4-Acryloylmorpholine

4-Acryloylmorpholine (4-AM) is a water-soluble monomer, an acrylamide derivative containing a heterocyclic tetrahydrooxazine substituent. Homo- and copolymers of 4-АМ have several valuable properties. They are soluble both in water and in many organic solvents such as alcohols, chloroform, tetrahydrofuran, and dioxane, are non-toxic, and are used for solid-phase synthesis of peptides in chromatography, as materials for composite semipermeable membranes, in catalysis, and for biomedical purposes. Various functional groups are introduced into poly-4-AM to expand its application fields. Random copolymers of 4-АМ with carboxylic acids (acrylic, 4-pentenoic, undecenoic, 2-acrylamido-2-methyl-1-propanesulfonic), behaving as anionic polyelectrolytes, and copolymers with N-hydroxysuccinimide ester of acrylic acid, acting as polymeric carriers, have been synthesized[2-3].

4-Acryloylmorpholine has a melting point of 35 °C and is clear liquid at room temperature. At 25 °C, it has a density of 1.122 g/mL. It needs to be stored at 2-8°C.

4-Acryloylmorpholine is used in adhesives, UV curable resins, industrial coatings, UV printing ink, oil recovery polymer, medicinal and commodity chemicals.

Using cobalt catalysis, diethylzinc promotes the conjugate reduction of 4-acryloylmorpholine to produce the corresponding ethylzinc enolate, which reacts with N-tosyl aldimines to afford β-aminoamides^[1].

Non flammable

A solution of 0.04 mol of the corresponding amine in 20 ml of anhydrous methylene chloride was slowly added at 0-5C to 0.02 mol of acryloyl chloride in 20 ml of anhydrous methylene chloride. The mixture was stirred for 3 h at room temperature in an inert atmosphere, and the precipitate was filtered off and washed with methylene chloride (2 á 10 ml). The organic layer was washed in succession with 5 ml of water and 5 ml of a saturated solution of NaHCO3 and dried over Na2SO4, the solvent was removed under reduced pressure, and the residue was purified by column chromatography on silica gel using hexane-ethyl acetate (5 : 1 to 1 : 1) as eluent. 4-Acryloylmorpholine, Yield 1.78 g (63%). IR spectrum, |í, cm-1: 2857, 1647, 1612, 1439, 1263, 1238, 1115, 1038, 953. 1H NMR spectrum, |, ppm: 3.51-3.73 m (8H, NCH2CH2O), 5.72 d.d (1H, 3-Hcis, 3J = 10.6, 2J = 1.9 Hz), 6.29 d.d (1H, 3-Htrans, 3J = 16.7, 2J = 1.9 Hz), 6.57 d.d (1H, 2-H, J = 16.7, 10.6 Hz). 13C NMR spectrum, |C, ppm: 41.74 and 45.66 (CH2N), 66.22 (CH2O), 126.64 (C2), 127.69 (C3), 164.92 (C1). Mass spectrum, m/z (Irel, %): 141 (36) [M]+, 140 (12), 126 (58), 112 (22), 111 (15), 110 (15), 109 (12), 98 (10), 96 (26), 86 (72), 83 (13), 70 (14), 68 (14), 57 (17), 56 (86), 55 (100), 42 (23).Fig. The synthetic method 2 of 4-Acryloylmorpholine

[1] PRIETO O, LAM H W. Cobalt-catalyzed reductive Mannich reactions of 4-acryloylmorpholine with N-tosyl aldimines[J]. Organic & Biomolecular Chemistry, 2007. DOI:10.1039/B715839D.
[2] T. Nekrasova. “pH- and thermosensitive copolymers of 4-acryloylmorpholine and 2-dialkylaminoethyl methacrylates and silver-containing nanocomposites based on these copolymers.” Materials Today Communications (2019).
[3] Yu. I. Zolotova. “Copolymers of 4-Acryloylmorpholine with 2-Dimethyl- and 2-Diethylaminoethyl Methacrylate and Silver-Containing Nanocomposites Based on Them.” Russian Journal of Applied Chemistry 91 4 (2018): 623–628.