Nitromethane → HCID 71076701, compound

Temperature

-10 °C

Following a general procedure,50 a stirred mixture of 3-Ts (7.73 g, 28.5 mmol) in the form of a finely ground powder, potassium acetate (2.24 g, 22.8 mmol), methylamine hydrochloride (1.54 g, 22.8 mmol), and acetic acid (0.1 mL) in absolute ethanol (10 mL) was treated with nitromethane (4.0 mL, 78 mmol). The mixture was stirred for 2 h, whereupon water was added (100 mL) and the resulting yellow precipitate was filtered by vacuum filtration. The solid filtered material was washed with water (200 mL) followed by cold ethanol (˜100 mL, 0° C.) until the eluant was clear. The yellow filtered solid was dried overnight under high vacuum. The crude solid material was dissolved in dry THF (117 mL, distilled). The solution was cooled to −10° C. (internal temperature, using an acetone bath with a few pieces of dry ice) under argon. The solution was treated with 95% LiBH4 (0.64 g, 28 mmol) all at once under vigorous stirring. The reaction mixture was stirred for ˜15 min at −10° C., until all of the starting material disappeared (starting material: CH═CHNO2: d, J=13.6 Hz, 8.56 ppm; product: CH2CH2NO2: t, J=7.3 Hz, 4.54 ppm and 3.36 ppm), whereupon the reaction mixture was quenched by slowly adding a cold saturated aqueous NH4Cl solution (200 mL, 0° C.). The mixture was extracted with ethyl acetate (200 mL). The organic layer was washed with brine, dried (Na2SO4), and concentrated to a solid. The solid was dried under high vacuum for 2 h. The crude solid material was dissolved in 100 mL of 2-propanol by refluxing in a hot water bath. Upon cooling the solution to −10° C. the product crystallized. The mixture was vacuum-filtered, and the resulting light brown crystals were dried under high vacuum (9.03 g, 82%): mp 85° C.; 1H NMR δ 1.92 (s, 3H), 2.43 (s, 3H), 3.36 (t, J=7.3 Hz, 2H), 4.54 (t, J=7.3 Hz, 2H), 7.34 (d, J=8.4 Hz, 2H), 7.34 (s, 1H), 7.66 (d, J=8.4 Hz, 2H); 13C NMR δ 10.5, 21.9, 24.3, 74.3, 105.2, 121.7, 124.3, 124.9, 126.9, 130.6, 135.6, 146.0; ESI-MS obsd 387.0024, calcd 387.0009 [(M+H)+, M=C14H15BrN2O4S];

1. additionwas added (100 mL)
2. filtrationthe resulting yellow precipitate was filtered by vacuum filtration
3. filtrationThe solid filtered material
4. washwas washed with water (200 mL)
5. customfollowed by cold ethanol (˜100 mL, 0° C.) until the eluant
6. filtrationThe yellow filtered solid
7. customwas dried overnight under high vacuum
8. dissolutionThe crude solid material was dissolved in dry THF (117 mL, distilled)
9. customwhereupon the reaction mixture was quenched
10. additionby slowly adding a cold saturated aqueous NH4Cl solution (200 mL, 0° C.)
11. extractionThe mixture was extracted with ethyl acetate (200 mL)
12. washThe organic layer was washed with brine
13. dry with materialdried (Na2SO4)
14. concentrationconcentrated to a solid
15. customThe solid was dried under high vacuum for 2 h
16. dissolutionThe crude solid material was dissolved in 100 mL of 2-propanol
17. temperatureby refluxing in a hot water bath
18. temperatureUpon cooling the solution to −10° C. the product
19. customcrystallized
20. filtrationThe mixture was vacuum-filtered
21. customthe resulting light brown crystals were dried under high vacuum (9.03 g, 82%)

ORD record

ord-d63e91dfbd7c46cc8da00538be8e66bd

Source dataset

uspto-grants-2016_04

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09303165B2