phlomisoic acid methyl ester | 1122507-27-0

• 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
• 英文名称: phlomisoic acid methyl ester
• 英文别名: methyl phlomisoate
• CAS: 1122507-27-0
• 化学式: C₂₁H₃₀O₃
• 分子量: 330.467
• InChiKey: ICLLWKRUKSKTCT-NRSPTQNISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.31
• 重原子数：
  24.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  39.44
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  phlomisoic acid methyl ester 在 氧气 、 copper diacetate 、 palladium diacetate 、 对苯醌 作用下， 以 乙醚 、 丙酸 、 乙腈 为溶剂， 反应 160.0h， 生成
  参考文献：
  名称：

  Synthetic transformations of higher terpenoids: XXXII. Synthesis of 16-alkenyl-substituted labdatrienes by oxidative coupling of methyl phlomisoate with alkenes

  摘要：

  Reactions of methyl phlomisoate with methyl acrylate, phenyl acrylate, methyl vinyl ketone, phenyl vinyl ketone, or N-substituted acrylamides catalyzed by Pd(OAc)(2) in the presence of Cu(OAc)(2), p-benzoquinone in the mixture of propionic acid and acetonitrile proceed regio- and stereoselectively with the formation of (E)-16-vinyl labdatrienoates. The oxidative coupling under these conditions of the methyl phlomisoate with styrene results in a mixture of 15,16-distyryl-, 16-styryl-, and 16-(1-phenylvinyl)-derivatives of furanolabdanoid.

  DOI：

  10.1134/s1070428013110225

文献信息

• Synthesis and analgesic activity of 1,3,5-trisubstituted pyrazoles containing a diterpenoid moiety
  作者：M. E. Mironov、A. I. Poltanovich、T. V. Rybalova、M. P. Dolgikh、T. G. Tolstikova、E. E. Shults

  DOI：10.1007/s11172-020-2795-6

  日期：2020.3

  Conjugates of terpenoids with 1,3,5-trisubstituted pyrazoles were synthesized by the cross-coupling of methyl 16-(2-chloro-2-oxoacetyl)labdatrienoate with terminal arylacetylenes via the Castro—Stephens reaction and heterocyclization of arylalkyne-1,2-diones with arylhydr-azines. The structure of one reaction product was established by X-ray diffraction. The conditions for the formation of furanolabdanoid

  萜类化合物与 1,3,5-三取代吡唑的结合物是通过 16-(2-氯-2-氧代乙酰基)labdatrienoate 与末端芳基乙炔通过 Castro-Stephens 反应和 arylalkyne-1,2 杂环化的交叉偶联合成的-二酮与芳基肼。一种反应产物的结构是通过 X 射线衍射确定的。发现了形成呋喃烷醇芳基炔-1,2-二酮的条件。新合成的吡唑在化学刺激模型中表现出镇痛活性。
• Synthetic transformations of higher terpenoids. XXI.* Preparation of phlomisoic acid and its N-containing derivatives
  作者：M. E. Mironov、Yu. V. Kharitonov、E. E. Shul’ts、M. M. Shakirov、I. Yu. Bagryanskaya、G. A. Tolstikov

  DOI：10.1007/s10600-010-9577-6

  日期：2010.5

  A method for preparing 15,16-epoxylabda-8(9),13(16),14-trien-18-oic (phlomisoic) acid was proposed. Its structure was confirmed by an XSA. N-containing derivatives of phlomisoic acid that contained amines, hydrazides, and methyl esters of amino acids on the C-18 atom in addition to (2-oxo-2-aminoacetyl)-substituted derivatives of the C-16 methyl ester of phlomisoic acid were prepared.

  提出了一种制备15,16-环氧实验树脂-8(9),13(16),14-三烯-18-酸（克伦庚酸）的方法。其结构通过XSA得到确认。还制备了克伦庚酸的含氮衍生物，这些衍生物在C-18原子上含有胺、肼和氨基酸的甲基酯，此外还有克伦庚酸C-16甲基酯的(2-氧-2-氨基乙酰基)取代衍生物。
• Synthetic transformations of higher terpenoids. XXVII.* Synthesis of 7-hydroxylabdanoids and their transformations
  作者：Yu. V. Kharitonov、E. E. Shul´ts、Yu. V. Gatilov、I. Yu. Bagryanskaya、M. M. Shakirov、G. A. Tolstikov

  DOI：10.1007/s10600-012-0215-3

  日期：2012.5

  Allylic oxidation of phlomisoic acid and its methyl ester by selenium dioxide occurred stereoselectively to form 7α-hydroxy derivatives of labdanoids, which were oxidized by active manganese dioxide to 7-ketofuranolabdanoids. Oximation of the last by hydroxylamine hydrochloride in MeOH in the presence of NaOAc gave pure (E)-ketooximes. Beckmann rearrangement of 7-ketooximes of phlomisoic acid and its methyl ester occurred with formation of the corresponding octahydro-1 H-benzoazepines.

  通过二氧化硒对菲罗米索酸及其甲基酯进行烯丙基氧化，可形成7α-羟基的拉伯烷衍生物，后者在活性二氧化锰的作用下被氧化为7-酮基呋喃拉伯烷。在甲醇中，在NaOAc的存在下，通过羟胺盐酸盐对后者进行肟化反应，可得到纯的（E）-酮肟。菲罗米索酸及其甲基酯的7-酮肟发生贝克曼重排，形成相应的八氢-1 H-苯并氮杂卓。
• Synthetic Transformations of Higher Terpenoids. 45#. Regioselective Synthesis of 5-Labdanoid-Substituted Pyrazoles and Assessment of Their Analgesic Activity
  作者：M. E. Mironov、A. I. Poltanovich、V. I. Krasnov、T. V. Rybalova、S. A. Borisov、T. G. Tolstikova、E. E. Shults

  DOI：10.1007/s10600-024-04408-1

  日期：2024.7

  A method for targeted structural modification of the methyl ester of phlomisoic acid was developed by introduction of an additional C-16 ketopyrazole moiety via cyclocondensation of diterpenoid alkyne-1,2- diones with arylhydrazines. The conditions for regioselective formation of labdanoid 1,3-diarylpyrazol-5- ylmethanones were found. The possibility of a sequential four-component reaction in a single

  通过二萜炔-1,2-二酮与芳基肼的环缩合引入额外的 C-16 酮吡唑部分，开发了一种对宿根异酸甲酯进行靶向结构修饰的方法。找到了区域选择性形成劳丹烷1,3-二芳基吡唑-5-基甲酮的条件。证明了在一个锅中连续进行四组分反应的可能性。建立了劳丹诺取代的二芳基吡唑在热刺激和化学刺激模型中的显着镇痛活性。
• Synthetic transformations of higher terpenoids: XXXVI. Synthesis of furanolabdanoid glycoconjugates with a 1,2,3-triazole linker
  作者：O. I. Kremenko、Yu. V. Kharitonov、E. E. Shul’ts

  DOI：10.1134/s1070428017010079

  日期：2017.1

  Procedures have been developed for the synthesis of 16-[(propargyloxy) methyl]- and 7- and 18-(propargyloxy) labda-8(9), 13,14-trienes from phlomisoic acid. Copper-catalyzed cycloaddition of the labdanoid alkynes to azido derivatives of alpha-D-glucose, D-galactose, D-xylose, and L-arabinose afforded the corresponding N-glycosyl-1,2,3- triazole conjugates.