三环[2.2.1.0(2,6)]庚烷-3-酮 | 695-05-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 中文名称: 三环[2.2.1.0(2,6)]庚烷-3-酮
• 英文名称: tricyclo[2.2.1.0^2,6]heptan-3-one
• 英文别名: tricyclo[2.2.1.02,6]heptan-3-one；3-nortricyclanone；nortricyclenone-3；2,6-cyclo-norbornan-3-one；2,6-Cyclo-norbornan-3-on
• CAS: 695-05-6
• 化学式: C₇H₈O
• mdl: MFCD06796342
• 分子量: 108.14
• InChiKey: ITDQUAQMICQLER-UHFFFAOYSA-N

物化性质

• 沸点：
  183 °C
• 密度：
  1.0811 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.857
• 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：

  三环[2.2.1.0(2,6)]庚烷-3-酮 在 氢氧化钾 、 一水合肼 、 1,3-丙二醇 作用下， 生成 三环(2.2.1.02,6)庚烷
  参考文献：
  名称：

  Energy Intake, Body Mass Index, Physical Activity, and the Colorectal Adenoma-Carcinoma Sequence

  摘要：

  Little is known about the precise relationship between energy intake, overweight, sedentary lifestyle, and steps in the colorectal adenoma-carcinoma pathway. We studied these parameters within a case-control study. Patients with adenomas < 10 mm (n = 154) or > 10 min (n = 208) were compared with polyp-free controls (n = 426) for determining factors associated with adenoma formation, i.e., observed for small and large adenomas, or with adenoma growth only. Colorectal cancer cases (n = 171) were compared with population controls (n = 309) to determine factors specific to the final stage, cancer. Exercise reduced the risk of cancer [odds ratio (OR) = 0.3, 95% confidence interval (CI) = 0.2-0.5 for high vs. low physical activity] but had little influence on adenomas. High energy intake increased the risk of cancer [OR for 5th vs. 1st quintile (OR5) = 1.6, 95% CI = 0.9-2.9, p = 0.02], but not of adenomas. High body mass index (BMI) significantly increased the risk of large adenomas (OR, = 2.1, 95% CI = 1.2-3.5, p = 0. 02 and OR5 = 1.7, 95% CI = 1.0-3.1, p = 0.25) for large and small adenomas vs. polyp-free controls. Neither height nor weight nor BMI influenced the risk of cancer. Results were unmodified when controlling for dietary risk factors and family history. Energy intake, a sedentary lifestyle, and high BMI were independently associated with a high risk of cancer use for large adenomas, which indicates an effect on promotion of colorectal tumors. These findings suggest that preventive advice regarding these factors should be provided, even late in life, to decrease the risk of colorectal cancer.

  DOI：

  10.1207/s15327914nc391_7
• 作为产物：
  描述：

  2,5-降冰片二烯 在 jones' reagent 、 三氟化硼乙醚 、 sodium methylate 作用下， 以 甲醇 、 丙酮 为溶剂， 反应 13.0h， 生成 三环[2.2.1.0(2,6)]庚烷-3-酮
  参考文献：
  名称：

  Nortricyclyl-norbornenyl 阳离子。同位素扰动和同位素加扰

  摘要：

  用氘同位素微扰法研究了由 3-降三环基或降冰片烯基前体形成的稳定碳正离子。来自两个碳的 /sup 13/C NMR 信号，如果快速相互转化的降冰片烯基结构之间存在平衡，预计将通过同位素扰动广泛分裂，仅显示小的、与温度无关的分裂。得出的结论是，可能存在最多约 1% 的平衡降冰片烯基离子。单一结构（具有广泛电荷离域的北三环基）足以代表阳离子。这通过 di-/sup 13/C 标记的阳离子前体进行了验证，该前体还提供了完整的 J/sub 12/ /sup 13/C-/sup 13/C 偶联常数。氘化离子和 1 的核磁共振谱，7-di/sup 13/C 标记的离子表明阳离子在 0/sup 0/C 以下经历至少三种不同的加扰过程。光谱显示最快的过程涉及到双环 (3.1.1) 庚烯基阳离子的可逆骨架重排。还发生更慢的过程，包括氢化物转变。观察到的重排最终导致阳离子中所有碳和氢的完全混乱。

  DOI：

  10.1021/ja00246a035

文献信息

• [EN] NOVEL COMPOUNDS<br/>[FR] NOUVEAUX COMPOSÉS
  申请人：GLAXOSMITHKLINE IP DEV LTD

  公开号：WO2015180612A1

  公开（公告）日：2015-12-03

  Disclosed are novel retinoid-related orphan receptor gamma (RORγ) modulators and their use in the treatment of diseases mediated by RORγ.

  揭示了新型视黄醇相关孤儿受体γ（RORγ）调节剂及其在通过RORγ介导的疾病治疗中的应用。
• The Preparation and Acetolyses of 5-Deuteriated <i>exo</i>-2-Norbornyl-<i>p</i>-bromobenzenesulfonates
  作者：N. H. Werstiuk、R. R. MacDonald、R. W. Ouwehand、W. L. Chan、F. P. Cappelli、J. G. Ballard、R. E. Young、R. E. Massey、G. Timmins、I. Goodwin、A. Walling、Miss Y. Teruta

  DOI：10.1139/v72-097

  日期：1972.3.1

  The deuterionorborneols 2a, b, c, and e have been prepared and converted to the brosylates 1a, b, c, and e. The deuterium isotope effects determined spectrophotometrically for solvolysis in HOAc–KOAc are 1.00 ± 0.01, 1.01 ± 0.01, 0.99 ± 0.01, and 1.11 ± 0.01, respectively. These data establish that: (a) a steric deuterium isotope effect does not operate at C-5 and therefore probably not at C-6; (b) hyperconjugative stabilization of the norbornonium ion to the C-5 hydrogens is confirmed to be not important, and (c) provides the first experimental evidence that the hydrogen (deuterium) shift – internal return pathway contribution to the γ-deuterium isotope effects observed for 1d and e is minor.

  已制备出2a、b、c和e的二氢异辛醇，并转化为1a、b、c和e的brosylates。在HOAc-KOAc中进行溶剂解离的质谱光度法测定的氘同位素效应分别为1.00±0.01、1.01±0.01、0.99±0.01和1.11±0.01。这些数据表明：(a)在C-5上没有立体氘同位素效应，因此可能在C-6上也没有；(b)证实了对C-5氢原子的环状溴代离子的超共轭稳定不重要；(c)提供了首个实验证据，即1d和e的γ-氘同位素效应中氢(氘)位移-内部回归途径的贡献很小。
• The Lithium Amide Induced Rearrangement of Epoxysulfones Derived from Bicyclo[2.2.1]heptane System
  作者：Odón Arjona、Roberto Menchaca、Joaquı́n Plumet

  DOI：10.1016/s0040-4020(00)00294-5

  日期：2000.6

  Lithium amides induce rearrangement of the title compounds 1 to afford nortricyclanones 4 via a ketocarbene intermediate. Compounds 4 undergo hydride transfer reduction and imino aldol condensation to afford the other observed reaction products.

  氨基化锂诱导标题化合物1的重排，从而通过酮卡宾中间体得到降三环烷酮4。化合物4进行氢化物转移还原和亚氨基羟醛缩合，得到其他观察到的反应产物。
• Relative Basicities of Some <i>Endo</i> and <i>Exo</i> Norbornylamines
  作者：A. Gilbert Cook、Laura R. Wesner、Sarah L. Folk

  DOI：10.1021/jo9710442

  日期：1997.10.1

  group to disperse a positive charge and the relative polarizabilities of the solvents. Semiempirical AM1 and PM3 methods along with ab initio HF/STO-3G, HF/3-21G, and HF/6-31G methods were used to calculate proton affinities and dipole moments for each of the amines. The results of the theoretical calculations correspond well with the experimental observations.

  合成了一系列内降冰片基胺和外降冰片基胺，并在乙腈和二甲基甲酰胺溶剂中测定了它们的相对碱性。在两种溶剂中，外型异构体总是比相应的内型异构体碱性更高。所有研究的双环胺在乙腈溶剂中的pK（a）都比在二甲基甲酰胺中的pK（a）高，除了2-吗啉代降冰片烷是相反的。这种作用可以通过吗啉基团分散正电荷的能力和溶剂的相对极化率来解释。半经验AM1和PM3方法以及从头算的HF / STO-3G，HF / 3-21G和HF / 6-31G方法用于计算每种胺的质子亲和力和偶极矩。理论计算结果与实验结果吻合良好。
• Insights into Regioselective Oxy (−O−) and Imino (−NH−) Group Insertions of 3-Nortricyclanone
  作者：Murray G. Rosenberg、Ulrike Haslinger、Udo H. Brinker

  DOI：10.1021/jo0159587

  日期：2002.1.1

  rile (15), lactam (16a), and novel hydroxycarbonitriles 19-21 were selectively formed when 3-nortricyclanone (1) was treated with aqueous hydroxylamine-O-sulfonic acid (HOSA). Since nitrile 15 neither hydrolyzed nor underwent intramolecular Ritter reaction under these conditions, mechanisms involving Beckmann rearrangement of 3 to nitrilium ion 9 (normal) and Beckmann fragmentation of 3 to cation 8

  内酰胺4-氮杂三环[3.2.1.0（2,7）]辛烷-3-酮（16a）已证明是在先前报道的声称形成内酰胺3-氮杂三环[3.2.1.0（2,7）]的反应中形成的。 octan-4-one（17a）。在相关的反应中，用3-nortricyclanone（1）处理三环[3.1.0]己-2-烯-内-6-腈（15），内酰胺（16a）和新型羟基腈19-21选择性地形成。羟胺-O-磺酸水溶液（HOSA）。由于在这些条件下腈15既不水解也不进行分子内Ritter反应，因此使用半经验计算研究了涉及3到3离子的贝克曼重排（正常）和3到阳离子8的贝克曼碎裂（异常）的机理。当使用碱性HOSA时，内酰胺16a和17a可能以1：2的比例形成，可能是通过恶二氮杂6a形成的。使用NH（3）/ NaOCl试剂溶液观察到相似的选择性，除两种内酰胺外，它还提供内酯4-氧杂三环[3.2.1.0（2,7）] octan-3-one（