5-methoxycarbonyl-5-methoxycarbonylmethyl-bicyclo[2.2.1]heptene | 68548-40-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 5-methoxycarbonyl-5-methoxycarbonylmethyl-bicyclo[2.2.1]heptene
• 英文别名: Methyl 2-(methoxycarbonyl)bicyclo[2.2.1]hept-5-ene-2-acetate；methyl 2-(2-methoxy-2-oxoethyl)bicyclo[2.2.1]hept-5-ene-2-carboxylate
• CAS: 68548-40-3
• 化学式: C₁₂H₁₆O₄
• 分子量: 224.257
• InChiKey: MLDORSKDIKGXTB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5-methoxycarbonyl-5-methoxycarbonylmethyl-bicyclo[2.2.1]heptene 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 4.0h， 生成 2-(hydroxymethyl)-bicyclo[2.2.1]hept-5-ene-2-ethanol
  参考文献：
  名称：

  Total Synthesis and Stereochemistry of Alternaric Acid

  摘要：

  Determination of the stereochemistry and the total synthesis of alternaric acid 1 has been achieved. The stereostructure of 1 has been elucidated by stereoselective synthesis of four diastereoisomers of the C(9)-C(14) fragment 6, which had been obtained as a degradation product during structural studies. Key reactions of the total synthesis of 1 include the Julia olefination of tertiary aldehyde 6 and phenylsulfone 7 and novel one-pot construction of 3-acyl-4-hydroxy-5,6-dihydro-2-pyrone via Fries-type rearrangement of the O-enol acyl group of beta-keto-delta-valerolactone toward the a-position of the delta-lactone. The absolute configuration of alternaric acid has been shown to be that illustrated in structure 1. The modified Fries-type rearrangement method has also been extended to the synthesis of some other compounds containing a tricarbonylmethane structure.

  DOI：

  10.1021/jo00096a016
• 作为产物：
  描述：

  衣康酸二甲酯 、 环戊二烯 在 三氯化铝 作用下， 以 苯 为溶剂， 反应 2.5h， 生成 5-methoxycarbonyl-5-methoxycarbonylmethyl-bicyclo[2.2.1]heptene
  参考文献：
  名称：

  Total Synthesis and Stereochemistry of Alternaric Acid

  摘要：

  Determination of the stereochemistry and the total synthesis of alternaric acid 1 has been achieved. The stereostructure of 1 has been elucidated by stereoselective synthesis of four diastereoisomers of the C(9)-C(14) fragment 6, which had been obtained as a degradation product during structural studies. Key reactions of the total synthesis of 1 include the Julia olefination of tertiary aldehyde 6 and phenylsulfone 7 and novel one-pot construction of 3-acyl-4-hydroxy-5,6-dihydro-2-pyrone via Fries-type rearrangement of the O-enol acyl group of beta-keto-delta-valerolactone toward the a-position of the delta-lactone. The absolute configuration of alternaric acid has been shown to be that illustrated in structure 1. The modified Fries-type rearrangement method has also been extended to the synthesis of some other compounds containing a tricarbonylmethane structure.

  DOI：

  10.1021/jo00096a016

文献信息

• COMPOUNDS FROM RENEWABLE RESOURCES
  申请人：REGENTS OF THE UNIVERSITY OF MINNESOTA

  公开号：US20170291906A1

  公开（公告）日：2017-10-12

  Compounds of formula III: and salts thereof are disclosed. Also disclosed are methods for preparing compounds of formula III, intermediates useful for preparing compounds of formula III and methods for preparing compounds and materials from compounds of formula III.

  公式III的化合物及其盐已被披露。还披露了制备公式III化合物的方法，用于制备公式III化合物的中间体以及从公式III化合物制备化合物和材料的方法。
• Norbornene-based ring-opening polymerization polymer, product of hydrogenation of norbornene-based ring-opening polymerization polymer, and processes for producing these
  申请人：Taguchi Kazunori

  公开号：US20050148746A1

  公开（公告）日：2005-07-07

  A norbornene ring-opened polymer which in the molecule has repeating units represented by the formula (1): wherein R 1 represents Q, R 2 represents Q or C(═O)R 5 , R 3 represents Q or C(═O)R 6 , and R 4 represents Q or X—C(═O)R 7 (wherein Q represents hydrogen, a C 1-10 hydrocarbon group, etc.; R 5 , R 6 and R 7 each represents hydroxyl, C 1-10 alkoxyl, etc., provided that R 6 and R 7 may be bonded to each other to constitute oxygen, NH, etc.; X represents methylene, etc., provided that when R 2 is Q, then R 3 is C(═O)R 6 and R 4 is X—C(═O)R 7 and that when R 4 is Q, then R 2 is C(═O)R 5 , R 3 is C(═O)R 6 , and the configuration of R 2 and R 3 is trans, and m is 0 or 1), the polymer having a weight-average molecular weight as determined by gel permeation chromatography of 1,000 to 1,000,000. Also provided is a hydrogenation product of the norbornene ring-opened polymer. The norbornene ring-opened polymer and the hydrogenation product are excellent in heat resistance, electrical properties, etc.

  分子中具有由公式（1）表示的重复单元的去氢萘环开环聚合物：其中R1表示Q，R2表示Q或C（═O）R5，R3表示Q或C（═O）R6，R4表示Q或X—C（═O）R7（其中Q表示氢，C1-10烃基等；R5，R6和R7分别表示羟基，C1-10烷氧基等，但是当R6和R7结合形成氧，NH等时除外；X表示亚甲基等，但是当R2为Q时，R3为C（═O）R6，R4为X—C（═O）R7，当R4为Q时，R2为C（═O）R5，R3为C（═O）R6，并且R2和R3的构型为反式，m为0或1），该聚合物的重均分子量由凝胶渗透色谱法确定为1,000至1,000,000。还提供了去氢萘环开环聚合物的氢化产物。去氢萘环开环聚合物和氢化产物在耐热性，电学性能等方面表现出色。
• Total synthesis of alternaric acid
  作者：Hiroyasu Tabuchi、Taisuke Hamamoto、Shokyo Miki、Tsuyoshi Tejima、Akitami Ichihara

  DOI：10.1016/s0040-4039(00)77605-2

  日期：1993.4

  A total synthesis of alternaric acid (1) has been achieved. Key reactions include the Julia olefination of tertiary aldehyde 4 and phenylsulfone 5, and novel one-pot construction of 3-acyl-4-hydroxy-5,6-dihydropyrone via Fries type rearrangement of O-enolacyl group of beta-keto-delta-valerolactone toward alpha-position of the delta-lactone. The absolute configuration of alternaric acid has been shown to be that illustrated in structure 1.
• JPH10120627A
  申请人：——

  公开号：JPH10120627A

  公开（公告）日：1998-05-12
• US7037993B2
  申请人：——

  公开号：US7037993B2

  公开（公告）日：2006-05-02