Succinic acid anhydrides condensation

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... 

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°. 

Cydopentane reagents used in synthesis are usually derived from cyclopentanone (R.A. Ellison, 1973). Classically they are made by base-catalyzed intramolecular aldol or ester condensations (see also p. 55). An important example is 2-methylcydopentane-l,3-dione. It is synthesized by intramolecular acylation of diethyl propionylsucdnate dianion followed by saponification and decarboxylation. This cyclization only worked with potassium t-butoxide in boiling xylene (R. Bucourt, 1965). Faster routes to this diketone start with succinic acid or its anhydride. A Friedel-Crafts acylation with 2-acetoxy-2-butene in nitrobenzene or with pro-pionyl chloride in nitromethane leads to acylated adducts, which are deacylated in aqueous acids (V.J. Grenda, 1967 L.E. Schick, 1969). A new promising route to substituted cyclopent-2-enones makes use of intermediate 5-nitro-l,3-diones (D. Seebach, 1977). 

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). 

The diacids are characterized by two carboxyHc acid groups attached to a linear or branched hydrocarbon chain. AUphatic, linear dicarboxyhc acids of the general formula HOOC(CH2) COOH, and branched dicarboxyhc acids are the subject of this article. The more common aUphatic diacids (oxaUc, malonic, succinic, and adipic) as weU as the common unsaturated diacids (maleic acid, fumaric acid), the dimer acids (qv), and the aromatic diacids (phthaUc acids) are not discussed here (see Adipic acid Maleic anhydride, maleic acid, and fumaric acid Malonic acid and derivatives Oxalic acid Phthalic acid and OTHERBENZENE-POLYCARBOXYLIC ACIDS SucciNic ACID AND SUCCINIC ANHYDRIDE). The bihinctionahty of the diacids makes them versatile materials, ideally suited for a variety of condensation polymerization reactions. Several diacids are commercially important chemicals that are produced in multimillion kg quantities and find appHcation in a myriad of uses. 

The principles set forth above account reasonably well for the course of bifunctional condensations under ordinary conditions and for the relative difficulty of ring formation with units of less than five or more than seven members. They do not explain the formation of cyclic monomers from five-atom units to the total exclusion of linear polymers. Thus 7-hydroxy acids condense exclusively to lactones such as I, 7-amino acids give the lactams II, succinic acid yields the cyclic anhydride III, and ethylene carbonate and ethylene formal occur only in the cyclic forms IV and V. 

Succinic anhydride is dimerised to 1,6-dioxaspiro [4.4] nonane-2,7-dione by heating with sodium hydroxide. Modification of an existing procedure by adding further sodium hydroxide after the initial reaction led to a severe exothermic reaction after heating for some 30 h which fused the glass flask to the heating mantle, probably at a temperature approaching 550°C. The reason for this was not known [1], At elevated temperatures and under influence of alkali, succinic acid condenses decarboxylatively beyond the dimeric spiroacetal, sometimes explosively. Contamination of the anhydride with base is to be avoided [2],... 

Methyl- 1,3-cyclopentanedione is a key intermediate for the total synthesis of steroids.2 A number of methods have been described for its preparation, among them the condensation of succinic acid with propionyl chloride,3 and that of succinic anhydride with 2-buten-2-ol acetate,4 both in the presence of aluminum chloride. It has also been obtained from 3-methylcyclopentane-1,2,4-trione by catalytic hydrogenation5 and Wolff-Kishner reduction 6 The base-promoted cyclization of 4-oxohexanoic acid ethyl ester and diethyl propionylsuccinate with tertiary alkoxides was first reported by Bucourt.7 The present cyclization process provides an experimentally simple route to 2-methyl-1,3-cyclopentanedione. Using the same procedure, 4-oxoheptanoic acid ethyl ester has been cyclized to give 2-ethyl-l,3-cyclopentanedione in 46% yield... 

Diphenylocta-1,3,5,7-tetraene can be prepared (Expt 6.140) by condensing two mols of cinnamaldehyde with succinic acid in the presence of acetic anhydride and lead oxide, in a reaction which bears similarities with those of the Perkin type discussed above. 

A very convenient method of preparation is that of ANSCHUTZ, Ann. 226, 8 (1884). In a i-l. round-bottomed flask fitted with a reflux condenser and a gas trap (Org. Syn. 14, 2) are placed 118 g. (1 mole) of succinic acid and 215 cc. (235 g., 3 moles) of acetyl chloride, and the mixture is gently refluxed on the steam bath until the solid is all dissolved (1.5-2 hours). The solution is allowed to cool undisturbed and finally cooled in an ice bath. The anhydride, which separates in beautiful crystals, is collected on a Buchner funnel, washed with two 75-cc. portions of ether, and dried in a vacuum desiccator. The yield of material melting at 118-1190 is 93-95 g. (93-95 per cent of the theoretical amount). 

P. A. Davidse, J. L. M. Dillen, A. M. Heyns, T. A. Modro, and P. H. van Rooyen, Photochromic systems. Part 1. Structural and spectroscopic study of photochemically active products of Stobbe condensation. 2,3-dibenzylidene-succinic acid and its anhydride, Can. J. Chem., 68, 741-746 (1990). 

Highly conjugated diphenylpolyenes, CjHj (CH= CH) C sHs, are obtained directly from the condensation of olefinic aldehydes such as cin-namaldehyde, C Hj CH=CHCHO, with sodium salts of phenylacetic or succinic acids in the presence of lead oxide and acetic anhydride. ° The unsaturated acids first formed are decarboxylated under the conditions of the condensation. 

A) Preparation of Succinic Anhydride (Sm.). Use the same apparatus as described for the preparation of acetyl chloride (Experiment 40 A). Place in the distilling tube 5 g of succinic acid and 9 ml of acetic anhydride. Adjust the micro condenser for reflux, and heat in the water bath at 90-100° for 30-45 minutes until a clear solution is obtained. Remove the distilling tube from the water bath and attach to the side arm (through a short rubber tubing) a calcium chloride tube. When the tube has acquired room temperature cool in an ice-salt mixture. Filter the crystals with suction and wash twice with 4 ml portion of ether. Place the product in a bottle. The yield is 3-4 g. 

Preparation. The precursor, ll,12-dihydroxy-9,10-quinone (3), has been prepared by two methods, neither of which is very well documented. In one phthalic anhydride is condensed with succinic acid and potassium acetate at 200-220° for 2 hrs. to give a,j8-diphthylidene-ethane (I, ethinediphthalide ), which on treatment with sodium methoxide and methanol, followed by acidification, is isomerized in part to the dihydroxynaphthacenequinone (3, isoethinediphthalide ), and in part to bis-diketohydrindene (2). The yield of the desired (3) is very low. A second... 

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