Nitrogen formation from amines

Condensa.tlon, This term covers all processes, not previously iacluded ia other process definitions, where water or hydrogen chloride is eliminated ia a reaction involving the combination of two or more molecules. The important condensation reactions are nitrogen and sulfur heterocycle formation, amide formation from acid chlorides, formation of substituted diphenyl amines, and misceUaneous cyclizations. 

Thermodynamics of complex formation of silver with several ligands such amines,368 hindered pyridine bases,369 nitrogen donor solvents,370 and azoles371 have been carried out. Other studies include the secondary-ion mass spectra of nonvolatile silver complexes,372 the relationship between Lewis acid-base behavior in the gas phase and the aqueous solution,373 or the rates of hydride abstraction from amines via reactions with ground-state Ag+.374... 

The scope of nitrolysis is huge, with examples of nitramine formation from the cleavage of tertiary amines, methylenediamines, carbamates, ureas, formamides, acetamides and other amides. The deflnition of nitrolysis must be extended to the nitrative cleavage of other nitrogen bonds because sulfonamides and nitrosamines are also important substrates for these reactions. The nitrative cleavage of silylamines and silylamides is also a form of nitrolysis (Section 5.7). 

The lactam formation from the oxidation of cyclic amines (353, for example) probably proceeds via intermediate 364. The nitrogen-iodine bond dissociates to give imine 365, which reacts again with a second equivalent of iodosobenzene to give another intermediate 366. Finally, 366 on reductive... 

Formation of amines from alkenes, carbon monoxide, water, and a nitrogen base was discovered by Reppe who used [Fe(CO)5] to catalyze the process to form amines in low yields 125 199... 

This precedents prompted several groups to develop reaction protocols that lead exclusively to the reduced products (the reductive PKR), in order to use them in synthesis. Thus, Becker obtained diazabicyclooctanones like 208 from amines (207) as the only reaction product when they used DSAC conditions under an inert atmosphere. The nitrogen atmosphere was essential as in air they obtained mixtures of the cyclopentanones and the cyclopentenones. This group has used this methodology for the synthesis of azaadamantanes like 209 as part of the structure of certain antagonists (Scheme 59) [ 182-184], Addition of TFA to the reaction favors the formation of reduced products. A series of alkynes produced cyclopentanones as the major product when reacted with norbornene, Co2(CO)8 and TFA. The authors think TFA reacts with the cobalt complex 210, prior to the reductive elimination that gives the final product 211 (Scheme 60) [185]. 

Para-rosaniline Chloride.—This carbinol is known as para-rosaniline, carbinol base. It is not a dye but when treated with acids it yields salts which are colored and which possess the properties of dyes. These salts result from one of the amino groups reacting with the acid, forming an ammonium salt, the tri-valent nitrogen of the amine becoming penta-valent in the salt, as in the formation of methyl ammonium chloride from methyl amine. 

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