Aminating agents

Various organophosphorus amine derivatives can be used as aminating agents (12.326-12.329). 

The A-amination of pyridazines with hydroxylamine-O-sulfonic acid and its aryl derivatives was summarized in CHEC-I 84CHEC-I(3B)1 . For 3-substituted pyridazines A-amination occurs at N-2 in the case of methyl and amino, but at N-1 in 3-methoxy derivatives. 

In the reaction of pyridazine 26 with perfIuoro-(2-butyl-3-propyloxaziridine) 38 both pyridazin-1-oxide 39 and T-(perf1uorobutanoyl)pyridazinium-l-aminide 40 were formed (Equation 9) 1996J(P1)2517 . In CHEC(1984) 1984CHEC(2)1 and CHEC-II(1996) 1996CHEC-11(6)1 , the N-amination with hydroxylamine-O-sulfonic acid and derivatives was covered. 

Azoles without a free NH group are also aminated (usually with O-mesitylsulfonylhydroxylamine or O-picrylhydroxylamine), giving A-aminoazolium salts, e.g. (129) (94JCS(Pl)84l). 

The diazonium ions of type (130) located at a (3-position to a nitrogen unsubstituted tetrazole cyclize onto the N-l position giving the fused tetrazolotriazines (131) (89LA83). Similarly, compound (132) is formed from 2-(o-aminophenyl)benzimidazole (66JHC289). 

Reactivity of Five-membered Rings with Two or More Heteroatoms 

Liquid Ammonia. The properties of liquid ammonia are compared with those of water in Table 8-1. 

Liquid ammonia resembles water in its general physical and chemical properties, as is apparent in the values of Table 8-1. It can also be seen, from the boiling point, for example, that the technique of ammonolysis may be different, depending on - vhether liquid ammonia or aqueous ammonia is used as the aminating agent. 

Both ammonia and water are associated liquids. The degree of association of ammonia from molecular-weight determinations (24.5) suggests an equilibrium mixture  

They form compounds with salts, are good solvents, and, although virtual nonconductors themselves, effect the ionization of electrolytes. The ionizing power of liquid ammonia is due largely to the high speed at which the ions of dissolved electrolytes move in this solvent. 

Liquid ammonia may be introduced into reaction systems, and am-monolysis then carried out at temperatures higher then the critical temperature. These are really examples of the use of gaseous ammonia as the aminating agent or of ammonia dissolved in one of the reactants or in an inert organic solvent. 

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The alkan olamines discussed here exhibit the chemical reactivity of both amines and alcohols, as is the case with other alkan olamines. Typically, they attack copper, brass, and aluminum, but not steel or iron. Alkan olamines are useful as amination agents however, the reactivity of both the amino and alcohol... 

Aminating agents 3.14 Other Lewis acids Electrophilic Attack at Carbon... 

The powerful aminating agents hydroxylamine O-sulfonic acid and O-mesitylenesulfonyl-hydroxylamine have been used to prepare compounds (270)-(274) (80JCR(M)0514,76CPB2267). 

Two substituents on two N atoms increase the number of diaziridine structures as compared with oxaziridines, while some limitations as to the nature of substituents on N and C decrease it. Favored starting materials are formaldehyde, aliphatic aldehydes and ketones, together with ammonia and simple aliphatic amines. Aromatic amines do not react. Suitable aminating agents are chloramine, N-chloroalkylamines, hydroxylamine-O-sulfonic acid and their simple alkyl derivatives, but also oxaziridines unsubstituted at nitrogen. Combination of a carbonyl compound, an amine and an aminating agent leads to the standard procedures of diaziridine synthesis. 

Amino-4//-l,2,4-triazole 16 was employed as an aminating agent in a reaction with l-methyl-4-nitropyrazole 81 the reaction gave a mixture of the 5-amino-4-nitropyrazole 82 and the adduct 83 in low yields of 20% and 13%, respectively (Equation 30) <2000CHE476, 2000KGS551>. 

The acylation product of hydroxylamine, /-butyl N-hydroxy-carbamate,6 is a valuable intermediate in the synthesis of O-sub-stituted hydroxylamines such as O-acyl- and O-sulfonylhydroxyl-amines, many of which are valuable aminating agents and have not been obtained in any other way.8-9... 

Lithium t-butyl A-tosyloxycarbamate, Bu C CNTos Li+, is an electrophilic aminating agent for organometallic compounds RM (MeLi, BuLi, j-BuLi and PhCu) to give,... 

The efficiencies of 0-(diphenylphosphinoyl)hydroxylamine and hydroxylamine-O-sulphonic acid as electrophilic aminating agents have been compared96. The conversion of... 

Recently, TATB (14) has been synthesized by treating TNB and picramide (53) with VNS aminating agents like 4-amino-1,2,4-triazole (ATA) and 1,1,1-trimethylhydrazinium iodide (TMHI) in the presence of sodium methoxide in Hydroxylamine has been used... 

Fig. 2.13 Examples of hydroboration/amination using Rh-QUINAP complexes and electrophilic aminating agents. (I) Catecholborane, 1 mol% (S)-QUINAP-Rh catalyst, THE, RT, 1 h 2 equiv. MeMgCI in THE, 30 min solid H2NOSO3H,...

Y. Tamura, J. Minamikawau. M. Ikeda, Synthesis 1977, 1-17 , 0-Mesitylenesulfonylhydroxylamine and Related Compounds - Powerful Aminating Agents". 

Mecamylamine, unlike the quaternary amine agents and trimethaphan, crosses the blood-brain barrier and readily enters the CNS. Sedation, tremor, choreiform movements, and mental aberrations have been reported as effects of mecamylamine. 

De-aminating agents, such as nitrous acid or compounds that can be metabolised to nitrous acid or nitrites. These reagents are capable of removing amino groups from cytosine, adenine and guanine. 

More recently, Srivastava and Nicholas discovered the direct allylic amination with nitroaromatics 38 as effective aminating agents under catalysis by the inexpensive [CpFe(CO)2]2 (Scheme 3.38) [134],... 

As regards the use of chloramine as aminating agent, dimethylalkylboranes have been used to prevent the loss of two alkyl residues [68,69]. This reaction tolerates functionality in the oiganoborane, but the yields decrease dramatically for a steri-cally demanding IV-chloralkylamine. 

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