REACTIONS WITH NITROGEN COMPOUNDS

Reaction with ammonia yields 5-cyanotetrazole, a nitrogen heterocychc ring compound. Reactions with alkyl amine, RNH2, yield dialkyloxalamidines RNHC(=NH)CH(=NH)NR with dialkylamine, R2NH, the product is N,N-diaIkylcyanoformamidine ... 

In a mechanistically similar process, the neutral palladium(II) dipyridylamine complex (24), obtained by deprotonation of complex (23), underwent reaction with benzoyl chloride to give the substituted complex (25) together with some free ligand (Scheme 8).33 This particular reaction sequence could not be generalized because of the relative instability of other metal complexes related to compound (24). However, a more extensive series of electrophilic substitutions could be carried out on the neutral complex (26), which displayed ambident nucleophilic behaviour by reaction with benzyl chloride and benzoyl chloride at nitrogen and reaction with benzenediazonium fluoroborate at carbon (Scheme 9). 

Hydroxy(tosyloxy)iodo]benzene and Its Analogues Reactionswith Alkenes and Allenes. Reactions with Alkynes and Alcohols. Reactions with Keto Compounds. Reactions with Nitrogen, Sulfur, and Other compounds. 

Electrolysis of mixtures with nitrogen compounds may form the explosive nitrogen trichloride. Reaction with burning lithium forms the dangerously reactive sodium. The molten salt at 1100° reacts explosively with water. Violent reaction with... 

Element (metal or nonmetal)-N protonic acid cleavage yields nitrogen compounds Reaction of (MejSi) N with CFjCOjH yields N H ... 

The nitrosyl carbonyls result from the action of NO on the polynuclear carbonyls of iron and cobalt. Like the carbonyls the nitrosyl carbonyls react with neutral molecules such as organic nitrogen compounds and with halogens, and in such reactions CO, and not NO, is replaced. Thus Fe(CO)2(NO)2 with iodine gives... 

Acyloxaziridines are easily obtained from compounds unsubstituted at nitrogen by reaction with acid chlorides or isocyanates. Acylation proceeds so smoothly that, in the amination of carbonyl compounds, oxaziridine compounds are obtained in better yields on addition of acid chlorides than in the absence of the acylating agent. With aliphatic aldehydes, amination does not succeed at all except in the presence of benzoyl chloride. Proof of structure comes from reduction by iodide to give the acid amide and carbonyl compound. 

There are oxygen counterparts to many of the reactions which occur between boranes and nitrogen compounds, but with important differences... 

Skell et have investigated the reactions of diatomic carbon, produced in a carbon arc under high vacuum, with simple organic compounds at surfaces cooled by liquid nitrogen. The reaction with alkanes and ethers gives rise to allenes as well as acetylene, whereas the reaction with propylene (two moles) yields 5,6-methano-l,4-heptadienes. 

The substrate-induced diastereoselectivity was investigated using an (R)- or (S)-1-phenylethyl group as a chiral auxiliary on the amide nitrogen. The reactions with the unprotected compounds went smoothly and diastereomeric mixtures were obtained in excellent yield and syn diastereoselectivity (> 99% syn) (entries 6-8). The results were better than those obtained with the butylamides. The facial selectivity was in the range of about 8 1. The protection of the hydroxyl group lowered both the facial selectivity and the yield (entry 8). 

Another, especially historically important copper-mediated radical aryl-aryl bond forming reaction is the Pschorr reaction (Gomberg-Bachmann reaction), which has been first described in 1896 for the preparation of phenanthrene and its derivatives [85]. Later, in 1924, Gomberg and Bachmann described an intermolecular version of this reaction and prepared several biphenyl derivatives in moderate yield [86]. The reaction is initiated by formation of diazonium salts from aromatic amines, which release nitrogen upon reaction with copper salts. The intermediary formed aryl radial then undergoes the desired coupling reaction and allows the isolation of biaryl compounds. An example of such a reaction is outlined in Scheme 12.23 [87],... 

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