinitromethyl-4-chloroanisole；4-chloro-2-trinitromethylanisole；4-chloro-1-methoxy-2-(trinitromethyl)benzene
• CAS: 110175-20-7
• 化学式: C₈H₆ClN₃O₇
• 分子量: 291.605
• InChiKey: BPRFMYPMHQNZSR-UHFFFAOYSA-N

物化性质

• 沸点：
  334.5±42.0 °C(Predicted)
• 密度：
  1.612±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  147
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  4-chloro-2-(trinitromethyl)anisole 以 氘代乙腈 为溶剂， 生成 5-氯-2-甲氧基苯甲酸
  参考文献：
  名称：

  Thermal and Photochemical Decomposition Pathways of Trinitromethylarenes. Part I. The Conversion of ArC(NO2)3 to ArNO2 -- a Rationalization of Apparent Solvent Effects.

  摘要：

  The thermal and photochemical decomposition of trinitromethylarenes in an inert solvent (dichloromethane or acetonitrile) has been investigated, using 1-methoxy-4-trinitromethylnaphthalene (2) and 2-trinitromethyl-4-chloroanisole (6) as representatives of reactive and unreactive ArC(NO2)(3), respectively. Compound 2 underwent slow thermal decomposition in both solvents to give 4-methoxy-1-naphthoic acid (3) and 1-methoxy-4-nitronaphthalene (5). The reaction was speeded up by additives, such as 1-methoxynaphthalene or nitrous acid. The decomposition of 2 was strongly accelerated by irradiation with light of lambda>430 nm. Both the thermal and photochemical processes were faster in acetonitrile than in dichloromethane. Spin trapping experiments resulted in the trapping of ArCOO. radicals, in both the thermal and photochemical reactions, indicating that the decomposition reaction is at least partially of radical nature. The acid 3 was shown to undergo fast thermal nitrodecarboxylation by treatment with NO2 in dichloromethane.Compound 6 exhibited similar behaviour, except that the rates were much slower, less than 100 times slower than those of 2.The mechanism suggested involves an initial nitro-->nitrito rearrangement of ArC(NO2)(3), followed by homolytic decomposition of the nitritodinitromethylarene formed. The finding that trinitromethylarenes have differing stabilities, depending on the nature of the ring substituent(s) and/or the solvents used, offers a reasonable explanation for the chemoselectivity of tetranitromethane-ArH photolyses.

  DOI：

  10.3891/acta.chem.scand.50-0885
• 作为产物：
  描述：

  4-chloro-2-trinitromethyl-5-nitritoanisole 以 乙腈 为溶剂， 生成 4-chloro-2-(trinitromethyl)anisole
  参考文献：
  名称：

  Eberson, Lennart; Hartshorn, Michael P.; Svensson, Jan Olof, Acta Chemica Scandinavica, 1993, vol. 47, # 9, p. 925 - 934

  摘要：

  DOI：

文献信息

• Annihilation of aromatic cation radicals by ion-pair and radical pair collapse. Unusual solvent and salt effects in the competition for aromatic substitution
  作者：S. Sankararaman、W. A. Haney、J. K. Kochi

  DOI：10.1021/ja00259a035

  日期：1987.12
• SANKARARAMAN, S.;HANEY, W. A.;KOCHI, J. K., J. AMER. CHEM. SOC., 109,(1987) N 25, 7824-7838
  作者：SANKARARAMAN, S.、HANEY, W. A.、KOCHI, J. K.

  DOI：——

  日期：——
• Eberson, Lennart; Hartshorn, Michael P.; Svensson, Jan Olof, Acta Chemica Scandinavica, 1993, vol. 47, # 9, p. 925 - 934
  作者：Eberson, Lennart、Hartshorn, Michael P.、Svensson, Jan Olof

  DOI：——

  日期：——
• Thermal and Photochemical Decomposition Pathways of Trinitromethylarenes. Part I. The Conversion of ArC(NO2)3 to ArNO2 -- a Rationalization of Apparent Solvent Effects.
  作者：Lennart Eberson、Michael P. Hartshorn、F. Radner、Jan Olof Svensson、Johan Springborg、Kristian Rønning Pedersen、Muhammed Nour Homsi、Frank K. H. Kuske、Monika Haugg、Nathalie Trabesinger-Rüf、Elmar G. Weinhold

  DOI：10.3891/acta.chem.scand.50-0885

  日期：——

  The thermal and photochemical decomposition of trinitromethylarenes in an inert solvent (dichloromethane or acetonitrile) has been investigated, using 1-methoxy-4-trinitromethylnaphthalene (2) and 2-trinitromethyl-4-chloroanisole (6) as representatives of reactive and unreactive ArC(NO2)(3), respectively. Compound 2 underwent slow thermal decomposition in both solvents to give 4-methoxy-1-naphthoic acid (3) and 1-methoxy-4-nitronaphthalene (5). The reaction was speeded up by additives, such as 1-methoxynaphthalene or nitrous acid. The decomposition of 2 was strongly accelerated by irradiation with light of lambda>430 nm. Both the thermal and photochemical processes were faster in acetonitrile than in dichloromethane. Spin trapping experiments resulted in the trapping of ArCOO. radicals, in both the thermal and photochemical reactions, indicating that the decomposition reaction is at least partially of radical nature. The acid 3 was shown to undergo fast thermal nitrodecarboxylation by treatment with NO2 in dichloromethane.Compound 6 exhibited similar behaviour, except that the rates were much slower, less than 100 times slower than those of 2.The mechanism suggested involves an initial nitro-->nitrito rearrangement of ArC(NO2)(3), followed by homolytic decomposition of the nitritodinitromethylarene formed. The finding that trinitromethylarenes have differing stabilities, depending on the nature of the ring substituent(s) and/or the solvents used, offers a reasonable explanation for the chemoselectivity of tetranitromethane-ArH photolyses.