1-(2,2,2-三氟乙氧基)金刚烷 | 74975-65-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 1-(2,2,2-三氟乙氧基)金刚烷
• 英文名称: 1-adamantyl 2,2,2-trifluoroethyl ether
• 英文别名: 1-(2,2,2-Trifluoroethoxy)adamantane
• CAS: 74975-65-8
• 化学式: C₁₂H₁₇F₃O
• 分子量: 234.262
• InChiKey: FWAJPPLFIOOVFG-UHFFFAOYSA-N

物化性质

• 沸点：
  242.5±35.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-(2,2,2-三氟乙氧基)金刚烷 在 吡啶 、 potassium osmate(VI) dihydrate 、 水 、 叔丁基锂 、 potassium carbonate 、 potassium hexacyanoferrate(III) 作用下， 以 乙醚 、 叔丁醇 、 正戊烷 为溶剂， 反应 22.5h， 生成 1-金刚烷醇
  参考文献：
  名称：

  三氟乙基 (TFE) 醚（一种新型醇保护基团）的碱基介导脱保护策略

  摘要：

  三氟乙基 (TFE) 醚被专门引入作为有机化学中的保护基团。讨论了它在vinigrol全合成中的首次战略应用和去除。这封信中介绍了两种锂碱介导的脱保护策略。在一种脱保护方法中，将三氟乙醚转化为二氟乙烯基醚，然后使用四氧化锇催化裂解，而在第二种方法中，形成二氟乙烯基阴离子并用亲电氧试剂 (MoOPH) 捕获以形成不稳定的二氟乙酸盐。为了进一步帮助读者，包括形成三氟乙基醚的方法的总结以及替代脱保护策略的讨论。

  DOI：

  10.1016/j.tetlet.2013.10.097
• 作为产物：
  描述：

  2-adamantyl tosylate 以35%的产率得到
  参考文献：
  名称：

  ALLARD B.; CASADEVALL A.; CASADEVALL E.; LARGEAU C., NOUV. J. CHIM., 1980, 4, NO 8-9, 539-545

  摘要：

  DOI：

文献信息

• Reactions of 1,3-dehydroadamantane with polyfluorinated alcohols
  作者：B. P. Gladkikh、V. M. Mokhov、G. M. Butov、I. A. Novakov

  DOI：10.1007/s11172-023-3830-3

  日期：2023.3

  A one-step synthesis of hard-to-reach adamantyl polyfluoroalkyl ethers in yields up to 95% comprises the reaction of strained 1,3-dehydroadamantane with polyfluorinated alcohols. In the competitive reactions of 1,3-dehydroadamantane with pentan-1-ol and its fluorinated analog, the latter compound is etherified predominantly (∼3:5).

  一种收率高达 95% 的难以达到的金刚烷基多氟烷基醚的一步合成包括应变 1,3-脱氢金刚烷与多氟化醇的反应。在 1,3-脱氢金刚烷与 pentan-1-ol 及其氟化类似物的竞争反应中，后一种化合物主要被醚化 (~3:5)。
• Solvolysis-decomposition ofN-1-adamantyl-N-p-tolylcarbamoyl chloride in hydroxylic solvents
  作者：Dennis N. Kevill、Veena Upadhyay

  DOI：10.1002/(sici)1099-1395(199708)10:8<600::aid-poc928>3.0.co;2-q

  日期：1997.8

  In hydroxylic solvents, N-1-adamantyl-N-p-tolylcarbamoyl chloride undergoes a facile rate-determing ionization with very little assistance from nucleophilic solvation (very low sensitivity to changes in solvent nucleophillcity). In the relatively nucleophilic aqueous ethanol or aqueous acetone, the cation formed reacts directly with the solvent. In fluoroalcohols, the low nucleophilicity of the solvent allows an effective competition from a pathway involving disproportionation to the 1-adamantyl cation and p-tolyl isocyanate, followed by reaction of the new cation either with solvent or with the chloride ion formed in the initial ionization, Grunwald-Winstein plots against Y-Cl values show for different binary solvent systems a marked dispersion, which can be considerably reduced by incorporation into the analyses of a term governed by the aromatic ring parameter. (I). (C) 1997 by John Wiley & Sons, Ltd.
• Solvolysis-decomposition of 1-adamantyl chloroformate: evidence for ion pair return in 1-adamantyl chloride solvolysis
  作者：Dennis N. Kevill、Jin Burm Kyong、Frederick L. Weitl

  DOI：10.1021/jo00301a019

  日期：1990.7
• Solvolyses of Bicyclo[2.2.2]oct-1-yl and 1-Adamantyl Systems Containing an Ethylidene Substituent on the 2-Position: Typical Examples of Rate Enhancements Ascribed to Relief of F-Strain
  作者：Yasushi Ohga、Motohiro Munakata、Toshikazu Kitagawa、Tomomi Kinoshita、Ken'ichi Takeuchi、Yasuo Oishi、Hiroshi Fujimoto

  DOI：10.1021/jo00094a012

  日期：1994.7

  The first typical examples are described on the solvolysis rate enhancements ascribed to the relief of F-strain between an alkyl group and the leaving group atom directly attached to the reaction center. The rates and products of solvolyses in ethanol were studied for 2-methylene- and (Z)- and (E)-2-ethylidenebicyclo[2.2.2]oct-1-yl triflates. Solvolyses were also conducted in ethanol and 2,2,2-trifluoroethanol (TFE) on 2-methylene- and (Z)- and (E)-2-ethylidene-1-adamantyl compounds having OMs, F, Cl, Br, or I asa leaving group. Ah the substrates gave the corresponding bridgehead substitution products as kinetic control products. The Z:E rate ratios at 25 degrees C were 217 +/- 6 for 2-ethylidenebicyclo[2.2.2]oct-1-yl triflates (ethanol) and 109 +/- Il(ethanol) and 117 fl(TFE)for 2-ethylidene-1-adamantyl mesylates. O-18 scrambling studies on the ethanolyses of(Z)- and (E)2-ethylidene-1-adamantyl mesylates showed that the titrimetrically determined Z:E rate ratios can be used as a measure of the rate ratios for the ionization step. The Z:E rate ratio in TFE at 25 degrees C for 2-ethylidene-1-adamantyl halides varied in the sequence F (ca. 70), Cl(1020 +/- 160), Br (2230 +/- 90), and I (9500 +/- 280). The significant increases in the rate ratio with the increase in the atomic size of halogen were explained in terms of the presence of F-strain in the Z substrates and its essential absence in the E substrates. Linear correlations were found in a plot of 1.36 x log[k(Z)/k(E)] against the MM2 steric energy difference between the Z and E isomers (slope 1.0) and against Hansch's Es, demonstrating the significance of F-strain effect in the enhanced rates of the (Z)-2-ethylidene-1-adamantyl system. These correlations showed an intercept of 0.8 kcal mol(-1), which suggested the greater stability of the (Z)-2-ethylidene-1-adamantyl cation than the corresponding E cation by this amount. Ab initio calculations (RHF/G-31G**) showed that the Z cation is more stable than the E cation by 1.0 kcal mol(-1), and that the large Z:E rate ratios are in part ascribed to the difference in the cation stability.
• Solvolysis in 2,2,2-trifluoroethanol-water and 2,2,2-trifluoroethanol-ethanol mixtures. Selectivity of the intermediates and N values
  作者：Joseph Kaspi、Zvi Rappoport

  DOI：10.1021/ja00531a027

  日期：1980.5