Replacement of metals by nitrogen

Of the many organometallic compounds, only Grignard reagents are used for formation of C-N bonds. Alkyl- and aryl-magnesium halides undergo various types of reaction with nitrogen compounds,1216 but few of these have major importance. 

Among these few is the formation of aliphatic and arylaliphatic amines by reaction of Grignard reagents with chloramine according to the scheme  

The reaction is carried out in ethereal solution it gives the best yields when alkylmagnesium chlorides are used the corresponding alkyl chlorides are by-products. The process has its main interest for preparation of primary amines whose amino group is attached to a secondary or tertiary carbon atom. Examples of its use and a tested. method of preparing chloramine are given in a review by Theilacker.1217 Also the unstable chloramine may be replaced by methoxylamine, which is easier to handle.1218 

1216 M. S. Kharasch and O. Reinmuth, Grignard Reactions of Nonmetallic Substances, Prentice-Hall Inc., New York, 1954, pp. i 199 et seq. 

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