4-(4-bromophenyl)-4-oxo-but-2-ynoic acid ethyl ester | 215675-07-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-(4-bromophenyl)-4-oxo-but-2-ynoic acid ethyl ester
• 英文别名: ethyl 4-(p-bromophenyl)-4-oxo-2-butynoate；Ethyl 4-(4-bromophenyl)-4-oxobut-2-ynoate
• CAS: 215675-07-3
• 化学式: C₁₂H₉BrO₃
• 分子量: 281.106
• InChiKey: VMUJBEFRQJNERD-UHFFFAOYSA-N

物化性质

• 熔点：
  32-34 °C
• 沸点：
  362.6±44.0 °C(Predicted)
• 密度：
  1.479±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 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：

  4-(4-bromophenyl)-4-oxo-but-2-ynoic acid ethyl ester 在 乙醇 、 二乙胺基三氟化硫 作用下， 反应 8.0h， 生成 2-[(4-bromophenyl)difluoromethyl]-4,5-dimethylcyclohexa-1,4-dienecarboxylic acid ethyl ester
  参考文献：
  名称：

  合成宝石-二氟-二元衍生物和杂环类似物的新灵活策略

  摘要：

  设计了一种新的制备宝石-二氟-二芳基衍生物的策略。它从容易获得的反应性宝石-二氟-炔丙基中间体开始，并通过狄尔斯-阿尔德-芳香化序列精制芳环。杂环体系也可以通过1，3偶极环加成获得，从而得到以CF 2为连接基的混合的芳族/杂芳族衍生物。由于该基序是O和CO的生物等排体，因此可以使用相应的二元支架制备生物活性天然产物和/或药物的氟化类似物的化学文库。

  DOI：

  10.1016/j.tet.2011.03.073
• 作为产物：
  描述：

  1-(3-氯丙基)-3-环己基脲 在 三乙胺 作用下， 以 苯 为溶剂， 500.0 ℃ 、13.33 Pa 条件下， 生成 4-(4-bromophenyl)-4-oxo-but-2-ynoic acid ethyl ester
  参考文献：
  名称：

  Koz'minykh; Berezina; Koz'minykh, Russian Journal of General Chemistry, 1998, vol. 68, # 3, p. 390 - 394

  摘要：

  DOI：

文献信息

• Chiral N,N′-dioxide/Sc(OTf)₃ complex-catalyzed asymmetric dearomatization of β-naphthols
  作者：Shulin Ge、Tengfei Kang、Lili Lin、Xiying Zhang、Peng Zhao、Xiaohua Liu、Xiaoming Feng

  DOI：10.1039/c7cc06388a

  日期：——

  An efficient N,N’-dioxide-scandium(III) complex catalytic system has been developed for the asymmetric dearomatization of β-naphthols through conjugate addition to alkynones. A variety of Z-predominated β-naphthalenone compounds were obtained in moderate to high yields with excellent enantioselectivities (up to 98% ee). Moreover, a possible transition state was proposed to explain the origin of the

  已经开发了一种有效的N，N'-二氧化-（III）络合物催化系统，用于通过将共轭物加成炔烃使β-萘酚不对称脱芳香化。以中等至高收率获得了许多Z为主的β-萘酮化合物，并具有出色的对映选择性（最高98％ee）。此外，提出了一种可能的过渡态来解释立体选择性的起源。
• Highly Efficient Asymmetric Synthesis of Chiral γ-Alkenyl Butenolides Catalyzed by Chiral <i>N,N</i>′-Dioxide–Scandium(III) Complexes
  作者：Jie Ji、Lili Lin、Qiong Tang、Tengfei Kang、Xiaohua Liu、Xiaoming Feng

  DOI：10.1021/acscatal.7b00590

  日期：2017.6.2

  The asymmetric synthesis of γ-alkenyl butenolides was accomplished by conjugated addition of butenolides to alkynones. Both terminal alkynones and nonterminal alkynones were applicable to the N,N′-dioxide–scandium(III) catalytic system. The corresponding products were obtained in good to excellent yields (up to 99%) with high E/Z ratios and high enantioselectivities (up to 98% ee). The novel methods

  γ-烯基丁烯化物的不对称合成是通过将丁烯化物共轭添加到炔烃中来完成的。末端炔基和非末端炔基均适用于N，N'-二氧化物-scan（III）催化体系。获得了具有高E / Z比和高对映选择性（高达98％ee）的高至极好产率（高达99％）的相应产品。构建γ-烯基丁烯化物和连续环氧化产物的新方法有助于构建具有生物活性的天然产物和合成中间体的核心结构。另外，一锅迈克尔加成/环氧化反应在我们的催化系统中表现良好。
• Concise Assembly of Highly Substituted Furan-Fused 1,4-Thiazepines and Their Diels−Alder Reactions with Benzynes
  作者：Hanfeng Ding、Yiping Zhang、Ming Bian、Weijun Yao、Cheng Ma

  DOI：10.1021/jo702299m

  日期：2008.1.1

  A facile and highly efficient three-component reaction of thiazole or benzothiazole carbenes, disubstituted ketenes, and activated alkynes is disclosed. With this methodology, a polysubstituted ring system containing furo[2,3-c]thiazepine core can be constructed from simple and readily accessible starting materials in good yields. The scope and limitation of this transformation were investigated in detail by using various thiazole carbene, ketene, and alkyne components. Furthermore, the synthetic utilities of these unique polyheterocyclic compounds were demonstrated via their Diels-Alder reactions with benzynes to furnish thiazepine-fused 7-oxanorbornadiene derivatives in excellent yields.
• A Ring-Expansion Methodology Involving Multicomponent Reactions: Highly Efficient Access to Polysubstituted Furan-Fused 1,4-Thiazepine Derivatives
  作者：Cheng Ma、Hanfeng Ding、Yiping Zhang、Ming Bian

  DOI：10.1002/anie.200602836

  日期：2006.11.27
• A new flexible strategy for the synthesis of gem-difluoro-bisarylic derivatives and heterocyclic analogues
  作者：Ali Khalaf、Danielle Grée、Hassan Abdallah、Nada Jaber、Ali Hachem、René Grée

  DOI：10.1016/j.tet.2011.03.073

  日期：2011.5

  designed for the preparation of gem-difluoro-bisarylic derivatives. It starts from easily accessible and reactive gem-difluoro-propargylic intermediates and elaborates the aromatic rings by a Diels–Alder-aromatization sequence. Heterocyclic systems can be also obtained by 1,3 dipolar cycloadditions, affording mixed aromatic/heteroaromatic derivatives with CF2 as a linker. Since this motif is a bioisostere

  设计了一种新的制备宝石-二氟-二芳基衍生物的策略。它从容易获得的反应性宝石-二氟-炔丙基中间体开始，并通过狄尔斯-阿尔德-芳香化序列精制芳环。杂环体系也可以通过1，3偶极环加成获得，从而得到以CF 2为连接基的混合的芳族/杂芳族衍生物。由于该基序是O和CO的生物等排体，因此可以使用相应的二元支架制备生物活性天然产物和/或药物的氟化类似物的化学文库。