N-o-tolyl-hydrazinecarboxylic acid tert-butyl ester | 380383-85-7

• 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-o-tolyl-hydrazinecarboxylic acid tert-butyl ester
• 英文别名: 1-tert-butoxycarbonyl-1-(2-methylphenyl)hydrazine；tert-butyl 1-(2-methylphenyl)hydrazinecarboxylate；tert-butyl N-amino-N-(2-methylphenyl)carbamate
• CAS: 380383-85-7
• 化学式: C₁₂H₁₈N₂O₂
• 分子量: 222.287
• InChiKey: BEDMTAITPIQSDF-UHFFFAOYSA-N

物化性质

• 沸点：
  310.5±35.0 °C(Predicted)
• 密度：
  1.109±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  55.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-o-tolyl-hydrazinecarboxylic acid tert-butyl ester 在 盐酸 、 palladium diacetate 、 caesium carbonate 、 tri tert-butylphosphoniumtetrafluoroborate 作用下， 以 乙醇 、 甲苯 为溶剂， 反应 3.0h， 生成 3-甲基联苯-4,4'-二胺
  参考文献：
  名称：

  Regioselective [5,5]-Sigmatropic Rearrangement Reactions of Aryl Hydrazides

  摘要：

  N,N'-Aryl hydrazides with substituents at the ortho or meta positions undergo highly regioselective [5,5]-sigmatropic rearrangement reactions to furnish benzidines in good to excellent isolated yields. The presence of single substituent at either the ortho or meta position provides sufficient bias, effectively suppressing the formation of diphenylene, the major byproduct of the conventional benzidine rearrangement reaction.

  DOI：

  10.1021/ol060451+
• 作为产物：
  描述：

  2-碘代甲苯 、 肼基甲酸叔丁酯 在 2-吡啶甲酸 、 copper(l) iodide 、 caesium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 以28%的产率得到N-o-tolyl-hydrazinecarboxylic acid tert-butyl ester
  参考文献：
  名称：

  Copper(I)-picolinic acid catalyzed N-arylation of hydrazides

  摘要：

  An efficient copper-catalyzed carbon-nitrogen bond formation is described. The copper(I) complex with commercially available 2-picolinic acid ligand was found to be effective in N-arylation of N-Boc-hydrazine. This methodology offers a regioselective N-arylation of hydrazides using a variety of substituted aryl iodides. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2008.08.050

文献信息

• CuI/4-Hydro-<scp>l</scp>-proline as a More Effective Catalytic System for Coupling of Aryl Bromides with <i>N</i>-Boc Hydrazine and Aqueous Ammonia
  作者：Liqin Jiang、Xu Lu、Hui Zhang、Yongwen Jiang、Dawei Ma

  DOI：10.1021/jo9006738

  日期：2009.6.19

  CuI/4-hydroxy-l-proline-catalyzed coupling of aryl bromides and N-Boc hydrazine takes place in DMSO at 80 °C to give N-aryl hydrazides. When aryl iodides are employed, this reaction completes at 50 °C and no ligand is required. Under the catalysis of CuI/4-hydroxy-l-proline, the coupling reaction of aqueous ammonia with aryl bromides proceeds smoothly at 50 °C to afford primary arylamines. In this

  CuI / 4-羟基-1-脯氨酸催化的芳基溴化物与N- Boc肼的偶合反应在DMSO中于80°C进行，得到N-芳基酰肼。当使用芳基碘化物时，该反应在50℃下完成并且不需要配体。在CuI / 4-羟基-1-脯氨酸的催化下，氨水与芳基溴化物的偶联反应在50℃下顺利进行，得到伯芳基胺。在这种情况下，发现K 2 CO 3是比Cs 2 CO 3更好的碱。这些过程允许组装N带有多种官能团的-芳基酰肼和伯芳基胺包括羟基，胺基，三氟甲基，酯基，硝基和酮。
• Enantioselective Synthesis of N–N Amide–Pyrrole Atropisomers via Paal–Knorr Reaction
  作者：Yuanlin Wei、Fan Sun、Guofeng Li、ShiYu Xu、Ming Zhang、Liang Hong

  DOI：10.1021/acs.orglett.3c03280

  日期：2024.3.29

  we present a highly efficient enantioselective synthesis of monoheteroaryl N–N atropisomers via an asymmetric Paal–Knorr reaction, affording a diverse array of N–N amide–pyrrole atropisomers with excellent enantioselectivities. Gram-scale synthesis and post-transformations of the product demonstrated the synthesis utility of this method. Racemization experiments confirmed the configurational stability

  单杂芳基 N-N 轴向手性化合物和手性五元芳基支架的催化不对称构建仍然具有挑战性。在此，我们通过不对称Paal-Knorr反应高效对映选择性合成单杂芳基N-N阻转异构体，提供了多种具有优异对映选择性的N-N酰胺-吡咯阻转异构体。产物的克级合成和后转化证明了该方法的合成实用性。外消旋化实验证实了这些 N-N 轴向手性产物的构型稳定性。这项研究不仅提供了第一个获得不对称单杂芳基 N-N 支架的从头环化实例，而且还提供了 N-N 阻转异构体家族的新成员，具有潜在的合成和医学应用。
• Synthesis of <i>N</i>-Aryl Hydrazides by Copper-Catalyzed Coupling of Hydrazides with Aryl Iodides
  作者：Martina Wolter、Artis Klapars、Stephen L. Buchwald

  DOI：10.1021/ol0168216

  日期：2001.11.1

  [GRAPHICS]A convenient method for intermolecular N-arylation of hydrazides with substituted aryl iodides in the presence of a copper catalyst and Cs(2)CO(3) is reported. The C-N coupling of N-Boc hydrazine with para- and meta-substituted aryl iodides afforded the N-arylated products A, regioselectively. A reversal in regioselectivity is observed for the arylation of benzoic hydrazide with ortho-substituted aryl iodides, providing the N'-arylated products B.