6,7-dimethyl-3-(trifluoromethyl)-2(1H)-quinoxalinone | 143309-78-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂萘
• 英文名称: 6,7-dimethyl-3-(trifluoromethyl)-2(1H)-quinoxalinone
• 英文别名: 6,7-dimethyl-3-(trifluoromethyl)quinoxalin-2(1H)-one；3-(Trifluoromethyl)-6,7-dimethylquinoxaline-2(1H)-one；6,7-dimethyl-3-(trifluoromethyl)-1H-quinoxalin-2-one
• CAS: 143309-78-8
• 化学式: C₁₁H₉F₃N₂O
• mdl: MFCD25949543
• 分子量: 242.2
• InChiKey: XGZDIJVLBIFYPB-UHFFFAOYSA-N

物化性质

• 密度：
  1.41±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  41.5
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  6,7-dimethyl-3-(trifluoromethyl)-2(1H)-quinoxalinone 在 5,5’-bis(diphenylphosphino)-4,4’-bi-1,3-benzodioxole 、 palladium (II) trifluoroacetate 、 氢气 作用下， 以 丙酮 为溶剂， 20.0 ℃ 、4.14 MPa 条件下， 反应 48.0h， 以89%的产率得到
  参考文献：
  名称：

  一种钯催化不对称氢化合成手性3-三氟甲基- 3,4-二氢喹喔啉酮的方法

  摘要：

  一种钯催化不对称氢化合成手性3‑三氟甲基‑3,4‑二氢喹喔啉酮的方法，催化体系为钯的手性双磷配合物，反应条件为：温度：0‑80℃；溶剂：2,2,2‑三氟乙醇或六氟异丙醇；压力：100‑1000psi；底物和催化剂的比例是33/l；用到的金属前体：三氟醋酸钯；用到的手性配体：手性双磷配体；催化剂的制备方法为：把钯的金属前体和手性双磷配体在丙酮中室温搅拌，然后真空浓缩得到催化剂。对含三氟甲基的喹喔啉酮氢化能得到相应的手性含三氟甲基的二氢喹喔啉酮，其对映体过量可达到99％。本发明操作简便实用，对映选择性高，产率好，且反应具有绿色原子经济性，对环境友好。

  公开号：

  CN111484459B
• 作为产物：
  描述：

  六氟环氧丙烷 、 4，5-二甲基-1，2-苯二胺 在 碳酸氢钠 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 12.0h， 以96%的产率得到6,7-dimethyl-3-(trifluoromethyl)-2(1H)-quinoxalinone
  参考文献：
  名称：

  Fluorine-19 NMR studies on the mechanism of riboflavin synthase. Synthesis of 6-(trifluoromethyl)-7-oxo-8-(D-ribityl)lumazine and 6-(trifluoromethyl)-7-methyl-8-(D-ribityl)lumazine

  摘要：

  The reactions of hexafluoropropene oxide (19), methyl trifluoropyruvate (21), and 1,1,1-trifluorobutane-2,3-dione (45) with a series of ortho diamines were investigated as an approach to the synthesis of trifluoromethyl-substituted quinoxalinones and lumazines. 6-(Trifluoromethyl)-7-oxo-8-(D-ribityl)lumazine (11) was synthesized by reaction of methyl trifluoropyruvate (21) with 5-amino-6-(D-ribitylamino)-2,4(1H,3H)-pyrimidinedione (3) hydrochloride and utilized as a F-19 NMR probe of the light riboflavin synthase of Bacillus subtilis. The fluorolumazine 11 was found to be an inhibitor of the enzyme with an inhibition constant K(I) = 55 muM. Equilibrium dialysis experiments indicated the binding of six molecules of 11 per enzyme molecule, corresponding to one molecule bound at each of the three donor and three acceptor sites of the enzyme. The apparent dissociation constants K(D) were approximately 4 and 112 muM. The enzyme-bound ligand gave rise to several broad F-19 NMR signals which were shifted to low field. The bound ligand 11 could be displaced from the enzyme by the enzyme product, riboflavin (2), and the product analog, 5-nitroso-6-(ribitylamino)-2,4(1H,3H)-pyrimidinedione (56). 6-(Trifluoromethyl)-7-methyl-8-(D-ribityl)lumazine (13) was synthesized by reaction of the hydrochloride salt of 3 with 1,1,1-trifluorobutane-2,3-dione (45). Three molecules of 13 can be bound relatively tightly per mole of riboflavin synthase, i.e., one ligand molecule per protein subunit. The inhibition constant K(I) was determined to be 75 muM, while dissociation constants of 17 and 70 muM were determined by equilibrium dialysis and F-19 NMR, respectively. The bound ligand 13 could also be displaced by riboflavin and product analog 56. A scheme for the catalytic cycle of riboflavin synthase is proposed.

  DOI：

  10.1021/jo00047a015

文献信息

• Revisiting the Hinsberg Reaction: Facile and Expeditious Synthesis of 3-Substituted Quinoxalin-2(1H)-ones under Catalyst-Free Conditions in Water
  作者：Sabbavarapu Narayana Murthy、Bandaru Madhav、Yadavalli Venkata Durga Nageswar

  DOI：10.1002/hlca.200900358

  日期：——

  Substituted benzene‐1,2‐diamine reacted with various α‐keto esters at 50° under mild conditions for 15 min using H2O as reaction medium, providing a variety of 3‐substituted quinoxalinone derivatives in excellent yields. The reaction was instantaneous, and products were isolated by simple filtration.

  以H 2 O为反应介质，取代的1,2-二胺与各种α-酮酯在50°下于温和的条件下反应15分钟，从而以优异的收率提供了各种3-取代的喹喔啉酮衍生物。该反应是瞬时的，并且通过简单过滤分离产物。
• Fluorine-19 NMR studies on the mechanism of riboflavin synthase. Synthesis of 6-(trifluoromethyl)-7-oxo-8-(D-ribityl)lumazine and 6-(trifluoromethyl)-7-methyl-8-(D-ribityl)lumazine
  作者：Mark Cushman、Hemantkumar H. Patel、Johannes Scheuring、Adelbert Bacher

  DOI：10.1021/jo00047a015

  日期：1992.10

  The reactions of hexafluoropropene oxide (19), methyl trifluoropyruvate (21), and 1,1,1-trifluorobutane-2,3-dione (45) with a series of ortho diamines were investigated as an approach to the synthesis of trifluoromethyl-substituted quinoxalinones and lumazines. 6-(Trifluoromethyl)-7-oxo-8-(D-ribityl)lumazine (11) was synthesized by reaction of methyl trifluoropyruvate (21) with 5-amino-6-(D-ribitylamino)-2,4(1H,3H)-pyrimidinedione (3) hydrochloride and utilized as a F-19 NMR probe of the light riboflavin synthase of Bacillus subtilis. The fluorolumazine 11 was found to be an inhibitor of the enzyme with an inhibition constant K(I) = 55 muM. Equilibrium dialysis experiments indicated the binding of six molecules of 11 per enzyme molecule, corresponding to one molecule bound at each of the three donor and three acceptor sites of the enzyme. The apparent dissociation constants K(D) were approximately 4 and 112 muM. The enzyme-bound ligand gave rise to several broad F-19 NMR signals which were shifted to low field. The bound ligand 11 could be displaced from the enzyme by the enzyme product, riboflavin (2), and the product analog, 5-nitroso-6-(ribitylamino)-2,4(1H,3H)-pyrimidinedione (56). 6-(Trifluoromethyl)-7-methyl-8-(D-ribityl)lumazine (13) was synthesized by reaction of the hydrochloride salt of 3 with 1,1,1-trifluorobutane-2,3-dione (45). Three molecules of 13 can be bound relatively tightly per mole of riboflavin synthase, i.e., one ligand molecule per protein subunit. The inhibition constant K(I) was determined to be 75 muM, while dissociation constants of 17 and 70 muM were determined by equilibrium dialysis and F-19 NMR, respectively. The bound ligand 13 could also be displaced by riboflavin and product analog 56. A scheme for the catalytic cycle of riboflavin synthase is proposed.
• 一种钯催化不对称氢化合成手性3-三氟甲基- 3,4-二氢喹喔啉酮的方法
  申请人：中国科学院大连化学物理研究所

  公开号：CN111484459B

  公开（公告）日：2021-11-02

  一种钯催化不对称氢化合成手性3‑三氟甲基‑3,4‑二氢喹喔啉酮的方法，催化体系为钯的手性双磷配合物，反应条件为：温度：0‑80℃；溶剂：2,2,2‑三氟乙醇或六氟异丙醇；压力：100‑1000psi；底物和催化剂的比例是33/l；用到的金属前体：三氟醋酸钯；用到的手性配体：手性双磷配体；催化剂的制备方法为：把钯的金属前体和手性双磷配体在丙酮中室温搅拌，然后真空浓缩得到催化剂。对含三氟甲基的喹喔啉酮氢化能得到相应的手性含三氟甲基的二氢喹喔啉酮，其对映体过量可达到99％。本发明操作简便实用，对映选择性高，产率好，且反应具有绿色原子经济性，对环境友好。