Catalytic conversion, succinic acid

The synthesis of succinic acid derivatives, /3-alkoxy esters, and a,j3-unsaturated esters from olefins by palladium catalyzed carbonylation reactions in alcohol have been reported (24, 25, 26, 27), but full experimental details of the syntheses are incomplete and in most cases the yields of yS-alkoxy ester and diester products are low. A similar reaction employing stoichiometric amounts of palladium (II) has also been reported (28). In order to explore the scope of this reaction for the syntheses of yS-alkoxy esters and succinic acid derivatives, representative cyclic and acyclic olefins were carbonylated under these same conditions (Table I). The reactions were carried out in methanol at room temperature using catalytic amounts of palladium (II) chloride and stoichiometric amounts of copper (II) chloride under 2 atm of carbon monoxide. The methoxypalladation reaction of 1-pentene affords a good conversion (55% ) of olefin to methyl 3-methoxyhexanoate, the product of Markov-nikov addition. In the carbonylation of other 1-olefins, f3-methoxy methyl esters were obtained in high yields however, substitution of a methyl group on the double bond reduced the yield of ester markedly. For example, the carbonylation of 2-methyl-l-butene afforded < 10% yield of methyl 3-methyl-3-methoxypentanoate. This suggests that unsubstituted 1-olefins may be preferentially carbonylated in the presence of substituted 1-olefins or internal olefins. The reactivities of the olefins fall in the order RCH =CHo ]> ci -RCH=CHR > trans-RCH =CHR >... 

The catalytic oxidation of cyclohexane is performed in the liquid phase with air as reactant and in the presence of a catalyst. The resulting product is a mixture of alcohol and ketone (Table 1, entry 12) [19]. To limit formation of side-products (adipic, glutaric, and succinic acids) conversion is limited to 10-12 %. In a process developed by To ray a gas mixture containing HC1 and nitrosyl chloride is reacted with cyclohexane, with initiation by light, forming the oxime directly (Table 1, entry 12). The corrosiveness of the nitrosyl chloride causes massive problems, however [20]. The nitration of alkanes (Table 1, entry 13) became important in a liquid-phase reaction producing nitrocyclohexane which was further catalytically hydrated forming the oxime. 

Preparation of acid chlorides. Phthaloyl chloride is an excellent reagent for the conversion of acids and anhydrides into the acid chlorides, provided the boiling points are suitable for separation of products by distillation. In the case of maleic and succinic anhydride a catalytic amount of zinc chloride is required. Maleic anhydride is isomerized in the process. Thus a mixture of 1 mole of maleic anhydride, 230 g. of commercial phthaloyl chloride, and 2 g. of anhydrous zinc chloride is... 

High yields to AA were obtained when a Co/Mn cluster complex was used, which was superior to the individual Co and Mn acetates [14kj at 90 ° C, and 37 atm pressure, in acetic acid and water solvents, the oxidation of cyclohexanone with air gave complete conversion and 76.3% yield to AA. The authors suggested that 1-hydro-xo-cyclohexen-2-one, the tautomeric form of 1,2-cyclohexandione, is the precursor for the formation of the glutaric and succinic acid by-products. Excellent yields were also reported [14m] for the oxidation of cyclohexanone using Mn(N03)2 and Co(N03)2 (molar ratio 1 1) in the presence of oxygen and catalytic quantities of nitric acid at atmospheric pressure. The conversion was 97.5% and the selectivity to AA was 93.4%. 

To eliminate the possible catalytic activity of the reactor walls and internal parts, we verified that under the standard reaction conditions, uncatalysed experiments gave negligible conversion of succinic acid (only 11 % conversion after 4 h at 190°C, compared to complete eonversion within 1 h in the catalyzed experiment). Also, negligible adsorption of the produets on the support was verified by measuring the same concentration of succinic acid in solution at 190°C, in the presence and absence of support. 

When this method is applied to cyclohexanone, it produces a mixture of 50% adipic acid, 19% glutaric acid, and 3% succinic acid. Further work is needed to steer the reaction to a high yield of the desired adipic acid. A chromium aluminum phosphate molecular sieve has been used with oxygen and a catalytic amount of a hydroperoxide to convert cyclohexane to a mixture of 48% cyclohexanone, 5% cyclohexanol, 6% cyclohexanehydroperoxide, and 40% adipic acid, at 10% conversion. The catalyst could be reused four times without loss of activity.205 Presumably, the products other than adipic acid could be recycled to the next run. The authors do not give the selectivity at higher conversions. Ideally, one would like a similar system that would give only adipic acid at 100% conversion. 

Succinic acid is a chemical which has found applications in many areas the most important ones being food additives, soldering fluxes, and pharmaceutical products (1). The conversion of succinic acid to industrially important chemicals such as 1,4-butanediol (EDO), tetrahydrofuran (THF), y butyrolactone (GEL), N-methyl pyrrolidinone (NMP), and 2-pyrrolidinone (2P) recently has been made possible by the development of a number of catalytic processes (2,3). This new development is expected to considerably expand the market for succinic acid. 

The main objective of this development was to produce a purified succinic acid product for the catalytic conversion and a solution of ammonium succinate for a new application. TTie process used was a two-stage desalting and watersplitting electrodialysis process. This double-dialysis process avoids the generation of large quantities of salt wastes, which is a common problem in the recovery of fermentation-derived organic acid such as citric acid by the gypsum process (21). The actual fermentation broths from the 75-liter and 500-liter scale-up experiments performed at ORNL were sent to ANL for use in the development of the product recovery and purification process. 

This chapter is an overview of architectures adopted for the catalytic/biocatalytic composites used in wide applications like the biomass valorization or fine chemical industry. On this perspective, the chapter updates the reader with the most fresh examples of construction designs and concepts considered for the synthesis of such composites. Their catalytic properties result from the introduction of catalytic functionalities and vary from inorganic metal species e.g., Ru, Ir, Pd, or Rh) to well-organized biochemical structures like enzymes e.g., lipase, peroxidase, (3-galactosidase) or whole cells. Catalytic/biocatalytic procedures for the biomass conversion into platform molecules e.g., glucose, GVL, Me-THF, sorbitol, succinic acid, and glycerol) and their further transformation into value-added products are detailed in order to make understandable the utility of these complex architectures and to associate the composite properties to their performances, versatility, and robustness. 

Summary of catalytic conversion pathways and potential products derived from succinic acid (From Varadarajan and Miller (1999), with permission)... 

The catalytic performances of the monometalUc gold catalysts in the catalytic wet air oxidation of succinic acid are presented on Fig. 2 and on Fig. 3 for the bimetallic Au-Pt and Au-Ru catalysts. As a preliminary test, a blank was performed to confirm that succinic acid is stable nnder the applied reaction conditions in the absence of catalyst. Furthermore, it is known that succinic acid might be intermediately degraded to acetic and acrylic acids or directly mineralized into CO2 and H2O [11]. In the presence of the ceria support 100% succinic acid conversion was achieved after 6h. Aciylic acid concentration was systematically very low and was not reported in the figures. 

As an application of equation 7.6-5, consider the effect of pH on the inhibition constants of fumarase, which have been determined for succinate, D-tartrate, L-tartrate, and meso-tartrate inhibitors (Wigler and Alberty, 1960). The kinetics of the conversion of fumarate to L-malate and the inhibition by these competitive inhibitors indicate that there are two acid groups in the catalytic site that affect the binding ... 

Szent Gyorgyi s conception of the catalytic action of fumarate, oxalacetate, and their precursors cannot account for the conversion of the dicarboxylic acids into succinate in the malonate-poisoned tissue. It follows that in addition to the reactions which Szent Gyorgyi postulates— the reversible oxidation and reduction of oxalacetate and malate—other reactions of the 4-carbon acids must occur, leading to their conversion, by oxidative processes, to succinate. The tricarboxylic acid cycle offers a complete explanation of the behavior of the dicarboxylic acids. 

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