Formate → 4-(Hydroxymethyl)-5-methyl-1,3-dioxol-2-one

4,5-dimethyl-2-oxo-1,3-dioxole (5 g, 43.82 mmol), NBS (8.19 g, 46.01 mmol), and benzoyl peroxide (20 mg) were dissolved in CCl4 (30 mL) and heated to 80° C. for 1.5 h. The reaction mixture was cooled to r.t and the solid was filtered off. The filtrate was concentrated. The residue was purified by silica gel column to give 8.29 g of 4-bromomethyl-5-methyl-2-oxo-1,3-dioxole as a yellow oil. TEA (12 mL, 86.1 mmol) was added dropwise to a solution of 4-bromomethyl-5-methyl-2-oxo-1,3-dioxole (6 g, 31.09 mmol) and formic acid (3.36 mL) in CH3CN (96 mL) while keeping the temperature under 20° C. The mixture was stirred at r.t. for 2 h and concentrated. The product was partitioned between H2O and EtOAc (3×). The organic layer was dried with Na2SO4, concentrated and dried in vacuo to give crude formate. The resulting formate was dissolved in MeOH (40 mL) and 0.5 mL of concentrated HCl was added. The mixture was stirred at r.t. for 5 h, concentrated, and co-evaporated with toluene. The crude product was purified by silica gel column to give 2.8 g of 4-hydroxymethyl-5-methyl-2-oxo-1,3-dioxole in 69% yield. 1H NMR (300 MHz, CDCl3): d 4.40 (s, 2H), 2.60 (broad, s, 1H), 2.20 (s, 3H).

1. customunder 20° C
2. concentrationconcentrated
3. customThe product was partitioned between H2O and EtOAc (3×)
4. dry with materialThe organic layer was dried with Na2SO4
5. concentrationconcentrated
6. customdried in vacuo
7. customto give crude formate
8. stirringThe mixture was stirred at r.t. for 5 h
9. concentrationconcentrated
10. customThe crude product was purified by silica gel column

ORD record

ord-2cbcf92d6f7a4243919b8cd6ab8b7ab6

Source dataset

uspto-grants-2013_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08586744B2