(adamant-2-yl)nitromethane | 244248-24-6

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: (adamant-2-yl)nitromethane
• 英文别名: 2-(Nitromethyl)adamantane
• CAS: 244248-24-6
• 化学式: C₁₁H₁₇NO₂
• 分子量: 195.261
• InChiKey: AJBNZVGSJBPCQQ-UHFFFAOYSA-N

物化性质

• 沸点：
  308.4±11.0 °C(Predicted)
• 密度：
  1.126±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  45.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (adamant-2-yl)nitromethane 在 硝酸 、 乙酸酐 作用下， 以 二氯甲烷 为溶剂， 生成 、 alkaline earth salt of/the/ methylsulfuric acid 、 alkaline earth salt of/the/ methylsulfuric acid
  参考文献：
  名称：

  Klimochkin; Leonova; Moiseev, Russian Journal of Organic Chemistry, 1997, vol. 33, # 3, p. 334 - 339

  摘要：

  DOI：
• 作为产物：
  描述：

  2-金刚烷醇 在 potassium tert-butylate 、 氢碘酸 、 丙酮 、 sodium iodide 作用下， 以 二甲基亚砜 为溶剂， 反应 52.0h， 生成 (adamant-2-yl)nitromethane
  参考文献：
  名称：

  Reactions of 2-Iodo- and 1,2-Dihaloadamantanes with Carbanions in DMSO by the S_RN1 Mechanism

  摘要：

  The reaction of 2-iodoadamantane (1) with the potassium enolate of acetophenone (2) did not occur in the dark but succeeded under irradiation or in the presence of FeBr2 to give the substitution product 3 in 62% and 88% yields, respectively. The photostimulated reaction was inhibited by p-dinitrobenzene (p-DNB). There was no reaction of 1 with the anion of nitromethane (4) in the dark or under irradiation. However, 4 reacted with 1 in the presence of acetone enolate ion (entrainment reaction) to yield 88% of the substitution product 2-adamantylnitromethane (5). The photostimulated reaction of 1 with anthrone (6), 2-naphthyl methyl ketone (9), and N-acetylthiomorpholine (11) anions afforded the substitution compounds 7 (37%), 10 (32%), and 12 (20%), respectively. There was no reaction of 1-chloro-2-iodoadamantane (13) with 2 in the dark (2 h), but under irradiation (5 min) it yielded 52% of the monosubstitution product alpha-(1-chloro-2-adamantyl)acetophenone (14). Under longer irradiation time (3 h), the same yield of 14 (52%) was obtained but the disubstitution product 15 was formed in 45% yield. Product 15 was also formed in the photostimulated reaction of 14 with 2. 2-Chloro-1-iodoadamantane (18) did not read with 2 in the dark (2 h), but the photostimulated reaction yielded the monosubstitution product alpha-(2-chloro-1-ladamantyl)acetophenone (19) in 53% and 15 in 4% yield. Products 14 and 19 are intermediates in the formation of 15 in these reactions. There was a slow dark reaction of 1,2-diiodoadamantane (20) with 4 in the presence of acetone enolate ion to afford the iodomonosubstitution compound 21 (40%) and the disubstitution product 22 (13%). The photostimulated reaction (25 min) gave 21 (48%) and 22 (41%). On the other hand, after 3 h of irradiation, only traces of 21 could be detected (<5%) and the product distribution consisted mainly of 22. The iodomonosubstitution product 21 is an intermediate in these reactions.

  DOI：

  10.1021/jo990156l

文献信息

• Reactions of halo- and dihaloadamantanes with nitromethane anions by theSRN1 mechanism
  作者：Ana N. Santiago、Carlos A. Toledo、Roberto A. Rossi

  DOI：10.1002/poc.603

  日期：2003.8

  1-bromo-, 2-bromo-, 1,3-dibromo- and 1,4-dibromoadamantane with −CH2NO2 anions were studied in DMSO and in liquid ammonia. The photostimulated reaction of 1-haloadamantane (1-AdX, X = Br, I) or 2-AdBr with −CH2NO2 anions gave good yields of the substitution product 1-AdCH2NO2 and 2-AdCH2NO2, respectively, in the presence of the enolate anions of acetone (entrainment conditions). On the other hand, 1-adamantanol

  1-溴，2-溴，1,3-二溴和1,4-二溴金刚烷用的反应- CH 2 NO 2的阴离子在DMSO中并在液氨进行了研究。1-haloadamantane的光刺激反应（1-的AdX，X = Br的，I）或2- AdBr与- CH 2 NO 2周的阴离子，得到取代产物的良好的产率1-ADCH 2 NO 2和2- ADCH 2 NO 2，分别在丙酮的烯醇阴离子存在下（夹带条件）。另一方面，1-金刚烷醇是在没有辐射的DMSO中而不是在液氨中进行的反应的主要产物。1,3-二溴和1,4-二溴金刚烷与-在丙酮的烯醇盐阴离子存在下于辐射下的CH 2 NO 2阴离子。第一种化合物给出了破坏性产物11，而第二种化合物给出了单溴代产物15和16，以及破坏性产物17。化合物15和16被证明是17的中间体。版权所有©2003 John Wiley＆Sons，Ltd.