Hydroxylamine complex compound with

Isatin (190) is a compound with interesting chemistry. It can be iV-acetylated with acetic anhydride, iV-methylated via its sodium or potassium salt and O-methylated via its silver salt. Oxidation of isatins with hydrogen peroxide in methanolic sodium methoxide yields methyl anthranilates (81AG(E)882>. In moist air, O-methylisatin (191) forms methylisatoid (192). Isatin forms normal carbonyl derivatives (193) with ketonic reagents such as hydroxylamine and phenylhydrazine and the reactive 3-carbonyl group also undergoes aldol condensation with active methylene compounds. Isatin forms a complex derivative, isamic acid (194), with ammonia (76JCS(P1)2004). 

Examples of the osmium and iridium complexes are Os(PPh3)2Cl(NO) and Ir(PPh3)3(NO), respectively [216]. The osmium compound gave, on reaction with HC1, the first characterized complex with the feature of an N-coordinated HNO, Os(PPh3)2Cl2(HNO), which was confirmed by X-ray crystallography. On the other hand, the nitrosylated iridium compound gave the hydroxylamine complex [216]. 

Compound 59a reacted with arylhydrazines to give complex mixtures as shown in Scheme 53 (70G745). The reaction presumably goes via an electron transfer process in which the diazo compound serves as electron acceptor. Similar reactions leading to even more complex mixtures were also observed with hydroxylamine, hydrazo compounds, and conjugate indole derivatives (70G757). 

While the condensation of amines with nitroso compounds appears to have wide applicability in the benzene series, it seems to lead to complex dye molecules in the naphthalene series. A method has been developed using a somewhat complex reaction between thionylamines and substituted hydroxylamines which does produce azo compounds derived from naphthalenes. This synthesis is of particular interest because it helped to settle the question whether true naphthylazo compounds with hydroxyl groups could exist [36]. 

One of the reactions which has been used to prepare azoxy compounds is the condensation of C-nitroso compounds with hydroxylamines. In the aliphatic series this reaction is quite general and permits the preparation of unsym-metrical azoxy compounds. In the case of aromatic compounds, however, only symmetrical azoxy compounds can be synthesized reliably. In the reaction of dissimilar aromatic nitroso compounds and aromatic hydroxylamines, a complex mixture of azoxy products is obtained. 

This means that, instead of one expected product with molecular weight (MW) = Mq + 29 (with O-methyl hydroxylamine as reagent), reaction mixtures may contain two additional compounds with MW = Mq + 47 and Mq + 76. This feature is negligible for analysis of individual compounds, but when samples are mixtures of components of interest, the analysis becomes impossible because of the complexity of the resultant interpretation. 

A number of addition derivatives may be used in the identification of the carbonyl compounds. Of these the crystalline derivatives formed with phenylhydrazine, C6H6NHNH2, and hydroxylamine, NH2OH, are the most important. The products formed with phenylhydrazine are called phenyUiydrazones, and have the general formula, RRiC=NNHC jls. The products formed with hydroxylamine are called oximes, and have the general formula, RRiC=NOH. Other crystalline addition compounds are formed with sodium bisulfite by aldehydes, and by those ketones which contain a methyl group. The addition compounds with ammonia, except in the case of acetaldehyde and a few other carbonyl compounds, are complex products. 

Organoboranes can be used for the synthesis of various organic compounds containing an amino group . The most common procedures involve the reaction of organoboranes with azides, with hydroxylamine derivatives, or with chloroamines. All amination reactions proceed via intermediate formation of a borate complex followed by anionotropic rearrangement to form the new C—N bond (Equation (21)). 

Free 1-boraadamantane (5) also readily reacts with dimethyl- <94CBI105> or diethylchloroamine, hydroxylamine-O-sulfonic acid, or 0-2,4-dinitrophenylhydroxylamine to give intramolecular complex compounds (110)-(112) via adducts of the type (109) (Scheme 41) <81JOM(220)1>. 

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