2-methoxycyclohexanone dimethyl acetal | 67820-35-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-methoxycyclohexanone dimethyl acetal
• 英文别名: 2-Methoxycyclohexanon-dimethylketal；1,1,2-Trimethoxy-cyclohexan；1,1,2-Trimethoxycyclohexan；1,1,2-trimethoxycyclohexane
• CAS: 67820-35-3
• 化学式: C₉H₁₈O₃
• 分子量: 174.24
• InChiKey: RWEKIQYJAYAAKM-UHFFFAOYSA-N

物化性质

• 沸点：
  83-84 °C(Press: 15 Torr)
• 密度：
  0.97±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-methoxycyclohexanone dimethyl acetal 生成 methyl 6,6-dimethoxyhexanoate
  参考文献：
  名称：

  有机电化学。二十六。烯胺、卤代烯烃和烯醇醚的电氧化

  摘要：

  烯胺在甲醇中的电氧化得到两种类型的甲氧基化烯胺。烯醇醚的类似处理得到三甲氧基化合物。卤代烯烃在乙酸中电解生成的产物为α-乙酰氧基卤代烯烃和α-乙酰氧基酮。

  DOI：

  10.1246/bcsj.51.2179
• 作为产物：
  描述：

  2-羟基环己酮二聚物 在 盐酸 亚硫酸二甲酯 作用下， 以 六甲基磷酰三胺 为溶剂， 生成 2-methoxycyclohexanone dimethyl acetal
  参考文献：
  名称：

  立体化学研究—XXVI：2-取代的环己酮缩酮的构象平衡

  摘要：

  在一系列2-取代的环己酮缩酮中，构象平衡的位置已经通过1 H NMR确定。对于乙烯缩酮6，发现赤道构象异构体在焓上是优选的。相比之下，其他缩酮系统（5、7–9）则显示出轴向整合子的优势。根据乙缩醛链的旋转异构构象讨论了这种行为的原因。

  DOI：

  10.1016/0040-4020(82)85169-7

文献信息

• A New<b><i>α</i></b>-Iodination of Ketones Using Iodine-Ammonium Cerium(IV) Nitrate in Alcohol or Acetic Acid
  作者：C. Akira Horiuchi、Shinji Kiji

  DOI：10.1246/bcsj.70.421

  日期：1997.2

  The direct α-iodination of various ketones using iodine-ammonium cerium(IV) nitrate in acetic acid or alcohol gave the corresponding α-iodo ketones in high yields. The effect of cerium salt on the iodination of ketones, and the iodination of 5α-cholestan-3-one using several methods are also discussed. In the reaction of 3,3,5-trimethylcyclohexanone and unsymmetrical ketones, such as 2-hexanone and

  在乙酸或酒精中使用碘铵铈 (IV) 对各种酮进行直接 α-碘化，以高产率得到相应的 α-碘酮。还讨论了铈盐对酮碘化的影响，以及使用几种方法碘化5α-cholestan-3-one。3,3,5-三甲基环己酮与2-己酮、2-庚酮等不对称酮在甲醇、乙醇、1-丙醇、2-丙醇的作用下反应，得到区域选择性碘化产物。在溴化的情况下，酮与溴和硝酸铈 (IV) 铵的反应也产生相应的 α-溴酮。
• Geminal acylation of α-heterosubstituted cyclohexanones and their ketals
  作者：Ian R. Pottie、Sheldon N. Crane、Anna Lee Gosse、David O. Miller、D. Jean Burnell

  DOI：10.1139/v10-097

  日期：2010.11

  Geminal acylation of derivatives of cyclohexanone with Br, Cl, F, and OCH₃ in the α position, and of their corresponding dimethyl ketals, could not be accomplished to a significant extent following published procedures. The transformation was accomplished in two steps. The initial BF₃·Et₂O-mediated reaction with 1,2-bis(trimethylsilyloxy)cyclobutene gave a cyclobutanone product as a mixture of diastereomers. Only with 2-chlorocyclohexanone did this occur with good diastereoselectivity. Then, pinacol rearrangement of the diastereomeric mixture mediated by Amberlyst-15 in benzene provided the heterosubstituted spirocyclic diketone.

  按照已公布的程序，环己酮衍生物与 α 位 Br、Cl、F 和 OCH3 的双原子酰化，以及与之相应的二甲基酮的双原子酰化，在很大程度上无法完成。转化分两步完成。最初由 BF3-Et2O 介导的与 1,2-双（三甲基硅氧基）环丁烯的反应生成的环丁酮是非对映异构体的混合物。只有 2-氯环己酮才具有良好的非对映选择性。然后，在 Amberlyst-15 的介导下，非对映异构体混合物在苯中发生频哪醇重排反应，得到杂取代的螺环二酮。
• Stereochemically defined cyclohexanediois through the regioselective ring-opening of silylated epoxy alcohols
  作者：Waldemar Adam、Michael Prein、Markus J. Richter

  DOI：10.1016/0040-4020(95)00977-9

  日期：1996.1

  The nucleophilic ring-opening of the silylated epoxy alcohol 2 leads to highly functionalized building blocks of defined stereochemistry, whereby the regioselectivity may be controlled through the proper choice of the nucleophile and the reaction conditions.

  甲硅烷基化的环氧醇的亲核开环2所导致高度官能化构建限定立体化学，由此所述区域选择性可通过亲核试剂的适当选择和反应条件来控制的块。
• Photo-Cleavage of Carbon-Carbon Bond of<b><i>α</i></b>-Iodocycloalkanones Giving<b><i>ω</i></b>,<b><i>ω</i></b>-Dialkoxyalkanoic Ester in Alcohol
  作者：Shun-Jun Ji、C. Akira Horiuchi

  DOI：10.1246/bcsj.73.1645

  日期：2000.7

  The irradiation at λ > 300 nm of α-iodocycloalkanones with a high-pressure mercury lamp in alcohols containing a small amount of water afforded the corresponding ω,ω-dialkoxyalkanoic ester (65—88%) by photochemical cleavage of the C(I)-C=O bond at room temperature. In the case of a commercial fluorescent lamp as the irradiating light source, photochemical ring-opening products were also obtained. The irradiation of 2α-iodo-5α- and 4β-iodo-5β-cholestan-3-ones in methanol gave methyl 2,2-dimethoxy-2,3-seco-5α-cholestan-3-oate and methyl 4,4-dimethoxy-3,4-seco-5β-cholestan-3-oate in 78 and 62% yields, respectively. The photochemical behavior of the cleavage reaction of α-iodocycloalkanones is also discussed on the basis of 2-hydroxycycloalkanone as an intermediate.

  在含有少量水的醇中，用高压汞灯在 λ > 300 纳米波长下照射 α-碘环烷酮，可在室温下通过 C(I)-C=O 键的光化学裂解得到相应的 ω,ω- 二烷氧基烷酸酯（65-88%）。在使用商用荧光灯作为照射光源的情况下，也能获得光化学开环产物。在甲醇中辐照 2α-iodo-5α- 和 4β-iodo-5β-cholestan-3- 酮，可得到 2,2-二甲氧基-2,3-seco-5α-胆甾烷-3-酸甲酯和 4,4-二甲氧基-3,4-seco-5β-胆甾烷-3-酸甲酯，收率分别为 78% 和 62%。此外，还以 2-hydroxycycloalkanone 为中间体，讨论了 α-iodocycloalkanones 裂解反应的光化学行为。
• Electrostatic modulation of hydroxyl group ionization in acidic media. Evidence for the competitive operation of intramolecular SN2 reactions
  作者：Joanna T. Negri、Leo A. Paquette

  DOI：10.1021/ja00049a014

  日期：1992.11

  The acid-catalyzed cyclodehydration of the cis and trans isomers of 2-substituted 1-(3-hydroxypropyl)cyclohexanols results in the formation of spirocyclic tetrahydrofurans. The stereochemical course of these reactions is highly varied, ranging from a dominant preference for retention when R = OCH3 to modestly favored inversion when R = CH3. Experiments with O-18-labeled diols show that in the methoxyl series most of the isotope is retained irrespective of relative stereochemistry. On the other hand, the pair of phenyl-substituted isomers responds by losing approximately 50% of the label. The isotopic level in the product erodes further when R = CH3. The stereochemical and isotopic labeling results are interpreted in terms of competing intramolecular S(N)2 and classical S(N)1 pathways. The extent to which cooperative nucleophilic attack with loss of the primary hydroxyl is facilitated reaches a maximum in the methoxyl-substituted diols, as a consequence of electrostatic inhibition of tertiary carbocation formation. As this effect is progressively lessened, the percentage of S(N)1 response rises. At no time, however, do the stereoisomeric carbocations interconvert conformationally prior to cyclization.