Dichloromethane → HCID 32578092, compound

To a suspension of 4-(acetyloxy)benzoic acid (17) (10.0 g, 55.5 mmol) in dichloromethane (200 ml) oxalyl chloride (15 ml, 172 mmol) and dimethylformamide (0.1 ml) were added. The reaction mixture was stirred at ambient temperature for 30 minutes and at reflux temperature for 1 hour. The volatiles were evaporated in vacuo, the residue was dissolved in benzene (100 ml) and the solvent was evaporated again. The procedure was repeated several times until the poignant smell disappeared after drying in vacuo. The viscous oil was dissolved in tetrahydrofuran (100 ml) and this solution slowly over 10 minutes was added to a prearranged mixture consisting of saturated NaHCO3 solution (100 ml), solid NaHCO3 (11 g), O-benzylhydroxylamine hydrochloride (9.90 g, 62 mmol), and tetrahydrofuran (150 ml). The resulting mixture was stirred at ambient temperature for 1 hour and the volume of the reaction mixture was decreased ca. twice by evaporating the mixture on vacuum rotary evaporator. The residue was extracted with ethyl acetate (3×100 ml), the combined organic extracts were successively washed with 2N HCl (100 ml), water (100 ml), brine (100 ml), and dried (Na2SO4). The solvents were evaporated and the residue was crystallized from toluene to give the title compound (14.275 g, 90%) as white crystals, m.p. 120-122° C. 1H NMR (CDCl3, HMDSO) δ: 2.30 (3H, s); 5.02 (2H, s); 7.14 (2H, d, J=8.6 Hz); 7.26-7.54 (5H, m); 7.69 (2H, d, J=8.6 Hz); 8.56 (1H, br s).

1. additionwere added
2. temperatureat reflux temperature for 1 hour
3. customThe volatiles were evaporated in vacuo
4. dissolutionthe residue was dissolved in benzene (100 ml)
5. customthe solvent was evaporated again
6. customafter drying in vacuo
7. dissolutionThe viscous oil was dissolved in tetrahydrofuran (100 ml)
8. additionthis solution slowly over 10 minutes was added to a prearranged mixture
9. stirringThe resulting mixture was stirred at ambient temperature for 1 hour
10. customby evaporating the mixture
11. customon vacuum rotary evaporator
12. extractionThe residue was extracted with ethyl acetate (3×100 ml)
13. washthe combined organic extracts were successively washed with 2N HCl (100 ml), water (100 ml), brine (100 ml)
14. dry with materialdried (Na2SO4)
15. customThe solvents were evaporated
16. customthe residue was crystallized from toluene

ORD record

ord-89cfef79fbba42cdb0ef3734dac1c6b3

Source dataset

uspto-grants-2008_12

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07465719B2