Patent GB-590513-A (GB)
Title: Improvements in and relating to the production of nitro olefines
IPC: C07C205/05
Filed: 1944-11-27
Abstract: Ammonium nitrite is prepared by treating ammonia with a dinitro derivative of a saturated aliphatic hydrocarbon of at least two carbon atoms, or a saturated alicyclic or aliphatic-alicyclic hydrocarbon having at least 5 carbon atoms in the ring in which the nitro groups are on adjacent carbon atoms, at least one of which has a hydrogen atom attached, or with a derivative of such a hydrocarbon containing only a nitro and a nitrite group on adjacent carbon atoms, a hydrogen atom being attached to the same carbon atom as the nitro group, in presence of a non-aqueous organic solvent in which the ammonium nitrite is insoluble.  A nitro-olefine is also produced. Solvents specified are carbon tetrachloride, methylated ether, acetone, ethyl acetate and dioxane, and the reaction may be carried out below 0 DEG C. or at temperatures up to the boiling point of the solvent, and at atmospheric or higher pressure.  Examples describe the reaction of dry gaseous ammonia with (1) 1.2-dinitro-2.4.4 trimethylpentane, (2) 1.2-dinitro-isobutane, (3) a mixture of 1.2-dinitro-2.4.4-trimethylpentane with 1-nitro-2.4.4-trimethylpentyl nitrite-2 obtained according to Specification 587,992, [Group IV], and (4) a mixture of 1.2-dinitroisobutane and nitrotertiary butyl nitrite obtained according to Specification 580,260, [Group IV].  A sample has been furnished under Sect. 2 (5) of 1.2-dinitro-cyclohexane, prepared from ammonia and 1.2-dinitrocyclohexane.ALSO:Nitro-olefines are prepared from the dinitro derivatives of saturated aliphatic hydrocarbons containing at least two carbon atoms or of saturated alicyclic or saturated aliphatic-alicyclic hydrocarbons having at least five carbon atoms in the ring, in which the nitro groups are on adjacent carbon atoms at least one of which has a hydrogen atom attached, or from the derivatives of said saturated hydrocarbons containing only nitro and nitrite groups, in which the nitro and nitrite groups are on adjacent carbon atoms and that carbon atom to which the nitrogroup is attached has also a hydrogen atom attached, or crude reaction products containing one or more of these substances, which comprises treating them in the substantial absence of water with ammonia in the presence of a non-aqueous organic solvent for the nitro compound which does not react with the reactants or products, or with a basic substance selected from urea, nitrogenous basic compounds and the alkoxides of the alkali metals, in the presence of a non-aqueous organic solvent for the nitro compound in which the said basic substance is soluble at least to some extent, and preferably freely so, and which does not react with the reactants or products.  If a nitro compound is employed containing two or three carbon atoms, the nitro-olefine is obtained largely as a polymer.  Solvents specified are carbon tetrachloride, methylated ether, acetone, ethyl acetate, and dioxane. The reaction may be carried out at temperatures up to the boiling point of the solvent, or below 0 DEG  C. if ammonia is used, and at atmospheric or greater pressure.  When ammonia is employed, ammonium nitrite is produced also, and is filtered off. In examples: (1) ammonia is reacted with 1.2-dinitro-2.4.4-trimethylpentane to give 1 - nitro - 2.4.4-trimethylpentene-1; (2) ammonia is reacted with 1.2-dinitroisobutane to give a -nitroisobutene; (3) ammonia is reacted with a reaction product comprising mainly 1.2-dinitro-2.4.4-trimethylpentane and 1 - nitro - 2.4.4 - trimethylpentyl nitrite-2 obtained according to Specification 587,992, to give 1-nitro-2.4.4-trimethylpentene-1; (4) ammonia is reacted with a mixture containing 1.2-dinitroisobutane and nitrotertiarybutyl nitrite obtained according to Specification 580,260, to give a -nitroisobutene; urea is heated with (5) 1.2-dinitroisobutane to give a -nitroisobutene, and (6) the mixture used under (3) above to give the product of (3).  Samples have been furnished under Sect. 2 (5) of (1) nitrocyclohexene, prepared from ammonia and 1.2-dinitrocyclohexane, and (2) 3-nitro-2.4.4 - trimethylpentene - 2, prepared from 2.3 - dinitro - 2.4.4 - trimethylpentane and sodium ethoxide.