降三环基溴化物 | 695-02-3

• 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
• 中文名称: 降三环基溴化物
• 英文名称: Nortricyclylbromid
• 英文别名: 3-bromonortricyclene；3-Brom-nortricyclen；3-nortricyclyl bromide；Nortricyclyl bromide；3-bromotricyclo[2.2.1.02,6]heptane
• CAS: 695-02-3
• 化学式: C₇H₉Br
• 分子量: 173.052
• InChiKey: RDIUINMODIQXGA-UHFFFAOYSA-N

物化性质

• 沸点：
  175.46°C (estimate)
• 密度：
  1.4658 (rough estimate)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  降三环基溴化物 在 乙醚 、 magnesium 作用下， 生成 2,6-cyclo-norbornane-3-carbanilide
  参考文献：
  名称：

  Intakes of Selected Nutrients and Food Groups and Risk of Ovarian Cancer

  摘要：

  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.

  DOI：

  10.1207/s15327914nc391_3
• 作为产物：
  描述：

  降冰片烯 在 N-溴代丁二酰亚胺(NBS) 、 tetrabutylammonium bifluoride 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以100%的产率得到降三环基溴化物
  参考文献：
  名称：

  Efficient utilization of tetrabutylammonium bifluoride in halofluorination reactions

  摘要：

  DOI：

  10.1021/jo00279a013

文献信息

• The surface nature of Grignard reagent formation
  作者：H. M. Walborsky、Marek Topolski

  DOI：10.1021/ja00035a044

  日期：1992.4

  bromide yielded a 1:1 mixture of endo- and exo-2-deuterionorbornane. Reaction of the epimeric bromides with Rieke magnesium in the presence of /e/-/-butyl alcohol and a 10-fold equivalent excess of the radical trap deuterated dicyclohexylphosphine resulted in only 8% deuterium incorporation in the products. Treatment of exo-5-bromo-2-norbornene under identical conditions (/erf-butyl alcohol-O-rf, -70 0C)

  外-2-降冰片基溴与里克镁在醚中在-70 0℃下在叔丁醇-O-rf存在下的反应仅产生外-2-氘代降冰片烷，而差向异构体enrfo-2-降冰片基溴产生内-和外-2-氘代降冰片烷的 1:1 混合物。在正丁醇和 10 倍当量过量的自由基捕集器氘代二环己基膦存在下，差向异构溴化物与 Rieke 镁的反应导致产物中只有 8% 的氘掺入。在相同条件下处理外-5-溴-2-降冰片烯（叔丁醇-O-rf，-70 0C）产生外-5-氘代-2-降冰片烯和3-氘代降冰片烯的65:35混合物。在叔丁醇和 10 倍过量的氘代二环己基膦存在下，外型 5-降冰片烯基溴化物的反应得到相同的产物混合物，但仅掺入了 8% 的氘。这些结果有力地支持了格氏形成反应的表面性质。
• 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。
• Organofluorosilicates in organic synthesis
  作者：Kohei Tamao、Masayuki Mishima、Jun-ichi Yoshida、Masataka Takahashi、Neyoshi Ishida、Makoto Kumada

  DOI：10.1016/s0022-328x(00)86818-7

  日期：1982.2

  together with IV and an unidentified product. GLC-monitoring of the reactions showed the higher reactivity of the norbornenyl derivative having the leaving group in theendo position irrespective of whether the leaving group is SiF5 or H. Since no inhibition was observed by the addition of hydroquinone in the dark, the reactions have been regarded as homoallylic electrophilic substitutions. A concerted

  考察了5-降冰片烯-2-基五氟硅酸钾（Ⅰ）和5-降冰片烯-2-基三甲基硅烷（Ⅱ）与NBS的反应。前一个反应从碳-硅键的裂解中产生了唯一可检测到的3-正三环基溴化物（IV）。然而，后者反应产生的主要产物为3-溴-1-正三环基三甲基硅烷（V），这是由于碳氢键α与硅以及IV和未确定的产物一起裂解所致。反应的GLC监测表明，在内位具有离去基团的降冰片烯基衍生物的反应性更高，而与离去基团是否为SiF 5无关由于在黑暗中未发现对苯二酚的抑制作用，因此该反应被认为是均烯丙基亲电子取代基。协调的机制似乎与实验数据一致。还研究了用一氯化碘裂解1-去甲环基三甲基硅烷得到1-碘代三环烯。
• Cross-linked poly-(4-vinylpyridine–styrene)–bromine complexes as stereoselective brominating agents
  作者：Y. Johar、M. Zupan、B. Šket

  DOI：10.1039/p19820002059

  日期：——

  containing 40–43% of pyridine rings, were transformed with bromine to provide three types of brominating agents (1), (2), and (3). Reactions of cis- and trans-1-phenylpropene with (1), (2), and (3) resulted in a high degree of anti-stereoselectivity. The reactivity increases from (1) to (3); solvent polarity has no significant effect on stereoselectivity, but affects the reactivity, being significantly greater

  用溴转化含有40-43％吡啶环的交联聚苯乙烯-4-乙烯基吡啶珠，以提供三种类型的溴化剂（1），（2）和（3）。的反应顺式-和反式-1-苯基丙烯与（1），（2），（3）导致了高度的抗-stereoselectivity。反应性从（1）增加到（3）；溶剂的极性对立体选择性没有显着影响，但会影响反应性，乙腈和氯仿中的环氧基和二恶烷中的环氧基显着更大。1-苯基环己烯与（1）和（3）的溴化反应导致反式的形成-1,2-二溴-1-苯基环己烷（9）和3-溴-2-苯基环己烯（10），温度仅影响产物的比例。用试剂（1），（2）和（3）溴降冰片烯的溴化反应形成了七种产物：2-外-溴降冰片烷（12），7-溴三环烷（13），2-外-溴，3-内- dibromonorbornane（14），2- exo -7-抗dibromonorbornane（15），2- exo，5-内-dibromonorbornane（16），2-
• Isomerism in the Diels-Alder Reaction. IV. Directive Influences in Addition Reactions of the Double Bond in Bicyclic Adducts^1,2
  作者：Harold Kwart、Lloyd Kaplan

  DOI：10.1021/ja01645a005

  日期：1954.8

表征谱图