methyl 3-(2-hydroxy-4-methoxyphenyl)propanoate | 69471-28-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: methyl 3-(2-hydroxy-4-methoxyphenyl)propanoate
• CAS: 69471-28-9
• 化学式: C₁₁H₁₄O₄
• 分子量: 210.23
• InChiKey: QPFCWJXXUBGYFW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 3-(2-hydroxy-4-methoxyphenyl)propanoate 在 palladium on activated charcoal 三氯化铝 作用下， 以 二苯醚 、 硝基甲烷 、 苯 为溶剂， 反应 11.5h， 生成 6-benzoyl-7-methoxycoumarin
  参考文献：
  名称：

  通过高度区域选择性的薯条重排合成6-酰基香豆素。线性酰化香豆素geijerin和dehydrogeijerin的总合成。

  摘要：

  由7-甲氧基香豆素以高收率制备的3-（2-酰氧基-4-甲氧基苯基）丙酸甲酯（7）是6-酰基香豆素的一般和有效合成的关键中间体。在标准的炸薯条重排条件下（7）与氯化铝在硝基甲烷中进行高度区域选择性的对位迁移。将所得的C-酰化产物（8）转化为6-酰基-7-甲氧基香豆素（4）。描述了重排的范围和局限性以及天然线性酰基香豆素，geijerin（4a）和dehydrogeijerin（4b）在总合成中的应用。

  DOI：

  10.1016/s0040-4020(01)90370-9
• 作为产物：
  描述：

  7-甲氧基香豆素 在 palladium on activated charcoal 氢气 作用下， 以 甲醇 、 乙酸乙酯 为溶剂， 25.0 ℃ 、101.33 kPa 条件下， 反应 6.0h， 生成 methyl 3-(2-hydroxy-4-methoxyphenyl)propanoate
  参考文献：
  名称：

  通过高度区域选择性的薯条重排合成6-酰基香豆素。线性酰化香豆素geijerin和dehydrogeijerin的总合成。

  摘要：

  由7-甲氧基香豆素以高收率制备的3-（2-酰氧基-4-甲氧基苯基）丙酸甲酯（7）是6-酰基香豆素的一般和有效合成的关键中间体。在标准的炸薯条重排条件下（7）与氯化铝在硝基甲烷中进行高度区域选择性的对位迁移。将所得的C-酰化产物（8）转化为6-酰基-7-甲氧基香豆素（4）。描述了重排的范围和局限性以及天然线性酰基香豆素，geijerin（4a）和dehydrogeijerin（4b）在总合成中的应用。

  DOI：

  10.1016/s0040-4020(01)90370-9

文献信息

• Revisiting Arene C(sp² )−H Amidation by Intramolecular Transfer of Iridium Nitrenoids: Evidence for a Spirocyclization Pathway
  作者：Yeongyu Hwang、Yoonsu Park、Yeong Bum Kim、Dongwook Kim、Sukbok Chang

  DOI：10.1002/anie.201808892

  日期：2018.10.8

  Two mechanistic pathways, that is, electrocyclization and electrophilic aromatic substitution, are operative in most intramolecular C−H amination reactions proceeding by metal nitrenoid catalysis. Reported here is an alternative mechanistic scaffold leading to benzofused δ‐lactams selectively. Integrated experimental and computational analysis revealed that the reaction proceeds by a key spirocyclization

  在通过金属类固醇催化进行的大多数分子内CH胺化反应中，有两种机理途径，即电环化和亲电子芳族取代。此处报道的是另一种机制性支架，可以选择性地导致苯并稠合的δ-内酰胺。综合的实验和计算分析表明，该反应通过关键的螺环化步骤进行，然后进行骨架重排。基于这种机理的见解，已开发出合成螺内酰胺的新途径。
• Efficient, highly regioselective fries rearrangements of methyl 3-(2-acyloxy-4-methoxyphenyl)propanoates: The first total syntheses of the linear acylated coumarins geijerin and dehydrogeijerin.
  作者：Nicholas Cairns、Laurence M. Harwood、David P.pp]Astles

  DOI：10.1016/s0040-4039(00)80285-3

  日期：1988.1

  Aluminium chloride catalysed para-Fries rearrangement of methyl 3-(2-acyloxy-4-methoxyphenyl)propanoates (5)in nitromethane furnishes the corresponding 5-acylated products (6) cleanly and in high yield. The rearrangement products may be converted into 6-acyl-7-methoxycoumarins (2) including the naturally occurring geijerin (2a) and dehydrogeijerin (2b).

  氯化铝催化的3-（2-酰氧基-4-甲氧基苯基）丙酸甲酯（5）在硝基甲烷中的对位-弗里斯重排可清洁且高收率地提供相应的5-酰化产物（6）。重排产物可以转化为6-酰基-7-甲氧基香豆素（2），包括天然存在的盖伊林（2a）和脱氢盖伊林（2b）。
• 2-(piperazinylalkyl)-1-benzothiepin, 1-benzoxepin, and 1,5-benzodioxepin
  申请人：Takeda Chemical Industries, Ltd.

  公开号：US04736031A1

  公开（公告）日：1988-04-05

  Novel condensed seven-membered heterocyclic compounds of the formula: ##STR1## wherein R.sub.1 and R.sub.2 are independently hydrogen, halogen, hydroxy, lower alkyl or lower alkoxy, R.sub.3 and R.sub.4 are independently hydrogen, optionally substituted lower alkyl, optionally substituted cycloalkyl or optionally substituted aralkyl, or both jointly form an optionally substituted ring together with the adjacent nitrogen atom, X is hydrogen, optionally substituted lower alkyl, optionally substituted aryl or a carboxyl group which may be esterified or amidated, Y is >C.dbd.O or >CH--OR.sub.5 in which R.sub.5 is hydrogen, acyl or optionally substituted carbamoyl, A is oxygen atom or sulfur atom, E is oxygen atom or methylene, and G is lower alkylene, provided that when A is sulfur atom, E is methylene, and salts thereof exhibit serotonin S.sub.2 receptor blocking activity, actions to relieve cerebral vasospasm and antithrombotic activity, and are of value as a prophylactic and therapeutic agent for ischemic cardiopathies, thrombosis, hypertension and cerebral circulatory disorders.

  本发明涉及一种化合物，其为七元杂环化合物，化学式为：##STR1## 其中R.sub.1和R.sub.2分别为氢、卤素、羟基、低碳基或低烷氧基；R.sub.3和R.sub.4分别为氢、可选取代的低碳基、可选取代的环烷基或可选取代的芳基烷基；或者两者共同形成一个可选取代的环，与相邻的氮原子一起；X为氢、可选取代的低碳基、可选取代的芳基或可酯化或酰胺化的羧基；Y为>C.dbd.O或>CH--OR.sub.5，其中R.sub.5为氢、酰基或可选取代的氨基甲酰基；A为氧原子或硫原子；E为氧原子或亚甲基；G为低碳基亚烷基。当A为硫原子时，E为亚甲基。该化合物的盐表现出5-羟色胺S.sub.2受体阻断活性，缓解脑血管痉挛和抗血栓活性，可作为缺血性心脏病、血栓形成、高血压和脑循环障碍的预防和治疗剂。
• Condensed seven-membered heterocyclic compounds, their production and use
  申请人：Takeda Chemical Industries, Ltd.

  公开号：EP0205264A1

  公开（公告）日：1986-12-17

  Novel condensed seven-membered heterocyclic compounds of the formula: wherein R, and R2 are independently hydrogen, halogen, hydroxy, lower alkyl or lower alkoxy, R3 and R4 are independently hydrogen, optionally substituted lower alkyl, optionally substituted cycloalkyl or optionally substituted aralkyl, or both jointly form an optionally substituted ring together with the adjacent nitrogen atom, X is hydrogen, optionally substituted lower alkyl, optionally substituted aryl or a carboxyl group which may be esterified or amidated, Y is C=O or CH-OR5 in which Rs is hydrogen, acyl or optioinally substituted carbamoyl, A is an oxygen atom or sulfur atome, E is an oxygen atom or methylene, and G is lower alkylene, provided that when A is a sulfur atom, E is methylene, and salts thereof exhibit serotonin S2 receptor blocking activity, actions to relieve cerebral vasospasm and antithrombotic activity, and are of value as a prophylactic and therapeutic agent for ischemic cardiopathies, thrombosis, hypertension and cerebral circulatory disorders.

  式中的新型缩合七元杂环化合物： 其中 R 和 R2 独立地为氢、卤素、羟基、低级烷基或低级烷氧基、 R3和R4独立地为氢、任选取代的低级烷基、任选取代的环烷基或任选取代的芳烷基，或两者与相邻的氮原子共同形成任选取代的环、 X 是氢、任选取代的低级烷基、任选取代的芳基或可酯化或酰胺化的羧基、 Y 是 C=O 或 CH-OR5，其中 Rs 是氢、酰基或被选择取代的氨基甲酰基、 A 是氧原子或硫原子，E 是氧原子或亚甲基，以及 G 是低级亚烷基，条件是当 A 是硫原子时，E 是亚甲基、 及其盐类具有 5-羟色胺 S2 受体阻断活性、缓解脑血管痉挛的作用和抗血栓活性，具有作为 具有预防和治疗缺血性心脏病、血栓形成、高血压和脑循环障碍的价值。
• Conversion of 7-methoxy-3,4-dihydro-2H-1-benzopyran-2-one into the corresponding dimethyl ortho ester
  作者：David G. Bourke、David J. Collins

  DOI：10.1016/s0040-4020(97)00007-0

  日期：1997.3

  7-Methoxy-3,4-dihydro-2H-1-benzopyran-2-one 2 was converted into 3-(2'-tert-butyldimethylsilyloxy-4'-methoxyphenyl)-N-Methyl-N-phenylpropanamide 25 and reaction of this with methyl trifluoromethanesulfonate, followed by reaction with sodium methoxide, gave 2,2,7-trimethoxy-2H-1-benzopyran 1a in 55% overall yield from 25. A similar methylation/methoxide sequence using 3-(2'-benzyloxy-4'-methoxyphenyl)-N-methyl-N-phenylpropanamide 18 gave a mixture which contained trimethyl 3-(2'-benzyloxy-4'-methoxyphenyl)orthopropanoate 20a and reaction of this mixture with a solution of sodium in tert-butanol gave a product in which 2,2,7-trimethoxy-2H-1-benzopyran 1a was detected, but not isolable. (C) 1997 Elsevier Science Ltd.