N-lithio 2-methoxyaniline

• 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: N-lithio 2-methoxyaniline
• 英文别名: 2-methoxyaniline lithium；2-methoxyanilino lithium；o-methoxyanilino lithium；N-lithio o-anisidine；LiNH(o-OMe)C6H4；lithium;(2-methoxyphenyl)azanide
• 化学式: C₇H₈NO*Li
• 分子量: 129.088
• InChiKey: AVYWQIYILZLMII-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.62
• 重原子数：
  10
• 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：
  10.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-lithio 2-methoxyaniline 在 lithium anilide 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 1-[N-(2-methoxyphenyl)amino]cyclopentadecanecarbaldehyde
  参考文献：
  名称：

  由环酮通过亚磺酰基氮丙啶类化合物合成环状α-氨基醛，氨基醇和α-氨基酸甲酯的新方法

  摘要：

  由环酮和氯甲基对甲苯基亚砜分三步以高收率处理1-氯乙烯基对甲苯基亚砜，得到高收率的亚磺酰基氮丙啶。在用N-硫代苯胺苯胺或N-硫代对氯苯胺处理时，亚磺酰基氮丙啶高产率地得到α-氨基醛。将α-氨基醛以中等至良好的产率转化为氨基醇和α-氨基酸甲基酯。该方法提供了从环状酮合成环状α-季α-氨基醛，氨基醇和α-氨基酸衍生物的有效方法。

  DOI：

  10.1016/j.tetlet.2004.03.124
• 作为产物：
  描述：

  邻甲氧基苯胺 在 正丁基锂 作用下， 以 正己烷 为溶剂， 反应 2.0h， 以93%的产率得到N-lithio 2-methoxyaniline
  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：

  N-苄叉苯胺 、 频那醇硼烷 在 N-lithio 2-methoxyaniline 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以99%的产率得到N-benzyl-4,4,5,5-tetramethyl-N-phenyl-1,3,2-dioxaborolan-2-amine
  参考文献：
  名称：

  邻甲氧基苯胺基锂在催化亚胺和硼烷硼氢化 反应中的应用

  摘要：

  本发明涉及邻甲氧基苯胺基锂的应用，具体涉及邻甲氧基苯胺基锂在催化亚胺和硼烷的硼氢化反应中的应用。依次将催化剂、硼烷和亚胺搅拌混合均匀，反应1～2小时，暴露于空气中终止反应，反应液减压除去溶剂，得到不同取代基的硼酸酯。本发明公开的邻甲氧基苯胺基锂可以在室温条件下高活性的催化亚胺和硼烷的硼氢化反应，催化剂用量仅为亚胺摩尔量的4~5 mol%，反应可达到90%以上的收率，与已有的催化体系相比，利用了简单的邻甲氧基苯胺基锂，反应条件温和，在优化条件下不同取代基的硼酸酯的产率可达99%。

  公开号：

  CN109251217B

文献信息

• Synthesis, characterization of bridged bis(amidinate) lanthanide amides and their application as catalysts for addition of amines to nitriles for monosubstituted N-arylamidines
  作者：Wenbo Li、Mingqiang Xue、Fan Xu、Jing Tu、Yong Zhang、Qi Shen

  DOI：10.1039/c2dt30400g

  日期：——

  showed a good scope of aromatic amines. Some key reaction intermediates were isolated and structurally characterized, including the amidinate complexes LLn[NPhCNAr1](PhCN) (Ln = Y (8), Ln = Yb (9)), LYb[NAr2CNAr1](Ar2CN) (10), and amide complex 5 prepared by protonation of 9 by Ar1NH2. Reactivity studies of these complexes suggest that the present catalytic formation of monosubstituted N-arylamidines

  桥联双（酰胺基）配体L，LLnNHAr 1（DME）（L = [Me 3 SiNC（Ph）N（CH 2）3 NC（Ph）NSiMe 3 ]，Ar 1 = 2， 6- i Pr 2 C 6 H 3，DME =二甲氧基乙烷，Ln为Y（1），PR（2），钕（3），钆（4），镱（5）），镱（μ 2 -NHPh）] 2（μ 2 -L）2（6）和[LYB] 2（μ 2 -NHAr 2）2（7）（AR 2 =（ø -OMe）C 6 H ^ 4），由LLnCl（THF）的反应，合成2用相应的酰胺酰胺以高收率得到产物，并通过X射线晶体结构分析对其结构进行表征。发现所有络合物都是用于将芳族胺催化加成到芳族腈中以得到单取代的N-芳基idine啶的预催化剂。镧系金属和酰胺基的催化活性受镧系金属和-NHAr 2 <的活性序列Y（1）
• A novel synthesis of cyclic α-amino aldehydes, amino alcohols, and α-amino acid methyl esters from cyclic ketones through sulfinylaziridines
  作者：Hiroyuki Ota、Toshio Chyouma、Shuyu Iso、Tsuyoshi Satoh

  DOI：10.1016/j.tetlet.2004.03.124

  日期：2004.5

  were synthesized from cyclic ketones and chloromethyl p-tolyl sulfoxide in three steps in good yields, with N-lithio arylamines gave sulfinylaziridines in high yields. On treatment with N-lithio aniline or N-lithio p-chloroaniline, the sulfinylaziridines gave α-amino aldehydes in high yields. The α-amino aldehydes were converted to amino alcohols and α-amino acid methyl esters in moderate to good yields

  由环酮和氯甲基对甲苯基亚砜分三步以高收率处理1-氯乙烯基对甲苯基亚砜，得到高收率的亚磺酰基氮丙啶。在用N-硫代苯胺苯胺或N-硫代对氯苯胺处理时，亚磺酰基氮丙啶高产率地得到α-氨基醛。将α-氨基醛以中等至良好的产率转化为氨基醇和α-氨基酸甲基酯。该方法提供了从环状酮合成环状α-季α-氨基醛，氨基醇和α-氨基酸衍生物的有效方法。
• Heterobimetallic lithium alkyltriimido aluminate cages containing the [R′Al(NR)₃]⁴⁻tetraanion (R′ = Buⁿ, Et; R = 2-OMeC₆H₄)
  作者：May C. Copsey、John C. Jeffery、Christopher A. Russell、John M. Slattery、Jennifer A. Straughan

  DOI：10.1039/b307589c

  日期：——

  Attempted metallation of a triamidoaluminane gives a complex containing the [R′Al(NR) 3 ] 4− anion whose formal tetranegative charge is the highest charge observed crystallographically for a simple mononuclear imido main group anion system.

  尝试对三氨基铝烷进行金属化，得到了一种含有 [Râ²Al(NR) 3 ] 4â 阴离子的复合物，其形式上的四负电荷是晶体学上观察到的简单单核亚氨基主基阴离子系统的最高电荷。
• Syntheses of titanium μ-arylimido and μ-pyridylimido complexes bearing (un)substituted cyclopentadienyl ligand
  作者：Zheng Li、Jiling Huang、Tianer Yao、Yanlong Qian、Meiyu Leng

  DOI：10.1016/s0022-328x(99)00732-9

  日期：2000.4

  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.
• A synthesis, including asymmetric synthesis, of α-quaternary α-amino aldehydes from ketones and chloromethyl p-tolyl sulfoxide via sulfinylaziridines
  作者：Tsuyoshi Satoh、Juri Endo、Hiroyuki Ota、Toshio Chyouma

  DOI：10.1016/j.tet.2007.03.067

  日期：2007.5

  p-tolyl sulfoxides, prepared from ketones and chloromethyl p-tolyl sulfoxide, with N-lithio arylamines resulted in the formation of sulfinylaziridines in good to high yields. The sulfinylaziridines were treated with N-lithio aniline or N-lithio p-chloroaniline to afford α-quaternary α-amino aldehydes in good yields. From α-quaternary α-amino aldehydes, α-quaternary α-amino acid esters and β-quaternary β-amino

  1-氯乙烯基治疗p -甲苯基砜，由酮和氯制备p -甲苯基砜，用Ñ -lithio芳基胺导致良好的形成sulfinylaziridines的产量高。用N-硫代苯胺或N-硫代对氯苯胺处理亚磺酰基氮丙啶，以高收率得到α-季α-氨基醛。由α-季α-氨基醛获得α-季α-氨基酸酯和β-季β-氨基醇。当旋光性氯甲基p在该步骤中使用了甲苯基亚砜，从而实现了一种光学活性α-季α-氨基醛的合成方法。描述了用于形成亚磺酰基氮丙啶的反应机理，包括不对称诱导。