Grignard reagent reaction with acids

Strictly speaking the alkyl halides are esters of the halogen acids, but since they enter into many reactions (t.g., formation of Grignard reagents, reaction with potassium cyanide to yield nitriles, etc.) which cannot be brought about by the other eaters, the alkyl halides are usually distinguished from the esters of the other inorganic acids. The preparation of a number of these is described below. 

Reaction of Acid Chlorides with Organometallic Reagents Grignard reagents react with acid chlorides to yield tertiary alcohols in which two of the substituents are the same. 

Grignard reagents react with acid chlorides to yield tertiary alcohols in which two of the substituents are the same. The mechanism of the reaction is similar to that of L1A1H4 reduction. The first equivalent of Grignard reagent adds to the acid chloride, loss of Cl from the tetrahedral intermediate delds a ketone, and a second equivalent of Grignard reagent immediately adds to the ketone to produce an alcohol. 

Organoiithium compounds react with esters, acid chiorides, and anhydrides in the same way as Grignard reagents. Reaction with carboxyiic acids gives ketones, but 2 moi of organoiithium are required. 

The formation of halogenation products from Grignard reagents and sulfonic acid anhydrides is the result of an oxidative reaction pathway . This side-reaction can be reduced by using sulfonic acid esters, however, in these cases alkylations as well as twofold sulfonylations (cf. corresponding results with sulfonyl fluorides ) are competing (equations 64 and 65). 

The free dithiocarboxylic acids can be isolated, but their salts are preferred. In some cases their metal complexes can be prepared directly by insertion of carbon disulfide into metal-carbon bonds. Thus, the reaction of Grignard reagents, RMgX, with CS2, followed by acid treatment gives the dithiocarboxylic acids RCSSH and metal complexes in good yields.311... 

Cumylamine, oxidation of, 323 Cupferron ammonium salt, 447 reaction with Grignard reagents, 352 free acid, 402 Cyanamides, 161 reaction with alcohols, 174 Cyanoallene, 24... 

Unactivated aryl iodides undergo the conversion Arl — ArCHj when treated with tris(diethylamino)sulfonium difluorotrimethylsilicate and a palladium catalyst.131 A number of methods, all catalyzed by palladium complexes, have been used to prepare unsymmetrical biaryls (see also 3-16). In these methods, aryl bromides or iodides are coupled with aryl Grignard reagents,152 with arylboronic acids ArB(OH)2,153 with aryltin compounds Ar-SnR3,154 and with arylmercury compounds.155 Unsymmetrical binaphthyls were synthesized by photochemically stimulated reaction of naphthyl iodides with naphthoxide ions in an SrnI reaction.156 Grignard reagents also couple with aryl halides without a palladium catalyst, by the benzyne mechanism.157 OS VI, 916 65, 108 66, 67. 

The reactions of Grignard reagents with aldehydes and ketones give alcohols, reaction with acid chlorides and esters give tertiary alcohols, reaction with carbon dioxide to give carboxylic acids, reaction with nitriles give ketones, and reaction with epoxides give alcohols. 

X-5 The reaction of a cadmium Grignard reagent (R2Cd) with an acid chloride. This reaction requires the formation or a cadmium Grignard which can be formed as shown below... 

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