Ethyl 2-acetamido Acrylate

Abstract

[23115-42-6] C7H11NO3 (MW 157.17) InChI = 1S/C7H11NO3/c1-4-11-7(10)5(2)8-6(3)9/h2,4H2,1,3H3,(H,8,9) InChIKey = AJTPFZSLRYHOCT-UHFFFAOYSA-N (reagent used as an amino-acid precursor, an electrophilic component in various conjugate or radical additions and metal-mediated couplings, and as a dienophile or dipolarophile in cycloadditions) Alternate Names: 2-propenoic acid-2-(acetylamino) ethyl ester; ethyl N-acetyl-α,β-dehydroalaninate; ethyl α-(N-acetylamino)acrylate; N-acetyl-dehydroalanine ethyl ester; 2-acetamidoacrylate ethyl ester; ethyl 2-acetamidoacrylate; 2-acetylaminoacrylic acid ethyl ester. Physical Data: mp 39.5–40.5 °C; bp 100–103 °C at 5 Torr. Solubility: soluble in chloroform, acetone, acetonitrile, ethanol, THF, acetic acid, N,N-dimethylformamide, and most organic solvents. Form Supplied in: colorless prisms. Analysis of Reagent Purity: 1H and 13C NMR, CHN (combustion) analysis. Preparative Methods: until the late 1970s, dehydroalanine derivatives were most commonly formed via base-mediated eliminations of β-chloroalanine,1N-acylserine2 and cysteine3 derivatives, or N-acyl-α-methoxyalanines,4 a tandem Mannich-decarboxylative Hofmann degradation of acetaminomalonate-monomethyl esters, dimethylamine, and formalin,5 base-induced dehydrohalogenation-isomerizations of N-halogeno-N-acyl alaninates6 or from a condensation of pyruvic acid with primary amines.7 Nowadays, higher yielding procedures, more amenable for large-scale synthesis are required. A more scalable synthesis has been reported in which ethyl 2-acetamido acrylate was obtained in good yield via an ammonium bromide-catalyzed elimination of methanol from the corresponding α-methoxyalaninate.8 Good yields could also be obtained from α-azido esters, using a base-mediated nitrogen elimination-acylation procedure.9 In addition, ethyl 2-acetamido acrylate can also be accessed in moderate yield via a biomimetic one-pot halogenation-decarboxylation procedure of N-acyl aspartic acid.10 In addition to the ethyl ester, methyl 2-acetamido acrylate is commercially available (CAS 35356-70-8, 1 g = $46.80, Sigma-Aldrich, April 2013)(eq 1). (1) Purification: trituration with n-hexane. Handling, Storage, and Precautions: store under nitrogen at 0–10 °C. Irritating to skin, the respiratory system, and eyes. Avoid breathing dust. Compatible with most organic solvents. Toxicity is yet to be determined, although, as with Michael acceptors in general, the substance should be treated as toxic.