p-nitrophenyl methoxyacetate | 31252-86-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚酯
• 英文名称: p-nitrophenyl methoxyacetate
• 英文别名: 4-nitrophenyl 2-methoxyacetate；(4-nitrophenyl) 2-methoxyacetate
• CAS: 31252-86-5
• 化学式: C₉H₉NO₅
• 分子量: 211.174
• InChiKey: VQIQBLPBAALGJT-UHFFFAOYSA-N

物化性质

• 沸点：
  337.3±27.0 °C(Predicted)
• 密度：
  1.305±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  81.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  p-nitrophenyl methoxyacetate 在 sodium molybdate 盐酸 、 buffer solution (0.01 M HEPES) 作用下， 以 乙腈 为溶剂， 生成 4-硝基苯酚阴离子
  参考文献：
  名称：

  Nucleophilic reactions of molybdate

  摘要：

  Although molybdate (MoO42-) is over 1000 times less basic than the phosphate dianion it is 35 times more nucleophilic toward p-nitrophenyl acetate (pNPA) and p-nitrophenyl thioacetate (pNPTA) at 27-degrees-C (Wikjord, B.; Byers, L. D. J. Am. Chem. Soc. 1992,114,5553). Based on Bronsted relationships for the reaction of a series of phosphonate dianions with these esters (beta(nuc) = 0.3 at 37-degrees-C), molybdate (pK(a2) = 3.9) is as reactive as a phosphonate with pK(a2) = 12. The activation parameters are DELTAH(double dagger) = 15.8 (+/-0.1) kcal/mol and DELTAS(double dagger) = -17.4 (+/-0.4) eu for the reaction with pNPA and DELTAH(double dagger) = 16.0 (+/-0.2) kcal/mol and DELTAS(double dagger) = -15.0 (+/-0.6) eu for the reaction with pNPTA. The second-order rate constant for the reaction of MoO42- with a series of 13 acyl-substituted p-nitrophenyl esters at 27-degrees-C shows nearly identical sensitivity to substituent effects (rho* = 2.8) as does the rate of alkaline hydrolysis or the equilibrium addition of hydroxide to aldehydes (Shames, S. L.; Byers, L. D. J. Am. Chem. Soc. 1981, 103, 6170), suggesting that the transition state for the molybdenolysis reaction closely resembles the tetrahedral intermediate. In addition to the reaction with activated carboxylic esters, molybdate catalyzes the hydrolysis of a variety of electrophiles. The second-order rate constants (M-1 min-1, 27-degrees-C, mu = 1.5 M) for the reactions of molybdate are 0.25 (+/-0.01) with ethyl pyruvate, (2.10+/-0.08) x 10(-2) with 2,4-dinitrofluorobenzene, and (7.2 +/-0.4) x 10(-5) with methyl iodide.

  DOI：

  10.1021/jo00051a026
• 作为产物：
  描述：

  对硝基苯基氯甲酸酯 在 dirhodium tetraacetate 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 p-nitrophenyl methoxyacetate
  参考文献：
  名称：

  铑（II）催化的β，γ-不饱和重氮化合物的分解

  摘要：

  在甲醇存在下，Rh II催化的β，γ-不饱和重氮酮1的分解通过乙烯基Wolff重排反应生成γ，δ-不饱和酯6（方案1和2）。当用手性四（吡咯烷羧基）或四（恶唑烷二酮）二（II）配合物进行反应时，可实现适度的不对称诱导。在相同的反应条件下，重氮乙酸乙烯酯和苯基重氮乙酸酯分别为11和20，或1-重氮-3-苯基-丙-2-酮（25）通过与MeOH的OH插入反应（方案3-5）。在不存在MeOH的情况下，重氮乙酸苯酯20和25分别经历分子内CH插入22和26中。即使在MeOH的存在下，N-芳基重氮酰胺23也会发生分子内CH插入（方案5）。

  DOI：

  10.1002/hlca.19930760806

文献信息

• Enhanced Selectivities for the Hydroxyl-Directed Methanolysis of Esters Using the 2-Acyl-4-aminopyridine Class of Acyl Transfer Catalysts:  Ketones as Binding Sites
  作者：Tarek Sammakia、T. Brian Hurley

  DOI：10.1021/jo991202k

  日期：2000.2.1

  compared to that of the previously described catalyst 2-formyl-4-pyrrolidinopyridine (FPP), which contains an aldehyde at the 2-position of the pyridine. The catalysts which contain ketones at the 2-position range in reactivity from 10 times slower to slightly faster than FPP, and certain of these are much more selective for the methanolysis of hydroxy esters than FPP. This increase in selectivity is ascribed

  在本文中，我们描述了一系列2-酰基-4-氨基吡啶的制备方法，以及它们作为α-羟基酯（而不是α-甲氧基酯）的羟基定向甲醇分解的催化剂的用途。这些催化剂在吡啶的2-位含有酮的催化剂的羟基方向是通过将羟基酯的醇可逆地加到酮中以提供相应的半缩酮来实现的。将它们的活性与前述催化剂2-甲酰基-4-吡咯烷基二吡啶（FPP）的活性进行比较，该催化剂在吡啶的2-位含有醛。在2位范围内含有酮的催化剂的反应活性比FPP慢10倍至稍快，某些催化剂对羟基酯的甲醇分解的选择性比FPP高得多。选择性的增加归因于与酮衍生的催化剂的非定向甲醇分解反应的速率的降低。证据表明，非定向反应不是通过分子间的通用基本机理进行的，而是通过亲核催化的机理进行的，其中将甲醇添加到FPP的醛中形成的半缩醛的羟基充当亲核剂。由于衍生自半缩酮的羟基比衍生自半缩醛的羟基更受阻且亲核性较小，因此对于以酮为结合位点的催化剂，非定向反应要慢得多。证据表
• Studies on the Mechanism of Action of 2-Formyl-4-pyrrolidinopyridine:  Isolation and Characterization of a Reactive Intermediate
  作者：Tarek Sammakia、T. Brian Hurley

  DOI：10.1021/jo982281n

  日期：1999.6.1

  action of 2-formyl-4-pyrrolidinopyridine (FPP, 1a) which is a catalyst for the hydroxyl-directed methanolysis of alpha-hydroxy esters. This species was initially designed to act as a nucleophilic catalyst; however, we have ruled out a nucleophilic mechanism by examining the activity of 6-substituted-FPP derivatives. These compounds are more hindered in the vicinity of the pyridine nitrogen than FPP itself

  本文介绍了2-甲酰基-4-吡咯烷二吡啶（FPP，1a）的作用机理，该催化剂是α-羟基酯的羟基定向甲醇分解的催化剂。该物种最初被设计用作亲核催化剂。但是，我们通过检查6-取代的FPP衍生物的活性，排除了亲核机理。与FPP本身相比，这些化合物在吡啶氮附近的受阻更大，但也是更具活性的催化剂。此外，发现对硝基苯酚（一种弱酸）的存在会加速催化反应。这些结果与亲核催化机理不一致。我们提供证据表明该反应反而是通过二氧戊环中间体10进行的。二氧戊环酮10可以通过在不存在甲醇的情况下在氯仿中用FPP处理乙醇酸的对硝基苯酯或五氟苯基酯来获得。当经受催化反应的条件时，已经分离，表征并显示出动力学上的能力。
• Conjugating Catalytic Polyproline Fragments with a Self-Assembling Peptide Produces Efficient Artificial Hydrolases
  作者：Kuei-Yen Huang、Chi-Ching Yu、Jia-Cherng Horng

  DOI：10.1021/acs.biomac.9b01620

  日期：2020.3.9

  of His-His or Ser-His was coupled with a self-assembling peptide MAX1 to design new hydrolases (H2H5 and H2S5) for catalyzing ester hydrolysis. Circular dichroism measurements indicated that the peptides change their conformation from random coils to β-sheets when pH increases from 5 to 10. IR spectra also displayed the vibration modes corresponding to their β-structures at pH 9.0. Transmission electron

  将含有His-His或Ser-His催化二聚体的多脯氨酸片段与自组装肽MAX1偶联，以设计用于催化酯水解的新水解酶（H2H5和H2S5）。圆二色性测量表明，当pH从5增加到10时，肽的构象从无规卷曲变为β-折叠。红外光谱还显示了在pH 9.0时对应于其β结构的振动模式。透射电子显微镜（TEM）和原子力显微镜（AFM）测量表明，在溶液中，设计的肽自组装成网络原纤维，对酯水解具有显着提高的催化效率。在乙酸对硝基苯酯（p-NPA）底物上，设计的肽在pH 9.0时显示出高催化效率（H2H5的kcat / KM = 12.1 M-1 s-1，H2S5的13.3 M-1 s-1），在pH 10.0时其效率甚至更高（对于H2H5，kcat / KM = 24.3 M-1 s-1，对于H2S5为99.4 M-1 s-1）。另外，H 2 H 5和H 2 S 5在催化对硝基苯基-（2-苯基）-丙酸酯（p-NP
• Synthesis of secondary α-perfluoroalkyl- and tertiary α,α-bis(perfluoroalkyl)-N-methylprolinols and their catalytic activities in the acyl transfer reaction
  作者：Kazumasa Funabiki、Akitsugu Shibata、Keisuke Hatano、Masaki Matsui

  DOI：10.1016/j.jfluchem.2009.02.002

  日期：2009.4

  were prepared and their organocatalytic activities in an acyl transfer reaction of 4-nitrophenyl 2-methoxyacetate with methanol-d4 in chloroform-d were examined. As a result, α-trifluoromethyl-N-methylprolinol was a more effective acyl transfer catalyst than not only secondary α-perfluorobutyl- and n-butyl-N-methylprolinols but also tertiary α,α-bis(perfluorobutyl)-N-methylprolinol.

  制备了各种手性α-全氟烷基-N-甲基脯氨醇，并考察了它们在4-硝基苯基2-甲氧基乙酸酯与甲醇-d 4在氯仿-d中的酰基转移反应中的有机催化活性。结果，不仅是仲α-全氟丁基-和正丁基-N-甲基脯氨醇，而且是叔α，α-双（全氟丁基）-N-甲基脯氨醇，α-三氟甲基-N-甲基脯氨醇是更有效的酰基转移催化剂。
• Cross-strand histidine–aromatic interactions enhance acyl-transfer rates in beta-hairpin peptide catalysts
  作者：M. Matsumoto、S. J. Lee、M. R. Gagné、M. L. Waters

  DOI：10.1039/c4ob01754d

  日期：——

  a nucleophile, thus closing a putative catalytic cycle. Variants of the hit peptide were studied to elucidate both the magnitude (up to 18 000-fold over background, kcat/kuncat = 94 000 000, or 45-fold over Boc-histidine methyl ester) and mechanism of acyl transfer catalysis. A combination of CH–π, cation–π and HisH+–O interactions in the cationic imidazole transition state is implicated in the rate

  使用反应性标签方法从β发夹肽的固相文库中选择对酰化试剂最具反应性的物种。发现从反应性组氨酸的链上带有富电子芳族残基的命中竞争性地被N-酰化。除了显示出快速的N-酰化速率外，在亲核试剂的存在下，命中肽还被脱酰，从而关闭了推定的催化循环。研究了命中肽的变体以阐明幅度（比背景高18000倍，k cat / k uncat = 9400万，或比Boc-组氨酸甲酯高45倍）和酰基转移催化的机理。CH–π，阳离子–π和HisH +的组合阳离子咪唑过渡态中的–O相互作用除β发夹折叠的保真度外，还涉及速率加速。此外，关于关键中间体或其模型的NMR结构数据表明，该催化剂的关键特征是能够沿着催化反应坐标获得几种不同的稳定构象。