Dimethyl P-(2-oxopropyl)phosphonate

CLEAR COLOURLESS TO LIGHT BROWN LIQUID

The dry and clean 500mL coil was heated to 135 ° C, to take Compound 6 (standard atmospheric pressure boiling point of 117 to 119 ° C) 1000g (0.7eq.10.81mol) placed in a feeding bottle A, adding 4000g of toluene diluted trimethyl phosphite (standard large Pressure of boiling point 112 ° C) 1878g (1.0eq.15.13mol) placed in the bottle B, 3122g of toluene was added to be diluted to be coiled The batch was started after the temperature was stabilized, and pump A (toluene solution of compound 6): 12.5 g / min, pump B (trimethyl phosphite): 12.5 g / min. Residence time 20min, the reaction pressure is 0.5 ~ 2.0Mpa. The discharge port is directly connected to the thin-film evaporation device to control the pressure4 to 10 × 102 Pa and temperature of 60 to 70 ° C. Finally, 1230 g of product 7 (boiling point 85 to 88 ° C., 666 Pa) was obtained in a yield of 88percent.Dimethyl 2-oxopropylphosphonate (52). A 2-liter eggplant type flask was charged with 179.2 g (1.08 1 mol) of potassium iodide, 300 ml of acetone and 250 ml of acetonitrile, to which 100 g (1.08 1 mol) of chloroacetone was added, thereby forming a whitesuspension. Further 134 g (1.08 1 mol) of trimethylphosphite was added and the resulting mixture was stirred for 6 hours at 20°C and 4 additional hours at 5 0°C. After that reaction mixture was filtered through the Celite pad and filtrate was distilled off to obtain a product in the form of brown oil. This oily product was subjected to fractional distillation under reduced pressure (8 1-85° C. and 0.02 mmHg) to obtain 127.5 g (45percent) of title compoundTo a stirred suspension of KI (33.2 g, 200 mmol) in acetone/CH3CN (120 mL, 3:4 v/v), chloroacetone SI-3 (15.9 mL, 200 mmol) was added and the obtained reaction mixture was stirred for 50 min at room temperature. Then, trimethylphosphite (23.6 mL, 200 mmol) was added and the obtained suspension was stirred overnight at room temperature. Finally, the reaction mixture was heated to 50°C, and stirring was continued for 1 h to ensure complete conversion. Then, the suspension was filtered over Celite and the residue was rinsed with acetone (2 × 20 mL). The filtrate was concentrated under reduced pressure and the SI-4residue was purified by vacuum distillation (product fraction was collected at 101 °C at 3.5 mbar). Ketone SI-4 was obtained as a colorless oil in 36percent yield (12.0 g). Rf 0.65 (CH2Cl2/MeOH 9:1 v/v);1H-NMR (300 MHz, CDCl3) δ = 2.32 (s, 3H, CH3), 3.11 (d (JH, P = 22.8 Hz), 2H, CH2), 3.80 (d (JH, P= 11.2 Hz), 6H, OCH3);13C-NMR (75 MHz, CDCl3): δ = 31.0, 41.0, 42.7, 52.7/52.8, 199.4 (two lines).Dimethyl methylphosphonate (119 mL, 1.10 mol) in abs. toluene (280 mL) was added at -80°C under nitrogen atmosphere to a solution of BuLi (660 mL, 1.10mol, 1.67 M/hexane) dissolved in abs. toluene (2.5 L). After stirring (10 min, -80°C) EtOAc (113 mL, 102 g, 1.16 mol) was added. After stirring (1 h, -80°C)the reaction mixture was poured into 1M NaHSO(1)

Molecular Weight:166.11
XLogP3:0.9
Hydrogen Bond Acceptor Count:4
Rotatable Bond Count:4
Exact Mass:166.03949583
Monoisotopic Mass:166.03949583
Topological Polar Surface Area:52.6
Heavy Atom Count:10
Complexity:157
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes