adamantylideneadamantan-4-one | 30979-67-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: adamantylideneadamantan-4-one
• CAS: 30979-67-0；83829-10-1
• 化学式: C₂₀H₂₆O
• 分子量: 282.426
• InChiKey: CDARRFNQVUSMGZ-HNENSFHCSA-N

物化性质

• 沸点：
  419.5±14.0 °C(Predicted)
• 密度：
  1.185±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.37
• 重原子数：
  21.0
• 可旋转键数：
  0.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  adamantylideneadamantan-4-one 在 lithium aluminium tetrahydride 、 18-冠醚-6 、 sodium hydride 作用下， 以 乙醚 为溶剂， 反应 18.17h， 生成 (1R^*,2S^*)-2-ethoxy-4-tricyclo[3.3.1.1^3,7]dec-2-ylidenetricyclo[3.3.1.1^3,7]decane
  参考文献：
  名称：

  Huang, Xicai; Bennet, Andrew J., Journal of the Chemical Society. Perkin Transactions 2 (2001), 1997, # 5, p. 1027 - 1033

  摘要：

  DOI：
• 作为产物：
  描述：

  (1R*,2R*)-2-Chloro-4-(tricyclo<3.3.1.1^3,7>decylidene)tricyclo<3.3.1.1^3,7>decane 在 sodium dichromate 、 硫酸 、 silver(l) oxide 作用下， 以 四氢呋喃 、 乙醚 、 水 为溶剂， 反应 7.0h， 生成 adamantylideneadamantan-4-one
  参考文献：
  名称：

  Stereochemistry of the Electrophilic Homoallylic Chlorination Reaction of Sterically Congested Alkenes with Benzenesulfenyl Chloride: The Structure of the Phenylthiiranium Ion Intermediate

  摘要：

  A methyl-substituted derivative (4) of the sterically congested alkene adamanylideneadamantane (Ad=Ad; 2) has been synthesized. Upon reaction with PhSCl, 4 shows a remarkable selectivity; only two of the remaining 15 homoallylic positions undergo reaction to give chlorinated products. The phenylthiiranium ion of the parent alkene Ad=Ad has been prepared and characterized by single-crystal X-ray diffraction and H-1 and C-13 NMR spectroscopy as its triflate salt (1d). Crystal data for [(C10H14)(2)S(C6H5)][SO3CF3]: triclinic, space group P (1) over bar; Z = 4; a = 10.983(3) Angstrom; b = 14.988- (3) Angstrom; c = 16.059(6) Angstrom; alpha = 95.60(2)degrees; beta = 93.39(2)degrees; gamma = 108.98(2)degrees; V = 2476 Angstrom(3); T = 216 K; R(F) = 0.052 for 4840 data (I-o greater than or equal to 2.5 sigma(I-o)) and 633 variables. The dimensions of the thiiranium (SC2) rings are S-C range 1.909(3)-1.937(3) Angstrom; (C-C) = 1.500 Angstrom; (C-S-C) = 46.1 degrees; C-C-S range 66.3(2)-67.9(2)degrees. The crystallographically independent cations display similarly asymmetric dispositions of the phenyl group: C-S-C-ipso are 108.5(2)degrees, 116.7(2)degrees, and 112.9(2)degrees, 117.6(2)degrees respectively; S-C-ipso = 1.789(3) Angstrom in both cases. In both cations the plane of the phenyl ring is approximately orthogonal to the plane of the thiiranium ring but nearly coplanar with one of the ring S-C bonds.

  DOI：

  10.1021/jo00102a042

文献信息

• Synthesis of aldehydes by a one-carbon homologation of ketones and aldehydes via α,β-unsaturated isocyanides
  作者：Janusz Moskal、Albert M. van Leusen

  DOI：10.1002/recl.19871060501

  日期：——

  Ketones and aldehydes react via a Wittig-Horner-Emmons reaction using diethyl (isocyanomethyl)phosphonate to form α,β-unsaturated isocyanides (4), which are either hydrolyzed as such, under acid conditions, or hydrolyzed after oxidation to α,β-unsaturated isocyanides (6) to give aldehydes containing one additional carbon atom. The scope of the reaction is demonstrated by 20 examples.

  酮和醛通过Wittig-Horner-Emmons反应，使用（异氰基甲基）膦酸二乙酯反应形成α，β-不饱和异氰酸酯（4），它们可以在酸性条件下如此水解，或者在氧化成α，β-后水解不饱和异氰酸酯（6），得到含有一个另外的碳原子的醛。反应的范围由20个实例证明。
• X⁺ transfer from the halonium ions of adamantylideneadamantane to acceptor olefins. The possibility of chiral induction in the transfer process
  作者：Alexei A. Neverov、Theresa L. Muise、R.S. Brown

  DOI：10.1139/v97-617

  日期：1997.12.1

  The bromonium ion of adamantylideneadamantane (Ad=Ad-Br+) has been used to induce the bromocyclization of a 4-pentenyl glycoside (10) and a 5-hexenyl glycoside (11) in dichloroethane. The kinetics of these processes have been studied at 25 °C in the presence of varying [Ad=Ad] and, in the case of the transfer to 10, in the presence of pentanol. The second-order rate constants for bromocyclization of

  金刚烷亚金刚烷 (Ad=Ad-Br+) 的溴离子已用于诱导 4-戊烯基糖苷 (10) 和 5-己烯基糖苷 (11) 在二氯乙烷中的溴环化。这些过程的动力学已经在 25 °C 下在不同 [Ad=Ad] 存在下进行了研究，在转移到 10 的情况下，在戊醇存在下进行了研究。这两种烯烃溴环化的二级速率常数分别为 (1.04 ± 0.06) × 10−1 M−1 s−1 和 (5.34 ± 0.2) × 10−1 M−1 s−1，并且在没有如果添加 Ad=Ad 或戊醇会改变反应速率。动力学行为被解释为直接从 Ad=Ad-Br+ 和 10 或 11 的 1:1 复合物发生的环化反应。 AdAd-Br+ 促进的 10 溴环化的手性诱导是在 20% ee 时测量的，(-)-(S)-四氢糠基溴是主要的立体异构体。Ad=Ad 分子在同位烯丙基碳之一上被轴向甲基（12）或两个甲基（轴向和赤道）取代，合成...
• Moskal, Janusz; Leusen, Albert M. van, Recueil des Travaux Chimiques des Pays-Bas, 1986, vol. 105, # 4, p. 141 - 142
  作者：Moskal, Janusz、Leusen, Albert M. van

  DOI：——

  日期：——
• A PROCESS FOR PREPARING SUBSTITUTED POLYCYCLO-ALKYLIDENE POLYCYCLO-ALKANES AS WELL AS SAID SUBSTITUTED POLYCYCLO-ALKYLIDENE POLYCYCLO-ALKANES
  申请人：RIJKSUNIVERSITEIT TE GRONINGEN

  公开号：EP0106863B1

  公开（公告）日：1986-08-20
• US4705847A
  申请人：——

  公开号：US4705847A

  公开（公告）日：1987-11-10