3-(2-硝基苯基)丙酸甲酯 | 1664-65-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 3-(2-硝基苯基)丙酸甲酯
• 英文名称: methyl 3-(2-nitrophenyl)propanoate
• CAS: 1664-65-9
• 化学式: C₁₀H₁₁NO₄
• 分子量: 209.202
• InChiKey: JZUUWUDINSQSRJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 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-(2-硝基苯基)丙酸甲酯 在 3,5-二乙酰基-1,4-二氢-2,6-二甲基吡啶 、 [bis(2,2′‐bipyridine)ruthenium(II)](chloride)₂ hexahydrate 、 铁粉 、 溶剂黄146 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 17.5h， 生成 3,4-二氢-2(1H)-喹啉酮
  参考文献：
  名称：

  Reductive Cyclizations of Nitroarenes to Hydroxamic Acids by Visible Light Photoredox Catalysis

  摘要：

  We have developed a photocatalytic reduction of nitroarenes as an efficient, chemoselective route to biologically important N-phenyl hydroxamic acid scaffolds. Optimal conditions call for 2.5 mol% of a ruthenium photocatalyst, visible light irradiation, and a dihydropyridine terminal reductant. Because of the mild nature of the visible light activation, functional groups that might be sensitive to other non-photochemical reduction methods are easily tolerated.

  DOI：

  10.1055/s-0033-1338419
• 作为产物：
  描述：

  p-toluenesulfonic acid o-nitrophenethyl ester 在 氯化亚砜 、 硫酸 作用下， 以 N-甲基吡咯烷酮 为溶剂， 反应 6.5h， 生成 3-(2-硝基苯基)丙酸甲酯
  参考文献：
  名称：

  5′-(2-Nitrophenylalkanoyl)-2′-deoxy-5-fluorouridines as potential prodrugs of FUDR for reductive activation

  摘要：

  Four 5'-(2-nitrophenylalkanoyl)-2'-deoxy-5-fluorouridines (1a-d) were designed and synthesized as potential prodrugs of FUDR for reductive activation. Two methyl groups were introduced alpha to the ester carbonyl to increase both the rate of cyclization activation and the stability of the conjugates towards serum esterases. Chemical reduction of the nitro group into an amino leads to cyclization and release of the active FUDR. Kinetic analysis of the cyclization activation process indicates that the two methyl groups alpha to the ester carbonyl restrict the rotational freedom of ground state molecule and promote the cyclization reaction. However, the two methyl groups also were found to render the conjugates as poor substrates of E. coli B nitroreductase. Conjugate 1c, without the two methyl groups, was reduced by E. coli B nitroreductase (t(1/2) = 8 h) to give two products, a N-hydroxyl lactam and the drug FUDR, suggesting that the enzymatic reduction and subsequent cyclization activation proceeded through the hydroxylamine intermediate. These results indicate that cyclization activation will occur once the nitro group is reduced either to an amino or to a hydroxylamino group. The fact that the amino intermediates cyclized easily to release the incorporated drug FUDR suggests the feasibility of using peptide-linked acyl 2-aminophenylalkanoic acid esters as potential prodrugs for proteolytic activation. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0968-0896(03)00426-7

文献信息

• Nitric acid in the presence of P2O5 supported on silica gel—a useful reagent for nitration of aromatic compounds under solvent-free conditions
  作者：Abdol Reza Hajipour、Arnold E. Ruoho

  DOI：10.1016/j.tetlet.2005.09.178

  日期：2005.11

  A variety of aromatic compounds are nitrated to parent nitro aromatic compounds under solvent-free conditions using 65% nitric acid in the presence of P2O5 supported on silica gel is described. This methodology is useful for nitration of activated and deactivated aromatic rings.

  描述了在65％硝酸在无溶剂条件下在硅胶上负载的P 2 O 5存在下将多种芳族化合物硝化为母体硝基芳族化合物。该方法学对于活化和失活的芳环的硝化是有用的。
• Novel <i>N</i>-transfer reagent for converting α-amino acid derivatives to α-diazo compounds
  作者：Guan-Han Lu、Tzu-Chia Huang、Hsiao-Chin Hsueh、Shin-Cherng Yang、Ting-Wei Cho、Ho-Hsuan Chou

  DOI：10.1039/d1cc01285a

  日期：——

  direct and effective transformation of α-amino ketones, acetamides, and esters to the corresponding α-diazo products under mild basic conditions has been developed. This one-step synthetic approach not only allows for generation of α-substituted-α-diazo carbonyl compounds from α-amino acid derivatives but also permits preparation of α-diazo dipeptides from N-terminal dipeptides (32 examples, up to 91%)

  开发了一种新型通用N-转移试剂，可在温和的碱性条件下直接有效地将 α-氨基酮、乙酰胺和酯转化为相应的 α-重氮产物。这种一步合成方法不仅允许从 α-氨基酸衍生物生成 α-取代-α-重氮羰基化合物，而且允许从N-末端二肽制备 α-重氮二肽（32 个例子，高达 91%） .
• Palladium-Catalyzed Cross-Coupling Reaction of Alkyltrifluorosilanes with Aryl Halides
  作者：Hayao Matsuhashi、Satoshi Asai、Kazunori Hirabayashi、Yasuo Hatanaka、Atsunori Mori、Tamejiro Hiyama

  DOI：10.1246/bcsj.70.437

  日期：1997.2

  A cross-coupling reaction of alkyltrifluorosilanes with aryl halides was achieved using a catalytic amount of tetrakis(triphenylphosphine)palladium(0) and excess of tetrabutylammonium fluoride (TBAF) at 100 °C with high chemoselectitvity. Functional groups like nitro, ketone carbonyl, and formyl tolerated the coupling conditions. Because potassium(18-crown-6) alkyltetrafluorosilicates also underwent

  使用催化量的四（三苯基膦）钯 (0) 和过量的四丁基氟化铵 (TBAF) 在 100 °C 下以高化学选择性实现烷基三氟硅烷与芳基卤化物的交叉偶联反应。硝基、酮羰基和甲酰基等官能团耐受偶联条件。因为钾（18-冠-6）烷基四氟硅酸盐也在额外摩尔量的 TBAF 存在下发生交叉偶联反应，所以假设偶联反应的活性物质是五配位硅酸盐。认为需要过量的 TBAF 来捕获交叉偶联反应的催化循环中产生的四氟硅烷。
• Deconstructive di-functionalization of unstrained, benzo cyclic amines by C–N bond cleavage using a recyclable tungsten catalyst
  作者：Yujing Zhang、Shuai Sun、Yijin Su、Jian Zhao、Yong-Hong Li、Bo Han、Feng Shi

  DOI：10.1039/c9ob00693a

  日期：——

  the C–N bond in unstrained, benzo cyclic amines to generate an ester group and nitro group simultaneously. The preliminary mechanistic studies suggested that the corresponding hydroxamic acid is the key intermediate for this transformation. Importantly, with the utilization of this transformation, we achieved an interesting approach for the ring contraction of quinoline to indole, an example of scaffold

  以H 2 WO 4为催化剂，H 2 O 2为氧化剂，我们在本文中报道了在未应变的苯并环胺中C–N键的解构二官能化，可同时生成酯基和硝基。初步的机理研究表明，相应的异羟肟酸是该转化的关键中间体。重要的是，利用这种转化，我们实现了一种有趣的方法，将喹啉环缩为吲哚，这是杂芳族体系中支架跳跃的一个例子。
• Suspension Ring-Opening Metathesis Polymerization:  The Preparation of Norbornene-Based Resins for Application in Organic Synthesis
  作者：Byoung Se Lee、Suresh Mahajan、Bruce Clapham、Kim D. Janda

  DOI：10.1021/jo049827s

  日期：2004.5.1

  obtained by aqueous suspension ring-opening metathesis polymerization (ROMP) and used as polymeric supports for organic synthesis. These resins were prepared from norbornene, norborn-2-ene-5-methanol, and cross-linkers such as bis(norborn-2-ene-5-methoxy)alkanes, di(norborn-2-ene-5-methyl)ether, and 1,3-di(norborn-2-ene-5-methoxy)benzene. The resulting unsaturated ROMP (U-ROMP) resins containing olefin

  通过水悬浮液开环复分解聚合（ROMP）获得了一系列的降冰片烯基树脂珠，并用作有机合成的聚合物载体。这些树脂由降冰片烯，降冰片烯-2-烯-5-甲醇和交联剂如双（降冰片烯-2-烯-5-甲氧基）烷烃，二（降冰片烯-2-烯-5-甲基）醚制备和1,3-二（降冰片-2-烯-5-甲氧基）苯。使用氢化，氢氟化，氯化和溴化反应对所得的包含烯烃重复单元的不饱和ROMP（U-ROMP）树脂进行化学改性，以生产具有不同化学和物理性质的饱和ROMP树脂。发现氢化的ROMP（H-ROMP）树脂对酸性，碱性，路易斯酸具有很高的抵抗力，和桦木还原条件，并被评估为一系列固相合成应用中的聚合物载体。发现H-ROMP树脂在芳族硝化和酰化反应中比聚苯乙烯-二乙烯基苯（PS-DVB）共聚物具有更好的性能。在乙内酰脲的常规五步固相合成中，对于H-ROMP和PS-DVB树脂都获得了相似的结果。还显示出U-ROMP树脂在苯并咪唑和苯并咪唑酮的固相合成中有效。