Perfluoro Alkyl Hypofluorites and Peroxides Revisited
作者:Jan H. Nissen、Thomas Drews、Benjamin Schröder、Helmut Beckers、Simon Steinhauer、Sebastian Riedel
DOI:10.1002/chem.201903620
日期:2019.11.18
A more convenient synthesis of the perfluoro alkyl hypofluorite (F3 C)3 COF as well as the hitherto unknown (C2 F5 )(F3 C)2 COF compound is reported. Both hypofluorites can be prepared by use of the corresponding tertiary alcohols RF OH and elemental fluorine in the presence of CsF. An appropriate access to these highly reactive hypofluorites is crucial. The hypofluorites are then transferred into
No Fear of Perfluorinated Peroxides: Syntheses and Solid-State Structures of Surprisingly Inert Perfluoroalkyl Peroxides
作者:Jan H. Nissen、Tony Stüker、Thomas Drews、Simon Steinhauer、Helmut Beckers、Sebastian Riedel
DOI:10.1002/anie.201814417
日期:2019.3.11
We report on the solid‐state structures of bis(nonafluoro‐tert‐butyl) peroxide [(F3C)3CO]2 and bis(undecafluoro‐2‐methyl‐2‐butyl) peroxide [(C2F5)(F3C)2CO]2. These peroxides were prepared from the corresponding hypofluorites and fluorinated silver wool. The solid‐state structures obtained after in situ crystallisation show unusual COOC dihedral angles of 180°, as well as elongated O−O bonds because
我们报告了双(九氟叔丁基)过氧化物[[F 3 C)3 CO] 2和双(十一氟二甲基-2-甲基-2-丁基)过氧化物[[C 2 F 5)( F 3 C)2 CO] 2。这些过氧化物是由相应的次萤石和氟化的银棉制得的。原位结晶后获得的固态结构显示异常的COOC二面角为180°,并且由于庞大的全氟化烷基基团而延长了O-O键。全氟烷基过氧化物对冲击(> 40 J)和摩擦(> 360 N)均不敏感,并且对无机酸(HX; X = F,Cl,Br)和元素卤素(X 2)具有抵抗力)。二茂铁被[(F 3 C)3 CO] 2氧化为[Fe III Cp 2 ] [OC(CF 3)3 ]。
Fluorinated tertiary alcohols and alkoxides from nucleophilic trifluoromethylation of carbonyl compounds
作者:Stefan P. Kotun、John D. O. Anderson、Darryl D. Des Marteau
DOI:10.1021/jo00030a018
日期:1992.2
(CH3)3SiCF3 reacts with fluoro ketones in the presence of excess KF in CH3CN to produce alkoxides derived from formal addition of CF3- to the carbonyl carbon. These alkoxides may be isolated as such or acidified to the corresponding alcohols. Ketones to which this technique was applied include (CF3)2C = O, CF3C(O)CF2Cl, CF3C(O)CF2H, and [(CF3)2CF]2C = O. The last compound reacts with replacement of one of its perfluoroisopropyl groups by CF3. With 2 equiv of TMS-CF3, the acid fluorides RC(O)F (R = CF3CF2, n-C3F7, n-C7F15) yield products of the form RC(CF3)2OX (X = K, H) due to both substitution and addition of CF3 at the carbonyl. Similarly, F2C = O with 3 equiv of TMS-CF3 provides a novel and high-yield synthesis of the perfluoro-tert-butoxide group. Phosgene does not appear to react directly with the TMS-CF3/KF system, but is converted first to F2C = O. The intermediate ketone CF3CF2C(O)CF3 is observed in reactions of equimolar amounts of CF3CF2C(O)F and TMS-CF3.
Preparation of α-halo-F-2-ketones and F-2-ketones via fluorination of α,α-dihalo-F-2-ketones
作者:Donald J. Burton、Howa Jeong In
DOI:10.1016/s0022-1139(00)80488-1
日期:1993.11
Fluorination of α,α-dichloro-F-2-ketones with antimonypentafluoride provided excellent yields of α-chloro-F-2- ketones and F-2-ketones regioselectively. However, fluorination of α,α-dibromo-F-2-ketones with antimonypentafluoride gave a mixture of α-bromo-F-2-ketones and F-2-ketones.