Patent GB-1081993-A (GB)
Title: Difluoramino compounds
Inventor: GIBSON JAMES ANDREW
IPC: C07D233/32
Filed: 1963-04-17
Abstract: Several difluoramino compounds (see Division C2) are described which may be used in propellent compositions.  A specific composition comprises N,N1 - bis - (difluoraminomethyl) urea, aluminium powder, ammonium perchlorate, nitrocellulose, nitroglycerine, triacetin, and 2-nitro-diphenylamine.ALSO:The invention comprises difluoramino compounds of the general formula <FORM:1081993/C2/1> where R1 is a monovalent or divalent atom or group having next to the nitrogen atom an electron-attracting group, for example carbonyl, halogeno, imino, nitro, difluoramino, mono- or bis-difluoraminomethylene, R2 is as R1 or is hydrogen, hydroxyl, alkyl, aryl, alkoxy, or a cyclic residue forming a cyclic structure with R1, x is 0 or 1 as R1 is divalent or monovalent, R3 is an alkylene group which may have as subtituent an alkyl, alkoxy, substituted alkyl or alkoxy, difluoramino or nitro group, and R1, R2 and R3 are such that the ratio of carbon atoms to difluoramino groups is not more than 6:1.  The compounds may be prepared by reacting a compound R1NHR2x with a difluoramino alcohol HO-R3-NF2 in the presence of a strongly water-absorbent or water-reactive substance, e.g. 96% sulphuric acid.  When R2 is hydrogen or a group having one or more amino substituent groups, further difluoramino alcohol may react to give compounds with two or more difluoramino substituents.  The difluoramino alcohol may be formed in situ from difluoramine and the corresponding aldehyde; for example, difluoramine, the aldehyde, and the compound containing the NH group are refluxed together to form the alcohol, and then the water-absorbent or water-reactive substance is added.  In Examples (1)-(4) urea, methylene diurea, or formylurea is converted to N,N1-bis (difluoraminomethyl) urea; (5) and (6) nitrourea is reacted to form N-difluoraminomethyl - N1 - nitrourea or N,N1 - bis (difluoraminomethyl) - N1 - nitrourea; (7) N,N1 - bis (difluoraminomethyl) - N - ethylurea is formed from monoethyl urea; (8) N - methoxy-N,N1 - bis (difluoraminomethyl) urea is formed from methoxyurea; (9) N,N-difluorourea is converted to N1 - difluoraminomethyl - N,N-difluorourea hydrate; (10) imidazolidine - 2-one is converted to 1,3-bis (difluoraminomethyl) imidazolidine - 2 - one; (11) tetrakis (difluoraminomethyl) glycoluril is formed from glycoluril; (12) nitroguanidine is converted to N,N1 - bis (difluoraminomethyl) - N - nitroguanidine; (13) N - (difluoraminomethyl) acetohydroxamic acid is formed from acetohydroxamic acid; (14) ethyl N-difluoraminomethyl carbamate is formed from ethyl carbamate; (15) ethyl N-fluorcarbamate is converted to ethyl N-difluoraminomethyl-N-fluorocarbamate; (16) tris (carbethoxyamino) methane is converted to N,N1,N11-tris (difluoraminomethyl) tris (carbethoxyamino) methane; (17) N,N-bis (difluoraminomethyl) nitramine is formed from nitramine; (18) methylene dinitramine is converted to N,N1-bis (difluoraminomethyl) methylene dinitramine.  In the above examples reaction is effected with a mixture of difluoramine and paraformaldehyde or aqueous formaldehyde solution, or with difluoramino-methanol. In Example (19) the product of Examples (1)-(4) is reacted with difluoramine and difluoraminomethanol to form tetrakis (difluoraminomethyl) urea; and in Example (20) urea is reacted with paraldehyde and difluoramine to form N,N1-bis (1-difluoraminoethyl) urea. The compounds may be used as ingredients of propellent compositions (see Division C1).