A.E. Pedler

The synthesis and dehydrofluorination of some polyfluoroalkanes

Abstract trans -1,2-Bis-(heptafluoro-n-propyl)- and trans -1,2-bis-(pentadecafluoro-n-heptyl)-ethylene were made from copper perfluoroalkyls. Fluorination over CoF 3 afforded perfluoro- and polyfluoro-n-octanes and -n-hexadecanes. Dehydrofluorination of 4 H -heptadeca- and 4 H ,5 H -hexadecafluoro-n-octane are much slower than those of undeca- and 1 H /2 H -deca-fluorocyclohexane.

The electrochemical oxidation of polyfluoroaromatic amines—I : The synthesis of fluorophenazines

Abstract Octafluorophenazine and decafluoroazobenzene have been obtained by the electrochemical oxidation of pentafluoroaniline at a platinum anode. Similarly, octafluorophenazine 2H-heptafluorophenazine and 1,2,3,4-tetrafluorophenazine have been obtained from 2-aminononafluorodiphenylamine, 2-amino-4′H-octafluorodiphenylamine and 2-amino-2′,3,4,5,6-pentafluorodiphenylamine, respectively. The synthesis of 2-nitro-, and 2-amino-polyfluorodiphenylamines is also described.

The fluorination of benzotrifluoride over cerium (IV) fluoride

Abstract Benzotrifluoride has been fluorinated over cerium (IV) fluoride at 480–510° and some of the products identified. These include deca- and 1H-nona-fluorocyclohexene, 1H-hepta- and 4H-hexafluorocyclohexa-1,4-diene, 1-trifluoromethylnonafluorocyclohexene, 1H,2-trifluoromethyloctafluorocyclohexene, 1,4-bistrifluoromethylhexafluorocyclohexa-1,4-diene and benzotrifluoride, all known compounds which were identified by Ir spectra. In addition, 1H,4-trifluoromethylhexafluorocyclohexa-1,4-diene and 1-trifluoromethyl-2H, 4H,-pentafluorocyclohexa-1,4-diene were isolated and characterized by UV and NMR spectroscopy and by fluorination to cis- and trans-4H-tridecafluoromethylcyclohexane and 2H/4H-dodecafluoromethylcyclohexane respectively. The polyfluorocyclohexanes were identified by NMR spectroscopy and their fluorination and dehydrofluorination reactions.

The reactions of aromatic compounds with bromine trifluoride (2): Octafluoronaphthalene

Abstract The reaction of bromine trifluoride with octafluoronaphthalene has been investigated, from which was obtained decafluoro-1,2-benzocyclohexa-1,4-diene, 2-bromo-undecafluorotetralin and a mixture of dibromotetradecafluorobicylo [4,4,0] decene isomers. Dehalogenation and reduction gave decafluoro-1,2-benzocyclohexa-1,3-diene in addition to the 1,4-diene and 2 H -undecafluorotetralin, a similar mixture being obtained from the dibromo decene. The reactions of the dienes and bromofluorotetralin with methoxide ion have also been studied.

The reactions of aromatic compounds with bromine trifluoride(I): hexafluorobenzene and its derivatives

Abstract The reactions of mixtures of bromine trifluoride and bromine with hexa-, penta- and bromopenta-fluorobenzene, with octafluorotoluene and decafluoro -p-xylene and 2,3,4,5,6-pentafluorotoluene and -anisole have been investigated. The initial products were polyfluorocyclohexa-1,4-dienes, substituent groups being in the 1-position for electron withdrawing and the 3-position for electron donating groups respectively. The dienes then reacted further to add bromine monofluoride across one or both of the diene double bonds to give bromofluorocyclohexene or polybromofluorocyclohexane isomer mixtures. In the absence of added bromine, no reaction occurred with hexafluorobenzene and reaction was less vigorous and complete with pentafluorobenzene and 2,3,4,5,6-pentafluoroanisole. The mechanism of reaction has been discussed in terms of the ionization potential of the aromatic substrates and the formation of radical cations.

Polyfluorobicyclo(2,2,1)heptanes Part VIII. Bis(undecafluorobicyclo(2,2,1)heptan-1-yl)- and bis(4H-decafluorobicyclo(2,2,1)heptan-1-yl)-mercury☆

Abstract The title compounds were prepared from 1-lithio-undecafluorobicylco(2,2,1)-heptane, and from 1H,4-lithio-decafluorobicyclo(2,2,1)heptane and 1H-decafluorobicyclo(2,2,1)hept-4-yl magnesium iodide with mercuric chloride. With sulphur and caesium fluoride in dimethyl formamide, both mercurials gave the corresponding thioxides and these on hydrolysis gave the known bridgehead thiols. With sulphur alone, the undecafluoro mercurial gave mainly the disulphide and a range of polysulphides, under conditions which left the 4H-decafluoro mercurial unchanged. Conventional d.c. polarography of the mercurials indicated an inconsistency in the use of this method for determining the acidities of highly fluorinated hydrocarbons.

The fluorination of benzene over cerium tetrafluoride

Abstract Benzene has been fluorinated over cerium tetrafluoride at temps between 250° and 480°. From the product obtained by fluorination at 480° there were isolated 1H-nona,- and 1H, 4H-octa-fluorocyclo-hexene 1H-hepta and 1H,4H-hexa-fluorocyclohexa-1,4-diene, 1H-hepta- and 1H,4H-hexa-fluorocyclohexa-1,3-diene, benzene and mono-, o- and p-di-, 1,2,4-tri-, 1,2,4,5-tetra- and 1,2,3,4-tetra-fluorobenzene.

The synthesis of polyfluoro-β-diketones and their copper derivatives

Abstract The synthesis of 3 H ,3 H -octadecafluoroundeca-2,4-dione, 9 H ,9 H -triconta-fluoroheptadeca-8, 10-dione and their copper chelates is described.

The electrochemical oxidation of polyfluoroaromatic amines—III : The synthesis of polyfluoroacridones

Abstract Electrochemical oxidation of 2-amino-nona- and 2-amino-2′,3′,4′,5′,6′-penta-fluorobenzo- phenone at a platinum anode gave octa- and 1,2,3,4-tetra-fluoroacridone respectively. 2-Amino-nona- fluorobenzophenone was prepared by reduction of the nitro-benzophenone, obtained by nitration of 2- H -nona-fluorobenzophenone. Reduction of the nitro compound also gave perfluoro-3-phenylanthranil which was converted to octafluoroacridone by pyrolysis.

Aromatic polyfluoro-compounds - Part LVI [1] The synthesis of polyfluoro-benzhydrols and -benzophenones

Abstract The synthesis of some polyfluoro-benzhydrols and -benzophenones is described and their anti-fungal and anti-bacterial activity mentioned.