甲基 (1R,4aR)-7-乙烯基-1,4a,7-三甲基-3,4,4b,5,6,9,10,10a-八氢-2H-菲-1-羧酸酯 | 3730-56-1

• 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: 甲基 (1R,4aR)-7-乙烯基-1,4a,7-三甲基-3,4,4b,5,6,9,10,10a-八氢-2H-菲-1-羧酸酯
• 中文别名: 甲基(1R,4aR)-7-乙烯基-1,4a,7-三甲基-3,4,4b,5,6,9,10,10a-八氢-2H-菲-1-羧酸酯
• 英文名称: pimara-8(14),15-dien-18-oic acid methyl ester
• 英文别名: Methyl pimarate；Pimarsaeure-methylester；Pimara-8(14),16-dien-18-saeure-methylester；methyl (1R,4aR,4bS,7S,10aR)-7-ethenyl-1,4a,7-trimethyl-3,4,4b,5,6,9,10,10a-octahydro-2H-phenanthrene-1-carboxylate
• CAS: 3730-56-1
• 化学式: C₂₁H₃₂O₂
• 分子量: 316.484
• InChiKey: BGCXKCIPDDNDEV-MIGBRYPXSA-N

物化性质

• 沸点：
  380.6±42.0 °C(Predicted)
• 密度：
  1.01±0.1 g/cm3(Predicted)
• 保留指数：
  2243;2198;2239;2214;2231;2234.4;2233.9

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.76
• 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：

  甲基 (1R,4aR)-7-乙烯基-1,4a,7-三甲基-3,4,4b,5,6,9,10,10a-八氢-2H-菲-1-羧酸酯 在 sodium iodide 作用下， 以 丙酮 为溶剂， 生成 methyl (1R,4aR,4bS,7R,10aR)-7-(iodomethyl)-1,4a,7-trimethyl-3,4,4b,5,6,9,10,10a-octahydro-2H-phenanthrene-1-carboxylate
  参考文献：
  名称：

  环化激进分子：构成新词的二等词类固醇

  摘要：

  类固醇化合物是通过自由基环化从匹马酸甲酯中获得的。

  DOI：

  10.1016/s0040-4039(00)96060-x
• 作为产物：
  描述：

  海松酸 生成 甲基 (1R,4aR)-7-乙烯基-1,4a,7-三甲基-3,4,4b,5,6,9,10,10a-八氢-2H-菲-1-羧酸酯
  参考文献：
  名称：

  第I部分环氧二萜酸酯：环氧的合成与活化衍生d'酸性树脂。

  摘要：

  用对硝基过苯甲酸将具有吡喃烷骨架的树脂酸的甲酯环氧化，可以分离环内双键的环氧化物。通过酸催化二萜环氧化物的异构化获得烯丙基二萜醇，并且已经研究了柯林斯试剂对这些烯丙基醇的作用。

  DOI：

  10.1016/s0040-4020(01)96547-0

文献信息

• Molecular Basis of Pimarane Compounds as Novel Activators of Large-Conductance Ca²⁺-Activated K⁺Channel α-Subunit
  作者：Yuji Imaizumi、Kazuho Sakamoto、Aki Yamada、Aya Hotta、Susumu Ohya、Katsuhiko Muraki、Masanobu Uchiyama、Tomohiko Ohwada

  DOI：10.1124/mol.62.4.836

  日期：2002.10.1

  Effects of pimaric acid (PiMA) and eight closely related compounds on large-conductance K+ (BK) channels were examined using human embryonic kidney (HEK) 293 cells, in which either the α subunit of BK channel (HEKBKα) or both α and β1 (HEKBKαβ1) subunits were heterologously expressed. Effects of these compounds (10 μM) on the membrane potential of HEKBKαβ1 were monitored by use of DiBAC4(3), a voltage-sensitive dye. PiMA, isopimaric acid, sandaracoisopimaric acid, dihydropimaric acid, dihydroisopimaric acid, and dihydroisopimarinol induced substantial membrane hyperpolarization. The direct measurement of BKαβ1 opening under whole-cell voltage clamp showed that these six compounds activated BKαβ1 in a very similar concentration range (1–10 μM); in contrast, abietic acid, sclareol, and methyl pimarate had no effect. PiMA did not affect the charybdotoxin-induced block of macroscopic BKαβ1 current. Single channel recordings of BKαβ1 in inside-out patches showed that 10 μM PiMA did not change channel conductance but significantly increased its open probability as a result of increase in sensitivity to Ca2+ and voltage. Because coexpression of the β1 subunit did not affect PiMA-induced potentiation, the site of action for PiMA is suggested to be BKα subunit. PiMA was selective to BK over cloned small and intermediate Ca2+ activated K+ channels. In conclusion, PiMA (>1 μM) increases Ca2+ and voltage-sensitivity of BKα when applied from either side of the cell membrane. The marked difference in potency as BK channel openers between PiMA and abietic acid, despite only very small differences in their chemical structures, may provide insight into the fundamental structure-activity relationship governing BKα activation.

  使用人胚肾（HEK）293细胞研究了皮马酸（PiMA）及八种密切相关化合物对大导电性钾离子（BK）通道的影响，这些细胞中异源表达了BK通道的α亚单位（HEKBKα）或同时表达了α和β1亚单位（HEKBKαβ1）。通过使用电压敏感染料DiBAC4(3)监测这些化合物（10 μM）对HEKBKαβ1膜电位的影响。皮马酸、异皮马酸、沙达卡异皮马酸、二氢皮马酸、二氢异皮马酸和二氢异皮马醇导致了显著的膜超极化。在全细胞电压钳下直接测量BKαβ1开启显示，这六种化合物在相似的浓度范围（1–10 μM）内激活BKαβ1；相比之下，阿比特酸、松香醇和甲基皮马酸没有影响。皮马酸不影响鞘毒素引起的宏观BKαβ1电流的阻断。在内外侧膜片的单通道记录中，10 μM的PiMA没有改变通道导电性，但显著增加了其开放概率，原因是对Ca2+和电压的敏感性增加。由于β1亚单位的共表达并未影响PiMA诱导的增强效果，因此推测PiMA的作用位点为BKα亚单位。PiMA对BK通道相对于克隆的小型和中型Ca2+激活的K+通道具有选择性。总之，PiMA（>1 μM）在从细胞膜任一侧应用时都能增加BKα对Ca2+和电压的敏感性。尽管PiMA和阿比特酸的化学结构仅有微小差异，但作为BK通道开启剂的显著作用差异，可能为理解BKα激活的基础结构-活性关系提供了新的见解。
• Partial synthesis of 9,10-syn-diterpenes via tosylhydrazone reduction: (-)-(9.beta.)-pimara-7,15-diene and (-)-(9.beta.)-isopimaradiene
  作者：Min Chu、Robert M. Coates

  DOI：10.1021/jo00043a013

  日期：1992.8

  (9-beta)-Pimara-7,15-diene (3), a proposed intermediate in the biosynthesis of the momilactone phytoalexins (1 and 2) from rice, and its C-13 epimer, (9-beta)-isopimara-7,15-diene (4), were synthesized from methyl pimara- and isopimara-8,15-dien-18-oates (8b and 8a, respectively). Allylic oxidation of 8a and 8b as well as the derived diterpene hydrocarbons 15a and 15b with chromium trioxide-dipyridine complex afforded 8,15-dien-7-ones 9a, 9b, 16a, and 16b (35-54%). Lithium-ammonia reduction of 9a, 16a, and 16b gave predominantly trans,anti,trans-isopimara- and -pimara-15-en-7-ones 10, 17a, and 17b. In contrast, catecholborane reduction of the tosylhydrazones of 9a and 9b provided methyl (9-beta)-isopimara- and (9-beta)-pimara-7,15-dien-20-oates (23a and 23b) having the 9,10-syn stereochemistry. The parent diterpenes, 3 and 4, were obtained by carboxyl-to-methyl conversions. In a collaborative investigation 3 was tentatively identified as one of five diterpene hydrocarbons produced upon incubation of (E,E,E)-geranylgeranyl pyrophosphate with a crude enzyme extract from UV-treated rice plants.

  (9-β)-坝沙烯-7,15-二烯(3)及其C-13表式异构体(4)是从水稻中产生的植保素类木菠萝烯(1和2)生物合成中的一个中间体。3和4从甲基巴沙和异巴沙-8,15-二烯-18酸(8b和8a)中合成。铬酸-二吡啶配合物对8a和8b以及它们的二烯烃15a和15b进行邻位氧化得到8,15-二烯-7-酮类化合物-9a、9b、16a和16b(35-54%产率)。用液氨-锂对9a、16a和16b进行还原,主要产率获得trans,anti,trans-异巴沙和巴沙-15-烯-7-酮(10,17a和17b)。相比之下,使用邻苯二酚硼烷还原9a和9b的犀角腙,得到具有9,10-顺式立体结构的甲基(9-β)-异巴沙-7,15-二烯-20酸和甲基(9-β)-巴沙-7,15-二烯-20酸(23a和23b)。通过羧酸基团转化为甲基基团得到这两种二烯烃的亲本化合物。合作研究发现,3是用紫外处理过的水稻粗酶提取液培养(E,E,E)-瑞香龙脑二磷酸酯后产生的五种二烯烃中的一种。
• John, Michael; Haslinger, Ernst, Liebigs Annalen der Chemie, 1992, # 10, p. 1019 - 1028
  作者：John, Michael、Haslinger, Ernst

  DOI：——

  日期：——
• Ayer, William A.; Macaulay, John B., Canadian Journal of Chemistry, 1987, vol. 65, p. 7 - 14
  作者：Ayer, William A.、Macaulay, John B.

  DOI：——

  日期：——
• Experiments Directed toward the Total Synthesis of Terpenes. IV. The Synthesis of (±)-Sandaracopimaradiene and (±)-Pimaradiene^1,2
  作者：Robert E. Ireland、Peter W. Schiess

  DOI：10.1021/jo01036a002

  日期：1963.1