3-Nitrophenyl cinnamate | 62222-44-0

• 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: 3-Nitrophenyl cinnamate
• 英文别名: m-nitrophenyl cinnamate；m-nitrophenylcinnamate；trans-Zimtsaeure-m-nitro-phenylester；(3-nitrophenyl) (E)-3-phenylprop-2-enoate
• CAS: 62222-44-0
• 化学式: C₁₅H₁₁NO₄
• 分子量: 269.257
• InChiKey: ZFKPYJMKBKCQED-MDZDMXLPSA-N

物化性质

• 沸点：
  438.8±34.0 °C(Predicted)
• 密度：
  1.295±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  72.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-Nitrophenyl cinnamate 在 aq. alkali 作用下， 以 1,4-二氧六环 为溶剂， 生成 肉桂酸 、 间硝基苯酚
  参考文献：
  名称：

  Associative and Dissociative Pathways in the Alkaline Hydrolysis of Aryl 2-Hydroxycinnamates

  摘要：

  Aryl 2-hydroxycinnamate esters hydrolyze in alkaline solutions (20% dioxane-water v/v) obeying the rate law k(obs) = k(2) + k(b)[OH-]/(1 + a(H)/K-a), where K-a is the ionization constant of the hydroxy group of the ester and kb is the second-order rate constant for the attack of hydroxide ion on the ionized ester. Kinetic data and activation parameters for the hydrolysis of the 2,4-dinitrophenyl ester show that the mechanism giving rise to the k(a) term cannot be a simple B(Ac)2 type process and suggest the occurrence of a E1cB mechanism involving an ''extended'' o-oxoketene intermediate. The Bronsted plot of the apparent second-order rate constants (k(a)K(a)/k(w)) versus the pK of the leaving group indicates that the reaction mechanism changes from E1cB to B(Ac)2 for esters with leaving groups having pK higher than about 6.

  DOI：

  10.1021/jo00106a016
• 作为产物：
  描述：

  肉桂酸 在 氯化亚砜 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 3-Nitrophenyl cinnamate
  参考文献：
  名称：

  肉桂酸衍生物及其杂芳环类似物作为潜在的高效杀青霉菌的生物活性和结构-活性关系

  摘要：

  合成了一系列肉桂酸衍生物及其杂芳族环类似物，并评价了其对against螨（Psoroptes cuniculi）的体外杀螨活性。其中，有8种化合物显示出更高的活性，中位致死浓度（LC 50）为0.36–1.07 mM（60.4–192.1 µg / mL），并且具有开发新型杀螨剂的巨大潜力。化合物40的最低LC 50值为0.36 mM（60.4 µg / mL），最小中值致死时间（LT 50）在4.5 mM时为2.6 h，与伊维菌素相当[LC 50  = 0.28 mM（247.4 µg / mL） ，LT 50 = 8.9 h]，这是一种杀螨药物标准。SAR分析表明，羰基对活性至关重要。酯部分中烷氧基的类型和链长以及酯基附近的空间位阻显着影响活性。该酯比相应的硫羟酸酯，酰胺，酮或酸更具活性。用α-吡啶基或α-呋喃基取代肉桂酸酯的苯基会显着提高活性。因此，出现了一系列具有优异杀螨活性的肉桂酸酯及其杂芳族环类似物。

  DOI：

  10.1016/j.bmcl.2017.08.051

文献信息

• Switching of polymerization activity of cinnamoyl-α-cyclodextrin
  作者：Motofumi Osaki、Yoshinori Takashima、Hiroyasu Yamaguchi、Akira Harada

  DOI：10.1039/b818241h

  日期：——

  Cinnamoyl α-cyclodextrin (α-CD) has been found to initiate polymerization of δ-valerolactone (δ-VL) to give a polymer in high yield. By the presence of the cinnamoyl group, hydrogen bond was formed between the carbonyl oxygen of δ-VL and the hydroxyl group of CD to activate the monomer, which was observed by FT-IR measurements. However, the cinnamoyl group at the C3- and C6-positions of α-CD did not affect the polymerization ability. Only that of the C2-position showed high polymerization activity. The polymerization activity could be switched by the photoisomerization of the cinnamoyl group attached to the rim of α-CD. Specific monomer recognition and polymerization in the active site of the α-CD cavity was changed by the photoisomerization.

  肉桂酰 α-环糊精 (α-CD) 已被发现能够引发 δ-戊内酯 (δ-VL) 的聚合，从而产生高产率的聚合物。通过肉桂酰基的存在，δ-VL 的羰基氧和 CD 的羟基之间形成氢键，从而激活单体，这是通过 FT-IR 测量观察到的。然而，α-CD C3-和C6-位上的肉桂酰基并不影响聚合能力。仅C2位表现出高聚合活性。聚合活性可以通过连接到α-CD 边缘的肉桂酰基的光异构化来切换。光异构化改变了α-CD 腔活性位点中的特定单体识别和聚合。
• Participation of an Extended p-Oxo Ketene Intermediate in the Dissociative Alkaline Hydrolysis of Aryl 4-Hydroxycinnamates
  作者：Giorgio Cevasco、Sergio Thea

  DOI：10.1021/jo00100a031

  日期：1994.10

  The alkaline hydrolysis of 4-hydroxycinnamate esters of acidic phenols follows an E1cB mechanism and involves the participation of an ''extended'' p-oxo ketene intermediate. The apparent bimolecular rate constant (k(a)K(a)/K-W) for the hydrolysis of the 2,4-dinitrophenyl ester is some 2500-fold larger than that determined from the Hammett relationship for the B(Ac)2 alkaline hydrolysis of substituted 2,4-dinitrophenyl cinnamates. The positive value of the entropy of activation for the hydrolysis of 2,4-dinitrophenyl 4'-hydroxycinnamate and trapping experiments with nitrogen nucleophiles are consistent with the dissociative pathway. A change from a E1cB to a B(Ac)2 mechanism is expected for esters with leaving groups having pK(a) higher than ca. 6.7. The higher E1cB reactivity of 2,4-dinitrophenyl 4'-hydroxycinnamate compared to that of the corresponding 4'-hydroxybenzoate is due to the vinylene group that further favors the dissociative route, probably increasing the stability of the unsaturated intermediate.
• Structure-reactivity relationships in nucleophilic reactions on cinnamoyl azide and phenyl cinnamates. Kinetic stability of the acyl azide and relative leaving ability of nitrogen and oxygen
  作者：Junghun Suh、Byung Hyun Lee

  DOI：10.1021/jo01303a034

  日期：1980.7
• Social Self-Sorting: Alternating Supramolecular Oligomer Consisting of Isomers
  作者：Naoki Tomimasu、Akira Kanaya、Yoshinori Takashima、Hiroyasu Yamaguchi、Akira Harada

  DOI：10.1021/ja903988c

  日期：2009.9.2

  The isomers of cinnamoyl alpha-CDs (2-CiO-alpha-CD and 3-CiO-alpha-CD) organize by themselves to give different types of supramolecular complexes in aqueous solutions. 2-CiO-alpha-CD was found to form a double-threaded dimer, which was characterized by single crystal X-ray analysis. The molecular sizes of supramolecular complexes consisting of CiO-alpha-CDs were estimated by pulsed field gradient spin-echo NMR, which gives the diffusion coefficient (D). D of 2-CiO-alpha-CD was found to be 2.3 x 10(-10) m(2)/s at concentrations over 10 mM and D was saturated. It should be noted that the hydrodynamic radius derived from D of 2-CiO-alpha-CD was found to be 9.6 angstrom, which closely matched the result from the single crystal X-ray analysis. D of 3-CiO-alpha-CD, however, was smaller than that of 2-CiO-alpha-CD at concentrations over 32 mM, indicating that 3-CiO-alpha-CD formed a supramolecular oligomer. Two-dimensional (2D)-ROESY spectra of the mixture of 2-CiO-alpha-CD and 3-CiO-alpha-CD did not show a correlation between the same species; rather, correlation peaks between 2-CiO-alpha-CD and 3-CiO-alpha-CD were observed. D's of a mixture of 2-CiO-alpha-CD and 3-CiO-alpha-CD were found to be larger than those of 2-CiO-alpha-CD and 3-CiO-alpha-CD, respectively, indicating that the mixture of 2-CiO-alpha-CD and 3-CiO-alpha-CD formed an alternative supramolecular oligomer and not a self- or random- supramolecular complex. CDs recognize a guest molecule and the substitutional position of a guest molecule on CD, suggesting that CDs have social self-sorting capability.
• Associative and Dissociative Pathways in the Alkaline Hydrolysis of Aryl 2-Hydroxycinnamates
  作者：Giorgio Cevasco、Sergio Thea

  DOI：10.1021/jo00106a016

  日期：1995.1

  Aryl 2-hydroxycinnamate esters hydrolyze in alkaline solutions (20% dioxane-water v/v) obeying the rate law k(obs) = k(2) + k(b)[OH-]/(1 + a(H)/K-a), where K-a is the ionization constant of the hydroxy group of the ester and kb is the second-order rate constant for the attack of hydroxide ion on the ionized ester. Kinetic data and activation parameters for the hydrolysis of the 2,4-dinitrophenyl ester show that the mechanism giving rise to the k(a) term cannot be a simple B(Ac)2 type process and suggest the occurrence of a E1cB mechanism involving an ''extended'' o-oxoketene intermediate. The Bronsted plot of the apparent second-order rate constants (k(a)K(a)/k(w)) versus the pK of the leaving group indicates that the reaction mechanism changes from E1cB to B(Ac)2 for esters with leaving groups having pK higher than about 6.