ethyl 3-oxo-5-(4-nitrophenyl)-4-(E)-pentenoate | 76842-84-7

• 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: ethyl 3-oxo-5-(4-nitrophenyl)-4-(E)-pentenoate
• 英文别名: ethyl (E)-3-oxo-5-(p-nitrophenyl)pent-4-enoate；ethyl (E)-5-(4-nitrophenyl)-3-oxopent-4-enoate；3-oxo-1t-(4-nitro-phenyl)-penten-(1)-oic acid-(5)-ethyl ester；3-Oxo-1t-(4-nitro-phenyl)-penten-(1)-saeure-(5)-aethylester
• CAS: 76842-84-7
• 化学式: C₁₃H₁₃NO₅
• 分子量: 263.25
• InChiKey: PPNKPLRWTPTNEK-VMPITWQZSA-N

物化性质

• 熔点：
  108 °C
• 沸点：
  396.6±27.0 °C(Predicted)
• 密度：
  1.260±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  89.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl 3-oxo-5-(4-nitrophenyl)-4-(E)-pentenoate 在 ketoreductase P₁-B₀₅ 作用下， 以 甲醇 、 水 、 异丙醇 为溶剂， 反应 24.0h， 以98%的产率得到
  参考文献：
  名称：

  Stereoselective synthesis of aryl γ,δ-unsaturated β-hydroxyesters by ketoreductases

  摘要：

  The biocatalytic reduction of aryl gamma,delta-unsaturated-beta-ketoesters was evaluated utilizing 24 different commercially available ketoreductases. In all cases, both (R) and (S)-enantiomers of gamma,delta-unsaturated beta-hydroxyesters were synthesized by one or more ketoreductases in excellent optical purity and yields. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcatb.2013.09.003
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 溶剂黄146 作用下， 生成 ethyl 3-oxo-5-(4-nitrophenyl)-4-(E)-pentenoate
  参考文献：
  名称：

  Lampe; Macierewicz, Roczniki Chemii, 1938, vol. 18, p. 668,670

  摘要：

  DOI：

文献信息

• Preparation of γ,δ-unsaturated-β-ketoesters: Lewis acid-catalysed C H insertion of ethyl diazoacetate into α,β-unsaturated aldehydes
  作者：Hirenkumar Gandhi、Timothy P. O'Sullivan

  DOI：10.1016/j.tetlet.2017.07.095

  日期：2017.9

  synthesis of γ,δ-unsaturated-β-keto esters was achieved by the Lewis acid-catalysed direct CH insertion of an α-diazoester into various α,β-substituted-unsaturated aldehydes. CH insertion of ethyl diazoacetate into alkyl- and aryl-substituted α,β-unsaturated aldehydes was performed under mild conditions to afford the corresponding γ,δ-unsaturated-β-keto esters in moderate to high yields as a mixture

  γ，δ-不饱和-β-酮酸酯的合成是通过路易斯酸催化的α-重氮酯直接C H插入各种α，β-取代的不饱和醛中来实现的。在温和的条件下将重氮基乙酸乙酯C H插入烷基和芳基取代的α，β-不饱和醛中，以中等至高收率的酮/烯醇混合物形式提供相应的γ，δ-不饱和-β-酮酸酯互变异构体。
• Ethyl 4-diphenylphosphinoyl-2-oxobutanoate: A convenient reagent for the synthesis of γ,δ-unsaturated β-ketoesters
  作者：J.A.M. van den Goorbergh、A. van der Gen

  DOI：10.1016/0040-4039(80)80252-8

  日期：1980.1

  Aldehydes and ketones can be converted into γ,δ-unsaturated-β-ketoesters by reaction with the dianion from phosphine oxide .

  通过与氧化膦中的二价阴离子反应，可以将醛类和酮类转化为γ，δ-不饱和-β-酮酸酯。
• Organocatalytic Asymmetric Formal [3+3] Cycloaddition Reactions of α,β-Unsaturated Aldehydes with Nazarov Reagents
  作者：Ming-Kui Zhu、Qiang Wei、Liu-Zhu Gong

  DOI：10.1002/adsc.200800174

  日期：2008.6.9

  An organocatalytic asymmetric formal [3+3] cycloaddition reaction of α,β-unsaturated aldehydes with Nazarov reagents promoted by prolinol derivatives afforded, after oxidation, 3,4-dihydropyranones in good yields with high enantioselectivities of up to 97% ee.

  α，β-不饱和醛与Nazarov试剂的有机催化不对称形式[3 + 3]环加成反应，由Prolinol衍生物促进，氧化后可提供高产率的3,4-二氢吡喃酮，对映选择性高达97％ee。
• Studies on Cerebral Protective Agents. VI. Synthesis of Novel 4-(4-Nitrobenzoyl)pyrimidine and Related Compounds with Anti-anoxic Activity.
  作者：Mitsuru OHKUBO、Atsushi KUNO、Hiroyoshi SAKAI、Yoshie SUGIYAMA、Hisashi TAKASUGI

  DOI：10.1248/cpb.42.1279

  日期：——

  Novel pyrimidine derivatives, possessing linkages between the aryl group and the pyrimidine nucleus at the C-4 position, were prepared and tested for anti-anoxic (AA) activity in mice. Among them, 5-(4-methylpiperazin-1-ylcarbonyl)-4-(4-nitrobenzoyl)-2-phenylpyrimidine (2f, FR76659) possessed significant AA activity (10-100 mg/kg, i.p.) with low acute toxicity (LD50>1000 mg/kg, i.p.). Structure-activity relationships in regard to AA activity of this series of compounds were examined.

  制备了新型嘧啶衍生物，在芳基和 C-4 位嘧啶核之间具有连接，并在小鼠中测试了其抗缺氧 (AA) 活性。其中，5-(4-甲基哌嗪-1-基羰基)-4-(4-硝基苯甲酰基)-2-苯基嘧啶(2f，FR76659)具有显着的AA活性(10-100 mg/kg，i.p.)且急性毒性低( LD50>1000 mg/kg，腹腔注射）。检查了该系列化合物的 AA 活性的构效关系。
• Enantioselective Syntheses of Multiply Functionalized Six‐Membered Carbocycles from Nitroalkenes and γ,δ‐Unsaturated ß‐Ketoesters using Chiral Catalysts Derived from Cobalt(III) and 1,2‐Diphenylethylenediamine
  作者：Katherine Wang、Nattamai Bhuvanesh、John A. Gladysz

  DOI：10.1002/adsc.202300972

  日期：2023.12.19

  stereocenters, as >99:1 to 85:15 mixtures of diastereomers (ten examples). The major diastereomers are isolated in 81–63% yields and 97–76% ee. When R4 and R6 are both aryl groups, additions of 1,1,3,3-tetramethylquanidine/CH3CN epimerize the CHNO2 moieties, affording 78:22 to 67:33 mixtures of the new/old diastereomers (2 h, RT). Alternatively, epimerization to >99:1 mixtures occurs spontaneously over 4

  标题离析物R 4 CH=CH(C=O)CH 2 CO 2 Et 和R 6 CH=CHNO 2在NEt 3和催化剂Λ-[Co(( S , S )-dpen) 3存在下的缩合] 3+ 2Cl − B(C 6 F 5 )4 −（均为 10 mol%，0 °C；dpen=1,2-二苯基乙二胺）得到 R 6 CHCH(NO 2 )CH(R 4 )CH 2 C(OH )CCO 2 Et，具有三个连续的碳立构中心，作为 >99:1 至 85:15 的非对映异构体混合物（十个示例）。主要非对映异构体的分离产率为 81-63%，ee 为 97-76%。当 R 4和 R 6均为芳基时，添加 1,1,3,3-四甲基胍/CH 3 CN 使 CHNO 2部分差向异构化，得到新/旧非对映体的 78:22 至 67:33 混合物（2 小时） ，RT）。或者，在己烷/异丙醇中，4 周内自发发生差向异构化，形成 >99:1