Crotonic acid hydrogenation

The catalysts were obtained from their respective commercial sources and for some of these tests they were subjected to RPT by heating them to 400°C for 2 hours under a flow of hydrogen. The enantioselective ketone hydrogenations were carried out in a 50 ml stainless steel autoclave stirred with a magnetic stirring bar with 10 to 30 mg of catalyst, 10 to 30 mg of MeOHCd, 5 ml substrate and 20 ml AcOH at 60 bar and 25°C for 30 minutes. The crotonic acid hydrogenations were carried out in an ethanolic solution at atmospheric pressure and room temperature stirred at 2000 rpm with a hollow shaft bubbling stirrer. 

However, the addition occurs contrary to the Markovnikov rule under irradiation by ultraviolet light or in the presence of peroxides 1 for instance, allyl-amine hydrochloride or a derivative thereof in alcoholic solution is thiolated by an excess of hydrogen sulfide under UV-irradiation, exclusively (yields up to 57%), to give 3-aminoalkanethiols.2 Addition of hydrogen sulfide is of use in the laboratory only when the reaction can be carried out in the liquid phase and is then preferably effected under the influence of a basic catalyst Dahl-bom,3 for instance, obtained 3-mefcapto-butyric acid from crotonic acid hydrogen sulfide in the presence of diethylamine in a closed vessel at 70° and 4-mercapto-4-methyl-2-pentanone is obtained in 80% yield from mesityl oxide and hydrogen sulfide with triethylamine as catalyst.4... 

Quantitative studies of the effect of pyridine on the rate of hydrogenation of imns-crotonic acid in the presence of a platinum catalyst have been carried out by Maxted and Walker who concluded that... 

With regard to the use of tungsten-based systems, Payne and Williams reported on the selective epoxidation of maleic, fumaric, and crotonic acids with a catalytic amount of sodium tungstate (2mol%) in combination with aqueous hydrogen... 

Table 2 Crotonic acid (CA) hydrogenation data (atmospheric pressure).

The reduction of acrylic acid was attempted at elevated temperatures. Surprisingly, the reaction was found to yield not only propionic acid, but also the dimer, a-methylglutaric acid. When the reaction was conducted in the absence of hydrogen, the product obtained was 3-methylglutaconic acid, which apparently is the precursor of the saturated dimer formed in a hydrogen atmosphere. Similarly, methacrylic acid yielded a-methylene-y,y-dimethylglutaric acid when heated with cyanocobaltate (II) in the absence of hydrogen. Its structure was established via ozonolysis. Similar dimerizations have been reported for acrylic acid (I, 14), methacrylate ester (7, 11), crotonic acid (13), and its diethylamide (15). 

A second-order dependence on crotonic acid has been observed in its Os(VIII)-catalysed oxidation with CAT in alkaline solution. The reaction rate varied linearly with the concentration of Os(VIII). A mechanism has been proposed.140 The kinetics of the ruthenium(III)-catalysed oxidation of the secondary amines with CAT in acidic medium have been obtained and mechanisms have been postulated.141 Uncatalysed and Ru(III)-catalysed oxidation of ethylenediamine, diethylenetriamine, triethylenete-tramine, aminoethylpiperazine, and isophoronediamine with CAT in HC1 solution showed a fractional dependence on the amine, hydrogen ions, and Ru(III), and it is independent of CAT concentration. TSNH2CI has been postulated as the reactive species and a mechanism has been suggested.142... 

Further, Maxted (36) studied the influence of several sulfur compounds on the activity of platinum black for the hydrogenation of crotonic acid in the liquid phase. He noticed that between 15 and 50°C the toxicity remains constant for a sulfur compound, pointing out the irreversibility of sulfur adsorption. Conversely, the toxicity of various compounds increases with the molecule size. For molecules containing two sulfur atoms, losing all freedom of rotation through this double adsorption, the toxicity is less than for molecules of the same length containing only one atom of sulfur. 

---