8-cyanoalloxazine | 80172-39-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 蝶啶及其衍生物
• 英文名称: 8-cyanoalloxazine
• 英文别名: 2,4-Dioxo-1,2,3,4-tetrahydrobenzo[g]pteridine-8-carbonitrile；2,4-dioxo-1H-benzo[g]pteridine-8-carbonitrile
• CAS: 80172-39-0
• 化学式: C₁₁H₅N₅O₂
• 分子量: 239.193
• InChiKey: IVEZWEYXGZXWKU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  108
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  5,5-二羟基六氢嘧啶-2,4,6-三酮 、 3,4-二氨基苯甲腈 在 硼酸 、 溶剂黄146 作用下， 反应 1.5h， 生成 7-cyanoalloxazine 、 8-cyanoalloxazine
  参考文献：
  名称：

  电子缺乏的四氧杂嗪鎓盐：轻度和化学选择性过氧化氢过氧化氢的高效有机催化剂

  摘要：

  AbstractA series of substituted alloxazinium perchlorates has been prepared and tested as catalysts for the oxidation of sulfides to sulfoxides with hydrogen peroxide. The logarithms of the observed rate constants of thioanisole oxidation correlate with the Hammett σ constants of the substituents on the alloxazinium catalysts, as well as with their reduction potentials E0′ and their pKR+ values, representing the alloxazinium salt/pseudobase equilibrium. The stronger the electron‐withdrawing substituent, the more efficient is the alloxazinium catalyst. The alloxazinium salts with a cyano or trifluoromethyl group in position 8 proved to be the most efficient, operating at room temperature at small loadings, down to 0.1 mol%, achieving turnover number values of up to 640 and acceleration by a factor of 350 relative to the non‐catalyzed oxidation. The 8‐cyanoalloxazinium perchlorate was evaluated as the best catalyst; however, due to its relatively good accessibility, the 8‐(trifluoromethyl)alloxazinium perchlorate seems to be the catalyst of choice for sulfoxidations with hydrogen peroxide. It was successfully tested for the sulfoxidation of a series of aliphatic and aromatic sulfides on a preparative scale. It produced the corresponding sulfoxides in quantitative conversions and with high isolated yields (87–98%). No over‐oxidation to sulfone was ever observed.magnified image

  DOI：

  10.1002/adsc.201300617

文献信息

• Electron-Deficient Alloxazinium Salts: Efficient Organocatalysts of Mild and Chemoselective Sulfoxidations with Hydrogen Peroxide
  作者：Petra Ménová、Hana Dvořáková、Václav Eigner、Jiří Ludvík、Radek Cibulka

  DOI：10.1002/adsc.201300617

  日期：2013.11.25

  AbstractA series of substituted alloxazinium perchlorates has been prepared and tested as catalysts for the oxidation of sulfides to sulfoxides with hydrogen peroxide. The logarithms of the observed rate constants of thioanisole oxidation correlate with the Hammett σ constants of the substituents on the alloxazinium catalysts, as well as with their reduction potentials E0′ and their pKR+ values, representing the alloxazinium salt/pseudobase equilibrium. The stronger the electron‐withdrawing substituent, the more efficient is the alloxazinium catalyst. The alloxazinium salts with a cyano or trifluoromethyl group in position 8 proved to be the most efficient, operating at room temperature at small loadings, down to 0.1 mol%, achieving turnover number values of up to 640 and acceleration by a factor of 350 relative to the non‐catalyzed oxidation. The 8‐cyanoalloxazinium perchlorate was evaluated as the best catalyst; however, due to its relatively good accessibility, the 8‐(trifluoromethyl)alloxazinium perchlorate seems to be the catalyst of choice for sulfoxidations with hydrogen peroxide. It was successfully tested for the sulfoxidation of a series of aliphatic and aromatic sulfides on a preparative scale. It produced the corresponding sulfoxides in quantitative conversions and with high isolated yields (87–98%). No over‐oxidation to sulfone was ever observed.magnified image