From nitroso compounds

With concentrated mineral acids azobenzene gives red salts, as may be shown by pouring hydrochloric acid on it. Addition of hydrogen leads to the re-formation of the hydrazo-compound. Oxygen is added on and the azoxy-compound formed by the action of hydrogen peroxide or nitric acid. The synthesis of asymmetrical aromatic azo-compounds from nitroso-compounds and primary amines was discussed above. 

Preparation of spiro[2.3]hexanes is possible by the addition of methylene or a methylene equivalent to an exocyclic C —C double bond. Generally, the Simmons Smith reaction is used (see Section l.A.1.2.1.), but formation of carbenes from nitroso compounds can also be used.73-75,333 The 1,1-dihalo derivative can be prepared by phase-transfer-catalyzed reactions.48 For example, reaction of a mixture of cis- and trans-1,2-dimethyl-3-methylenecyclobutane with dibromo-carbene gave a mixture of cis- and lrans-1,1-dibromo-4,5-dimcthylspiro[2.3]hexanc (2).48... 

A fourth type of product, a carbamate RNHCOOR , can be obtained from primary or secondary amines, if these are treated with CO, O2, and an alcohol R OH in the presence of a catalyst. " Primary amines react with dimethyl carbonate in supercritical CO2 (see p. 414) to give a carbamate. " Carbamates can also be obtained from nitroso compounds, by treatment with CO, R OH, Pd(OAc)2, and Cu(OAc)2, " and from nitro compounds. " When allylic amines (R2C=CHRCHRNR 2) are treated with CO and a palladium-phosphine catalyst, the CO inserts to produce the p,y-unsa-turated amides (R2C=CHRCHRCONR 2) in good yields. " Ring-expanded lactams are obtained from cyclic amines via a similar reaction (see also, 16-22). Silyloxy carbamates (RNHC02SiR 3) can be prepared by the reaction of a primary amine with carbon dioxide and triethylamine, followed by reaction with triisopropylsilyl triflate and tetrabutylammonium fluoride. ... 

Anil formation from nitroso compound and 2,4,6-trinitrotoluene, 293 Anhydride, conversion to thioacid with HjS, 276... 

Nitro from nitroso compounds with simultaneous oxidation of hydrocarbons to carboxylic acids... 

Azoxy compounds from nitroso compounds RNO + H2NR and amines... 

Amines can be easily mono- and di-alkylated, especially methylated, via their fluoroacetyl derivatives. Nitrones can be obtained under mild conditions from nitroso compounds and hydrazones... 

An equimolar amount of methanolic 10%-KOH added with stirring and Dry Ice-acetone cooling at -40° to a soln. of diphenyl a-anilino-p-nitrobenzylphospho-nate in tetrahydrofuran, then 2-pyridinecarboxaldehyde in tetrahydrofuran added product. Y ca. 100%. F. e., also amidines from nitroso compounds, s. H. Zimmer and J. P. Bercz, A. 686, 107 (1965). 

Hydrogen peroxide trifluoroacetic acid Nitro from nitroso compounds... 

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