3-Brom-7-methylphthalid | 63113-05-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 英文名称: 3-Brom-7-methylphthalid
• 英文别名: 3-bromo-7-methyl-3H-2-benzofuran-1-one
• CAS: 63113-05-3
• 化学式: C₉H₇BrO₂
• 分子量: 227.057
• InChiKey: QZSAWPARDSTZRU-UHFFFAOYSA-N

物化性质

• 沸点：
  329.4±42.0 °C(Predicted)
• 密度：
  1.660±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-Brom-7-methylphthalid 在 2,2,6,6-四甲基哌啶 、 水 、 C₁₂H₁₈N₂ 作用下， 以 甲苯 为溶剂， 反应 10.0h， 生成 (S)-4-methyl-3-oxo-1,3-dihydroisobenzofuran-1-yl 2,2-diphenylacetate
  参考文献：
  名称：

  手性双环咪唑催化的酰基动力学动力学拆分合成手性邻苯二甲酰基酯

  摘要：

  利用手性双环咪唑有机催化剂并采用连续注射工艺，已开发出另一种途径，可通过对映选择性酰化作用（3-99％ee）动态动力学拆分3-羟基邻苯二酚来有效合成手性邻苯二甲酸酯基前药。计算研究表明，一般的基础催化机理不同于广泛接受的亲核催化机理。关键过渡态的结构分析表明，催化剂与底物之间的CH-π相互作用而不是先前考虑的阳离子/π-π相互作用是引起观察到的立体控制的主要因素。

  DOI：

  10.1002/anie.202012445
• 作为产物：
  描述：

  methyl 2,6-di(bromomethyl)benzoate 在 palladium on activated charcoal calcium hydroxide 、 N-溴代丁二酰亚胺(NBS) 、 过氧化氢苯甲酰 、 氢气 作用下， 以 1,4-二氧六环 、 四氯化碳 为溶剂， 180.0 ℃ 、275.79 kPa 条件下， 反应 50.0h， 生成 3-Brom-7-methylphthalid
  参考文献：
  名称：

  Aromatische Spirane, 21. Mitt: Darstellung von Methylphthalaldehyds�uren und ihren Ethylund Methylestern als Synthone f�r Synthesen von methylierten 2,2?-Spirobiindandionen

  摘要：

  The isomeric methyl phthalaldehydic acids 11 were obtained from phthalides 4 by bromation (NBS) to the 3-bromo derivatives 7 and subsequent hydrolysis with water. 4 in turn were accessible from dimethyl methyl benzoates 1 by dibromination with NBS and subsequent thermical cyclization to the bromo derivatives 3 which, on catalytic dehalogenation, afforded the phthalides 4. Reaction of 11 with methanol or ethanol gave the pseudo-esters 13 and 14, resp. Short treatment of 11 with diazomethane on the other hand yielded the methyl formyl benzoates 15b to 15e. Prolonged reaction (several hours) gave the oxiranyl compounds 17; in addition, the acetonyl derivatives 18 were also found, obviously formed by a double methylene insertion into 15. All reactions proceeded with good to excellent yields.

  DOI：

  10.1007/bf00807401

文献信息

• Enantioselective synthesis of 3-aryl-phthalides through a nickel-catalyzed stereoconvergent cross-coupling reaction
  作者：Si-Yu Xu、Rui Zhang、Shu-Sheng Zhang、Chen-Guo Feng

  DOI：10.1039/d1ob00487e

  日期：——

  A nickel-catalyzed asymmetric Suzuki–Miyaura cross-coupling of racemic 3-bromo-phthalides and arylboronic acids was realized for the synthesis of diverse chiral 3-aryl-phthalides in moderate to excellent reaction yields. The reaction proceeded in a stereoconvergent manner and high enantioselectivities were observed for most examined examples. A number of functional groups like aldehyde, ester and bromide

  外消旋 3-溴代苯酞和芳基硼酸的镍催化不对称 Suzuki-Miyaura 交叉偶联可用于以中等至优异的反应产率合成多种手性 3-芳基苯酞。反应以立体收敛的方式进行，并且对于大多数检查的实施例都观察到了高对映选择性。许多官能团如醛、酯和溴化物具有良好的耐受性。杂芳族硼酸也是该反应中的有效偶联伙伴。
• Meyer,A. et al., Chemische Berichte, 1977, vol. 110, p. 1403 - 1420
  作者：Meyer,A. et al.

  DOI：——

  日期：——
• US4244966A
  申请人：——

  公开号：US4244966A

  公开（公告）日：1981-01-13
• Chiral Bicyclic Imidazole‐Catalyzed Acylative Dynamic Kinetic Resolution for the Synthesis of Chiral Phthalidyl Esters
  作者：Muxing Zhou、Tatiana Gridneva、Zhenfeng Zhang、Ende He、Yangang Liu、Wanbin Zhang

  DOI：10.1002/anie.202012445

  日期：2021.1.18

  Utilizing a chiral bicyclic imidazole organocatalyst and adopting a continuous injection process, an alternative route has been developed for the efficient synthesis of chiral phthalidyl ester prodrugs via dynamic kinetic resolution of 3‐hydroxyphthalides through enantioselective acylation (up to 99 % ee). The computational studies suggest a general base catalytic mechanism differing from the widely

  利用手性双环咪唑有机催化剂并采用连续注射工艺，已开发出另一种途径，可通过对映选择性酰化作用（3-99％ee）动态动力学拆分3-羟基邻苯二酚来有效合成手性邻苯二甲酸酯基前药。计算研究表明，一般的基础催化机理不同于广泛接受的亲核催化机理。关键过渡态的结构分析表明，催化剂与底物之间的CH-π相互作用而不是先前考虑的阳离子/π-π相互作用是引起观察到的立体控制的主要因素。
• Aromatische Spirane, 21. Mitt: Darstellung von Methylphthalaldehyds�uren und ihren Ethylund Methylestern als Synthone f�r Synthesen von methylierten 2,2?-Spirobiindandionen
  作者：H. K. Neudeck

  DOI：10.1007/bf00807401

  日期：1996.2

  The isomeric methyl phthalaldehydic acids 11 were obtained from phthalides 4 by bromation (NBS) to the 3-bromo derivatives 7 and subsequent hydrolysis with water. 4 in turn were accessible from dimethyl methyl benzoates 1 by dibromination with NBS and subsequent thermical cyclization to the bromo derivatives 3 which, on catalytic dehalogenation, afforded the phthalides 4. Reaction of 11 with methanol or ethanol gave the pseudo-esters 13 and 14, resp. Short treatment of 11 with diazomethane on the other hand yielded the methyl formyl benzoates 15b to 15e. Prolonged reaction (several hours) gave the oxiranyl compounds 17; in addition, the acetonyl derivatives 18 were also found, obviously formed by a double methylene insertion into 15. All reactions proceeded with good to excellent yields.