Primary amine cation

Drummond et al. [54] synthesized protic ionic liquids by combining Bronsted acid/base pairs where the primary amine cations were of the form RNH3 and R(OH) NH3 combined with organic anions of the form RCOO, R(OH)COO or with an inorganic anion. They studied physicochemical properties of synthesized PILs at nominally equimolar ratio of anion and cation (1 1 stoichiometry) and in the presence... 

Nitrosation (Section 22 15) Nitrosation of amines occurs when sodium nitrite is added to a solution containing an amine and an acid Primary amines y e d alkyl diazonium salts Alkyl diazonium salts are very unstable and yield carbo cation derived products Aryl diazonium salts are exceedingly useful synthetic in termediates Their reactions are de scribed in Table 22 7... 

The protonated form of poly(vinyl amine) (PVAm—HCl) has two advantages over many cationic polymers high cationic charge densities are possible and the pendent primary amines have high reactivity. It has been appHed in water treatment, paper making, and textiles (qv). The protonated forms modified with low molecular weight aldehydes are usehil as fines and filler retention agents and are in use with recycled fibers. As with all new products, unexpected appHcations, such as in clear antiperspirants, have been found. It is usehil in many metal complexation appHcations (49). 

The common impurities found in amines are nitro compounds (if prepared by reduction), the corresponding halides (if prepared from them) and the corresponding carbamate salts. Amines are dissolved in aqueous acid, the pH of the solution being at least three units below the pKg value of the base to ensure almost complete formation of the cation. They are extracted with diethyl ether to remove neutral impurities and to decompose the carbamate salts. The solution is then made strongly alkaline and the amines that separate are extracted into a suitable solvent (ether or toluene) or steam distilled. The latter process removes coloured impurities. Note that chloroform cannot be used as a solvent for primary amines because, in the presence of alkali, poisonous carbylamines (isocyanides) are formed. However, chloroform is a useful solvent for the extraction of heterocyclic bases. In this case it has the added advantage that while the extract is being freed from the chloroform most of the moisture is removed with the solvent. 

We mention Williams work briefly here because it may also explain Blangey s observations strongly basic primary amines unequivocally form 7V-nitrosoanilinium ions in strongly acidic media. In contrast to the rate-limiting deprotonations of the less basic aromatic and heteroaromatic nitrosoamine cations discussed in this section, the TV-nitroso cation of a strongly basic amine deprotonates extremely slowly. Therefore, the nitroso rearrangement, the Fischer-Hepp reaction, competes effectively with the 7V-deprotonation. 

Rosenblatt etal have examined the effect of structure and isotopic substitution upon the permanganate oxidation of some alky famines (Table 4). The isotope effect of 1.84 is considered to be sufficiently low to be compatible with aminium radical-cation formation, and it is felt that, while C-H cleavage is significant for oxidation of primary amines, the dominant mode of oxidation of tertiary amines is electron-transfer, e.g. 

The first structurally characterized example of a platinum(II) derivative containing a saturated tetraamine macrocycle, 6,13-dimethyl-l,4,8,ll-tetraazacyclotetradecane-6,13-diamine has been reported (80).251 The species crystallizes as the colorless tetra-cationic complex from dilute HC104 solution by slow evaporation, where the two pendant primary amines are protonated. Other macrocyclic tetraamine complexes including [Pt([14]aneN4)]Cl2 have also been described.252... 

The primary, secondary, and tertiary aliphatic amines do not form simple addition complex ions with bare transition metal ions. Only Ag+ reacts with MeNH2 to form a simple addition product [AgMeNH2]+ (107). The Pb+ ion also forms addition products, [PbMeNH2]+ and [Pb(MeNH2)2]+, with methylamine (143). Other bare transition metal ions (144) react with amines via removal of one hydrogen to form the metal hydride and the amine cation with one hydrogen removed [RR N]+. 

In the first report, PAMAM dendrimers with primary amine surface groups were used [27]. It was found that complex formation is dependent both upon the size (generation) of the dendrimers used and the charge ratio between the (cationic and anionic species, i.e. ammonium groups on PAMAM to phosphate groups on DNA). Retardation of DNA migration was not observed with... 

Photochemical addition of ammonia and primary amines to aryl olefins (equation 42) can be effected by irradiation in the presence of an electron acceptor such as dicyanoben-zene (DCNB)103-106. The proposed mechanism for the sensitised addition to the stilbene system is shown in Scheme 7. Electron transfer quenching of DCNB by t-S (or vice versa) yields the t-S cation radical (t-S)+ Nucleophilic addition of ammonia or the primary amine to (t-S)+ followed by proton and electron transfer steps yields the adduct and regenerates the electron transfer sensitizer. The reaction is a variation of the electron-transfer sensitized addition of nucleophiles to terminal arylolefins107,108. 

The cyclic metabolite 11.169 was also a substrate in further biotransformations, being (V-demethylated to the corresponding endocyclic imine, and oxidized to phenolic metabolites. Very little if any of the secondary amine metabolite (11.168) appeared to undergo direct (V-demethylation to the primary amine, in contrast to many other tertiary amines, presumably due to very rapid cyclization of the secondary amine facilitated by steric and electronic factors. The possibility for the iminium cation (11.169 H+) to become deprotonated (a reaction impossible for the iminium 11.166 in Fig. 11.20) should also drive the cyclization reaction. 

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