methyl 2-(3',4'-methylenedioxyphenyl)cyclohex-2-enylcarbamate | 161196-44-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: methyl 2-(3',4'-methylenedioxyphenyl)cyclohex-2-enylcarbamate
• 英文别名: methyl N-[2-(1,3-benzodioxol-5-yl)cyclohex-2-en-1-yl]carbamate
• CAS: 161196-44-7
• 化学式: C₁₅H₁₇NO₄
• 分子量: 275.304
• InChiKey: MLYHPDJJAUCSFH-UHFFFAOYSA-N

物化性质

• 沸点：
  431.623±45.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  1.272±0.10 g/cm3(Temp: 25 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  56.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 2-(3',4'-methylenedioxyphenyl)cyclohex-2-enylcarbamate 在 2,2'-联吡啶 、 正丁基锂 、 偶氮二异丁腈 、 碘代三甲硅烷 、 三正丁基氢锡 、 copper(l) chloride 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 7.0h， 生成 2-oxo-3a-<3,4-(methylenedioxy)phenyl>-2,3,3a,4,5,6,7,7a-octahydroindole
  参考文献：
  名称：

  Synthetic Studies of cis-3a-Aryloctahydroindole Derivatives by Copper-Catalyzed Cyclization of N-Allyltrichloroacetamides:  Facile Construction of Benzylic Quaternary Carbons by Carbon−Carbon Bond-Forming Reactions

  摘要：

  Cyclization of N-(2-aryl-2-cyclohexen-1-yl)trichloroacetamides by a copper catalyst was investigated. It is crucially important for successful cyclization under mild conditions that alkoxycarbonyl groups are introduced to the nitrogen atom of the N-allyltrichloroacetamides as well as that CuCl(bipyridine) is used as the catalyst. Three compounds, N-(2-phenyl-2-cyclohexen-1-yl)-, N-[2-(3,4-dimethoxyphenyl)-2-cyclohexen-1-yl]-, and N-[2-(3,4-methylenedioxyphenyl)-2-cyclohexen-1-yl]-trichloroacetamides, where the Cbz or MeO2C- group was attached to the nitrogen atom, were instantly converted to the corresponding trichlorinated cis-3a-aryloctahydroindol-2-ones in high yields at room temperature. The reactions offer a facile access to alkaloid skeletons such as mesembrines and crinines; as the simplest examples, total synthesis of (+/-)-mesembrane and (+/-)-crinane was accomplished. The effect of alkoxycarbonyl substituents in the amide group was compared with that of the methyl substituent. N-Methyl-N-(2-phenyl-2-cyclohexen-1-yl)trichloro- acetamide quickly reacted in the presence of CuCl(bipyridine) catalyst; however, the products were a mixture of complicated materials including a small amount of the desired lactam. The role of the alkoxycarbonyl group was discussed in terms of rate of rotation of the N-C bond in the N-allyltrichloroacetamides; variable-temperature NMR studies and X-ray structure determination of related compounds were carried out as supporting evidence.

  DOI：

  10.1021/jo9912146
• 作为产物：
  描述：

  2-bromocyclohex-2-enylamine 在 四(三苯基膦)钯 sodium carbonate 作用下， 以 乙醇 、 氯仿 、 水 、 苯 为溶剂， 反应 27.0h， 生成 methyl 2-(3',4'-methylenedioxyphenyl)cyclohex-2-enylcarbamate
  参考文献：
  名称：

  Banwell, Martin G.; Cowden, Cameron J., Australian Journal of Chemistry, 1994, vol. 47, # 12, p. 2235 - 2254

  摘要：

  DOI：

文献信息

• Concise synthetic route to both enantiomeric forms of 2,3,4,4a-tetrahydro[1,3]dioxolo[4,5-j]phenanthridin-6(5H)-one, the tetracyclic skeleton associated with the narcissus alkaloids lycoricidine and narciclasine
  作者：Martin G. Banwell、Cameron J. Cowden、Maureen F. Mackay

  DOI：10.1039/c39940000061

  日期：——

  Both enantiomeric forms, (S)-4 and (R)-4, of the tetracyclic skeleton associated with the title alkaloids 1 and 2 have been prepared; the key step involved silver isocyanate-promoted ring-opening of gem-dibromocyclopropane 5 and trapping of the resulting allylic isocyanate (±)-6 with (–)-menthol.

  与标题生物碱1和2相关的四环骨架的两种对映体形式(S)-4和(R)-4已被制备；关键步骤涉及异氰酸银促进宝石-二溴环丙烷 5 的开环，并用 (–)-薄荷醇捕获生成的烯丙基异氰酸酯 (±)-6。
• Banwell, Martin G.; Cowden, Cameron J., Australian Journal of Chemistry, 1994, vol. 47, # 12, p. 2235 - 2254
  作者：Banwell, Martin G.、Cowden, Cameron J.

  DOI：——

  日期：——
• Synthetic Studies of <i>cis</i>-3a-Aryloctahydroindole Derivatives by Copper-Catalyzed Cyclization of <i>N</i>-Allyltrichloroacetamides:  Facile Construction of Benzylic Quaternary Carbons by Carbon−Carbon Bond-Forming Reactions
  作者：Sho-ichi Iwamatsu、Kouki Matsubara、Hideo Nagashima

  DOI：10.1021/jo9912146

  日期：1999.12.1

  Cyclization of N-(2-aryl-2-cyclohexen-1-yl)trichloroacetamides by a copper catalyst was investigated. It is crucially important for successful cyclization under mild conditions that alkoxycarbonyl groups are introduced to the nitrogen atom of the N-allyltrichloroacetamides as well as that CuCl(bipyridine) is used as the catalyst. Three compounds, N-(2-phenyl-2-cyclohexen-1-yl)-, N-[2-(3,4-dimethoxyphenyl)-2-cyclohexen-1-yl]-, and N-[2-(3,4-methylenedioxyphenyl)-2-cyclohexen-1-yl]-trichloroacetamides, where the Cbz or MeO2C- group was attached to the nitrogen atom, were instantly converted to the corresponding trichlorinated cis-3a-aryloctahydroindol-2-ones in high yields at room temperature. The reactions offer a facile access to alkaloid skeletons such as mesembrines and crinines; as the simplest examples, total synthesis of (+/-)-mesembrane and (+/-)-crinane was accomplished. The effect of alkoxycarbonyl substituents in the amide group was compared with that of the methyl substituent. N-Methyl-N-(2-phenyl-2-cyclohexen-1-yl)trichloro- acetamide quickly reacted in the presence of CuCl(bipyridine) catalyst; however, the products were a mixture of complicated materials including a small amount of the desired lactam. The role of the alkoxycarbonyl group was discussed in terms of rate of rotation of the N-C bond in the N-allyltrichloroacetamides; variable-temperature NMR studies and X-ray structure determination of related compounds were carried out as supporting evidence.