Fluoro compounds

C-Fst 1400-1000 Strong, oftrai more than one band (rotational isomers), oftrai not resolved. In Raman, weak to medium 

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Various bromofluoromethanes have been described and proposed for use as fire extinguishing agents (qv). Two that have been recommended highly for this purpose are dibromo difluoromethane [75-61-6] CBr2p2, and bromotrifluoromethane [75-65-8], CBrF, (94). Bromochlorodifluoromethane [353-59-3], CBrClF2, is another fire extinguishing agent. These and similar substituted methanes are potentially useful for the synthesis of other halo—fluoro compounds. 

The progression from hydroxypyrazines/quinoxalines through the halo derivatives to the amines is a logical sequence in that, for practical purposes, this is the best method of synthesis of the amino compounds (see preceding Section). The ammonolysis proceeds most easily in the case of fluoro compounds. Fluoropyrazine reacts with aqueous ammonia at room temperature, whereas the reaction with chloropyrazine requires higher temperature and pressure. 

An interesting aromatic fluoro compound is polytrifluoromethylstyrene, which is claimed to have excellent optical properties (ref. 14). 

The use of CFCs such as fluorotrichloromethane became quite widespread, particularly as for many years the material was believed to cause few toxic and environmental problems. However, evidence that such materials were damaging the ozone layer became substantial and the use of such materials is to be discouraged and is illegal in many countries. To some extent CFCs have been substituted by methylene chloride (also illegal in some countries) and other fluoro compounds, but these too may prove to be environmentally unacceptable. For this reason there has been increased dependence on the use of the isocyanate-water reaction to generate sufficient carbon dioxide to give products of the required density. 

A reagent which is primarily of interest as a means of converting alcohols into fluorides has been used to dehydrate C-11 alcohols in high yields. 1 la-Alcohols dehydrate rapidly with 2-chloro-l-diethylamino-l,l,2-trifluoro-ethane reagent at low temperature, while 11 j5-alcohols require refluxing methylene chloride. Traces of fluoro compounds have been detected in the products. 

The chloroform solution from which the insoluble 21-fluoro compound has been removed is concentrated in vacuo and the residue recrystallized twice from 95% alcohol. The resulting oxetanone (46) has mp 272-274° ... 

The anions of malonaldehyde [106, 107] and of organophosphonates [108, 109, 110] are fluorinated in good yields to provide interesting fluorinated intermediates The At-fluoro compound B in Table 3a is also effective in the fluonnation of phosphonate anions [109] (equations 60 and 61). 

CL Amino-(i-hydroxy esters in which the amino group is protected as a 4,5 diphenyl-3-oxazohne-2-one moiety undergo fluontiation with DAST to give the corresponding (1 fluoro compounds as the main products along with the dehydrated compounds [/2(5] (equation 64)... 

Nitrated fluoro compounds are synthesized by electrophilic (NOz+), radical (NO2 ), or nucleophilic (NO2-) methods Indirect nitration routes can suppress the side reactions associated with severe reaction conditions and some nitration reagents Novel fluoronitro compounds, unobtainable by direct nitration, can also be pre pared For example, the nitration of (2-fluoro-2,2-dinitroethoxy)acetaldoxime followed by oxidation of the nitroso intermediate with hydrogen peroxide yields 2-fluoro-2,2-dinitioethyl 2,2-dinitroethyl ether [f] (equation 1)... 

Nilrosated fluoro compounds are frequently prepared by electrophilic nitrosation on an electron-nch center of oxygen, nitrogen, or carbon The preparation of fluorochloronitronitrosomethane from the decarboxylation of fluorochloronitro-acetic acid in nitric acid is unique [f ] (equation 1)... 

Fluorovinyllithium compounds, as well as perfluoroalkyllithium and per-fluoroalkyletherlithium compounds [f ], are important intermediates m the synthesis of a variety of fluorine-containing compounds Although experimental details must be carefully adhered to, these synthons provide a convenient route to many fluoro compounds... 

Since the discovery of the first perfluoroalkyllithium and -magnesium compounds, their reactions with various carbonyl compounds [68] have been actively studied. These reactions could lead to functionally substituted fluoro compounds, as shown in equation 36... 

Extensive reviews of the effects of fluonnation on stmeture and bonding are available [75, 76, 77], and only the charactenstic trends in bond strengths will be covered here. The bond energies cited are average values corrected for the revised heats of formation of alkyl radicals [78], but their precision is seldom better than 2 kcal/mol for the fluoro compounds. 

Cobalt provides only a few examples of this oxidation state, namely some fluoro compounds and mixed metal oxides, whose purity is questionable and, most notably, the thermally stable, brown, tetraalkyl, [Co(l-norbomyl)4]. Prepared by the reaction of C0CI2 and Li(l-norbomyl), it is the only one of a series of such compounds obtained for the first row transition... 

Several oxohalides are also known, mostly of the types An OaXa, An OaX, An OXa and An "OX, but they have been less thoroughly studied than the halides. They are commonly prepared by oxygenation of the halide with O2 or Sb203, or in case of AnOX by hydrolysis (sometimes accidental) of AnX3. As is to be expected, the higher oxidation states are formed more readily by the lighter actinides thus An02X2, apart from the fluoro compounds, are confined to An = U. Conversely the lower oxidation states are favoured by the heavier actinides (from Am onwards). 

Spectroscopic evidence indicates that protonation of 2-fluoro-and 2-chloro-quinoline is not appreciable in O.OlJf aqueous hydrochloric acid. Protonation becomes evident in more strongly acidic solution in the case of the chloro compound without any accompanying decomposition, but the fluoro compound hydrolyzes to carbostyril under the latter conditions. The hydrolysis is acid-catalyzed, but it is doubtful whether protonation on the heterocyclic nitrogen is responsible, owing to its low basicity (presumably below that for the chloro compound). An alternative explanation in this case would be hydrogen bond formation with fluorine, Ar—F. .. H-O+H2. 

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