cis-12,13-epoxystearic acid | 32381-04-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: cis-12,13-epoxystearic acid
• 英文别名: cis-12,13-Epoxy-octadecancarbonsaeure；11-[(2S,3R)-3-pentyloxiran-2-yl]undecanoic acid
• CAS: 32381-04-7；32381-05-8；38003-80-4；61827-10-9
• 化学式: C₁₈H₃₄O₃
• 分子量: 298.466
• InChiKey: AHXFZOAYPPCFEB-SJORKVTESA-N

物化性质

• 沸点：
  422.7±18.0 °C(Predicted)
• 密度：
  0.956±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  21
• 可旋转键数：
  15
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  49.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  cis-12,13-epoxystearic acid 在 哌啶 、 sodium hydroxide 、 盐酸羟胺 、 溴 、 nickel diacetate 、 过碘酸 作用下， 以 甲醇 、 乙醇 、 水 、 xylene 、 叔丁醇 为溶剂， 反应 46.42h， 生成 11-氨基十一酸
  参考文献：
  名称：

  藜芦酸合成12-氨基十二烷酸和11-氨基十一烷酸

  摘要：

  Abstract12‐Aminododecanoic acid and 11‐aminoundecanoic acid, monomer precursors for nylon‐12 and nylon‐11, respectively, have been synthesized from vernolic (cis‐12,13‐epoxy‐cis‐9‐octadecenoic) acid via a reaction sequence that includes the formation of 12‐oxododecanoic acid oxime. Saponification of vernonia oil, followed by a low‐temperature recrystallization at −20°C, gave 51% vernolic acid (97% purity, m.p. 23–25°C). Hydrogenation afforded cis‐12,13‐epoxystearic acid (m.p. 52–54°C, lit. m.p. 52–54°C), which upon oxidation with periodic acid in tertiary butyl alcohol gave 12‐oxododecanoic acid with an isolated yield of 71.0%. Reaction of the oxoacid with hydroxylamine hydrochloride gave 12‐oxododecanoic acid oxime, which was catalytically reduced to give 12‐aminododecanoic acid with a yield greater than 85% and a melting point of 184–186°C (lit. m.p. 185–187°C). 11‐Aminoundecanoic acid was prepared from the 12‐oxododecanoic acid oxime via a three‐step reaction sequence that involved a Beckmann rearrangement, Hofmann degradation, and hydrolysis. Thus, the aldoxime acid was hydrolyzed in the presence of nickel acetate tetrahydrate to give 11‐carbamoylundecanoic acid (48% yield, m.p. 129–131°C, lit. m.p. 129–130°C). The amide was then treated with a solution of sodium methoxide and bromine at 70–80°C to give 11‐(methoxycarbonylamino)undecanoic acid at 75% yield (m.p. 84–86°C; elemental analysis, calculated for C13H25NO4: C, 60.19; H, 9.73; N, 5.40; O, 24.68%; found C, 60.02; H, 9.81; N, 5.26; O, 24.91%), which upon alkaline hydrolysis and subsequent neutralization gave 11‐aminoundecanoic acid at 34% yield (m.p. 189–192°C, lit. m.p. 190°C). Mass spectrometric and 13C nuclear magnetic resonance data of the previously unreported 11‐(methoxycarbonylamino)undecanoic acid is provided.

  DOI：

  10.1007/s11746-997-0176-z
• 作为产物：
  描述：

  (+/-)-顺式-12,13-环氧-9(Z)-十八碳烯酸 在 platinum(IV) oxide 氢气 作用下， 以 甲醇 为溶剂， 反应 0.75h， 以93%的产率得到cis-12,13-epoxystearic acid
  参考文献：
  名称：

  藜芦酸合成12-氨基十二烷酸和11-氨基十一烷酸

  摘要：

  Abstract12‐Aminododecanoic acid and 11‐aminoundecanoic acid, monomer precursors for nylon‐12 and nylon‐11, respectively, have been synthesized from vernolic (cis‐12,13‐epoxy‐cis‐9‐octadecenoic) acid via a reaction sequence that includes the formation of 12‐oxododecanoic acid oxime. Saponification of vernonia oil, followed by a low‐temperature recrystallization at −20°C, gave 51% vernolic acid (97% purity, m.p. 23–25°C). Hydrogenation afforded cis‐12,13‐epoxystearic acid (m.p. 52–54°C, lit. m.p. 52–54°C), which upon oxidation with periodic acid in tertiary butyl alcohol gave 12‐oxododecanoic acid with an isolated yield of 71.0%. Reaction of the oxoacid with hydroxylamine hydrochloride gave 12‐oxododecanoic acid oxime, which was catalytically reduced to give 12‐aminododecanoic acid with a yield greater than 85% and a melting point of 184–186°C (lit. m.p. 185–187°C). 11‐Aminoundecanoic acid was prepared from the 12‐oxododecanoic acid oxime via a three‐step reaction sequence that involved a Beckmann rearrangement, Hofmann degradation, and hydrolysis. Thus, the aldoxime acid was hydrolyzed in the presence of nickel acetate tetrahydrate to give 11‐carbamoylundecanoic acid (48% yield, m.p. 129–131°C, lit. m.p. 129–130°C). The amide was then treated with a solution of sodium methoxide and bromine at 70–80°C to give 11‐(methoxycarbonylamino)undecanoic acid at 75% yield (m.p. 84–86°C; elemental analysis, calculated for C13H25NO4: C, 60.19; H, 9.73; N, 5.40; O, 24.68%; found C, 60.02; H, 9.81; N, 5.26; O, 24.91%), which upon alkaline hydrolysis and subsequent neutralization gave 11‐aminoundecanoic acid at 34% yield (m.p. 189–192°C, lit. m.p. 190°C). Mass spectrometric and 13C nuclear magnetic resonance data of the previously unreported 11‐(methoxycarbonylamino)undecanoic acid is provided.

  DOI：

  10.1007/s11746-997-0176-z

文献信息

• Syntheses of 12-aminododecanoic and 11-aminoundecanoic acids from vernolic acid
  作者：Folahan O. Ayorinde、Erick Y. Nana、Pete D. Nicely、Anthony S. Woods、Elvis O. Price、Chukwuma P. Nwaonicha

  DOI：10.1007/s11746-997-0176-z

  日期：1997.5

  Abstract12‐Aminododecanoic acid and 11‐aminoundecanoic acid, monomer precursors for nylon‐12 and nylon‐11, respectively, have been synthesized from vernolic (cis‐12,13‐epoxy‐cis‐9‐octadecenoic) acid via a reaction sequence that includes the formation of 12‐oxododecanoic acid oxime. Saponification of vernonia oil, followed by a low‐temperature recrystallization at −20°C, gave 51% vernolic acid (97% purity, m.p. 23–25°C). Hydrogenation afforded cis‐12,13‐epoxystearic acid (m.p. 52–54°C, lit. m.p. 52–54°C), which upon oxidation with periodic acid in tertiary butyl alcohol gave 12‐oxododecanoic acid with an isolated yield of 71.0%. Reaction of the oxoacid with hydroxylamine hydrochloride gave 12‐oxododecanoic acid oxime, which was catalytically reduced to give 12‐aminododecanoic acid with a yield greater than 85% and a melting point of 184–186°C (lit. m.p. 185–187°C). 11‐Aminoundecanoic acid was prepared from the 12‐oxododecanoic acid oxime via a three‐step reaction sequence that involved a Beckmann rearrangement, Hofmann degradation, and hydrolysis. Thus, the aldoxime acid was hydrolyzed in the presence of nickel acetate tetrahydrate to give 11‐carbamoylundecanoic acid (48% yield, m.p. 129–131°C, lit. m.p. 129–130°C). The amide was then treated with a solution of sodium methoxide and bromine at 70–80°C to give 11‐(methoxycarbonylamino)undecanoic acid at 75% yield (m.p. 84–86°C; elemental analysis, calculated for C13H25NO4: C, 60.19; H, 9.73; N, 5.40; O, 24.68%; found C, 60.02; H, 9.81; N, 5.26; O, 24.91%), which upon alkaline hydrolysis and subsequent neutralization gave 11‐aminoundecanoic acid at 34% yield (m.p. 189–192°C, lit. m.p. 190°C). Mass spectrometric and 13C nuclear magnetic resonance data of the previously unreported 11‐(methoxycarbonylamino)undecanoic acid is provided.