lithium N-methylanilide | 35954-01-9

• 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: lithium N-methylanilide
• 英文别名: N-lithio N-methylaniline；lithium methylphenylamide；lithium;methyl(phenyl)azanide
• CAS: 35954-01-9
• 化学式: C₇H₈LiN
• 分子量: 113.088
• InChiKey: ZGWHYOHRKVNVER-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.67
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  lithium N-methylanilide 在 氢氧化钾 、 dimethyl sulfide borane 作用下， 以 四氢呋喃 为溶剂， 生成 N-(2,2-difluoroethyl)aniline
  参考文献：
  名称：

  Electrolytic Reactions of Fluoroorganic Compounds. 14. Regioselective Anodic Methoxylation of N-(Fluoroethyl)amines. Preparation of Highly Useful Fluoroalkylated Building Blocks

  摘要：

  Anodic methoxylation of various types of N-(fluoroethyl)amines, ArRNCH(2)R(f) (R(f) = CF3, CHF2, CH2F, etc.) has been systematically studied and it was found that a methoxy group was exclusively or preferentially introduced into the position a to the fluoromethyl (R(f)) group, depending on the R(f) and R groups. The effect of the R(f) group on the promotion of the anodic alpha-methoxylation decreased in the order CF3, CHF2, and CH2F. This remarkable promotion effect and unique regioselectivity can be explained mainly in terms of the alpha-CH kinetic acidities of the cation radicals formed by one-electron oxidation of the amines. The alpha-methoxylated products are highly useful precursors for the construction of carbon-carbon bonds alpha to the trifluoromethyl and difluoromethyl groups, which is difficult by other methods.

  DOI：

  10.1021/jo00082a018
• 作为产物：
  描述：

  N-甲基苯胺 在 正丁基锂 作用下， 以 正己烷 为溶剂， 反应 1.0h， 生成 lithium N-methylanilide
  参考文献：
  名称：

  在有氧环境温度条件下，在可持续溶剂中使用氨基锂对酯进行超快酰胺化。

  摘要：

  氨基锂是合成化学中最常用的一类试剂。然而，尽管有许多应用，但它们的使用受到低温要求的限制，以控制它们的反应性，以及需要干燥的有机溶剂和保护性惰性气氛协议来防止它们的快速分解。促进空气和水分相容的极性有机金属化学的发展，报道了由氨基锂介导的酯的化学选择性和超快酰胺化。建立一种新的可持续获取甲酰胺的途径，这是通过以下方式实现的使用甘油或 2-MeTHF 作为溶剂，在空气中直接裂解一系列酯的 C-O 键。在环境温度下操作时观察到高产率和良好的选择性，无需过渡金属调解，并且该协议扩展到转酰胺过程。作为酰胺化过程中的关键步骤，有机底物与活性氨基锂的预配位已被评估，从而能够阐明配位加合物 [{Li(NPh 2 )(O CPh(NMe 2 ))} 2 ]的结构( 8) 当使用甲苯作为溶剂时。当使用供体 THF 作为溶剂时，没有发现形成这种类型复合物的证据。提供了对 2-MeTHF 中选定氨基锂的构成的结

  DOI：

  10.1039/d0sc01349h
• 作为试剂：
  描述：

  4-(4-chloro-phenyl)-heptanedinitrile 在 四氢呋喃 、 lithium aluminium tetrahydride 、 乙醚 、 硫酸 、 氢溴酸 、 lithium N-methylanilide 作用下， 生成 5-(4-chloro-phenyl)-cyclooctanone
  参考文献：
  名称：

  Conformational Analysis. IV. The Conformations of the Cycloöctanone Ring^1,2

  摘要：

  DOI：

  10.1021/ja01530a050

文献信息

• Acyclische isomere von aminofluorsilanen, intramolekulare cyclisierung
  作者：Uwe Klingebiel

  DOI：10.1016/s0022-328x(00)81268-1

  日期：1978.5

  Fluorosilanes react with lithiated amines to yield aminofluorosilanes. Iso- and sec-butylaminofluorosilanes with bulky ligands form the isomers (I–VII). The cyclisation of monoorganofluorosilanes depends on the size of the substituents. IV and V dimerise by HF-elimination (VIII, IX) and VII cyclises by migration of a methanide ion (X). The mass, 1H, 19F and 29Si NMR spectra of the compounds are reported

  氟硅烷与锂化胺反应生成氨基氟硅烷。具有庞大配体的异丁基和仲丁基氨基氟硅烷形成异构体（I–VII）。单有机氟硅烷的环化取决于取代基的大小。IV和V通过HF消除（VIII，IX）进行二聚，而VII通过甲烷离子（X）的迁移环化。报告了化合物的质量，1 H，19 F和29 Si NMR光谱。
• Aluminum complexes incorporating symmetrical and asymmetrical tridentate pincer type pyrrolyl ligands: synthesis, characterization and reactivity study
  作者：Pei-Hsin Liu、Fu-Jung Chuang、Cheng-Yi Tu、Ching-Han Hu、Tzu-Wei Lin、Yu-Tang Wang、Chia-Her Lin、Amitabha Datta、Jui-Hsien Huang

  DOI：10.1039/c3dt51133b

  日期：——

  A series of aluminum complexes incorporating substituted symmetrical and asymmetrical tridentate pyrrolyl ligands are synthesized conveniently and the treatment of the derivatives with small organic molecules are analyzed. The reaction of lithiated [C4H2NH(2-CH2NHtBu)(5-CH2NR1R2)], where for 1, R1 = R2 = Me; 2, R1 = H, R2 = tBu, with AlCl3 in diethyl ether affords Al[C4H2N(2-CH2NHtBu)(5-CH2NMe2)]Cl2 (3) and Al[C4H2N(2,5-CH2NHtBu)2]Cl2 (4), respectively, in high yields. Furthermore, subjecting 3 and 4 to reaction with one equiv. of LiNMePh in diethyl ether generates Al[C4H2N(2-CH2NHtBu)(5-CH2NMe2)][NMePh]Cl (5) and Al[C4H2N(2,5-CH2NHtBu)2][NMePh]Cl (6), respectively, while eliminating one equiv. of LiCl. The reaction between compound 4 with two equiv. of LiO-Ph-4-Me in diethyl ether yields the aluminum di-phenoxide compound Al[C4H2N(2,5-CH2NHtBu)2](O-Ph-4-Me)2 (7) whereas the combination of 3 and two equiv. of LiNHtBu, produces Al[C4H2N(2-CH2NtBu)(5-CH2NMe2)](NHtBu)(NH2tBu) (8). Additionally, the mixing of 1 and one equiv. of AlMe3 renders Al[C4H2N(2-CH2NHtBu)(5-CH2NMe2)]Me2 (9). Adding one more equiv. of AlMe3 with 9 affords Al[C4H2N(2-CH2NHtBu)(5-CH2NMe2)AlMe3]Me2} (10), which can also be obtained by treating 1 with two equiv. of AlMe3 directly. The treatment of 9 with one equiv. of 2,6-dimethylphenol in diethyl ether gives the aluminum alkoxide derivative, Al[C4H2N(2-CH2NHtBu)(5-CH2NMe2)](O-C6H3-2,6-Me2)Me (11). Furthermore, the reaction between 9 and one equiv. of 1-ethyl-1-phenyl ketene, initiates the aluminum dimethyl complex AlC4H2N[2-CH2CEtPh-C(O)-NHtBu](5-CH2NMe2)}Me2 (12) with a C–N bond breakage and a C–C bond formation. All the Al-derivatives are characterized by 1H and 13C NMR spectroscopy and the molecular structures are determined by single crystal X-ray diffractometry in solid state.

  一系列包含取代对称和非对称三齿吡咯烷配体的铝配合物被方便地合成,其与小有机分子的反应被分析。在二乙醚中,与AlCl3反应,lithiated [C4H2NH(2-CH2NHtBu)(5-CH2NR1R2)]分别高产率地生成Al[C4H2N(2-CH2NHtBu)(5-CH2NMe2)]Cl2(3)和Al[C4H2N(2,5-CH2NHtBu)2]Cl2(4),其中1, R1 = R2 = Me;2, R1 = H, R2 = tBu。此外,在二乙醚中,3和4分别与一份当量的LiNMePh反应,生成Al[C4H2N(2-CH2NHtBu)(5-CH2NMe2)][NMePh]Cl(5)和Al[C4H2N(2,5-CH2NHtBu)2][NMePh]Cl(6),同时释放一份当量的LiCl。4与两份当量的LiO-Ph-4-Me在二乙醚中反应生成双苯氧基铝化合物Al[C4H2N(2,5-CH2NHtBu)2](O-Ph-4-Me)2(7),而3与两份当量的LiNHtBu反应生成Al[C4H2N(2-CH2NtBu)(5-CH2NMe2)](NHtBu)(NH2tBu)(8)。此外,1与一份当量的AlMe3混合生成Al[C4H2N(2-CH2NHtBu)(5-CH2NMe2)]Me2(9)。9再与一份当量的AlMe3反应生成Al[C4H2N(2-CH2NHtBu)(5-CH2NMe2)AlMe3]Me2}(10),这也可以通过1与两份当量的AlMe3直接反应得到。9与一份当量的2,6-二甲基苯酚在二乙醚中反应生成铝醇盐衍生物Al[C4H2N(2-CH2NHtBu)(5-CH2NMe2)](O-C6H3-2,6-Me2)Me(11)。此外,9与一份当量的1-乙基-1-苯基乙烯酮反应,引发铝二甲基配合物AlC4H2N[2-CH2CEtPh-C(O)-NHtBu](5-CH2NMe2)}Me2(12)的生成,伴随着C-N键的断裂和C-C键的形成。所有铝衍生物通过1H和13C NMR谱表征,分子结构通过单晶X射线衍射法在固态中测定。
• Metal Tetrahydroborates and Tetrahydroborato Metallates, 30 [1]. Alkoxo-Substituted Alkali Metal Tetrahydroborates: Studies in Solution and Structures in the Solid State
  作者：Jörg Knizek、Heinrich Nöth、Markus Warchhold

  DOI：10.1515/znb-2006-0906

  日期：2006.9.1

  BH3 ·THF in THF solution. It is unstable to disproportionation. Compound (C6F5O)3B·THF was isolated and its crystal structure determined. Reaction of LiBH4 with F5C6OH in hexane generated a solid that proved to be Li[H2B(OC6F5)2]. It is unstable in THF. On the other hand, 2,2’-dihydroxydiphenyl in the presence of secondary amines reacts to give Li[C12H8O2B(NR2)2] (3 - 5). Li[B(O2C12H8)2], 2, is formed

  摘要 MBH4 (M = Li, Na, K) 与 tBuOH、Ph3COH、PhOH、F5C6OH 和 2,4-tBu2C6H3OH 在 THF 中以 1:1 的比例进行反应，然后进行 11B NMR 光谱分析。未检测到 M[H2B(OR)2] 物质，但检测到少量 M[H3BOR] 和大量 M[HB(OR)3]。在 LiBH4 与 2,4-tBu2C6H3OH 的反应中，也生成了相当比例的 (RO)2BH。全氟苯酚硼烷(F5C6O)2BH·THF由苯酚和BH3·THF在THF溶液中制备。对歧化不稳定。分离出化合物(C6F5O)3B·THF并确定其晶体结构。LiBH4 与 F5C6OH 在己烷中的反应生成固体，证明是 Li[H2B(OC6F5)2]。在 THF 中不稳定。另一方面，2,2'-二羟基二苯基在仲胺存在下反应生成 Li[C12H8O2B(NR2)2] (3 - 5)。Li[B(O2C12H8)2]
• Reaction of magnesium carbenoids with N-lithio arylamines: a novel method for generation of non-stabilized α-amino-substituted carbanions and a new synthesis of α-amino acid derivatives
  作者：Tsuyoshi Satoh、Atsushi Osawa、Atsushi Kondo

  DOI：10.1016/j.tetlet.2004.07.069

  日期：2004.8

  with a Grignard reagent at low temperature afforded magnesium carbenoids in quantitative yields. The magnesium carbenoids were found to be reactive with N-lithio alkylamines and N-lithio arylamines. The reaction with N-lithio alkylamines afforded an olefin, which was derived from dimerization of the magnesium carbenoid, in moderate yield. The reaction with N-lithio arylamines gave the adducts, α-amino-substituted

  在低温下用格氏试剂处理1-氯烷基苯基亚砜，以定量收率得到镁类胡萝卜素。发现镁类胡萝卜素可与N-硫代烷基胺和N-硫代芳基胺反应。与N-硫代烷基胺的反应以中等收率得到了烯烃，其衍生自羧甲基镁的二聚。与N-硫代芳基胺的反应以高收率得到加合物α-氨基取代的碳负离子。从这些中间体，实现了α-氨基酸衍生物和在α位具有氘的N，N-二烷基芳基胺的新颖合成。
• Relative metal-hydrogen, -oxygen, -nitrogen, and -carbon bond strengths for organoruthenium and organoplatinum compounds; equilibrium studies of Cp*(PMe3)2RuX and (DPPE)MePtX systems
  作者：Henry E. Bryndza、Lawrence K. Fong、Rocco A. Paciello、Wilson Tam、John E. Bercaw

  DOI：10.1021/ja00239a026

  日期：1987.3

  A series of ruthenium, Cp*(PMe/sub 3/)/sub 2/RuX (Cp* = eta/sup 5/-C/sub 5/Me/sub 5/), and platinum, (DPPE)MePtX (DPPE = Ph/sub 2/PCH/sub 2/CH/sub 2/PPh/sub 2/), compounds have been prepared. The equilibria L/sub n/M-X + H-Y in equilibrium L/sub n/M-Y + H-X (L/sub n/M = (DPPE)MePt or Cp*(PMe/sub 3/)/sub 2/Ru; X, Y = hydride, alkoxide, hydroxide, amide, alkyl, alkynyl, hydrosulfide, cyanide) have been

  一系列钌，Cp*(PMe/sub 3/)/sub 2/RuX (Cp* = eta/sup 5/-C/sub 5/Me/sub 5/)，和铂，(DPPE)MePtX (DPPE) = Ph/sub 2/PCH/sub 2/CH/sub 2/PPh/sub 2/)，已制备化合物。平衡 L/sub n/MX + HY 在平衡 L/sub n/MY + HX (L/sub n/M = (DPPE)MePt 或 Cp*(PMe/sub 3/)/sub 2/Ru; X, Y = 氢化物、醇盐、氢氧化物、酰胺、烷基、炔基、氢硫化物、氰化物）已被检验。Ru-N键强度的下限已经通过对Cp*(PMe/sub 3/)/sub 2/RuNPh/sub 2/的热分解动力学的分析来估计。平衡常数允许确定每个系列化合物的相对 MX、MY 键解离能 (BDE)。对于两个不同的金属中心，发现 L/sub n/MX 与 HX