2-Allyl-5-methoxy-1,4-benzoquinone | 19936-75-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-Allyl-5-methoxy-1,4-benzoquinone
• 英文别名: 5-allyl-2-methoxy-1,4-benzoquinone；5-allyl-2-methoxy-p-benzoquinone；2-Methoxy-5-allyl-1,4-benzophenon；2-Methoxy-5-prop-2-enylcyclohexa-2,5-diene-1,4-dione
• CAS: 19936-75-5
• 化学式: C₁₀H₁₀O₃
• 分子量: 178.188
• InChiKey: GAFABXOLDYEEEC-UHFFFAOYSA-N

物化性质

• 熔点：
  102-104 °C(Solv: methanol (67-56-1))
• 沸点：
  284.2±39.0 °C(Predicted)
• 密度：
  1.13±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 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-Allyl-5-methoxy-1,4-benzoquinone 在 titanium(IV) isopropylate 、 四氯化钛 、 三氟乙酸 作用下， 以 various solvent(s) 为溶剂， 反应 2.0h， 生成 2-(1,3-benzodioxol-5-yl)-7-methoxy-3-methyl-4-prop-2-enyl-2,3-dihydro-1-benzofuran-5-ol
  参考文献：
  名称：

  用相同的原料立体选择性合成三种新木脂素

  摘要：

  路易斯酸催化的2-烷氧基-5-烯丙基-1,4-苯醌与苯乙烯的反应可以形成burchellin或guianin neolignans，或4-烯丙基-2-芳基-3-甲基-2,3-二氢苯并呋喃。

  DOI：

  10.1016/s0040-4039(00)60310-6
• 作为产物：
  描述：

  4,5-二甲氧基-2-(2-丙烯基)苯酚 在 lithium perchlorate 作用下， 以 水 、 乙腈 为溶剂， 以83%的产率得到2-Allyl-5-methoxy-1,4-benzoquinone
  参考文献：
  名称：

  Shizuri, Yoshikazu; Yamamura, Shosuke, Tetrahedron Letters, 1983, vol. 24, # 45, p. 5011 - 5012

  摘要：

  DOI：

文献信息

• Ruthenium-Catalyzed Oxidative Dearomatization of Phenols to 4-(tert-Butylperoxy)cyclohexadienones: Synthesis of 2-Substituted Quinones from p-Substituted Phenols
  作者：Shun-Ichi Murahashi、Noriko Miyaguchi、Shinji Noda、Takeshi Naota、Akiko Fujii、Yasutaka Inubushi、Naruyoshi Komiya

  DOI：10.1002/ejoc.201100740

  日期：2011.9

  The ruthenium-catalyzed oxidation of phenols with tert-butylhydroperoxide efficiently gives the corresponding 4-(tert-butylperoxy)cyclohexadienones. The oxidation proceeds selectively because of ruthenium's ability for rapid single-electron transfer. This biomimetic oxidation reaction is highly useful to obtain the metabolic compounds desired for confirming the safety of medicines and related compounds

  用叔丁基氢过氧化物在钌催化下氧化苯酚有效地得到相应的 4-（叔丁基过氧化）环己二烯酮。由于钌具有快速单电子转移的能力，氧化选择性地进行。这种仿生氧化反应对于获得用于确认药物和相关化合物安全性所需的代谢化合物非常有用。通常，通过这种仿生氧化反应很容易获得雌性激素雌酮的第一种代谢化合物。所得的 4-（叔丁基过氧）环己二烯酮是通用的合成中间体，可通过酸催化剂处理转化为 2-取代的 1,4-苯醌。酸促进重排和 Diels-Alder 反应为稠环化合物的合成提供了新的策略，如萘醌和蒽醌衍生物，来自容易获得的酚类。非天然的 1,4-二乙酰氧基甾体骨架是通过雌酮氧化和锌介导的迁移获得的。维生素 K3 是从对甲酚选择性合成的，总产率为 79%，分 4 个步骤，合成包括钌催化氧化。
• 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。
• Studies on the constituents of the plants of illicium species. III. Structure elucidations of novel phytoquinoids, illicinones and illifunones from Illicium tashiroi Maxim. and I. arborescens Hayata.
  作者：KENICHI YAKUSHIJIN、TOMOKO TOHSHIMA、EIJI KITAGAWA、RIKA SUZUKI、JUNKO SEKIKAWA、TAKAYUKI MORISHITA、HIROYUKI MURATA、SHENGTEN LU、HIROSHI FURUKAWA

  DOI：10.1248/cpb.32.11

  日期：——

  Chemical constituents of the leaves of Illicium tashiroi and I. arborescens (Illiciaceae) were examined. Novel phytoquinoids, (+)-illicinone-A (1a), -B (2a), -C (3a), and -D (4a), and illifunone-A (5a) and -B (5b) were isolated from I. tashiroi, and characterized. As constituents of I. arborescens, enantiomers (1b and 2b) of (+)-illicinone-A (1a) and -B (2a), and diastereoisomers (2c, 3b, 4b, and 4c) of (+)-illicinone-B (2a), -C (3a), and -D (4a) were characterized. The absolute stereochemistry of (-)-illicinone-A was established by analysis of the circular dichroism (CD) spectra of the α-hydroxy ketones (15 and 16) derived from 1b. The stereochemistries of other illicinones and illifunones deduced from the chemical and/or biogenetic correlations.

  研究了Illicium tashiroi和I. arborescens（Illiciaceae）叶片的化学成分。从 I. tashiroi 中分离出了新的植物喹啉类化合物 (+)-illicinone-A (1a)、-B (2a)、-C (3a) 和 -D (4a)，以及 illifunone-A (5a) 和 -B (5b)，并对其进行了表征。作为 I. arborescens 的成分，(+)-illicinone-A (1a) 和 -B (2a) 的对映体（1b 和 2b），以及 (+)-illicinone-B (2a)、-C (3a) 和 -D (4a) 的非对映异构体（2c、3b、4b 和 4c）均已表征。通过分析由 1b 衍生出的α-羟基酮（15 和 16）的圆二色（CD）光谱，确定了(-)-紫杉酮-A 的绝对立体化学性质。根据化学和/或生物遗传相关性推断出了其他伊利西酮和伊利西酮的立体化学结构。
• Regioselective Lewis Acid-Directed Reactions of 2-Alkoxy-5-alkyl-1,4-benzoquinones with Styrenes: Synthesis of Burchellin and Guianin Neolignans
  作者：Thomas A. Engler、Dong Donna Wei、Michael A. Letavic、Keith D. Combrink、Jayachandra P. Reddy

  DOI：10.1021/jo00101a017

  日期：1994.11

  Reactions of 2-carbomethoxy-5-methoxy-1,4-benzoquinone with (E)-propenylbenzenes promoted by Ti(IV) regio- and stereoselectively yield trans 2-aryl-4-carbomethoxy-7-methoxy-3-methyl-2,3-dihydro-5-benzofuranols. However, the products found in Lewis acid-promoted reactions of 2-alkoxy-5-alkyl-1,4-benzoquinones with (E)-propenylbenzenes depend on the nature of the Lewis acid. Low-temperature reactions with SnCl4 produce rel-(1R,6S,7S,8R)-4-alkoxy-1-alkyl-7-aryl-8-methylbicyclo[4.2.0]oct-5-ene-2,5-diones 21-23 and products derived from them. Allowing the reactions to warm to room temperature results in rel-(2S,3S,3aR)-3a-alkyl-2-aryl-5-hydroxy-3-methyl-2,3,3a,6-tetrahydro-6-oxobenzofurans as mixtures of keto-enol tautomers 26/27 and 28/ 29. With Ti(IV) as promoter, the reactions can be made to produce either 21-23 or the regioisomeric rel-(1S,6R,7R,8S)-4-alkoxy-1-alkyl-8-aryl-7-methylbicyclo[4.2.0]oct-3-ene-2,5-diones 18-20. The ratio of the two depends upon the makeup of the Ti(IV) promoter and the substituents on the propenylbenzene. A mechanistic rationale is presented involving regioselective coordination of the different Lewis acids to the quinone. Thus, SnCl4 binds to the C-1 carbonyl and C-2 alkoxy oxygens, forming a complex possessing a 2-alkoxy-5-alkyl-4-oxa-2,5-cyclohexadienyl carbocation moiety (e.g. 30) which undergoes a thermally allowed 4 pi + 2 pi (5 + 2) cycloaddition with propenylbenzene to give a bicyclo[3.2.1]octenyl carbocation 31; this cation then rearranges to the observed products. On the other hand, the Ti(IV)-promoted reactions give either bicyclo[3.2.1]octenyl carbocation 31 or 34, depending upon reaction conditions, followed by rearrangement. Cyclobutanes 18-20 undergo protic acid rearrangement to give trans 7-alkoxy-4-alkyl-2-aryl-3-methyl-2,3-dihydro-5-benzofuranols 15-17, whereas cyclobutanes 21-23 yield 5-alkyl-7-aryl-3-hydroxy-6-methylbicyclo[3.2.1]oct-3-ene-2,8-diones 24/25. The reactions provide an efficient and stereoselective route to neolignans of the guianin and burchellin classes.
• Ruthenium-Catalyzed Oxidation of Phenols with Alkyl Hydroperoxides. A Novel, Facile Route to 2-Substituted Quinones
  作者：Shun-Ichi Murahashi、Takeshi Naota、Noriko Miyaguchi、Shinji Noda

  DOI：10.1021/ja954009q

  日期：1996.1.1