(4R)-4-甲基环庚烷-1-酮 | 13609-59-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: (4R)-4-甲基环庚烷-1-酮
• 英文名称: (R)-4-methylcycloheptanone
• 英文别名: (S)-4-methylcycloheptanone；(R)-4-methyl-cycloheptanone；(R)-4-Methyl-cycloheptanon；(-)-(4R)-Methylcycloheptanon；(4R)-4-Methylcycloheptanon；(4R)-4-Methylcycloheptan-1-one
• CAS: 13609-59-1
• 化学式: C₈H₁₄O
• 分子量: 126.199
• InChiKey: WXVNSHRGPVHBPD-SSDOTTSWSA-N

物化性质

• 沸点：
  184.9±8.0 °C(Predicted)
• 密度：
  0.897±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2914299000

反应信息

• 作为产物：
  描述：

  (R)-4-methylcyclohexylidenemethyl(4-methoxyphenyl)iodonium tetrafluoroborate 在 2,2,2-三氟乙醇 作用下， 反应 16.0h， 以90%的产率得到(4R)-4-甲基环庚烷-1-酮
  参考文献：
  名称：

  4-甲基环己叉基甲基碘盐的溶剂化：手性探针法合成伯乙烯基阳离子中间体。

  摘要：

  制备了光学活性的4-甲基环己叉基甲基（芳基）碘化四氟硼酸酯（1.BF（4）（-）），并在60℃下于各种溶剂中进行了溶剂分解。主要产物是在无缓冲溶剂中伴随有碘芳烃的旋光性4-甲基环庚酮（或其烯醇衍生物）。重排的产物始终保持起始1的光学纯度。其立体化学符合一种机制，该机制涉及通过sigma键参与核反应堆的离开而进行重排，然后捕获所得的手性5-甲基环庚-1-烯阳离子亲核溶剂。也就是说，在反应过程中不涉及非手性伯乙烯基阳离子。还可以在未缓冲的甲醇，乙醇和乙酸中以小部分获得未重排的取代产物，但不是在三氟乙醇或六氟-2-丙醇中：甲醇分解的甲氧基产物在很大程度上消旋，但乙酰化产物主要是通过保留构型获得的。1与溴化物，乙酸盐和三氟乙酸盐在氯仿中的反应在不同的转化度下产生未排列的取代产物。这些未重排的产物被认为是通过直接亲核取代形成的。在甲醇中添加碱（如乙酸钠）会导致外消旋的完全重排的甲氧基产物重新排列，这

  DOI：

  10.1021/jo020398c

文献信息

• Solvolysis of chiral cyclohexylidenemethyl triflate. Evidence against a primary vinyl cation intermediate
  作者：Morifumi Fujita、Akiyo Yamamoto、Takashi Sugimura、Tadashi Okuyama

  DOI：10.1002/poc.485

  日期：2002.8

  Solvolysis of (R)-4-methylcyclohexylidenemethyl triflate (6) was examined at 140 °C in various aqueous methanol and some other alcoholic solvents. The main product was (R)-4-methylcycloheptanone that maintains the stereochemical purity of 6, with accompanying 4-methylcyclohexanecarbaldehyde. In the presence of bromide ion, the bromide substitution product was also obtained, mostly with inversion of

  （R）-4-甲基环己叉基甲基三氟甲磺酸酯（6）在140℃下在各种甲醇水溶液和一些其他醇溶剂中的溶剂化进行了检查。主要产物是（R）-4-甲基环庚酮，其保持6的立体化学纯度，并伴有4-甲基环己烷甲醛。在存在溴化物离子的情况下，也获得了溴化物取代产物，大部分具有构型反转。结论是，溶剂分解不涉及伯乙烯基阳离子的形成，而是通过σ键参与而进行的，以形成作为中间体的重排的环庚烯阳离子。版权所有©2002 John Wiley＆Sons，Ltd.
• Solvolysis of Optically Active 4-Methylcyclohexylidenemethyl Triflate: Evidence against a Primary Vinyl Cation as an Intermediate
  作者：Morifumi Fujita、Akiyo Yamamoto、Takashi Sugimura、Tadashi Okuyama

  DOI：10.1246/cl.2001.806

  日期：2001.8

  Solvolysis of (R)-4-methylcyclohexylidenemethyl triflate in aqueous methanol at 140 °C gave stereospecifically (R)-4-methylcycloheptanone to definitively rule out intermediate formation of the achiral primary vinyl cation. The rearrangement must occur via concerted σ-bond participation.

  (R)-4-甲基亚环己基甲基三氟甲磺酸酯在 140°C 的含水甲醇中的溶剂分解产生立体定向的 (R)-4-甲基环庚酮，以明确排除非手性伯乙烯基阳离子的中间体形成。重排必须通过协同的 σ-键参与发生。
• Analysis of cycloheptanone conformation from temperature dependent circular dichroism measurements of (+)-(3R)-methylcycloheptanone and (−)-(4R)-methylcycloheptanone
  作者：D.A. Lightner、E.L. Docks

  DOI：10.1016/0040-4020(79)87022-2

  日期：1979.1

  Conformational analysis of methylcycloheptanones was achieved by relating CD rotational strengths to conformational free energies. Twist conformers with C1 on the symmetry axis (TC1) were found to be more stable than those with C2 or C7 on the symmetry axis (TC2 or TC7). The free energy differences were found to range from 0.2 to 1.2kcalmole. A similar analysis of (+)(3R)-methylcyclohexanone showed

  甲基环庚酮的构象分析是通过将CD旋转强度与构象自由能相关来实现的。发现在对称轴上具有C 1的扭曲构象（TC 1）比在对称轴上具有C 2或C 7的扭曲构象（TC 2或TC 7）更稳定。发现自由能差为0.2至1.2kcalmole。对（+）（3 R）-甲基环己酮的类似分析显示，赤道椅构象最稳定，范围为0.50-0.75 kcalmole。
• Cycloheptyne Intermediate in the Reaction of Chiral Cyclohexylidenemethyliodonium Salt with Sulfonates
  作者：Morifumi Fujita、Yuichi Sakanishi、Masayoshi Nishii、Tadashi Okuyama

  DOI：10.1021/jo0203995

  日期：2002.11.1

  Reactions of (R)-4-methyleyclohexylidenemethyl(phenyl)iodonium salt and its 3-trifluoromethylphenyl and 4-methoxyphenyl derivatives (1) with tetrabutylammonium mesylate and triflate were carried out in chloroform at 60 degreesC. The products include (S)-4-methylcyclohexylidenemethyl sulfonate (2) and (R)-5-methylcyclohept-1-enyl sulfonate (3) as well as iodoarene. Reactions of (S)-1 were confirmed to provide the counterpart results. The rearranged triflate (R)-3Tf formed in the reaction with triflate maintains mostly the ee (enantiomeric excess) of (R)-1, while the ee of the mesylate product 3Ms is largely lost. The C-13-labeling at the exocyclic position of 1 results in the isotopic scrambling of C-1 and C-2 of 3Ms in the mesylate reaction. The degree of the scrambling agrees well with that of the loss of ee of (R)-3Ms obtained from (R)-1, implying that the racemization is not due to the intermediate formation of achiral, primary 4-methylcyclohexylidenemethyl cation. Reaction of 1 with mesylate in the presence of CH3OD provided the 3Ms deuterated at the 2-position. When tetraphenylcyclopentadienone was added to the mesylate reaction system, the adduct of the 4-methylcycloheptyne intermediate was obtained in 24% yield, but the normal products 2Ms and 3Ms were still formed. The 3Ms obtained here in a low yield maintains the high ee of 1. These results indicate that the cycloheptyne is an intermediate responsible for the formation of racemic product 3Ms in the mesylate reaction. It is also concluded that the unrearranged products 2 are formed via the competitive pathways of in-plane and out-of-plane S(N)2 reactions.
• Chirality Transfer from 4-Methylcyclohexylidenemethyl(phenyl)iodonium Tetrafluoroborate to 4-Methylcycloheptanone during Solvolysis:  Evidence against a Primary Vinylic Cation as Intermediate
  作者：Morifumi Fujita、Yuichi Sakanishi、Tadashi Okuyama

  DOI：10.1021/ja001509x

  日期：2000.9.1