D,L-3,6-diphenylpiperazine-2,5-diphenylpiperazine-2,5-dione

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪烷类
• 英文名称: D,L-3,6-diphenylpiperazine-2,5-diphenylpiperazine-2,5-dione
• 英文别名: (3S,6R)-3,6-diphenylpiperazine-2,5-dione；(3R,6S)-3,6-diphenylpiperazine-2,5-dione
• 化学式: C₁₆H₁₄N₂O₂
• 分子量: 266.299
• InChiKey: BMGJGWGTAAJISM-OKILXGFUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  58.2
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (3S,6S)-3,6-双(苯甲基)-2,5-哌嗪二酮 在 sodium isopropylate 作用下， 以 异丙醇 为溶剂， 反应 0.5h， 生成 D,L-3,6-diphenylpiperazine-2,5-diphenylpiperazine-2,5-dione
  参考文献：
  名称：

  15N NMR spectroscopy. 19—spectroscopic characterization of cyclodipeptides (2,5-dioxopiperazines)

  摘要：

  AbstractVarious cyclodipeptides containing glycine, alanine, leucine, valine, phenylalanine, phenylglycine and sarcosine units were synthesized by cyclization of dipeptide pentachlorophenyl esters. The 13C and natural abundance 15N NMR spectra of these heterocycles were measured in trifluoroacetic acid and compared with the spectra of the corresponding amino acids and polypeptides. The 13C NMR carbonyl signals of all cyclodipeptides show a 1.5–4.0 ppm upfield shift relative to the corresponding polypeptides. The 15N NMR signals show no such consistent relationship. The substituent effects and the neighbouring residue effects observed in the 15N NMR spectra of the cyclodipeptides are different from those of polypeptides, while the one bond NH coupling constant of cis and trans amide groups was almost identical. The nitrogen and the carbonyl signal of the Gly units in cyclo‐Gly‐Phe show an extraordinary downfield shift, reflecting the interaction of the phenyl group with the 2,5‐dioxopiperazine ring.

  DOI：

  10.1002/mrc.1270130111

文献信息

• Heterogeneous Catalytic Hydrogenation of Chiral Amino Acid Methyl Esters to Amino Alcohols with Retention of Configuration Over Mg-Modified Cu/ZnO/Al2O3 Catalyst
  作者：Bing Zhan、Shuangshuang Zhang、Jun Yu、Xiuzheng Xiao、Xiaoming Guo、Dongsen Mao、Guanzhong Lu

  DOI：10.1007/s10562-017-2116-3

  日期：2017.8

  hydrogenation of amino acid methyl esters to chiral amino alcohols is an important and fascinating process. The CuZn0.3Mg0.1AlOx catalyst for the synthesis of chiral amino alcohols was prepared by the fractional co-precipitation method in the 50–100 g scale. The effect of the reduction gas on the catalytic activity, and the effects of the reaction conditions (R-p-m/Cat, temperature, reaction time, H2 pressure

  将氨基酸甲酯选择性氢化为手性氨基醇是一个重要且引人入胜的过程。用于合成手性氨基醇的 CuZn0.3Mg0.1AlOx 催化剂是通过分级共沉淀法以 50-100 g 的规模制备的。考察了还原气体对催化活性的影响，以及反应条件（Rpm/Cat、温度、反应时间、H2压力和溶剂）对R-苯基甘氨酸甲酯催化加氢反应（记为Rpm）的影响. 当 Rpm 在乙醇溶剂中在 5 MPa 的 H2 和 80°C 下在该被 H2 还原的催化剂上加氢 10 小时时，获得了 87.7% 的产率，具有~100% ee 值的 R-苯基甘氨醇，其反应活化能（Ea ) 为 36.7 kJ/mol。重复使用16次后，其催化活性几乎没有变化。
• Penicillin acylase-catalyzed peptide synthesis: a chemo-enzymatic route to stereoisomers of 3,6-diphenylpiperazine-2,5-dione
  作者：Luuk M van Langen、Fred van Rantwijk、Vytas K Švedas、Roger A Sheldon

  DOI：10.1016/s0957-4166(00)00027-6

  日期：2000.3

  Chiral dipeptides of phenylglycine were synthesized using immobilized Escherichia coli penicillin acylase. The high selectivity of penicillin acylase for L-amino acids as the nucleophile resulted in the efficient acylation of L-phenylglycine by D-phenylglycine amide at pH 9.7 to give D-phenylglycyl-L-phenylglycine in 69% yield. No isomers or tripeptides were formed. The low enantiospecificity of the enzyme for the acyl donor provided the possibility of preparing the corresponding L,L-dipeptides, starting from L-phenylglycine methyl ester as both donor and acceptor at pH 7.5, resulting in a 63% yield of L-phenylglycyl-Lphenylglycine methyl ester. The product precipitated under the reaction conditions; this effectively prevented the formation of oligomers as well as chemical transformation of the product.The dipeptide esters of phenylglycine easily cyclized to diketopiperazines in aqueous methanol. L-Pheny-glycyl-L-phenylglycine methyl ester formed L,L-3,6-diphenylpiperazine-2,5-dione (cis); the achiral trans isomer was obtained from D-phenylglycyl-L-phenylglycine methyl ester. (C) 2000 Elsevier Science Ltd. All rights reserved.
• 15N NMR spectroscopy. 19—spectroscopic characterization of cyclodipeptides (2,5-dioxopiperazines)
  作者：Hans R. Kricheldorf

  DOI：10.1002/mrc.1270130111

  日期：1980.1

  AbstractVarious cyclodipeptides containing glycine, alanine, leucine, valine, phenylalanine, phenylglycine and sarcosine units were synthesized by cyclization of dipeptide pentachlorophenyl esters. The 13C and natural abundance 15N NMR spectra of these heterocycles were measured in trifluoroacetic acid and compared with the spectra of the corresponding amino acids and polypeptides. The 13C NMR carbonyl signals of all cyclodipeptides show a 1.5–4.0 ppm upfield shift relative to the corresponding polypeptides. The 15N NMR signals show no such consistent relationship. The substituent effects and the neighbouring residue effects observed in the 15N NMR spectra of the cyclodipeptides are different from those of polypeptides, while the one bond NH coupling constant of cis and trans amide groups was almost identical. The nitrogen and the carbonyl signal of the Gly units in cyclo‐Gly‐Phe show an extraordinary downfield shift, reflecting the interaction of the phenyl group with the 2,5‐dioxopiperazine ring.