环己酮-1-¹³C | 63603-42-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 环己酮-1-¹³C
• 英文名称: <1-13C>-Cyclohexanon
• 英文别名: 1-13C-Cyclohexanon；(113C)Cyclohexanone
• CAS: 63603-42-9
• 化学式: C₆H₁₀O
• 分子量: 99.1338
• InChiKey: JHIVVAPYMSGYDF-PTQBSOBMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  环己酮-1-¹³C 在 potassium hydrogensulfate 、 magnesium 作用下， 生成 -1-methylcyclohexene
  参考文献：
  名称：

  The thermal Aromatization of Methyl-1,3-cyclohexadienes - an important argument against commonly accepted sigmatropic 1,7-H-shift reactions

  摘要：

  It has been demonstrated that the methyl and ring C-atoms of methyl-1,3-cyclohexadienes interchange their positions intramolecularly during the thermal conversion to toluene at temperatures above 600-degrees-C in a quartz flow system. Gas phase pyrolysis of double C-13-labeled methyl-1,3-cyclohexadienes with C-13-labels for the primary and the tertiary C-atom gave definite C-13-distribution patterns in the aromatic ring systems of the formed toluene as well as benzene with far-reaching similarities. The NMR data of the [C-13(2)]toluene isotopomers definitely rule out that the observed integration of the methyl C-atom into the ring system proceeds via the hitherto well-established sequence: electrocyclic ring opening of the 5-methyl-1,3-cyclohexadiene to 1,3,5-heptatriene, its sigmatropic 1,7-H shift and ensuing recyclization of the 1,3,5-heptatriene to methyl-1,3-cyclohexadienes.

  DOI：

  10.1002/prac.19943360303
• 作为产物：
  描述：

  dilithium;(1,7-13C2)heptanedioate 以85%的产率得到
  参考文献：
  名称：

  YUAN, SUN-SHINE;AJAMI, A. M., J. LABELLED COMPOUNDS AND RADIOPHARM., 1983, 20, N 1, 79-82

  摘要：

  DOI：

文献信息

• Enantioselective Intermolecular Aldehyde-Ketone Cross-Coupling through an Enzymatic Carboligation Reaction
  作者：Patrizia Lehwald、Michael Richter、Caroline Röhr、Hung-wen Liu、Michael Müller

  DOI：10.1002/anie.200906181

  日期：2010.3.22

  substrate tolerance of the enzyme is very broad and includes cyclic and open‐chain ketones, as well as diketones and α‐ and β‐ketoesters as acceptor substrates. The absolute configurations of two enzymatic products were determined by single‐crystal structure analysis.

  Happy new YerE：标题反应的第一个例子是使用 ThDP 依赖性酶催化剂呈现的。该酶的底物耐受性非常广泛，包括环状和开链酮，以及作为受体底物的二酮和 α- 和 β-酮酯。通过单晶结构分析确定两种酶产物的绝对构型。
• Revising the Role of a Dioxirane as an Intermediate in the Uncatalyzed Hydroperoxidation of Cyclohexanone in Water
  作者：Elena Rozhko、Stefania Solmi、Fabrizio Cavani、Angelo Albini、Paolo Righi、Davide Ravelli

  DOI：10.1021/acs.joc.5b00861

  日期：2015.6.19

  molecules rationalized the formation of the dioxirane intermediate via addition of the hydroperoxide anion to the ketone and revealed that this species is not involved in the formation of the Criegee adduct. The direct addition of hydrogen peroxide to the ketone is predicted to be favored over hydrolysis of the dioxirane, the latter in competition with ring opening to carbonyl oxide followed by hydration.

  研究了过氧化氢水溶液氧化环己酮的机理。实验表明，在与酮平衡的状态下，初步形成了一种中间体，称为环己叉二环氧乙烷，然后形成了1-hydroperoxycyclohexanol（Criegee加合物）。显式包含最多两个水分子的计算分析通过向酮中添加氢过氧化物阴离子使二环氧乙烷中间体的形成合理化，并表明该物种不参与Criegee加合物的形成。预计将过氧化氢直接加到酮中比二环氧乙烷的水解更有利，二环氧乙烷的竞争是与羰基氧化物的开环竞争，然后水合。然而，
• Detection of cyclohexyl hydroperoxide as an intermediate in Gif type oxidation of cyclohexane to cyclohexanone using 13C NMR spectroscopy
  作者：Derek H. R. Barton、Eva Csuhai、Dar�o Doller、Gilbert Balavoine

  DOI：10.1039/c39900001787

  日期：——

  The oxidation of [1-13C]cyclohexane to cyclohexanone under GoAggII conditions is followed using 13C NMR spectroscopy; cyclohexyl hydroperoxide is an intermediate which is transformed quantitatively into cyclohexanone.

  在GoAggII条件下，使用13C NMR光谱法监测[1-13C]环己烷氧化为环己酮的过程；环己基过氧化氢是一种中间产物，可定量转化为环己酮。
• Wolfschuetz, Roland; Franke, Wilfried; Heinrich, Nikolaus, Zeitschrift fur Naturforschung, Teil B: Anorganische Chemie, Organische Chemie, 1982, vol. 37, # 9, p. 1169 - 1173
  作者：Wolfschuetz, Roland、Franke, Wilfried、Heinrich, Nikolaus、Schwarz, Helmut、Blum, Wolfgang、Richter, Wilhelm J.

  DOI：——

  日期：——
• The gas-phase Smiles rearrangement: a heavy atom labeling study
  作者：Peter C. H. Eichinger、John H. Bowie、Roger N. Hayes

  DOI：10.1021/ja00194a011

  日期：1989.6