1,3-dimethyllumichrome | 14684-48-1

• 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: 1,3-dimethyllumichrome
• 英文别名: 7,8-dimethyl-1,3-dimethylalloxazine；1,3,7,8-tetramethylalloxazine；1,3-dimethyl-lumichrome；1,3-diMe lumichrome；1,3,7,8-tetramethyl-1H-benzo[g]pteridine-2,4-dione；1,3,7,8-Tetramethyl-1H-benzo[g]pteridin-2,4-dion；Benzo[g]pteridine-2,4(1H,3H)-dione, 1,3,7,8-tetramethyl-；1,3,7,8-tetramethylbenzo[g]pteridine-2,4-dione
• CAS: 14684-48-1
• 化学式: C₁₄H₁₄N₄O₂
• 分子量: 270.291
• InChiKey: YWHPEKPXGLQMJO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  66.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,3-dimethyllumichrome 在 盐酸 、 palladium 10% on activated carbon 、 氢气 作用下， 以 乙醇 、 水 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 48.0h， 生成 7,8-dimethyl-1,3-dimethyl-5-ethyl-4a-hydroperoxyalloxazine
  参考文献：
  名称：

  Organocatalytic Dakin Oxidation by Nucleophilic Flavin Catalysts

  摘要：

  Flavin catalysts perform the first organocatalytic Dakin oxidation of electron-rich arylaldehydes to phenols under mild, basic conditions. Catechols are readily prepared, and the oxidation of 2-hydroxyacetophenone was achieved. Aerobic oxidation is displayed in the presence of Zn(0) as a reducing agent. This reactivity broadens the scope of biomimetic flavin catalysis in the realm of nucleophilic oxidations, providing a framework for mechanistic investigations for related oxidations, such as the Baeyer-Villiger oxidation and Weitz-Scheffer epoxidation.

  DOI：

  10.1021/ol3010326
• 作为产物：
  描述：

  4，5-二甲-2-硝基苯胺 在 盐酸 、 tin(ll) chloride 作用下， 生成 1,3-dimethyllumichrome
  参考文献：
  名称：

  Kuhn; Rudy, Chemische Berichte, 1934, vol. 67, p. 1826,1828

  摘要：

  DOI：

文献信息

• Flavin–iodine coupled organocatalysis for the aerobic oxidative direct sulfenylation of indoles with thiols under mild conditions
  作者：Ryoma Ohkado、Tatsuro Ishikawa、Hiroki Iida

  DOI：10.1039/c8gc00117k

  日期：——

  A unique coupled redox organocatalysis system using flavin and iodine catalysts efficiently promoted the metal-free aerobic oxidative direct sulfenylation of indoles with thiols at ambient temperature without any sacrificial reagents, except environmentally benign molecular oxygen. Biomimetic flavin catalysis plays multiple roles in aerobic oxidative transformations, not only regenerating I2 from in

  使用黄素和碘催化剂的独特偶联氧化还原有机催化系统可在环境温度下有效地促进吲哚类化合物与金属的无金属有氧氧化直接亚磺酰化反应，而无需使用任何牺牲试剂，除了对环境有益的分子氧。仿生催化黄素起着有氧氧化转换多个角色，不仅再生我2从原位生成的I - ，也将硫醇成二硫化物。
• Comparison of riboflavin-derived flavinium salts applied to catalytic H₂O₂oxidations
  作者：Takuya Sakai、Takuma Kumoi、Tatsuro Ishikawa、Takahiro Nitta、Hiroki Iida

  DOI：10.1039/c8ob00856f

  日期：——

  properties, and their catalytic activity in H2O2 oxidations of sulfide, tertiary amine, and cyclobutanone. Reflecting the difference between the π-conjugated ring structures, the flavinium salts displayed very different redox properties, with reduction potentials in the order of: 5-ethylisoalloxazinium > 5-ethylalloxazinium > 1,10-ethylene-bridged alloxazinium. A comparison of their catalytic activity revealed

  从市场上可买到的核黄素制备了一系列黄酮盐，5-乙基异all杂嗪鎓，5-乙基ethyl杂嗪鎓和1,10-乙烯桥联的四氧嘧啶鎓三氟甲磺酸盐。这项研究提出了它们的光学和氧化还原特性，以及它们在H 2 O 2中的催化活性之间的比较。硫化物，叔胺和环丁酮的氧化。反映了π-共轭环结构之间的差异，黄酮盐显示出非常不同的氧化还原性质，其还原电位的顺序为：5-乙基异四氮杂鎓> 5-乙基四氧杂鎓> 1，10-乙烯桥联的四氧杂嗪鎓。比较它们的催化活性表明，三氟甲磺酸5-乙基异恶唑嗪能特异性氧化硫化物和环丁酮，而三氟甲磺酸5-乙基异恶唑嗪能平稳地氧化叔胺。1,10-桥联的三氟甲磺酸铝恶唑鎓盐，可以很容易地从核黄素中大量获得，对硫化物和环丁酮的H 2 O 2氧化表现出中等的催化活性。
• Turning a riboflavin-binding protein into a self-sufficient monooxygenase by cofactor redesign
  作者：Gonzalo de Gonzalo、Christian Smit、Jianfeng Jin、Adriaan J. Minnaard、Marco W. Fraaije

  DOI：10.1039/c1cc14039f

  日期：——

  By cofactor redesign, self-sufficient monooxygenases could be prepared. Tight binding of N-alkylated flavins to riboflavin-binding protein results in the creation of artificial flavoenzymes capable of H2O2-driven enantioselective sulfoxidations. By altering the flavin structure, opposite enantioselectivities could be achieved, in accordance with the binding mode predicted by in silicoflavin-protein docking of the unnatural flavin cofactors. The study shows that cofactor redesign is a viable approach to create artificial flavoenzymes with unprecedented activities.

  通过辅因子重设计，可以制备自给自足的单氧化酶。N-烷基化黄素与核黄素结合蛋白的紧密结合会产生能够驱动过氧化氢进行对映选择性亚磺氧化反应的人工黄酶。通过改变黄素结构，可以实现相反的对映选择性，这与通过计算机模拟的不天然黄素辅因子的结合模式预测一致。该研究表明，辅因子重设计是一种创造具有前所未有活性的人工黄酶的可行方法。
• Insight into the catalytic activity of alloxazinium and isoalloxazinium salts in the oxidations of sulfides and amines with hydrogen peroxide
  作者：Petra Ménová、Radek Cibulka

  DOI：10.1016/j.molcata.2012.07.012

  日期：2012.11

  amount of an acid. On the other hand, only alloxazine derivatives, i.e. dihydroalloxazines 1-H2 and their methoxy adducts 1-OCH3 or alloxazinium salts 1 can be used as catalysts for the oxidation of tertiary amines, as the catalytic activity of isoalloxazinium salts 1 and their derivatives is inhibited under basic conditions. The different reactivity of the alloxazinium and isoalloxazinium catalysts

  除了已知的有机催化剂二氢-5-乙基四氮杂嗪1-H 2和5-乙基异四氮杂嗪鎓盐2外，还显示了四氮杂嗪和异四恶嗪（黄素）的其他衍生物可以用过氧化氢高效催化硫化物氧化为亚砜。在别恶嗪系列中，也可以使用C 4a-甲氧基加合物1-OCH 3或5-乙基别拉嗪鎓盐1，但是后者仅在碱存在下作为助催化剂。在异恶嗪系列中，C4a-羟基加合物2-OH或二氢型2-H 2也可以仅在催化量的酸的存在下使用该化合物。另一方面，只有异恶嗪衍生物1，H 2及其甲氧基加合物1-OCH 3或异恶嗪鎓盐1，可以用作氧化叔胺的催化剂，因为异恶嗪鎓盐1及其衍生物具有催化活性。在基本条件下被抑制。由于它们与亲核试剂反应的能力显着不同，因此，四氧嘧啶鎓和异四氧嘧啶鎓催化剂的反应性不同是催化速率确定步骤改变的结果。
• 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