butyl 3-hydroxy-2-methylene-3-(4-nitrophenyl)propanoate | 282521-87-3

• 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: butyl 3-hydroxy-2-methylene-3-(4-nitrophenyl)propanoate
• 英文别名: butyl 2-(hydroxy(4-nitrophenyl)methyl)acrylate；2-[(4-nitrophenyl)hydroxymethyl]acrylic acid butyl ester；2-(hydroxy(4-nitrophenyl)methyl)acrylic acid butyl ester；Butyl 2-[hydroxy-(4-nitrophenyl)methyl]prop-2-enoate
• CAS: 282521-87-3
• 化学式: C₁₄H₁₇NO₅
• 分子量: 279.293
• InChiKey: TUQBEUKFVLRRAX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  92.4
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  butyl 3-hydroxy-2-methylene-3-(4-nitrophenyl)propanoate 在 吡啶 、 三乙烯二胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 0.25h， 生成 2-[(4-nitrophenyl)phenoxymethyl]acrylic acid butyl ester
  参考文献：
  名称：

  The Baylis–Hillman chemistry in aqueous media: elucidation of mechanism for synthesis of ether side-product leads to an efficient approach to C–O bond formation

  摘要：

  The formation of an ether from the Baylis-Hillman (BH) adduct during the BH reaction of 5-isoxazolecarboxaldehydes is a common phenomenon if the reaction is allowed to proceed for longer periods. The amount of formation of such ethers depends on the acrylates used and is most significant for tert-butyl acrylates. A study of the plausible mechanism for the formation of these side-products led to reactions of acetates of BH adducts with phenol in aqueous media to yield the corresponding 3-phenoxy alk-2-enoates in good yields. The successful translation of solution phase methodology to solid phase for application towards combinatorial chemistry is discussed. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(02)01561-2
• 作为产物：
  描述：

  丙烯酸丁酯 、 对硝基苯甲醛 在 1,3,5-三氮杂-7-磷杂金刚烷 作用下， 反应 15.0h， 以79%的产率得到butyl 3-hydroxy-2-methylene-3-(4-nitrophenyl)propanoate
  参考文献：
  名称：

  第一种对Baylis-Hillman反应稳定的空气稳定且高效的亲核三烷基膦有机催化剂

  摘要：

  1,3,5，-Triaza-7-phosphaadamantane（PTA）首次被报道是一种用于Baylis-Hillman反应的便捷有效的亲核三烷基膦有机催化剂。因此，在15-20 mol％的PTA和实际条件下，芳族和脂族醛均与活化的烯烃（如丙烯酸酯和甲基乙烯基酮）反应，以相当高的收率获得相应的加合物。

  DOI：

  10.1002/adsc.200505403

文献信息

• Dramatic Rate Acceleration of the Baylis−Hillman Reaction in Homogeneous Medium in the Presence of Water
  作者：Juexiao Cai、Zhenghong Zhou、Guofeng Zhao、Chuchi Tang

  DOI：10.1021/ol027197f

  日期：2002.12.1

  [reaction: see text] In homogeneous H(2)O/solvent medium, the reaction rate of aromatic aldehydes and acrylonitrile or acrylate was greatly accelerated, which led to shorter reaction time, lower reaction temperature, and higher yield. In this reaction, Me(3)N, DMAP, DABCO, and urotropine were good catalysts. Except for low-carbon alcohols, tetrahydrofuran, 1,4-dioxane, and acetonitrile could be chosen

  [反应：见正文]在均相H（2）O /溶剂介质中，芳族醛与丙烯腈或丙烯酸酯的反应速率大大提高，导致反应时间更短，反应温度更低，产率更高。在该反应中，Me（3）N，DMAP，DABCO和乌罗托品是良好的催化剂。除低碳醇外，可以选择四氢呋喃，1,4-二恶烷和乙腈作为溶剂。在此条件下，硝基苯甲醛与丙烯酸L-薄荷基酯的非对映选择性反应的de-为88-99％。
• Replacing a stoichiometric silver oxidant with air: ligated Pd(<scp>ii</scp>)-catalysis to β-aryl carbonyl derivatives with improved chemoselectivity
  作者：Mari Vellakkaran、Murugaiah M. S. Andappan、Nagaiah Kommu

  DOI：10.1039/c3gc42504e

  日期：——

  Air was employed as a green reoxidant of Pd(0), replacing stoichiometric and toxic silver salt, in the chelation-controlled Pd(ii)-modulated arylative enolization of prop-2-en-1-ols to acquire synthetically-important β-aryl carbonyl derivatives.

  空气被用作Pd（0）的绿色氧化剂，取代了化学计量且有毒的银盐，在以螯合控制的Pd（II）调控下进行的烯醇化反应中，将丙烯-1-醇芳基化，以获得具有合成重要性的β-芳基酮衍生物。
• The First Air-Stable and Efficient Nucleophilic Trialkylphosphine Organocatalyst for the Baylis–Hillman Reaction
  作者：Zhengrong He、Xiaofang Tang、Yaoming Chen、Zhengjie He

  DOI：10.1002/adsc.200505403

  日期：2006.3

  1,3,5,-Triaza-7-phosphaadamantane (PTA) is first reported to be a convenient and efficient nucleophilic trialkylphosphine organocatalyst for the Baylis–Hillman reaction. Thus, under the mediation of 15–20 mol % of PTA and practical conditions, both aromatic and aliphatic aldehydes react with the activated alkenes like acrylates and methyl vinyl ketone to afford the corresponding adducts in fair to

  1,3,5，-Triaza-7-phosphaadamantane（PTA）首次被报道是一种用于Baylis-Hillman反应的便捷有效的亲核三烷基膦有机催化剂。因此，在15-20 mol％的PTA和实际条件下，芳族和脂族醛均与活化的烯烃（如丙烯酸酯和甲基乙烯基酮）反应，以相当高的收率获得相应的加合物。
• The Aqueous Trimethylamine Mediated Baylis-Hillman Reaction
  作者：Deevi Basavaiah、Marimganti Krishnamacharyulu、Anumolu Jaganmohan Rao

  DOI：10.1080/00397910008087256

  日期：2000.6

  Aqueous trimethylamine mediated Baylis-Hillman coupling of alkyl acrylates with aldehydes is described.
• Baylis–Hillman reaction promoted by a recyclable protic-ionic-liquid solvent–catalyst system: DABCO–AcOH–H2O
  作者：Ying Song、Haihua Ke、Nan Wang、Limin Wang、Gang Zou

  DOI：10.1016/j.tet.2009.09.049

  日期：2009.11

  A recyclable protic-ionic-liquid solvent-catalyst system, DABCO-AcOH-H2O, has been developed and used in the Baylis-Hillman reaction of aromatic aldehydes, aliphatic aldehydes, and cinnamaldehydes with acrylates and acrylonitrile, showing comparable performance to free DABCO in traditional solvents. The DABCO-AcOH-H2O solvent-catalyst system could be reused for at least five times without significant loss of activity. (C) 2009 Elsevier Ltd. All rights reserved.