Diethyl Ether → HCID 23370793, compound

CH3I (18.5 mL, 297 mmol) in 50 mL of ether was added slowly, to maintain reflux, to a suspension of Mg (6.0 g, 250 mmol) in 50 mL of ether. The solution was vigorously stirred during the addition. After the magnesium was consumed, the solution was chilled with an ice bath to ≅5° C. Acetylacetaldehyde dimethyl acetal (16.5 mL, 124 mmol) in 50 mL of ether was added very slowly, over a period of 2 h. After the addition was complete, the reaction was stirred for an additional hour while warming to room temperature. The reaction was quenched with 1 mL of saturated (NH4)2SO4 (aq) and filtered. The residue was washed with ether (2×50 mL). The combined filtrates were dried over Na2SO4, and the solvent was removed under water aspirator vacuum (67 mmol, 54% yield). Distillation of the residue yielded 9.9 g of 3-hydroxymethylbutanal dimethyl acetal, bp4.2 53°-56° C. bp10 60°-65° C., bp14 72°-79° C. in agreement with Malik, O. P.; Kapil, R. S., Anand, N., Ind. J. Chem. 14B (1976) 449); 1H--NMR (200 MHz, CDCl3) δ 1.24 (s, 6H, CH3), 1.80 (d, J=5.9 Hz, 2 H, CH2), 3.36 (s, 6 H, CH3O), 3.41 (s, 1 H, OH), 4.66 (t, J=5.9 Hz, 1 H, CH), 13C--NMR (50 MHz, CDCl3) δ 29.46 (CH3), 43.85 (CH2), 52.61 (CH3O), 68.63 (COH), 102.51 (CH).

1. temperatureto maintain
2. customAfter the magnesium was consumed
3. temperaturethe solution was chilled with an ice bath
4. customto ≅5° C
5. additionAfter the addition
6. stirringthe reaction was stirred for an additional hour
7. customThe reaction was quenched with 1 mL of saturated (NH4)2SO4 (aq)
8. filtrationfiltered
9. washThe residue was washed with ether (2×50 mL)
10. dry with materialThe combined filtrates were dried over Na2SO4
11. customthe solvent was removed under water
12. distillationDistillation of the residue

ORD record

ord-9e087cd4d22b4f59a0483f2491951645

Source dataset

uspto-grants-1996_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05576426