di-tert-butyl 1,2-phenylenedicarbamate | 438533-54-1

• 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: di-tert-butyl 1,2-phenylenedicarbamate
• 英文别名: N,N'-Bis(tert-butoxycarbonyl)-o-phenylenediamine；tert-butyl N-[2-[(2-methylpropan-2-yl)oxycarbonylamino]phenyl]carbamate
• CAS: 438533-54-1
• 化学式: C₁₆H₂₄N₂O₄
• 分子量: 308.378
• InChiKey: ODPWRGXKKBXCIT-UHFFFAOYSA-N

物化性质

• 熔点：
  104-106 °C
• 沸点：
  339.9±25.0 °C(Predicted)
• 密度：
  1.152±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  76.7
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  di-tert-butyl 1,2-phenylenedicarbamate 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 palladium 10% on activated carbon 、 氢气 、 sodium hydride 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 20.0~60.0 ℃ 、506.66 kPa 条件下， 反应 56.0h， 生成 di(tert-butyl) 2,3,4,5-tetrahydro-1,6-benzodiazocine-1,6-dicarboxylate
  参考文献：
  名称：

  A ring-closing metathesis approach to eight-membered benzannelated scaffolds and subsequent internal alkene isomerizations

  摘要：

  A set of eight-membered benzannelated heterocycles containing two heteroatoms (O,O, NR,NR and O,NR where R=protecting group) was synthesized by ring-closing metathesis from the corresponding orthobis-allyl precursors. In this manner, 7-methoxy-2,5-dihydro-1,6-benzodioxocine, 1,2,5,6-tetrahydro-1,6-benzodiazocines, 5,6-dihydro-2H-1,6-benzoxazocines and 5,6,9,10-tetrahydropyrido[2,3-b][1,4]diazocine were synthesized. A number of these compounds were then treated with the catalyst [RuClH(CO)(PPh3)(3)] to facilitate isomerization of the alkene into conjugation with the heteroatoms in the eight-membered ring. Quite surprisingly, an equal ratio of regioisomers was obtained, even if the heteroatoms were different (c) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.12.043
• 作为产物：
  描述：

  二碳酸二叔丁酯 、 2-硝基苯胺 在 tin 、 氯化铵 作用下， 以 甲醇 为溶剂， 反应 4.5h， 以79%的产率得到di-tert-butyl 1,2-phenylenedicarbamate
  参考文献：
  名称：

  Ultrasound Promoted ‘One Pot’ Conversion of Nitrocompounds to Carbamates

  摘要：

  首次利用Sn-NH4Cl实现了高效的促进超声波作用下，将硝基化合物直接转化为N-(叔丁氧羰基)胺及N-(乙氧羰基胺)的新颖直接转换过程。

  DOI：

  10.1055/s-2002-25338
• 作为试剂：
  描述：

  对硝基苯甲醛 、 4-甲基环己酮 在 L-脯氨酸 、 di-tert-butyl 1,2-phenylenedicarbamate 作用下， 以 甲苯 为溶剂， 反应 120.5h， 生成 (2S,4S)-2-((R)-hydroxy(4-nitrophenyl)methyl)-4-methylcyclohexanone 、 4(R),2(R)-2-[(S)-hydroxy(4-nitrophenyl)methyl]-4-methylcyclohexanone 、 2-[1-hydroxy-1-(4-nitrophenyl)methyl]-4-methylcyclohexan-1-one
  参考文献：
  名称：

  脯氨酸催化的简单直接羟醛反应对手性环己酮的高度对映和非对映选择性有机催化脱对称

  摘要：

  醛醇缩合不对称的灵丹妙药：我们描述了脯氨酸催化的4取代环己酮的不对称化的简便方法，它使用不同的氢键供体作为助催化剂（参见方案），从而显着提高了脯氨酸在不对称化反应中的催化效率。

  DOI：

  10.1002/chem.200900488

文献信息

• Protic ionic liquid [TMG][Ac] as an efficient, homogeneous and recyclable catalyst for Boc protection of amines
  作者：Jafar Akbari、Akbar Heydari、Leila Ma’mani、Seyed Hassan Hosseini

  DOI：10.1016/j.crci.2009.10.003

  日期：2010.5

  Résumé An efficient and practical protocol for the chemoselective N-Boc protection of various structurally different aryl, aliphatic and heterocyclic amines was carried out with (Boc)2O using protic 1, 1, 3, 3-tetra-methylguanidinium acetate (10 mol%) as recyclable catalyst under solvent free condition at ambient temperature. No competitive side reactions (isocyanate, urea and N, N-di-Boc) were observed. α-Amino alcohols afforded the N-Boc-derivative without oxazolidinone formation.

  简历 一种高效且实用的化学选择性N-Boc保护各种结构不同的芳基、脂肪族和杂环胺的协议，通过在无溶剂条件下使用质子化的1,1,3,3-四甲基胍乙酸盐（10 mol%）作为可回收催化剂，在室温下使用(Boc)2O进行。未观察到竞争性的副反应（异氰酸酯、脲和N,N-二Boc）。α-氨基醇提供了N-Boc衍生物而不形成噁唑烷酮。
• General solvent-free highly selective N-tert-butyloxycarbonylation strategy using protic ionic liquid as an efficient catalyst
  作者：Swapan Majumdar、Jhinuk De、Ankita Chakraborty、Dilip K. Maiti

  DOI：10.1039/c4ra02670e

  日期：——

  transformation of amines to tert-butyloxycarbonyl protected derivatives (NHBoc) using Boc2O and imidazolium trifluoroacetate protic ionic liquid (5–20 mol%). Unwanted side products such as isocyanate, urea or N,N-di-Boc were not detected. The scope of the protection strategy was successfully explored for substrate alcohols, phenols and thiol at elevated temperatures. Optically pure amino acids, amino acid esters

  描述了一种简单，快速且无溶剂的方案，该方案使用Boc 2 O和三氟乙酸咪唑鎓质子离子液体（5-20​​ mol％）将胺化学选择性转化为叔丁氧羰基保护的衍生物（NHBoc ）。未检测到不需要的副产物，例如异氰酸酯，尿素或N，N -di-Boc。在高温下成功探索了底物醇，酚和硫醇的保护策略范围。光学纯的氨基酸，氨基酸酯和氨基醇被有效地转化为相应的N-Boc以优异的收率保护了衍生物，而在手性中心没有外消旋作用。该方法的显着优点是：操作简单，反应更清洁，选择性高，产率高，反应收敛快，催化剂易于制备和可回收利用。
• ZnO Nanorods as an Efficient and Heterogeneous Catalyst for N-Boc Protection of Amines and Amine Derivatives
  作者：Azita Nouri、Jafar Akbari、Akbar Heydari、Arezu Nouri

  DOI：10.2174/157017811794557859

  日期：2011.1.1

  An efficient ZnO nano catalyst, which was readily prepared from Zn(CH3CO2)2, 2H2O and PVP by a chemical solution approach has successfully catalyzed N-tertbutoxy carbonylation of amines. The ZnO nanorods were successful and gave promising results for highly active and chemoselective as well as easily recyclable catalyst for the NBoc protection reaction of a wide variety of amines. The catalyst could be easily recycled for five times without noticeable decrease in catalytic activity. The ZnO nanocatalyst was characterized with XRD and SEM.

  一种高效的ZnO纳米催化剂，通过化学溶液法制备，原料为Zn(CH3CO2)2·2H2O和PVP，成功催化了胺的N-叔丁氧羰基化反应。ZnO纳米棒作为催化剂表现出色，为各种胺的NBoc保护反应提供了高活性、化学选择性且易于回收的催化剂，并显示出良好的结果。该催化剂可轻松回收利用五次，催化活性未见明显下降。通过XRD和SEM对ZnO纳米催化剂进行了表征。
• Preparation, characterization and application of succinimidinium hydrogensulfate ([H-Suc]HSO₄) as an efficient ionic liquid catalyst for the N-Boc protection of amines
  作者：Farhad Shirini、Omid Goli Jolodar、Mohadeseh Seddighi、Hojatollah Takbiri Borujeni

  DOI：10.1039/c4ra14130j

  日期：——

  Succinimidinium hydrogensulfate ([H-Suc]HSO₄), which is prepared from the reaction of succinimide and sulfuric acid, showed excellent catalytic activity for theN-Boc protection of various amines under solvent free conditions.

  琥珀酰亚胺硫酸氢盐([H-Suc]HSO4)，由琥珀酰亚胺和硫酸反应制备，在无溶剂条件下对各种胺的N-Boc保护显示了出色的催化活性。
• Environmentally Benign <i>N</i>-Boc Protection under Solvent- and Catalyst-Free Conditions
  作者：Xueshun Jia、Qing Huang、Jian Li、Shaoyu Li、Qiushi Yang

  DOI：10.1055/s-2007-970755

  日期：2007.3

  A practical and highly efficient method for the protection of amines to their corresponding N-Boc derivatives is reported. In the absence of any solvent and catalyst, the present strategy works well for a series of electron-deficient and electron-rich aromatic amines as well as some sterically hindered substrates.

  报道了一种实用且高效的胺类化合物保护方法，将其转化为相应的N-Boc衍生物。在无溶剂和催化剂的条件下，该策略适用于一系列缺电子和富电子的芳香胺以及某些立体位阻较大的底物。