4-[N-[(1,1-dimethylethoxy)carbonyl]amino]-1,2-dihydro-1,5-dimethyl-2-phenyl-3H-pyrazol-3-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 4-[N-[(1,1-dimethylethoxy)carbonyl]amino]-1,2-dihydro-1,5-dimethyl-2-phenyl-3H-pyrazol-3-one
• 英文别名: (1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)carbamic acid tert-butyl ester；tert-butyl N-(1,5-dimethyl-3-oxo-2-phenylpyrazol-4-yl)carbamate
• 化学式: C₁₆H₂₁N₃O₃
• 分子量: 303.361
• InChiKey: RIJKTPFDFMVNTM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  61.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-[N-[(1,1-dimethylethoxy)carbonyl]amino]-1,2-dihydro-1,5-dimethyl-2-phenyl-3H-pyrazol-3-one 在 硫酸 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以98%的产率得到4-氨基安替比林
  参考文献：
  名称：

  Efficient cleavage of carboxylic tert-butyl and 1-adamantyl esters, and N-Boc-amines using H2SO4 in CH2Cl2

  摘要：

  A new procedure for the deprotection of carboxylic tert-butyl and 1-adamantyl esters, and N-Boc-amines using H2SO4 in CH2Cl2 is described. The proposed method is simple, cheap, eco-friendly and represents a valid alternative to existing ones, with special significance in large scale applications. (C) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.01.129
• 作为产物：
  描述：

  4-氨基安替比林 、 二碳酸二叔丁酯 以 叔丁醇 为溶剂， 反应 3.0h， 以94%的产率得到4-[N-[(1,1-dimethylethoxy)carbonyl]amino]-1,2-dihydro-1,5-dimethyl-2-phenyl-3H-pyrazol-3-one
  参考文献：
  名称：

  N - BOC胺和N - BOC氨基酸衍生物的选择性硝化脱保护

  摘要：

  使用HNO去保护的方法的延伸3在CH 2氯2到多个适当选择的Ñ -BOC-掩蔽胺和天然氨基酸的衍生物进行了研究。发现该方法对几乎所有测试的底物均有效，但活化的芳族胺和杂环不可避免地会经历更快的氧化。丙氨酸，苯丙氨酸，丝氨酸和赖氨酸衍生物以及二肽Ala–Phe被有效地脱保护，保留了底物的构型且不影响共存的Z和酯功能，对酸敏感的t具有显着的选择性。丁酯。分离出并以硝酸盐的形式表征的所得氨基酸酯被证明是适用于肽合成的中间体。

  DOI：

  10.1016/s0040-4020(01)00900-0

文献信息

• Selective nitrolytic deprotection of N -BOC-amines and N -BOC-amino acids derivatives
  作者：Paolo Strazzolini、Tiziana Melloni、Angelo G Giumanini

  DOI：10.1016/s0040-4020(01)00900-0

  日期：2001.10

  configuration of the substrates and without affecting copresent Z and ester functions, with a remarkable selectivity towards acid sensitive t-butyl esters. The obtained amino acids esters, isolated and characterized in the form of nitrates salts, proved to be suitable intermediates to be used in peptide synthesis.

  使用HNO去保护的方法的延伸3在CH 2氯2到多个适当选择的Ñ -BOC-掩蔽胺和天然氨基酸的衍生物进行了研究。发现该方法对几乎所有测试的底物均有效，但活化的芳族胺和杂环不可避免地会经历更快的氧化。丙氨酸，苯丙氨酸，丝氨酸和赖氨酸衍生物以及二肽Ala–Phe被有效地脱保护，保留了底物的构型且不影响共存的Z和酯功能，对酸敏感的t具有显着的选择性。丁酯。分离出并以硝酸盐的形式表征的所得氨基酸酯被证明是适用于肽合成的中间体。
• Indium(III) Halides as New and Highly Efficient Catalysts for <i>N</i>-<i>tert</i>-Butoxycarbonylation of Amines
  作者：Asit Chakraborti、Sunay Chankeshwara

  DOI：10.1055/s-2006-942492

  日期：2006.8

  Indium(III) bromide and chloride efficiently catalysed the N-tert-butoxycarbonylation of amines with (Boc)2O at room temperature and under solvent-free conditions. Various aromatic, heteroaromatic and aliphatic amines were converted to N-tert-butylcarbamates in excellent yields in short times. Chiral amines, esters of α-amino acids and β-amino alcohols afforded optically pure N-t-Boc derivatives in high yields. The reactions were chemoselective and no competitive side reactions such as isocyanate, urea, and N,N-di-t-Boc formation were observed. Chemoselective conversion to N-tert-butylcarbamates took place with amino alcohols without any formation of oxazolidinones.

  溴化铟(III)和氯化铟(III)在室温下以及无溶剂条件下有效地催化胺类与(Boc)2O的N-叔丁氧羰基化反应。多种芳香、杂芳香和脂肪胺类在短时间内高效转化为N-叔丁基氨基甲酸酯。手性胺、α-氨基酸酯和β-氨基醇在较高产率下得到光学纯的N-t-Boc衍生物。反应具有化学选择性，未观察到异氰酸酯、脲和N,N-二-t-Boc形成等竞争性副反应。氨基醇也能进行化学选择性转化为N-叔丁基氨基甲酸酯，而不形成噁唑烷酮。
• HClO₄–SiO₂as a new, highly efficient, inexpensive and reusable catalyst for N-tert-butoxycarbonylation of amines
  作者：Asit K. Chakraborti、Sunay V. Chankeshwara

  DOI：10.1039/b605074c

  日期：——

  Perchloric acid adsorbed on silica-gel (HClO4–SiO2) was found to be a new, highly efficient, inexpensive and reusable catalyst for chemoselective N-tert-butoxycarbonylation of amines at room temperature and under solvent-free conditions.

  吸附在硅胶上的高氯酸（HClO4–SiO2）被发现是一种新的、高效、廉价且可重复使用的催化剂，可在室温和无溶剂条件下选择性地对胺进行N-特丁氧基碳酰化反应。
• Copper(II) tetrafluoroborate as a novel and highly efficient catalyst for N-tert-butoxycarbonylation of amines under solvent-free conditions at room temperature
  作者：Sunay V. Chankeshwara、Asit K. Chakraborti

  DOI：10.1016/j.tetlet.2005.12.044

  日期：2006.2

  Commercially available copper(II) tetrafluoroborate hydrate was found to be a highly efficient catalyst for chemoselective N-tert-butoxycarbonylation of amines with di-tert-butyl dicarbonate Under solvent-free conditions and at room temperature. Various aromatic airlines were protected as their N-tert-butyl carbamates in high yields and in short times. No competitive side reactions Such as isocyanate, urea, and N,N-di-t-Boc formation was observed. Chemoselective N-tert-butoxycarbonylation was achieved with Substrates hearing OH and SH groups. Chiral alpha-amino acid esters afforded the corresponding N-t-Boc derivatives in excellent yields. (c) 2005 Elsevier Ltd. All rights reserved.
• Catalyst-Free Chemoselective <i>N</i>-<i>tert</i>-Butyloxycarbonylation of Amines in Water
  作者：Sunay V. Chankeshwara、Asit K. Chakraborti

  DOI：10.1021/ol0611191

  日期：2006.7.1

  Catalyst-free N-tert-butyloxycarbonylation of amines in water is reported. The N-t-Boc derivatives were formed chemoselectively without any isocyanate, urea, N, N-di-t-Boc, and O/S-t-Boc as side products. Chiral amines, esters of alpha-amino acids, and beta-amino alcohol afforded optically pure N-t-Boc derivatives. Amino alcohol and 2-aminophenol afforded the N-t-Boc derivative without oxazolidinone formation. Selectivity was observed during competition of aromatic amine vs aliphatic amine, amine vs amino acid ester, amine vs amino alcohol, and primary amine vs secondary amine.