Acetic Acid → (2,2-Dimethyl-5-oxo-[1,3]dioxolan-4-ylidene)-acetic acid

The crude (Z)-2,2-dimethyl-5-(tert-butyldimethylsilyloxycarbonyl-methylene)-1,3-dioxolan-4-one (72.4 mmol) in tetrahydrofuran (50 ml) was treated at 22° C. with acetic acid (13 ml, 0.227 mmol) followed by 73 ml (73.0 mmol) of a 1M solution of tetrabutylammonium fluoride in tetrahydrofuran. After 1 h at 22° C., the reaction mixture was diluted with ethyl acetate (500 ml), washed with water, brine and dried (anhydrous magnesium sulfate). Evaporation of the solvent under reduced pressure and trituration of the residual solid with toluene (50 ml) gave 7.70 g (62% yield for 3 steps) of the title Z-isomer as a white crystalline solid. Concentration of the mother liquors yielded another 0.2 g of a 75:25 mixture of Z and E isomers. Z-Isomer; 1H NMR (400 MHz, CDCl3) δ: 1.78 (s, 3), 5.89 (s, 1). E-Isomer: 1H NMR (400 MHz, CDCl3) δ: 1.80 (s, 3), 6.03 (s, 1).

1. washwashed with water, brine
2. dry with materialdried (anhydrous magnesium sulfate)
3. customEvaporation of the solvent under reduced pressure and trituration of the residual solid with toluene (50 ml)
4. customgave 7.70 g (62% yield for 3 steps) of the title Z-isomer as a white crystalline solid
5. customConcentration of the mother liquors yielded
6. additionanother 0.2 g of a 75:25 mixture of Z and E isomers

ORD record

ord-9f0609e0498141999d985e4feecea655

Source dataset

uspto-grants-2006_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07109186B2