Grignard reagents silver salts

Grignard reagents/silver salt Allylamines. a-Amino nitnie... 

RCOX, SF4, X2, HOX, or RX with alcohols, ethers, diazonium compounds, Grignard reagents, silver salts of acids, acids, amides, aromatic compounds, aldehydes, ketones, olefins, and amines. Many other organic compounds also undergo these reactions. 

Kinetic experiments have been performed on a copper-catalyzed substitution reaction of an alkyl halide, and the reaction rate was found to be first order in the copper salt, the halide, and the Grignard reagent [121]. This was not the case for a silver-catalyzed substitution reaction with a primary bromide, in which the reaction was found to be zero order in Grignard reagents [122]. A radical mechanism might be operative in the case of the silver-catalyzed reaction, whereas a nucleophilic substitution mechanism is suggested in the copper-catalyzed reaction [122]. The same behavior was also observed in the stoichiometric conjugate addition (Sect. 10.2.1) [30]. 

Vinylphosphonium bromide 208 reacts with Grignard reagents, forming alkylphospho-nium ylides. These ylides react with aldehydes, giving alkenes in a one-pot sequence. In this reaction, catalytic amounts of both copper and silver salts are necessary (equation... 

Imidazolium ligands, in Rh complexes, 7, 126 Imidazolium salts iridium binding, 7, 349 in silver(I) carbene synthesis, 2, 206 Imidazol-2-ylidene carbenes, with tungsten carbonyls, 5, 678 (Imidazol-2-ylidene)gold(I) complexes, preparation, 2, 289 Imidazopyridine, in trinuclear Ru and Os clusters, 6, 727 Imidazo[l,2-a]-pyridines, iodo-substituted, in Grignard reagent preparation, 9, 37—38 Imido alkyl complexes, with tantalum, 5, 118—120 Imido-amido half-sandwich compounds, with tantalum, 5,183 /13-Imido clusters, with trinuclear Ru clusters, 6, 733 Imido complexes with bis-Gp Ti, 4, 579 with monoalkyl Ti(IV), 4, 336 with mono-Gp Ti(IV), 4, 419 with Ru half-sandwiches, 6, 519—520 with tantalum, 5, 110 with titanium(IV) dialkyls, 4, 352 with titanocenes, 4, 566 with tungsten... 

Aromatic Grignard reagents react smoothly with ethoxymethyleneaniline to give imines which are easily hydrolyzed to aldehydes. The reaction is easy to cary out, is adaptable to large-scale preparations, and gives high yields (65-82%). Its use is limited by the availability of the ethoxymethyleneaniline, which may be prepared in a pure condition from the dry silver salt of formanilide and ethyl iodide. 

Conductivity measurements have revealed that DMF and carboxylic acid chlorides form salt-like adducts (22) in an equilibrium reaction (equation 12). Such adducts can be prepared either from DMF and acid halides (chlorides and bromides) or from chloromethyleneiminium salts and salts of carboxylic acids. Acyloxyiminium salts (23) can be prepared in the pure state by reacting acid amides with carboxylic acid chlorides in the presence of silver trifluoromethanesulfonate (equation 13). Salts of type (24 equation 14) are regarded as being intermediates in the synthesis of ketones from carboxylic acids and Grignard reagents in the presence of a-chloroenamines as well as in the preparation of acyl halides (F, Cl, Br, I) by action of a-haloenamines on carboxylic acids. ... 

Decarboxylation of an aliphatic acid to the hydrocarbon is best effected by the so-called salt degradation method. That method is to treat the silver or mercury salt of, preferably, an aliphatic or alicyclic carboxylic acid with bromine in an inert solvent a halogenated hydrocarbon is then formed, together with carbon dioxide and the metal bromide, usually in an exothermic reaction, and the bromine can then usually be readily removed either cata-lytically or by means of a Grignard reagent (the Hunsdiecker reaction) ... 

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