8-allyloxy-1,4-dimethoxy-6-methoxymethoxy-3,7-dimethylnaphthalene-2-carboxylic acid β-trimethylsilylethyl ester | 406214-28-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 8-allyloxy-1,4-dimethoxy-6-methoxymethoxy-3,7-dimethylnaphthalene-2-carboxylic acid β-trimethylsilylethyl ester
• 英文别名: 2-Trimethylsilylethyl 1,4-dimethoxy-6-(methoxymethoxy)-3,7-dimethyl-8-prop-2-enoxynaphthalene-2-carboxylate
• CAS: 406214-28-6
• 化学式: C₂₅H₃₆O₇Si
• 分子量: 476.642
• InChiKey: NHFOJVACVJFQTH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.52
• 重原子数：
  33
• 可旋转键数：
  13
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  溴甲基甲基醚 、 8-allyloxy-1,4-dimethoxy-6-methoxymethoxy-3,7-dimethylnaphthalene-2-carboxylic acid β-trimethylsilylethyl ester 在 N-溴代丁二酰亚胺(NBS) 、 硫酸 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 10.5h， 以76%的产率得到8-allyloxy-5-bromo-1,4-dimethoxy-6-methoxymethoxy-3,7-dimethylnaphthalene-2-carboxylic acid β-trimethylsilylethyl ester
  参考文献：
  名称：

  Synthesis of highly functionalized naphthoate precursors to damavaricin D — Observation of kinetically stable benzocyclohexadienones in the bromination reactions of highly functionalized β-naphthol derivatives

  摘要：

  Selective syntheses of the highly substituted bromonaphthoates 4a, 4b, 19, and 22 are reported. These compounds were targeted as precursors to the naphthoquinone nucleus of damavaricin D; compound 22 ultimately was used in the successful total synthesis. The synthesis of 22 features the Diels-Alder reaction of the oxygenated diene 5 and 2,6-dibromo-3-methylbenzoquinone 6 to establish the core naphthalenic unit. The quinone was protected throughout this synthesis as a 1,4-bis-methoxymethyl-1,4-dihydroquinone (see 36). The C-2-carboalkoxy group of 22 was added by carboxylation of the aryllithium intermediate generated from 36, and protected as a beta -trimethylsilylethyl ester. Finally, the C-8-Br substituent was introduced by NBS bromination of 38. This reaction proceeds by way of bromobenzocyclohexadienone 39. Related bromobenzo-cyclohexadienones 13 and 29 were observed in the NBS brominations of the highly functionalized beta -naphthyl MOM ethers 11 and 28. The bromobenzocyclohexadienones 29 and 39 undergo facile substitution reactions with chloride ion and reduction with bromide ion at rates competitive with base-promoted aromatization. The surprising kinetic stability of these intermediates is attributed to a combination of steric and stereoelectronic factors.

  DOI：

  10.1139/cjc-79-11-1711
• 作为产物：
  描述：

  5-allyloxy-3-bromo-7-methoxymethoxy-2,6-dimethyl-[1,4]-naphthoquinone 在 sodium tetrahydroborate 、 正丁基锂 、 cerium(III) chloride 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 水 为溶剂， 反应 13.5h， 生成 8-allyloxy-1,4-dimethoxy-6-methoxymethoxy-3,7-dimethylnaphthalene-2-carboxylic acid β-trimethylsilylethyl ester
  参考文献：
  名称：

  Synthesis of highly functionalized naphthoate precursors to damavaricin D — Observation of kinetically stable benzocyclohexadienones in the bromination reactions of highly functionalized β-naphthol derivatives

  摘要：

  Selective syntheses of the highly substituted bromonaphthoates 4a, 4b, 19, and 22 are reported. These compounds were targeted as precursors to the naphthoquinone nucleus of damavaricin D; compound 22 ultimately was used in the successful total synthesis. The synthesis of 22 features the Diels-Alder reaction of the oxygenated diene 5 and 2,6-dibromo-3-methylbenzoquinone 6 to establish the core naphthalenic unit. The quinone was protected throughout this synthesis as a 1,4-bis-methoxymethyl-1,4-dihydroquinone (see 36). The C-2-carboalkoxy group of 22 was added by carboxylation of the aryllithium intermediate generated from 36, and protected as a beta -trimethylsilylethyl ester. Finally, the C-8-Br substituent was introduced by NBS bromination of 38. This reaction proceeds by way of bromobenzocyclohexadienone 39. Related bromobenzo-cyclohexadienones 13 and 29 were observed in the NBS brominations of the highly functionalized beta -naphthyl MOM ethers 11 and 28. The bromobenzocyclohexadienones 29 and 39 undergo facile substitution reactions with chloride ion and reduction with bromide ion at rates competitive with base-promoted aromatization. The surprising kinetic stability of these intermediates is attributed to a combination of steric and stereoelectronic factors.

  DOI：

  10.1139/cjc-79-11-1711