2-chloro-1-iodoadamantane | 118453-03-5

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机碘化物
• 英文名称: 2-chloro-1-iodoadamantane
• CAS: 118453-03-5
• 化学式: C₁₀H₁₄ClI
• 分子量: 296.579
• InChiKey: BACDITFXGMKKJX-UHFFFAOYSA-N

物化性质

• 沸点：
  309.2±15.0 °C(Predicted)
• 密度：
  1.72±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.61
• 重原子数：
  12.0
• 可旋转键数：
  0.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  2-chloro-1-iodoadamantane 、 苯乙酮 在 potassium tert-butylate 作用下， 以 二甲基亚砜 为溶剂， 反应 2.0h， 以53%的产率得到α-(2-chloroadamant-2-yl)acetophenone
  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
• 作为产物：
  描述：

  4-protoadamantanone 在 磷酸 、 potassium chloride 、 potassium iodide 作用下， 以 六甲基磷酰三胺 为溶剂， 反应 192.0h， 生成 2-chloro-1-iodoadamantane
  参考文献：
  名称：

  1,2分布的金刚烷的合成

  摘要：

  4-外-和4-内-环氧亚甲基原金刚烷（1）和4-原金刚烷酮（2）的亲电催化反应提供了各种1,2-二取代的金刚烷。1与路易斯酸（例如氯化铝，溴化物和碘化物）在-78°C下的反应以优异的收率得到了2-氯-，2-溴-和2-碘-1-（羟甲基）金刚烷。当1与三氟化硼反应形成2-氟-1-（羟甲基）金刚烷时，发生了有趣的氟离子转移。1在溴化铝存在下与苯反应生成1-（羟甲基）-2-苯基金刚烷，产率为70％。通过酸催化的2的加氢卤代酸的加成和重排，获得了优异的2-卤代-1-金刚烷醇和1，2-二重金刚烷烷的产率。2-卤代-1-金刚烷醇用作合成另外十二种1,2-二卤代金刚烷烷的起始原料。三氟化硼催化的2与乙酸酐的反应以84％的收率提供了1,2-二乙酰氧基金刚烷。讨论了这些各种反应的机理。

  DOI：

  10.1016/s0040-4020(01)90330-8

文献信息

• ABDEL-SAYED, ASHRAF N.;BAUER, LUDWIG, TETRAHEDRON, 44,(1988) N 7, 1873-1882
  作者：ABDEL-SAYED, ASHRAF N.、BAUER, LUDWIG

  DOI：——

  日期：——
• Syntheses of 1,2-distributed adamantanes
  作者：Ashraf N. Abdel-Sayed、Ludwig Bauer

  DOI：10.1016/s0040-4020(01)90330-8

  日期：1988.1

  addition and rearrangement of 2 with hydrohalic acids there were obtained excellent yields of 2-halo-l-adamantanols and 1,2-dihaloadamantanes. 2-Halo-l-adamantanols served as starting materials for the synthesis of twelve additional 1,2- dihaloadamantanes. The boron trifluoride catalyzed reaction of 2 with acetic anhydride furnished 1,2-diacetoxyadamantane in 84% yield. Mechanisms for these various reactions

  4-外-和4-内-环氧亚甲基原金刚烷（1）和4-原金刚烷酮（2）的亲电催化反应提供了各种1,2-二取代的金刚烷。1与路易斯酸（例如氯化铝，溴化物和碘化物）在-78°C下的反应以优异的收率得到了2-氯-，2-溴-和2-碘-1-（羟甲基）金刚烷。当1与三氟化硼反应形成2-氟-1-（羟甲基）金刚烷时，发生了有趣的氟离子转移。1在溴化铝存在下与苯反应生成1-（羟甲基）-2-苯基金刚烷，产率为70％。通过酸催化的2的加氢卤代酸的加成和重排，获得了优异的2-卤代-1-金刚烷醇和1，2-二重金刚烷烷的产率。2-卤代-1-金刚烷醇用作合成另外十二种1,2-二卤代金刚烷烷的起始原料。三氟化硼催化的2与乙酸酐的反应以84％的收率提供了1,2-二乙酰氧基金刚烷。讨论了这些各种反应的机理。
• Reactions of 2-Iodo- and 1,2-Dihaloadamantanes with Carbanions in DMSO by the S_RN1 Mechanism
  作者：Andrés E. Lukach、Roberto A. Rossi

  DOI：10.1021/jo990156l

  日期：1999.8.1

  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.