Olefins conversion into amines

Reduction of t-azides to amines. An improved method for conversion of tertiary alcohols (or their corresponding olefins) into amines is illustrated in equation (I) for the preparation of a,o-dimethylbenzylamine. This method of reduction can be used also for azides containing benzyloxy groups or double bonds. ... 

CF2 CFa CF2 CF SAg (not isolated) -- (with EtI at 75 °C) CF2 CF2 CF2 CF SEt (21%). Raman and photoelectron spectral data are available for some CFs S-compounds, and so are e.s.r. parameters for the radical CFs S CHs-CBu a [generated via photolysis of a solution of the appropriate olefin in (CFs-S)2]. Unsuccessful attempts have been made to generate a radical anion via electrochemical or chemical (NaK alloy) reduction of 3,4-bis(tri luoromethyl)-l,2-dithieten. i Reactions between trifluoromethanesulphenyl chloride and JV-chloro-amines are portrayed in Scheme 26 (p. 216) and some involving hexafluorothioacetone dimer in Scheme 27 (p. 217) many unsuccessful attempts are claimed to have been made to isolate bis(trifluoromethyl)methanethiol from the products of the reactions of the dimer with amines, the conversion into hexafluoroisopropylidenimines being... 

Amines. o-Mesitylenesulphonylhydroxylamine is superior to hydroxylamine o-sulphonic acid or chloramine for use in the conversion of olefins into amines via hydroboration. ... 

Fatty acid esters are generally obtained from the transesterification of fats and oils with a lower alcohol, e.g. methanol, along with glycerol. More than 90% of all oleochemical reactions (conversion into fatty alcohols and fatty amines) of fatty acid esters (or acids) are carried out at the carboxy functionality. However, transformation of unsaturated fatty acid esters by reactions of the carbon-carbon double bond, such as hydrogenation, epoxidation, ozonolysis, and dimerization, are becoming increasingly of industrial importance. Here we will discuss another catalytic reaction of the carbon-carbon double bond, viz. the olefin metathesis reaction, in which olefins are converted into new products via the rupture and reformation of carbon-carbon double bonds [2]. Metathesis of unsaturated fatty acid esters provides a convenient route to various chemical products in only a few reaction steps. 

Amides may also be prepared by conversion of olefins into amines followed by acylation. See section 104 (Amines from Olefins)... 

A one-step, efficient, and neral conversion of olefins into amines is an important development. This reaction can be achieved using olefins, carbon monoxide, water, and a nitro n source in the presence of rhodium-based catalysts. A typical example of the process is represented by the conversion of cyclohexene into [Pg.253]

An analogous reaction is the conversion of olefins into primary amines by the consecutive action of BH3. THF and trimethylsilyl azide171. The observation172 that organoboranes and chloramine give primary amines is the basis of an amine synthesis in which olefins are treated with the complex BH3 THF, followed by aqueous ammonia and aqueous sodium hypochlorite173. Imines are reduced by the chiral dioxaborolidine 162 to yield optically active amines. 1-Imino-l-phenylpropane, for instance, affords 1-phenylpropylamine in 73% enantiomeric excess (equation 59)174. 

Deamination via sulphonamide intermediates allows the conversion of the carbon-nitrogen bond into the carbon-oxygen bond. Conditions have been established such that nitrates may be obtained from the deamination of primary amines with dinitrogen tetroxide at low temperature rather than alcohols/ The oxidation of amines to nitriles has been carried out using copper(l) chloride in pyridine under an oxygen atmosphere/ which is a milder reagent than those previously used to perform this transformation. Cleavage of tertiary amines with ethyl chloroformate affords a simple preparation of di- and tri-substituted olefinic synthons (Scheme... 

In a similar vein, the cyclization of aliphatic amino-olefins to nitrogen hetero-cycles has been accomplished by conversion of the amine into the corresponding toluene-/ -sulphonamide, followed by Pd -catalysed intramolecular amination of the olefin."... 

Nitrous oxide is reduced by CO in the presence of [Rh(C0)2C1]2 and base to N2 and C02 21 The mechanism of the reduction of aromatic nitro compounds by CO to give isocyanates has been studied by IR the catalyst is trans-PdCl2(pyridine)2.212 PeiCOg, Ru3(C0)x2 Rh6(C0)xg convert ortho-nitrostyrenes and CO into indoles in up to 75 selectivity (eq.21).213 Nil2(PPh3)2 under CO pressure catalyses the conversion of nitrobenzene and aniline to diphenylurea and CO2 the amine is used as the solvent.214 Ru3(C0)i2 catalyses the carbonylation of amines to formamides and the hydroamidation of olefins to carboxylic amides.215... 

It has been shown that the presence of catalytic amounts of carboxylic acid such as trani-l,2-cyclohexyldicarboxylic or 3,4,5-trifluorobenzoic acid improved the ruthenium-catalysed sp C-H bond alkylation of cyclic amines by terminal olefins and allowed reaching full conversion of less reactive A -pyridylpiperidine derivatives. Thus, in the absence of CO but in the presence of tra s-l,2-cyclohexyldi-carboxylic acid, the A -pyridylpiperidine 38 was efficiently hexylated into mono- 39 and dialkylated 40 piperidine derivatives, whereas in the absence of carboxylic acid... 

Although clearly of use in the synthesis of certain alkylboron compounds, particularly tri-n-alkylboranes and alkylboron hydrides, the hydroboration reaction (developed mainly by H. C. Brown) is of considerable significance in synthetic organic chemistry, as the resulting organoboron compound can be used (without being isolated) as an intermediate in the conversion of olefins or acetylenes into other hydrocarbons (parafi or olefins), alcohols, aldehydes, ketones, carboxylic acids or amines. 

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