Ethyl succinate, reactions

A good grade of absolute alcohol is required. For this purpose ordinary absolute alcohol may be dried by treating with a little sodium, adding a few cubic centimeters of ethyl succinate, and distilling directly into the reaction flask (see also Org. Syn. Coll. Vol. i, 255). 

An example is the synthesis of ethyl a-ethoxalylpropionate (R = CH,) in 70% yield. Ethyl oxalate and ethyl succinate form ethyl a-ethoxalyl-succinate (83%). In a mixed ester condensation, the use of a more reactive ester, such as the phenyl or biphenyl ester, helps to prevent side reactions. Simple heterocyclic esters, namely, ethyl nicotinate and ethyl 8-quinolinecarboxylate, undergo the mixed ester condensation in good yields. The internal condensation of ethyl adipate to give 2-carbethoxycyclopentanone (Dieckmann reaction) is an example of cyclization (81%). ... 

If the reaction with the acid chloride is carried out in ether solution larger amounts of methyl ethyl succinate are formed, and the jdeld of keto ester is only 42-59%. 

The methyl ethyl succinate apparently results from the reaction of the acid chloride with ether. 

A. A.Frost and W.C.Schwemer, The Kinetics of Consecutive Competitive Second-order Reactions The Saponification of Ethyl Adipate and Ethyl Succinate, Journal of the American Chemical Society, 74,1268-1273(1952). 

Let x denote the amount of ethyl succinate, A, which has been transformed at the time t a - x will then denote the amount remaining in the solution at the same time. Similarly, if the system contains b of sodium hydroxide, B, at the beginning of the reaction, at the time t, x of this will have been consumed in the formation of sodium ethyl succinate, M, and y in the formation of sodium succinate, D, hence b - x - y of sodium hydroxide, B, and x - y of sodium ethyl succinate, M, will be present in the system at the time t. The rate of formation of sodium ethyl succinate, M, is therefore... 

Diester derivatives of maleic and fumaric acid (see Chapter 3) are not easily polymerized. However, they do yield soft, tacky thermoplastics with free-radical generating initiators such as BPO. Diethyl fumarate, for example, polymerizes to an 89% yield of poly (ethyl succinate) when heated in the presence of 2% BPO for 7 Liquid-phase (neat) reaction at high pressure (5000 psi) improves the yield.Polymers of higher softening point and higher molecular weight may be prepared by emulsion-polymerization techniques. 

Succinic esters condense with aldehydes and ketones in the presence of bases, eg, sodium alkoxide or piperidine, to form monoesters of alkybdenesuccinic acids, eg, condensation of diethyl succinate with acetone yields ethyl 2-isopropyhdenesuccinate (eq. 3). This reaction, known as Stobbe condensation, is specific for succinic esters and substituted succinic esters (98,99). 

The formation of a DPP molecule was first reported in 1974 as a minor product in low yield from the reaction of benzonitrile with ethyl bro-moacetate and zinc. A fascinating study by research chemists at Ciba Geigy into the mechanistic pathways involved in the formation of the molecules led to the development of an efficient one-pot synthetic procedure to yield DPP pigments from readily available starting materials, as illustrated in Scheme 4.10. The reaction involves the treatment of diethyl succinate (1 mol) with an aromatic cyanide (2 mol) in the presence of a strong base. The reaction proceeds through the intermediate 88, which may be isolated and used to synthesise unsymmetrical derivatives. 

N,N-Diethyl-N -phenyI-2,2-dichloro-acetamidine, 41, 23 Diethyl succinate, for synthesis of tri-ethyl oxalylsucdnate, 44, 67 reaction with 3-hydroxycinchoninic acid to yield 3-hydroxyquinoline, 40,56... 

The use of Fe, indium, and zinc as sacrificial anodes in the electrochemically assisted Reformatsky reaction of ethyl 2-bromoalkanoates with succinic anhydride is found to be effective, giving l-ethyl-3-oxohexanedioates in 49 80%... 

Dicarbethoxy-l,4-cyclohexanedione has been prepared by the self-condensation of diethyl succinate by use of sodium or sodixim ethoxide catalyst (with or without a solvent) and by reaction of ethyl 4-bromo-3-ketobutanoate or ethyl 4-chloro-3-ketobutanoate with sodium ethoxide in ethanol. 

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