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 stiffing 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 stiffing 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. waitAfter stiffing for 20 min
8. customthe cooling bath was removed
9. additionsaturated aqueous sodium bicarbonate solution (1.5 L) was added
10. customwas partitioned
11. extractionThe aqueous layer was further extracted with dichloromethane (2×800 mL)
12. dry with materialthe combined layers were dried over sodium sulfate
13. filtrationThe solids were filtered
14. concentrationthe filtrate was concentrated
15. customThe residue obtained
16. customwas purified by flash-column chromatography on silica gel (100% diethyl ether)

ORD record

ord-13af59771ac24279afab31fe3e3b0eda

Source dataset

uspto-grants-2011_06

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07960559B2