methyl (+/-)-2-(2-nitrophenyl)-5-hexenoate | 778640-87-2

• 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: methyl (+/-)-2-(2-nitrophenyl)-5-hexenoate
• 英文别名: methyl 2-(2-nitrophenyl)hex-5-enoate
• CAS: 778640-87-2
• 化学式: C₁₃H₁₅NO₄
• 分子量: 249.266
• InChiKey: SRVBDZMELZNWBE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 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：

  methyl (+/-)-2-(2-nitrophenyl)-5-hexenoate 在 sodium tetrahydroborate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 生成
  参考文献：
  名称：

  On the Mechanism of Intramolecular Sensitization of Photocleavage of the 2-(2-Nitrophenyl)propoxycarbonyl (NPPOC) Protecting Group

  摘要：

  A spectroscopic study of a variety of covalently linked thioxanthone(TX)-linker-2-(2-nitrophenyl)propoxycarbonyl(NPPOC)-substrate conjugates is presented. Herein, the TX chromophore functions as an intramolecular sensitizer to the NPPOC moiety, a photolabile protecting group used in photolithographic DNA chip synthesis. The rate of electronic energy transfer between TX and NPPOC was quantified by means of stationary fluorescence as well as nanosecond and femtosecond time-resolved laser spectroscopy. A dual mechanism of triplet-triplet energy transfer has been observed comprising a slower mechanism involving the Ti(pi pi*) state of TX with linker-length-dependent time constants longer than 20 ns and a fast mechanism with linker-length-dependent time constants shorter than 3 ns. Evidence is provided that the latter mechanism is due to energy transfer from the T-2(n pi*) state which is in fast equilibrium with the fluorescent S-1(pi pi*) state. In the case of direct linkage between the aromatic rings of TX and NPPOC, the spectroscopic properties are indicative of one united chromophore which, however, still shows the typical NPPOC cleavage reaction triggered by intramolecular hydrogen atom transfer to the nitro group.

  DOI：

  10.1021/ja072355p
• 作为产物：
  描述：

  dimethyl 2-(3-butenyl)malonate 在 caesium carbonate 、 sodium chloride 作用下， 以 二甲基亚砜 为溶剂， 反应 15.0h， 生成 methyl (+/-)-2-(2-nitrophenyl)-5-hexenoate
  参考文献：
  名称：

  乙醇与硝基反应生成硝基

  摘要：

  在60°C下，用氢氧化钠的甲醇溶液处理在α位具有2-硝基苯基的酮。在这些条件下，源自酮的烯醇化物在分子内与硝基反应形成各种硝酮。其他实验结果，包括意外分离出副产物N-羟基吲哚酮，导致了通过α-羟基酮发生的拟议反应机理。所得的硝基酮与烯烃进行分子间和分子内的1，3-偶极环加成反应，得到多环异恶唑烷。

  DOI：

  10.1021/acs.orglett.1c00603

文献信息

• Diastereoselective synthesis of substituted 2,3,4,5-tetrahydro-1<i>H</i>-1-benzazepine-5-carboxylic esters by a tandem reduction-reductive animation reaction
  作者：Richard A. Bunce、Lara B. Johnson、Elizabeth M. Holt

  DOI：10.1002/jhet.5570410413

  日期：2004.7

  diastereoselective synthesis of substituted and unsubstituted 2,3,4,5-tetrahydro-1H-1-benzazepine-5-carboxylic esters has been developed based on the tandem reduction-reductive amination reac tion. Catalytic hydrogenation of a series of 2-(2-nitrophenyl)-5-oxoalkanoic esters initiates a reaction sequence involving (1) reduction of the aromatic nitro group, (2) condensation of the N-hydroxylamino (or amino)

  基于串联还原-还原胺化反应，已经开发了一种有效的非对映选择性合成取代的和未取代的2,3,4,5-四氢-1 H -1-苯并ze庚因-5-羧酸酯。一系列2-（2-硝基苯基）-5-氧代链烷酸酯的催化加氢引发了一个反应序列，涉及（1）芳族硝基的还原，（2）N-羟基氨基（或氨基）氮与侧链的缩合（3）还原七元环亚胺。对于具有C 2烷基和C 5酯基为顺式的产物，产生2-烷基-2,3,4,5-四氢-1 H -1-苯并pine庚因-5-羧酸酯的环化是非对映体选择。在这些反应中，环戊酸酯基团对环状亚胺中间体的还原具有很强的立体定向作用，尽管不如以前的2-烷基-1,2,3,4-四氢喹啉-4-羧酸的闭合反应所观察到的强。酯。非对映选择性的降低归因于（1）酯与亚胺双键之间的距离更大，以及（2）较大环的构象迁移率增加，这两者都减弱了酯的立体定向作用。最后，七元环的形成足够缓慢，以至于在一些反应中与侧链酯基团的反应与杂环的形成竞争。
• Nitrone Formation by Reaction of an Enolate with a Nitro Group
  作者：Hiroaki Shimizu、Kohei Yoshinaga、Satoshi Yokoshima

  DOI：10.1021/acs.orglett.1c00603

  日期：2021.4.2

  enolates derived from the ketones intramolecularly reacted with the nitro group to form a variety of nitrones. Additional experimental results, including the unexpected isolation of N-hydroxyindolinone as a byproduct, led to a proposed reaction mechanism, occurring via an α-hydroxyketone. The resultant nitrones underwent inter- and intramolecular 1,3-dipolar cycloaddition with olefins to afford polycyclic

  在60°C下，用氢氧化钠的甲醇溶液处理在α位具有2-硝基苯基的酮。在这些条件下，源自酮的烯醇化物在分子内与硝基反应形成各种硝酮。其他实验结果，包括意外分离出副产物N-羟基吲哚酮，导致了通过α-羟基酮发生的拟议反应机理。所得的硝基酮与烯烃进行分子间和分子内的1，3-偶极环加成反应，得到多环异恶唑烷。
• On the Mechanism of Intramolecular Sensitization of Photocleavage of the 2-(2-Nitrophenyl)propoxycarbonyl (NPPOC) Protecting Group
  作者：Dominik Wöll、Stefan Laimgruber、Marina Galetskaya、Julia Smirnova、Wolfgang Pfleiderer、Björn Heinz、Peter Gilch、Ulrich E. Steiner

  DOI：10.1021/ja072355p

  日期：2007.10.1

  A spectroscopic study of a variety of covalently linked thioxanthone(TX)-linker-2-(2-nitrophenyl)propoxycarbonyl(NPPOC)-substrate conjugates is presented. Herein, the TX chromophore functions as an intramolecular sensitizer to the NPPOC moiety, a photolabile protecting group used in photolithographic DNA chip synthesis. The rate of electronic energy transfer between TX and NPPOC was quantified by means of stationary fluorescence as well as nanosecond and femtosecond time-resolved laser spectroscopy. A dual mechanism of triplet-triplet energy transfer has been observed comprising a slower mechanism involving the Ti(pi pi*) state of TX with linker-length-dependent time constants longer than 20 ns and a fast mechanism with linker-length-dependent time constants shorter than 3 ns. Evidence is provided that the latter mechanism is due to energy transfer from the T-2(n pi*) state which is in fast equilibrium with the fluorescent S-1(pi pi*) state. In the case of direct linkage between the aromatic rings of TX and NPPOC, the spectroscopic properties are indicative of one united chromophore which, however, still shows the typical NPPOC cleavage reaction triggered by intramolecular hydrogen atom transfer to the nitro group.