1-hydroxybicyclo[4.3.1]decan-2-one | 121455-48-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-hydroxybicyclo[4.3.1]decan-2-one
• CAS: 121455-48-9
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: BKTYVLLHJBCJLM-UHFFFAOYSA-N

物化性质

• 熔点：
  122-123 °C(Solv: pentane (109-66-0))
• 沸点：
  291.5±23.0 °C(Predicted)
• 密度：
  1.146±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-hydroxybicyclo[4.3.1]decan-2-one 在 2,6-二甲基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.67h， 生成 1-Methoxy-bicyclo[4.3.1]decan-2-one
  参考文献：
  名称：

  Solvolyses of 2-Oxo Bridgehead Compounds:  A Critical Examination of π-Conjugative Stabilization of α-Carbonyl Carbocations

  摘要：

  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.

  DOI：

  10.1021/jo970454n

文献信息

• Structural Factors for the Formation of Propellane-Type Products in the Solvolysis of Bicyclic Bridgehead Compounds
  作者：Kazuhiko Tokunaga、Seiichiro Tachibana、Takao Okazaki、Yasushi Ohga、Toshikazu Kitagawa、Ken'ichi Takeuchi

  DOI：10.1021/jo000444d

  日期：2000.8.1

  the corresponding propellanone in 12%, 20%, or 3.2% yield, respectively, beside substitution or rearranged products under typical conditions. No propellane-type product was obtained in the solvolyses of 1-bromobicyclo[3.3.1]nonane, 2-methylidenebicyclo[3.3.1]non-1-yl heptafluorobutyrate, and 3, 3-dimethyl-2-thioxobicyclo[3.3.1]non-1-yl tosylate. The factors that permit the formation of the propellane-type

  2-氧代双环[3.3.1]壬-1-基三氟甲磺酸酯，3、3-二甲基-2-氧代双环[3.3.1]壬-1-基三氟甲磺酸酯和2-氧代双环[4]的甲醇水解。3.1]甲磺酸癸-1-基酯在典型条件下除取代或重排产物外，分别以12％，20％或3.2％的产率得到相应的螺酮。在1-溴双环[3.3.1]壬烷，2-亚甲基双环[3.3.1]壬-1-基七氟丁酸酯和3,3-二甲基-2-硫代双环[3.3.1]的溶剂解中未获得丙炔类产物] 1-甲苯磺酸壬基酯。在PM3和B3LYP / 6-31G的理论计算的帮助下，研究了允许由中间桥头阳离子形成丙炔型产物的因素。
• 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.