NH/ROH

Among the peculiar features of 2-bromoamides there are the following i) possibility of substitution at the tertiary C-Br (RCO2H, RR NH, or a saccharide, as the nucleophiles) ii) chiral stability and stereochemical control at the secondary C-Br atom (RR NH, ROH or a saccharide as the nucleophiles) iii) the presence of bromine allows cyclic voltammetry and electroreduction at controlled potential both of starting compounds and relevant intermediates iv) the Ca polarity can be reversed upon electroreduction, and the resulting Ca enolate forms a C-C bond (CO2 as the electrophile). 

The relative concentrations of >NCH20CHj, >NH, ROH, and melamine can be measured quantitatively by Infrared methods. 

Me3Si)2NH, Me3SiCl, Pyr, 20°, 5 min, 100% yield. ROH is a carbohydrate. Hexamethyldisilazane (HMDS) is one of the most common sily-lating agents and readily silylates alcohols, acids, amines, thiols, phenols, hydroxamic acids, amides, thioamides, sulfonamides, phosphoric amides, phosphites, hydrazines, and enolizable ketones. It works best in the presence of a catalyst such as X-NH-Y, where at least one of the group X or Y is electron-withdrawing. ... 

Hexafluoroacetone azine accepts nucleophiles (ROH, RSH, R NH) in positions 1 and 2 to yield hydrazones [27] Phosphites give open-chain products via a skeletal rearrangement [22] Radical addition reactions are also reported [22] Treatment of tnfluoropyruvates with tosylhydrazine and phosphorus oxychlo-ride-pyndme yields tnfluoromethyl-substituted diazo compounds [24] (equation 3)... 

Esters of [1-(diethoxyphosphinyloxy)perfluoro-l-alkene]-phosphonic acid appear to be effective reagents for the synthesis of perfluoro-a,B-unsaturated carboxylic acids and their derivatives presumably an initially-generated perfluoroketene (166 ) is acted upon by a nucleophile (NuH=RNH2, I NH, or ROH). The ( E) / (Z) ratio of the product components increases with increasing length of R. 2 ... 

The potential of carbamic acid ester prodrugs (R-O-CO-NR R") is well-established by a number of studies on their stability and metabolism. Upon hydrolysis, they liberate the active agent ROH and the carbamic acid R R"N-COOH, which, being unstable, breaks down to the amine R R"NH and C02 (see also Sect. 8.7). The mechanism of HCT-catalyzed hydrolysis of carbamates, summarized in Fig. 8.7,b, is more complex than that of carbonates [153][158][159]. In the case of N,N-disubstituted carbamates (R-O-CO-NR R"), the only possible mechanism is as for carbonates (Fig. 8.7,b, Reaction a), which is, presumably, also the mechanism of enzyme-catalyzed hydrolysis for all carbamates. 

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