Unsaturated dicarboxylic acids, synthesis

Warwel, S., Sojka, M., and Rusch, M. Synthesis of Dicarboxylic Acids by Transition-Metal Catalyzed Oxidative Cleavage of Terminal-Unsaturated Fatty Acids. 164, 79-98 (1993). Wexle.r, D., Zink, J. I., and Reber, C. Spectroscopic Manifestations of Potential Surface Coupling Along Normal Coordinates in Transition Metal Complexes. 171,173-204 (1994). Willett, P., see Artymiuk, P. J. 174, 73-104 (1995). 

Warwel, S., Sojka, M., and Rusch, M. Synthesis of Dicarboxylic Acids by Transition-Metal Catalyzed Oxidative Cleavage of Terminal-Unsaturated Fatty Acids. 164, 79-98 (1993). 

An important reaction for synthesis of alkyl and dialkylethanoic acids (RX and R X are primary or secondary alkyl halides) dicarboxylic acids (RX = haloester) unsaturated acids (RX = an unsaturated halide, best for allylic halides) /3-keto acids (R = acyl chloride) (see Sections 18-8C and 18-8D). 

As well as the illustrative synthesis of a simple carboxylic acid (pentanoic acid, Expt 5.127), examples are given of the synthesis of some dicarboxylic acids, aryl substituted carboxylic acids, and the unsaturated acid, vinylacetic acid (Expt 5.128). 

The amidation of unsaturated acids or esters (not necessarily a,(3 unsaturated ones) leads to derivatives of the corresponding dicarboxylic acids and may serve as a method for the synthesis of dicarboxylic acids from unsaturated monocarboxylic acids (10,13, 14). This reaction of formamide with oc,(3-unsaturated acid derivatives besides being of synthetic value has some interesting aspects as far as free radical chemistry and photochemistry are concerned. We shall start this section in discussing the last point, i.e. the photochemical aspects of the reaction. This point is of primary interest to the synthetic organic chemist, who must be aware of it, otherwise he may fail in his synthetic work purely because of photochemical reasons. 

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