2-{(exo-2,exo-3)-3-[Carbonyl(phenyl)methyl]bicyclo[2.2.1]hept-2-yl}-2-oxoessigsaeure-methylester | 98171-28-9

• 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: 2-{(exo-2,exo-3)-3-[Carbonyl(phenyl)methyl]bicyclo[2.2.1]hept-2-yl}-2-oxoessigsaeure-methylester
• CAS: 98171-28-9
• 化学式: C₁₈H₁₈O₄
• 分子量: 298.339
• InChiKey: LGAUOLNYVHOMOF-XRGAULLZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-{(exo-2,exo-3)-3-[Carbonyl(phenyl)methyl]bicyclo[2.2.1]hept-2-yl}-2-oxoessigsaeure-methylester 在 盐酸 作用下， 以90%的产率得到methyl (1S,2R,6R,7R,8R)-3-chloro-5-oxo-6-phenyl-4-oxatricyclo[6.2.1.02,7]undecane-3-carboxylate
  参考文献：
  名称：

  Christl, Manfred, Gazzetta Chimica Italiana, 1986, vol. 116, # 1, p. 1 - 18

  摘要：

  DOI：
• 作为产物：
  描述：

  6-Oxo-5-phenyl-6H-[1,3,4]oxadiazine-2-carboxylic acid methyl ester 以 四氯化碳 、 氘代氯仿 为溶剂， 反应 1.0h， 生成 2-{(exo-2,exo-3)-3-[Carbonyl(phenyl)methyl]bicyclo[2.2.1]hept-2-yl}-2-oxoessigsaeure-methylester
  参考文献：
  名称：

  Christl, Manfred; Lanzendoerfer, Ulrike; Groetsch, Maria M., Angewandte Chemie, 1985, vol. 97, # 10, p. 888 - 889

  摘要：

  DOI：

文献信息

• Addition of Bromine to Ketenes and Bisketenes:  Electrophilic Attack at Carbonyl Carbon and Neighboring Group Participation
  作者：R. S. Brown、Manfred Christl、Alan J. Lough、Jihai Ma、Eva-Maria Peters、Karl Peters、Frank Sammtleben、Henryka Slebocka-Tilk、Kuangsen Sung、Thomas T. Tidwell

  DOI：10.1021/jo980684h

  日期：1998.8.1

  Addition of bromine to bisketene (Me(3)SiC=C=O)(2) (1) gave the fumaryl dibromide E-7, whose stereochemistry was proven by X-ray structure determination. Upon warming, E-7 rearranged to the furanone 8, and this process was faster in the more polar CD(3)CN compared to CDCl(3), consistent with an ionization pathway for the rearrangement. The bromination of 1 in CH(2)ClCH(2)Cl followed second-order kinetics

  将溴添加到双烯酮中（Me（3）SiC = C = O）（2）（1）得到富马酰二溴化物E-7，其立体化学通过X射线结构测定得到证实。加热后，E-7重排至呋喃酮8，与CDCl（3）相比，极性更大的CD（3）CN中此过程更快，这与重排的电离途径一致。CH（2）ClCH（2）Cl中1的溴化反应遵循二级动力学，速率常数为（2.1 +/- 0.1）x 10（4）M（-）（1）s（-）（1） 25°C。向[Br（2）]上添加1的溴的一阶依赖性归因于分子内的亲核助剂，该分子是由第二个烯基部分在1和Br（2）的初始配合物中得到E-7形成的。从头算方法已经计算出该过程的过渡结构。相比之下，PhMe（2）SiCH = C = O 11和γ-氧杂环丁烯16通过三级动力学进行溴化，在[Br（2）]中为二级，表明在限速步骤中不存在相邻基团。双烯酮Me（2）Si（CH = C = O）（2）（13）通过混合动力学与[Br（2）]中的一阶和二阶项进行溴化。
• Christl, Manfred; Lanzendoerfer, Ulrike; Groetsch, Maria M., Chemische Berichte, 1990, vol. 123, # 10, p. 2031 - 2037
  作者：Christl, Manfred、Lanzendoerfer, Ulrike、Groetsch, Maria M.、Ditterich, Elke、Hegmann, Joachim

  DOI：——

  日期：——
• Cycloadditionen von 6H-1,3,4-Oxadiazin-6-onen (4,5-Diaza-?-Pyronen). 14. Nicht katalysierte und durch Trifluoressigs�ure katalysierte Reaktionen von 6H-1,3,4-Oxadiazin-6-onen mit Norbornen
  作者：Manfred Christl、Gabriele Bodenschatz、Erich Feineis、Joachim Hegmann、Gerhard H�ttner、Stefan Mertelmeyer、Klaus Sch�tzlein、Hartmut Schwarz

  DOI：10.1002/prac.199533701140

  日期：——

  In 11 out of 13 non-catalysed reactions of oxadiazinones 1 with norbornene, gamma-oxoketenes 4 were observed and could be isolated in three cases (4b,d,m). Except for 4m, all gamma-oxoketenes isomerised to enollactones of type 5 on thermolysis. However, 4b furnished the cyclobutene derivative 10 as the major product. No gamma-oxoketenes were detected in the reactions of Ik and 11, which gave rise to the formation of 5k and the enollactone 19, respectively. The latter was converted into 51 on treatment with trifluoroacetic acid (TFA). Four oxadiazinones 1 were allowed to react with norbornene in the presence of TFA. Three of them (1a,b,l) afforded mixtures of enollactones of type 5 and their diastereomers 12. Heating of 4 in the presence of norbornene led to the formation of the symmetrical delta-lactones 6. This process was observed to be efficient only where the conversion 4 --> 5 is slow (4b) or inoperative (4m). In five cases, the treatment of the components with boron trifluoride etherate proved to be a useful preparative alternative (6a,d,g,h,m). On treatment of 4a with methanol, the pseudoester 7a was formed, whereas 4b gave mixtures of 7b and the esters 8b and 15. Hydrogen chloride converted 4b into the pseudochloride 14, which furnished pseudoester 7b on methanolysis. Reaction of 4b,m with formic acid gave rise to pseudoanhydrides of type 13. From 4b and TFA a mixture of the enollactones 5b and 12b was obtained. Boron trifluoride etherate transformed 4i to enollactone 12i; analogously, 12m resulted on treatment of 4m with trifluoromethanesulfonic acid.
• Tidwell, Thomas T.; Sammtleben, Frank; Christl, Manfred, Journal of the Chemical Society. Perkin transactions I, 1998, # 13, p. 2031 - 2035
  作者：Tidwell, Thomas T.、Sammtleben, Frank、Christl, Manfred

  DOI：——

  日期：——
• Hegmann, Joachim; Ditterich, Elke; Huettner, Gerhard, Chemische Berichte, 1992, vol. 125, # 8, p. 1913 - 1918
  作者：Hegmann, Joachim、Ditterich, Elke、Huettner, Gerhard、Christl, Manfred、Peters, Eva-Maria、et al.

  DOI：——

  日期：——