1-苯基-1H-吡唑-3-羧酸乙酯 | 115315-95-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 中文名称: 1-苯基-1H-吡唑-3-羧酸乙酯
• 英文名称: ethyl 1-phenyl-1H-pyrazole-3-carboxylate
• 英文别名: 3-ethoxycarbonyl-1-phenylpyrazole；ethyl 1-phenylpyrazole-3-carboxylate
• CAS: 115315-95-2
• 化学式: C₁₂H₁₂N₂O₂
• 分子量: 216.239
• InChiKey: HNQSUSPWELMLBU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  44.1
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 海关编码：
  2933199090
• 危险性防范说明：
  P261,P280,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H332,H335

反应信息

• 作为反应物：
  描述：

  1-苯基-1H-吡唑-3-羧酸乙酯 在 正丁基锂 、 氨基磺酰氯 、 potassium carbonate 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 3.5h， 生成
  参考文献：
  名称：

  Discovery of TAK-981, a First-in-Class Inhibitor of SUMO-Activating Enzyme for the Treatment of Cancer

  摘要：

  DOI：

  10.1021/acs.jmedchem.0c01491
• 作为产物：
  描述：

  苯肼 在 sodium iodide 作用下， 以 水 、 乙酸乙酯 、 甲苯 为溶剂， 生成 1-苯基-1H-吡唑-3-羧酸乙酯
  参考文献：
  名称：

  [3+2]偶极环加成电化学合成吡唑啉和吡唑

  摘要：

  电化学引发的 [3 2] 环加成反应容易获得且毒性较低的起始材料使吡唑啉和吡唑的合成变得容易。双相系统和碘化钠作为介质和电解质的双重作用的应用允许选择性反应对可扩展性具有出色的鲁棒性。

  DOI：

  10.1002/anie.202214820

文献信息

• Palladium-catalyzed late-stage mono-aroylation of the fully substituted pyrazoles via aromatic C–H bond activation
  作者：Miao-Miao Chen、Ling-Yan Shao、Li-Jun Lun、Yu-Liang Wu、Xiao-Pan Fu、Ya-Fei Ji

  DOI：10.1016/j.cclet.2018.09.022

  日期：2019.3

  5-diaryl-1H-pyrazole-3-carboxylates has been developed via direct and exclusive mono-Csp2 H bond activation with broad substrate scope and good functional group tolerance. A dual-core dimeric palladacycle is confirmed by X-ray single crystal crystallography, and probably serves as an active species in the catalytic cycle.

  摘要通过直接和排他的单-Csp2 H键活化，具有宽的底物范围和良好的官能团耐受性，开发了钯催化的4-甲基-1,5-二芳基-1H-吡唑-3-羧酸酯的后期芳基化反应。X射线单晶晶体学证实了双核二聚体帕拉达环，并且可能在催化循环中用作活性物质。
• Cu‐Promoted Sydnone Cycloadditions of Alkynes: Scope and Mechanism Studies
  作者：Júlia Comas‐Barceló、Robert S. Foster、Béla Fiser、Enrique Gomez‐Bengoa、Joseph P. A. Harrity

  DOI：10.1002/chem.201406118

  日期：2015.2.16

  reaction of sydnones and terminal alkynes, providing significant reduction in reaction times. Specifically, the use of Cu(OTf)2 is found to provide 1,3‐disubstituted pyrazoles, whereas simply switching the promoter system to Cu(OAc)2 allows the corresponding 1,4‐isomers to be produced. The mechanism of the Cu‐effect in each case has been investigated by experimental and theoretical studies, and they

  已发现铜盐可促进sydnones和末端炔烃的环加成反应，从而显着缩短反应时间。具体而言，发现使用Cu（OTf）2可以提供1,3-二取代的吡唑，而简单地将启动子系统转换为Cu（OAc）2则可以生产相应的1,4-异构体。通过实验和理论研究已经研究了每种情况下Cu的作用机理，他们认为Cu（OTf）2通过路易斯酸活化了sydnone起作用，而Cu（OAc）2促进了反应性Cu I乙酰化物的形成。。
• Haloacetylated enol ethers.<b>11</b>. Synthesis of 1-methyl- and 1-phenyl pyrazole-3(5)-ethyl esters. A one-pot procedure
  作者：Marcos A. P. Martins、Rogério A. Freitag、Adriano Da Rosa、Alex F. C. Flores、Nilo Zanatta、Helio G. Bonacorso

  DOI：10.1002/jhet.5570360133

  日期：1999.1

  A one-pot synthesis of 1-methyl- and 1-phenylpyrazole-3(5)-ethyl esters 2,3a-e by the cyclocondensation of β-alkoxyvinyl trichloromethyl ketones 1a-e with methyl and phenyl hydrazine hydrochloride under mild conditions, is reported. A study using compounds 1a-e with different substituents proved that these are versatile building blocks for the synthesis of pyrazole derivatives, having a 3(5)-ethoxycarbonyl

  在温和的条件下，通过β-烷氧基乙烯基三氯甲基酮1a-e与甲基和苯基肼盐酸盐的环缩合反应，一锅合成1-甲基-和1-苯基吡唑-3（5）-乙酯2,3a-e报告。一项使用具有不同取代基的化合物1a-e进行的研究证明，这些化合物是吡唑衍生物合成的通用构建基，具有3（5）-乙氧羰基取代基，产率高（60-89％）。观察到肼和β-烷氧基乙烯基三氯甲基酮取代基对反应区域化学对形成1，3-和1，5-异构体的影响。
• The Reaction of<i>N</i>-Aryl-<i>C</i>-ethoxycarbonylnitrilimine with Olefins
  作者：Tomio Shimizu、Yoshiyuki Hayashi、Toshiyuki Nishio、Kazuhiro Teramura

  DOI：10.1246/bcsj.57.787

  日期：1984.3

  C-Ethoxycarbonylnitrilimines treated with monosubstituted olefins predominantly gave 5-substituted 3-ethoxycarbonyl-2-pyrazolines. From the analysis of the relative rate and regioselectivity of a variety of monosubstituted olefins for the cycloaddition, the nitrilimine is shown to have reactivity and regioselectivity similar to the throughly studied diphenylnitrilimine. The cycloaddition regioselectivity is discussed in terms of frontier orbital energies and coefficients.

  用单取代的烯烃处理C-乙氧基羰基氮亚胺主要产生5-取代的3-乙氧基羰基-2-吡唑啉。通过对各种单取代烯烃环加成反应的相对速率和区域选择性的分析，表明氮亚胺具有与经过深入研究的二苯基氮亚胺类似的反应活性和区域选择性。根据前沿轨道能量和系数讨论了环加成区域选择性。
• Palladium-Catalyzed Chelation-Assisted Regioselective Oxidative Dehydrogenative Homocoupling/<i>Ortho</i>-Hydroxylation in <i>N</i>-Phenylpyrazoles
  作者：Harikrishna Batchu、Soumya Bhattacharyya、Ruchir Kant、Sanjay Batra

  DOI：10.1021/acs.joc.5b00733

  日期：2015.8.7

  A palladium-catalyzed pyrazole-directed regioselective oxidative C(sp2)-H functionalization of the N-phenyl ring in N-phenylpyrazoles to afford either a biaryl bis-pyrazole (via dehydrogenative homocoupling) or N-(o-hydroxyphenyl)pyrazole (via C-H oxygenation) or their mixture is described. The substitutions on the N-phenyl ring and the pyrazole ring and the dilution of the reaction medium with respect to the TFA/TFAA mixture (substrate concentration) have a remarkable influence on the outcome of the reaction. It was discovered that if the reactions were performed under highly dilute conditions (ca. 10 times) then N-(o-hydroxyphenyl)pyrazoles were the major or the sole products.