5-(三氟甲基)二苯并[b,d]硒吩鎓三氟甲烷磺酸酯 | 129922-33-4

• 分子结构分类: 有机化合物 - 苯类化合物
• 中文名称: 5-(三氟甲基)二苯并[b,d]硒吩鎓三氟甲烷磺酸酯
• 中文别名: 硒-（三氟甲基）二苯并硒基三氟甲磺酸盐
• 英文名称: Se-(trifluoromethyl)dibenzoselenophenium triflate
• 英文别名: Trifluoromethanesulfonate; 5-(trifluoromethyl)dibenzoselenophen-5-ium；trifluoromethanesulfonate;5-(trifluoromethyl)dibenzoselenophen-5-ium
• CAS: 129922-33-4
• 化学式: CF₃O₃S*C₁₃H₈F₃Se
• 分子量: 449.232
• InChiKey: JBCKNNSFQMKYGM-UHFFFAOYSA-M

物化性质

• 熔点：
  170-172°C

计算性质

• 辛醇/水分配系数(LogP)：
  4.27
• 重原子数：
  25
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  65.6
• 氢给体数：
  0
• 氢受体数：
  9

安全信息

• 危险品标志：
  Xi
• 安全说明：
  S22,S36/37/39,S45
• 危险类别码：
  R23/25,R33
• 危险品运输编号：
  UN 3283

反应信息

• 作为反应物：
  描述：

  5-(三氟甲基)二苯并[b,d]硒吩鎓三氟甲烷磺酸酯 在 nitronium trifluoromethanesulfonate 作用下， 反应 3.0h， 以83%的产率得到3,7-dinitro-Se-(trifluoromethyl)dibenzoselenophenium triflate
  参考文献：
  名称：

  功率可变的亲电三氟甲基化剂。S-、Se-和Te-(三氟甲基)二苯并硫代-、-硒-和-碲鎓盐系统

  摘要：

  S-、Se-和 Te-三氟甲基化二苯并杂环鎓盐、它们的衍生物和相关盐是通过 2-[（三氟甲基）硫代或硒代]联苯和三氟甲磺酸 (TfOH) 或 HBF 的混合物的直接氟化合成的4 醚化物，通过使用 Tf 2 O 和 (CH 3 ) 2 SO 对 2-[(三氟甲基) 碲] 联苯进行新型碲活化，或通过鎓的衍生，用 Tf 2 O 处理相应的亚砜和硒氧化物得到的盐。反应性检查表明，与非杂环盐相比，三氟甲基杂环盐具有很强的反应性，并表明该杂环盐体系可作为广泛适用的三氟甲基化剂的来源

  DOI：

  10.1021/ja00059a009
• 作为产物：
  描述：

  2-<(trifluoromethyl)seleno>biphenyl 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 1,1,2-三氯三氟乙烷（CFC-113） 为溶剂， 反应 2.0h， 生成 5-(三氟甲基)二苯并[b,d]硒吩鎓三氟甲烷磺酸酯
  参考文献：
  名称：

  功率可变的亲电三氟甲基化剂。S-、Se-和Te-(三氟甲基)二苯并硫代-、-硒-和-碲鎓盐系统

  摘要：

  S-、Se-和 Te-三氟甲基化二苯并杂环鎓盐、它们的衍生物和相关盐是通过 2-[（三氟甲基）硫代或硒代]联苯和三氟甲磺酸 (TfOH) 或 HBF 的混合物的直接氟化合成的4 醚化物，通过使用 Tf 2 O 和 (CH 3 ) 2 SO 对 2-[(三氟甲基) 碲] 联苯进行新型碲活化，或通过鎓的衍生，用 Tf 2 O 处理相应的亚砜和硒氧化物得到的盐。反应性检查表明，与非杂环盐相比，三氟甲基杂环盐具有很强的反应性，并表明该杂环盐体系可作为广泛适用的三氟甲基化剂的来源

  DOI：

  10.1021/ja00059a009

文献信息

• Enantioselective electrophilic trifluoromethylation of β-keto esters with Umemoto reagents induced by chiral nonracemic guanidines
  作者：Shun Noritake、Norio Shibata、Yoshinori Nomura、Yiyong Huang、Andrej Matsnev、Shuichi Nakamura、Takeshi Toru、Dominique Cahard

  DOI：10.1039/b909641h

  日期：——

  Chiral nonracemic guanidines act as Brønsted bases to generate guanidinium enolates for the enantioselective electrophilic trifluoromethylation of β-keto esters by means of S-(trifluoromethyl)dibenzothiophenium tetrafluoroborate (Umemoto reagent) with good enantioselectivity of 60–70% range. Despite the fact that the ees are still improvable, the model reported in this work could spark the imagination

  手性非外消旋胍充当布朗斯台德碱，通过以下方法生成β-酮酯的对映选择性亲电子三氟甲基化胍基烯醇盐。 S-（三氟甲基）二苯并噻吩四氟硼酸盐（梅本试剂）具有良好的对映选择性，范围为60–70％。尽管仍然可以改善ee的事实，但这项工作中报道的模型仍可以激发化学家的想象力，以设计新的手性碱来改善立体化学结果。
• Power-variable trifluoromethylating agents, (trifluoromethyl)dibenzothio- and -selenophenium salt system
  作者：Umemoto Teruo、Ishihara Sumi

  DOI：10.1016/s0040-4039(00)94447-2

  日期：1990.1
• Useful electrophilic trifluoromethylating agents; S-, Se- and Te-(trifluoromethyl)dibenzo-thio-, -seleno- and -telluro-phenium-3-sulfonates
  作者：Teruo Umemoto、Sumi Ishihara、Kenji Adachi

  DOI：10.1016/0022-1139(95)03253-a

  日期：1995.9

  Se, Se- and Te-(Trifluoromethyl) dibenzo-thio-, -seleno- and -telluro-phenium-3-sulfonates and their dimethyl and nitro derivatives have been synthesized in good yield by sulfonation of the corresponding (trifluoromethyl)dibenzocyclic chalcogen salts with fuming sulfuric acid or by sulfonation followed by nitration. The practical use of these power-variable trifluoromethylating agents has been demonstrated. Thus, they provide good yields of trifluoromethylated products, and the by-product (a salt of dibenzothiophene-3-sulfonic acid or an analog) was easily removed from the products by filtration or by washing with water. S-(Perfluoro-ethyl, -n-butyl- and -n-octyl)dibenzothiophenium-3-sulfonates have also been synthesized and a similar perfluoroalkylation using one of them has been accomplished.
• New Method for Trifluoromethylation of Enolate Anions and Applications to Regio-, Diastereo- and Enantioselective Trifluoromethylation
  作者：Teruo Umemoto、Kenji Adachi

  DOI：10.1021/jo00098a030

  日期：1994.9

  Assessment was made of the effectiveness of different boron Lewis acids in mediating the trifluoromethylation of reactive enolate anions with S- and Se-(trifluoromethyl)chalcogen salts. Treatment of potassium or lithium enolates derived in situ from carbonyl compounds or enol trimethylsilyl ethers with S-(trifluoromethyl)dibenzothiophenium triflate (1) in the presence of 2-phenyl-1,3,2-benzodioxaborole (4) produced trifluoromethylated carbonyl compounds in high yields. Iq this manner, various alpha-CF3 ketones, gamma-CF3-alpha,beta-unsaturated ketones, and an alpha-CF3 ester were synthesized. Perfluorooctylation was similarly conducted using S-(perfluorooctyl)dibenzothiophenium triflate and 4. Thus, a balance of the reactivity of the reactants was essential for these electrophilic perfluoroalkylations. The deprotonation of 2-methylcyclohexanone with KN(SiMe(3))(2) followed by trifluoromethylation gave the 6-trifluoromethylated product regioselectively. In the trifluoromethylation of potassium enolate 16 of 4,4a,5,6,7,8-hexahydro-4a-methyl-2(3H)-naphthalenone, the use of bulky 2-mesitylphenanthro[9,10-d]-1,3,2-dioxaborole (15) led to the diastereo-selective formation of the thermodynamically less stable CF3-isomer 17 beta. For enantioselective trifluoromethylation, optically active (S)-4-phenyldinaphtho[2,1-d:1',2'-f][1,3,2]dioxaborepin(19) and its 3,3'-diphenyl derivative 20 were synthesized. The trifluoromethylation of the potassium enolate of propiophenone with 1 in the presence of 20 afforded optically active alpha-CF3-propiophenone in 45% ee yield. Thus, a new and versatile method for selective trifluoromethylation has been developed.