[3-Ethoxy-3-oxo-2-[tri(propan-2-yl)phosphaniumylmethyl]prop-1-enylidene]azanide | 183995-00-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: [3-Ethoxy-3-oxo-2-[tri(propan-2-yl)phosphaniumylmethyl]prop-1-enylidene]azanide
• CAS: 183995-00-8
• 化学式: C₁₅H₂₈NO₂P
• 分子量: 285.367
• InChiKey: OKZYYFDBTWNJRE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  19
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  27.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  [3-Ethoxy-3-oxo-2-[tri(propan-2-yl)phosphaniumylmethyl]prop-1-enylidene]azanide 在 sodium iodide 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 48.0h， 生成 [2-cyano-2-ethoxycarbonyl-2-(2,4-dinitrophenyl)ethyl]triisopropylphosphonium iodide
  参考文献：
  名称：

  碳负离子与 2​​,4-二硝基氟苯反应生成稳定的七三烯化物部分

  摘要：

  在 Et3 N 存在下，NCCH2COOMe 1a 和 CH2(CN)21b 与 2,4-二硝基氟苯 2 的反应会产生深颜色的结晶稳定盐 4a,4b，其中的阴离子包含共轭键系统。2 与在碳负离子中心带有乙氧基和氰基的含磷两性离子 6 的类似反应是导致形成具有带负电荷的庚三烯部分的 P-两性离子 9 的反应的第一个例子。该反应通过中间体 σ-配合物 7 的新分解途径进行，同时形成氟甲酸乙酯。© 2007 Wiley Periodicals, Inc. 杂原子化学 18:108–115, 2007; 在线发表于 Wiley InterScience (www.interscience.wiley.com)。DOI 10.1002/hc.20267

  DOI：

  10.1002/hc.20267
• 作为产物：
  描述：

  2-氰基丙酸乙酯 、 三异丙基膦 生成 [3-Ethoxy-3-oxo-2-[tri(propan-2-yl)phosphaniumylmethyl]prop-1-enylidene]azanide
  参考文献：
  名称：

  Dual reactivity of the phosphonium zwitterion formed by the reaction of triisopropylphosphine with ethyl 2-cyanoacrylate toward 2,4-dinitro- and 2,4,6-trinitrofluorobenzenes

  摘要：

  DOI：

  10.1016/j.mencom.2007.06.017

文献信息

• Novel reaction of iso(thio)cyanates. Insertion reaction of iso(thio)cyanates into CC bond
  作者：Yuri G. Gololobov、Nazhmudin A. Kardanov、Viktor N. Khroustalyov、Pavel V. Petrovskii

  DOI：10.1016/s0040-4039(97)01750-4

  日期：1997.10

  products of the initially formed adducts 2. The molecular structure of compounds 4 was confirmed by X-ray diffraction study. The formation of zwitter-ions 3 and 4 is a result of the insertion of iso(thio)cyanates into the CC bond of the starting zwitter-ion 1, under the action of the positively charged phosphorus atom (intramolecular electrophilic catalysis).

  两性离子1与芳基异氰酸酯（ae）和异硫氰酸苯酯的相互作用导致稳定的两性离子3（ae）和4，这可能代表了最初形成的加合物2的重排产物。通过X射线衍射研究证实了化合物4的分子结构。两性离子3和4的形成是在带正电荷的磷原子的作用下，异硫氰酸酯插入到两性离子1的CC键中的结果（分子内亲电催化）。
• Formation of substituted pyrazolines in the reaction of C,N-diphenylnitrilimine with a zwitterion derived from triisopropylphosphine and ethyl 2-cyanoacrylate
  作者：Yu. G. Gololobov、O. A. Linchenko、Yu. G. Trishin、P. V. Petrovskii、S. A. Starikova

  DOI：10.1023/b:rucb.0000037859.83219.10

  日期：2004.4

  The reaction of C,N-diphenylnitrilimine with a P-zwitterion derived from Pri3P and H2C=C(CN)CO2Et afforded the first representative of 2-pyrazolines containing the phosphonium group and products of the addition of nitrilimine to Pri3P and H2C=C(CN)CO2Et. The reaction of the P-zwitterion with C-4-nitrophenyl-N-phenylnitrilimine gave rise to a condensation product of one Pri3P molecule and two nitrilimine

  C,N-二苯基腈亚胺与衍生自 Pri3P 和 H2C=C(CN)CO2Et 的 P-两性离子的反应提供了含有鏻基团的 2-吡唑啉的第一个代表以及将腈亚胺加成到 Pri3P 和 H2C=C（ CN)CO2Et。P-两性离子与C-4-硝基苯基-N-苯基腈亚胺的反应产生一个Pri3P分子和两个腈亚胺分子的缩合产物。通过X射线衍射分析确定了合成化合物的三维结构。
• ——
  作者：Yu. G. Gololobov、M. A. Galkina、O. V. Dovgan、I. Yu. Krasnova、P. V. Petrovskii、M. Yu. Antipin、I. I. Voronzov、K. A. Lyssenko、R. Schmutzler

  DOI：10.1023/a:1009538620098

  日期：——

  The reactions of the zwitterion derived from triisopropylphosphine and ethyl 2-cyanoacrylate with mercuric chloride and aryl isothiocyanates containing Cl atoms in the ortho positions of the benzene ring follow an unusual pathway because this zwitterion represents "latent" triisopropylphosphine due to the reversibility of the reaction of triisopropylphosphine with ethyl 2-cyanoacrylate. The molecular structures of the adducts of triisopropylphosphine with 2,6-dichloro- and 2,4,6-trichlorophenyl isothiocyanates were confirmed by X-ray diffraction study. Protonation of the adduct of triisopropylphosphine with 2,6-dichlorophenyl isothiocyanate occurred at the nitrogen atom, whereas methylation with methyl trifluoromethanesulfonate afforded an S-methylation product. The results of X-ray diffraction study of the resulting compounds are presented.
• ZWITTERIONIC SPECIES FROM TRIISOPROPYLPHOSPHINE AND 2-CYANOACRYLATES: SYNTHESIS, STRUCTURE AND PROPERTIES
  作者：Yuri G. Gololobov、Vastly A. Pinchuk、Holger Thönnessen、Peter G. Jones、Reinhard Schmutzler

  DOI：10.1080/10426509608037951

  日期：1996.8.1

  Triisopropylphosphine reacts with 2-cyanoacrylates with formation of the P-zwitterionic species 2a and 2b. The reaction of 2b with trimethylsilyltriflate, in the presence of traces of water, leads to the phosphonium triflate 3. 2b is alkylated at the carbon atom with methyl iodide with formation of the phosphonium iodide 4. The initially formed adducts of the zwitterionic species 2a and 2b with tosyl azide and with tosyl isocyanate are thermodynamically unstable. In the first case, the final products of the reaction are tosyl iminotriisopropylphosphine imide 6 and 2-cyanoacrylate polymers. In the second case, the reaction leads to the zwitterionic product 8, and, in the presence of traces of water, to the molecular complexes 9a and 9b. The reaction of the zwitterionic species 2a and 2b with methylisocyanate proceeds in an unusual way, resulting in the formation of the zwitterionic species 12a and 12b, as a result of the insertion of methylisocyanate into the C-C bond of the starting zwitterionic adducts. The identity and structure of all the new products were established by elemental analysis, IR spectroscopy, H-1-, C-13-, and P-31-NMR spectroscopy, as well as by single-crystal X-ray structure analyses for 2b, 8, 9a and 12b. The structures of 2b, 9a and 12b are closely similar as regards the molecular backbone. In all four structures there is evidence for some delocalisation of negative charge to the C(:O) and CN group.
• Novel nucleophilic aromatic substitution of the fluorine atom yielding a stable heptatrienide structure
  作者：Yu. G. Gololobov、O. A. Linchenko、Z. A. Starikova、I. A. Garbuzova、P. V. Petrovskii

  DOI：10.1007/s11172-006-0142-1

  日期：2005.10