Water → Methyl 1-formylcyclopentanecarboxylate

Temperature

45 °C

To a 12 L flask equipped with a mechanical stirrer, thermometer and condenser containing a nitrogen inlet was added Raney nickel (1 kg, 50% slurry in water, as sold by the Aldrich Chemical Co.). This material was washed with distilled water and decanted (3×0.8 L). Formic acid (88% 7 L) was added (stirring started) followed by a solution of methyl 1-cyanocyclopentanecarboxylate (696 g, 4.54 mol) in formic acid (88%, 1 L). Gas evolved and the exothermic mixture (temperature increased to 45° C.) was stirred at 75° C. for 5 h. After the reaction mixture cooled to room temperature and the catalyst settled, the majority of the solvent was decanted off through a fiberglass filter. The residue was mixed with water (6 L) and filtered. The collected solid was washed with water (1 L) and CH2Cl2 (1 L) and all the filtrates were combined. The aqueous phase was separated and extracted with CH2Cl2 (6 L), and the combined organic phases were washed with saturated aqueous NaHCO3 and brine. Drying (MgSO4), filtering, and concentrating afforded material that was immediately distilled (Vigreux® column, fraction boiling at 93° C., 16 mm Hg collected) to provide methyl 1-formylcyclopentanecarboxylate as a clear colorless liquid (491 g, 69% yield). 1H-NMR (400 MHz, CDCl3) δ 9.65 (s, 1 H), 3.76 (s, 3 H), 2.19-2.04 (m, 4 H), 1.78-1.58 (m, 4 H); 13C NMR (100.6 MHz, CDCl3) δ 197.0, 172.6, 64.3, 51.9, 31.0, 25.3; EI-MS exact mass calcd for: C8H13O3 ; 157.0865; found: 157.0864. This compound has been reported previously by C. R. Davis et al., J. Org. Chem. 1993, 58, 6843.

1. customTo a 12 L flask equipped with a mechanical stirrer
2. additionthermometer and condenser containing a nitrogen inlet
3. washThis material was washed with distilled water
4. customdecanted (3×0.8 L)
5. additionFormic acid (88% 7 L) was added
6. stirringwas stirred at 75° C. for 5 h
7. temperatureAfter the reaction mixture cooled to room temperature
8. customthe majority of the solvent was decanted off through a fiberglass
9. filtrationfilter
10. additionThe residue was mixed with water (6 L)
11. filtrationfiltered
12. washThe collected solid was washed with water (1 L) and CH2Cl2 (1 L) and all the filtrates
13. customThe aqueous phase was separated
14. extractionextracted with CH2Cl2 (6 L)
15. washthe combined organic phases were washed with saturated aqueous NaHCO3 and brine
16. dry with materialDrying (MgSO4)
17. filtrationfiltering
18. concentrationconcentrating
19. customafforded material that
20. distillationwas immediately distilled
21. custom(Vigreux® column, fraction boiling at 93° C., 16 mm Hg collected)

ORD record

ord-ceeaca28ceda4312ae2aedd7739e338d

Source dataset

uspto-grants-1999_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05948935