Succinates, preparation

Cellulose esters of aromatic acids, aUphatic acids containing more than four carbon atoms and aUphatic diacids are difficult and expensive to prepare because of the poor reactivity of the corresponding anhydrides with cellulose Httle commercial interest has been shown in these esters. Of notable exception, however, is the recent interest in the mixed esters of cellulose succinates, prepared by the sodium acetate catalyzed reaction of cellulose with succinic anhydride. The additional expense incurred in manufacturing succinate esters is compensated by the improved film properties observed in waterborne coatings (5). 

Nakamichi, K., H. Yasuura, H. Fukui, M. Oka, and S. Izumi. 2001. Evaluation of a oating dosage form of nicardipine hydrochloride and hydroxypropylmethylcellulose acetate succinate prepared using a twin-screw extrudetnt J Pharm218 103-112. 

M Sodium succinate—Dilute 0.5 M sodium succinate, prepared as below (5 ml of 0.5 M sodium succinate + 45 ml of H20). Refrigerate. Stable for 1 week. 

Nakamichi, K. Yasuura, H. Fukui, H. Oka, M. Izumi, S. Evaluation of a floating dosage form of nicardipine hydrochloride and hydroxypropyhnethylcellulose acetate succinate prepared nsing a twin-screw extruder. Int. J. Pharm. 2001, 218(1-2), 103-112. 

Large cyclic ether-esters from oxyethyleneglycol succinate, prepared by dilute solution transesterification, were also characterized by FAB-MS. " As for the PDT cyclic oligomer, the molar cyclization equilibrium constant was found in agreement with the Jacobson-Stockmayer theory. 

Liu CF, Sun RC, Zhang AP, Ren JL, Geng ZC. Structural and thermal characterization of sugarcane bagasse cellulose succinates prepared in ionic liquid. Polym Degrad Stab 2006 91 3040-3047. 

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. 

In the following preparation, this reaction is exemplified by the union of anthracene with maleic anhydride, to form 9,io-dihydroanthracene-9,io-e do-a -succinic anhydride note that as a result of this reaction both the outer rings of the anthracene system become truly aromatic in character. 

Derivatives. The precise identification of a compound normally depends upon the preparation of a derivative and the determination of physical constants such as m.p. in the case of a solid. Many simple compounds can, however, be identified with a fair degree of certainty by intelligently-selected qualitative tests alone, e.g., formates, oxalates, succinates, lactates, tartrates, chloral hydrate. 

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. 

Anhydrides of dibasic acids (succinic or glutaric acid type) may be prepared ... 

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

The preparation of the cyclic ketone a-tetralone possesses a number of interesting features. Succinic anhydride is condensed with pure benzene in the presence of anhydrous aluminium chloride (slightly over two equivalents see 1 above) to yield (3-benzoylpropionlc acid ... 

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. 

Friedel-Crafts acylation of 3,3-dimethyl-2-indolinone by succinic anhydride gives 3,3-dimethyl-5-(3-catboxyptopionyl)-2-indoline, which is used as an intermediate in the preparation of inotropic agents for treatment of heart failure (94). Antibacterial phlotophenone derivatives have been prepared by Friedel-Crafts acylation with ptopanoyl chlotide (95). 

Docusate Calcium. Dioctyl calcium sulfosuccinate [128-49-4] (calcium salt of l,4-bis(2-ethylhexyl)ester butanedioic acid) (11) is a white amorphous soHd having the characteristic odor of octyl alcohol. It is very slightly soluble in water, and very soluble in alcohol, polyethylene glycol 400, and com oil. It may be prepared directly from dioctyl sodium sulfo succinate dissolved in 2-propanol, by reaction with a methan olic solution of calcium chloride. 

Typical reaction conditions are 150 to 300°C and up to 2 MPa pressure. Polyalkenyl succinic anhydrides are prepared under these conditions by the reaction of polyalkenes in a nonaqueous dispersion of maleic anhydride, mineral oil, and surfactant (33). 

Other preparative routes iaclude hydrogenation of succinonitdle in the presence of methylamine and hydrogenation of solutions of maleic or succinic acid and methylamine (82,83). Properties are Hsted in Table 3. l-Meth5i-2-pyrrohdinone is completely miscible with water, lower alcohols, lower ketones, ether, ethyl acetate, chloroform, and benzene. It is moderately soluble in aUphatic hydrocarbons and dissolves many organic and inorganic compounds. 

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]. 

An important use of dialkyl succinates is in the preparation of dialkyl succinyl succinates (35,53—56), which are intermediates in the manufacture of quinacridone pigments. The reaction is carried out in the presence of alkaU metal alkoxides (eq. 2). 

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). 

Other preparations of succinic acid mentioned in the Hterature are electrochemical reduction of maleic or fumaric acid (153,154), ultrasound-promoted Zn—acetic acid reduction of maleic or fumaric acid (155), reduction of maleic acid with H2PO2 at room temperature (156),... 

Succinic anhydride can be prepared from succinic acid by dehydration it operates in high boiling solvent (31), in the presence of clays as a catalyst (32), or at room temperature with triphosgene (33). 

The total consumption of succinic acid and succinic anhydride in 1990 was 1,500 t in the United States, 2,500 t in Europe, 7,500 t in Japan, and 1,500 t in other countries. Production was 500 t in the United States, 2,500 t in Europe, and 11,000 t in Japan. The total installed capacity is in the 18,000—20,000-t/yr range. The total consumption decreased slightly between 1990 and 1994 mainly because of the replacement of succinic acid by fumaric acid in bath preparations, which is one of the main uses of succinic acid in Japan. The principal producers are Buffalo Color in the United States, Lon2a SpA and Chemie Tin 2 in Europe, Kawasaki Kasei, Nippon Shokubai, Takeda Chemical, Kyowa Hakko, and New Japan Chemical in Japan. 

Table 3 summarizes many of the uses mentioned in the literature. The main use of succinic acid in Japan is for bath preparations (314—322). This application in 1994 accounted for nearly 80% of total consumption. After recording a more than 10% yearly increase in the late 1980s, the growth of this apphcation has slowed down, and consumption is decreasing on account of the replacement of succinic acid by fumaric acid for economic reasons. This trend is expected to continue in the coming years. 

Dicarboxyhc acids, eg, succinic or adipic, do not dissolve titanic acid. A phthalate has been prepared by adding acidic titanium sulfate solution to sodium phthalate solution. 

Tetraacylates have been prepared ia this way from stearic, ben2oic, cinnamic, and other acids, as well as from diacids such as succinic and adipic acids (14) (129). In some cases, TiCl may also be used. 

Friedel-Crafts Acylation. The Friedel-Crafts acylation procedure is the most important method for preparing aromatic ketones and thein derivatives. Acetyl chloride (acetic anhydride) reacts with benzene ia the presence of aluminum chloride or acid catalysts to produce acetophenone [98-86-2], CgHgO (1-phenylethanone). Benzene can also be condensed with dicarboxyHc acid anhydrides to yield benzoyl derivatives of carboxyHc acids. These benzoyl derivatives are often used for constmcting polycycHc molecules (Haworth reaction). For example, benzene reacts with succinic anhydride ia the presence of aluminum chloride to produce P-benzoylpropionic acid [2051-95-8] which is converted iato a-tetralone [529-34-0] (30). 

Mixed esters containing the dicarboxylate moiety, eg, cellulose acetate phthalate, are usually prepared from the partially hydroly2ed lower aUphatic acid ester of cellulose in acetic acid solvent by using the corresponding dicarboxyhc acid anhydride and a basic catalyst such as sodium acetate (41,42). Cellulose acetate succinate and cellulose acetate butyrate succinate are manufactured by similar methods as described in reference 43. 

Alkyl-substituted succiiiimides are prepared by reaction of alkyleneamines such as TETA or TEPA with the corresponding alkyl substituted succinic anhydride (43). 

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