Diethyl benzylphosphonate → HCID 86673406, compound

To a solution of diethyl benzylphosphonate (4.57 mL, 21.91 mmol) in dimethylformamide (50 mL) at room temperature was added sodium methoxide (2.367 g, 43.8 mmol) and 18-Crown-6 (2.316 g, 8.76 mmol). After stirring at room temperature for 5 min, the reaction was cooled to 0° C. and treated with 6-bromopicolinaldehyde (4.89 g, 26.3 mmol) as a solid in one portion. The ice bath was removed and the reaction stirred at room temperature for 1 h. The reaction was gradually warmed to 120° C. and held there for 2 h. The reaction was cooled to room temperature and poured into water (500 mL) with vigorous stirring. The resulting suspension was extracted with diethyl ether, washed with water (3×), then brine, dried over magnesium sulfate, and concentrated to an oil. The oil was dissolved in hexanes and reconcentrated to give something that appeared to be crashing out as a solid. The resulting residue (solid in oil) was suspended in ethanol, concentrated, and pumped under high vacuum to give a dark-colored, moist solid. The resulting residue was suspended in ethanol (total volume (solid+solution)=20 ml). The resulting suspension was placed in the freezer and held there overnight. The resulting precipitate was collected by filtration to give 2.46 g (43%) as a faint tan powder. 1H-NMR (CDCl3, 500 MHz) δ 7.69 (d, J=16.2, 1H), 7.60 (d, J=8.9, 2H), 7.53 (dd, J=7.9, 7.6, 1H), 7.41 (dd, J=7.6, 7.3, 2H), 7.31-7.38 (m, 3H), 7.11 (d, J=16.2, 1H). 13C-NMR (CDCl3, 126 MHz) δ 157.2, 142.3, 138.8, 136.3, 134.5, 128.9, 128.8, 127.4, 126.4, 126.2, 120.7.

1. temperaturethe reaction was cooled to 0° C.
2. customThe ice bath was removed
3. stirringthe reaction stirred at room temperature for 1 h
4. temperatureThe reaction was gradually warmed to 120° C.
5. waitheld there for 2 h
6. temperatureThe reaction was cooled to room temperature
7. additionpoured into water (500 mL) with vigorous stirring
8. extractionThe resulting suspension was extracted with diethyl ether
9. washwashed with water (3×)
10. dry with materialbrine, dried over magnesium sulfate
11. concentrationconcentrated to an oil
12. dissolutionThe oil was dissolved in hexanes
13. customto give something that
14. concentrationconcentrated
15. customto give a dark-colored, moist solid
16. waitheld there overnight
17. filtrationThe resulting precipitate was collected by filtration
18. customto give 2.46 g (43%) as a faint tan powder

ORD record

ord-36e8b528e5254083967eb8c45c1492bf

Source dataset

uspto-grants-2014_04

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08691821B2