1-(2-Adamantylidene)-1-methoxy-1-phenylmethane | 113849-79-9

• 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: 1-(2-Adamantylidene)-1-methoxy-1-phenylmethane
• 英文别名: Methoxy (phenyl)methylidene adamantane；2-(Methoxyphenylmethylene)adamantane
• CAS: 113849-79-9
• 化学式: C₁₈H₂₂O
• 分子量: 254.372
• InChiKey: DHZDVGLAGGHLLB-ZCXUNETKSA-N

物化性质

• 熔点：
  94-95 °C
• 沸点：
  379.8±21.0 °C(Predicted)
• 密度：
  1.089±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  19.0
• 可旋转键数：
  2.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  1-(2-Adamantylidene)-1-methoxy-1-phenylmethane 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 (2-羟基金刚烷-2-基)(苯基)甲酮
  参考文献：
  名称：

  甲基三氟甲基二环氧乙烷氧化。烯醇醚的环氧化

  摘要：

  分离出的甲基三氟甲基二环氧乙烷4b已用于实现烯醇醚（如烷氧基（芳基）亚甲基金刚烷1a-e和甲氧基（2-萘基）亚甲基2-bornane 1f）的快速低温环氧化，可提供出色的相应螺并氧杂环戊烷（92–97％）的收成。

  DOI：

  10.1016/s0040-4039(00)95175-x
• 作为产物：
  描述：

  苯甲醛二甲缩醛 在 正丁基锂 、 三甲基氯硅烷 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 75.0h， 生成 1-(2-Adamantylidene)-1-methoxy-1-phenylmethane
  参考文献：
  名称：

  Use of the Wadsworth–Emmons reaction for preparing hindered vinyl ethers and related 1,2-dioxetanes

  摘要：

  芳香醛缩醛可以与三甲基磷酸酯反应，生成相应的二甲基α-甲氧基苯基磷酸酯，这些磷酸酯可用于Wadsworth-Emmons反应，与亚当坦酮反应生成受阻的甲基乙烯醚。这些乙烯醚在制备化学发光的1,2-二噁烷中非常有用。反应的范围已被探索。

  DOI：

  10.1039/b002101f

文献信息

• Oxidation of enol ethers by metal(vi)oxide diperoxides
  作者：Ruggero Curci、Luigi Lopez、Luigino Troisi、S.M.Khaledur Rashid、A.Paul Schaap

  DOI：10.1016/0040-4039(88)85108-6

  日期：1988.1

  Alkoxy(aryl) adamantylidenes react with chromium(VI) or molybenum(VI) oxide diperoxides in CHCl3 under argon yielding the corresponding 1,2-dioxetanes and/or carbonyl products derived from the fragmentation of the dioxetanes. The reaction most likely proceeds via preliminary epoxidation of the unsaturaled substrates.

  烷氧基（芳基）金刚烷在氩气中与CHCl 3中的氧化铬（VI）或氧化钼（VI）二过氧化物反应，生成相应的1,2-二氧杂环丁烷和/或衍生自二氧杂环丁烷断裂的羰基产物。该反应最有可能通过不饱和底物的初步环氧化进行。
• Synthesis of 1,2-dioxetanes via 9,10-dicyanoanthracene-sensitized chain electron-transfer photooxygenations
  作者：Luigi Lopez、Luigino Troisi、S.M.Khaledur Rashid、A.Paul Schaap

  DOI：10.1016/s0040-4039(00)95235-3

  日期：1989.1

  Thermally stable 1,2-dioxetanes have been synthesized by 9,10-dicyano-anthracene (DCA)-sensitized photooxygenation of alkoxy (aryl)-methylidene adamantanes. The reactions most likely proceed via a chain electron-transfer process.

  通过对烷氧基（芳基）-亚甲基金刚烷类的9，10-二氰基蒽（DCA）敏化光氧合合成了热稳定的1，2-二氧杂环丁烷。该反应最有可能通过链电子转移过程进行。
• Synthesis of 1,2-dioxetanes via electron-transfer oxygenation
  作者：Ruggero Curci、Luigi Lopez、Luigino Troisi、S.M.K. Rashid、A.Paul Schaap

  DOI：10.1016/s0040-4039(00)96719-4

  日期：1987.1
• Electron-transfer reactions on enol-ethers induced by aminium salts syntheses of 1,2-dioxetanes and/or ketones
  作者：Luigi Lopez、Luigino Troisi

  DOI：10.1016/s0040-4020(01)88269-7

  日期：1992.1

  Thermally stable 4-alkoxy-4-(aryl)spiro [1,2-dioxetane-3,2'-adamantanes] 2a-e have been synthesized by reaction of oxygen-saturated methylene chloride solutions of alkoxy(aryl) methylidene adamantanes 1a-e with catalytic amounts of one electron oxidizing agents as tris-p-bromophenyl ammoniumyl and/or tris-o,p-dibromophenyl ammoniumyl hexachloroantimonates (reagents A,B). Similar reactions carried out on 1a-d, under argon-atmosphere, yield adamantyl-arylketones 5a-c together with the corresponding alcohols 6a-b. Both processes most likely involve the formation of radical cation intermediates (1+), leading to the reaction products through chain electron-transfer mechanisms.
• Face Selection in the Capture of Anionic Carbon
  作者：Vani R. Bodepudi、William J. le Noble

  DOI：10.1021/jo00091a009

  日期：1994.6

  Several reactions of 2-(5-phenyladamantyl) derivatives have been examined with the objective of determining the stereochemistry of addition of electrophiles to a trigonal center Ct carrying a full or partial negative charge. These reactions included the carbonation and bromination of the 2-lithioadamantane(s) attack at the zu face was found to be predominant. Methylation of 5-phenyl-2-adamantanone with either methyllithium or lithium dimethylcuprate gave mixtures of the methyl alcohols in which the E-isomer is the main product. Attempts to study the reactions of the enolate anion derived from the (E)- and (Z)-phenyl 2-(5-phenyladamantyl) ketones 7-Ph were not successful: bromination could not be forced at all, and methylation and protonation occur at oxygen. The enol ether and enol were studied also; brominations of these neutral species occur at the zu face. It is concluded that even the imposition of negative charge upon the trigonal center does not engender the type of hyperconjugation envisioned by Anh in the capture of electrophiles. Protonation of the enol ether led to an equilibrium mixture of ketones 7-Ph; protonation of the enol itself gave an excess of the E-isomer. Possible reasons for this unexpected outcome are discussed.