methyl 5-oxo-6,7,8,9-tetrahydro-5H-benzo[7]annulene-6-carboxylate | 74821-55-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 5-oxo-6,7,8,9-tetrahydro-5H-benzo[7]annulene-6-carboxylate
• 英文别名: 2-methoxycarbonyl-1-benzosuberone；methyl 5-oxo-6,7,8,9-tetrahydrobenzo[7]annulene-6-carboxylate
• CAS: 74821-55-9
• 化学式: C₁₃H₁₄O₃
• mdl: MFCD23743203
• 分子量: 218.252
• InChiKey: JDXIXQIVFXMNGR-UHFFFAOYSA-N

物化性质

• 沸点：
  124-128 °C(Press: 2 Torr)
• 密度：
  1.160±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.384
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 5-oxo-6,7,8,9-tetrahydro-5H-benzo[7]annulene-6-carboxylate 在 水 、 氯乙酸 作用下， 反应 14.0h， 生成 6,7-dihydro-1H-benzo[6,7]cyclohepta[1,2-d]pyrimidine-2,4(3H,5H)-dione
  参考文献：
  名称：

  Synthesis and HIV-1 inhibitory properties of new tetrahydrobenzoquinazolinedione and tetrahydrobenzocycloheptenuracil derivatives and of their thioxo analogues

  摘要：

  Some new tetrahydrobenzoquinazolinediones 2a-4a, tetrahydrobenzocycloheptenuracils 5a, 6a and their thioxo analogues 2b-6b were synthesized within a project aimed at obtaining new HIV-1 tricyclic inhibitors whose scaffold includes a pyrimidine and a phenyl ring, which are present in various HIV-1 non-nucleoside inhibitors. Among the tetrahydrobenzaquinazolinediones 2a-4a, compounds 3a and 4a, in which the tricyclic system is respectively in an angular or linear arrangement, proved to possess a HIV-1 inhibitory activity which was in the micromolar range, while compound 2a, in which the tricyclic system is in the angular arrangement opposite to that of 3a, was found to be completely inactive. As regards the tetrahydrobenzocycloheptenuracil derivatives (5a and 6a), only 5a showed an inhibitory activity similar to that of 3a and 4a. Furthermore, all thioxo analogues 2b-6b were found to be devoid of any activity. (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0014-827x(99)00024-5
• 作为产物：
  描述：

  (5-oxo-6,7,8,9-tetrahydro-5H-benzocyclohepten-6-yl)-glyoxylic acid methyl ester 在 甲醇 、 硼酸 作用下， 生成 methyl 5-oxo-6,7,8,9-tetrahydro-5H-benzo[7]annulene-6-carboxylate
  参考文献：
  名称：

  Seven-membered Ring Compounds. IV.¹ Benzosuberoneglyoxylates

  摘要：

  DOI：

  10.1021/ja01100a051

文献信息

• Cooperative Indium(III)/Silver(I) System for Oxidative Coupling/Annulation of 1,3-Dicarbonyls and Styrenes: Construction of Five-Membered Heterocycles
  作者：Tae Yun Ko、So Won Youn

  DOI：10.1002/adsc.201600280

  日期：2016.6.16

  A cooperative indium(III)/silver(I) system for the synthesis of various five‐membered heterocycles, including dihydrofurans, pyrroles, spirolactones, and spiroiminolactones, through the sequential oxidative coupling/annulation reaction of 1,3‐dicarbonyl compounds with styrenes has been developed. Four different heterocyclic systems were successfully synthesized depending on the substitution pattern

  通过1,3-二羰基化合物与苯乙烯的顺序氧化偶合/环化反应，用于合成五元杂环（包括二氢呋喃，吡咯，螺内酯和螺氨基内酯）的铟（III）/银（I）协作系统具有已开发。使用容易获得的起始材料，根据底物的取代方式成功合成了四个不同的杂环系统。该系统的优点是底物范围广，化学产率中等到良好，操作上简单易行，反应时间短。
• Air- and Light-Stable <i>S</i>-(Difluoromethyl)sulfonium Salts: <i>C</i>-Selective Electrophilic Difluoromethylation of β-Ketoesters and Malonates
  作者：Sheng-Le Lu、Xin Li、Wen-Bing Qin、Jian-Jian Liu、Yi-Yong Huang、Henry N. C. Wong、Guo-Kai Liu

  DOI：10.1021/acs.orglett.8b03067

  日期：2018.11.2

  Air- and light-stable electrophilic difluoromethylating reagents, S-(difluoromethyl)-S-phenyl-S-(2,4,6-trialkoxyphenyl) sulfonium salts were successfully developed, and the introduction of intramolecular hydrogen bonds plays a crucial role for the stabilities and reactivities of these reagents. C-selective difluoromethylation of a broad range of β-ketoesters and malonates proceeded smoothly under mild

  空气和光稳定的亲电子二氟甲基化试剂，S-（二氟甲基）-S-苯基-S-（2,4,6-三烷氧基苯基）salts盐已成功开发，并且分子内氢键的引入对于该化合物起着至关重要的作用。这些试剂的稳定性和反应性。在温和的反应条件下，各种β-酮酸酯和丙二酸酯的C选择性二氟甲基化反应平稳进行，从而以良好的C / O区域选择性提供了良好至优异的收率。
• Carbon-Selective Difluoromethylation of Soft Carbon Nucleophiles with Difluoromethylated Sulfonium Ylide
  作者：Jiansheng Zhu、Hanliang Zheng、Xiao-Song Xue、Yisa Xiao、Yafei Liu、Qilong Shen

  DOI：10.1002/cjoc.201800383

  日期：2018.11

  highly carbon‐selective difluoromethylation of soft carbon nucleophiles including β‐ketoesters, malonates, oxindoles, benzofuranones and ketene silyl acetals with a difluoromethylated sulfonium ylide under mild conditions was described. Mechanistic studies suggest that these difluoromethylating reactions proceed via a difluorocarbene pathway.

  描述了在温和条件下用二氟甲基化叶立德对软碳亲核试剂（包括β-酮酸酯，丙二酸酯，羟吲哚，苯并呋喃酮和乙烯酮甲硅烷基乙缩醛）进行高碳选择性二氟甲基化。机理研究表明，这些二氟甲基化反应是通过二氟卡宾途径进行的。
• Bench‐Stable <i>S</i> ‐(Monofluoromethyl)sulfonium Salts: Highly Efficient <i>C</i> ‐ and <i>O</i> ‐Regioselective Monofluoromethylation of 1,3‐Dicarbonyl Compounds
  作者：Wen‐Bing Qin、Jian‐Jian Liu、Zhongyan Huang、Xin Li、Wei Xiong、Jia‐Yi Chen、Guo‐Kai Liu

  DOI：10.1002/ejoc.202000998

  日期：2020.9.30

  Novel bench‐stable S‐(monofluoromethyl)‐S‐phenyl‐S‐(2,4,6‐trialkoxyphenyl)sulfonium salts were readily prepared for C‐ and O‐regioselective monofluoromethylation of 1,3‐dicarbonyl compounds in good to excellent yields under mild reaction conditions.

  新型稳定的S-（单氟甲基）-S-苯基-S-（2,4,6-三烷氧基苯基）ulf盐易于制备，可用于1,3-二羰基化合物的C和O区域选择性单氟甲基化在温和的反应条件下。
• Guanidinium iodide-catalyzed oxidative α-nitroalkylation of β-ketoamides
  作者：Koji Yasui、Takanari Kato、Kohei Kojima、Kazuo Nagasawa

  DOI：10.1039/c4cc08581g

  日期：——

  Oxidative nitroalkylation of β-ketoamides and nitroalkanes, mediated by hypoiodide generated from tert-butyl hydrogen peroxide and a catalytic amount of guanidinium iodide, afforded the corresponding α-nitroalkyl-β-ketoamides in up to 97% yield.

  使用叔丁基过氧化氢和少量胍碘生成的次碘酸根介导的β-酮酰胺和硝基烷的氧化亚硝基化反应，得到了相应的α-硝基烷基-β-酮酰胺，产率高达97%。