Ammonia model structure

Addition of ammonia as a model nucleophile to nitrile oxides was studied by a semiempirical MNDO method, for fulminic acid and acetonitrile oxide (121). The reaction is exothermic and proceeds in two steps. The first (and rate-determining) step is the formation of a zwitterionic structure as intermediate. The second step, which involves transfer of a proton, is very fast and leads to the formation of Z-amidoximes in accordance with experimental data. Similar results were... 

Chemists and biochemists have studied the complex enzyme nitrogenase for all of modem scientific times. Many models for the enzyme s efficient reduction and protonation of dinitrogen to the useful product ammonia have been put forward. Many different research groups have based these models on analytical and instmmental observations. Crystallization of the enzyme s subunits and subsequent X-ray crystallographic structures in the 1990s yielded an intimate portrait informing all aspects of research on nitrogenase. In spite of the many structural and analytical successes, aspects of the enzyme s structure and function remain controversial or unclear up to the present time. 

Self-association of substances with acidic hydrogens82, including amines (to form, in a first approximate model, dimers mainly by hydrogen bonding interactions), is a long known problem. There are numerous reports in the literature on the thermodynamic, spectroscopic and structural aspects of self-association and dimer formation of water, alcohols, ammonia, amines and hydrogen sulphide83. 

Pyrroles are found in the volatiles of most heated foods [29], although they have received less attention than some other classes of aroma volatiles. Some pyrroles may contribute desirable aromas, e.g. 2-acetylpyrrole has a caramel-like aroma, and pyrrole-2-carboxaldehyde is sweet and corn-like, but alkylpyrroles and ac-ylpyrroles have been reported to have unfavourable odours [22]. Many more volatile pyrroles have been found in coffee than in other foods [30], and they are common products of amino acid-sugar model systems. Pyrroles are closely related in structure to the furans, and they are probably formed in a related manner from the reaction of a 3-deoxyketose with ammonia or an amino compound followed by dehydration and ring closure (cf Scheme 12.2). 

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