3-羟基-2-甲氧基-6-(甲氧基甲基)苯甲醛 | 115319-76-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 中文名称: 3-羟基-2-甲氧基-6-(甲氧基甲基)苯甲醛
• 英文名称: 3-hydroxy-2-methoxy-6-(methoxymethyl)benzaldehyde
• CAS: 115319-76-1
• 化学式: C₁₀H₁₂O₄
• 分子量: 196.203
• InChiKey: SXPFIFUYWIGWNK-UHFFFAOYSA-N

物化性质

• 沸点：
  320.6±37.0 °C(Predicted)
• 密度：
  1.205±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-羟基-2-甲氧基-6-(甲氧基甲基)苯甲醛 在 caesium carbonate 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 生成 trans-1-hydroxy-2,5,6-trimethoxydihydrobenzocyclobutene
  参考文献：
  名称：

  Stereoselective photocyclization of some phenolic, highly congested benzophenones and benzaldehydes. Use of cis-2-arylbenzocyclobutenol methyl ethers for the synthesis of lignans

  摘要：

  Irradiation of some highly congested, phenolic 2-(methoxymethyl)benzophenones provides a rapid, efficient and stereoselective entry to the corresponding 1-aryl-1-hydroxy-2-methoxybenzocyclobutenes in high chemical yield. The analogous photocyclization reaction of phenolic benzaldehydes appears to be more limited in scope. According to semiempirical (AM1) calculations on the thermal ring opening of a large number of benzocyclobutene derivatives, alpha,alpha'-dioxygenated o-quinodimethanes are significantly more stable (5-7 kcal/mol) than the corresponding benzocyclobutene derivatives, thereby suggesting that 1-hydroxy-2-alkoxybenzocyclobutenes are unlikely to be thermally derived from the corresponding o-QDM's during photolysis of o-(methoxymethyl)benzophenones. Hydrogenolysis (H-2, Pd/C) of either the cis or trans isomers of 1-aryl-1-hydroxy-2-methoxybenzocyclobutenes gives rise to cis-trans mixtures of 1-methoxy-2-arylbenzocyclobutenes enriched in the cis isomer. These enriched mixtures undergo thermal isomerization to the desired trans 1-methoxy-2-arylbenzocyclobutenes. The cis-enriched mixture directly derived from the hydrogenolysis step can be used as a precursor of the required (E,E)-alpha-aryl-alpha'-methoxy-o-quinodimethane for the synthesis of lignanes via the intermolecular Diels-Alder approach.

  DOI：

  10.1021/jo00049a033
• 作为产物：
  描述：

  4-羟基-3-甲氧基苄醇 在 正丁基锂 、 对甲苯磺酸 作用下， 以 四氢呋喃 为溶剂， 生成 3-羟基-2-甲氧基-6-(甲氧基甲基)苯甲醛
  参考文献：
  名称：

  全合成阿凡韦洛尔

  摘要：

  报道了海洋天然产物阿夫那韦尔的首次全合成。总合成的特征是将甲苯磺酰和硼酸的无过渡金属的偶联首次用于制备复杂的天然产物，以及该偶联与受阻二邻位取代substrate底物的偶联的第一个实例。

  DOI：

  10.1021/acs.joc.7b02028

文献信息

• On the metalation of phenolic compounds: Ready access to highly substituted phenols.
  作者：Antonio Costa、José M. Saá

  DOI：10.1016/s0040-4039(00)96778-9

  日期：1987.1

  studied. Those substrates possesing an electron-withdrawing group in a 1,3 relationship with the coordinating (-CH2OMe) group underwent regioselective metalation by the action of n-BuLi/THF. Highly substituted phenols can thus be readly prepared.

  已经研究了几种对羟基苄基甲基醚的直接金属化。那些具有与配位基团（-CH 2 OMe）成1,3关系的吸电子基团的底物在n-BuLi / THF的作用下进行了区域选择性金属化。因此可以容易地制备高度取代的酚。
• Metalation of phenols. Synthesis of benzoquinones by the oxidative degradation approach
  作者：Jose M. Saa、Antonia Llobera、Angel Garcia-Raso、Antonio Costa、Pedro M. Deya

  DOI：10.1021/jo00253a019

  日期：1988.9
• COSTA, ANTONIO;SAA, JOSE M., TETRAHEDRON LETT., 28,(1987) N 45, 5551-5554
  作者：COSTA, ANTONIO、SAA, JOSE M.

  DOI：——

  日期：——
• Total Synthesis of Avrainvilleol
  作者：Aaron Wegener、Kenneth A. Miller

  DOI：10.1021/acs.joc.7b02028

  日期：2017.11.3

  The first total synthesis of the marine natural product avrainvilleol is reported. The total synthesis features the first application of the transition-metal-free coupling of a tosyl hydrazone and a boronic acid to the preparation of a complex natural product, and the first example of this coupling with a hindered diortho substituted hydrazone substrate.

  报道了海洋天然产物阿夫那韦尔的首次全合成。总合成的特征是将甲苯磺酰和硼酸的无过渡金属的偶联首次用于制备复杂的天然产物，以及该偶联与受阻二邻位取代substrate底物的偶联的第一个实例。
• Stereoselective photocyclization of some phenolic, highly congested benzophenones and benzaldehydes. Use of cis-2-arylbenzocyclobutenol methyl ethers for the synthesis of lignans
  作者：Gloria Coll、Antoni Costa、Pere M. Deya、Francina Flexas、Carmen Rotger、Jose M. Saa

  DOI：10.1021/jo00049a033

  日期：1992.11

  Irradiation of some highly congested, phenolic 2-(methoxymethyl)benzophenones provides a rapid, efficient and stereoselective entry to the corresponding 1-aryl-1-hydroxy-2-methoxybenzocyclobutenes in high chemical yield. The analogous photocyclization reaction of phenolic benzaldehydes appears to be more limited in scope. According to semiempirical (AM1) calculations on the thermal ring opening of a large number of benzocyclobutene derivatives, alpha,alpha'-dioxygenated o-quinodimethanes are significantly more stable (5-7 kcal/mol) than the corresponding benzocyclobutene derivatives, thereby suggesting that 1-hydroxy-2-alkoxybenzocyclobutenes are unlikely to be thermally derived from the corresponding o-QDM's during photolysis of o-(methoxymethyl)benzophenones. Hydrogenolysis (H-2, Pd/C) of either the cis or trans isomers of 1-aryl-1-hydroxy-2-methoxybenzocyclobutenes gives rise to cis-trans mixtures of 1-methoxy-2-arylbenzocyclobutenes enriched in the cis isomer. These enriched mixtures undergo thermal isomerization to the desired trans 1-methoxy-2-arylbenzocyclobutenes. The cis-enriched mixture directly derived from the hydrogenolysis step can be used as a precursor of the required (E,E)-alpha-aryl-alpha'-methoxy-o-quinodimethane for the synthesis of lignanes via the intermolecular Diels-Alder approach.