2-methoxy-3-(3'-methyl-2'-butenyl)-6-methyl-1,4-benzoquinone

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 2-methoxy-3-(3'-methyl-2'-butenyl)-6-methyl-1,4-benzoquinone
• 英文别名: 3-Methoxy-5-methyl-2-(3-methylbut-2-enyl)cyclohexa-2,5-diene-1,4-dione
• 化学式: C₁₃H₁₆O₃
• 分子量: 220.268
• InChiKey: ALMVXMGDYPTOTA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  4-[(二甲氨基)甲基]-2-甲氧基-6-甲基苯酚 在 三异辛胺 disodium hydrogenphosphate 、 sodium dihydrogenphosphate 、 lithium tetrachloropalladate 、 potassium nitrososulfonate 、 氨 、 sodium acetate 、 lithium 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 水 、 苯 为溶剂， 反应 52.58h， 生成 2-methoxy-3-(3'-methyl-2'-butenyl)-6-methyl-1,4-benzoquinone
  参考文献：
  名称：

  Synthesis of prenylated quinones by the oxidative degradation approach. Birch vs vinylogous Birch hydrogenolysis (BIHY vs VIBIHY) in controlling 2.DELTA. stereochemistry of the prenyl chain

  摘要：

  Two novel approaches toward prenylated quinones are described. The first (route A) involves the following three basic operations: (a) construction of a 4-hydroxybenzylamine carrying a tertiary allyl alcohol (cinnamyl alcohol) side chain of appropriate length (C5, C-10, etc), followed by (b) vinylogous Birch reductive cleavage with concomitant isomerization of the double bond (vinylogous Birch hydrogenolysis, VIBIHY) and (c) Fremy's salt oxidative degradation of the resulting prenylated phenolic benzylamines to the corresponding quinones. The required phenolic cinnamyl alcohols were successfully synthesized by means of two alternative routes, namely: (1) cyclopalladation of phenolic benzylamines followed by ketovinylation and treatment of the resulting beta-aryl substituted alpha,beta unsaturated ketone with methyllithium and (2) reaction of the dilithio derivatives of the appropriate phenolic benzylamine with the desired alpha,beta unsaturated aldehyde, followed by acid rearrangement. The key feature of this approach, namely, the so-called vinylogous Birch hydrogenolysis (VIBIHY) takes place very efficiently on the phenolic tertiary cinnamyl alcohol stage, provided that the reaction (Li/NH3) is carried out on its bissilylated derivative. Unfortunately, its stereochemistry cannot be properly controlled, as it leads to the formation of ca 2.5:1 (E/Z) mixture of (DELTA2) alkenes. The second generation approach (route B), which solves this problem, requires the following: (a) preparation of a 4-hydroxybenzylamine carrying a 3-methyl-2-buten-1-ol (dimethylallyl alcohol) side chain, or higher homologue, followed by (b) Birch hydrogenolysis (BIHY) and step c above. The key Birch hydrogenolysis takes place with almost complete control of the stereochemically labile DELTA2 double bond, thereby making this approach the one of choice for the synthesis of isoprenyl benzoquinones.

  DOI：

  10.1021/jo00054a012

文献信息

• Synthesis of prenylated quinones by the oxidative degradation approach. Birch vs vinylogous Birch hydrogenolysis (BIHY vs VIBIHY) in controlling 2.DELTA. stereochemistry of the prenyl chain
  作者：Pablo Ballester、Magdalena Capo、Xavier Garcias、Jose M. Saa

  DOI：10.1021/jo00054a012

  日期：1993.1

  Two novel approaches toward prenylated quinones are described. The first (route A) involves the following three basic operations: (a) construction of a 4-hydroxybenzylamine carrying a tertiary allyl alcohol (cinnamyl alcohol) side chain of appropriate length (C5, C-10, etc), followed by (b) vinylogous Birch reductive cleavage with concomitant isomerization of the double bond (vinylogous Birch hydrogenolysis, VIBIHY) and (c) Fremy's salt oxidative degradation of the resulting prenylated phenolic benzylamines to the corresponding quinones. The required phenolic cinnamyl alcohols were successfully synthesized by means of two alternative routes, namely: (1) cyclopalladation of phenolic benzylamines followed by ketovinylation and treatment of the resulting beta-aryl substituted alpha,beta unsaturated ketone with methyllithium and (2) reaction of the dilithio derivatives of the appropriate phenolic benzylamine with the desired alpha,beta unsaturated aldehyde, followed by acid rearrangement. The key feature of this approach, namely, the so-called vinylogous Birch hydrogenolysis (VIBIHY) takes place very efficiently on the phenolic tertiary cinnamyl alcohol stage, provided that the reaction (Li/NH3) is carried out on its bissilylated derivative. Unfortunately, its stereochemistry cannot be properly controlled, as it leads to the formation of ca 2.5:1 (E/Z) mixture of (DELTA2) alkenes. The second generation approach (route B), which solves this problem, requires the following: (a) preparation of a 4-hydroxybenzylamine carrying a 3-methyl-2-buten-1-ol (dimethylallyl alcohol) side chain, or higher homologue, followed by (b) Birch hydrogenolysis (BIHY) and step c above. The key Birch hydrogenolysis takes place with almost complete control of the stereochemically labile DELTA2 double bond, thereby making this approach the one of choice for the synthesis of isoprenyl benzoquinones.