Cyclic anhydrides reaction with ammonia

Cyclic anhydrides react with ammonia or an amine in the same general way as acyclic anhydrides however, the reaction yields a product that is both an amide and an ammonium salt. Acidifying the ammonium salt gives a compound that is both an amide and an acid ... 

Reaction of perthiophosphonic anhydrides (64) with amines leads first to (105) and then, by further attack, to (106). With ammonia itself the second addition proceeds at the same phosphorus atom as the initial attack, giving (107) and (108). The anhydride (64) is also reported to react with 1,3-dioIs to give cyclic phosphonyl disulphides (109). Thermal decomposition of phenylphosphinic anhydride (110) may lead to the formation of PhP since in the presence of benzil the formation of the phosphorane (111) was observed. ... 

Solid cyclic carboxylic anhydrides react with gaseous ammonia to give amide ammonium salts with quantitative yield. This has been observed with the labile Diels-Alder adduct 259 [25] (Scheme 38). Aliphatic amine vapors are equally able to open anhydride rings to form the amide salts from where the free amide acids can be obtained in 100% yield. The reaction of 261 with ethylamine to give 262 is an example of a large-scale preparative application [11-12]. Conversely, solid pyromellitic bis-anhydride (263) and methylamine vapor react exother-mally (rise to 95 °C) and quantitatively to yield the tetraamide 264. Interest-... 

This reaction, similar in scope and mechanism8S2 to 0-52, can be carried out with ammonia or primary or secondary amines.853 However, ammonia and primary amines can also give imides, in which two acyl groups are attached to the nitrogen. This is especially easy with cyclic anhydrides, which produce cyclic imides.854... 

Cyclic anhydrides of dibasic acids react with ammonia and certain amines to give cyclic imides, such as phthalimide (97%) and a-ethyl-glutarimide (85%). Aqueous ammonia, ammonium carbonate, and dry ammonia gas have been used. 2-Aminopyridine and phthalic anhydride react at 180° to yield N-(2 pyridyl)-phthalimide (76%). t-Butylphthali-mide is made by the action of phthalic anhydride on /-butylurea at 200-240°. The use of alkylureas in this reaction is general. ... 

With the platinum-metal catalysts, this reaction can be suppressed by conducting the hydrogenation in acid solution or in acetic anhydride, which removes the amine from the equilibrium as its salt or as its acetate. For reactions with Raney nickel, where acid cannot be used, secondary amine formation is prevented by addition of ammonia. Hydrogenation of nitriles containing other functional groups may lead to cyclic compounds. For example, indoUzidine and quinoUzidine derivatives have been obtained in certain cases (7.21). 

Template reactions are those in which formation of a complex places the ligands in the correct geometry for reaction. One of the earliest was for the formation of phthalocyanines (Figure 12.17). The study of this chanistry began in 1928, after discovery of a blue impurity in phthalimide prepared by reaction of phthalic anhydride with ammonia in an enameled vessel. This impurity was later discovered to be an iron phthalocyanine complex, created from iron released into the mixture via a scratch in the enamel surface. A similar reaction takes place with copper intermediates isolated from this reaction are shown in Hgure 12.17. Phthalic acid and ammonia first form phthalimide, then l-keto-3-iminoisoindoline, and then l-amino-3-iminoisoindolenine. The cyclization reaction then occurs, probably with the assistance of the metal ion, which holds the chelated reactants in position. This is confirmed by the lack of cyclization in the absence of the metals. The essential feature of these reactions is the formation of the cyclic compound by coordination to a metal ion. 

Amides can be prepared by the reaction of an acid chloride, acid anhydride, or an ester with ammonia or an amine. Acids and amines can be coupled in the presence of a dehydrating agent such as DCC. Amines react with carboxylic acids to give ammonium salts. Heating these salts to around 200°C will usually give the amide. Lactams are cyclic amides. 

Single crystals of difluoromethane bis(sulfinic acid) anhydride 17 were isolated, after the cesium salt 119 was stored in the presence of traces of water vapor for several weeks <1998JFC(89)55>. Treatment of difluoromethane-l,l-bis(sulfonyl fluoride) 120 with liquid ammonia led to the formation of the cyclic ammonium imide 121 <1997ZNB359, 1997WO9731909>, while reaction of sulfamide 122 with trifluoroacetaldehyde O-ethyl hemiacetal afforded the cyclic aminal 60 (Scheme 41) < 1999S1731 >. 

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