endo-2-carboxy-exo-5-bromo-endo-6-hydroxynorbornane lactone | 123536-32-3

• 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
• 英文名称: endo-2-carboxy-exo-5-bromo-endo-6-hydroxynorbornane lactone
• 英文别名: 6-bromohexahydro-2H-3,5-methanocyclopenta[b]furan-2-one；(+/-)-6c-bromo-(3ar)-hexahydro-3,5-methano-cyclopenta[b]furan-2-one；(+/-)-6c-Brom-(3ar)-hexahydro-3,5-methano-cyclopenta[b]furan-2-on；(1S,2S,3S,6S,7R)-2-bromo-4-oxatricyclo[4.2.1.03,7]nonan-5-one
• CAS: 123536-32-3
• 化学式: C₈H₉BrO₂
• 分子量: 217.062
• InChiKey: ZFCNOHNDCYYXIK-REQIZBSHSA-N

物化性质

• 沸点：
  349.0±25.0 °C(Predicted)
• 密度：
  1.755±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  endo-2-carboxy-exo-5-bromo-endo-6-hydroxynorbornane lactone 在 氢氧化钾 作用下， 以 甲醇 、 乙醚 、 水 为溶剂， 反应 6.0h， 生成 endo-6-Carbomethoxybicyclo<2.2.1>heptan-2-one
  参考文献：
  名称：

  Strecker 合成和 Bucherer - Bergs 反应的一些立体化学方面

  摘要：

  Strecker 和 Bucherer-Bergs 反应均将降冰片烷酮酯甲酯双环[2.2.1]hept-6-one-2-endo-carboxylate 转化为内酰胺 6-endo-aminobicyclo[2.2.1]heptane-2-endo-carboxylate羧酸-γ-内酰胺-6-外-羧酸。这种内酰胺异常稳定，不能水解成相应的氨基酸。Strecker 反应中的立体化学（其中氨基为内基）与文献先例所预期的相反。Bucherer-Bergs 反应中的立体化学，其中氨基也是 endo，已通过中间体螺乙内酰脲 (±)-bicyclo[2.2.1]heptane-2-endo-carboxy acid- 的 X 射线晶体学分析得到证实。 6-螺-5'-乙内酰脲。

  DOI：

  10.1071/ch03202
• 作为产物：
  描述：

  5-降冰片烯-2-羧酸 在 溴 、 碳酸氢钠 作用下， 以 水 为溶剂， 反应 16.0h， 以35%的产率得到endo-2-carboxy-exo-5-bromo-endo-6-hydroxynorbornane lactone
  参考文献：
  名称：

  Strecker 合成和 Bucherer - Bergs 反应的一些立体化学方面

  摘要：

  Strecker 和 Bucherer-Bergs 反应均将降冰片烷酮酯甲酯双环[2.2.1]hept-6-one-2-endo-carboxylate 转化为内酰胺 6-endo-aminobicyclo[2.2.1]heptane-2-endo-carboxylate羧酸-γ-内酰胺-6-外-羧酸。这种内酰胺异常稳定，不能水解成相应的氨基酸。Strecker 反应中的立体化学（其中氨基为内基）与文献先例所预期的相反。Bucherer-Bergs 反应中的立体化学，其中氨基也是 endo，已通过中间体螺乙内酰脲 (±)-bicyclo[2.2.1]heptane-2-endo-carboxy acid- 的 X 射线晶体学分析得到证实。 6-螺-5'-乙内酰脲。

  DOI：

  10.1071/ch03202

文献信息

• A Highly Efficient Method for the Bromination of Alkenes, Alkynes and Ketones Using Dimethyl Sulfoxide and Oxalyl Bromide
  作者：Hongyu Tian、Baoguo Sun、Rui Ding、Jiaqi Li、Wenyi Jiao、Mengru Han、Yongguo Liu

  DOI：10.1055/s-0037-1609560

  日期：2018.11

  α-bromoketones. The pairing of DMSO and oxalyl bromide is reported as a highly efficient brominating reagent for various alkenes, alkynes and ketones. This bromination approach demonstrates remarkable advantages, such as mild conditions, low cost, short reaction times, provides excellent yields in most cases and represents a very attractive alternative for the preparation of dibromides and α-bromoketones.

  摘要 据报道，DMSO和草酰溴的配对是用于各种烯烃，炔烃和酮的高效溴化试剂。这种溴化方法显示出显着的优势，例如条件温和，成本低，反应时间短，在大多数情况下提供优异的收率，并且是制备二溴化物和α-溴代酮的极具吸引力的替代方法。 据报道，DMSO和草酰溴的配对是用于各种烯烃，炔烃和酮的高效溴化试剂。这种溴化方法显示出显着的优势，例如条件温和，成本低，反应时间短，在大多数情况下提供优异的收率，并且是制备二溴化物和α-溴代酮的极具吸引力的替代方法。
• A Convenient Method for Bromolactonization
  作者：Richard C. Cambie、Peter S. Rutledge、Robyn F. Somerville、Paul D. Woodgate

  DOI：10.1055/s-1988-27790

  日期：——

  Bromolactones are conveniently obtained from unsaturated acids, bromine, and thallium(I) carbonate.

  溴内酯可以方便地从不饱和酸、溴和碳酸铊(I)中获得。
• The role of neat substrates in phase-vanishing and tandem phase-vanishing reactions
  作者：Nicole Windmon、Veljko Dragojlovic

  DOI：10.1016/j.tetlet.2008.09.007

  日期：2008.11

  Phase-vanishing reactions are triphasic reactions, which involve a reagent, a liquid perfluoroalkane as a phase screen and a Substrate. Aromatization, isomerization and halogenation of neat Substrates under phase-vanishing conditions gave the expected products in good to excellent yields. In tandem single-phase-phase-vanishing reaction, two reactants, placed in the top phase, afforded the intermediate, which in a Subsequent phase-vanishing reaction reacted with the reagent from the bottom phase to give the final product. The reaction worked well under solvent-free conditions on liquid Substrates and intermediates. With solids, results were better if an additional solvent was employed. (C) 2008 Elsevier, Ltd. All rights reserved.
• Monoamine oxidase-catalyzed oxidation of endo,endo -2-amino-6-[( Z )-2′-phenyl]ethenylbicyclo[2.2.1]heptane, a potential probe for a radical cation intermediate
  作者：Xueqing Wang、Richard B Silverman

  DOI：10.1016/s0968-0896(00)00094-8

  日期：2000.7

  An 11-step synthesis of endo,endo-2-amino-6-[(E)-2'-phenyl]ethenylbicyclo[2.2.1]heptane (6) and the corresponding (Z)-isomer (7) was carried out in an attempt to make a compound that could trap the purported amine radical cation intermediate during monoamine oxidase (MAO)-catalyzed oxidation of amines. The E-isomer was not a substrate for MAO, and the Z-isomer was a very poor substrate. No trapping product was observed. Possible explanations for the inability of these compounds to trap a potential radical cation intermediate are discussed. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Intakes of Selected Nutrients and Food Groups and Risk of Ovarian Cancer
  作者：Susan E. McCann、Kirsten B. Moysich、Curtis Mettlin

  DOI：10.1207/s15327914nc391_3

  日期：2001.1

  In a hospital-based case-control study, we examined dietary intakes of selected nutrients and food groups and ovarian cancer risk among 496 women with primary, histologically confirmed epithelial ovarian cancer and 1,425 women with nonneoplastic diagnoses, ages 20-87 years, admitted to Roswell Park Cancer Institute between 1982 and 1998. Data on diet and other relevant risk factors in the few years before admission were collected with a se administered questionnaire. Odds ratios (OR) and 95% confidence intervals (CI) were estimated by unconditional logistic regression adjusting for age, education, region of residence, regularity of menstruation, family. history of ovarian cancer, parity, age at menarche, oral contraceptive use, and energy intake. Women in the highest vs. the lowest quartile of total energy had a weak increase in risk (OR = 1.25, 95% CI = 0.90-1.73). Significantly reduced risks were associated with higher intakes of dietary fiber (OR = 0.57, 95% CI = 0.38-0.87), vitamin A (OR = 0.66, 95% CI = 0.45-0.98), carotenoid (OR = 0.64, 95% CI = 0.43-0.93), vitamin E (OR = 0.58, 95% CI = 0.38-0.88), beta -carotene (OR = 0.68, 95% CI = 0.46-0.98), and total fruit and vegetable intake (OR = 0.62, 95% CI = 0.42-0.92). Our findings suggest that a diet high in plant foods may be important in reducing risk of ovarian cancer.