Carboxylic acids reactions with epoxides

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. 

Finally, fluorinated carboxylic acids react with epoxides (trimethylaluminum-catalyzed).- and conveniently with diazo conipounds. Cycloaddition is observed with diazo-methane. Reaction of compound 7 with trifluoroacetic acid alone is relatively slow (Freon 113, reflux, 12 h, for completion of reaction) however, catalytic amounts of copper(ll) perchlorate increase the rate of formation of ester 8 (rt, 5 min). ... 

TETRINE ACID (60-00-4) CioH.sNjOg A weak organic (carboxylic) acid. Reaction with dithiocarbamates, isocyanates, mercaptans, nitrides, nitrites, sulfides, forms flammable and/or toxic gases + heat. Incompatible with acids, azo compounds, epoxides and other polymerizable compounds oxidizers, sulfuric acid, reducing agents bases, ammonia, aliphatic amines alkanolamines, alkylene oxides cyanide salts and cyanide solutions (forms... 

The use of much-neglected bismuth derivatives for the oxidation of organic compounds has been reviewed.74 Bismuth(III) carboxylates, obtained by reaction of Bi2C>3 with pyridine mono- and di-carboxylic acids and with phthalic acid, act as catalysts for the oxidation of styrene oxide to benzoic acid in DM SO in the presence of 02.75 It is proposed that the bismuth may activate both epoxide and oxidant in a solvate, from which dimethyl sulfide evolution and elimination leads to a ketoalkoxide-bismuth complex (and hence to the initial product, 2-hydroxyacetophenone). Further oxidation to tlie ketoaldehyde and acid requires molecular oxygen, but is also found to be catalysed by bismuth. 

Because of the particular functionality of DOW CORNING 108 emulsion, coreactions can be affected with many types of plastics and chemicals. Reactions with epoxides, urethanes, and carboxylic acids can desirably alter the properties of these organic polymers by acting as a flexible crosslinker for the cured organic polymer. 

Iona group -with jSJaotoma, 826 Carboxylic acida. reaction with axirMUnea, 653 epoxides, 366-82 etliylene auliidea. 612 o,CarboxyiitilbBne, perbenxoic acid Oxi-datlOD, 63, 373 Car-3 ene, epoxidation, 43 AB-Carene, peracetic acid oxidation, 381... 

Selective reductions. Brown et al.2 conducted an extensive study of reductions with diborane in THF. Most aldehydes and ketones are readily reduced unusually high stereoselectivity was realized in the case of norcamphor, which was reduced to 98% endo-norbornanol and 2% exo-norbornanol. p-Benzoquinone is reduced to hydroquinone at a moderate rate, but reduction of anthraquinone is sluggish. Carboxylic acids are reduced very rapidly indeed this group can be reduced selectively in the presence of many other substituents. Acid chlorides react much more slowly than carboxylic acids. Esters and ketones are reduced relatively slowly. Reactions with epoxides are relatively slow and complex. 

Sorokin, et. al. (9) proposed that the initial step is either solvolysis of the anhydride (reaction 3) or reaction of the tertiary amine with a co-catalyst (water, alcohol, or carboxylic acid) (reaction 4), followed by catalytic reaction of the monoester with the epoxide group (reaction 5). 

Shechter and Wynstra (8) proposed that the following reactions could occur with a carboxylic acid and an epoxide ... 

The uncatalyzed reaction of acid anhydrides with epoxides is slow even at 200 C however, with either acidic or basic catalysts the reaction proceeds readily with the formation of ester linkages. The reaction of acid anhydrides with conventional commercial epoxy resins is probably initiated by water or hydroxyl and carboxyl compounds present in the mixture. The following sequence is illustrative of initiation by a hydroxyl-containing material ... 

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