Hexachloroethane → 2-Chloro-3-methoxybenzaldehyde

Temperature

0 °C

To a sol. of N,N′,N′-trimethylethylendiamine (2.77 g, 21.4 mmol) in toluene (50 mL) was added BuLi (13.0 mL, 20.8 mmol) dropwise at 0° C. After stirring for 15 min at 0° C., m-anisaldehyde (2.44 g, 20 mmol) was added, and the mixture was stirred 30 min at 0° C. PhLi (30 mL, 60 mmol) was then added at 0° C., and the mixture was stirred at rt for 4 h. The mixture was cooled to −30° C., and 25 mL THF were added followed by hexachloroethane (14.2 g, 60 mmol) in THF (25 mL). The cooling bath was removed and the mixture was stirred for 3 h. Then it was poured with stirring onto aq. 5M HCl (20 mL). The aq. layer was extracted with EtOAc (2×). The combined org. extracts were washed successively with aq. 1M NaOH, aq. 1M HCl, and brine. The org. layer was dried over MgSO4, filtered, and the solvents were removed under reduced pressure. Purification of the crude by FC (EtOAc/heptane 5:95→1:9) afforded the desired aldehyde, which was further purified by crystallization (EtOAc/heptane, 0° C.) to give 1.50 g of pure title product. LC-MS: tR=0.88 min.

1. stirringthe mixture was stirred 30 min at 0° C
2. stirringthe mixture was stirred at rt for 4 h
3. temperatureThe mixture was cooled to −30° C.
4. customThe cooling bath was removed
5. stirringthe mixture was stirred for 3 h
6. additionThen it was poured
7. stirringwith stirring onto aq. 5M HCl (20 mL)
8. extractionThe aq. layer was extracted with EtOAc (2×)
9. washextracts were washed successively with aq. 1M NaOH, aq. 1M HCl, and brine
10. dry with materiallayer was dried over MgSO4
11. filtrationfiltered
12. customthe solvents were removed under reduced pressure
13. customPurification of the crude by FC (EtOAc/heptane 5:95→1:9)

ORD record

ord-7fad3ed76cc74a7290c1fe0893b03264

Source dataset

uspto-grants-2012_03

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08138340B2