The Bucherer Reaction
Naphthols and the corresponding naphthylamines are interconvertible in aqueous media containing sulphite or bisulphite ion at elevated temperatures23. Thus naphthols may be converted to naphthylamines by reaction with ammonia and ammonium sulphite in aqueous solution, usually in the temperature range 90-150 the corresponding dinaphthylamine is sometimes obtained as a byproduct reaction 15 . MonoaLkylamines and dialkylamines similarly give the alkylamino- and dialkylaminonaphthalenes, though...
O 1
RNH2 - RNHCO CH2 3CH3 t'BuOBr gt RNBrCO CH2 3CH3 passing that, in the aromatic series, rearrangement of imidates provides a useful source of diarylamines Chapman rearrangement reaction 48 7B. RC - RCONArAr1 - ArNHAr1 48 A somewhat different approach to the synthesis of primary and secondary amines is involved in the use of blocking groups that so reduce the nucleophilicity of ammonia or a primary amine that alkylation does not proceed to the quaternary stage. For the conversion of ammonia to...
C Photoamlnation of Cyclohexane
Direct photoamination of cyclohexane with hydrazine in -butanol solution has recently been demonstrated, the most favourable yield of cyclohexylamine being 45 . Cyclohexanol occurs as a by-product, but its yield may be reduced by excluding oxygen21. Other byproducts include bicyclohexyl and cyclohexylhydrazine, but the latter is not apparently an intermediate in the formation of cyclohexylamine 22. A radical process is favoured for this reaction, with N N bond fission as the important...
A The Alkylation of Ammonia and Amines
The preparation of amines and quaternary ammonium salts through displacement of halide ion from alkyl halides by ammonia or amines is commonly referred to as alkylation of ammonia or amines alkyl esters of other strong acids have also been used in similar alkylation procedures. Equations 19 to 22 represent in simple terms the sequence of reactions which may occur in the interaction of ammonia or an amine with an alkyl halide. In principle, these reactions lead to a wide range of amines and...
chchchchchch
with amines to give allylic amines and quaternary salts which may contain the original or the rearranged allylic group reaction 29 39. MeCH CHCH2CI MeCH CHCH2NEt2 lt NHEt3 MeCHClCH CH2 29 Primary allylic halides generally give normal products, whilst secondary allylic halides frequently give rearranged products, or mixtures of normal and rearranged products. A general discussion of the factors relevant to reactions of allylic compounds with nucleophiles, including amines, has been given in the...
A Direct Amination of Aromatic Compounds in the Presence of Lewis Acids
Examples of the amination of aromatic compounds by various electrophilic species, derived from hydroxylamineand from hydrogen azide2, have been known for some time. Aromatic compounds which have been aminated in this way range from benzene and alkylbenzenes to substances such as anthraquinone3. Recently, some of these reactions have been systematically examined, and the principal mechanistic features elucidated, mainly by Kovacic and coworkers. Direct amination of toluene can be effected with...