5-bromo-2(3-methyl-2-butenyloxy)benzylidene malonic acid dimethyl ester | 163434-34-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: 5-bromo-2(3-methyl-2-butenyloxy)benzylidene malonic acid dimethyl ester
• 英文别名: Dimethyl 2-[[5-bromo-2-(3-methylbut-2-enoxy)phenyl]methylidene]propanedioate；dimethyl 2-[[5-bromo-2-(3-methylbut-2-enoxy)phenyl]methylidene]propanedioate
• CAS: 163434-34-2
• 化学式: C₁₇H₁₉BrO₅
• 分子量: 383.239
• InChiKey: TWSMLCIOZILXHJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  5-bromo-2(3-methyl-2-butenyloxy)benzylidene malonic acid dimethyl ester 在 三氟乙酸 作用下， 反应 1.0h， 以95%的产率得到methyl 6-bromocoumarin-3-carboxylate
  参考文献：
  名称：

  Intramolecular Ene Reactions vs Competitive Pericyclic Processes: The Effect of Solvents and Salts on the Reaction of 5-Bromo-2-(3-methyl-2-butenyloxy)benzylidenemalonic Acid Dimethyl Ester

  摘要：

  The reactivity of 5-bromo-2-(3-methyl-2-butenyloxy)benzylidene-malonic acid dimethyl ester (3) was studied in several reaction media. In aprotic solvents intramolecular ene reaction (IER) occurred to give cis and trans chroman derivatives (4) and (5), and some kinetic determinations were performed. In protic solvents, besides IER adducts, the products of intramolecular hetero-Diels-Alder reaction and Claisen rearrangement (10 and 12 respectively) were obtained. In strong protic media, deallylation occurs to give the chromen-2-one derivative (6). Finally, the reaction was investigated in acetonic solutions of inorganic perchlorate (barium, lithium, magnesium, and sodium), and these conditions enhanced chemo- and stereo-selectivity and increased the rate. The kinetic effect was dramatic for magnesium perchlorate.

  DOI：

  10.3987/com-94-s72
• 作为产物：
  描述：

  1-溴-3-甲基-2-丁烯 在 哌啶 、 potassium carbonate 、 溶剂黄146 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 10.25h， 生成 5-bromo-2(3-methyl-2-butenyloxy)benzylidene malonic acid dimethyl ester
  参考文献：
  名称：

  镍（ii）催化的1,7-二烯的不对称分子内Alder-ene反应†

  摘要：

  通过使用手性N，N′-二氧化物/镍（II）配合物作为催化剂，开发了与烯作为亲亲物的高度非对映选择性和对映选择性的分子内Alder-ene反应。该方案为合成各种3,4-二取代的苯并二氢吡喃，四氢喹啉，哌啶和硫代苯并二氢吡喃衍生物提供了一条简便的途径，并具有良好的非对映选择性和对映选择性。

  DOI：

  10.1039/c9cc01521c

文献信息

• Inorganic perchlorates and pericyclic reactions. IV. 1 Rate enhancement by specific cation-substrate interaction or by increased internal pressure?
  作者：Giuseppe Faita、PierPaolo Righetti

  DOI：10.1016/0040-4020(95)00507-5

  日期：1995.8

  The kinetic behaviour of Diels-Alder and ene reactions was investigated in several inorganic perchlorate-organic solvent solutions. The observed rate accelerations are the result either of specific solute-cation interactions or of the increased internal pressure of the media, depending on substrates, solvents, and metal cations.

  在几种无机高氯酸盐-有机溶剂溶液中研究了Diels-Alder和烯反应的动力学行为。观察到的速率加​​速是特定溶质阳离子相互作用或介质内部压力增加的结果，具体取决于基材，溶剂和金属阳离子。
• A nickel(<scp>ii</scp>)-catalyzed asymmetric intramolecular Alder-ene reaction of 1,7-dienes
  作者：Wen Liu、Pengfei Zhou、Jiawen Lang、Shunxi Dong、Xiaohua Liu、Xiaoming Feng

  DOI：10.1039/c9cc01521c

  日期：——

  A highly diastereo- and enantioselective intramolecular Alder-ene reaction with an alkene as the enophile has been developed by using a chiral N,N′-dioxide/nickel(II) complex as the catalyst. This protocol provides a facile route towards the synthesis of diverse 3,4-disubstituted chroman, tetrahydroquinoline, piperidine and thiochroman derivatives in high yields with good to excellent diastereo- and

  通过使用手性N，N′-二氧化物/镍（II）配合物作为催化剂，开发了与烯作为亲亲物的高度非对映选择性和对映选择性的分子内Alder-ene反应。该方案为合成各种3,4-二取代的苯并二氢吡喃，四氢喹啉，哌啶和硫代苯并二氢吡喃衍生物提供了一条简便的途径，并具有良好的非对映选择性和对映选择性。
• Intramolecular Ene Reactions vs Competitive Pericyclic Processes: The Effect of Solvents and Salts on the Reaction of 5-Bromo-2-(3-methyl-2-butenyloxy)benzylidenemalonic Acid Dimethyl Ester
  作者：Giovanni Desimoni、Giuseppe Faita、Pier Paolo Righetti、Francesca Vietti

  DOI：10.3987/com-94-s72

  日期：——

  The reactivity of 5-bromo-2-(3-methyl-2-butenyloxy)benzylidene-malonic acid dimethyl ester (3) was studied in several reaction media. In aprotic solvents intramolecular ene reaction (IER) occurred to give cis and trans chroman derivatives (4) and (5), and some kinetic determinations were performed. In protic solvents, besides IER adducts, the products of intramolecular hetero-Diels-Alder reaction and Claisen rearrangement (10 and 12 respectively) were obtained. In strong protic media, deallylation occurs to give the chromen-2-one derivative (6). Finally, the reaction was investigated in acetonic solutions of inorganic perchlorate (barium, lithium, magnesium, and sodium), and these conditions enhanced chemo- and stereo-selectivity and increased the rate. The kinetic effect was dramatic for magnesium perchlorate.