Diacylamines salts

Substitutions with N,N-diacylamines are best carried out under salt-free conditions in order to minimize the concentration of base in the reaction medium and to circumvent the low solubility of salts in THF. For example, potassium phthalimide could not be reacted in THF because of its insolubility. The reaction under salt-free conditions proceeded smoothly even with LI as the ligand (Table 9.3). 

Alkyl lV,lV-dinitramines (154) have been prepared from the reaction of the tetraalkylam-monium salts (155) of primary nitramines with nitryl fluoride in acetonitrile at subambient temperature. The same reaction with the primary nitramine or its alkali metal salts yields the corresponding nitrate ester. Treatment of the ammonium, potassium, or lithium salts of primary nitramines (156) with a solution of nitronium tetrafluoroborate in acetonitrile at subambient temperature yield alkyl iV,iV-dinitramines. ° The same reactions in ether or ester solvents enables the free nitramine to be used. The nitrolysis of A-alkylnitramides (157) and N,N-diacylamines with nitronium tetrafluoroborate in acetonitrile, and the nitration of aliphatic isocyanates with nitronium tetrafluoroborate and nitric acid in acetonitrile, also yield alkyl A,A-dinitramines (154). 

Vakognavine formed a bis-hydrazone, which was characterized as the reineckate salt. On catalytic hydrogenation, a hexahydro-product (37) was obtained. Selective acid hydrolysis with 50% sulphuric acid afforded, after 4 minutes, a diacylamine (38) after I35 minutes, a monoacylamine (39) and after 2 hours, a completely deacylated alkamine (40). These structures were assigned from the spectral data. 

The overall rates of polymerizations depend on the concentrations of acyllactams and diacylamine groups as well as on the lactam anions. The latter result form dissociations of the lactam salts, depending upon the nature of the metal ... 

High yields of diacylamines can be easily obtained from imino-chlorides and acids by Mumm-Hesse rearrangement . Certain aromatic amines can be conveniently oxidized to nitroso and nitro compounds with hydrogen peroxide . A facile synthesis of amidi-nium salts has been reported . 

Deformation vibrations 2 Depolarisation ratio 3 Depolarised 3 Diacyl peroxides 105. 130 Diacylamines 145 Diamides 146 Diamines 108 Diamond 327 Diazirines 80 Diazo compounds 24, 90 Diazoketones 80, 90 Diazonium salts 12,24,86,92 Diboranes 247 Dicarbonyl compounds 116 Dicarboxylic acids 125 Dichromate ions 284, 287 Dienes 68,71 Diesters 132... 

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