(E)-1,1,1-trifluoro-6,10-dimethylundeca-5,9-dien-2-one | 60244-37-3

• 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: (E)-1,1,1-trifluoro-6,10-dimethylundeca-5,9-dien-2-one
• 英文别名: (5E)-1,1,1-trifluoro-6,10-dimethylundeca-5,9-dien-2-one
• CAS: 60244-37-3
• 化学式: C₁₃H₁₉F₃O
• 分子量: 248.288
• InChiKey: VCHIQJZLMXWVDR-DHZHZOJOSA-N

物化性质

• 沸点：
  289.1±40.0 °C(Predicted)
• 密度：
  1.019±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (E)-1,1,1-trifluoro-6,10-dimethylundeca-5,9-dien-2-one 在 四溴化碳 、 sodium hydride 、 二异丁基氢化铝 、 tris(tetra-n-butylammonium) hydrogen pyrophosphate 、 三苯基膦 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 3.5h， 生成 13-trifluorofarnesyl diphosphate
  参考文献：
  名称：

  Synthesis of analogs of farnesyl diphosphate

  摘要：

  Syntheses of analogs of farnesyl diphosphate (FPP) bearing substitutions at C3 are described The mono-, di-, and trifluoromethylFPP derivatives were prepared by alkylation of appropriately substituted acetoacetates with geranyl bromide, followed by decarboxylation to obtain fluorinated ketones and a Wittig condensation to give the farnesyl skeleton. A similar sequence was used to synthesize 13-desmethylFPP.

  DOI：

  10.1016/0040-4020(95)00909-r
• 作为产物：
  描述：

  [(2E)-3,7-dimethylocta-2,6-dienyl] 4,4,4-trifluoro-3-oxobutanoate 以56%的产率得到
  参考文献：
  名称：

  SHIMIZU, ISAO;ISHII, HIROTOSHI;TASAKA, ATSUMA, CHEM. LETT.,(1989) N, C. 1127-1128

  摘要：

  DOI：

文献信息

• Insect chemistry—VI
  作者：F. Camps、R. Canela、J. Coll、A. Messeguer、A. Roca

  DOI：10.1016/0040-4020(78)89023-1

  日期：1978.1

  Preparation of two trifluoromethyl analogs of JH-III, methyl 10,11-epoxy-7,11-dimethyl-3-trifluoromethyldodeca-2, 6-dienoate (1a) and methyl 10,11-epoxy-3,11-dimethyl-7-trifluoromethyldodeca-2,6-dienoate (1b) is described. The stereochemistry of trisubstituted double bonds, bearing one trifluoromethyl substituent, could be assigned easily by 19F NMR spectroscopy. Some peculiarities of the Wittig reactions

  制备JH-III的两个三氟甲基类似物，即10,11-环氧-7,11-甲基-3-甲基三氟甲基dodeca-2,6-二烯酸酯（1a）和10,11-环氧-3,11-二甲基-7甲基描述了-三氟甲基十二烷基-2，6-二烯酸酯（1b）。带有一个三氟甲基取代基的三取代双键的立体化学可通过19 F NMR光谱轻松确定。指出了三氟甲基酮的Wittig反应的一些特征。
• Synthesis of fluorine analogues of vitamin E.
  作者：ITSUMARO KUMADAKI、MIHOKO TAMURA、AKIRA. ANDO、TAKABUMI NAGAI、MAYUMI KOYAMA、TAKUICHI MIKI

  DOI：10.1248/cpb.36.515

  日期：——

  As part of a search for biologically active analogues of vitamin E, fluorine derivatives of tocotrienol and related compounds were synthesized by the ring-closure of trifluoroprenols with trimethylhydroquinone. For this purpose, the trifluoroprenols were synthesized by the Wittitg-Horner reaction of trifluoroacetone or its prenyl homologues with triethylphosphonoacetate followed by reduction of the trifluoromethylated acrylic ester derivatives. Although 4, 4, 4-trifluoroprenol itself did not react with the hydroquinone, 7, 7, 7-trifluorodiprenol and higher prenols gave 6-chromanols with a trifluofomethylated side-chan.

  在寻找具有生物活性的维生素 E 类似物的过程中，通过三氟丙烯醇与三甲基对苯二酚的环闭反应合成了生育三烯酚和相关化合物的氟衍生物。为此，三氟丙烯醇是通过三氟丙酮或其炔基同系物与三乙基膦酰基乙酸酯的 Wittitg-Horner 反应合成的，然后还原三氟甲基化丙烯酸酯衍生物。虽然 4，4，4-三氟丙烯醇本身不与对苯二酚反应，但 7，7，7-三氟二丙烯醇和更高的前烯醇会产生具有三氟甲基化侧链的 6-铬醇。
• Synthesis of Fluorine Analogs of Vitamin E. IV. Synthesis of Bis(trifluoromethyl)tocopherols.
  作者：Mayumi KOYAMA、Toshiyuki TAKAGI、Akira ANDO、Itsumaro KUMADAKI

  DOI：10.1248/cpb.43.1466

  日期：——

  We previously synthesized mono(trifluoromethyl)tocopherols, which were used for investigation of the mobility and orientation of tocopherol in Iliposomes by 19F-NMR. For more precise investigation of the behavior of vitamin E in liposomes, tocopherols having two trifluoromethyl groups, one on the prenyl side chain and the other on the chromanol ring, were synthesized. Thusn, dimethylhydroquinones were treated with 6-chloro-3-methyl-2-hexenol in the presence of zinc chloride to give 2-(3-chloropropyl)trimethylchromanol derivatives. These were converted to phosphonium salts, which, upon condensation with trifluoromethylated ketones followed by hydrogenation, gave tocopherols with a trifluoromethyl group on the side chain and a hydrogen on the chromanol part. These were halogenated on the chromanol part and treated with trifluoromethyl iodide and copper powder to give the title compounds.

  我们之前合成了单（三氟甲基）生育酚，用于通过 19F-NMR 研究生育酚在脂质体中的迁移率和取向。为了更精确地研究维生素 E 在脂质体中的行为，合成了具有两个三氟甲基的生育酚，一个在异戊烯基侧链上，另一个在苯并二氢吡喃醇环上。因此，在氯化锌存在下用6-氯-3-甲基-2-己烯醇处理二甲基氢醌，得到2-(3-氯丙基)三甲基苯并二氢吡喃醇衍生物。将它们转化为鏻盐，与三氟甲基化酮缩合，然后氢化，得到侧链上有三氟甲基且苯并二氢吡喃醇部分上有氢的生育酚。将它们在苯并二氢吡喃醇部分上卤化，并用三氟甲基碘和铜粉处理，得到标题化合物。
• Synthesis of fluorine analogues of vitamin E. II. Synthesis of 2-(3-chloropropyl)-2,5,7,8-tetramethyl-6-chromanol and its application for stereocontrolled Wittig reaction with trifluoromethyl ketones.
  作者：MAYUMI KOYAMA、MIHOKO TAMURA、AKIRA ANDO、TAKABUMI NAGAI、TAKUICHI MIKI、ITSUMARO KUMADAKI

  DOI：10.1248/cpb.36.2950

  日期：——

  As the extension of our research to find a biologically active analogue of vitamin E, a more convenient method for the synthesis of fluorine derivatives of 6-chromanol than our previous method was developed. Thus, 2-(3-chloropropyl)-2, 5, 7, 8-tetramethyl-6-chromanol (3) was synthesized by the reaction of 6-chloro-3-methyl-2-hexen-1-ol (2) and trimethylhydroquinone, and the phosphonium ylides (5 and 6) derived from 3 were condensed with trifluoromethylated ketones to give 2-(trifluoroprenyl)-6-chromanol compounds (1a, 1b and 1c) by means of the Wittig reaction as modified by Schlosser. By the use of this revised procedure, the total yields of the chromanols were much improved. Further, the modified Wittig reaction showed higher stereoselectivity than the previous syntheses of these compounds. The double bonds of the side-chain of the products were reduced to give fluorine derivatives of tocopherol analogues. Compound 3 was found to be a useful intermediate for the facile synthesis of vitamin E derivatives.

  作为我们寻找维生素 E 生物活性类似物研究的延伸，开发了一种比我们之前的方法更方便的 6-苯并二氢吡喃醇氟衍生物的合成方法。因此，通过6-氯-3-甲基-2-己烯-1-醇(2)的反应合成2-(3-氯丙基)-2,5,7,8-四甲基-6-苯并二氢吡喃醇(3)和三甲基氢醌，以及由3衍生的鏻叶立德(5和6)与三氟甲基化酮缩合，通过Schlosser改进的Wittig反应得到2-(三氟异戊二烯基)-6-苯并二氢吡喃醇化合物(1a、1b和1c)。通过使用这一修改后的程序，苯并二氢吡喃醇的总产率得到了很大提高。此外，改进的维蒂希反应比以前合成的这些化合物显示出更高的立体选择性。产物侧链双键被还原，得到生育酚类似物的氟衍生物。化合物 3 被发现是一种有用的中间体，可用于轻松合成维生素 E 衍生物。
• KUMADZUKI, TAKAMARU
  作者：KUMADZUKI, TAKAMARU

  DOI：——

  日期：——