1-(quinoxalin-2-yl)-2-bromopropanone | 178960-88-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂萘
• 英文名称: 1-(quinoxalin-2-yl)-2-bromopropanone
• 英文别名: 2-Bromo-1-quinoxalin-2-ylpropan-1-one
• CAS: 178960-88-8
• 化学式: C₁₁H₉BrN₂O
• 分子量: 265.109
• InChiKey: BHWRHNBLFQMYCU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  42.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-(quinoxalin-2-yl)-2-bromopropanone 、 Mo(η5-C5H5)2(SH)2 在 EtN(i-Pr)2 作用下， 以 二氯甲烷 为溶剂， 以49%的产率得到Cp2Mo(η(2)-SC(2-quinoxalinyl)C(Me)S)
  参考文献：
  名称：

  Direct Conversion of α-Substituted Ketones to Metallo-1,2-enedithiolates

  摘要：

  A new synthetic route to metallo-1,2-enedithiolates is presented. The addition of 1 equiv of the a-bromo ketones Ar-C(O)CHXR (X = Pr) {Ar = 2-quinoxaline, 2-, 3-, or 4-pyridine, Ph, CI-Ph, and pyrene (R = H); Ar = 2-quinoxaline (R = Me); and Ar = R = Ph} to Cp(2)Mo(SH)(2) followed by the addition of base results in the formation of the corresponding metallo-l,2-enedithiolate Cp(2)Mo{mu(2)-SC(Ar)C(R)S}. The alpha-tosyl ketones quinoxaline -C(O)CHR-tosyl {R = H, Me} and the alpha-phosphorylated ketone 3-pyridine-C(O)CH2-O-P(O)(OEt)(2) yield the same products as the corresponding alpha-bromo ketones upon reaction with Cp(2)Mo(SH)(2). The addition of acid to the heterocyclic substituted complexes yields Cp(2)Mo{eta(2)-SC(HetH(+))C(R)S}. Both Cp(2)Mo{eta(2)-SC(quinoxaline)C(H)S} and [Cp(2)Mo{eta(2)-SC(quinoxalinium)C(H)S}][BF4] have been crystallographically characterized. Cp(2)Mo{eta(2)-SC(quinoxaline)C(H)S} crystalizes in the C2/c space group with a = 21.451(2) Angstrom, b = 15.474 Angstrom, c = 12.2201(13) Angstrom, and beta = 107.440(7)degrees. [Cp(2)Mo{ space group with a = 7.4009(8) Angstrom, b = 10.1192(13)degrees Angstrom, c 15.930(4) Angstrom; alpha = 81.49(2)degrees, beta = 76.14(2)degrees, and gamma = 85.784 degrees. In the solid state [Cp(2)Mo{eta(2)-SC(quinoxalinium)C(H)S}][BF4] pi-stacks the heterocycle of two adjacent molecules with atom-atom distances of approximate to 3.6 Angstrom. The stacks are limited to pairs of molecules, and there is no long-range order. The pK(a) values for the quinoxalinium (R = H and Me) and the 2-, 3-, and 4-pyridinium (R = H) complexes have been determined in acetonitrile to be 1-3 units larger than the free heterocycles. The pK(a) of the pyridinium complexes follows the substitution trend 2 approximate to 4 > 3 > free pyridinium and is consistent with resonance stabilization of pyridinium by the metallo-l,2-enedithiolate. Electronic transitions in these complexes have been assigned to a LMCT transition and an ILCT transition by comparison of the various complexes accompanied with solvent sensitivity studies.

  DOI：

  10.1021/ic9602052

文献信息

• Synthesis and Properties of Heterocyclic Substituted 1,2-Enedithiolates of Nickel, Palladium, and Platinum
  作者：Sharada P. Kaiwar、John K. Hsu、Louise M. Liable-Sands、Arnold L. Rheingold、Robert S. Pilato

  DOI：10.1021/ic970194s

  日期：1997.9.1

  A convenient new synthetic route to metallo-1,2-enedithiolates was applied to the synthesis of (dppe)MS2C2-(heterocycle)(H)}; dppe 1,2-bis(diphenyldiphosphino)ethane, hi Ni, Pd, and Pt, and heterocycle = 2-quinoxaline, 2-, 3-, and 4-pyridine, and 2-pyrazine. These complexes were prepared from the corresponding bis(hydrosulfido) complexes (dppe)M(SH)(2) and the alpha-bromo ketones, heterocycle-C(O)CH2Br. Zn the solid state, (dppe)NiS2C2(2-pyrazine)(H)} is a slightly distorted square plane with a planar five-membered metallo-1,2-enedithiolate ring. The metallo-l,2-dithiolate is approximate to 6 degrees from being coplanar with the pyrazine ring, These complexes all have a UV-visible band assignable to an intraligand transition (ILCT) that is best described as a 1,2-enedithiolate pi-->heterocycle pi* charge transfer transition. The energy of the ILCT transition tracks with the reduction potential of the appended aromatic heterocycle. The pK(a) of the protonated complexes is 1-3 units higher than that of the parent heterocycle, independent of the metal, and consistent with resonance stabilization of the protonated heterocycle by the 1,2-enedithiolate ligand.