o-methylanilinyl lithium

• 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: o-methylanilinyl lithium
• 英文别名: o-methylaniline lithium；o-methylanilino lithium；N-lithio o-toluidine；LiNH(o-CH3-Ph)；Lithium;(2-methylphenyl)azanide
• 化学式: C₇H₈LiN
• 分子量: 113.088
• InChiKey: CHECLPFNIOYQTO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.32
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  [Rh(CO)Cl(bis(diphenylphosphino)methane)2] 、 o-methylanilinyl lithium 以 乙二醇二甲醚 为溶剂， 以66%的产率得到(μ-amido-o-methyl-phenyl)(carbonyl)2(μ-(diphenylphosphino)methane)(μ-diphenylmethanide)(rhodium)2
  参考文献：
  名称：

  Ge, Yuan-Wen; Peng, Fei; Sharp, Paul R., Journal of the American Chemical Society, 1990, vol. 112, # 7, p. 2632 - 2640

  摘要：

  DOI：
• 作为产物：
  描述：

  邻甲苯胺 在 正丁基锂 作用下， 以 正己烷 为溶剂， 反应 2.0h， 以95%的产率得到o-methylanilinyl lithium
  参考文献：
  名称：

  Syntheses of titanium μ-arylimido and μ-pyridylimido complexes bearing (un)substituted cyclopentadienyl ligand

  摘要：

  The reactions of (eta(5)-C5H4CH2CH2Br)TiBr3, (eta(5)-C5H4CH2CH2OCH3)TiCl3, (eta(5)-C5H4-CH2-cyclo-C4H7O)TiCl3 and (eta(5)-C5H5)TiCl3 with an equivalent of 2-MeOC6H4NHLi in the presence of Et3N afford mu-arylimido complexes, [(eta(5)-C5H4CH2CH2Br)Ti(Br)(mu-NC6H4OCH3-2)](2) (1), [(eta(5)-C5H4CH2OCH3)Ti(Cl)(mu-NC6H4OCH3-2)](2) (2), [(eta(5)-C5H4-CH2-cyclo-C4H7O)Ti(Cl)(mu-NC6H4-OCH3-2)](2) (3), [(eta(5)-C5H5)Ti(Cl)(mu-NC6H4OCH3-2)](2) (4), which include intramolecular titanium and oxygen coordination. Complex 4 can also be obtained by reaction of the (eta(5)-C5H5)(2)TiCl2 with 2-MeOC6H4NHLi. Meanwhile refluxing of (eta 5-C5H5)(3)TiCl2 with an equivalent of 2-Me2NC6H4NMg.THF in toluene gives another mu-arylimido complex, [(eta(5)-C5H5)Ti(Cl)(mu-NC6H4NMe2-2)](2), which contains intramolecular titanium and nitrogen coordination. In addition, the analogous reactions of the above substituted half-sandwich Cp titanium complexes with PhNHLi in the presence of Et3N lead to [(eta(5)-C5H4CH2CH2Br)Ti(Br)(mu-NPh)](2), [(eta(5)-C5H4CH2OCH3)Ti(Cl)(mu-NPh)](2). The addition of 2-MeC6H4NHLi to (eta(5)-C5H4CH2CH2OCH3)TiCl3 and (eta(5)-C5H5)TiCl3 affords imido derivatives [(eta(5)-C5H5)Ti(Cl)(mu-NC6H4CH3-2)](2) and [(eta(5)-C5H4CH2OCH3)Ti(Cl)(mu-NC6H4CH3-2)](2). [(eta(5)-C5H5)Ti(Cl)(mu-NC6H3Me2-2,6)](2) is prepared by refluxing of (eta(5)-C5H5)TiCl3 and 2,6-Me2C6H3NMg.THF in toluene. The titanium mu-pyridylimido complexes, [(eta(5)-C5H5)Ti(Cl)(mu-NPy-2)](2), [(eta 5-C5H4CH2CH2OCH3)Ti(Cl)(mu-NPy-2)](2) and [(eta(5)-C5H4CH2CH2Br)Ti(Br)(mu-NPy-2)](2), are synthesized by reactions of the above corresponding half sandwich Cp titanium complexes with an equivalent of 2-PyNHLi in the presence of Et3N, respectively. Compound 1 crystallizes in the triclinic space group P (1) over bar (no. 2) with a = 9.942(2), b = 10.057(3), c = 8.457(2) Angstrom, alpha = 111.28(2), beta = 106.71(2), gamma = 98.12(2)degrees, V = 725.5(4) Angstrom(3), Z = 2.The catalytic activity and selectivity of compound 4 for the styrene polymerization is also investigated. (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(99)00732-9
• 作为试剂：
  描述：

  2,4,6-三甲基苯甲醛 、 频那醇硼烷 在 o-methylanilinyl lithium 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以99%的产率得到4,4,5,5-tetramethyl-2-((2,4,6-trimethylbenzyl)oxy)-1,3,2-dioxaborolane
  参考文献：
  名称：

  邻甲基苯胺基锂在催化醛和硼烷硼氢化反应中的应用

  摘要：

  本发明公开了邻甲基苯胺基锂在催化醛与硼烷硼氢化反应中的应用，无水无氧环境下，惰性气体氛围中，在经过脱水脱氧处理的反应瓶中加入硼烷，然后加入催化剂邻甲基苯胺基锂，混合均匀，再加入醛，进行硼氢化反应，然后暴露于空气中终止反应，得到硼酸酯；所述醛选自芳香醛、杂环醛。本发明公开的催化剂对于不同取代位置、不同电子效应的芳香醛以及对杂环醛有着较好的普适性，为得到不同取代基结构的硼酸酯化合物提供更多的选择。

  公开号：

  CN108659027A

文献信息

• Direct alkenylation of arylamines at the ortho-position
  作者：Tsuyoshi Satoh、Yumi Ogino、Masatomo Nakamura

  DOI：10.1016/j.tetlet.2004.06.024

  日期：2004.7

  gave ortho-alkenylated arylamines in moderate to good yields. The reaction was found to proceed in a highly stereospecific manner at the carbenoid carbon. This reaction offers a quite novel and direct alkenylation of arylamines at the ortho-position of the aromatic ring.

  镁烷叉卡宾的治疗，这是从1氯乙烯基生成p -甲苯基砜与异丙基氯化镁在甲苯中-78℃下，用Ñ -lithio芳基胺，得到邻-alkenylated芳基胺在中度至良好的产率。发现该反应在类胡萝卜素碳上以高度立体定向的方式进行。该反应在芳环的邻位提供芳胺的相当新颖和直接的烯基化。
• Organometallic amido nitrosyl complexes of molybdenum and tungsten
  作者：Peter Legzdins、Steven J. Rettig、Kevin J. Ross

  DOI：10.1021/om00030a021

  日期：1993.6

  Treatment of Cp*M(NO)Cl2 (Cp* = eta5-C5Me5; M = Mo, W) with arylamines, ArNH2 (Ar = phenyl, o-tolyl, or p-tolyl) affords 18-valence-electron adducts of the type Cp*M(NO)Cl2.NH2-Ar. These adducts can be dehydrohalogenated with a strong base to produce the amido chloro complexes Cp*M(NO)(NHAr)Cl in good yields. These latter complexes can also be prepared by treatment of Cp*M(NO)Cl2 with 1 equiv of a lithium amide. Interestingly, treatment of Cp*M(NO)Cl2 with excess primary alkylamines produces directly the amido chloro complexes, Cp*M(NO)(NHR)CI(R=alkyl). Mixed alkyl amido and alkoxo amido complexes are preparable by sequential treatment of Cp*M(NO)Cl2 with 1 equiv of an alkylating reagent or lithium alkoxide followed by treatment with excess alkylamine. The solid-state molecular structures of the two representative complexes, Cp*Mo(NO)Cl2.PhNH2 (1) and Cp*W(NO)(OCMe3)-(NHCMe3) (18) have been established by single-crystal X-ray diffraction analyses. Crystals of 1 are monoclinic, space group P2(1)/c, with a = 8.590(1) angstrom, b = 9.430(2) angstrom, c = 22.386(2) angstrom, beta = 94.16(1)-degrees, and Z = 4; the structure was solved by conventional heavy-atom methods and was refined by full-matrix least-squares procedures to R(F) = 0.030 and R(wF) = 0.029 for 2366 reflections with I greater-than-or-equal-to 3sigma(I). Crystals of 18 are also monoclinic, space group P2(1)/c, with a = 10.103(2) angstrom, b = 15.372(3) angstrom, c = 13.908(2) angstrom, beta = 103.08(1)-degrees, and Z = 4; R(F) = 0.028 and R(wF) = 0.024 for 2684 reflections with I greater-than-or-equal-to 3sigma(I). All new complexes isolated have been characterized by elemental analysis and H-1 and C-13 NMR, IR, and mass spectroscopies. The IR spectroscopic and electrochemical properties of some complexes are specifically compared and discussed in terms the relative electron-donating properties of the various ligands when attached to Cp*M(NO) fragments.
• trans-Ir(PPh3)2(CO)(NHAr) Complexes: Their Syntheses, Characterization, and Reactions with CO
  作者：Marufur Rahim、Kazi J. Ahmed

  DOI：10.1021/om00017a035

  日期：1994.5

  The synthesis and characterization of Ir(I)-arylamido complexes, trans-Ir(PPh3)2(CO)(NHAr), where Ar = C6H5, p-C6H4Me, o-C6H4Me, 3,5-C6H3Me2, 2,6-C6H3Me2, p-C6H4Cl, and p-C6H4NO2, are described. These complexes, except trans-Ir(PPh3)2(CO)[NH(p-C6H4NO2)], undergo rapid reactions with CO at atmospheric pressure and ambient temperatures. For the complexes containing the sterically bulky NH(3,5-C6H3Me2) and NH(2,6-C6H3Me2) ligands, the CO reactions generate carbamoyl moieties, which result from an insertion of CO into the iridium-nitrogen bond. The end products in the reactions of the other arylamido complexes with CO contain orthometalated carbamoyl moieties, with the generation of hydrido-Ir(III) centers. Intermediates leading to the formation of the orthometalated complexes are discussed. Crystal data for trans-Ir(PPh3)2(CO)[NH(3,5-C6H3Me2)].0.5C6H6: C48H43IrNOP2; triclinic P1BAR, a = 9.072(2) angstrom, b = 11.667(2) angstrom, c = 21.133(4) angstrom, alpha = 88.74(2)-degrees, beta = 81.24(2)-degrees, gamma = 73.74(2)-degrees, V = 2121.9(7) angstrom3, Z = 2, R(F) = 0.035, and R(w)(F) = 0.049 for 5038 (F > 5sigma(F)) reflections.