Ph2C=N(O)C6H4Cl-p | 1272377-56-6

• 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: Ph2C=N(O)C6H4Cl-p
• 英文别名: N-(4-chlorophenyl)-1,1-diphenylmethanimine oxide
• CAS: 1272377-56-6
• 化学式: C₁₉H₁₄ClNO
• 分子量: 307.779
• InChiKey: ARMSSAZPEDYJPP-UHFFFAOYSA-N

物化性质

• 沸点：
  466.7±47.0 °C(Predicted)
• 密度：
  1.225±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  28.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Ph2C=N(O)C6H4Cl-p 以 二氯甲烷 为溶剂， 反应 8.0h， 生成 2-(4-Chlorophenyl)-5-ethyl-3,3-diphenyl-1,2,4-oxadiazole
  参考文献：
  名称：

  A Palladium(II) Center Activates Nitrile Ligands toward 1,3-Dipolar Cycloaddition of Nitrones Substantially More than the Corresponding Platinum(II) Center

  摘要：

  Palladium(II)-coordinated NCR1 (R-1 = Et (1), NMe2 (2), Ph (3)) species react smoothly with acyclic nitrones such as the ketonitrones Ph2C=N(O)R-4 (R-4 = p-MeC6H4 (4), p-ClC6H4 (5)) and the aldonitrone p-MeC6H4CH=N(O)Me (6) in the corresponding nitrile media. This reaction proceeds as a consecutive two-step intermolecular cycloaddition to give the mono- and bis-2,3-dihydro-1,2,4-oxadiazole complexes [PdCl2((RCN)-C-1){N-a=C (R-1) ON (R-4)C-b((RR3)-R-2)}}((a-b)) (7a-13a; R-2, R-3 = Ph; R-4 = C6H4Me-p, R-1 = Et (7), NMe2 (8), Ph (9); R4 = C6H4C1-p, = Et (10), NMe2 (11), Ph (12); R2 = H, R-3 = C6H4Me-p, R-4 = Me, R-1 = NMe2 (13)) and [PdCl2{Na= C(R-1)ON(R-4)Cb((RR3)-R-2)}(2)]((a-b)) (7b-13b), respectively. Inspection of the obtained data and their comparison with the previous results indicate that the Pd-II centers provide substantially greater activation of RCN ligands toward the 1,3-dipolar cycloaddition than the relevant Pt-II centers. The palladium(II)-mediated 1,3-dipolar cycloaddition of ketonitrones to nitriles is reversible. All complexes were characterized by elemental analyses (C, H, N), high-resolution ESI-MS, and IR and H-1 and C-13{H-1} NMR spectroscopy. The structure of trans7b was determined by single-crystal X-ray diffraction. Metal-free 5-NR'2-2,3-dihydro-1,2,4-oxadiazoles (7c-13c) were liberated from the corresponding (2,3-dihydro-1,2,4-oxadiazole)2Pd(II) complexes by treatment with 1,2-(diphenylphosphino)ethane, and the heterocycles were characterized by high-resolution ESI+-MS and H-1 and 13C{IFI} spectroscopy.

  DOI：

  10.1021/ic301866y
• 作为产物：
  描述：

  4-氯亚硝基苯 、 二苯基重氮甲烷 以 乙醚 为溶剂， 以85%的产率得到Ph2C=N(O)C6H4Cl-p
  参考文献：
  名称：

  钯结合的异氰化物配体的选择性亲核加氧：路线为亚胺配合物，可作为无铜/无磷Sonogashira反应的高效催化剂

  摘要：

  顺式[PdCl 2（CNR）2 ]之间的金属介导反应（R = Xy（1），Cy（2），t Bu（3），C 6 H 3（Cl-2）Me-6（4））和酮基硝酮博士2 C = N（O）C 6 H ^ 4 R'（R'=我（5），CL（6））继续进行以1：1的摩尔比选择性亲核氧合，并提供该亚胺胩配合物[的PdCl 2 {N（C 6 H ^ 4 R'）═CPh 2 }（CNR）]（7– 14：R'= Me，R = Xy（7），Cy（8），t Bu（9），C 6 H 3（Cl-2）Me-6（10）；R'= Cl，R = Xy（11），Cy（12），t Bu（13），C 6 H 3（Cl-2）Me-6（14）），产率极高（90-94％），而所述的反应顺式- [的PdCl 2（CNR）2 ]配合物醛硝酮以1,3-偶极环加成反应进行，生成卡宾加合物，然后将其转化为亚胺配合物。DFT水平的理论计算表明，在醛基亚

  DOI：

  10.1021/om4000665

文献信息

• Cycloaddition of C,C-Disubstituted Ketonitrones with Acceptor Methylenecyclopropanes and Subsequent Rearrangement Cascade of 5-Spirocyclopropane-isoxazolidines
  作者：Tung Q. Tran、Vyacheslav V. Diev、Galina L. Starova、Vladislav V. Gurzhiy、Alexander P. Molchanov

  DOI：10.1002/ejoc.201200039

  日期：2012.4

  A new reaction cascade to give tricyclic cores of 2,4-dihydro-1H-azeto[1,2-a]quinolines (benzocarbacephems) and pyrrolo[1,2-a]quinolines starting from acyclic N-aryl ketonitrones and acceptor ring substituted methylenecyclopropanes has been reported. This reaction includes 1,3-dipolar cycloaddition of N-aryl-C,C-diaryl or N-aryl-C,C-bis(methoxycarbonyl) nitrones 1 to the double bond of dimethyl me

  从无环 N-芳基酮硝酮和受体环取代的 2,4-二氢-1H-azeto[1,2-a] 喹啉（苯并碳头烯类）和吡咯并 [1,2-a] 喹啉的三环核心的新反应级联亚甲基环丙烷已有报道。该反应包括 N-芳基-C,C-二芳基或 N-芳基-C,C-双（甲氧基羰基）硝酮 1 与亚甲基环丙烷-1,2-二甲酸二甲酯 2 或亚苄基环丙烷的双键的 1,3-偶极环加成反应-1,1-二羧酸酯 3，然后对最初形成的 5-螺环丙烷-异恶唑烷环加合物进行 Brandi-Guarna 重排，得到 2,4-二氢-1H-azeto[1,2-a] 喹啉 4 或吡咯并 [1,2] -a]喹啉 6.
• Facile and Reversible 1,3-Dipolar Cycloaddition of Aryl Ketonitrones to Platinum(II)-Bound Nitriles: Synthetic, Structural, and Theoretical Studies
  作者：Andreii S. Kritchenkov、Nadezhda A. Bokach、Maxim L. Kuznetsov、Fedor M. Dolgushin、Tran Q. Tung、Alexander P. Molchanov、Vadim Yu. Kukushkin

  DOI：10.1021/om201026n

  日期：2012.1.23

  The reaction between trans-[PtCl2(NCR)(2)] (R = Et 1, NMe2 2, NEt2 3, NC5H10 4) and the acyclic triaryl ketonitrones Ph2C=N(O)C6H4R'-p (R' = H 5, Me 6, Cl 7, OMe 8) proceeds as a facile and consecutive two-step intermolecular cycloaddition to give the mono-cycloaddition products trans-[PtCl2(NCR)N-a= C(R)ON(C6H4R'-p)(CPh2)-Ph-b}]((a-b)) (R/R' = Et/H 9, Et/Me 10, Et/Cl 11, Et/OMe 12, NMe2/H 13, NMe2/Me 14, NMe2/Cl 15, NMe2/OMe 16, NEt2/H 17, NEt2/Me 18, NEt2/Cl 19, NEt2/OMe 20, NC5H10/H 21, NC5H10/Me 22, NC5H10/Cl 23, NC5H10-/OMe 24) and then the bis-2,3-dihydro-1,2,4-oxadiazole complexes trans[PtC12N-a=C(R)ON(C6H4R'-p)(CPh2)-Ph-b}(2)]((a-b)) (R/R' = Et/H 25, Et/Me 26, Et/Cl 27, Et/OMe 28, NMe2/H 29, NMe2/Me 30, NMe2/Cl 31, NMe2/OMe 32, NEt2/H 33, NEt2/Me 34, NEt2/Cl 35, NEt2/OMe 36, NC5H10/H 37, NC5H10/Me 38, NC5H10/Cl 39, NC5H10/OMe 40). The ketonitrones Ph2C=N(O)C6H4R'-p were found to be unexpectedly much more reactive toward the platinum(II)-bound nitriles than the related aldonitrones p-R ''' C6H4CH=N(O)R ''(R '' = Me, Ph; R ''' = H, Me), and the difference in the reactivity in 1,3-dipolar cycloaddition (DCA) of the keto- and aldonitrones was interpreted by theoretical calculations and was explained in terms of the orbital arguments as a result of the increase of the HOMOnitrone energy from aldo- to ketonitrones. The first example of the reversibility in metal-mediated DCA of nitrones to nitriles was observed, and this phenomenon, as follows from the performed theoretical study, is justified by the thermodynamic instability of the Pt-II-bound 3,3-diary1-2,3-dihydro-1,2,4-oxadiazoles. Metal-free C-5-dipheny1-2,3-dihydro-1,2,4-oxadiazoles 42 and 43 were liberated from corresponding (oxadiazole)(2)Pt-II complexes 26 and 30 by treatment with excess NaCN, and these heterocycles were characterized by high-resolution ESI+-MS and H-1 and C-13H-1} NMR spectroscopies.