2-methoxy-5-(3'-methyl-2'-butenyl)-4-<(dimethylamino)methyl>phenol | 127757-24-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 2-methoxy-5-(3'-methyl-2'-butenyl)-4-<(dimethylamino)methyl>phenol
• 英文别名: 4-[(Dimethylamino)methyl]-2-methoxy-5-(3-methyl-2-butenyl)phenol；4-[(dimethylamino)methyl]-2-methoxy-5-(3-methylbut-2-enyl)phenol
• CAS: 127757-24-8
• 化学式: C₁₅H₂₃NO₂
• 分子量: 249.353
• InChiKey: NHKFZYKPTFVJHD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  32.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-methoxy-5-(3'-methyl-2'-butenyl)-4-<(dimethylamino)methyl>phenol 在 三异辛胺 disodium hydrogenphosphate 、 sodium dihydrogenphosphate 、 potassium nitrososulfonate 作用下， 以 二氯甲烷 、 水 为溶剂， 以80%的产率得到2-甲氧基-5-(3-甲基丁-2-烯基)环己-2,5-二烯-1,4-二酮
  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：

  4-[(二甲氨基)甲基]-2-甲氧基苯酚 在 lithium tetrachloropalladate 、 氨 、 sodium acetate 、 lithium 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 苯 为溶剂， 反应 52.58h， 生成 2-methoxy-5-(3'-methyl-2'-butenyl)-4-<(dimethylamino)methyl>phenol
  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

• Prenylation of aromatics. Lithium-ammonia reduction of o-silylated tertiary cinnamyl alcohols.
  作者：Pablo Ballester、Magdalena Capó、José M. Saá

  DOI：10.1016/s0040-4039(00)88801-2

  日期：——

  phenolic or non-phenolic tertiary cinnamyl alcohols undergo metalammonia induced hydrogenolysis with concomitant double bond isomerization, thus providing a unique entrance to prenyl substituted aromatics. Chiral alcohols yielded E:Z mixtures enriched (2.5:1) in the E isomer

  甲硅烷基保护的酚或非酚叔肉桂醇经历了金属氨诱导的氢解反应，并伴有双键异构化，因此为异戊二烯基取代的芳族化合物提供了独特的入口。手性醇产生富集（2.5：1）E异构体的E：Z混合物
• BALLESTER, PABLO;CAPO, MAGDALENA;SAA, JOSE M., TETRAHEDRON LETT., 31,(1990) N, C. 1339-1342
  作者：BALLESTER, PABLO、CAPO, MAGDALENA、SAA, JOSE M.

  DOI：——

  日期：——
• 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.