Patent GB-906825-A (GB)
Title: Organic compounds
IPC: C07C205/51
Filed: 1959-08-07
Abstract: In a modification of the process of Claim 3 of the parent Specification wherein nitric oxide is reacted with a polyfluoroolefin having not more than 25 carbon atoms and having the formula <FORM:0906825/IV(a)/1> where Ra and Rb represent fluorine, chlorine, hydrogen, alkyl or haloalkyl, the polyfluoroalkene is reacted with nitric oxide in a molar ratio of 1:1 to 1:10 at a temperature from 0 DEG  to 150 DEG  C.; or in a modification of the process claimed in Claim 2 of the parent Specification wherein nitric oxide is reacted with a polyfluorodiene having not more than 25 carbon atoms, hexafluorobutadiene is reacted with nitric oxide in a molar ratio of 1:1 to 1:6 at a temperature of 0 DEG  to 50 DEG  C. and a pressure of 1 to 20 atmospheres to give polymers containing nitrogen and fluorine.  The reaction may be effected in the presence of solvents, e.g. hexane, benzene, toluene, dioxane, ether, chloroform, carbon tetrachloride and perfluoromethylcyclohexane; small amounts of nitrogen dioxide, which may be formed in situ by the addition of oxygen; and glass wool.  The products may be liquids or greases suitable as lubricants, or elastomers which may be used for making tubes, gaskets, hoses, films and coatings.  Products containing hydrogen may be cross-linked by peroxides and amines.  Preferred polyfluoroolefins are tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene and perfluoropropene, and known initiators, e.g. benzoyl peroxide and ultra violet light, may be employed.  Examples describe the reaction of (I-III) tetrafluoroethylene with nitric oxide; (IV, V and VI) tetrafluoroethylene with nitroso compound intermediate obtained by reacting tetrafluoroethylene with nitric oxide; (VII) tetrafluoroethylene and nitric oxide in the presence of benzoyl peroxide and azobisisobutyronitrile; (VIII) chlorotrifluoroethylene and trifluoroethylene with nitric oxide; chlorotrifluoroethylene with nitroso compound intermediates obtained by reacting (IX) chlorotrifluoroethylene and (X) tetrafluoroethylene with nitric oxide; (XI) perfluoropropene with nitric oxide and (XII) hexafluorobutadiene with nitric oxide.ALSO:Compounds of formulae O2NRfNO and <FORM:0906825/IV (b)/1> in which Rf represents a fluoroalkene unit are prepared by a modification of the process of Claim 3 of the parent Specification wherein nitric oxide is reacted with a polyfluoro-olefin having not more than 25 carbon atoms and having the formula <FORM:0906825/IV (b)/2> where Ra and Rb represent fluorine, chlorine, hydrogen, alkyl or haloalkyl, in which the polyfluoroalkene is reacted with nitric oxide in a molar ratio of 1:1 to 1:10 at a temperature from 0 to 150 DEG C.  Preferred polyfluoroolefins are tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene and perfluoropropene.  The reaction may be effected in the presence of solvents, e.g. hexane, benzene, toluene, dioxane, ether, chloroform, carbon tetrachloride and perfluoromethyl cyclohexane; small amounts of nitrogen dioxide, which may be formed in situ by the addition of oxygen; glass wool; and initiators such as benzoyl peroxide, azodiisobutyronitrile and ultra violet light. Examples describe (I, II and III) the preparation of nitroso and oxazetidine compounds from nitric oxide and tetrafluoroethylene and (IV, V and VI) the preparation of the oxazetidine compound by reacting the nitroso compound with excess tetrafluoroethylene; and the preparation of the nitroso compounds by reacting nitric oxide with (VIII) chlorotrifluoroethylene and (XI) perfluoropropene.  In Examples I and II the formation of by-products comprising the dinitro compound CF2NO2.CF2NO2, acyl fluorid CF2NO2COF and nitro nitrite CF2NO2.CF2ONO is described.