Cyclohexanone, 2-(3,3-dimethyl-2-oxobutyl)- | 144536-58-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Cyclohexanone, 2-(3,3-dimethyl-2-oxobutyl)-
• 英文别名: 2-(3,3-dimethyl-2-oxobutyl)cyclohexan-1-one
• CAS: 144536-58-3
• 化学式: C₁₂H₂₀O₂
• 分子量: 196.29
• InChiKey: MZKARWNNTCFONE-UHFFFAOYSA-N

物化性质

• 沸点：
  294.3±13.0 °C(Predicted)
• 密度：
  0.963±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Cyclohexanone, 2-(3,3-dimethyl-2-oxobutyl)- 在 二(三甲基硅烷基)亚膦酸酯 、 水 作用下， 生成 8-tert-butyl-6,7,8-trihydroxy-7-phosphabicyclo<4.3.0> 7-oxide 、 8-tert-butyl-7,8-dihydroxy-6-trimethylsilyloxy-7-phosphabicyclo<4.3.0>nonane 7-oxide
  参考文献：
  名称：

  Biryukov, S. V.; Rostovskaya, M. F.; Vysotskii, V. I., Russian Journal of General Chemistry, 1995, vol. 65, # 4.1, p. 536 - 546

  摘要：

  DOI：
• 作为产物：
  描述：

  N-(1-Chloro-3,3-dimethyl-2-butylidene)isopropylamine 在 四丁基溴化铵 作用下， 以 四氢呋喃 为溶剂， 反应 26.0h， 生成 Cyclohexanone, 2-(3,3-dimethyl-2-oxobutyl)-
  参考文献：
  名称：

  NMR Studies of Five-Coordinate Tin Enolate: An Efficient Reagent for Halo Selective Reaction toward .alpha.-Halo Ketone or .alpha.-Halo Imine

  摘要：

  NMR studies of tin enolates 1, in the presence of HMPA, revealed the presence of a five-coordinate O-stannyl enolate 1(h) which contributes to upfield shifts of Sn peaks in the Sn-119 NMR spectrum and increased coupling constants J(Sn-119-C-13), compared with the four-coordinate tin enolate 1(e). The tautomeric equilibrium between C-stannyl ketone 1(k) and O-stannyl enolate 1(e) was changed by the addition of HMPA, the percentage of enol form being increased. The resulting five-coordinate tin enolates 1(h) showed high reactivity and selectivity for halide displacement in reactions with alpha-halo ketones 2. The tin enolates, when coordinated by Bu(4)NBr, effected a selective reaction with alpha-halo imines 5 to give a variety of gamma-imino ketones 6, which were subsequently hydrolyzed to 1,4-diketones or cyclodehydrated to substituted pyrroles 9.

  DOI：

  10.1021/jo00095a011

文献信息

• Cross-Coupling Reaction of α-Chloroketones and Organotin Enolates Catalyzed by Zinc Halides for Synthesis of γ-Diketones
  作者：Makoto Yasuda、Shoki Tsuji、Yusuke Shigeyoshi、Akio Baba

  DOI：10.1021/ja0258172

  日期：2002.6.1

  catalyzed by zinc halides. In contrast to the exclusive formation of 1,4-diketones 3 under catalytic conditions, uncatalyzed reaction of 1 with 2 gave aldol-type products 4 through carbonyl attack. NMR study indicates that the catalyzed reaction includes precondensation between tin enolates and α-haloketones providing an aldol-type species and their rearrangement of the oxoalkyl group with leaving halogen

  锡烯醇化物 1 与 α-氯代酮或溴酮 2 的反应得到 γ-二酮（1,4-二酮）3，由卤化锌催化。与在催化条件下仅形成 1,4-二酮 3 相比，1 与 2 的未催化反应通过羰基攻击得到羟醛型产物 4。NMR 研究表明，催化反应包括锡烯醇化物和 α-卤代酮之间的预缩合，提供醇醛型物质，以及它们的氧代烷基与离开卤素的重排以产生 1,4-二酮。催化剂卤化锌在每个步骤中都起着重要作用。预缩合的羰基攻击被催化剂作为路易斯酸加速，中间锌酸盐通过释放氧和与卤素键合促进重排。将各种类型的锡烯醇化物和 α-氯代酮和溴酮应用于锌催化的交叉偶联。另一方面，没有羰基部分的烯丙基卤化物对锌催化与锡的偶联反应惰性。
• Oxovanadium-induced oxidative desilylation for the selective synthesis of 1,4-diketones
  作者：Takashi Fujii、Toshikazu Hirao、Yoshiki Ohshiro

  DOI：10.1016/0040-4039(92)89041-a

  日期：1992.9

  Silyl enol ethers underwent the VO(OR)Cl2-induced homo- or cross-coupling giving 1,4-diketones selectively via one-electron oxidative desilylation.

  甲硅烷基烯醇醚经过VO（OR）Cl 2诱导的均偶联或交叉偶联，通过单电子氧化脱甲硅基选择性地产生1,4-二酮。
• PALLADIUM OR RUTHENIUM CATALYZED REACTION OF α-HALO KETONES WITH TRIBUTYLTIN ENOLATES: PREPARATION OF UNSYMMETRICAL 1,4-DIKETONES
  作者：Masanori Kosugi、Izumi Takano、Motoi Sakurai、Hiroshi Sano、Toshihiko Migita

  DOI：10.1246/cl.1984.1221

  日期：1984.7.5

  Palladium or ruthenium catalyzed cross-coupling of α-halo ketones with tributyltin enolates gave unsymmetrical 1,4-diketones, The method was applied to the dihydrojasmone synthesis.

  钯或钌催化α-卤代酮与三丁基锡烯醇化物的交叉偶联得到不对称的1,4-二酮，该方法应用于二氢茉莉酮的合成。
• Dichloro(2,2,2-trifluoroethoxy)oxovanadium(V). A Remarkably Effective Reagent for Promoting One-Electron Oxidative Cyclization and Unsymmetrical Coupling of Silyl Enol Ethers
  作者：Kendal Ryter、Tom Livinghouse

  DOI：10.1021/ja973585e

  日期：1998.3.1
• KOSUGI, MASANORI;TAKANO, IZUMI;SAKURAI, MOTOI;SANO, HIROSHI;MIGITA, TOSHI+, CHEM. LETT., 1984, N 7, 1221-1224
  作者：KOSUGI, MASANORI、TAKANO, IZUMI、SAKURAI, MOTOI、SANO, HIROSHI、MIGITA, TOSHI+

  DOI：——

  日期：——