erythro/threo-1-(4-Methoxyphenyl)-2-methoxy-1-propanol | 138169-69-4

• 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: erythro/threo-1-(4-Methoxyphenyl)-2-methoxy-1-propanol
• 英文别名: 1-(4-methoxyphenyl)-2-methoxy-1-propanol；2-methoxy-1-(4-methoxyphenyl)propan-1-ol；anethole glycolmethyl ether；Anetholglykolmethylaether；1¹-Oxy-4.1²-dimethoxy-1-propyl-benzol
• CAS: 138169-69-4
• 化学式: C₁₁H₁₆O₃
• 分子量: 196.246
• InChiKey: UTGSXLNXHCTQCB-UHFFFAOYSA-N

物化性质

• 沸点：
  171-175 °C(Press: 65-70 Torr)
• 密度：
  1.065±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  erythro/threo-1-(4-Methoxyphenyl)-2-methoxy-1-propanol 在 Co(III)W 、 水 、 溶剂黄146 作用下， 生成 4-甲氧基苯甲醛
  参考文献：
  名称：

  Kinetic and Product Studies on the Side-Chain Fragmentation of 1-Arylalkanol Radical Cations in Aqueous Solution: Oxygen versus Carbon Acidity

  摘要：

  A kinetic and product study of the side-chain fragmentation reactions of a series of 1-arylalkanol radical cations (4-MeOC6H4CH(OH)R.+) and some of their methyl ethers was carried out; the radical cations were generated by pulse radiolysis and gamma radiolysis in aqueous solution. The radical cations undergo side-chain fragmentation involving the C-alpha-H andior C-alpha-C-beta bonds, and their reactivity was studied both in acidic (pH14) and basic (pH 10-11) solution. At pH 4, the radical cations decay with first-order kinetics, and the exclusive reaction is C-alpha-H deprotonation for 1(.+) 2(.+), and 3(.+) (R = H, Me, and Et, respectively) but C-alpha-C-beta bond cleavage for 5(.+)-, 6(.+), and 7(.+) (R = tBu, CH(OH)Me, and CH(OMe)Me, respectively). Both types of cleavage are observed for 4(.+) (R = iPr). The radical cations of the methyl ethers 8(.+), 9(.+), and 10(.+) (R = H, Et, and iPr, respectively) undergo exclusive deprotonation, whereas C-C fragmentation predominates for 11(.+) (R = tBu). Large C-alpha deuterium kinetic isotope effects (4.5 and 5.0, respectively) were found for 1(.+) and its methyl ether 8(.+). Replacement of an alpha-OH group by OMe has a very small effect on the decay rate when the radical cation undergoes deprotonation, but a very large, negative effect in the case of C-C bond cleavage. It is suggested that hydrogen bonding of the alpha-OH group with the solvent stabilizes the transition state of the C-C bond fragmentation reaction but not that of the deprotonation process; however, other factors could also contribute to this phenomenon. The decay of the radical cations is strongly accelerated by HO-, and all the alpha-OH substituted radical cations react with HO- at a rate (approximate to 10(10) M-1 s(-1)) very close to the limit of diffusion control and independent of the nature of the bond that is finally broken in the process (C-H or C-C). The methyl ether 8(.+), which exclusively undergoes C-H bond cleavage, reacts significantly slower (by a factor of ca. 50) than the corresponding alcohol 1(.+). These data indicate that 1-arylalkanol radical cations, which display the expected carbon acidity in water, become oxygen acids in the presence of a strong base such as HO- and undergo deprotonation of the O-H group; diffusion-controlled formation of the encounter complex between HO- and the radical cation is the rate-determining step of the reaction. It is suggested that, within the complex, the proton is transferred to the base to give a benzyloxyl radical, either via a radical zwitterion (which undergoes intramolecular electron transfer) or directly (electron transfer coupled with deprotonation). The latter possibility seems more in line with the general base catalysis (beta approximate to 0.4) observed in the reaction of 5(.+), which certainly involves O-H deprotonation. The benzyloxyl radical can then undergo a beta C-C bond cleavage to form 4-methoxybenzaldehyde and R-. or a formal 1,2-H shift to form an alpha-hydroxybenzyl-type radical. The factors of importance in this carbon/oxygen acidity dichotomy are discussed.

  DOI：

  10.1002/(sici)1521-3765(19990604)5:6<1785::aid-chem1785>3.0.co;2-0
• 作为产物：
  描述：

  2-methoxy-1-(4-methoxy-phenyl)-propan-1-one 在 sodium tetrahydroborate 作用下， 以 异丙醇 为溶剂， 生成 erythro/threo-1-(4-Methoxyphenyl)-2-methoxy-1-propanol
  参考文献：
  名称：

  芳基链烷醇自由基阳离子的侧链断裂。碳-碳和碳-氢键断裂以及 α- 和 β-OH 基团的作用

  摘要：

  12-钨钴酸(III)钾(缩写为Co(III)W)对许多1-芳基丙醇、1,2-二芳基乙醇和它们的一些甲基醚进行单电子氧化的产物分析和动力学研究进行了醋酸水溶液，并通过脉冲辐解实验进行了补充。氧化通过自由基阳离子发生，这些阳离子经历涉及 Cα-H 和/或 Cα-Cβ 键的侧链断裂。对于 1-(4-甲氧基苯基)-2-甲氧基丙烷 (1)，仅观察到自由基阳离子的去质子化。相反，去除环甲氧基会导致自由基阳离子中的 C-C 键断裂。用 β-OH 代替侧链 β-OMe，自由基阳离子经历 C-C 和 C-H 键裂解，两种途径都被碱催化。α-OH 基团也增强了自由基阳离子中的 C-C 键断裂，如 1-(4-甲氧基苯基)-2,2-二甲基-1-丙醇 (7) 所示，该途径也是碱催化的，是唯一观察到的途径。有趣的是，α-和β-OH基团表现出...

  DOI：

  10.1021/ja954236s

文献信息

• Alkoxyl Radicals Generated under Photoredox Catalysis: A Strategy for anti‐Markovnikov Alkoxylation Reactions
  作者：Anne‐Laure Barthelemy、Béatrice Tuccio、Emmanuel Magnier、Guillaume Dagousset

  DOI：10.1002/anie.201806522

  日期：2018.10.15

  involves alkoxyl radicals generated from N‐alkoxypyridinium salts. A wide range of alkenes are smoothly difunctionalized in an anti‐Markovnikov fashion, affording various functionalized alkyl alkyl ethers. Notably, this mild process tolerates a number of functional groups and is efficiently carried out under both batch and flow conditions. Importantly, electron paramagnetic resonance (EPR) experiments

  本文报道的是一种新型的光氧化还原催化的醚合成方法，它涉及由N-烷氧基吡啶鎓盐生成的烷氧基自由基。各种各样的烯烃以反马尔可夫尼可夫的方式平稳地进行双官能化，从而提供了各种官能化的烷基烷基醚。值得注意的是，这种温和的方法可以耐受许多官能团，并且可以在间歇和流动条件下有效地进行。重要的是，通过自旋俘获进行了电子顺磁共振（EPR）实验，以表征参与该自由基/阳离子过程的自由基中间体。
• Mameli, Gazzetta Chimica Italiana, 1909, vol. 39 II, p. 164
  作者：Mameli

  DOI：——

  日期：——
• Side-Chain Fragmentation of Arylalkanol Radical Cations. Carbon−Carbon and Carbon−Hydrogen Bond Cleavage and the Role of α- and β-OH Groups
  作者：Enrico Baciocchi、Massimo Bietti、Lorenza Putignani、Steen Steenken

  DOI：10.1021/ja954236s

  日期：1996.1.1

  hoxypropane (1), only deprotonation of the radical cation is observed. In contrast, removing the ring methoxy group leads to exclusive C−C bond cleavage in the radical cation. Replacing the side-chain β-OMe by β-OH, the radical cation undergoes both C−C and C−H bond cleavage, with both pathways being base catalyzed. C−C bond breaking in the radical cation is also enhanced by an α-OH group, as shown

  12-钨钴酸(III)钾(缩写为Co(III)W)对许多1-芳基丙醇、1,2-二芳基乙醇和它们的一些甲基醚进行单电子氧化的产物分析和动力学研究进行了醋酸水溶液，并通过脉冲辐解实验进行了补充。氧化通过自由基阳离子发生，这些阳离子经历涉及 Cα-H 和/或 Cα-Cβ 键的侧链断裂。对于 1-(4-甲氧基苯基)-2-甲氧基丙烷 (1)，仅观察到自由基阳离子的去质子化。相反，去除环甲氧基会导致自由基阳离子中的 C-C 键断裂。用 β-OH 代替侧链 β-OMe，自由基阳离子经历 C-C 和 C-H 键裂解，两种途径都被碱催化。α-OH 基团也增强了自由基阳离子中的 C-C 键断裂，如 1-(4-甲氧基苯基)-2,2-二甲基-1-丙醇 (7) 所示，该途径也是碱催化的，是唯一观察到的途径。有趣的是，α-和β-OH基团表现出...
• Kinetic and Product Studies on the Side-Chain Fragmentation of 1-Arylalkanol Radical Cations in Aqueous Solution: Oxygen versus Carbon Acidity
  作者：Enrico Baciocchi、Massimo Bietti、Steen Steenken

  DOI：10.1002/(sici)1521-3765(19990604)5:6<1785::aid-chem1785>3.0.co;2-0

  日期：1999.6.4

  A kinetic and product study of the side-chain fragmentation reactions of a series of 1-arylalkanol radical cations (4-MeOC6H4CH(OH)R.+) and some of their methyl ethers was carried out; the radical cations were generated by pulse radiolysis and gamma radiolysis in aqueous solution. The radical cations undergo side-chain fragmentation involving the C-alpha-H andior C-alpha-C-beta bonds, and their reactivity was studied both in acidic (pH14) and basic (pH 10-11) solution. At pH 4, the radical cations decay with first-order kinetics, and the exclusive reaction is C-alpha-H deprotonation for 1(.+) 2(.+), and 3(.+) (R = H, Me, and Et, respectively) but C-alpha-C-beta bond cleavage for 5(.+)-, 6(.+), and 7(.+) (R = tBu, CH(OH)Me, and CH(OMe)Me, respectively). Both types of cleavage are observed for 4(.+) (R = iPr). The radical cations of the methyl ethers 8(.+), 9(.+), and 10(.+) (R = H, Et, and iPr, respectively) undergo exclusive deprotonation, whereas C-C fragmentation predominates for 11(.+) (R = tBu). Large C-alpha deuterium kinetic isotope effects (4.5 and 5.0, respectively) were found for 1(.+) and its methyl ether 8(.+). Replacement of an alpha-OH group by OMe has a very small effect on the decay rate when the radical cation undergoes deprotonation, but a very large, negative effect in the case of C-C bond cleavage. It is suggested that hydrogen bonding of the alpha-OH group with the solvent stabilizes the transition state of the C-C bond fragmentation reaction but not that of the deprotonation process; however, other factors could also contribute to this phenomenon. The decay of the radical cations is strongly accelerated by HO-, and all the alpha-OH substituted radical cations react with HO- at a rate (approximate to 10(10) M-1 s(-1)) very close to the limit of diffusion control and independent of the nature of the bond that is finally broken in the process (C-H or C-C). The methyl ether 8(.+), which exclusively undergoes C-H bond cleavage, reacts significantly slower (by a factor of ca. 50) than the corresponding alcohol 1(.+). These data indicate that 1-arylalkanol radical cations, which display the expected carbon acidity in water, become oxygen acids in the presence of a strong base such as HO- and undergo deprotonation of the O-H group; diffusion-controlled formation of the encounter complex between HO- and the radical cation is the rate-determining step of the reaction. It is suggested that, within the complex, the proton is transferred to the base to give a benzyloxyl radical, either via a radical zwitterion (which undergoes intramolecular electron transfer) or directly (electron transfer coupled with deprotonation). The latter possibility seems more in line with the general base catalysis (beta approximate to 0.4) observed in the reaction of 5(.+), which certainly involves O-H deprotonation. The benzyloxyl radical can then undergo a beta C-C bond cleavage to form 4-methoxybenzaldehyde and R-. or a formal 1,2-H shift to form an alpha-hydroxybenzyl-type radical. The factors of importance in this carbon/oxygen acidity dichotomy are discussed.