2- succinic acid

Succinic acid (1,4-butanedioic acid) is a four-carbon acid which occurs as a constituent of almost all plant and animal tissues and microorganisms. It has been of considerable interest in recent years as a renewable feedstock for various petrochemical-based large-volume chemicals, owing to the reactivity of its functional groups. Succinic acid received its name from the Latin name succinum meaning amber, from which it was first isolated. 

National Aniline began production in the United States in 1929 using an electrolytic reduction of maleic anhydride. The fermentative production of succinic acid was studied in Japan in the 1970s utilizing a variety of feedstocks such as paraffins, sucrose, and isopropyl alcohol (Kirk-Othmer 1983). 

Succinic acid also is produced as a by-product of adipic acid manufacture and can be sold as a mixture with other organic acids from this process. Annual world production of adipic acid exceeds a billion pounds, and a large amount of by-product succinic acid is obtained. Succinic acid is also sold as a purified product and sells in the range of 2.- 2.80/lb, as listed in a Chemical Prices section of the Chemical Marketing Reporter of January 10, 2000. 

Owing to the reactivity of succinic acid, it can be converted to a variety of products, including large-volume chemicals such as 1,4 butanediol and tetrahydrofuran. The use of renewable resources and carbohydrates derived from agricultural materials 

At present succinic acid is a specialty chemical with an annual production volume of about 30 000 tons worldwide. Fossil-based succinic acid is most commonly prepared via hydrogenation of maleic anhydride (by oxidation of n-butane or benzene) [73]. In the field of bio-based chemicals and building blocks succinic acid is considered to be one of the most important platform chemicals [1, 74, 75], and as a result of the introduction of biosuccinic acid the production volume is expected to double or triple within years. Several fermentation processes have been described to produce bio-based succinic acid. Common feedstocks for these processes include glucose, starch and xylose [76]. The commercial potential for bio-succinic acid is illustrated by the numerous initiatives by companies that are working towards, or already 

Myriant (United States) received a grant Irom the US Department of Energy for their activities on the production of bio-succinic acid. These activities include building of a 20 000 litre reactor in Louisiana, modification of a leased facility of 15 000 ton/year and the construction of a greenfield plant also with a capacity of 15 000 ton/year. The Myriant process uses E. coli and unrefined sugar as feedstock. 

Marin et al., 2003), whereas sorbic acid is less linked to pH (Shtenberg and Ignat ev, 1970). 

Properties.—Colourless prisms m. p. 180°. On distillation, the acid loses water and is converted into the anhydride. 

Reaeiion.— i. Make a neutral solution by boiling with an excess of ammonia, and add to one portion, calcium chloride no precipitate is formed to another portion add a drop or two of ferric chloride a brown precipitate of ferric succinate is thrown down. Appendix, p. 261. 

CH CHs) = (C00H)2 Methylmalonic acid. Iso-succinic acid. CH(C2H5) = (C00H)2 Ethyl malonic acid. 

H3C—C(C2H5) = (C00H)2 Methyl-ethyl malonic acid. 

Succinic Acid HOOC—CH2—CH2—COOH. Butan-di-oic Acid 

As oxalic acid is derived from ethan-di-ol, ethylene glycol, and malonic acid is derived from 1-3-propan-di-ol, so the next member in such a series will be derived from i- -hiitan-di-ol, as follows  

Synthesis from Ethylene Bromide.—Such an acid is known as a commonly occurring substance in nature and is called succinic acid. It has the composition C4H6O4 and is plainly isomeric with methyl malonic acid. Its constitution as given above is, however, proven by the following syntheses Ethylene bromide, or symmetrical di-brom ethane, which is made by the addition of bromine to ethylene gas, yields by treatment with potassium cyanide a symmetrical di- 

The acid (pKi =4.19 pK2 = 5.63) is appfied as a plasticizer in dough making. Succinic acid monoesters with glycerol are used as emulsifiers in the baking industry. The acid is synthesized by catalytic hydrogenation of fumaric or maleic acids. 

426 (W) 1 Pudding powders, confectionary and candies, ice creams, pop (effervescent) drinks 

445 (W) Mayonnaise, soups, puddings, desserts, confectionary and candy products 

485 (W) III Beverages, fruit preserves, confectionary and candy products, honey-like products, sea salmon, crabs 

453-456 (CH) Fat, beverages, soups, pudding, water, confectiontiry and candy products, yoghurt 

the formation constant of ferric enterobactin had never been 

ACS Symposium Series American Chemical Society Washington, DC, 1980. 

Instead, the stability constant of enterobactin has been determined spectrophotometrically by competition with EDTA, as described by the equation  

It is necessary to take advantage of the strong pH dependence of Eq. 1. At neutral or basic pH, this equilibrium lies completely on the side of ferric enterobactin. At pH 5, however, a measurable distribution of ferric ion is obtained with less than a tenfold excess of EDTA. The Intense charge transfer band of ferric enterobactin provides a convenient way of determining the concen- 

Energy or Animal feed e.g. Straw/Bagasse Chemicals and Proteins 

Hydrogenation Xylitol, Erythritol, Glycerin Ethylene, Glycol, Methanol 

Arabitol, Glycerin, Ethylene Furan, Furfuryl Alcohol, Furancarboxyllic 

Glycol, Methanol acid, Furvlacrylic acid. Maleic Acid 

Fermentation Ethanol, Levulinic acid. Lactic acid. Acetone, Butanol, Glycerin 

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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. 

Corrosion inhibitors partial esters of succinic acid, fatty acids, sulfonates, phenates, amine phosphates. 

Although some dibasic acids, e.g, succinic acid and phthalic acid, readily lose water on heating with the formation of cyclic anhydrides, most monobasic... 

When cinnamaldehyde, succinic acid and acetic anhydride are heated in the presence of litharge (PbO), the aldehyde and the succinic acid condense to give the dicarboxylic acid (I), which undergoes decarboxylation to give the pale yellow crystalline 1,8-diphenyloctatetrene (II), Kuhn has shown that as the... 

This tetra ethyl ester is difficult to hydrolyse the corresponding tetra-methyl ester can, however, be hydrolysed to give ethane tetracarboxylic acid, (HOOC)jCH CH(COOH)j. The latter readily loses 2 molecules of carbon dioxide (on being heated or even on boiling with water) to give succinic acid, HOOCCHjCHjCOOH. 

The isolation of an aliphatic acid from its aqueous solution, particularly in the presence of metallic salts, is a tedious operation (cf. p. 56), although a few such acids, e.g., succinic acid, can be extracted with ether. Since, however, a solution of an acid or one of Its salts is admirably suited for most of the tests in this series, the isolation of the free acid is rarely necessary except as a nieans of distinguishing (as in (i)) between aliphatic and aromatic members. 

I. Fluorescein test. Fuse together carefully in a dry test-tube for about 1 minute a few crystals of resorcinol and an equal quantity of succinic acid or a succinate, moistened with 2 drops of cone. H2SO4. Cool, dissolve in water and add NaOH solution in excess. A red solution is produced which exhibits an intense green fluorescence.-f-... 

To distinguish these anhydrides from the corresponding acids, note that succinic anhydride (m.p. 120°) is almost insoluble in cold water, whereas succinic acid (m.p. 185 ) is readily soluble. Phthalic anhydride has m.p. 132° and phthalic acid has m.p. 196-199° with decomposition. Each of these anhydrides when heated with water hydrolyses to the corresponding acids. 

The fluorescein test for succinic acid (p. 349) and the phthalein and fluorescein tests for phthalic acid (p. 351) are obviously given also by succinic anhydride and phthalic anhydride, as these tests depend upon the initial formation of the anhy dride in each case. 

Weigh out accurately about 2-5 g. of pure powdered succinic acid, transfer to a 100 ml. graduated flask, dissolve in distilled water, make the solution up to the graduation mark and mix well. Now, by means of a pipette, transfer 25 ml. of the solution to a 150 ml. conical flask, add a drop of phenolphthalein solution and titrate with A/ 2 NaOH or KOH solution to obtain consistent results. 

If the third substance dissolves in both liquids (and the solubility in each of the liquids is of the same order), the mutual solubility of the liquids will be increased and an upper C.S.T. will be lowered, as is the case when succinic acid or sodium oleate is added to the phenol - water system. A 0 083 molar solution of sodium oleate lowers the C.S.T. by 56 -7° this large effect has been applied industrially in the preparation of the disinfectant sold under the name of Lysol. Mixtures of tar acids (phenol cresols) do not mix completely with water at the ordinary temperature, but the addition of a small amount of soap ( = sodium oleate) lowers the miscibility temperature so that Lysol exists as a clear liquid at the ordinary temperature. 

With some acids (e.g., succinic acid and sulplianilic acid) more satisfactory results are obtained by reversing the order of mixing, i.e., by adding the solution of the so um salt of the acid to the reagent. It should be pointed out that the melting points of the derivatives as determined on the electric hot plate (Fig. II, 11, 1) may differ by 2-3° from those obtained by the capillary tube method. In view of the proximity of the melting points of the derivatives of many acids, the mixed m.p. test (Section 1,17) should be applied. 

Method A. In a 500 ml. round-bottomed flask, fitted with a reflux condenser attached to a gas trap (Fig. II, 13, 8), place 59 g. of succinic acid and 117-5 g. (107-5 ml.) of redistilled acetyl chloride. Reflux the mixture gently upon a water bath until all the acid dissolves (1-2 hours). Allow the solution to cool undisturbed and finally cool in ice. Collect the succinic anhydride, which separates in beautiful crystals, on a Buchner or sintered glass funnel, wash it with two 40 ml. portions of anhydrous ether, and dry in a vacuum desiccator. The yield of succinic anhydride, m.p. 118-119°, is 47 g. 

Method B. In a 500 ml. round-bottomed flask, provided with a reflux condenser protected by a cotton wool (or calcium chloride) drying tube, place 59 g. of succinic acid and 102 g. (94-5 ml.) of redistilled acetic anhydride. Reflux the mixture gently on a water bath with occasional shaking until a clear solution is obtamed ca. 1 hour), and then for a further hour to ensure the completeness of the reaction. Remove the complete assembly from the water bath, allow it to cool (observe the formation of crystals), and finally cool in ice. Collect the succinic anhydride as in Method A. The yield is 45 g., m.p. 119-120°. 

Diethyl succinate. Reflux a mixture of 58 g. of A.R. succinic acid, 81 g. (102-5 ml.) of absolute ethyl alcohol, 190 ml. of sodium-dried... 

Both acids 3deld succinic acid, m.p. 185°, upon catalytic reduction (see Section 111,150), thus establishing their structures. Maleic and fumaric acids are examples of compounds exhibiting cis-trans isomerism (or geometric isomerism). Maleic acid has the cm structure since inter alia it readily 3delds the anhydride (compare Section 111,93). Fumaric acid possesses the trans structure it does not form an anhydride, but when heated to a high temperature gives maleic anhydride. 

The oxidation of cyctopentanone (Section 111,73) with dilute nitric acid gives glutaric acid accompanied by some succinic acid the latter is removed as the sparingly-soluble barium salt ... 

An alternative method of separation consists in treating the dry residue several times with a warm mixture of benzene and ether. The residual solid (about 20 g.) is moderately pure succinic acid, m.p. 183-184°. Upon evaporating the benzene - ether extract, and recrystallising the residue from chloroform or from benzene, about 70 g. of glutaric acid, m.p. 95-96°, are obtained. 

Di lve 20 g. of the cyano ester in 100 ml. of rectified spirit and add a solution of 19 2 g. of pure potassium cyanide in 40 ml. of water. Allow to stand for 48 hours, then distil oflF the alcohol on a water bath. Add a large excess of concentrated hydrochloric acid and heat under reflux for 3 hours. Dilute with water, saturate the solution with ammonium sulphate, and extract with four 75 ml. portions of ether. Dry the combined ethereal extracts with anhydrous sodium or magnesium sulphate, and distil off the ether. RecrystaUise the residual acid from excess concentrated hydrochloric acid, and dry in the air. The yield of pure ew-dimethyl-succinic acid, m.p. 141-142°, is 12 g. 

The appropriate succinic acid can be prepared by condensation of the iinsaturatod (yano ester with alcoholio potassium cyanide. 

Acids. Acetic acid re-Caproic acid Benzoic acid Phenylacetic acid Succinic acid Adipic acid Anthranihc acid. 

Determination of melting points (a-naphthylamine, a-naphthol, benzoic acid, succinic acid and p-nitrobenzoic acid). Use the apparatus shown in Fig. II, 10, 2, a. Construction of calibration curve for thermometer. Determination of m.p. of unknown compound. 

Supplement II, 2nd 1929 152-194 Oxalic acid, 502. Succinic acid, 601. Fumaric acid, 737... 

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