Fluorinated isocyanates

The Preparation and Reactions of Fluoromethyleiies Fluorinated Isocyanates and Their Denvatives as Intermediates for Biologically Active Stibsianccs (Ccr) Radical Reactions of Polyfliioroaromatic Compounds (Russ )... 

Fluorinated Isocyanates and Their Derivatives as Intermediates for Biologically Active Substances ... 

E. Kuhle, E. Klauke, Fluorinated isocyanates and their derivatives as intermediates for biologically active compounds, Angew. Chem., Int. Ed. Engl. 16 (1977) 735. 

Another route for the preparation of fluorinated isocyanates 4 in good yield is the thermal decomposition of perfluoro(5-alkyl-l, 3,4-dioxazol-2-ones). l3°... 

Wilson et al.68 69 have summarized the experimental details for the preparation of C1F. This compound has been found to add across the N=C bond of various fluorinated isocyanates with essentially no N—C bond breakage.70 Good yields of salts of the cation OSClF2 can be obtained by the reaction of F2SO with a C12F+ salt or with C1F and the appropriate MF5.71... 

Polyfluoro-imines have also been encountoed in work on perfluoro-vinyl iso< anates (see Schemes 38, 39), peifluoro-jV-fluoromorpholine (see Schmes 21, 22), 4 electrochemical fluorination of -alkyl-pyrrolidines and -piperidines (see Schranes 18,19), fluorination of 1,3,3-trichloroisoindolenines (see Sdione 20), fluorinated isocyanates (see p. 227),. fluoro-ol ns (see pp. 71, 73), fluorinated... 

G. H. Sprenger, K. J. Wright, J. M. Shreeve, Inorg. Chem. 1973, 12, 2890-2893. Polttf additions of chlorine monofluoride and chlorine fluorosulfate to fluorinated isocyanates. 

The well-defined fluorinated isocyanate (F6-IMCI or Fg-IMCI) was mixed with appropriate amounts of SLO and N3300 (cross-linker) in butyl acetate. The overall OH/NCO molar ratio was maintained at about 1.1 to ensure full conversion of the NCO groups. After a homogeneous mixture was formed, a coating was applied onto a clean aluminum panel by spin coating. The coating was then cured at 80°C for 2 h. 

Polytetrafluoroethylene contains only C—C and C—F bonds. These are both very stable and the polymer is exceptionally inert. A number of other fluorine-containing polymers cU e available which may contain in addition C—H and C—Cl bonds. These are somewhat more reactive and those containing C—H bonds may be cross-linked by peroxides and certain diamines and di-isocyanates. 

Acetylene works Acrylates works Aldehyde works Aluminum works Amines works Ammonia works Anhydride works Arsenic works Asbestos works Benzene works Beryllium works Bisulfate works Bromine works Cadmium works Carbon disulfide works Carbonyl works Caustic soda works Cement works Ceramic works Chemical fertilizer works Chlorine works Chromium works Copper works Di-isocyanate works Electricity works Fiber works Fluorine works Gas liquor works Gas and coke works Hydrochloric acid works Hydrofluoric acid works Hydrogen cyanide works Incineration works Iron works and steel works... 

M - 2 Aromatic isocyanates Aromatic phenols Certain butenols Certain fluorinated amines e.g., C8F17CH2CHICH2NH2 or CF3(CF2)7CH2CH2CH2NH2 Possible Precursor Compounds Polynuclear aromatics (e.g., dihydroxyphenanthrene) Ethylsilanes (dimers to heptamers)... 

Chlorine atoms in (trichloromethyl)benzenes which have fluoro, chloro, dichloromethyl, chloroformyl, cyano, isocyanato, jV-phthalimino or methyl substituents in the ring are substituted by fluorine using antimony(III) fluoride (Swarts reaction).3 4 2-(Trifluoromethyl)phen-yl isocyanate, 4-chloro-2-(trifluoromethyl)phenyl isocyanate, 2,4- and 2,5-bis(trifluoro-methyl)phenyl isocyanate, and 2,4-bis(trifluoromethyl)-l,5-phenylenc diisocyanate can be obtained in this way.5... 

Side chain fluormated aryl isocyanates are an important group of substances used in the manufacture of biologically active compounds The synthetic routes to the meta- and para trifluoromethylphenyl isocyanates permit the chlorine-fluorine exchange with hydrogen fluoride to proceed under moderate conditions and m a virtually quantitative manner (equation 22)... 

The action of A-chlorosuccinimide, or a source of positive fluorine such as Selectfluor , in aqueous acetonitrile on the alkene 138 (R1 = Me) is to open the azetidine ring by attack at the allylic position to yield the cyclobuten-3-ol 139 (R OH, R2 = H, R3 = Me) <2003JOC5292>. Chlorosulfonyl isocyanate (CSI) reacts with 138 (R = Et) to give both a chlorobutene 139 (R1 = Cl R2 = CONH2 R3 = Et) and the bicyclic reduced pyrimidone 140 (R1 = Et). However, the action of CSI on the more substituted 2-azabicyclo[2.2.0]hex-5-ene 141 provided the reduced mono-cyclic pyrimidone 142 <2003JOC1626>. 

Isocyanates and polyisocyanates, mostly nonfluorinated types, which are used because of their considerably lower cost in comparison with fluorinated ones ... 

The present volume, Supplement D2 retains the title of its direct predecessor, Supplement D The chemistry of halides, pseudo-halides and azides, even though it deals only with derivatives of fluorine, chlorine, bromine, iodine and astatine. Hence, in order to keep the Chemistry of the functional groups series complete and up-to-date, it will be necessary to publish, in the not too distant future, an additional supplementary volume ( D3 ) discussing the recent advances in the chemistry of azides, cyanates, isocyanates and their thio derivatives. 

Likewise, unsymmetrical fluorine containing carbodiimides are obtained from a-hydro-perfluoroisopropyl isocyanate. ... 

Fluorinated ketones can be formed by ozonolysis or by cleavage of isocyanates with peracids. " ... 

Isocyanates of fluorinated compounds can readily be obtained either from trimethylsilyl isocyanate and, e.g. trifluoroacetyl chloride, with yields of isocyanate in the region of 64%. or more conveniently by Curtius degradation of fluorinated acid chlorides. ... 

Four-membered heterocydes are easily formed via [2+2] cycloaddition reac tions [63] These cycloaddition reactions normally represent multistep processes with dipolar or biradical intermediates The fact that heterocumulenes, like isocyanates, react with electron-deficient C=X systems is well-known [77d] Via this route, p lactones are formed on addition of ketene derivatives to hexafluoroacetone [777, 77S] The presence of a trifluoromethyl group adjacent to the C=N bond in quinoxalines, l,4-benzoxazin-2-ones, l,2,4-tnazin-5-ones, and l,2,4-tnazm-3,5-diones accelerates [2+2] photocycloaddition processes with ketenes and allenes [106] to yield the corresponding azetidine derivatives Starting from olefins, fluorinated oxetanes are formed thermally and photochemically [779, 720] The reaction of 577-1,2-azaphospholes with fluonnated ketones leads to [2+2] cycloadducts [727] (equation 27)... 

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