2-Methoxy-5-tert-butyl-benzochinon-(1,4) | 1774-86-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-Methoxy-5-tert-butyl-benzochinon-(1,4)
• 英文别名: 2-methoxy-5-tert-butyl-1,4-benzoquinone；2-Methoxy-5-tert.-butyl-1,4-benzochinon；2-Tert-butyl-5-methoxycyclohexa-2,5-diene-1,4-dione
• CAS: 1774-86-3
• 化学式: C₁₁H₁₄O₃
• 分子量: 194.23
• InChiKey: WQGQXSAJSRCSIR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-Methoxy-5-tert-butyl-benzochinon-(1,4) 在 苄胺 作用下， 以 乙醇 为溶剂， 反应 1.0h， 以17%的产率得到N-苄烯丁胺
  参考文献：
  名称：

  Model Studies of Topaquinone-Dependent Amine Oxidases. 1. Oxidation of Benzylamine by Topaquinone Analogs

  摘要：

  The aerobic oxidation of benzylamine by model compounds of topaquinone, the active site organic cofactor in copper-containing amine oxidases, was studied in order to elucidate the chemical function of the cofactor in substrate oxidation. In this study, topaquinone hydantoin (1(ox)) and a series of 2-hydroxy-5-alkyl-1,4-benzoquinones which differ in the bulk of their alkyl substituent (5, 6, 7, and 8) were employed as model compounds of the cofactor. The p-quinones (9, 10, 11, and 12) and the o-quinones (13 and 14) were prepared in order to compare them to the topaquinone analogs. Benzylamine was oxidized by the topaquinone analogs (1(ox), 5, 6, 7, and 8) to yield N-benzylidenebenzylamine (PhCH=NCH(2)Ph) as a sole product in acetonitrile at room temperature, The quinones bearing a bulky substituent (1(ox), 5, and 6) were found to be more efficient catalysts than those bearing a small primary alkyl group (7 and 8). In the latter case, the dimers (16 and 17) of the substrate Schiff base intermediates (15, R = methyl, ethyl) were isolated. The p-quinones (9, 10, 11, and 12) were catalytically inactive, The o-quinones (13 and 14) had detectable catalytic activity at room temperature, In anaerobic reactions of the o-quinones (13 and 14) with benzylamine, quantitative formation of the product (PhCH=NCH(2)Ph) was observed. For both o-quinones, products and intermediates which support a transamination mechanism were identified by H-1 NMR spectroscopy. The order of reactivity of quinones (5 > 14 > 13) reflects their redox potentials, such that regeneration of quinone may be rate-determining with o-quinones. These results demonstrate a substantial role of the 2-hydroxyl group of the topaquinone in preventing the formation of Michael adducts with substrate amine and in facilitating the reoxidation of aminoresorcinol intermediates.

  DOI：

  10.1021/ja00139a002
• 作为产物：
  描述：

  1,2,4-苯三酚 在 硫酸 、 溶剂黄146 、 对苯醌 作用下， 生成 2-Methoxy-5-tert-butyl-benzochinon-(1,4)
  参考文献：
  名称：

  Flaig et al., Justus Liebigs Annalen der Chemie, 1955, vol. 597, p. 196,211

  摘要：

  DOI：

文献信息

• A Catalytic Oxidative Quinone Heterofunctionalization Method: Synthesis of Strongylophorine-26
  作者：Wanwan Yu、Per Hjerrild、Kristian M. Jacobsen、Henriette N. Tobiesen、Line Clemmensen、Thomas B. Poulsen

  DOI：10.1002/anie.201805580

  日期：2018.7.26

  functionalization with a collection of O, N, and S nucleophiles, using oxygen as the terminal oxidant. Preliminary mechanistic observations and the first synthesis of the cytotoxic natural product strongylophorine‐26 is presented.

  理想情况下，杂原子取代的对苯醌的制备是通过直接添加亲核试剂，然后进行原位再氧化来完成的。尽管是一种引人注目的策略，但对p-醌部分的反应性不容易驯服，也没有广泛适用的杂原子官能化方法。这里示出的是，钴（OAC）2和Mn（OAc）3 ⋅2ħ 2 ö充当强大催化剂氧化p为O，N的集合-quinone官能化，和S的亲核试剂，使用氧作为氧化剂终端。介绍了初步的机械观察结果和细胞毒性天然产物Strongylophorine-26的首次合成。
• Water, an Essential Element for a Zn ^II ‐Catalyzed Asymmetric Quinone Diels‐Alder Reaction: Multi‐Selective Construction of Highly Functionalized <i>cis</i> ‐Decalins
  作者：Kyosuke Morimoto、Thien Phuc Le、Sudipta Kumar Manna、I. N. Chaithanya Kiran、Shinji Tanaka、Masato Kitamura

  DOI：10.1002/asia.201900995

  日期：2019.10

  A ZnII complex of a C2 -chiral bisamidine-type sp2 N bidentate ligand (LR ) possessing two dioxolane rings at both ends catalyzes a highly efficient quinone asymmetric Diels-Alder reaction (qADA) between o-alkoxy-p-benzoquinones and 1-alkoxy-1,3-butadienes to construct highly functionalized chiral cis-decalins, proceeding in up to a >99:1 enantiomer ratio with a high generality in the presence of H2

  两端均具有两个二氧戊环的C2-手性双am型sp2 N二齿配体（LR）的ZnII配合物催化邻烷氧基-对苯醌和1-烷氧基之间的高效醌不对称Diels-Alder反应（qADA）。 -1,3-丁二烯构建高度官能化的手性顺式十氢化萘，在H2 O存在下（H2 O：ZnII = 4-6：1）以高> 99：1的对映体比例进行合成。在没有水的情况下，几乎没有反应发生。具有较高的Zn / LR比，手性配体的负载量可以最小化至0.02mol％。首次成功归因于底物的超分子3D排列，其中两个“ H2 O-ZnII”反应性质子与一个二氧戊环氧原子和一个单点结合的二烯形成线性氢键网络。ZnII原子通过n-π*吸引作用捕获固定在另一个二氧戊环氧原子上的接受电子的两点结合醌。该机理得到1 H NMR研究，动力学，相关ZnLR配合物的X射线晶体学分析以及配体和底物结构-反应性-选择性的关系的支持。
• A divergent and selective synthesis of ortho- and para-quinones from phenols
  作者：Zheng Huang、Ohhyeon Kwon、Kenneth Virgel N. Esguerra、Jean-Philip Lumb

  DOI：10.1016/j.tet.2015.04.095

  日期：2015.9

  We describe a divergent synthesis of substituted ortho- and para-quinones by catalytic aerobic oxygenation of phenols. Substituted quinones are omnipresent in chemistry and biology, but their synthesis frequently suffers from low efficiency and poor scope. Our methodology employs a catalytic aerobic di-functionalization of phenols to aryloxy-ortho-quinones. Regioselective substitution with an alcohol provides the alkoxy substituted ortho- or para-quinone, while hydrolysis affords the para-hydroxyquinone. These are mild and selective conditions for the synthesis of diversely substituted quinones from readily available phenol starting materials. (C) 2015 Elsevier Ltd. All rights reserved.
• NITRO MUSKS. I. ISOMERS, HOMOLOGS, AND ANALOGS OF MUSK AMBRETTE
  作者：M. S. CARPENTER、W. M. EASTER、T. F. WOOD

  DOI：10.1021/jo01144a011

  日期：1951.4
• Iron porphyrin-catalyzed oxidation of 1,2-dimethoxyarenes: a discussion of the different reactions involved and the competition between the formation of methoxyquinones or muconic dimethyl esters
  作者：Isabelle Artaud、Khaled Ben-Aziza、Daniel Mansuy

  DOI：10.1021/jo00064a026

  日期：1993.6

  This paper describes the oxidation of an alpha,beta-diarylpropane lignin dimer model and other dimethoxyarenes by several iron porphyrin-based biomimetic systems. From l-(3,4-dimethoxyphenyl)-2-phenylpropanol (1), three types of products are identified: the 3,4-dimethoxybenzaldehyde derived from the C(alpha)-C(beta) cleavage of the propyl side chain and either quinones or muconic dimethyl esters resulting from oxidations at the level of the dimethoxyaryl group. The selectivity of the reaction is discussed with respect to the nature and reactivity of the high-valent iron-oxo species formed upon reaction of the oxidants, H2O2 or magnesium monoperoxyphthalate (MMP), with the iron porphyrins. Fe(TF5PP)CI-catalyzed oxidation of 1 by H2O2 in an aprotic medium (CH3CN/CH2Cl2), yields a clean ''lignin peroxidase-like'' reaction with selective formation of the aldehyde. In an aqueous buffered solution, MMP oxidation of para-substituted 1,2-dimethoxyarenes catalyzed by an iron tetrakis(pentafluorophenyl)-beta-tetrasulfonatoporphyrin, Fe(TF5PS4P), clearly depends on the electronic properties of the para-substituent. The reaction is selective for para-quinone formation in the case of an electron-releasing group and for muconic dimethyl ester formation in the case of an electron-withdrawing group.