2,4,5-Trimethylbenzyl nitrate | 60367-99-9

• 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: 2,4,5-Trimethylbenzyl nitrate
• 英文别名: 2,4,5-trimethylbenzylnitrate；(2,4,5-trimethylphenyl)methyl nitrate
• CAS: 60367-99-9
• 化学式: C₁₀H₁₃NO₃
• 分子量: 195.218
• InChiKey: SNBXTBDHDAGMQC-UHFFFAOYSA-N

物化性质

• 沸点：
  297.0±19.0 °C(Predicted)
• 密度：
  1.123±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  2,4,5-Trimethylbenzyl nitrate 在 sodium azide 作用下， 以 二甲基亚砜 为溶剂， 生成 1-(azidomethyl)-2,4,5-trimethylbenzene
  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：

  1,2,4-三甲基苯 在 盐酸 、 silver nitrate 作用下， 以 溶剂黄146 、 乙腈 为溶剂， 反应 8.5h， 生成 2,4,5-Trimethylbenzyl 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

• 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.
• Fischer,A.; Leonard,D.R.A., Canadian Journal of Chemistry, 1976, vol. 54, p. 1795 - 1806
  作者：Fischer,A.、Leonard,D.R.A.

  DOI：——

  日期：——
• Aromatic iodination: evidence of reaction intermediate and of the .sigma.-complex character of the transition state
  作者：Carlo Galli

  DOI：10.1021/jo00010a013

  日期：1991.5

  The reactivity of four different procedures of aromatic iodination is compared under the same experimental conditions, and their selectivity toward two substrates in competition, i.e., mesitylene (1,3,5-trimethylbenzene, MES) and durene (1,2,4,5-tetramethylbenzene, DUR), is evaluated. Two of these procedures, namely, S2O8(2-)/I2 and Ce(IV)/I2, present strong oxidizing capacity. Since the same MES/DUR relative reactivity is obtained from the four procedures, it becomes possible to state that a common reactive intermediate, most likely the I+ ion, is generated. The use of the MES/DUR mechanistic probe allows one to describe the reactivity picture of the iodination reaction as one of electrophilic substitution at the aromatic nucleous, with a transition state properly represented in terms of a sigma-complex. The radical cation of durene also forms when the iodination is carried out by means of oxidizing agents, but it is solely responsible for the formation of side-chain substitution products and is not involved in the nuclear substitution process.
• Photochemical Nitration by Tetranitromethane. Part XXXIII. Adduct Formation in the Photochemical Reactions of 1,2,4,5- and 1,2,3,5-Tetramethylbenzene.
  作者：Craig P. Butts、Lennart Eberson、Karen L. Fulton、Michael P. Hartshorn、Ward T. Robinson、David J. Timmerman-Vaughan、Muhammed Nour Homsi、Frank K. H. Kuske、Monika Haugg、Nathalie Trabesinger-Rüf、Elmar G. Weinhold

  DOI：10.3891/acta.chem.scand.50-0991

  日期：——

  The photolysis of the charge-transfer complex of tetranitromethane and 1,2,4,5-tetramethylbenzene in dichloromethane or acetonitrile gives the epimeric 1,3,4,6-tetramethyl-3-nitro-6-trinitromethylcyclohexa-1,4-dienes 8 and 9, in addition to products of nuclear nitration 12 and side-chain modification 10, 11, and 13-18. Similar reactions of 1,2,3,5-tetramethylbenzene gave trans-1,3,5,6-tetramethyl-6-nitro-3-trinitromethylcyclohexa-1,4-diene 30 and two isomeric 'double' adducts 31 and 32, in addition to products of nuclear nitration 27 and side-chain modification 26, 28 and 29. The eliminative rearrangements of adducts 8 and 30 to give re-aromatized products in acetonitrile or [H-2(3)]acetonitrile and in [H-2]chloroform are reported. The photolysis of the charge-transfer complexes of tetranitromethane with either 1,2,4,5-tetramethylbenzene or 1,2,3,5-tetramethylbenzene in 1,1,1,3,3,3-hexafluoropropan-2-ol (HFP) gives a marked increase in the yields of ring-nitration products 12 or 27, respectively, reactions presumed to proceed via a nitrosation-oxidation sequence. Reaction of 1,2,4,5-tetramethylbenzene with excess nitrogen dioxide in HFP also results in extensive ring nitration to give 12 and 2,3,5,6-tetramethyl-1,4-dinitrobenzene (25); the latter compound is seen as arising via the 2,3,5,6-tetramethyl- 1,4-dinitrosobenzene (34). Similar reaction of 1,2,3,5-tetramethylbenzene gives ring-nitration product 27 as the major product. X-Ray crystal structures are reported for 2,4,6-trimethyl-1-(2',2',2'-trinitroethyl)benzene (26) and trans-1,3,5,6-tetramethyl-6-nitro-3-trinitromethyl-cyclohexa-1,4-diene (30). (C) Acta Chemica Scandinavica 1996.
• GALLI, CARLO, J. ORG. CHEM., 56,(1991) N0, C. 3238-3245
  作者：GALLI, CARLO

  DOI：——

  日期：——