3-hydroxy-4-homoadamantanone | 97382-24-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-hydroxy-4-homoadamantanone
• 英文别名: 3-hydroxytricyclo[4.3.1.13,8]undecan-4-one
• CAS: 97382-24-6
• 化学式: C₁₁H₁₆O₂
• 分子量: 180.247
• InChiKey: UCCJAVMRTDBGHX-UHFFFAOYSA-N

物化性质

• 熔点：
  242.5-244.5 °C
• 沸点：
  312.3±25.0 °C(Predicted)
• 密度：
  1.239±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.52
• 重原子数：
  13.0
• 可旋转键数：
  0.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  37.3
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  3-hydroxy-4-homoadamantanone 在 对甲苯磺酸 、 溶剂黄146 作用下， 以 乙醚 为溶剂， 反应 1.5h， 生成 1-金刚烷甲酮
  参考文献：
  名称：

  A New Route to 3-Labeled or 3-Substituted 4-Homoadamantanones

  摘要：

  C-4位含有碳-13、氘、烷基或芳基取代基的3,4-二羟基高金刚烷的频哪醇重排为获得标题化合物提供了一条新途径。

  DOI：

  10.1055/s-1991-26374
• 作为产物：
  描述：

  3,4-homoadamantanediol 在 铬酸 作用下， 以32%的产率得到3-hydroxy-4-homoadamantanone
  参考文献：
  名称：

  通过三氟甲磺酸1-金刚烷基酯与一氧化碳反应轻松合成3,4-高金刚烷二醇

  摘要：

  三氟甲磺酸催化的三氟甲磺酸1-金刚烷基酯（1）与一氧化碳和金刚烷的反应提供了作为主要产物的3-羟基-4-高金刚烷基1-金刚烷羧酸酯（2），可以轻松转化为3,4-高金刚烷二醇（5 ）-3,4-双功能高金刚烷衍生物的有前途的原料。

  DOI：

  10.1016/s0040-4039(00)89173-x

文献信息

• 3,4-Homoadamantadiene:  Generation and Regioselective [2+2] Cycloaddition of a Novel Tricyclic Bridgehead Allene
  作者：Kohei Ogawa、Takao Okazaki、Tomomi Kinoshita

  DOI：10.1021/jo026046n

  日期：2003.2.1

  Dehalogenation of 3-bromo-4-iodo-4-homoadamantene with n-BuLi gave rise to 3,4-homoadamantadiene, a novel tricyclic bridgehead allene, which readily dimerized to head-to-head and head-to-tail [2+2] cycloadducts in a ratio of 96:4. Trapping with 1,3-diphenylisobenzofuran was successful to yield the corresponding Diels-Alder adduct.

  3-溴4-碘-4-碘金刚烷与正丁基锂的脱卤反应生成了3,4-氨金刚烷二烯，这是一种新型的三环桥头烯，可以很容易地从头到尾和头到尾二聚化[2+ 2]比例为96：4的环加合物。用1，3-二苯基异苯并呋喃捕集成功地得到相应的Diels-Alder加合物。
• Reaction of 1-adamantyl cation with carbon monoxide in the presence of adamantane and trifluoromethanesulfonic acid: a convenient route to 3,4-homoadamantanediol
  作者：Ken'Ichi Takeuchi、Fumio Akiyama、Tadakazu Miyazaki、Itsuko Kitagawa、Kunio Okamoto

  DOI：10.1016/s0040-4020(01)90004-3

  日期：——

  ic acid (triflic acid) and adamantane affords 3-hydroxy-4-homoadamantyl l-adamantanecarboxylate (2) in 70% yield under appropriate conditions. Among various l-adamantyl cation precursors tested, l-adamantyl trifluoromethanesulfonate (triflate) and methanesulfonate (mesylate) have given the best, comparable results. As to the acid catalyst, fluorosulfonic acid is less effective than triflic acid, and

  在常压下，在三氟甲烷磺酸（三氟甲磺酸）和金刚烷的存在下，在四氯化碳中用一氧化碳对l-金刚烷阳离子进行羰基化反应，在70％的收率下，以70％的收率得到3-羟基-4-高金刚烷基l-金刚烷羧酸酯（2）。适当的条件。在测试的各种L-金刚烷基阳离子前体中，L-金刚烷基三氟甲磺酸盐（三氟甲磺酸盐）和甲磺酸盐（甲磺酸盐）给出了最佳的可比结果。对于酸催化剂，氟磺酸的效果不如三氟甲磺酸，而100％的硫酸和甲磺酸对生成2的硫酸完全无效。。建议每摩尔L-金刚烷基甲磺酸酯或三氟甲磺酸酯分别使用三氟甲磺酸和金刚烷五摩尔。该反应通过将1-金刚烷羰基阳离子加到1-金刚烷甲醛中（一种过渡中间体）而进行，然后进行Wagner-Meerwein重排。羟基酯2容易转化为3,4-高金刚烷二醇，这是3,4-双官能高金刚烷衍生物的有前途的原料。
• Effects of γ-cyano substituent in allylic bridgehead solvolyses: evidence for cyano π conjugation in carbocations
  作者：Ken'ichi Takeuchi、Toshikazu Kitagawa、Yasushi Ohga、Akitoshi Nakakimura、Motohiro Munakata

  DOI：10.1016/s0040-4020(97)00505-x

  日期：1997.6

  solvolyzes 2 × 105 times faster than rigid 2-methylene-1-adamantyl mesylate. Placement of a cyano substituent on the (E) position of the vinylic carbon of these systems hardly alter the rate ratio (6 × 105). The result suggests fortuitous cancellation of the inductive destabilizing effect of the cyano substituent by its mesomeric stabilizing effect toward the partially conjugated allylic cation. PM3 calculations

  略带挠性的甲磺酸4-亚甲基-3-高金刚烷基酯的溶剂分解速度比刚性的甲磺酸2-亚甲基-1-金刚烷基酯快2×10 5倍。在这些体系的乙烯基碳的（E）位置上放置氰基取代基几乎不会改变速率比（6×10 5）。该结果表明，通过氰基取代基对部分共轭的烯丙基阳离子的介观稳定作用，偶然消除了氰基取代基的感应去稳定作用。作为模型的简单烯丙基阳离子的PM3计算支持了实验结果。
• Solvolysis of 2-methylene bicyclic bridgehead derivatives: a model for gradual variation of .pi.-conjugation in carbocations
  作者：Kenichi Takeuchi、Toshikazu Kitagawa、Yasushi Ohga、Masayasu Yoshida、Fumio Akiyama、Akio Tsugeno

  DOI：10.1021/jo00027a050

  日期：1992.1

  The rates of solvolysis in ethanol or 80% ethanol at 25-degrees-C have been determined on 2-methylenebicyclo[2.2.2]oct-1-yl triflate (4a), 2-methylenebicyclo[3.2.1]oct-1-yl triflate (5a), 2-methylenebicyclo[3.2.2]non-1-yl mesylate (6a), 2-methylenebicyclo[3.3.1]non-1-yl mesylate (7a-OMs) and heptafluorobutyrate (7a-OHFB), 1-chloro-2-methylenebicyclo[4.2.2]decane (8a), 2-methylenebicyclo[4.3.1]dec-1-yl trifluoroacetate (9a), and 4-methylene-3-homoadamantyl heptafluorobutyrate (10a) and on their corresponding parent 1-bicycloalkyl and 3-homoadamantyl derivatives 4b-10b containing the respective leaving group. The rate ratios for 4a/4b, 5a/5b, 10a/10b, 6a/6b, 7a/7b, 8a/8b, and 9a/9b are 10(-3.9), 10(-1.9), 10(-1.1), 10(0.8), 10(0.9) (for mesylate), 10(-0.2), and 10(0.7), respectively. A plot of the logarithms of the rate ratios against olefinic strain energies of their corresponding unsubstituted bridgehead olefins shows that the smaller the olefinic strain energy, the greater the rate ratio, providing a methodology to gradually change the conjugative ability of bridgehead carbocations. The enhancement of allylic conjugation with increasing skeletal flexibility has been further verified by the enhanced solvolysis rate of (E)-2-ethylidenebicyclo[3.2.2]non-1-yl mesylate ((E)-6e) relative to 6a by a factor of 259. A similar study on much more rigid (E)-2-ethylidenebicyclo[2.2.2]oct-1-yl triflate ((E)-4e) gave a (E)-4e/4a rate ratio of 6.3. AM1 semiempirical molecular orbital calculations on pertinent 2-methylene and (E)-2-ethylidene bridgehead carbocations and corresponding hydrocarbons (L = hydrogen) also supported the increase in the conjugation with increasing skeletal flexibility. The solvolysis products were solely bridgehead substitution products, no indication for the formation of bridgehead olefin via an S(N)1' mechanism having been obtained.
• Solvolyses of 2-Oxo Bridgehead Compounds:  A Critical Examination of π-Conjugative Stabilization of α-Carbonyl Carbocations
  作者：Ken'ichi Takeuchi、Yasushi Ohga、Masayasu Yoshida、Keizo Ikai、Tadashi Shibata、Midori Kato、Akio Tsugeno

  DOI：10.1021/jo970454n

  日期：1997.8.1

  The methodology of changing ring flexibility to detect the pi-conjugative stabilization of bridgehead carbocations has been applied to eight 2-oxo (X = O) bridgehead carbocations. On the basis of the solvolytic behavior observed in kinetics and product analyses, the eight 2-oxo bridgehead substrates were classified into three categories: three substrates solvolyzing without ion-pair return that leads to primary isomers (class A), three substrates that form primary isomers by ion-pair return during solvolysis (class B), and two substrates that undergo solvent addition to the carbonyl group to form hemiacetals during solvolysis (class C). It was concluded that the substrates of class C could not be used for the present purpose. Essentially constant ethanolysis rate ratios, k(X = O)/k(X = H-2), of 10(-8.2)-10(-8.7) at 25 degrees C were obtained between four 2-oxo substrates in classes A and B and the corresponding parent unsubstituted ones. The result was interpreted to suggest that the pi-conjugative stabilization of tertiary alpha-carbonyl carbocations is negligibly small, if present. Slightly more negative k(X = O)/k(X = H-2) values of 10(-9.7) and 10(-9.2) for highly flexible bicyclo[4.2.2]dec-1-yl and bicyclo[4.3.1]dec-l-yl systems, respectively, were attributed to complex conformations in the ground and incipient carbocations. PM3 calculations on some 2-methylene and 2-oxo bridgehead carbocations supported the experimental results. Comparison of the solvolysis rates of 1,1,3,3-tetramethyl-2-oxobutyl mesylate with those of 1,1,3,3-tetramethylbutyl mesylate estimated from the rates of the corresponding chloride also failed to support the pi-conjugative stabilization of alpha-carbonyl carbocations.