Oxygen Fluorides Hypofluorites

Similar to the nitrogen fluorides, compounds having an O-F bond are also very strong oxidants and, when utilized as such, effective sources of electrophilic fluorine. Because the O-F bond is so weak, the chemistry of such compounds approaches that of F2 itself, and such chemistry can be free radical or electrophilic in nature, depending on the conditions and the reactants. 

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Pentafluorosulfur hypofluorite is a very reactive colorless gas having an odor resembling that of oxygen fluoride. It reacts with aqueous KI and aqueous KOH according to the equations ... 

Although fluonnation of peroxoanions [S2] has been examined, the major emphasis in the fluonnation of oxygenated material is the preparation offhioroxy compounds The simplest, trifluoromethyl hypofluorite, can be prepared almost quantitatively by the action of fluorine on carbonyl fluoride (fluorophosgene) in the presence of various catalysts [Si, 84] Addition of fluorine to trifluoroacetic acid [S5] or its sodium salt [S6] gives rise to FjCF(OF)2 Long-chain fluoroxy compounds can also... 

Bromine bromate, 0276 Bromine dioxide, 0258 Bromine perchlorate, 0235 Bromine trioxide, 0259 Bromyl fluoride, 0239 Chlorine dioxide, 4042 Chlorine perchlorate, 4101 Chlorine trifluoride oxide, 3982 Chlorine trioxide, 4044 Chloryl hypofluorite, 3973 Chloryl perchlorate, 4104 Dichlorine oxide, 4095 Dichlorine trioxide, 4100 Dicyanogen AW -dioxidc. 0998 Dioxygen difluoride, 4320 Fluorine perchlorate, 3976 Hexaoxygen difluoride, 4327 Iodine dioxide trifluoride, 4334 Iodine(V) oxide, 4627 Iodine(VII) oxide, 4628 Oxygen difluoride, 4317 Perbromyl fluoride, 0240 Perchloryl fluoride, 3974... 

Nitrosyl tetrafluorochlorate, 3985 Nitrous acid, 4435 Nitryl chloride, 4025 Nitryl fluoride, 4303 Nitryl hypochlorite, 4026 Nitryl hypofluorite, 4304 Nitryl perchlorate, 4029 Osmium hexafluoride, 4370 Osmium(VIII) oxide, 4858 Oxygen (Gas), 4831 Oxygen (Liquid), 4832 Oxygen difluoride, 4317 Ozone, 4846... 

The hypofluorite, fluorine fluorosulfate (12), reacts explosively with sulfur tetrafluoride at liquid nitrogen temperature to afford a low yield of pentafluorosulfur fluorosulfate (13), together with sulfuryl fluoride, sulfur hexafluoride and oxygen.217... 

The fact that functionalization of polymers and small molecules is observed to occur predominately on terminal (methyl) carbon atoms does not imply that the oxyfluorination reaction is truly selective. Although the reaction mechanism has not been studied in detail, it is undoubtedly a free-radical process. Molecular oxygen reacts spontaneously with the fluorocarbon—hydrogen radicals generated by fluorine during the fluorination process. Acid fluorides are retained on terminal carbon atoms because they are stable in 1 atm of elemental fluorine. Hypofluorites, which may be short-lived intermediates of oxygen reactions with methylene radical sites along the carbon chain, are not observed in the functionalized polymers. It is probable that, if they are intermediates, they are cleaved and removed by the excess elemental fluorine. 

Nitrogen dioxide, 4720 Nitrogen oxide, 4719 Nitrosyl chloride, 4017 Nitrosyl fluoride, 4296 Nitrosyl perchlorate, 4021 Nitrosyl tetrafluorochlorate, 3979 Nitrosylsulfuric acid, 4432 Nitrous acid, 4429 Nitryl chloride, 4019 Nitryl fluoride, 4297 Nitryl hypochlorite, 4020 Nitryl hypofluorite, 4298 Nitryl perchlorate, 4023 Osmium hexafluoride, 4364 Osmium(VIII) oxide, 4852 Oxygen difluoride, 4311 Oxygen (Gas), 4825 Oxygen (Liquid), 4826 Ozone, 4840... 

Acetylenes 1 react smoothly with oxygen difluoride to produce a,a-difluoro ketones 2. " The intermediates of this addition are a-fluorovinyl hypofluorites, which rearrange with a fluorine shift to the observed difluoro ketones. In all cases small amounts of acyl fluorides are formed as byproducts. 

Oxyfluorides of Carbon. The literature on compounds containing only carbon, oxygen, and fluorine is extensive, numerous reviews are available, and many compounds are of industrial importance. Functional groups included under this classification are ketones, acid fluorides, ethers, epoxides, peroxides, and hypofluorites. Only very simple molecules are mentioned here as representatives of this large class of compounds. 

Trifluoromethyl hypofluorite, CF3OF, is formed by the reaction of fluorine in excess with carbon monoxide, carbon dioxide, methanol, or other compounds containing both carbon and oxygen. In the procedure described below, carbon monoxide first reacts with an excess of fluorine to give largely carbonyl fluoride. The mixture is then passed through a hot tube where nearly all of the carbonyl fluoride reacts with fluorine to give trifluoromethyl hypofluorite. It is desirable to use somewhat more than two volumes of fluorine per volume of carbon monoxide. If this is not done, much perfluorodimethyl peroxide [bis(trifluoromethyl) peroxide] is formed by the combination of carbonyl fluoride with tr fluoromethyl hypofluorite by the reaction ... 

ACIDE SULFHYDRIQUE (French) (7783-06-4) A highly flammable and reactive gas. Violent reaction with strong oxidizers, metal oxides, metal dusts and powders, bromine penta-fluoride, chlorine trifluoride, chromium trioxide, chromyl chloride, dichlorine oxide, nitrogen trichloride, nitryl hypofluorite, oxygen difluoride, perchloryl fluoride, phospham, phosphorus persulfide, silver fulminate, soda-lime, sodium peroxide. Incompatible with acetaldehyde, chlorine monoxide, chromic acid, chromic anhydride, copper, nitric acid, phenyldiazonium-chloride, sodium. Forms explosive material with benzenediazonium salts. Flow or agitation of substance may generate electrostatic charges due to low conductivity. Attacks many metals. 

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