pentamethylbenzyl nitrate | 19405-90-4

• 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: pentamethylbenzyl nitrate
• 英文别名: Pentamethyl-benzylnitrat；2,3,4,5,6-Pentamethylbenzyl-nitrat；(2,3,4,5,6-Pentamethylphenyl)methyl nitrate
• CAS: 19405-90-4
• 化学式: C₁₂H₁₇NO₃
• 分子量: 223.272
• InChiKey: FBKAQBBTBZVMGE-UHFFFAOYSA-N

物化性质

• 熔点：
  95-97 °C
• 沸点：
  341.9±21.0 °C(Predicted)
• 密度：
  1.082±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  55
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  pentamethylbenzyl nitrate 在 水 作用下， 以 二甲基亚砜 为溶剂， 生成 2,3,4,5,6-五甲基苯甲醇
  参考文献：
  名称：

  Cort, Antonella Dalla; Mandolini, Luigi, Gazzetta Chimica Italiana, 1984, vol. 114, # 5/6, p. 283 - 284

  摘要：

  DOI：
• 作为产物：
  描述：

  五甲基苯 在 盐酸 、 silver nitrate 作用下， 以 水 、 溶剂黄146 、 乙腈 为溶剂， 反应 8.5h， 生成 pentamethylbenzyl nitrate
  参考文献：
  名称：

  Direct observation of the kinetic acidities of transient aromatic cation radicals. The mechanism of electrophilic sidechain nitration of the methylbenzenes

  摘要：

  DOI：

  10.1021/ja00188a048

文献信息

• A NOVEL CLEAVAGE WITH NITRIC ACID OF POLYMETHYLATED DIBENZYL SELENIDES AND SELENOXIDES
  作者：Hitomi Suzuki、Kazumasa Ohnishi

  DOI：10.1246/cl.1981.111

  日期：1981.1.5

  When treated with nitric acid at low temperature, the title selenides and selenoxides undergo a novel cleavage reaction to give the corresponding benzyl nitrates and elemental selenium.

  在低温下用硝酸处理时，标题中的硒化物和硒氧化物会发生一种新颖的裂解反应，生成相应的苄基硝酸盐和元素硒。
• An Interpretation of the Puzzling Dichotomy of the Reaction Modes Observed during the Side-chain Nitration of Alkylaromatics with HNO₃/CH₂Cl₂and HNO₃/(CH₃CO)₂O
  作者：Hitomi Suzuki、Hideki Koide、Yukiko Taki、Eiichi Ohbayashi、Takuji Ogawa

  DOI：10.1246/cl.1987.891

  日期：1987.5.5

  Nitration of substituted pentamethylbenzenes has been carried out under various conditions using the title nitrating systems in order to elucidate the peculiar dependence of the modes of side-chain substitution on the reagent employed; nitrooxylation with HNO3/CH2Cl2 and nitration with HNO3/(CH3CO)2O. Based on the evidence obtained from product variations with substituents, electrochemical nitrodecarboxylation

  已使用标题硝化系统在各种条件下对取代的五甲基苯进行硝化，以阐明侧链取代模式对所用试剂的特殊依赖性；用 HNO3/CH2Cl2 硝化和用 /(CH3CO)2O 硝化。基于从具有取代基的产物变化、芳基乙酸酯的电化学硝基脱羧和侧链反应初始阶段的 ESR 检查中获得的证据，提出多取代芳烃的侧链取代通过与 的杂溶路径发生/ 并通过与 /(CH3CO)2O 的均裂路径。
• Intermediate Stages of the Nitration of Hexamethylbenzene to Dinitroprehnitene
  作者：Hitomi Suzuki

  DOI：10.1246/bcsj.43.879

  日期：1970.3

  A syrupy substance formed in quantity during the nitration of hexamethylbenzene to dinitroprehnitene has been found to be a complex mixture of varying amounts, depending markedly on the conditions, of 2,3,4,5,6-pentamethylbenzyl nitrate, 5,6-bis(nitrooxymethyl)-1,2,3,4-tetramethylbenzene, nitropentamethylbenzene, 6-nitro-2,3,4,5-tetramethylbenzyl nitrate, 2,3,4,5,6-pentamethylphenylnitromethane, bis (2,3,4,5,6-pentamethylbenzyl) ether, pentamethylbenzaldehyde, and several other unidentified carbonyl compounds, nitrite esters, and aliphatic nitro compounds. On the basis of the products isolated, a possible path by which hexamethylbenzene can be converted into dinitroprehnitene has been suggested.

  在将六甲基苯硝化成二硝基苯的过程中，发现了一种大量形成的糖浆状物质，它是由 2,3,4,5,6-五甲基苄基硝酸盐、5,6-双(硝基氧甲基)-1,2,3,4-四甲基苯硝基五甲基苯、6-硝基-2,3,4,5-四甲基苄基硝酸盐、2,3,4,5,6-五甲基苯基硝基甲烷、双（2,3,4,5,6-五甲基苄基）醚、五甲基苯甲醛以及其他几种不明羰基化合物、亚硝酸酯和脂肪族硝基化合物。根据分离出的产物，提出了将六甲基苯转化为二硝基苯的可能途径。
• Thermal and Photochemical Nitration of Aromatic Hydrocarbons with Nitrogen Dioxide
  作者：E. Bosch、J. K. Kochi

  DOI：10.1021/jo00091a018

  日期：1994.6

  Aromatic hydrocarbons (ArH) are readily nitrated by nitrogen dioxide (NO2) in dichloromethane at room temperature and below (in the dark). The red colors, transiently observed, arise from the metastable precursor complex [ArH, NO+]NO3-, which is formed in the prior disproportionation of nitrogen dioxide induced by the aromatic donor (eq 7). The deliberate irradiation of the diagnostic (red) charge-transfer absorption band (h nu(CT)) of [ArH, NO+] NO3- at low temperatures results directly in aromatic nitration, even at -78 degrees C, where the thermal nitration is too slow to compete. The mechanism of the photochemical (charge-transfer) nitration is established by time-resolved laser spectroscopy to proceed via the aromatic cation radical (ArH.+) formed spontaneously upon the charge-transfer excitation of [ArH, NO+]NO3- in Scheme 1. The related thermal activation of [ArH, NO+]NO3- derives from the adiabatic electron transfer that produces the same radical pair [ArH.+ NO.] as the reactive intermediate in Scheme 3. The close relationship between the thermal/photochemical nitrations with nitrogen dioxide and those conventionally carried out with nitric acid (in the presence of nitrous acid) is delineated by Scheme 4.
• Photochemical Nitration by Tetranitromethane. Part XXXIV. The Photochemical Reactions of Pentamethylbenzene and Hexamethylbenzene with Tetranitromethane. The Formation and Rearrangement of Labile Adducts from Pentamethylbenzene.
  作者：Lennart Eberson、Michael P. Hartshorn、David J. Timmerman-Vaughan、Yincai Su、Markku Leskelä、Mika Polamo、Muhammed Nour Homsi、Frank K. H. Kuske、Monika Haugg、Nathalie Trabesinger-Rüf、Elmar G. Weinhold

  DOI：10.3891/acta.chem.scand.50-1121

  日期：——

  The photolysis of the charge transfer (CT) complex of tetranitromethane and pentamethylbenzene (13) in dichloromethane at -50 or -78 degrees C gives the labile epimeric 1,2,3,4,6-pentamethyl-3-nitro-6-trinitromethylcyclohexa-1,4-dienes 18 and 19. Adduct 18 rearranges rapidly in [H-2(2)]dichloromethane at 22 degrees C (half-life 9 min) to give 2,3,4,5-tetramethyl-1-(2',2',2'-trinitroethyl)benzene (21), 2,3,4,5-tetramethylphenylnitromethane (26), 2,3,4,5-tetramethylbenzyl nitrate (32) and 2,3,4,5-tetramethylbenzyl nitrite (36). The photolysis of the tetranitromethane-13 CT complex in dichloromethane at 20 degrees C gives compounds 21, 26, 32 and 36, in addition to their 2,3,4,6-tetramethyl analogues 20, 25, 31 and 35, the latter set of products probably arising from the rearrangement of the highly labile epimeric 1,2,3,5,6-pentamethyl-3-nitro-6-trinitromethylcyclohexa-1,4-dienes 54. The photolysis of the tetranitromethane-13 CT complex in acetonitrile gives mainly the phenylnitromethane 26, while similar reaction in 1,1,1,3,3,3-hexafluoropropan-2-ol yields pentamethylnitrobenzene 24, the latter by a nitrosation/oxidation sequence. Reaction of 13 with nitrogen dioxide in dichloromethane gives mainly compounds 26 and 30.No adducts were detected in the photolysis of the CT complex of hexamethylbenzene 14 in dichloromethane at accessible reaction temperatures (greater than or equal to-20 degrees C), but products of side-chain modification 37-46 were formed. In acetonitrile similar reaction gave in addition to the above products 37-46 the N-nitrosoacetamide 47 and its precursor 49. Compounds 47 and 49 are also formed, along with the major products pentamethylbenzyl nitrate 39 and the mono- and di-nitromethyl compounds 40 and 43, on reaction of 14 with nitrogen dioxide in acetonitrile.EPR spectroscopic examination of the photolysis of acidic (trifluoroacetic ) solutions of tetranitromethane and 13 or 14 demonstrated the formation of the corresponding radical cation or a transformation product thereof, i.e. the 1,2,3,4,5,6,7,8-octamethylanthracene radical cation from 13 or 14(.+) from 14.