Succinic hydrogenation

Colourless prisms m.p. 130 C. Manufactured by treating maleic anhydride with water. It is converted to the anhydride by heating at By prolonged heating at 150 "C or by heating with water under pressure at 200 C, it is converted to the isomeric (trans) fumaric acid. Reduced by hydrogen to succinic acid. Oxidized by alkaline solutions of potassium permanganate to mesotartaric acid. When heated with solutions of sodium hydroxide at 100 C, sodium( )-malate is formed. Used in the preparation of ( )-malic acid and in some polymer formulations. 

Butanediol. 1,4-Butanediol [110-63-4] tetramethylene glycol, 1,4-butylene glycol, was first prepared in 1890 by acid hydrolysis of N,]S3-dinitro-l,4-butanediamine (117). Other early preparations were by reduction of succinaldehyde (118) or succinic esters (119) and by saponification of the diacetate prepared from 1,4-dihalobutanes (120). Catalytic hydrogenation of butynediol, now the principal commercial route, was first described in 1910 (121). Other processes used for commercial manufacture are described in the section on Manufacture. Physical properties of butanediol are Hsted in Table 2. 

V-Phenylsuccinimide [83-25-0] (succanil) is obtained in essentially quantitative yield by heating equivalent amounts of succinic acid and aniline at 140—150°C (25). The reaction of a primary aromatic amine with phosgene leads to formation of an arylcarbamoyl chloride, that when heated loses hydrogen chloride to form an isocyanate. Commercially important isocyanates are obtained from aromatic primary diamines. 

Pyrrohdinone (2-pyrrohdone, butyrolactam or 2-Pyrol) (27) was first reported in 1889 as a product of the dehydration of 4-aminobutanoic acid (49). The synthesis used for commercial manufacture, ie, condensation of butyrolactone with ammonia at high temperatures, was first described in 1936 (50). Other synthetic routes include carbon monoxide insertion into allylamine (51,52), hydrolytic hydrogenation of succinonitnle (53,54), and hydrogenation of ammoniacal solutions of maleic or succinic acids (55—57). Properties of 2-pyrrohdinone are Hsted in Table 2. 2-Pyrrohdinone is completely miscible with water, lower alcohols, lower ketones, ether, ethyl acetate, chloroform, and benzene. It is soluble to ca 1 wt % in aUphatic hydrocarbons. 

Succinic anhydride [108-30-5] (3,4-dihydro-2,5-furandione butanedioic anhydride tetrahydro-2,5-dioxofuran 2,5-diketotetrahydrofuran succinyl oxide), C H O, was first obtained by dehydration of succinic acid. In the 1990s anhydride is produced by hydrogenation of maleic anhydride and the acid by hydration of the anhydride, by hydrogenation of aqueous solutions of maleic acid, or as a by-product in the manufacture of adipic acid (qv) (see Maleic ANHYDRIDE, MALEIC ACID, AND FUMARIC ACID). 

Dimethyl succinate [106-65-0] (mp 19°C, bp 196°C at atmospheric pressure) can be produced from methanol and the anhydride or the acid, or by hydrogenation of dimethyl maleate (38,39). The same methods can be used to prepare diethyl succinate [123-25-1] (mp — 18°C, bp 216.5°C at atmospheric pressure) and diisopropyl succinate [924-88-9]. 

Succinic acid diesters are also obtained by one-step hydrogenation (over Pd on charcoal) and esterification of maleic anhydride dissolved in alcohols (40) carbonylation of acrylates in the presence of alcohols and Co complex catalysts (41—43) carbonylation of ethylene in alcohol in the presence of Pd or Pd—Cu catalysts (44—50) hydroformylation of acetylene with Mo and W complexes in the presence of butanol (51) and a biochemical process from dextrose/com steep Hquor, using Jinaerobiumspirillum succiniciproducens as a bacterium (52). 

Oxidation. Succinic acid reacts with hydrogen peroxide, giving different products that depend on the experimental conditions peroxysuccinic acid [2279-96-1] (CH2COOOH)2, oxosuccinic acid [328-42-7] (oxaloacetic acid) malonic acid [141-82-2] or a mixture of acetaldehyde, malonic acid, and make acid [6915-15-7]. Succinic anhydride in dimethylformamide (DMF) with H2O2 gives monoperoxysuccinic acid [3504-13-0], HOOCCH2CH2COOOH, mp 107°C (70). 

Hydrogenation. Gas-phase catalytic hydrogenation of succinic anhydride yields y-butyrolactone [96-48-0] (GBL), tetrahydrofiiran [109-99-9] (THF), 1,4-butanediol (BDO), or a mixture of these products, depending on the experimental conditions. Catalysts mentioned in the Hterature include copper chromites with various additives (72), copper—zinc oxides with promoters (73—75), and mthenium (76). The same products are obtained by hquid-phase hydrogenation catalysts used include Pd with various modifiers on various carriers (77—80), Ru on C (81) or Ru complexes (82,83), Rh on C (79), Cu—Co—Mn oxides (84), Co—Ni—Re oxides (85), Cu—Ti oxides (86), Ca—Mo—Ni on diatomaceous earth (87), and Mo—Ba—Re oxides (88). Chemical reduction of succinic anhydride to GBL or THF can be performed with 2-propanol in the presence of Zr02 catalyst (89,90). 

V-Alkyl or A/-aryl succinimides can be prepared from the corresponding amines (107) or from succinic anhydride, ammonia, and the corresponding alcohol (108). Succinimides are also obtained by vapor-phase hydrogenation of the corresponding maleimides ia the presence of a catalyst (109). 

Reactions with Sulfur Compounds. Thiosuccinic anhydride [3194-60-3] is obtained by reaction of diethyl or diphenyl succinate [621-14-7] with potassium hydrogen sulfide followed by acidification (eq. 10). Thiosuccinic anhydride is also obtained from succinic anhydride and hydrogen sulfide under pressure (121). 

Succinic anhydride is manufactured by catalytic hydrogenation of maleic anhydride [108-31-6]. In the most widely used commercial process this reaction is performed in the Hquid phase, at temperatures of 120—180°C and at moderate pressures, in the range of 500—4000 kPa (72—580 psi). Catalysts mentioned in the patent Hterature include nickel (124), Raney nickel (125,126), palladium on different carriers (127,128), and palladium complexes (129). The hydrogenation of the double bond is exothermic Ai/ = —133.89 kJ/mol (—32 kcal/mol) (130). 

After separation of the catalyst by filtration, raw succinic anhydride is purified by distillation under reduced pressure, ie, 4—13 kPa (30—98 mm Hg), and flaked. The material of constmction of the plant is stainless steel. Typical specific consumptions for the production of one metric ton of succinic anhydride are maleic anhydride at 1050 kg hydrogen, 300 m steam, 4500 kg cooling water, 100 m electricity, 350 kW nitrogen, 100 m and methane,... 

In the early 1990s, processes were developed for the production of 1,4-butanediol and y-butyrolactone by gas-phase catalytic hydrogenation of maleic anhydride (131—134). Succinic anhydride is obtained as a partial hydrogenation by-product in these processes. It can be recycled to complete the hydrogenation to the desired products, or be separated and purified. This process could in the future become a significant commercial route for succinic anhydride. 

Succinic acid can also be produced by catalytic hydrogenation of aqueous solutions of maleic or fumaric acid in the presence of noble metal catalysts, ie, palladium, rhodium, mthenium, or their mixtures, on different carriers (135—139) or on Raney nickel (140). 

Sodium hydrogen succinate [2922-54-5] M 140.0. Crystd from water and dried at 110°. 

Apply colloidal palladium solution to the starting [29] point (diameter 8 to 10 mm) and dry Then apply sample solution and gas with hydrogen (desiccator) for 1 h Maleic and fumanc acids yield succinic acid etc, which may also be separated chromatographically... 

It IS interesting that the rates of elimination of hydrogen fluoride from all fluormated succinic acids span hardly 1 order of magnitude, whereas the rates of preferential dehydrofluorination of both a-bromo-a -fluorosuccimc acids are higher by almost 2 orders of magnitude [35, 36, 37, 38] (Table 3)... 

Figure 6-18 shows a bell-shaped pH-rate profile for the hydrolysis of monomethyl dihydrogen phosphate. Other examples are the hydrolysis of o-carboxyphenyl hydrogen succinate and the hydration of fumaric acid. ... 

Fe= Catalase Flavin adenine dinucleotide (FAD) Hydrogen atoms Succinate dehydrogenase... 

The enzyme succinate dehydrogenase (SDH) is competitively inhibited by malo-nate. Figure 14.14 shows the structures of succinate and malonate. The structural similarity between them is obvious and is the basis of malonate s ability to mimic succinate and bind at the active site of SDH. However, unlike succinate, which is oxidized by SDH to form fumarate, malonate cannot lose two hydrogens consequently, it is unreactive. 

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