6-methyl-1-hydroxybenzotriazole | 26198-26-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并三唑类
• 英文名称: 6-methyl-1-hydroxybenzotriazole
• 英文别名: 6-methyl-1H-benzo[d][1,2,3]triazol-1-ol；1-Hydroxy-6-methylbenzotriazole
• CAS: 26198-26-5
• 化学式: C₇H₇N₃O
• 分子量: 149.152
• InChiKey: PEFBAFXTCWVHCL-UHFFFAOYSA-N

物化性质

• 熔点：
  178-179 °C
• 沸点：
  350.7±35.0 °C(Predicted)
• 密度：
  1.42±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  50.9
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  6-methyl-1-hydroxybenzotriazole 在 三苯基膦氯金 、 silver trifluoromethanesulfonate 作用下， 以 1,4-二氧六环 、 1,2-二氯乙烷 为溶剂， 生成 4-hydroxy-1-(5-methyl-1H-benzo[d][1,2,3]triazol-4-yl)hexan-2-one
  参考文献：
  名称：

  Gold-Catalyzed Addition of N-Hydroxy Heterocycles to Alkynes and Subsequent 3,3-Sigmatropic Rearrangement

  摘要：

  Gold-catalyzed intermolecular addition of hydroxybenzotriazole derivatives to alkynes at room temperature, gives vinyl ethers 3 in high yields and with excellent regioselectivity. Unlike many other vinyl ethers, 3 can easily be purified by regular silica-gel chromatography. On heating, 3,3-sigmatropic rearrangement of 3 gives access to highly functionalized benzotriazoles. This two-step sequence represents an efficient oxygen transfer protocol which incorporates a nucleophilic oxygen atom Into an alkyne group. Reaction of 3 with an electrophilic fluorinating reagent (Selectfluor) gives a fluorinated ketone regioselectively and in high yield.

  DOI：

  10.1021/ol4000789
• 作为产物：
  描述：

  3-氯-4-硝基甲苯 在 一水合肼 作用下， 以 乙醇 为溶剂， 反应 20.0h， 生成 6-methyl-1-hydroxybenzotriazole
  参考文献：
  名称：

  通过铜介导的CN键偶联反应合成1-乙烯基/芳基苯并三唑3-氧化物

  摘要：

  1-乙烯基的有效合成/ arylbenzotriazole 3氧化物通过的铜促进的偶联Ñ与链烯基-或芳基硼酸报道-hydroxybenzotriazoles。该策略具有温和的反应条件，良好的官能团耐受性，广泛的底物范围以及将苯并三唑N-氧化物部分快速引入分子的特点。密度泛函理论计算表明，有利的N耦合产物的形成取决于动力学上更有利的C–N键形成途径。

  DOI：

  10.1002/adsc.201700462
• 作为试剂：
  描述：

  1-(3,4-二甲氧基苯基)-2-苯氧基-1-乙醇 在 Trametes villosa (viz. Poliporus pinsitus) laccase 、 氧气 、 6-methyl-1-hydroxybenzotriazole 作用下， 以 1,4-二氧六环 为溶剂， 反应 16.0h， 以31%的产率得到1-(3,4-二甲氧基苯基)-2-苯氧基-1-乙酮
  参考文献：
  名称：

  Comparing the catalytic efficiency of ring substituted 1-hydroxybenzotriazoles as laccase mediators

  摘要：

  A series of ring substituted 1-hydroxybenzotriazoles (6-X-HBTs) have been tested as mediators in the laccase-promoted oxidation of 4-methoxybenzyl alcohol, 3,4-dimethoxybenzyl alcohol, and the dimeric lignin model 1-(3,4-dimethoxyphenyl)-2-phenoxyethanol. The effect of the aryl substituents on the yields of oxidation products is remarkable. The catalytic mediation efficiency increases as the electron releasing (ER) properties of the substituent increases up to a maximum value for 6-CH3-HBT, which resulted a very efficient mediator. Both the oxidation of the 6-X-HBTs to the N-oxyl radicals (6-X-BTNO) by laccase and the hydrogen atom transfer (HAT) process from the benzylic C H to the 6-X-BTNO contribute to the overall reactivity. The former process is favored by ER substituents that lower the mediator redox potentials. On the other hand, ER substituents decrease the 6-X-BTNO reactivity in the HAT process due to a decrease in the NO-H BDE value, as assessed in this study through a radical equilibration technique. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2014.02.068

文献信息

• Importance of π-Stacking Interactions in the Hydrogen Atom Transfer Reactions from Activated Phenols to Short-Lived<i>N</i>-Oxyl Radicals
  作者：Marco Mazzonna、Massimo Bietti、Gino A. DiLabio、Osvaldo Lanzalunga、Michela Salamone

  DOI：10.1021/jo500789v

  日期：2014.6.6

  A kinetic study of the hydrogen atom transfer from activated phenols (2,6-dimethyl- and 2,6-di-tert-butyl-4-substituted phenols, 2,2,5,7,8-pentamethylchroman-6-ol, caffeic acid, and (+)-cathechin) to a series of N-oxyl radical (4-substituted phthalimide-N-oxyl radicals (4-X-PINO), 6-substituted benzotriazole-N-oxyl radicals (6-Y-BTNO), 3-quinazolin-4-one-N-oxyl radical (QONO), and 3-benzotriazin-4-one-N-oxyl

  活化酚（2,6-二甲基-和2,6-二叔丁基-4-取代的酚，2,2,5,7,8-五甲基苯并吡喃-6-ol，咖啡酸和（+）-儿茶素）形成一系列N-氧基（4-取代的邻苯二甲酰亚胺-N-氧基（4-X-PINO），6-取代的苯并三唑-N-氧基（6-Y- BTNO），3-喹唑啉-4-酮-N-氧基（QONO）和3-苯并三嗪-4-酮-N-氧基（BONO））是通过激光闪光光解法在CH 3 CN中进行的。观察到N-氧基自由基结构对氢转移速率常数（k H）有显着影响。k H值随N-羟胺的NO–H键解离能（BDE NO-H）的增加而单调增加。对动力学数据的分析以及理论计算的结果表明，这些反应是通过氢原子转移（HAT）机理进行的，其中N-氧基和酚式芳环采用π堆积排列。理论计算还表明，N-氧基自由基对在π堆积构象中发生的电荷转移具有明显的结构作用。k H的比较在这项研究中测得的值与先前报道的氢原子转移至枯基过氧自由基的那些值表明，6-CH
• Synthesis of <i>N</i>-(2-Hydroxyaryl)benzotriazoles via Metal-Free <i>O</i>-Arylation and N–O Bond Cleavage
  作者：Zhi-Xin Wang、Wei-Min Shi、Hong-Yan Bi、Xiao-Hua Li、Gui-Fa Su、Dong-Liang Mo

  DOI：10.1021/acs.joc.6b01390

  日期：2016.9.2

  metal-free method for synthesis of N-(2-hydroxyaryl)benzotriazoles via O-arylation of N-hydroxybenzotriazoles with readily available diaryliodonium salts and sequential N–O bond cleavage under mild conditions has been developed. The [3,3]-rearrangement of N–O bond cleavage could take place on the N instead of C atom. The reaction was compatible with diverse functional groups and a new type of P,N-ligand

  用于合成不含金属的方法ñ - （2-羟基芳基）苯并三唑经由ø的-arylation Ñ与容易获得的二芳基碘盐和温和的条件下连续N-O键裂解-hydroxybenzotriazoles已经研制成功。N–O键断裂的[3,3]重排可发生在N而不是C原子上。该反应与各种官能团相容，并且通过三个步骤合成了新型的P，N-配体。
• Mild and General Access to Diverse 1<i>H</i>-Benzotriazoles<i>via</i>Diboron-Mediated NOH Deoxygenation and Palladium- Catalyzed CC and CN Bond Formation
  作者：Venkateshwarlu Gurram、Hari K. Akula、Ramesh Garlapati、Narender Pottabathini、Mahesh K. Lakshman

  DOI：10.1002/adsc.201400889

  日期：2015.2.9

  diverse benzotriazoles. Herein, we demonstrate a new, broadly applicable method to diverse 1H-benzotriazoles via a mild diboron-reagent mediated deoxygenation of 1-hydroxy-1H-benzotriazoles. We have also evaluated sequential deoxygenation and Pd-mediated C-C and C-N bond formation as a one-pot process for further diversification of the benzotriazole moiety. However, results indicated that purification

  苯并三唑是一类非常重要的化合物，在药物化学，有机合成助剂，冶金应用，飞机除冰剂和制动液以及航空摄影除雾剂等多种领域中都有广泛的应用。尽管有很多方法可以制备N-取代的苯并三唑，但是基本上所有N-未取代的苯并三唑的通用方法是通过邻苯二胺的重氮化，这会受到合适前体的可用性的限制。N-未取代的苯并三唑的其他方法是非常专门的。尽管已知1-羟基-1H-苯并三唑的还原反应不是特别方便或不能广泛应用。这就限制了各种苯并三唑的容易获得和可用性。在这里，我们演示一个新的 通过温和的二硼试剂介导的1-羟基-1H-苯并三唑的脱氧，可广泛应用于各种1H-苯并三唑。我们还评估了顺序脱氧以及Pd介导的CC和CN键的形成，作为一锅过程，进一步分散了苯并三唑部分。但是，结果表明，在Pd介导的反应之前纯化脱氧产物对于此类反应的成功至关重要。整体化学性质使得可以轻松获得各种新的苯并三唑。连同给出的几个例子，描述了方法的优点，以
• Aminooxygenation of Ynamides with <i>N-</i>Hydroxybenzotriazoles: Synthesis of α-Benzotriazolyl Carbonyl Compounds
  作者：Jangbin Im、Sang Ik Shin、Cheon-Gyu Cho、Seunghoon Shin

  DOI：10.1021/acs.joc.0c00174

  日期：2020.6.5

  any catalyst but could be efficiently catalyzed by Zn(OTf)2. Crossover experiments confirmed that the rearrangement is an intramolecular process, most likely via a concerted mechanism. However, heating the mixture above 110 °C resulted in isomerization of N2 into N1 product, via heterolytic C–N bond dissociation. This tandem addition–rearrangement sequence provides an efficient and atom-economical synthetic

  将N-羟基苯并三唑加到乙酰胺上引起自发的重排，从而导致α-苯并三唑基酰亚胺。该转化在不存在任何催化剂的情况下在室温下进行，但是可以被Zn（OTf）2有效地催化。交叉实验证实重排是分子内过程，最有可能通过协同机制进行。但是，将混合物加热到110°C以上会导致N2通过杂化C–N键解离异构化为N1产物。这种串联加成-重排序列为合成α-苯并三唑基羰基化合物提供了一种有效且原子经济的合成途径。
• C−H Fluoromethoxylation of Arenes by Photoredox Catalysis
  作者：Giulia Bertoli、Ángel Manu Martínez、Jonas F. Goebel、Debora Belmonte、Nardana Sivendran、Lukas J. Gooßen

  DOI：10.1002/anie.202215920

  日期：2023.1.26

  A new class of [N−OCH2F] redox-active reagents were synthetized via electrodecarboxylative C(sp3)−O coupling of N-hydroxybenzotriazoles with fluoroacetic acid and subsequent alkylation. By irradiation with blue LEDs in the presence of a photosensitizer, these bench stable reagents allow the synthesis of monofluoromethyl aryl ethers via functionalization of C−H bonds.

  通过 N-羟基苯并三唑与氟乙酸的电羧化 C(sp 3 )-O 偶联和随后的烷基化，合成了一类新的 [N−OCH 2 F] 氧化还原活性试剂。通过在存在光敏剂的情况下用蓝色 LED 照射，这些稳定的试剂允许通过 C-H 键的功能化合成单氟甲基芳基醚。