Cyanopropionates

Additions. Halogens, hydrogen haUdes, and hydrogen cyanide readily add to acryUc acid to give the 2,3-dihalopropionate, 3-halopropionate, and 3-cyanopropionate, respectively (21). 

Cyan-, of or combined with cyanogen, cyano-(as Cyanpropionadure, cyanopropionic acid), cyanide of (as Cyanammonium, ammonium cyanide), -alkali, n. alkali cyanide, -alkyl, n. alkyl cyanide. 

Ethylenimine, 30, 38 toxic properties of, 30, 40 Ethyl o-ethoxybenzoate, 32, 75 Ethyl formate, 32, 32 Ethyl glycidyl ether, 31, 3 2-Ethylhexanaldoxime, 32, 67 2-Ethylhexanamide, 32, 65 2-Ethylhexanoic acid, 32, 66 2-Ethylhexanonitrile, 32, 65 Ethylidene bromide, 32, 55 Ethyl iodide, 31, 34 Ethyl isodehydroacetate, 32, 76 Ethyl lactate, 31, 59, 60 5-ETHYL-2-METHYLPYRIDINE, 30, 41 Ethyl orthocarbonate, 32, 68 Ethyl orthoformate, 32, 5 Ethyl orthosilicate, 32, 5 Ethyl phenylazoacetoacetate, 32, 85 Ethyl phenylcyanoacetate, 30,43,80 Ethyl 0-phenyl-/3-cyanopropionate, 30, 84... 

Surprisingly, a-cyanoacrylic acid is reported to react spontaneously with triethylsilane in the absence of any additional acid to give a quantitative yield of the triethylsilyl ester of a-cyanopropionic acid.236 Ethyl a-cyanoacrylate requires the presence of trifluoroacetic acid to undergo reduction to ethyl 2-cyanopropionate.236 Many of these reductions are highly stereoselective. For example, treatment of... 

A series of frani -chelating chiral biferrocene diphosphine ligands enable a rhodium(I)-catalysed aldol reaction of 2-cyanopropionates to proceed in up to 93%... 

Recently, Smulik and Vedejs have reported that amination of ester enolates and enim-inates with 0-(p-nitrobenzoyl)hydroxylamine 21 takes place with good yields . However, reaction of enolates derived from ethyl phenylacetate and phenylacetonitrile gave lower yields compared with stabilized enolates derived from diethyl malonate, diethyl 2-phenylmalonate and 2-phenyl-2-cyanopropionate (Scheme 23). 

Williams group observed low enantioselectivities for the Michael addition of a prochiral nucleophile, ethyl 2-cyanopropionate 623, to methyl vinyl ketone 624 catalyzed by chiral platinum complexes (Scheme 8.196)." The NMR analysis indicated that these cationic Pt complexes act as Lewis acids toward nitriles. The X-ray crystal structure as well NMR analysis showed that the solvent ligand that is readily displaced by an organic substrate is situated cis to the nitrogen donor in the Pt complex and, therefore, is in a chiral pocket created by the oxazoline ring. 

A. Ethyl -phenyl-p-cyanopropionate. In a 5-1. round-bottomed three-necked flask suspended in an oil bath and fitted with a mechanical stirrer, a reflux condenser, and a 250-ml. dropping funnel is placed a solution of 200 g. (0.806 mole) of diethyl ben-zalmalonate Mn 2 1. of absolute ethanol. The stirrer is started, and a solution of 56 g. (0.87 mole) of potassium cyanide in 100 ml. of water is added rapidly from the separatory funnel a small amount of the potassium cyanide precipitates. The temperature of the oil bath is raised to 70° and maintained at 65-75° for 18 hours. 

The mixture is cooled to 15°, and the precipitated potassium bicarbonate is collected on a Buchner funnel. The solid (weight 70-72 g.) is washed on the funnel with 100 ml. of 95% ethanol. The combined filtrate and wash liquor is transferred to a 5-1. round-bottomed flask and made slightly acid Caution Note 1) with dilute hydrochloric acid (about 15-20 ml. of the 10% acid is required). The solution is then concentrated under reduced pressure to a semi-solid residue (Note 1). The cooled residue is shaken with a mixture of 300 ml. of water and 500 ml. of ether. The material dissolves completely the water layer is separated and washed with 200 ml. of ether. The ether solutions are combined, dried over 20 g. of calcium chloride, filtered into a 2-1. round-bottomed flask equipped with a glass joint, and concentrated by distillation (heating on a steam bath). The crude ethyl /3-phenyl-/3-cyanopropionate remains as a clear red oil weighing 130-140 g. It is sufficiently pure for use in the next step (Note 2). 

The oxidation of glutamic acid to cyanopropionic acid with CAB in acid solution showed an inverse fractional dependence on acidity. Similarly in alkaline medium, the order in alkali is fractional inverse.143 Kinetics of ruthenium(III)-catalysed oxidation of diols with CAB have been obtained. The products arise due to a fission of the glycol bond.144 The oxidation of isatins with CAB, in alkaline solutions, showed a first-order dependence on CAB and isatin and fractional order in alkali. The rates correlate with the Hammett relationship, the reaction constant p being —0.31. The observed results have been explained by a plausible mechanism and the related rate law has been deduced.145 The oxidation of cysteine with CAB in sulfuric acid medium is first order in CAB and cysteine and the rate is decreased with an increase in the hydrogen ion concentration.146... 

Addition of nitriles to acetylenic compounds proceeds with chemoselectivity in contrast with the corresponding base-promoted reactions, where the products derived from acetylides are contaminants. The RuH2(PPh3)4-catalyzed reaction of ethyl 2-cyanopropionate (12) with methyl propiolate (14) at room temperature gave 15 in 90 % yield. 

The resulting chiral organometallic materials were used as catalysts in the Michael addition reaction of methyl vinyl ketone to (R/S)-ethyl a-iso-cyanopropionate, and after 24 h a conversion of 63% was obtained as compared to 80% conversion observed for the covalently immobilized [PtI(NCN-COOK)]. As for the latter, no chirality transfer was observed (see Sect. 2). 

Hydrolysis, of dihydropyran, 30, 48 of ethyl 3-benzyl-2-cyano-3-methyl-pentanoate, 35, 8 of ethyl enanthylsuccinate, 34, S3 of ethyl 8-phenyl- 3-cyanopropionate,... 

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