2-Benzyloxycarbonyl-1-(t-butyloxycarbonyl)-1-(ethoxycarbonylmethyl)hydrazine | 258526-03-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2-Benzyloxycarbonyl-1-(t-butyloxycarbonyl)-1-(ethoxycarbonylmethyl)hydrazine
• 英文别名: Ethyl 2-[(2-methylpropan-2-yl)oxycarbonyl-(phenylmethoxycarbonylamino)amino]acetate
• CAS: 258526-03-3
• 化学式: C₁₇H₂₄N₂O₆
• 分子量: 352.387
• InChiKey: VJERFPMZPLDOLL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  25
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  94.2
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  三苯基铋 、 2-Benzyloxycarbonyl-1-(t-butyloxycarbonyl)-1-(ethoxycarbonylmethyl)hydrazine 在 copper diacetate 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 23.0h， 以97%的产率得到2-Benzyloxycarbonyl-1-(t-butyloxycarbonyl)-1-(ethoxycarbonylmethyl)-2-phenylhydrazine
  参考文献：
  名称：

  Synthesis of Hydrazines with Aromatic Substituents Using Triarylbismuth Reagents

  摘要：

  在温和的条件下，使用三芳基铋烷在醋酸铜和胺的存在下完成了两种三保护肼试剂的平滑单芳基化反应，得到了产率极高的产物 3 和 6。在对 N 1 上带有烷基或芳基取代基的衍生物进行选择性脱保护后，N 2 上的芳基化反应也得到了化合物 8 和 9。此外，由这些试剂衍生出的具有游离 N-烷基和 N-芳基官能团的其他产物也会发生同样的反应，生成 10 和 11 等物质。因此，原始肼试剂的应用范围得到了进一步扩展。一些参考化合物也是直接从苯肼中制备出来的。

  DOI：

  10.1055/s-2000-7600
• 作为产物：
  描述：

  1-苄基1,2-二(2-甲基-2-丙基)1,1,2-肼三羧酸酯 在 sodium hydroxide 、 magnesium(II) perchlorate 、 四丁基硫酸氢铵 作用下， 以 甲苯 、 乙腈 为溶剂， 反应 0.25h， 生成 2-Benzyloxycarbonyl-1-(t-butyloxycarbonyl)-1-(ethoxycarbonylmethyl)hydrazine
  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

• 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 of Hydrazines with Aromatic Substituents Using Triarylbismuth Reagents
  作者：Olavi Loog、Uno Mäeorg、Ulf Ragnarsson

  DOI：10.1055/s-2000-7600

  日期：——

  Smooth monoarylation of two triprotected hydrazine reagents under mild conditions has been accomplished using triarylbismuthanes in the presence of copper acetate and amine to give products 3 and 6 in excellent yield. Arylation on N 2 after selective deprotection of derivatives with alkyl or aryl substituents on N 1, resulting in compounds 8 and 9, is also demonstrated. Furthermore, other products derived from these reagents with free N-alkyl and N-aryl functions undergo the same reaction to give substances such as 10 and 11. As a result, the scope of the original hydrazine reagents has been further extended. A few reference compounds have also been prepared directly from phenylhydrazine.

  在温和的条件下，使用三芳基铋烷在醋酸铜和胺的存在下完成了两种三保护肼试剂的平滑单芳基化反应，得到了产率极高的产物 3 和 6。在对 N 1 上带有烷基或芳基取代基的衍生物进行选择性脱保护后，N 2 上的芳基化反应也得到了化合物 8 和 9。此外，由这些试剂衍生出的具有游离 N-烷基和 N-芳基官能团的其他产物也会发生同样的反应，生成 10 和 11 等物质。因此，原始肼试剂的应用范围得到了进一步扩展。一些参考化合物也是直接从苯肼中制备出来的。
• 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.