Grignard reagent carboxylic acids from

KETONES FROM CARBOXYLIC ACIDS AND GRIGNARD REAGENTS METHYL 6-OXODECANOATE (Oecanolc acid, 6-oxo-, nethyl ester]... 

KETONES FROM CARBOXYLIC ACIDS AND GRIGNARD REAGENTS ... 

Ketones from Carboxylic Acids and Grignard Reagents Methyl 6-Oxodecanoate... 

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. ... 

In some instances a carbon-carbon bond can be formed with C-nucleophiles. For example, 3-carboxamido-6-methylpyridazine is produced from 3-iodo-6-methylpyridazine by treatment with potassium cyanide in aqueous ethanol and l,3-dimethyl-6-oxo-l,6-dihydro-pyridazine-4-carboxylic acid from 4-chloro-l,3-dimethylpyridazin-6-(lH)-one by reaction with a mixture of cuprous chloride and potassium cyanide. Chloro-substituted pyridazines react with Grignard reagents. For example, 3,4,6-trichloropyridazine reacts with f-butyl-magnesium chloride to give 4-t-butyl-3,5,6-trichloro-l,4-dihydropyridazine (120) and 4,5-di-t-butyl-3,6-dichloro-l,4-dihydropyridazine (121) and both are converted into 4-t-butyl-3,6-dichloropyridazine (122 Scheme 38). 

Table 11.5. Substituted cyclopropanols 31 from carboxylic acid esters and alkenes via ligand-exchanged titanium intermediates generated from Grignard reagents and XTi(OiPr)3 (X = OiPr, Cl, Me).

Carboxylic acids are obtained from Grignard reagents by reaction with carbon dioxide. Scheme 7.3 includes some specific examples of procedures described in Organic Syntheses. 

If the carboxyl group is attached to a tertiary, or even a secondary carbon atom, the Sn2 reaction with cyanide will not be so good and the carboxylation of a Grignard reagent is probably better. Pivalic acid 44 is available but can be made from r-BuCl in good yield.13 A detailed... 

Show how to synthesize carboxylic acids from oxidation of alcohols and aldehydes. Problems 20-36, 39, and 44 carboxylation of Grignard reagents, oxidative cleavage of alkenes and alkynes, hydrolysis of nitriles, and oxidation of alkylbenzenes. 

The product is a N,jV-disubstituted amine, which can be formed by reduction of an amide. The amide results from treatment of an acid chloride with the appropriate amine. The acid chloride is the product of the reaction of SOCI2 with a carboxylic acid that is formed by carboxylation of the Grignard reagent synthesized from the starting material. 

Alcohols, aldehydes, ketones and carboxylic acids can be prepared from Grignard reagents. ArMgBr, and organolithium compounds, ArLi. by reaction with molecules with an electron-delicieni site. 

The Grignard reagent adds to the carbon- oxygen double bond just as in the reaction with aldehydes and ketones (Sec. 15.12). The product is the magnesium salt of the carboxylic acid, from which the free acid is liberated by treatment with mineral acid. 

Couh ot, P., Youssefi-Tabrizi, M., and Grison, C., Diethyl (chloromagnesio)methanephosphonate. A novel Grignard reagent and its use in organic synthesis, J. Organomet. Chem., 316, 13, 1986. Razumov, A.I., and Moskva, V.V., Derivatives of phosphonic and phosphinic acids. Part 26. Synthesis of phosphorylated carboxylic acids from aldehydes and acetals, Zh. Obshch. Khim., 35, 1149, 1965 J. Gen. Chem. USSR (Engl. Transl.), 35, 1151, 1965. 

The problem indicates this acid formed from the alcohol, C, is identical to A. note that in the synthesis of the carboxylic acid from C, a carbon atom must be added. (Preparation of carboxylic acids through a Grignard reagent will add one carbon atom to the skeleton.) Consider... 

Addition of Grignard reagents to carbon-carbon double bonds Synthesis of carboxylic acids from ethylene derivs. 

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