| 摘要 |
1,127,431. Difluoramino compounds. AEROJET GENERAL CORP. 6 Sept., 1963 [6 Sept., 1962], No. 35390/63. Heading C2C. The invention comprises gem-difluoramino compounds of the formula where A is an alkylene radical of at least two carbon atoms, R 1 and R 2 are hydrogen, alkyl, or haloalkyl, and m is 0 to 4; compounds in which R 1 and R 2 form part of a carbocyclic ring and m is 0 or 1 are also included. The compounds are prepared by reaction of an aldehyde or ketone ,with difluoramine in the presence of a strong dehydrating acid, for example boron trifluoride, sulphur trioxide, or concentrated or fuming sulphuric acid. Inert solvents such as water or lower alkanols may be present. A preferred reaction temperature is between - 10‹ and 35‹ C. The difluoramine may be prepared from unsymmetrical difluorourea as described in Specification 960,126. In Examples (I) acetone is refluxed with difluoramine and concentrated sulphuric acid to form 2,2-bis (difluoramino) propane; (II) 1,1-bis(difluoramino) cyclopentane is similarly prepared from cyclopentanone; (III) 3,3-bis(difluoramino)- pentane is similarly prepared from 3-pentanone; sulphur trioxide may be used in place of the sulphuric acid; (IV) 1,1-bis(difluoramino) cyclohexane is similarly prepared from cyclohexanone; (V) 1-chloro-2,2-bis(difluoramino) propane is formed from chloroacetone; (VI) 1,1,4,4- tetrakis(difluoramino) cyclohexane is prepared from 1,4-cyclohexanedione; (VII) concentrated sulphuric acid is added slowly to propionaldehyde in difluoramine to produce 1,1-bis(difluoramino) propane; boron trifluoride may be used in place of the sulphuric acid; (VIII) acetonyl acetone is reacted with difluoramine using first concentrated and then fuming sulphuric acid; the reaction mixture is poured over crushed ice and extracted with methylene chloride; a fraction separated by gas chromatography consists of 2,2,5,5-tetrakis(difluoramino) hexane; (IX) bis(difluoramino) methane is prepared from strioxane (which yields formaldehyde) and difluoramine in the presence of fuming sulphuric acid; (X) 3-methyl-2,2-bis(difluoramino) pentane is formed from 3-methyl-2-pentanone; (XI) 2,2,7,7-tetrakis (difluoramino) octane is prepared from 2,7-octanedione. Other suitable aldehyde and ketone reactants are referred to. The compounds are useful as explosives and as oxidizers and monomers in rocket propellants. They may also be used as plasticizers for nitrocellulose and nitropolymers.
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