(E)-β,3,4-tetramethoxystyrene | 136114-02-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (E)-β,3,4-tetramethoxystyrene
• 英文别名: (1E)-2-(3,4-dimethoxyphenyl)-1-methoxyethene；trans-1-(3,4-dimethoxyphenyl)-2-methoxyethene；(E)-1,2-dimethoxy-4-(2-methoxyethenyl)benzene；Benzene, 1,2-dimethoxy-4-(2-methoxyethenyl)-；1,2-dimethoxy-4-[(E)-2-methoxyethenyl]benzene
• CAS: 136114-02-8
• 化学式: C₁₁H₁₄O₃
• 分子量: 194.23
• InChiKey: ZRQLVVDHVBUPEZ-VOTSOKGWSA-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：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-β,3,4-tetramethoxystyrene 、 对甲苯基溴化镁 在 nickel diacetate 、 三苯基氧化膦 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 以64%的产率得到(E)-1,2-dimethoxy-4-[2-(4-methylphenyl)ethenyl]benzene
  参考文献：
  名称：

  在温和条件下镍催化的烯基甲基醚与格氏试剂的交叉偶联体系

  摘要：

  描述了在温和条件下镍催化的链烯基甲基醚与格利雅试剂的交叉偶联。这些条件允许获得各种斯蒂芬烯和杂环斯蒂芬烯衍生物以及潜在的抗癌剂DMU-212。

  DOI：

  10.1021/acs.orglett.8b00313
• 作为产物：
  描述：

  3,4-dimethoxyphenylacetaldehyde dimethyl acetal 在 正丁基锂 、 一氧化碳 作用下， 以 乙醚 、 正己烷 为溶剂， 以87%的产率得到(E)-β,3,4-tetramethoxystyrene
  参考文献：
  名称：

  Napolitano, Elio; Morsani, Massimo; Fiaschi, Rita, Gazzetta Chimica Italiana, 1991, vol. 121, # 5, p. 249 - 255

  摘要：

  DOI：

文献信息

• Synthesis of Substrates for Aldolase-Catalysed Reactions: A Comparison of Methods for the Synthesis of Substituted Phenylacetaldehydes
  作者：Derar Al-Smadi、Thilak Enugala、Thomas Norberg、Jan Kihlberg、Mikael Widersten

  DOI：10.1055/s-0036-1591963

  日期：2018.6

  Methods for the synthesis of phenylacetaldehydes (oxidation, one-carbon chain extension) were compared by using the synthesis of 4-methoxyphenylacetaldehyde as a model example. Oxidations of 4-methoxyphenylethanol with activated DMSO (Swern oxidation) or manganese dioxide gave unsatisfactory results; whereas oxidation with 2-iodoxybenzoic acid (IBX) produced 4-methoxyphenylacetaldehyde in reasonable

  以4-甲氧基苯乙醛的合成为例，比较了苯乙醛的合成方法（氧化、单碳链延长）。用活化的 DMSO（Swern 氧化）或二氧化锰氧化 4-甲氧基苯基乙醇的结果不令人满意；而用 2-碘氧基苯甲酸 (IBX) 氧化以合理 (75%) 的产率生成 4-甲氧基苯基乙醛。然而，用甲氧基亚甲基-三苯基膦进行 Wittig 型单碳链扩展，然后水解，从 4-甲氧基苯甲醛（一种廉价的起始材料）得到 4-甲氧基苯乙醛的产率非常高（总产率为 81%）。该方法随后被用于合成一组 10 种取代的苯乙醛，收率非常好。
• Pyrolysis of Lignin in the Presence of Tetramethylammonium Hydroxide:  A Convenient Method for S/G Ratio Determination
  作者：Ken-ichi Kuroda、Natsuno Nishimura、Akiko Izumi、Donald R. Dimmel

  DOI：10.1021/jf011198p

  日期：2002.2.1

  in the presence of tetramethylammonium hydroxide (TMAH) was applied to the determination of the ratio of the abundances of the syringyl beta-aryl ether subunits to those of the guaiacyl equivalents (S/G) in lignin. Diazomethane-methylated kenafs (Hibiscus cannabinus and Hibiscus sabdariffa) and beech (Fagus crenata) in situ lignins were employed. Relative abundances of pyrolysis products derived from

  在四甲基氢氧化铵（TMAH）存在下，采用热解气相色谱法测定木质素中丁香基β-芳基醚亚基与愈创木基当量（S / G）的丰度比。使用重氮甲烷甲基化的洋麻（Hibiscus cannabinus和Hibiscus sabdariffa）和山毛榉（Fagus crenata）原位木质素。测定了衍生自愈创木基和丁香基β-芳基醚亚基的热解产物的相对丰度。原位木质素的S / G比值以平均3.1％的相对标准偏差获得，至少重复六次。在TMAH存在下，通过热解确定的S / G比与通过硫代酸解确定的S / G比吻合得很好，线性回归显着（R（2）= 0.9867）。
• A Catalytic Asymmetric Pictet–Spengler Platform as a Biomimetic Diversification Strategy toward Naturally Occurring Alkaloids
  作者：Manuel J. Scharf、Benjamin List

  DOI：10.1021/jacs.2c06664

  日期：2022.8.31

  N-carbamoyl-β-arylethylamines with diverse aldehydes toward enantioenriched THIQs. The obtained products proved to be competent intermediates in the synthesis of THIQ, aporphine, tetrahydroberberine, morphinan, and androcymbine natural products. Novel catalyst design with regard to the stabilization of cationic intermediates was crucial to accomplish high reactivity while simultaneously achieving unprecedented

  四氢异喹啉 (THIQ) 生物碱是一大类生物活性天然产物，其母体化合物和相关的下游生物合成次级代谢物跨越数千个孤立的结构。针对相关 THIQ 的化学酶合成方法依赖于 Pictet-Spenglerase，例如去甲克劳林合成酶 (NCS)，其范围严格限于与多巴胺相关的酚类底物。为了克服化学合成背景下的这些限制，我们在此报告了N的不对称 Pictet-Spengler 反应-氨基甲酰基-β-芳基乙胺与不同的醛对对映体富集的 THIQ。所得产物证明是合成THIQ、阿吗啡、四氢小檗碱、吗啡喃和雄仙碱天然产物的有效中间体。关于阳离子中间体稳定化的新型催化剂设计对于实现高反应性至关重要，同时实现生物相关底物反应的前所未有的立体选择性。
• Strategies for the construction of morphinan alkaloid AB-rings: regioselective Friedel-Crafts-type cyclisations of γ-aryl-β-benzoylamido acids with asymmetrically substituted γ-aryl rings
  作者：Stephen G. Davies、Euan C. Goddard、Paul M. Roberts、Angela J. Russell、Andrew D. Smith、James E. Thomson、Jonathan M. Withey

  DOI：10.1016/j.tetasy.2016.02.010

  日期：2016.4

  The regioselectivity of the Friedel-Crafts-type cyclisation of a range of gamma-aryl-B-benzoylamido acids, bearing oxy substituents at the C(3)- and C(4)-positions of the gamma-aryl ring, has been investigated. In all of the cases examined (with 3,4-dimethoxy, 3,4-methylenedioxy and 3-hydroxy-4-methoxy substituents) the Lewis acid promoted cyclisation proceeds with exclusive regioselectivity for attack at the C(6)-position rather than at the C(2)-position, and furnishes the corresponding N- and O-protected 3-amino-6,7-dihydroxy-1-tetralone derivatives. This inherent regioselectivity can be overturned by the regioselective introduction of chlorine as a blocking group for the C(6)-position; subsequent Lewis acid promoted cyclisation then proceeds with exclusive regioselectivity for attack at the C(2)-position to deliver the corresponding N- and O-protected 3-amino-5-chloro-7,8-dihydroxy-1-tetralone derivative. These complementary cyclisation protocols represent useful methods for the preparation of these benzo-fused carbocyclic ring systems, which are the functionalised AB-rings of a range of morphinan alkaloids. (C) 2016 Published by Elsevier Ltd.
• Asymmetric pictet-spengler synthesis of tetrahydroisoquinolines. An enantioselective synthesis of (−)-laudanosine.
  作者：Daniel L. Comins、Mohamed M. Badawi

  DOI：10.1016/0040-4039(91)80669-w

  日期：1991.6

  A chiral auxiliary mediated Pictet-Spengler reaction was utilized in a synthesis of the tetrahydroisoquinoline alkaloid, (-)-laudanosine.