(+/-)-2-oxo-1,8-cineole

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (+/-)-2-oxo-1,8-cineole
• 英文别名: 6-ketocineole；(+/-)-1,8-epoxy-p-menthan-2-one；(+/-)-1,8-Epoxy-p-menthan-2-on；(1S,4R)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-6-one
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: CCBAAZXPXFYPBE-XCBNKYQSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+/-)-2-oxo-1,8-cineole 在 盐酸 、 氢氧化钾 、 sodium amide 、 苯 作用下， 生成 6-methoxy-3,3,6-trimethyl-tetrahydro-isobenzofuran-1,7-dione
  参考文献：
  名称：

  Gandini, Gazzetta Chimica Italiana, 1940, vol. 70, p. 438,445

  摘要：

  DOI：
• 作为产物：
  描述：

  (+/-)-endo-2-hydroxy-1,8-cineol 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以70%的产率得到(+/-)-2-oxo-1,8-cineole
  参考文献：
  名称：

  摄入1,8-Cineole的胶囊后手性1,8-Cineole代谢物的合成及其对映体组成的测定

  摘要：

  摄入含1,8-桉树脑（桉树脑）的肠溶胶囊（Soledum）后，研究了人类尿液中的手性代谢物。为了鉴定各种对映异构体，对映体纯的（-/ +）-α2-羟基-1,8-桉树脑，（-/ +）-β2-羟基-1,8-桉树脑，（-/ +）-9-羟基制备了-1,8-桉树脑和（-/ +）-2-氧代-1,8-桉树脑。为实现这一目标，在合成的外消旋2-羟基和9-羟基-1,8-桉树脑被乙酰化后，猪肝酯酶或酵母介导的水解作用为（-）-醇及其对映异构体的对映体（+）-乙酸酯提供了对映体超过33–100％。通过拆分乙酸盐的水解获得的Dess-Martin高碘烷对醇（+）-α2-羟基-1,8-桉树脑的氧化，提供了相应的（+）-2-氧代-1,8-桉树脑，同时进行了氧化（-）-α2-羟基-1,8-桉树脑的化合物得到（-）-2-2-氧-1,8-桉树脑。使用这些标准品的七个代谢物（+/-）-α2-羟基-1,8-桉树脑，（+/-）-β2-羟基-1

  DOI：

  10.1002/cplu.201200253

文献信息

• In vivo and in vitro hydroxylation of cineole and camphor by cytochromes P450CYP101A1, CYP101B1 and N242A CYP176A1
  作者：Jeanette E. Stok、Emma A. Hall、Isobella S.J. Stone、Margaret C. Noble、Siew Hoon Wong、Stephen G. Bell、James J. De Voss

  DOI：10.1016/j.molcatb.2016.03.004

  日期：2016.6

  Cytochromes P450 (P450s) are valuable enzymes that can generate a range of useful compounds via biocatalytic oxidations that complement traditional synthetic chemistry. In this study three bacterial P450s, qP450(cam) (CYP101A1), CYP101B1 and the mutant N242A-P450(cin) (N242A-CYP176A1), were used to produce a range of products from the oxidation of the monoterpenes (1R)- and (1S) -camphor and 1,8-cineole. We demonstrate that both in vitro and in vivo catalytic turnover with these P450s can produce a complement of up to seven hydroxycamphors and seven hydroxycineoles, in addition to compounds produced from further oxidation. The CYP101B1 whole cell catalytic system was found to produce 300-600 mg/L of culture of oxidation products that could be easily separated chromatographically. The CYP101B1 in vitro oxidation of 1,8-cineole primarily produced (1S)-5 alpha-hydroxycineole, which was 78% of the total product formed. However, the amount of (1S)-5a-hydroxycineole was reduced to 42% of the total products when isolated from the CYP101B1 whole cell system. (1S)-6 alpha-Hydroxycineole (96% ee) could be isolated from a whole cell catalytic turnover of 1,8-cineole by N242A-P450c,n in a yield of 46 mg/L (98% of the total product). However, the amount of product isolated ((1R)-5-endo-hydroxycamphor, 75% of the total products) from the whole cell catalytic oxidation of (1R) -camphor with N242A-P450c,n was much lower (6 mg/L) due to the inefficient use of reducing equivalents (3.5 + 0.5%) for substrate oxidation. These compounds will assist in the identification of specific structures in mechanistic investigations and structure elucidation, but further optimisation is required to generate larger quantities for synthetic applications. (C) 2016 Elsevier B.V. All rights reserved.
• Carman, Raymond M.; Fletcher, Mary T., Australian Journal of Chemistry, 1984, vol. 37, # 5, p. 1117 - 1122
  作者：Carman, Raymond M.、Fletcher, Mary T.

  DOI：——

  日期：——
• Gandini, Gazzetta Chimica Italiana, 1937, vol. 67, p. 113,116
  作者：Gandini

  DOI：——

  日期：——
• Sandris; Ourisson, Bulletin de la Societe Chimique de France, 1958, p. 338,344
  作者：Sandris、Ourisson

  DOI：——

  日期：——
• Cusmano, Gazzetta Chimica Italiana, 1942, vol. 72, p. 68,72
  作者：Cusmano

  DOI：——

  日期：——