{TiCl4(PhCOCOPh)} | 12564-61-3

• 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: {TiCl4(PhCOCOPh)}
• CAS: 12564-61-3
• 化学式: C₁₄H₁₀Cl₄O₂Ti
• 分子量: 399.924
• InChiKey: NJCBTNICNYAAGO-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  {TiCl4(PhCOCOPh)} 、 异氰基乙酸乙酯 以 甲苯 为溶剂， 以90%的产率得到{mer-TiCl3(η3-OC(Mes)(H)C(Cl)NCH2C(OEt)O)}
  参考文献：
  名称：

  四氯化钛辅助的Passerini反应的非有机金属途径

  摘要：

  The Passerini reaction assisted by TiCl4 is a three component reaction (RNC, R'2CO, TiCl4) leading to C-C bond formation between the carbonyl and the isonitrile groups, and the formation of alpha-hydroxy amides. In order to clarify the mechanism of the reaction, we have isolated TiCl4-RNC and TiCl4-R2CO adducts, {2,6-Me2C6H3NC)TiCl3]2(mu-Cl)2}2, 2, [TiCl4{mu2-CO=C(OEt)CH2NC}]2, 3, [TiCl4{mu2-O=P(OEt)2CH2NC}]2,4, and [TiCl4{PhC(O)-C(O)Ph}], 5. Spectroscopic and X-ray analysis on 2 and 3 ruled out any insertion of the isocyanide into Ti-Cl bonds, as required by the accepted mechanism of this reaction. The reaction on the ketone- or isocyanide-TiCl4 adducts with the third component of the Passerini reaction led us to the isolation and full characterization of [mer-TiCl3(eta3-OC(Mes)(H)C(Cl)=NCH2C(OEt)=O], 6, [mer-TiCl3(eta3-OC(Ph)(Me)C(Cl)=NCH2C(OEt)=O], 7, [mer-TiCl3(eta3-OC(Ph)(Me)C(Cl)=NCH2P(OEt)2=O], 10, and [mer-TiCl3(eta3-OC(Ph)(OCPh)C(Cl)=NCH2C(OEt)=O], 12, derived from the reaction of MesCHO and PhCOMe with EtOOCCH2NC, of PhCOCH3 with O=P(OEt)2CH2NC, and PhCOCOPh with EtOOCH2NC, respectively. These are high yield reactions and form, as imposed by the planar assembled ligand, the mer-isomer only. The hydrolysis of 6, 7, 10, and 12 gave the expected alpha-hydroxy amide derivatives, 8, 9, 11, and 13, respectively. The overall mechanism of the TiCl4-assisted Passerini reaction can be described as the electrophilic activation of a carbonyl group by TiCl4 followed by the nucleophilic attack on the carbonylic carbon by the RNC nucleophile. Crystallographic details: 2 is monoclinic, space group P2(1)/n, a = 13.943(1) angstrom, b = 8.045(1) angstrom, c = 12.141(1) angstrom, alpha = gamma = 90-degrees, beta = 104.76(1)degrees, Z = 2, R = 0.048; 4 is monoclinic, space group P2(1)/c, a = 12.961(1) angstrom, b = 11.770(1) angstrom, c = 10.917(1) angstrom, alpha = gamma = 90-degrees, beta = 114.13(1)degrees, Z = 2, R = 0.049; 5 is triclinic, space group P1BAR, a = 10.549(1) angstrom, b = 10.668(1) angstrom, c = 9.533(1) angstrom, alpha = 115.08(1)degrees, beta = 115.47(1)degrees, gamma = 95.01(1)degrees, Z = 2, R = 0.035; 7 is triclinic, space group P1BAR, a = 9.731(2) angstrom, b = 10.552(3) angstrom, c = 8.978(2) angstrom, alpha = 96.66(2)degrees, beta = 101.86(2)degrees, gamma = 95.30(2)degrees, Z = 2, R = 0.042; 10 is monoclinic, space group P2(1)/c, a = 11.503(2) angstrom, b = 14.095(2) angstrom, c = 15.110(2) angstrom, alpha = gamma = 90-degrees, beta = 96.79(2)degrees, Z = 4, R = 0.116; 12 is triclinic, space group P1BAR, a = 9.272(4) angstrom, b = 9.965(4) angstrom, c = 15.029(6) angstrom, alpha = 101.84(3)degrees, beta = 104.12(3)degrees, gamma = 99.53(3)degrees, Z = 2, R = 0.092.

  DOI：

  10.1021/om00031a047
• 作为产物：
  描述：

  四氯化钛 、 联苯甲酰 以 二氯甲烷 为溶剂， 生成 {TiCl4(PhCOCOPh)}
  参考文献：
  名称：

  Maier, Guenther; Seipp, Ulrich; Kalinowski, Hans-Otto, Chemische Berichte, 1994, vol. 127, # 8, p. 1427 - 1436

  摘要：

  DOI：

文献信息

• Mechanism of the Mukaiyama Aldol Reaction: The First Solid-State Characterization of a Trichlorotitanium Aldolate
  作者：Pier Giorgio Cozzi、Carlo Floriani、Angiola Chiesi-Villa、Corrado Rizzoli

  DOI：10.1021/om00017a087

  日期：1994.5

  The reaction of the silyl ketene acetal Me2C=C(OMe)OSiMes (1) with preformed TiCl4 carbonyl adducts (the monomeric [PhC(O)C(O)PhTiCl4] (2) and the dimeric [MesCHOTi(Cl)3]2(mu-Cl)2} (Mes = 2,4,6-Me3C6H2; 3)) led to the isolation and structural characterization of the corresponding titanium aldolate complexes [(PhCO)PhC(O)C(Me2)C(OMe)OTi(Cl)2]2(mu-Cl)2} (4) and [MesCH(O)C(Me2)C(OMe)OTi(Cl)2]2(mu-Cl)2} (5), in which the aldolate fragment functions as a bidentate ligand in dimeric titanium complexes bridged by two chlorine atoms. Crystallographic details: 4 is monoclinic, space group P2(1)/n, with a = 9.029(1) angstrom, b = 17.468(2) angstrom, c - 13.165(2) angstrom, beta = 98.81(2)-degrees, Z = 2, and R = 0.53.