七氟苄碘 | 79865-03-5

• 物质功能分类: 有机原料 - 烃类化合物及其衍生物 - 烃类卤化物
• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 七氟苄碘
• 中文别名: 二氟碘甲基五氟苯
• 英文名称: perfluorobenzyl iodide
• 英文别名: heptafluorobenzyl iodide；1-[difluoro(iodo)methyl]-2,3,4,5,6-pentafluorobenzene
• CAS: 79865-03-5
• 化学式: C₇F₇I
• mdl: MFCD00153184
• 分子量: 343.97
• InChiKey: KBTGPFZDZIZYLB-UHFFFAOYSA-N

物化性质

• 沸点：
  153 °C(lit.)
• 密度：
  2.185 g/mL at 25 °C(lit.)
• 闪点：
  >230 °F

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.142
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  7

安全信息

• 危险等级：
  IRRITANT
• 危险品标志：
  Xi,C
• 安全说明：
  S26,S36/37/39,S45
• 危险类别码：
  R34
• WGK Germany：
  3
• 海关编码：
  2903999090
• 危险品运输编号：
  UN 1760 8/PG 2

反应信息

• 作为反应物：
  描述：

  七氟苄碘 在 2,6-二甲基吡啶 、 sodium tetrahydroborate 、 Ir(ppy)2(dtb-bpy)PF₆ 、 (2R,5S)-2-(tert-butyl)-3,5-dimethylimidazolidin-4-one trifluoroacetate 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 9.0h， 生成 (S)-2-(perfluorobenzyl)octan-1-ol
  参考文献：
  名称：

  Enantioselective α-Trifluoromethylation of Aldehydes via Photoredox Organocatalysis

  摘要：

  The first enantioselective, organocatalytic alpha-trifluoromethytation and alpha-perfluoroalkylation of aldehydes have been accomplished using a readily available iridium photocatalyst and a chiral imidazolidinone catalyst. A range of alpha-trifluoromethyl and alpha-perfluoroalkyl aldehydes were obtained from commercially available perfluoroalkyl halides with high efficiency and enantioselectivity. The resulting alpha-trifluoromethyl aldehydes were subsequently shown to be versatile precursors for the construction of a variety of enantioenriched trifluoromethylated building blocks.

  DOI：

  10.1021/ja9053338
• 作为产物：
  描述：

  八氟甲苯 在 potassium iodide 作用下， 以 二乙二醇二甲醚 为溶剂， 反应 5.0h， 生成 七氟苄碘
  参考文献：
  名称：

  A new route to polyfluorinated trifluoromethanesulfonates. Synthesis of perfluoroallyl and perfluorobenzyl triflates

  摘要：

  Polyfluoroalkyl trifluoromethanesulfonates (triflates) can be prepared in good to excellent yields by the reaction of halofluoroalkanes such as CFC-11, CFC-113 and CFC-112 with boron triflate at 20-25 degrees C. Hexafluoropropene (HFP) is more active and reacts with B(OSO2CF3)(3) even at 0 degrees C to give perfluoroallyl triflate in 68% yield. Octafluorotoluene, 1,1,2-trichloro-3,3,3-trifluoroprop-1-ene and hexafluoro-2,3-dichloro-but-2-ene also produce the corresponding triflates in 30-60% yields on reaction with boron triflate.

  DOI：

  10.1016/0022-1139(94)03210-q

文献信息

• A novel double insertion of the difluoromethylene unit from trifluoromethylcopper into the carbon–copper bond of perfluoroaryl- and perfluorovinylcopper reagents: preparation, mechanism and applications of new fluorinated copper reagents
  作者：Zhen-Yu Yang、Donald J. Burton

  DOI：10.1016/s0022-1139(99)00247-x

  日期：2000.3

  (E)-CF3CFCFCF2CF2Cu, which could be trapped with allyl bromide to give (E)-CF3CFCFCF2CF2CH2CHCH2. When CF2CFCu was used as a substrate, (E)-CF3CFCFCF2CF2Cu was observed, but in low yield. A mechanism for this novel double CF2 insertion is proposed to involve a copper difluorocarbenoid complex intermediate, which inserted into the carbon–copper bond of the fluorinated phenyl and vinyl coppers to form fluorinated

  CF 3 Cu与由CuBr和五氟苯基镉C 6 F 5 CdX制备的五氟苯基铜反应，得到双CF 2单元插入产物C 6 F 5 CF 2 CF 2 Cu，产率为70-80％。在室温下，在CuBr存在下，CF 3 MX（M = Cd，Zn; X = Br，CF 3）和C 6 F 5 CdX的插入反应也很好，得到C 6 F 5 CF 2 CF 2 Cu。使用乙烯基铜类似物（Z）-CF 3CFCFCu，双CF 2插入也发生导致的形成（ë）-CF 3 CFCFCF 2 CF 2铜，其可以与烯丙基溴被捕获，得到（É）-CF 3 CFCFCF 2 CF 2 CH 2 CHCH 2。当使用CF 2 ＝ CFCu作为衬底时，观察到（E）-CF 3 CF ＝CFCF 2 CF 2 Cu，但是产率低。这种新型双CF 2的机理有人建议将其插入二氟卡宾铜络合物中间体中，然后将其插入氟化苯基和乙烯基铜的碳-铜键
• Perfluorobenzyl Complexes of Cobalt and Rhodium. Unusual Coupling between Pentafluorophenyl and Pentamethylcyclopentadienyl Rings
  作者：Russell P. Hughes、Danielle C. Lindner、Arnold L. Rheingold、Glenn P. A. Yap

  DOI：10.1021/om9607255

  日期：1996.12.24

  Oxidative addition of perfluorobenzyl iodide to [M(η5-C5R5)(CO)2] (M = Co, R = H, Me; M = Rh, R = Me) in benzene affords the perfluorobenzyl complexes [M(η5-C5R5)(CF2C6F5)I(CO)] (M = Co, R = H (1a), Me (2a); M = Rh, R = Me (2b)). Further reaction of 1a or 2a with PMe3 in benzene results in a substitution reaction to give complexes [Co(η5-C5R5)(CF2C6F5)I(PMe3)] (R = H (3a), Me (4a)) . While the reaction

  氧化加成perfluorobenzyl碘与[M（η 5 -C 5 - [R 5）（CO）2 ]（M = CO，R = H，甲基; M = RH，R = Me）的在苯，得到perfluorobenzyl络合物[M（ η 5 -C 5 - [R 5）（CF 2 ç 6 ˚F 5）I（CO）]（M = CO，R = H（1A）中，Me（图2a）; M = RH，R =我（图2b））。的进一步反应1A或2A与PME 3在苯结果在取代反应中，得到的复合物[CO（η 5 -C 5 - [R 5）（CF2 C 6 F 5）I（PMe 3）]（R = H（3a），Me（4a））。（五甲基环戊二烯基）钴配合物2a与PMe 3在苯中的反应生成4a时，在THF中的类似反应导致烷基CHH活化和芳基CF活化，以及五甲基环戊二烯基配体与全氟苄基配体的偶合9a。类似地，2a与PMe 2 Ph在THF中的反应提供了类似的
• A Simple Method for Asymmetric Trifluoromethylation of <i>N</i>-Acyl Oxazolidinones via Ru-Catalyzed Radical Addition to Zirconium Enolates
  作者：Aaron T. Herrmann、Lindsay L. Smith、Armen Zakarian

  DOI：10.1021/ja302552e

  日期：2012.4.25

  good levels of stereocontrol. Preliminary studies have shown notable compatibility with functional groups, aromatics, and certain heteroaromatic substituents. The described method provides a useful alternative for the synthesis of fluorinated materials in an experimentally convenient manner.

  已经开发了 Ru 催化的 N-酰基恶唑烷酮的直接热三氟甲基化和全氟烷基化。该反应在实验上很简单，需要廉价的试剂，同时提供良好的立体控制水平的产品收率。初步研究表明，与官能团、芳烃和某些杂芳烃取代基具有显着的相容性。所描述的方法为以实验方便的方式合成氟化材料提供了一种有用的替代方法。
• α-Fluoroalkylation of carbonyl compounds mediated by a highly reactive alkyl-rhodium complex
  作者：Kazuyuki Sato、Satoshi Yamazoe、Yukiko Akashi、Tetsuya Hamano、Arisa Miyamoto、Shuhei Sugiyama、Atsushi Tarui、Masaaki Omote、Itsumaro Kumadaki、Akira Ando

  DOI：10.1016/j.jfluchem.2009.10.012

  日期：2010.1

  Treatment of silyl enol ethers of various carbonyl compounds with Et2Zn and fluoroalkyl halides (Rf–X) in the presence of RhCl(PPh3)3 in DME gave the corresponding α-Rf carbonyl compounds. A highly reactive alkyl-rhodium complex which was derived from RhCl(PPh3)3 and Et2Zn must be crucial in this reaction by accelerating the reaction rate and improving the yields dramatically. This reaction overcomes

  在RhME（PPh 3）3存在下，在DME中用Et 2 Zn和氟代烷基卤化物（R f –X）处理各种羰基化合物的甲硅烷基烯醇醚，得到相应的α- Rf羰基化合物。衍生自RhCl（PPh 3）3和Et 2 Zn的高反应性烷基铑络合物必须通过加快反应速率和显着提高产率来在该反应中发挥关键作用。该反应克服了由于R f –X的反极化而在合成α- Rf羰基化合物时遇到的困难。
• Rhodium-catalyzed α-fluoroalkylation reaction of ketones using silyl enol ethers
  作者：Kazuyuki Sato、Makoto Higashinagata、Takashi Yuki、Atsushi Tarui、Masaaki Omote、Itsumaro Kumadaki、Akira Ando

  DOI：10.1016/j.jfluchem.2007.08.013

  日期：2008.1

  The treatment of silyl enol ethers with fluoroalkyl halides (Rf–X) in the presence of RhCl(PPh3)3 gave α-fluoroalkylated ketones. It seems that a rhodium complex derived from the silyl enol ether and RhCl(PPh3)3 played an important role for the oxidative addition of fluoroalkyl halides and the reductive elimination of the product.

  在RhCl（PPh 3）3存在下用氟代烷基卤化物（R f –X）处理甲硅烷基烯醇醚，得到α-氟代烷基化的酮。似乎衍生自甲硅烷基烯醇醚和RhCl（PPh 3）3的铑配合物对于氟代烷基卤化物的氧化加成和产物的还原消除起着重要作用。