Methylamine → 4-Methylaminomethyl-2-phenyl-1,3-dioxane

To a solution of 4-hydroxymethyl-2-phenyl-1,3-dioxane (0.80 g, 4.12 mmol) in dichloromethane (20 mL) was added diisopropylethylamine (1.702 ml, 10.30 mmol) and the solution was cooled in an ice bath. Methanesulfonyl chloride (0.414 ml, 5.35 mmol) was added and the solution was allowed to warm to RT. After 1 h, it was washed with 2M aq HCl, saturated aq NaHCO3, dried and concentrated to a syrup (1.15 g). A solution of (0.9 g, 3.30 mmol) of this material in DMSO (8 mL) containing 40% aq methylamine (2.85 ml, 33.0 mmol) was stoppered and heated at ˜75-80° C. for 24 h. The solution was cooled, chloroform was added and washed twice with water, dried and concentrated. Chromatography afforded title compound (0.465 g, 2.24 mmol, 68%) as a syrup. 1H NMR (CDCl3) δ 7.50-7.47 (2H, m), 7.39-7.30 (3H, m), 5.52 (1H, s), 4.31-4.25 (1H, m), 4.09-3.93 (2H, m), 2.80 (1H, dd, J=12.3, 8.0 Hz), 2.67 (1H, dd, J=12.3, 3.4 Hz), 2.45 (3H, s), 1.96-1.83 (2H, m), 1.49 (1H, dd, J=13.2, 1.2 Hz); 13C NMR δ 139.0, 129.2, 128.6, 126.5, 101.6, 76.8, 67.2, 57.0, 36.8, 29.5.

1. temperaturethe solution was cooled in an ice bath
2. washit was washed with 2M aq HCl, saturated aq NaHCO3
3. customdried
4. concentrationconcentrated to a syrup (1.15 g)
5. temperatureheated at ˜75-80° C. for 24 h
6. temperatureThe solution was cooled
7. washwashed twice with water
8. customdried
9. concentrationconcentrated

ORDレコード

ord-b088fe747c6c4c759143a916a9b3d901

出典データセット

uspto-grants-2014_10

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US08853224B2