5-ethyl-3-methyllumiflavinium perchlorate

• 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: 5-ethyl-3-methyllumiflavinium perchlorate
• 英文别名: 5-ethyl-3,7,8,10-tetramethylisoalloxazinium perchlorate；3-methyl-5-ethyllumiflavinium perchlorate；5-Ethyl-3-methyl-lumiflaviniumperchlorate；5-ethyl-3,7,8,10-tetramethylbenzo[g]pteridin-5-ium-2,4-dione;perchlorate
• 化学式: C₁₆H₁₉N₄O₂*ClO₄
• 分子量: 398.803
• InChiKey: FPUCZWVNILWNEG-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -4.09
• 重原子数：
  27
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  130
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5-ethyl-3-methyllumiflavinium perchlorate 以 乙腈 为溶剂， 生成 1,5-dihydro-5-ethyl-3-methyllumiflavin
  参考文献：
  名称：

  Mechanistic and synthetic aspects of amine oxidations promoted by 3-methyl-5-ethyllumiflavinium perchlorate

  摘要：

  Preparative and kinetic aspects of the chemistry of 3-methyl-5-ethyllumiflavinium perchlorate (1) with primary and secondary amines have been investigated. Reactions of 1 with primary and secondary amines leads to rapid production of modestly stable C4a-adducts. The rates of these processes, determined by stopped-flow kinetic methods, parallel amine nucleophilicities. The C4a-adducts undergo benzylamine promoted elimination reactions to produce N-benzylaldimine products with fates that parallel reactivity profiles expected for E(2)-elimination processes. Finally, flavinium salt 1 serves as a catalyst for oxidations of primary and secondary amines under aerobic conditions. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)00206-8
• 作为产物：
  描述：

  光黃素 在 盐酸 、 palladium 10% on activated carbon 、 氢气 、 caesium carbonate 作用下， 以 乙醇 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 50.0h， 生成 5-ethyl-3-methyllumiflavinium perchlorate
  参考文献：
  名称：

  Flavin-Catalyzed Insertion of Oxygen into Rhenium–Methyl Bonds

  摘要：

  Flavins and related molecules catalyze organic Baeyer-Villiger reactions. Combined experimental and DFT studies indicate that these molecules also catalyze the insertion of oxygen into metal-carbon bonds through a Baeyer-Villiger-like transition state.

  DOI：

  10.1021/ja3054139
• 作为试剂：
  描述：

  芳樟醇 在 氧气 、 5-ethyl-3-methyllumiflavinium perchlorate 、 一水合肼 、 苯酚 作用下， 以 乙腈 为溶剂， 反应 5.0h， 以96%的产率得到二氢芳樟醇
  参考文献：
  名称：

  用合成黄素催化剂原位生成二亚胺使好氧还原烯烃

  摘要：

  通过用中性和阳离子合成黄素催化剂1和2对肼进行好氧氧化，可以有效地生成通用的还原剂二酰亚胺。该技术为有氧还原烯烃提供了一种方便，安全的方法，该方法是在O 2或空气中以1当量的肼进行的。高肼效率，简便安全的处理方法和独特的化学选择性已证明了其与传统的基于气体的方法相比具有综合优势。维生素B 2衍生物6由于具有很高的利用率和可回收性，因此可作为一种高度实用，坚固的催化剂。1 b的缔合体具有树枝状2,5-双（酰基氨基）吡啶15的化合物表现出空前的催化活性，当将更高级的树枝状大分子用作缔合催化剂的主体对时，芳烃和羟基烯烃的还原速度显着加快。在用树枝状聚合物催化剂对非芳族或非羟基烯烃进行类似处理时，观察到相反的阻滞作用。对照实验和动力学研究表明，这些催化反应包括由肼生成二酰亚胺的两个独立的厌氧和好氧过程。树枝状大分子对催化反应的正面和负面影响归因于肼和烯烃底物在缔合络合物催化剂的类酶反应腔中的特定包含。

  DOI：

  10.1002/chem.201003278

文献信息

• Mechanistic analysis of the 3-methyllumiflavin-promoted oxidative deamination of benzylamine. A potential model for monoamine oxidase catalysis
  作者：Jong Man Kim、Michael A. Bogdan、Patrick S. Mariano

  DOI：10.1021/ja00076a017

  日期：1993.11

  An investigation designed to probe flavin-promoted oxidative deaminations of amines is described. 3-Methyllumiflavin (3MLF) has been found to promote clean conversion of benzylamine to N-benzylbenzaldimine under acid (HCl or MgCl 2 ) catalyzed, thermal (80 o C) conditions. The reaction is subject to multiple turnover. Amine structure (1 o >2 o >3 o ) and α-electrofugal group leaving ability (TMS +

  描述了旨在探测黄素促进的胺氧化脱氨基的研究。已发现 3-甲基发光黄素 (3MLF) 在酸（HCl 或 MgCl 2 ）催化的热（80 o C）条件下促进苄胺向 N-苄基苯扎二亚胺的清洁转化。该反应受多重周转的影响。发现胺结构 (1 o >2 o >3 o ) 和 α-电离基团离开能力 (TMS + >H + ) 会影响反应性。此外，发现使用 PhCHDNH 2 为基态反应测量的内部 d-同位素效应为 4.3，该值与在几乎相同（20 o C 而不是 80 o C) 条件
• Synthesis and structural studies of flavin and alloxazine adducts with O-nucleophiles
  作者：Petra Ménová、Václav Eigner、Jan Čejka、Hana Dvořáková、Miloslav Šanda、Radek Cibulka

  DOI：10.1016/j.molstruc.2011.08.002

  日期：2011.10

  1a-OH, 1b-OH, and 2a-OMe, the crystal structures were determined by X-ray diffraction. Flavinium and alloxazinium salts are in rapid equilibria with their adducts in water or methanolic solutions without the presence of a base. It was found that the equilibrium constants for flavin adduct formation is higher by six orders of magnitude than those for alloxazine derivatives. The presence of the sp3 hybridized

  摘要 五种黄素 (isoalloxazine) 和 alloxazine 与 O-亲核试剂、5-ethyl-4a-hydroxy-3,7,8,10-tetramethyl-4a,5-dihydroisoalloxazine (1a-OH)、5-ethyl-4a-hydroxy-3,7,8,10-dihydroisoalloxazine (1a-OH) 的加合物-3,10-二甲基-4a,5-二氢异咯嗪 (1b-OH), 5-乙基-4a-甲氧基-3,10-二甲基-4a,5-二氢异恶嗪 (1b-OMe), 5-乙基-4a-羟基-1,3-二甲基-4a,5-二氢咯嗪 (2a-OH) 和 5-乙基-4a-甲氧基-1,3-二甲基-4a,5-二氢咯嗪 (2a-OMe) 由相应的盐制备，5 -乙基-3,7,8,10-四甲基异恶嗪鎓 (1a)、5-乙基-3,10-二甲基异恶嗪鎓 (1b) 和 5-乙基-1,3-二甲基异恶嗪鎓
• Anion effect of 5-ethylisoalloxazinium salts on flavin-catalyzed oxidations with H2O2
  作者：Hiroki Iida、Tatsuro Ishikawa、Keisuke Nomura、Shun-Ichi Murahashi

  DOI：10.1016/j.tetlet.2016.08.076

  日期：2016.10

  with an efficient catalytic activity. In fact, the isoalloxazinium triflate 1b is an excellent organocatalyst for the chemoselective oxidations of a sulfide to a sulfoxide, Bayer–Villiger reaction of a cyclobutanone to a γ-butyrolactone, Dakin reaction of an arylaldehyde to a phenol, and oxidation of an aldehyde to a carboxylic acid using aq H2O2 as a terminal oxidant under mild conditions.

  为了设计更实用，更安全的可替代传统高氯酸盐的黄酮盐催化剂，研究了5-乙基异all嗪鎓盐对硫化氢与H 2 O 2氧化的阴离子活性。发现形成更强共轭酸的阴离子可加速催化的硫氧化反应。核黄素衍生的三氟甲磺酸异别恶嗪鎓盐被选为易于获得的黄素，具有有效的催化活性。实际上，异氟甲磺酸三氟甲磺酸盐1b是出色的有机催化剂，可用于硫化物化学选择性氧化为亚砜，环丁酮向γ-丁内酯的Bayer-Villiger反应，芳基醛向苯酚的Dakin反应以及使用H 2 H 2将醛氧化为羧酸O 2在温和条件下作为末端氧化剂。
• Catalytic effect of alloxazinium and isoalloxazinium salts on oxidation of sulfides with hydrogen peroxide in micellar media
  作者：Radek Cibulka、Lenka Baxová、Hana Dvořáková、František Hampl、Petra Ménová、Viktor Mojr、Baptiste Plancq、Serkan Sayin

  DOI：10.1135/cccc2009030

  日期：——

  Three novel amphiphilic alloxazinium salts were prepared: 3-dodecyl-5-ethyl-7,8,10-trimethylisoalloxazinium perchlorate (1c), 1-dodecyl-5-ethyl-3-methylalloxazinium perchlorate (2b), and 3-dodecyl-5-ethyl-1-methylalloxazinium perchlorate (2c). Their catalytic activity in thioanisole (3) oxidation with hydrogen peroxide was investigated in micelles of sodium dodecylsulfate (SDS), hexadecyltrimethylammonium nitrate (CTANO₃) and Brij 35. Reaction rates were strongly dependent on the catalyst structure, on the type of micelles, and on pH value. Alloxazinium salts 2 were more effective catalysts than isoalloxazinium salts 1. Due to the contribution of micellar catalysis, the v_cat/v₀ ratio of the catalyzed and non-catalyzed reaction rates was almost 80 with salt 2b solubilized in CTANO₃ micelles. Nevertheless, the highest acceleration was observed with non-amphiphilic 5-ethyl-1,3-dimethylalloxazinium perchlorate (2a) in CTANO₃ micelles (v_cat/v₀ = 134). In this case, salt 2a presumably acts as a phase-transfer catalyst bringing hydrogen peroxide from the aqueous phase into the micelle interior. Synthetic applicability of the investigated catalytic systems was verified on semi-preparative scale.

  制备了三种新型的两性离子氧杂环盐：3-十二烷基-5-乙基-7,8,10-三甲基异氧杂环盐酸盐（1c）、1-十二烷基-5-乙基-3-甲基氧杂环盐酸盐（2b）和3-十二烷基-5-乙基-1-甲基氧杂环盐酸盐（2c）。在十二烷基硫酸钠（SDS）、十六烷基三甲基溴化铵硝酸盐（CTANO₃）和Brij 35的胶束中，研究了它们在过氧化氢氧化硫苯的催化活性。反应速率强烈依赖于催化剂结构、胶束类型和pH值。氧杂环盐2比异氧杂环盐1更有效的催化剂。由于胶束催化的贡献，v_cat/v₀催化和非催化反应速率的比值几乎为80，当盐2b溶解在CTANO₃胶束中时。然而，在CTANO₃胶束中，非两性离子5-乙基-1,3-二甲基氧杂环盐酸盐（2a）表现出最高的加速作用（v_cat/v₀=134）。在这种情况下，盐2a可能作为相转移催化剂，将过氧化氢从水相带入胶束内部。研究的催化系统的合成适用性在半制备规模上得到验证。
• Aromatic hydroxylations by flavins: evidence on direct attack of phenylalanine by flavin radical species.
  作者：Humphrey I.X. Mager、Shiao-Chun Tu

  DOI：10.1016/s0040-4020(01)80687-6

  日期：1994.5

  the protonated form of a flavinoxy radical 3a,b, a product of a homolysis of the OO bond in a dihydroflavin hydroperoxide. As an alternative to the homolysis mentioned, the one-electron oxidation of 1 provides the principle to develop a new hydroxylating model system that does not require a dihydroflavin hydroperoxide as a starting compound. Using phenylalanine as a test substrate, the anaerobic formation

  在0.05-12.0 N的酸性溶液中，相应的黄酮阳离子4自发地产生了5-乙基-3-甲基lumlavlavosemiquinone 5（和/或5H +）。将温度从20°C升高至50°C，可显着提高反应速率，而收率5（5H +）则无明显变化。的自发单电子还原4需要具有的单电子氧化偶合另一黄素如5-乙基-4-一个羟基-3-甲基-4-一个，5- dihydroflavin pseudobase 1。后者与4处于平衡状态，可以被氧化生成瞬态5-乙基-4一-羟基-3- methyllumiflavin自由基2。这是黄烷氧基自由基3a ，b的质子化形式，是二氢黄素氢过氧化物中O = O键均质化的产物。作为提到的均质方法的替代方法，单电子氧化1提供了开发新的羟基化模型系统的原理，该系统不需要二氢黄素氢过氧化物作为起始化合物。使用苯丙氨酸作为测试基板，所述厌氧酪氨酸的形成及其ö -和米建立了-羟基苯丙氨酸异