5-allyloxy-3-bromo-7-methoxymethoxy-2,6-dimethyl-[1,4]-naphthoquinone | 198124-44-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 5-allyloxy-3-bromo-7-methoxymethoxy-2,6-dimethyl-[1,4]-naphthoquinone
• 英文别名: 3-Bromo-7-(methoxymethoxy)-2,6-dimethyl-5-prop-2-enoxynaphthalene-1,4-dione
• CAS: 198124-44-6
• 化学式: C₁₇H₁₇BrO₅
• 分子量: 381.223
• InChiKey: XGRMWGMTODRCMQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  5-allyloxy-3-bromo-7-methoxymethoxy-2,6-dimethyl-[1,4]-naphthoquinone 在 咪唑 、 正丁基锂 、 sodium dithionite 、 Adogen 464(R) 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 25.83h， 生成 8-Allyloxy-6-(tert-butyl-diphenyl-silanyloxy)-1,4-bis-methoxymethoxy-3,7-dimethyl-naphthalene-2-carboxylic acid
  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：

  3-Bromo-5,7-dihydroxy-2,6-dimethyl-[1,4]naphthoquinone 在 phosphorus pentoxide 、 silver(l) oxide 作用下， 以 氯仿 为溶剂， 反应 20.0h， 生成 5-allyloxy-3-bromo-7-methoxymethoxy-2,6-dimethyl-[1,4]-naphthoquinone
  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

文献信息

• Total Synthesis of (+)-Damavaricin D
  作者：William R. Roush、D. Scott Coffey、David J. Madar

  DOI：10.1021/ja971828x

  日期：1997.11.1
• Synthesis of highly functionalized naphthoate precursors to damavaricin D — Observation of kinetically stable benzocyclohexadienones in the bromination reactions of highly functionalized β-naphthol derivatives
  作者：William R. Roush、David J. Madar、D. Scott Coffey

  DOI：10.1139/cjc-79-11-1711

  日期：——

  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.