1,4-二甲氧基-1,4-二甲基-2,5-环己二烯 | 132907-18-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 1,4-二甲氧基-1,4-二甲基-2,5-环己二烯
• 英文名称: 3,6-dimethoxy-3,6-dimethylcyclohexa-1,4-diene
• 英文别名: 3,6-Dimethoxy-3,6-dimethyl-1,4-cyclohexadiene
• CAS: 132907-18-7
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: TVEIJVCNJNXJOR-UHFFFAOYSA-N

物化性质

• 沸点：
  206.1±40.0 °C(Predicted)
• 密度：
  0.95±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,4-二甲氧基-1,4-二甲基-2,5-环己二烯 在 盐酸 作用下， 以 乙醇 为溶剂， 反应 0.5h， 以90%的产率得到2,5-二甲基苯酚
  参考文献：
  名称：

  Reactivity of 3,6-dimethoxy-3, 6-dimethylcyclohexa-1, 4-diene: nuclear versus benzylic nucleophilic substitution

  摘要：

  DOI：

  10.1016/s0040-4020(01)89773-8
• 作为产物：
  描述：

  1,4-dimethyl-4-nitrocyclohexa-2,5-dien-1-ol 、 甲醇 生成 1,4-二甲氧基-1,4-二甲基-2,5-环己二烯
  参考文献：
  名称：

  FISCHER A.; HENDERSON G. N.; SMYTH T. A., CAN. J. CHEM., 64,(1986) N 6, 1093-1101

  摘要：

  DOI：

文献信息

• Electroorganic reactions. Part 56: Anodic oxidation of 2-methyl- and 2-benzylnaphthalenes: factors influencing competing pathways
  作者：James H.P Utley、Gregor G Rozenberg

  DOI：10.1016/s0040-4020(02)00495-7

  日期：2002.6

  carbon. However, little side-chain anodic oxidation is observed under any conditions tried; the radical–cations of electron-rich substrates preferentially dimerise and a strongly electron-withdrawing substituent at the 6-position (EtOSO2) promotes nuclear substitution. In contrast, oxidation with DDQ in aqueous acetic acid gives efficient side-chain oxidation for electron rich substrates, consistent

  系统地研究了在萘核的6位和苄基侧链的4-苯基位取代的2-甲基和2-苄基萘在亲核介质中的阳极氧化作用，以确定有利于环境的因素侧链取代。循环伏安法证实6-取代对萘核的氧化电位有深远的影响，13 C化学位移表明在苄基碳上有极性作用。然而，在任何尝试的条件下，几乎都没有观察到侧链阳极氧化。富电子底物的自由基阳离子优先二聚，并且在6位上具有强吸电子取代基（EtOSO 2）促进核替代。相反，在含水乙酸中用DDQ氧化可对富含电子的底物进行有效的侧链氧化，这与氢化物转移（可能在分子内通过电荷转移络合物）转移一致。
• Reactivity of 3,6-dimethoxy-3,6-dimethylcyclohexa-1,4-diene (Part 3). Regioselective α-arylation of ketones via their silyl enol ethers
  作者：Francisco Alonso、Miguel Yus

  DOI：10.1016/s0040-4020(01)86514-5

  日期：1991.11

  The reaction of 3,6-dimethoxy-3,6-dimethylcyclohexa-1,4-diene (1) with an excess of different silyl enol ethers derived from ketones in the presence of zinc dichloride leads to the corresponding ketones regioselectively arylated at the α position.

  3,6-二甲氧基-3,6-二甲基环己-1,4-二烯（1）与过量的由酮衍生的不同甲硅烷基烯醇醚在二氯化锌存在下的反应导致相应的酮在α处区域选择性芳基化位置。
• Reactivity of 3,6-dimethoxy-3,6-dimethylcyclohexa-1,4-diene (part 2). Regioselective arylation of electron-rich aromatic compounds
  作者：Francisco Alonso、Miguel Yus

  DOI：10.1016/s0040-4020(01)80926-1

  日期：1991.1

  The reaction of 3,6-dimethoxy-3,6-dimethylcyclohexa-1,4-diene (1) with electron-rich heterocycles (furan, thiophene, pyrrole, 2-methyl-furan indole) and 1,3,5-trimethoxybenzene in the presence of catalytic amounts of zinc dichloride or concentrated sulftiric acid leads to the corresponding 2-aryl substituted p-xylenes4 in good yields and in a regioselective manner.

  3,6-二甲氧基-3,6-二甲基环己-1,4-二烯（1）与富电子杂环（呋喃，噻吩，吡咯，2-甲基呋喃吲哚）和1,3,5-三甲氧基苯的反应在催化量的二氯化锌或浓硫酸存在下，以良好的产率和区域选择性的方式得到相应的2-芳基取代的对二甲苯4。
• Easy synthesis of 2,4-dialkyl substituted phenols and anisoles from p-bensoquinone
  作者：Francisco Alonso、Miguel Yus

  DOI：10.1016/s0040-4020(01)88530-6

  日期：1992.3

  The reaction of p-benzoquinone (1) with several organolithium compounds (methyl-, ethyl-, n-butyl, phenyllithium) leads directly, after acid hydrolysis, to the corresponding 2,4-dialkylphenols 4a-d, resulting from a rearrangement/aromatization process of the corresponding intermediate diols 3. The use of two different alkyllithium reagents leads to the mixed products 4e.f. Alternatively, the same results are obtained treating the crude isolated diols 3 with a catalytic amount of concentrated sulfuric acid. Applying this last methodology to the diethers 2, 2,4-dialkylanisoles 8 are obtained. A possible mechanism is proposed.
• The role of ion-molecule pair intermediates in acid-catalyzed solvolysis. General base-catalyzed formation of 4-methylbenzyl carbocation and its trapping by nucleophiles
  作者：Alf Thibblin

  DOI：10.1021/jo00078a022

  日期：1993.12

  The specific acid-catalyzed hydrolysis of 3,6-dimethoxy-3,6-dimethyl-1,4-cyclohexadiene (1) in 25 vol % acetonitrile in water at 25-degrees-C provides 2,4-dimethylphenol (2a), 2,5-dimethylphenol (2b), 2,4-dimethylanisole (3a), 4-methylbenzyl alcohol (4), and small amounts of 2,5-dimethylanisole (3b) and 4-methylbenzyl methyl ether (5). The formation of 3b and 5 is proposed to involve intramolecular rearrangement of carbocation-molecule pair intermediates. The formation of 4-methylbenzyl alcohol (4) is catalyzed by general bases, indicating that dehydronation of the cyclohexadienyl carbocation is rate-limiting in its reaction to benzylic products. The Bronsted parameter was measured with carboxylate anions as beta = 0.28. The 4-methylbenzyl carbocation, which is postulated to be an intermediate in this reaction, discriminates between added nucleophiles and solvent water: k(SCN)/k(HOH) = 37, k(Cl)/k(HOH) = 9.8, k(HOH)/k(HOH) = 1.9, and k(MeOH)/k(HOH) = 2.1 (ratios of second-order rate constants). The rate constant for reaction of the carbocation with solvent water is estimated as k(HOH) = 1.4 X 10(8) M-1s-1 (5.6 x 10(9) s-1), assuming a diffusion-controlled rate constant of 5 x 10(9) M-1s-1 for its reaction with thiocyanate anion. The nucleophilic selectivity values are considerably smaller than those exhibited by 4-methylbenzyl bromide under the same reaction conditions: k(Cl)/k(HOH) = 210, k(EtOH)/k(HOH) = 3.8, and k(MeOH)/k(HOH) = 5.3. These differences are concluded to be due to different mechanisms. The bromide reacts by a concerted bimolecular S(N)2 mechanism with chloride anion. With alcohols and water, the reactions occur either by a concerted uncoupled mechanism or via the ion pairs.