Succinate, diethyl

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... 

The condensation of aldehydes and ketones with succinic esters in the presence of sodium ethoxide is known as the Stobbe condensation. The reaction with sodium ethoxide is comparatively slow and a httlo reduction of the ketonic compound to the carbinol usually occurs a shorter reaction time and a better yield is generally obtained with the more powerful condensing agent potassium ieri.-butoxide or with sodium hydride. Thus benzophenone condenses with diethyl succinate in the presence of potassium [Pg.919]

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 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). 

B. a-Ketoglularic acid. The ester obtained by the foregoing procedure is mixed with 600 ml. of concentrated hydrochloric acid and left overnight. The mixture is concentrated by distillation (Note 5) until the temperature of the liquid reaches 140°. It is poured into an evaporating dish and allowed to cool. The solid mass, weighing 11(3-112 g., is then pulverized. The yield of a-ketoglutaric acid is 92-93% of the theoretical for the last step, or 75-77% based upon diethyl succinate. The light tan product, obtained as described above, is suitable for most purposes, but a purer add, m.p. 109-110° (corr.) may be obtained by recrystallization from an acetone-benzene mixture. 

Method 2. In the apparatus described above is placed 4.8-5.0g. ( 0.2 g.-atorn) of clean sodium and 8.0-8.2 g. ( 0.2 g.-atom) of clean potassium (Ilotes 3, 4). The flask is heated with a heat gun to form the low-melting alloy, and then 300-350 ml. of anhydrous ether is added from a freshly opened can. The stirrer is operated at full speed until the alloy is dispersed and then at a slower speed for the remainder of the reaction (Notes 5, 6). A mixture of 17.4 g. (0.1 mole) of diethyl succinate (Note 7), 44g. (0.4 mole) of chlorotrimethylsilane (Note 8), and 125 ml. of anhydrous ether is then added at a rate sufficient to keep the reaction under control (Note 14). The purple mixture is stirred for another 4-6 hours (Note 9) and then filtered and washed as above in a nitrogen dry-box (Note ll). The product is distilled as above forerun 0.5-2 g. to 80° (10 mm.) and then at 82-86° (10 mm.) as a colorless liquid, 13.8-16.1 g. (60-70%), 1.4323-1.4330 (Notes 15-19). 

Diethyl succinate was obtained by the submitters from Eastman Organic Chemicals and used without purification. The checkers obtained the ester from British Drug Houses, Ltd., and distilled it at 100° (11 mm.). In general, it is preferable to distill or crystallize and dry all esters before attempting acyloin condensations. 

The synthesis of 2-hydroxycyclobutanone was chosen as a model for the use of a trapping agent because diethyl succinate was the most accessible of 1,2-diesters and because the hydrolysis step for this compound is more difficult than most. Procedures developed for succinoin have been found broadly applicable in preparation of other sensitive acy loins. 

C. 3-Hydroxyquinoline. A 1-1. beaker is fitted with a thermometer and mechanical stirrer and clamped firmly on an efficient electric heater (Note 14). Diethyl succinate (400 ml.) (Note 15) is placed in the beaker and heated to boiling (215-220°) with stirring. 3-Hydroxycinchoninic acid (part B) (94.6 g., 0.5 mole) is added in portions to the boiling solution by means of a metal spoon or Scoopula. Care is taken to prevent too vigorous evolution of carbon dioxide. The addition requires 2-3 minutes, during which time a temperature drop is noted unless good heating is maintained. 

Commercial diethyl succinate from Carl)idc and Carbon... 

The utility of base catalyzed condensations of esters to give jS-ketoesters is well known. A straightforward example of this reaction is the intermolecular cyclization of diethyl succinate giving 2,5-dicarbethoxy-l,4-cyclohexanedione, which can in turn be easily decarboxylated to give 1,4-cyclohexanedione. 

I. 2,5-Dicarbethoxy-1,4-cyclohexanedione (7) A 500-ml, three-necked, round-bottom flask is fitted with a condenser (drying tube) and arranged for magnetic stirring. A solution of sodium ethoxide is prepared in the flask by the addition of sodium (9.2 g, 0.4 g-atom) in small pieces to 90 ml of absolute ethanol. The mixture is heated at reflux for 3 hours (oil bath) to complete the reaction. Diethyl succinate (34.8 g, 0.2 mole) is added to the hot solution in one portion exothermic ) and the mixture is refluxed for 24 hours. (A pink precipitate forms and persists during the reflux.)... 

It is evident that, in order to obtain accurate results, the method of working must be clearly and minutely adhered to, especially so in view of the fact that the determination of ester by the method of steam distillation is a very valuable indication as to the purity of an oil, serving to detect the fraudulent addition to oils of such esters as diethyl succinate, triethyl citrate, and diethyl oxalate, the free acids of which are nonvolatile in steam. It will not detect glyceryl acetate, terpinyl acetate, nor the esters of coconut oil fatty acids. 

Hydrogenation of diethylmaleate in the vapor phase over a nonprecious metal catalyst produces diethyl succinate. Successive hydrogenation produces y-butyrolactone, butanediol, and tetrahydrofuran. 

Diethyl succinate, reaction with sodium ethoxide, 46, 25... 

Sodium azide, reaction with l butyl chloroacetate, 46, 47 reaction with diazomum salt from o amino-f> -ni trobiphcny L, 46, 86 Sodium chlorodifluoroacetate, 47, SO reaction with tnphenylphosphme and benzaldehyde, 47, SO Sodium ethoxide, 46, 2S reaction with diethyl succinate, 46,2S Sodium formate as reducing agent in preparation of palladium catalyst, 46, 90... 

Preparation of l,2-bis(trimcthylsilyloxy)cyclobutene from diethyl succinate (Riihlmann condensation using Na and TMSC1), and of 2-hydroxycyclo-Ibutanone. 

Diethyl succinate, reaction with 3 hy droxycinchomnic acid to yield 3-hydroxyquinoline, 40, 56 N,N-Diethyl-2,2,2-trichloroacetamide, 41, 21... 

Hydroxybenzaldehyde, condensation with hydantoin, 43, 49 5-(/>-Hydroxybenzal)hydantoin, 43, 49 3-Hydroxydnchoninic add, 40, 55 reaction with diethyl succinate to yield 3-hydroxyquinoline, 40, 56... 

C1SH20O2 56-53-1) see Diethylstilbestrol dipropionate Diethylstilbestrol disulfate Dimestrol Fosfestrol diethyl succinate... 

---