4-二甲氨基甲基-3-(1-羟基-3-甲基-丁-2-烯基)-2-甲氧基-6-甲基-苯酚 | 1026331-64-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 中文名称: 4-二甲氨基甲基-3-(1-羟基-3-甲基-丁-2-烯基)-2-甲氧基-6-甲基-苯酚
• 英文名称: 4-[(Dimethylamino)methyl]-3-(1-hydroxy-3-methylbut-2-enyl)-2-methoxy-6-methylphenol
• CAS: 1026331-64-5
• 化学式: C₁₆H₂₅NO₃
• 分子量: 279.379
• InChiKey: XRUKOCGDDFQXNP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  52.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-二甲氨基甲基-3-(1-羟基-3-甲基-丁-2-烯基)-2-甲氧基-6-甲基-苯酚 在 磷酸 作用下， 以 1,4-二氧六环 为溶剂， 反应 4.0h， 生成 3-(3'-hydroxy-3'-methylbutenyl)-2-methoxy-4-<(dimethylamino)methyl>-6-methylphenol
  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
• 作为产物：
  描述：

  3-甲基-2-丁烯醛 、 4-[(二甲氨基)甲基]-2-甲氧基-6-甲基苯酚 在 正丁基锂 作用下， 生成 4-二甲氨基甲基-3-(1-羟基-3-甲基-丁-2-烯基)-2-甲氧基-6-甲基-苯酚
  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.