Dimethylformamide → 3-Methoxyfuran-2-carbaldehyde

Temperature

0 °C

A 3-L, one-necked, round-bottomed flask was equipped with a Teflon-coated magnetic stirbar. The system was flame-dried and flushed with argon. The flask was charged with a solution of N,N-dimethylformamide (31.9 mL, 413 mmol, 1.35 equiv) in dichloromethane (1.2 L). The solution was cooled to 0° C. in a dry ice-acetone bath, and then oxalyl chloride (32.5 mL, 367 mmol, 1.2 equiv) was added over 16 min. Vigorous bubbling occurred and a white solid precipitated. After stirring for 20 min, the reaction mixture was cooled to −40° C. by addition of dry ice to the cooling bath and a solution of 3-methoxyfuran (Meister, C.; Scharf, H.-D. Synthesis 1981, 737-739) (30 g, 306 mmol, 1 equiv) in dichloromethane (100 mL) was added via cannula. A dark-brown color formed during the addition. After stirring for 20 min, the cooling bath was removed and saturated aqueous sodium bicarbonate solution (1.5 L) was added. The biphasic mixture was stirred vigorously for 6 hours, and then was partitioned. The aqueous layer was further extracted with dichloromethane (2×800 mL). The organic layers were combined and the combined layers were dried over sodium sulfate. The solids were filtered and the filtrate was concentrated. The residue obtained was purified by flash-column chromatography on silica gel (100% diethyl ether) to furnish 3-methoxyfurfural 6 (21.2 g, 55%) as a light-yellow solid.

1. customThe system was flame-dried
2. customflushed with argon
3. customVigorous bubbling
4. customa white solid precipitated
5. temperaturethe reaction mixture was cooled to −40° C. by addition of dry ice to the cooling bath
6. customA dark-brown color formed during the addition
7. stirringAfter stirring for 20 min
8. customthe cooling bath was removed
9. additionsaturated aqueous sodium bicarbonate solution (1.5 L) was added
10. stirringThe biphasic mixture was stirred vigorously for 6 hours
11. customwas partitioned
12. extractionThe aqueous layer was further extracted with dichloromethane (2×800 mL)
13. dry with materialthe combined layers were dried over sodium sulfate
14. filtrationThe solids were filtered
15. concentrationthe filtrate was concentrated
16. customThe residue obtained
17. customwas purified by flash-column chromatography on silica gel (100% diethyl ether)

ORD record

ord-fa1a7056e7294bd7a02aae38c765a538

Source dataset

uspto-grants-2014_12

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08907104B2