Bicyclo<2.2.1>hepta-2,5-dien-2,3-dicarbonyldichlorid | 81378-07-6

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 酰卤
• 英文名称: Bicyclo<2.2.1>hepta-2,5-dien-2,3-dicarbonyldichlorid
• 英文别名: bicyclo[2.2.1]hepta-2,5-diene-2,3-dicarbonyl chloride；2,5-norbornadiene-2,3-dicarboxylic acid dichloride；Bicyclo[2.2.1]hepta-2,5-dien-2,3-dicarbonyldichlorid
• CAS: 81378-07-6
• 化学式: C₉H₆Cl₂O₂
• 分子量: 217.051
• InChiKey: XVWXPELQTPMCSK-UHFFFAOYSA-N

物化性质

• 沸点：
  34 °C(Press: 0.003 Torr)
• 密度：
  1.549±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.02
• 重原子数：
  13.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  34.14
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (R)-(-)-2-丁醇 、 Bicyclo<2.2.1>hepta-2,5-dien-2,3-dicarbonyldichlorid 在 吡啶 作用下， 以 乙醚 为溶剂， 反应 4.0h， 以55%的产率得到2,3-bis(((R)-1-methylpropoxy)carbonyl)norbornadiene
  参考文献：
  名称：

  Probing the Stereoselectivity of the Ruthenium-Catalyzed Ring-Opening Metathesis Polymerization of Norbornene and Norbornadiene Diesters

  摘要：

  The ring-opening metathesis polymerization (ROMP) of two optically active 2,3-dicarboalkoxynorbornadienes derived from (S)-(-)-2-methyl-1-butanol and (R)-(-)-2-butanol were carried out in the presence of the [RuCl2(P-cymene)](2) catalyst precursor activated by trimethylsilyldiazomethane (TMSD). H-1 and C-13 NMR analyses showed that a high degree of stereoregularity was achieved, and homonuclear proton-proton COSY spectroscopy indicated that the major trans fractions of the polymers were most likely isotactic, while the minor cis fractions were syndiotactic. Ring-opened metathesis polymers were also made from 2,3-dicarbomethoxynorbornadiene and exo,exo-2,3-dicarbomethoxy-5-norbornene. They were hydrogenated into the corresponding polynorbornanes using diimide. The NMR spectra of the reduced materials confirmed that the unsaturated parent polymers had an all-trans highly isotactic microstructure. A tentative mechanism involving arene loss, carbene formation, and monomer chelation is proposed to account for the observed stereoselectivities.

  DOI：

  10.1021/ma021315x
• 作为产物：
  描述：

  环戊二烯 、 丁炔二酸 在 五氯化磷 作用下， 以 四氯化碳 为溶剂， 反应 5.0h， 以66%的产率得到Bicyclo<2.2.1>hepta-2,5-dien-2,3-dicarbonyldichlorid
  参考文献：
  名称：

  Maier, Guenther; Jung, Werner A., Chemische Berichte, 1982, vol. 115, # 2, p. 804 - 807

  摘要：

  DOI：

文献信息

• O'Dell, Richard; McConville, David H.; Hofmeister, Gretchen E., Journal of the American Chemical Society, 1994, vol. 116, # 8, p. 3414 - 3423
  作者：O'Dell, Richard、McConville, David H.、Hofmeister, Gretchen E.、Schrock, Richard R.

  DOI：——

  日期：——
• Bridged Tolanes: A Twisted Tale
  作者：Sebastian Menning、Maximilian Krämer、Andrew Duckworth、Frank Rominger、Andrew Beeby、Andreas Dreuw、Uwe H. F. Bunz

  DOI：10.1021/jo5010235

  日期：2014.7.18

  The rotational motion of tolanes along their acetylene axis is not fully understood. What happens to the optical and electronic properties if the tolane backbone is forced into a twisted conformation? Several tethers were investigated to obtain tolanophanes, fixing the torsion angle of the two phenyl rings. X-ray crystal structures revealed tether-specific torsion angles in the solid state. The absorption, emission, and excitation spectra were recorded. Twisted tethered tolane conformers showed blue-shifted absorption; emission spectra were all torsionally independent and identical. The tethered tolanes were embedded in a rigid matrix by freezing to 77 K; well-resolved emission spectra were recorded for planar tolanes, but for twisted systems unexpectedly long-lived phosphorescence was observed. How is this triplet emission explained? Quantum chemical calculations (TDDFT/cam-B3LYP/6-31G*) of the unsubstituted tolane showed that intersystem crossing (ISC) is favored with large spin-orbit coupling, which occurs when the molecular orbitals are orthogonal to each other; this is the case at the crossing of S-1/T-7. Also, a small energy difference between singlet and triplet states is required; we found that ISC can favorably take place at four crossings: S-1/T-6, S-1/T-7, S-1/T-8,T-9, S-1/T-10.
• MAIER, G.;JUNG, W. A., CHEM. BER., 1982, 115, N 2, 804-807
  作者：MAIER, G.、JUNG, W. A.

  DOI：——

  日期：——