3- Cyanopropionic acid

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. 

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... 

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... 

Analysis of the reaction products showed that during conversion of succinonitrile into 3-cyanopropionic acid, succinamic acid (H2NOC-CH2-CH2-COOH) was detected as a free intermediate in the reaction mixture, suggesting that enzymatic activities other than nitrilases (i.e. nitrile hydratase) were present in the cell... 

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). 

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... 

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. 

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 C2-symmetric biferrocene 16 has been reported by Ito and co-workers to behave as a frans-spanning chelating ligand. The combination of C2-symmetry and trans coordination geometry is conceptually new in the field and bears promises for future development. TRAP (the abbreviation for this kind of compounds) affords high enantioselectivities in the Rh-catalyzed asymmetric Michael reaction of 2-cyanopropionates [17], the hydrosilylation of simple ketones [18], the hydrogenation of )3,/9-disubstituted A-acetylaminoacrylic acid... 

Other methods for the synthesis of cyanoacrylate monomers include pyrolysis of 3-alkoxy-2-cyanopropionates (1), transesterification of cyanoacrylates with alcohols (19,20), displacement of monomer from the corresponding anthracene Diels-Alder adduct by treatment with maleic anhydride (7,21), esterification of cyanoacrylic acid or cyanoacryloyl chloride with alcohols (22), and the oxidation of alkyl 2-cyanopropionate phenyl selenides with hydrogen peroxide (23). These alternative methods are particularly useful for the preparation of monomers not readily prepared by thermal decomposition of cyanoacrylate polymer. 

A mixture of ethyl -acetamido-a-cyanopropionate, LiBH4, and dry tetrahydro-furan refluxed 2 hrs., dil. with methanol, acidified with HCl, evaporated to dryness, twice more dissolved in methanol, heated to boiling and evaporated to remove boric acid as methyl borate, the residue refluxed 8 hrs. with 6 N HCl a-methylserine. Y 84%. F. e. s. J. M. Stewart, J. Org. Chem. 26, 3360 (1961). 

The Michael reaction of nitriles with unsaturated carbonyl compounds was examined using the SA-NEtj catalyst As shown in Table 1.6, the SA-NEtj showed the highest catalytic activity for the Michael reaction of ethyl 2-cyanopropionate with ethyl acrylate to afibrd 2-cyano-2-methyl glutaric acid diethyl ester in 94% yield (entry 1). SiOj-NEtj was much less active under the reaction conditions (entry 2). Neither triethylamine nor sihca-alumina promoted the desired addition reaction (entries 3 and 4). Notably, the reaction scarcely proceeded with the... 

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