双环[3,1.0]2-己酮 | 4160-49-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 双环[3,1.0]2-己酮
• 英文名称: bicyclo[3.1.0]hexan-2-one
• CAS: 4160-49-0
• 化学式: C₆H₈O
• mdl: MFCD20040018
• 分子量: 96.1289
• InChiKey: HFCMQKFXCMZZMZ-UHFFFAOYSA-N

物化性质

• 沸点：
  58 °C(Press: 13 Torr)
• 密度：
  1.144±0.06 g/cm3(Predicted)
• 稳定性/保质期：
  存在于主流烟气中。

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.833
• 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

• 作为反应物：
  描述：

  双环[3,1.0]2-己酮 在 对甲苯磺酰叠氮 作用下， 以 二氯甲烷 为溶剂， 反应 108.0h， 生成 3-diazobicyclo-[3.1.0]hexan-2-one
  参考文献：
  名称：

  Ring Expansion and Contraction of a Two-Carbon Bridged Spiropentane

  摘要：

  The reactions of tricyclo[4.1.0.0(1,3)]heptan-4-one (5) and two related systems with diazomethane and m-CPBA were examined in order to determine the relative reactivity and migratory aptitudes for the three compounds. The reactions of 5 with diazomethane and m-CPBA yielded new derivatives of the tricyclo[5.1.0.0(1,3)]octane ring system that showed that migration of cyclopropylcarbinyl is favored over cyclopropyl migration in this system. Photolysis of 5-diazotricyclo[4.1.0.0(1,3)]heptan-4-one (23) in methanol and dimethylamine did not lead to ring contraction to the tricyclo[3.1.0.0(1,3)]hexane ring system, but an interesting product was derived from an unusual rearrangement process in the photolysis in dimethylamine. Matrix photolysis of 23 at 15 K gave a decrease in the diazo band at 2085 cm(-1) and the appearance of a new band at 2117 cm(-1), which is a normal position expected for a small-ring ketene such as cyclopropylketene. Thus, matrix photolysis appears to have yielded a derivative of the previously unknown tricyclo[3.1.0.0(1,3)]hexane ring system. The lithium enolate of 5 was characterized by NMR spectroscopy at -80 degrees C and was found to rearrange to m-cresol at -65 degrees C. The geometries of the bridged spiropentanes of this work were optimized at the MP2(frozen core)/6-31G* level of theory, and group equivalent values were derived in order to calculate the heats of formation for these compounds using the calculated energies.

  DOI：

  10.1021/jo970980e
• 作为产物：
  描述：

  1,4-环己二醇 在 chromium(VI) oxide 、 sodium hydride 作用下， 以 1,4-二氧六环 、 吡啶 、 溶剂黄146 、 丙酮 为溶剂， 反应 3.5h， 生成 双环[3,1.0]2-己酮
  参考文献：
  名称：

  2-双环[3.1.0]己酮的微波旋转谱、电偶极矩和几何结构

  摘要：

  摘要 我们报告了 2dbicyclo[3.1.0] 己酮在其振动基态和与五元环的弯曲模式 ν B 相关的振动激发态的微波旋转光谱。旋转常数随 ν B 的变化可以得出以下结论：尽管模式 v B 由不对称势能函数控制，但五元环实际上是平面的。在许多跃迁中测量斯塔克效应导致电偶极矩的分量 μ α = 3.28 ± 0.02 D 和 μ b = 1.81 ± 0.2 D。

  DOI：

  10.1016/0022-2860(84)80238-0

文献信息

• Cyclopropanation of alkenes with metallocarbenes generated from monocarbonyl iodonium ylides
  作者：Tristan Chidley、Graham K. Murphy

  DOI：10.1039/c8ob02636j

  日期：——

  Reacting Wittig reagents and the hypervalent iodine reagent iodosotoluene, in the presence of 10 mol% Cu(tfacac)2 and 5 equiv. of alkene, results in a novel cyclopropanation reaction. The reagent combination is believed to generate a transient monocarbonyl iodonium ylide (MCIY) in situ, which can be intercepted by the copper catalyst to give a metallocarbene. Both ester and ketone derived phosphoranes

  在10摩尔％Cu（tfacac）2和5当量的存在下，使Wittig试剂和高价碘试剂碘代甲苯反应。烯的合成导致新的环丙烷化反应。据信，该试剂组合可在原位产生瞬态单羰基碘鎓内鎓盐（MCIY），可被铜催化剂拦截以生成金属卡宾。可以使用酯和酮衍生的膦烷，也可以使用苯乙烯基和非苯乙烯基的烯烃，后者可提供高达81％的收率的环丙烷。
• De Novo Synthesis of Benzannelated Heterocycles
  作者：Johannes Feierfeil、Thomas Magauer

  DOI：10.1002/chem.201705662

  日期：2018.1.26

  functionalize commercially available heterocycles or resort to transformations that make use of benzene‐derived building blocks. Here, we report a powerful cascade reaction that enables the de novo construction of variously substituted indoles, indazoles, benzofurans and benzothiophenes from readily available bicyclo[3.1.0]hexan‐2‐ones. The transformation can be conducted under mild, non‐anhydrous conditions

  苯并环杂环如吲哚和吲唑是在天然产物、药物和农用化学品中发现的重要结构基序。对于他们的合成，化学家传统上要么对市售的杂环进行功能化，要么求助于利用苯衍生的结构单元的转化。在这里，我们报告了一种强大的级联反应，该反应能够从容易获得的双环[3.1.0]hexan-2-ones 从头构建各种取代的吲哚、吲唑、苯并呋喃和苯并噻吩。转化可以在温和、无水的条件下进行。对于吲哚的合成，机理研究表明，双环系统的电环开环和芳构化先于 3,3-σ 重排。
• THE DEAMINATION OF ALICYCLIC α-AMINOKETONES
  作者：O. E. Edwards、M. Lesage

  DOI：10.1139/v63-218

  日期：1963.6.1

  α-aminocyclohexanones has been shown to give cyclopentane carboxylic acids, bicyclo[3,1,0]hexane-2-ones, and 2-methyl-2-cyclopentene-1-ones. Deamination of 3-endo-aminocamphor gave cyclocamphanone, 6-isopropenyl-6-methyl-2-cyclohexen-1-one, and 6- (1′-hydroxy-1′-methylethyl)-6-methyl-2-cyclohexen-1-one.The formation of bicyclo[3,1,0]hexane by deamination of cyclohexylamine is reported for the first time. The

  已显示 α-氨基环己酮的脱氨基得到环戊烷羧酸、双环 [3,1,0] 己烷-2-酮和 2-甲基-2-环戊烯-1-酮。3-endo-aminocamphor 脱氨基得到环樟酮、6-isopropenyl-6-methyl-2-cyclohexen-1-one 和 6-(1'-hydroxy-1'-methylethyl)-6-methyl-2-cyclohexen-1一、首次报道了环己胺脱氨基生成双环[3,1,0]己烷。它和冰片胺的产物与相应的α-氨基酮产物之间的差异是根据C-C参与相应碳正离子的量来合理化的。
• Stereoselective synthesis of 2,4-methanoproline homologues
  作者：Oleksandr O. Grygorenko、Oleksiy S. Artamonov、Gennady V. Palamarchuk、Roman I. Zubatyuk、Oleg V. Shishkin、Igor V. Komarov

  DOI：10.1016/j.tetasy.2005.12.009

  日期：2006.1

  The stereoselective synthesis of 2-azabicyclo[2.2.1]heptane-1-carboxylic acid and 6-azabicyclo[3.2.1]octane-5-carboxylic acid, novel rigid bicyclic proline analogues, is reported. The synthesis was performed in five steps from the corresponding 2-cycloalken-1-ones. A known approach to 2,4-methanoproline is improved. The three amino acids constitute a library of conformationally constrained proline

  报道了新颖的刚性双环脯氨酸类似物2-氮杂双环[2.2.1]庚烷-1-羧酸和6-氮杂双环[3.2.1]辛烷-5-羧酸的立体选择性合成。由相应的2-环烯-1-酮以五个步骤进行合成。改进了已知的2，4-甲基脯氨酸的方法。这三个氨基酸构成了构象受限的脯氨酸类似物的文库，其可用于拟肽和肽模型的设计。
• Rhodium (II) compounds with functionalized metalated phosphines as bridging ligands
  作者：F. Estevan、P. Lahuerta、J. Lloret、D. Penno、M. Sanaú、M.A. Úbeda

  DOI：10.1016/j.jorganchem.2004.10.062

  日期：2005.10

  The reaction of Rh2(O2CCH3)4 · 2CH3OH with the phosphine P(4-BrC6H4)2(C6H5), 2, results in the formation of the monometalated compound Rh2(O2CCH3)3[PC] · 2CH3CO2H (PC representing a metalated P(4-BrC6H4)2(C6H5)). The reaction involves selective metalation of the phosphine at one Br-substituted ring (12:1 isomer ratio). The reaction of Rh2(O2CCH3)3[(4-BrC6H3)P(4-BrC6H4)(C6H5)] · 2CH3CO2H, 4, with one

  Rh 2（O 2 CCH 3）4  ·2CH 3 OH与膦P（4-BrC 6 H 4）2（C 6 H 5），2的反应导致形成单金属化合物Rh 2（O 2 CCH 3）3 [PC]·2CH 3 CO 2 H（PC表示金属化的P（4-BrC 6 H 4）2（C 6 H 5））。该反应涉及在一个Br-取代的环（异构体比例为12：1）上对膦进行选择性金属化。Rh 2（O 2 CCH 3）3 [（4-BrC 6 H 3）P（4-BrC 6 H 4）（C 6 H 5）]·2CH 3 CO 2 H，4与另外一摩尔的反应三苯基膦的合成产生两种主要立体异构体Rh 2（O 2 CCH 3）2 [（4-BrC 6 H 3）P（4-BrC 6 H 4）的混合物）（C 6 H 5）] [（C 6 H 4）P（C 6 H 5）2 ]·2CH 3 CO 2 H，5a和5b分离为纯净化合物。这两种化合物以三氟乙酸酯衍生物