Fluorinations with potassium tetrafluorocobaltate [III]. Part VIII fluorinations of toluene and of phenylacetic acid |
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| Institution: | 1. Department of Thermal Science and Energy Engineering, University of Science and Technology of China, Hefei 230027, China;2. School of Aeronautics and Astronautics, Zhejiang University, Hangzhou, China;3. School of Computer Science and Technology, Southwest University of Science and Technology, Mianyang, Sichuan 621010, China;4. Department of Mechanical Engineering, Texas Tech University, Lubbock, TX 79409, USA;1. Department of Chemistry and Engineering Research Center for Eco-dyeing and Finishing of Textiles, MOE, Zhejiang Sci-Tech University, Hangzhou 310018, China;2. Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong SAR, China;3. Department of Physics, University of Osnabrueck, 49069 Osnabrueck, Germany;1. Department of Chemistry, Faculty of Science, Gebze Technical University, Gebze, Kocaeli, Turkey;2. Department of Chemistry, Faculty of Art and Science, Namık Kemal University, Tekirdag, Turkey;3. Mudurnu Sureyya Astarci Vocational School, Abant Izzet Baysal University, Bolu, Turkey;1. State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi''an, Shaanxi 710072, China;2. National & Local Joint Engineering Research Center for Precision Thermalforming Technology of Advanced Metal Materials, Northwestern Polytechnical University, Xi''an, Shaanxi 710072, China;3. Computational Alloy Design Group, IMDEA Materials Institute, Getafe, Madrid 28906, Spain;1. Pcovery ApS, Ole Maaløes Vej 3, 2200 Copenhagen N, Denmark;2. Department of Plant and Environmental Sciences, University of Copenhagen, DK-1871 Frederiksberg, Denmark |
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| Abstract: | At 340 °C, toluene gave five 1-trifluoromethyl-substituted compounds:- -2H,4H,5H-tetrafluorocyclohexa-1,4-diene (IX); -2H-4H/5H-hexafluorocyclohex-1-ene (X); -2H-octafluorocyclohex-1-ene (IV); -nonafluorocyclohex-1-ene (III); also perfluoromethylcyclohexane (II); traces of perfluorocyclohexane (I) were found. The 1-difluoromethyl-substituted analogues of these five were also obtained:- compounds XII, XV, VIII, VI, and V, respectively. A further five 1-difluoromethyl-substituted derivatives were found:- -nonafluorocyclohex-3-ene (VII); an inseparable mixture of the -2H,4H- and -2H, 5H-heptafluorocyclohex-1-enes (XI); -2H-3H/4H-hexafluorocyclohex-1-ene (probably) (XIV); and (difluoromethyl)benzene (XIII).Structures of the unknown products were established by analysis and by nmr and ir spectroscopy. Further, the key intermediate (XII) was oxidized to difluoromalonic acid, whilst compound XV was dehydrofluorinated, to give 2H-(difluoromethyl)tetrafluorobenzene (XXI), together with an inseparable mixture of 2H,4H- and 2H,5H-1-(difluoromethyl)pentafluorocyclohexa-1,4-diene (XX). Dehydrofluorination of mixed heptafluoro-enes XI afforded 2H -1-(difluoromethyl)hexafluorocyclohexa-1,4-diene (XVIII), and mixed 2H-1- and 1H -2- (difluoromethyl)hexafluorocyclohexa-1,3-diene (XIX).Difluoromethylundecafluorocyclohexane (V) did not dehydrofluorinate.Phenylacetic acid was fluorinated likewise, and gave a similar range of products, but also one (originally an acid fluoride ?) which was converted to the methyl ester of tridecafluoro(cyclohexylacetic) acid (XVII).The probable pathway of the fluorination process could be worked out. |
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