1-benzyl-1,2-bis(tert-butoxycarbonyl)-2-benzyloxyhydrazine | 202980-93-6

• 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: 1-benzyl-1,2-bis(tert-butoxycarbonyl)-2-benzyloxyhydrazine
• 英文别名: tert-butyl N-benzyl-N-[(2-methylpropan-2-yl)oxycarbonyl-phenylmethoxycarbonylamino]carbamate
• CAS: 202980-93-6
• 化学式: C₂₅H₃₂N₂O₆
• 分子量: 456.539
• InChiKey: YAGKODDHZHGNTB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  33
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  85.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1-benzyl-1,2-bis(tert-butoxycarbonyl)-2-benzyloxyhydrazine 在 magnesium(II) perchlorate 作用下， 以 乙腈 为溶剂， 以98%的产率得到tert-butyl N-benzyl-N-(phenylmethoxycarbonylamino)carbamate
  参考文献：
  名称：

  Synthesis of Substituted Hydrazines from Triprotected Precursors.

  摘要：

  Full details related to the preparation and application of two triprotected reagents, 1,2,2-Boc(3)-hydrazine (1) and 1,2-Boc(2)-2-Z-hydrazine (2), for stepwise synthesis of substituted hydrazines are presented. In the presence of base these compounds undergo substitution at N-1, often accompanied by partial loss of protecting groups at N-2. Optimized alkylation procedures, eliminating or greatly diminishing these side reactions, involving phase-transfer catalysis are reported. The initial products can be selectively deprotected at N-2 to provide a new alkylation site. Twice alkylated derivatives of 1 and 2 differ in their potential to undergo further selective cleavage, and only the latter are capable of such. A limited number of partly protected substituted hydrazine derivatives have been made using the novel procedures. Compounds 1 and 2 both exist as mixtures of two conformers which have been assigned, whereas in alkylated derivatives up to four such are present. For two dialkylated compounds all conformers have also been assigned and their relative distribution experimentally determined. The results are in good agreement with those from theoretical calculations.

  DOI：

  10.3891/acta.chem.scand.53-1127
• 作为产物：
  描述：

  肼基甲酸苄酯 在 4-二甲氨基吡啶 、 sodium hydroxide 、 四丁基硫酸氢铵 、 锌 作用下， 以 溶剂黄146 、 甲苯 为溶剂， 生成 1-benzyl-1,2-bis(tert-butoxycarbonyl)-2-benzyloxyhydrazine
  参考文献：
  名称：

  Synthesis, application and scope of a new protected hydrazine reagent

  摘要：

  A novel triprotected hydrazine reagent, 1,2-Boc(2)-2-Z-hydrazine (3), has been made and investigated with respect to stepwise alkylation/acylation and intermediary deprotection in order to prepare multisubstituted hydrazine derivatives. Alkylation of 3 requires particularly mild basic conditions. Regiospecific cleavage of one Boc-group with acid in monoalkylated product 4 is difficult but on be accomplished with catalytic amounts of Mg(ClO4)(2) in MeCN at 50 degrees C in 15 min, furnishing 5 which can easily be alkylated to 6. This product has recently been converted to fully substituted derivatives 7. (C) 1998 Elsevier Science Ltd. All lights reserved.

  DOI：

  10.1016/s0040-4039(97)10634-7

文献信息

• Acidity of Di- and Triprotected Hydrazine Derivatives in Dimethyl Sulfoxide and Aspects of Their Alkylation
  作者：Ulf Ragnarsson、Leif Grehn、Juta Koppel、Olavi Loog、Olga Tšubrik、Aleksei Bredikhin、Uno Mäeorg、Ilmar Koppel

  DOI：10.1021/jo050680u

  日期：2005.7.1

  and diethyl azodicarboxylate in the Mitsunobu reaction. The dependence of the reactivity on the intrinsic acidity of the hydrazines in this reaction is highlighted. Furthermore, the regioselective alkylation of an N,N‘-diprotected hydrazine can be rationalized on the basis of the presented data.

  使用电位滴定法已经确定了22种二保护和三保护的肼NH酸和两种单取代的肼在DMSO中的p K a值。比较了代表性的单取代，二取代和三取代肼在气相酸度的B3LYP / 6-311 + G **水平上的密度泛函理论计算结果与相关的已发表和新颖的实验滴定数据进行了比较。在这项工作的过程中，已经得出了DMSO中肼的p K a值的粗略估计值（约38.0）。对于这类典型的三保护化合物，其含有适度吸电子的氨基甲酸酯和亚氨基二碳酸酯或芳构磺酰基氨基甲酸酯，其p K a该值落在15.1-17.3的范围内，而对于具有氨基甲酸酯和芳族磺酰基的N，N'-双保护肼，相应的值是12.7-14.5。这些三保护衍生物中的几种最近已在相转移催化剂的存在下制备用于烷基卤化物作为亲电试剂逐步合成取代的肼的过程中，其中一些已成功地用苄醇在模型实验中进行了研究，三苯膦和偶氮二羧酸二乙酯在Mitsunobu反应中。在该反应中反应性对肼
• Synthesis of Substituted Hydrazines from Triprotected Precursors.
  作者：Uno Mäeorg、Tönis Pehk、Ulf Ragnarsson

  DOI：10.3891/acta.chem.scand.53-1127

  日期：——

  Full details related to the preparation and application of two triprotected reagents, 1,2,2-Boc(3)-hydrazine (1) and 1,2-Boc(2)-2-Z-hydrazine (2), for stepwise synthesis of substituted hydrazines are presented. In the presence of base these compounds undergo substitution at N-1, often accompanied by partial loss of protecting groups at N-2. Optimized alkylation procedures, eliminating or greatly diminishing these side reactions, involving phase-transfer catalysis are reported. The initial products can be selectively deprotected at N-2 to provide a new alkylation site. Twice alkylated derivatives of 1 and 2 differ in their potential to undergo further selective cleavage, and only the latter are capable of such. A limited number of partly protected substituted hydrazine derivatives have been made using the novel procedures. Compounds 1 and 2 both exist as mixtures of two conformers which have been assigned, whereas in alkylated derivatives up to four such are present. For two dialkylated compounds all conformers have also been assigned and their relative distribution experimentally determined. The results are in good agreement with those from theoretical calculations.
• Synthesis, application and scope of a new protected hydrazine reagent
  作者：Uno Mäeorg、Ulf Ragnarsson

  DOI：10.1016/s0040-4039(97)10634-7

  日期：1998.2

  A novel triprotected hydrazine reagent, 1,2-Boc(2)-2-Z-hydrazine (3), has been made and investigated with respect to stepwise alkylation/acylation and intermediary deprotection in order to prepare multisubstituted hydrazine derivatives. Alkylation of 3 requires particularly mild basic conditions. Regiospecific cleavage of one Boc-group with acid in monoalkylated product 4 is difficult but on be accomplished with catalytic amounts of Mg(ClO4)(2) in MeCN at 50 degrees C in 15 min, furnishing 5 which can easily be alkylated to 6. This product has recently been converted to fully substituted derivatives 7. (C) 1998 Elsevier Science Ltd. All lights reserved.