(13alpha,17alpha)-7alpha-乙酰氧基-21,23-环氧-4,4,8-三甲基-24-去甲-5alpha-胆甾-1,14,20,22-四烯-3,16-二酮 | 26241-51-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 中文名称: (13alpha,17alpha)-7alpha-乙酰氧基-21,23-环氧-4,4,8-三甲基-24-去甲-5alpha-胆甾-1,14,20,22-四烯-3,16-二酮
• 英文名称: azadiradione
• 英文别名: [(5R,7R,8R,9R,10R,13S,17R)-17-(furan-3-yl)-4,4,8,10,13-pentamethyl-3,16-dioxo-6,7,9,11,12,17-hexahydro-5H-cyclopenta[a]phenanthren-7-yl] acetate
• CAS: 26241-51-0
• 化学式: C₂₈H₃₄O₅
• 分子量: 450.575
• InChiKey: KWAMDQVQFVBEAU-HMWIRDDCSA-N

物化性质

• 熔点：
  >99°C (dec.)
• 沸点：
  552.1±50.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)
• 溶解度：
  可溶于氯仿（少许）、甲醇（少许）

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  33
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  73.6
• 氢给体数：
  0
• 氢受体数：
  5

安全信息

• WGK Germany：
  3

反应信息

• 作为反应物：
  描述：

  (13alpha,17alpha)-7alpha-乙酰氧基-21,23-环氧-4,4,8-三甲基-24-去甲-5alpha-胆甾-1,14,20,22-四烯-3,16-二酮 生成 (5R,7R,8R,10S,13S,17R)-17-(furan-3-yl)-7-hydroxy-4,4,8,10,13-pentamethyl-6,7,9,11,12,17-hexahydro-5H-cyclopenta[a]phenanthrene-3,16-dione
  参考文献：
  名称：

  SIDDIQUI, SALIMUZZAMAN;SIDDIQUI, BINA SHAHEEN;FAIZI, SHAHEEN;MAHMOOD, TAR+, NEW TRENDS NATUR. PROD. CHEM., 1986. PROC. 2ND INT. SYMP. AND PAKISTAN-US+

  摘要：

  DOI：
• 作为产物：
  描述：

  nimbocinol 、 乙酸酐 生成 (13alpha,17alpha)-7alpha-乙酰氧基-21,23-环氧-4,4,8-三甲基-24-去甲-5alpha-胆甾-1,14,20,22-四烯-3,16-二酮
  参考文献：
  名称：

  COREY, E. J.;HAHL, ROBERT W., TETRAHEDRON LETT., 30,(1989) N3, C. 3023-3026

  摘要：

  DOI：

文献信息

• Ethylbenzene Hydroperoxide: An efficient oxidizing agent for diastereoselective synthesis of Spiroepoxy oxindoles
  作者：Praveen K. Valmiki、Mohan Banyangala、Sunil Varughese、Sasidhar B. Somappa

  DOI：10.1016/j.tetlet.2022.154126

  日期：2022.10

  Ethylbenzene hydroperoxide (EBHP) has been studied for the epoxidation of oxindole chalcones with various inorganic bases and different solvent systems. 10 M solution of NaOH with EBHP in hexane furnished a high yield of spiro epoxy oxindoles in a short reaction time at room temperature. The reaction condition applicable to electron-deficient, electron-rich arylideneindolin-2-ones, heteroarylideneindolin-2-ones

  已经研究了乙苯过氧化氢 (EBHP) 用于各种无机碱和不同溶剂体系对羟吲哚查耳酮的环氧化反应。10 M NaOH 与 EBHP 在己烷中的溶液在室温下的短反应时间内提供了高产率的螺环环氧羟吲哚。该反应条件适用于缺电子、富电子的亚芳基二氢吲哚-2-酮、杂亚芳基二氢吲哚-2-酮和亚烷基二氢吲哚-2-酮，得到非对映选择性芳基/杂芳基和烷基螺环氧乙烷。过氧化物试剂中的比较研究表明，EBHP 在非对映选择性、产率和反应时间方面是最好的。同位素标记实验表明水分子参与了这种氧化机制。
• Biocatalysis: fungi mediated novel and selective 12β- or 17β-hydroxylation on the basic limonoid skeleton
  作者：Saikat Haldar、Swati P. Kolet、Hirekodathakallu V. Thulasiram

  DOI：10.1039/c3gc40193f

  日期：——

  Basic limonoids carrying a 4,4,8-trimethyl-17-furanylsteroid skeleton are a class of triterpenoids and well-known for their insecticidal as well as a vast array of pharmacological activities. Rare and synthetically challenging 12β- and 17β-hydroxylation was achieved on the basic limonoid skeleton to produce a novel series of hydroxylated limonoids using fungi-mediated biocatalysis. The fungal system belonging to the genera of Mucor efficiently converted azadiradione, epoxyazadiradione, gedunin and their derivatives into corresponding 12β- and/or 17β-hydroxy derivatives. The position and stereochemistry of hydroxylation was determined by rigorous spectroscopic and crystallographic studies. This fungi-mediated stereo- and regio-selective hydroxylation process was highly efficient and mild enough to sustain chemically sensitive functional groups around the basic limonoid skeleton. Modifications of specific functional groups and variation in biocatalyst were shown to bring selectivity among 12β- or 17β-hydroxylation.

  具有4,4,8-三甲基-17-呋喃基类固醇骨架的基本柠檬素是一类三萜类化合物，以其杀虫性和广泛的药理活性而闻名。在基本柠檬素骨架上实现了罕见的、合成上极具挑战性的12β-和17β-羟基化反应，利用真菌介导的生物催化作用生产了一系列新型羟基化柠檬素。属于毛霉属的真菌系统能够有效地将印楝素、环氧印楝素、根皮苷及其衍生物转化为相应的12β-和/或17β-羟基衍生物。羟基化的位置和立体化学结构通过严格的光谱和晶体学研究确定。这种真菌介导的立体和区域选择性羟基化过程非常高效且温和，能够保护基本柠檬素骨架周围的化学敏感官能团。研究表明，特定官能团的修饰和生物催化剂的变化能够带来12β-或17β-羟基化的选择性。
• Transformation of Azadiradione to Nimbocinol and 17β-Hydroxynimbocinol, and StructurePesticidal-Activity Relationship of Triterpenoids isolated fromAzadirachta indica A. Juss. (Neem)
  作者：Bina S. Siddiqui、Munawwer Rasheed、Shaheen Faizi、Firdous、S. Tariq Ali、Rajput M. Tariq、Syed Naeem-ul-Hassan Naqvi

  DOI：10.1002/hlca.200390277

  日期：2003.10

  During studies on the structurepesticidal-activity relationship of Azadirachta indica constituents, azadiradione (1) was treated with methanolic K2CO3 to obtain 7-deacetyl derivative nimbocinol (2). Unexpectedly, 17β-hydroxynimbocinol (3), reported earlier as a natural product, was also formed. The structurepesticidal-activity relationship of triterpenoids 1–16 against Anopheles stephensi Liston is described

  期间的structurepesticidal -活性关系研究印楝成分，azadiradione（1）中的溶液用甲醇K处理2 CO 3，得到7-脱乙酰衍生物nimbocinol（2）。出乎意料的是，还形成了17β-羟基苯丁二酚（3），较早时被报道为天然产物。三萜类化合物1 – 16对斯蒂芬按蚊的结构杀虫活性关系描述Liston旨在理解负责具有阿朴双烯（apotirucallaneane）和gedunin skeleta的三萜类化合物的杀虫活性的活性功能。三萜类化合物的杀虫活性2 - 8报告首次。
• 7-Deacetyl-17β-hydroxyazadiradione, a new limonoid insect growth inhibitor from Azadirachta indica
  作者：S.Mark Lee、Jay I. Olsen、Martin P. Schweizer、James A. Klocke

  DOI：10.1016/0031-9422(88)80661-7

  日期：1988.1

  tetranortriterpenoid of the limonoid type, 7-deacetyl-17β-hydroxyazadiradione, and the known compound azadiradione, were isolated from the seeds of Azadirachta indica . The structure of the new compound was established by spectroscopic methods. The activity of the new compound as an insect growth inhibitor against Heliothis virescens was found to be greater than that of azadiradione and 7-deacetylazadiradione.

  摘要 从印楝种子中分离得到一种新的柠檬苦素型四降三萜，7-脱乙酰基-17β-羟基氮杂二二酮和已知化合物氮杂二二酮。新化合物的结构是通过光谱方法确定的。发现这种新化合物作为昆虫生长抑制剂对 Heliothis virescens 的活性高于氮杂双二酮和 7-脱乙酰氮杂双二酮的活性。
• Whole-Cell Mediated 11β-Hydroxylation on the Basic Limonoid Skeleton by <i>Cunninghamella echinulata</i>
  作者：Saikat Haldar、Fayaj A. Mulani、Thiagarayaselvam Aarthy、Hirekodathakallu V. Thulasiram

  DOI：10.1021/acs.joc.5b00417

  日期：2015.6.19

  Regio- and stereoselective 11 beta-hydroxylation was achieved on the basic limonoid skeleton through microbial transformation. Whole cells of Cunninghamella echinulata efficiently converted basic limonoids such as epoxyazadiradione, azadiradione, and gedunin to their 11 beta-hydroxy analogues as the sole metabolite. Fermentation conditions affecting the efficiency (96%) of biotransformation including substrate concentration, incubation period, pH, and temperature were optimized. The position and stereochemistry of hydroxyl functionality on the isolated metabolites were established through extensive spectroscopic and spectrometric studies (1D, 2D NMR, ESI-MS, and MS/MS).