1-methoxy-4-trinitromethylnaphthalene | 169178-80-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1-methoxy-4-trinitromethylnaphthalene
• 英文别名: 1-Methoxy-4-(trinitromethyl)naphthalene；1-methoxy-4-(trinitromethyl)naphthalene
• CAS: 169178-80-7
• 化学式: C₁₂H₉N₃O₇
• 分子量: 307.219
• InChiKey: IBVNCJOBVLTGGZ-UHFFFAOYSA-N

物化性质

• 沸点：
  406.9±45.0 °C(Predicted)
• 密度：
  1.512±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 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：

  1-methoxy-4-trinitromethylnaphthalene 在 1-甲氧基萘 作用下， 以 二氯甲烷 为溶剂， 反应 150.0h， 以29%的产率得到4-甲氧基-1-萘甲酸
  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：

  四硝基甲烷 、 1-甲氧基萘 以 二氯甲烷 为溶剂， 反应 1.0h， 以24.1%的产率得到1-methoxy-4-trinitromethylnaphthalene
  参考文献：
  名称：

  Butts, Craig P.; Eberson, Lennart; Hartshorn, Michael P., Acta Chemica Scandinavica, 1995, vol. 49, # 4, p. 253 - 264

  摘要：

  DOI：

文献信息

• Thermal and Photochemical Decomposition Pathways of Trinitromethylarenes. Part II. The Effects of Ethanol on the Photolysis Reactions of Some Alkoxy- and Dialkoxyarenes in the Presence of Tetranitromethane. Enhancement of Adduct and Trinitromethyl Substitution Product Formation.
  作者：Craig P. Butts、Lennart Eberson、Michael P. Hartshorn、Ola Persson、Ward T. Robinson、Bryan R. Wood、Ward T. Robinson、Björn O. Roos、Claire Vallance、Bryan R. Wood

  DOI：10.3891/acta.chem.scand.51-0718

  日期：——

  The photolysis of the charge transfer (CT) complex of tetranitromethane 1-methoxynaphthalene, 1,4-dimethoxybenzene, 1,2-dimethoxybenzene 1,2-methylenedioxybenzene or 2-methylanisole is reported for dichloromethane acetonitrile, dichloromethane-ethanol and acetonitrile-ethanol solvent systems, The effects of adding ethanol (8% v/v similar to 1.4 mol dm(-3)) to dichloromethane or acetonitrile as reaction solvents include: (i) the stabilization of alkoxytrinitromethylarenes, thus reducing their normal tendency for decomposition according ArC(NO2)(3) -->ArCOOH -->ArNO2, (ii) a reduction in the nucleophilicity of trinitromethanide ion, and (iii) changes in the regioselectivity of trinitromethanide ion attack on the radical cations of alkoxy-aromatic compounds away from attack ipso to the alkoxy substituent.Adducts are also stabilized, as shown by the photolysis of the CT complex of 1,4-dimethoxybenzene-tetranitromethane in dichloromethane-ethanol (8% v/v) gives the epimeric 1,4-dimethoxy-3-nitro-6-trinitromethylcyclohexa-1,4-dienes and 1,4-dimethoxy-2-trinitromethylbenzene, in addition to 1,4- dimethoxy-2-nitrobenzene. The adducts are detected also among the products of photolysis reactions in neat dichloromethane or acetonitrile.
• Butts, Craig P.; Eberson, Lennart; Hartshorn, Michael P., Acta Chemica Scandinavica, 1995, vol. 49, # 4, p. 253 - 264
  作者：Butts, Craig P.、Eberson, Lennart、Hartshorn, Michael P.、Persson, Ola、Robinson, Ward T.

  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.