tri-tert-butyl 2-methylhydrazine-1,1,2-tricarboxylate | 185456-28-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: tri-tert-butyl 2-methylhydrazine-1,1,2-tricarboxylate
• 英文别名: 1,1,2-Tris(1,1-dimethylethyl) 2-methyl-1,1,2-hydrazinetricarboxylate；tert-butyl N-[bis[(2-methylpropan-2-yl)oxycarbonyl]amino]-N-methylcarbamate
• CAS: 185456-28-4
• 化学式: C₁₆H₃₀N₂O₆
• 分子量: 346.424
• InChiKey: QBLWFTNHFUIXNC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.81
• 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：

  tri-tert-butyl 2-methylhydrazine-1,1,2-tricarboxylate 在 吡啶 、 4-二甲氨基吡啶 、 magnesium(II) perchlorate 作用下， 以 乙腈 为溶剂， 反应 132.5h， 生成 1,2-diBoc-1-acetyl-2-methylhydrazine
  参考文献：
  名称：

  Combination of tert-Butoxycarbonyl and Triphenylphosphonium Protecting Groups in the Synthesis of Substituted Hydrazines

  摘要：

  [GRAPHICS]A new reagent for the systematic synthesis of substituted hydrazines is reported. Unlike previously developed reagents, this one contains only two protecting groups, thus providing a faster approach to multisubstituted derivatives. The selective introduction of alkyl and acyl groups is illustrated by a few examples, Also a new fast method for the deprotection of the triphenylphosphonium group is presented.

  DOI：

  10.1021/ol0160856
• 作为产物：
  描述：

  二碳酸二叔丁酯 在 palladium on activated charcoal 4-二甲氨基吡啶 、 氢气 作用下， 以 甲醇 、 乙腈 、 苯 为溶剂， 反应 3.5h， 生成 tri-tert-butyl 2-methylhydrazine-1,1,2-tricarboxylate
  参考文献：
  名称：

  Maeeorg, Uno; Grehn, Leif; Ragnarsson, Ulf, Angewandte Chemie, 1996, vol. 108, # 22, p. 2802 - 2803

  摘要：

  DOI：

文献信息

• Highly homogeneous antibody modification through optimisation of the synthesis and conjugation of functionalised dibromopyridazinediones
  作者：Calise Bahou、Daniel A. Richards、Antoine Maruani、Elizabeth A. Love、Faiza Javaid、Stephen Caddick、James R. Baker、Vijay Chudasama

  DOI：10.1039/c7ob03138f

  日期：——

  reagents, particularly in the field of antibody conjugation. Despite this, relatively little work has been performed on the optimisation of their synthesis and subsequent reaction with immunoglobulins. Herein we present a novel synthetic route towards functionalised dibromopyridazinediones, proceeding via an isolatable dibromopyridazinedione-NHS ester. Reaction of this activated intermediate with a variety

  由于其出色的半胱氨酸选择性，出色的稳定性以及功能性重结合二硫键的能力，二溴哒嗪二酮正在成为令人兴奋的新型生物偶联试剂，特别是在抗体偶联领域。尽管如此，在优化它们的合成以及随后与免疫球蛋白的反应方面进行的工作相对较少。在这里，我们提出了一种新的合成途径，向功能化的二溴哒嗪二酮，通过一种可分离的二溴哒嗪二酮-NHS酯。该活化的中间体与多种胺的反应产生功能良好的二溴代哒嗪二酮，产率高至优异。在临床上相关的IgG1曲妥珠单抗上优化了这些试剂的二硫键再杂交能力，从而产生了一种通用方法，该方法可以生成具有90％以上同质性（无需二硫键加扰）的位点选择性修饰的天然曲妥珠单抗，而无需进行蛋白质工程或酶结合。
• Preparation of Multiply Protected Alkylhydrazine Derivatives by Mitsunobu and PTC Approaches
  作者：Nicolas Brosse、Maria-Fatima Pinto、Brigitte Jamart-Grégoire

  DOI：10.1002/ejoc.200300445

  日期：2003.12

  Alkylation reactions of hydrazine derivatives by Mitsunobu or PTC approaches are described. It has been shown that aminophthalimide derivatives are better acidic partners than their aminoimidodicarbonate (NBoc2) analogues, the presence of the phthaloyl group increasing the acidity of the sole proton and concomitantly reducing steric hindrance. Moreover, N-aminophthalimide derivatives can be efficiently

  描述了通过 Mitsunobu 或 PTC 方法对肼衍生物进行烷基化反应。已经表明，氨基邻苯二甲酰亚胺衍生物是比它们的氨基亚氨基二碳酸酯 (NBoc2) 类似物更好的酸性伙伴，邻苯二甲酰基的存在增加了唯一质子的酸度并同时减少了空间位阻。此外，N-氨基邻苯二甲酰亚胺衍生物可以在非常温和的条件下通过三阶段、一瓶程序有效地转化为相应的 N-氨基-亚胺二碳酸酯。这些程序也可以有效地用于制备正交 Nα,Nβ-diprotected α-肼酯。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• Site-selective multi-porphyrin attachment enables the formation of a next-generation antibody-based photodynamic therapeutic
  作者：Antoine Maruani、Huguette Savoie、Francesca Bryden、Stephen Caddick、Ross Boyle、Vijay Chudasama

  DOI：10.1039/c5cc06985h

  日期：——

  A next-generation antibody-based photodynamic therapeutic is assembled and shown to be potent and selective in vitro.

  一种新一代基于抗体的光动力治疗方法已经组装并在体外显示出强效和选择性。
• 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.