Benzoic Acid → Acetamide, 2-(benzoyloxy)-

In the reaction vessel, 4.3 grams (0.09 mole) of a 50% suspension of sodium hydride in mineral oil was washed with two portions of 50 ml each of hexane, then two portions of 50 ml each of toluene. Dry toluene, 75 ml, was added and with stirring a solution of 10.0 grams (0.082 mole) of benzoic acid in 200 ml of dry toluene was added dropwise. The exothermic reaction caused the temperature of the reaction mixture to rise from 27° to 32°. Upon completion of the addition, the reaction mixture was heated under reflux for 1.5 hour. The mixture was cooled to ambient temperature and 8.4 grams (0.09 mole) of 2-chloroacetamide was added in portions. Upon completion of the addition, the reaction mixture was heated under reflux for 18 hours. An additional 150 ml of dry toluene was added and heating under reflux continued an additional 24 hours. The reaction mixture was cooled to ambient temperature and a solid precipitate collected by filtration. The filtrate was extracted with two portions of 200 ml each of water. The milky organic layer was dried twice with sodium sulfate and filtered. the filtrate was evaporated under reduced pressure to a solid residue, which produced bubbling in the presence of aqueous saturated sodium bicarbonate solution, and was concluded to be unreacted benzoic acid. The solid collected by filtration from the original reaction mixture was dissolved in 200 ml of ethyl acetate and washed with two portions of 100 ml each of water. The organic layer was dried with sodium sulfate and filtered. The filtrate was evaporated under reduced pressure to a solid residue. The solid was recrystallized from toluene to give 3.7 grams of (aminocarbonyl)methyl benzoate; mp 118°-120 . The ir and the nmr spectra were consistent with the proposed structure.

1. washIn the reaction vessel, 4.3 grams (0.09 mole) of a 50% suspension of sodium hydride in mineral oil was washed with two portions of 50 ml each of hexane
2. additionDry toluene, 75 ml, was added
3. additionwas added dropwise
4. customThe exothermic reaction
5. customto rise from 27° to 32°
6. additionUpon completion of the addition
7. temperaturethe reaction mixture was heated
8. temperatureunder reflux for 1.5 hour
9. additionUpon completion of the addition
10. temperaturethe reaction mixture was heated
11. temperatureunder reflux for 18 hours
12. temperatureheating
13. temperatureunder reflux
14. temperatureThe reaction mixture was cooled to ambient temperature
15. filtrationa solid precipitate collected by filtration
16. extractionThe filtrate was extracted with two portions of 200 ml each of water
17. dry with materialThe milky organic layer was dried twice with sodium sulfate
18. filtrationfiltered
19. customthe filtrate was evaporated under reduced pressure to a solid residue, which
20. customproduced
21. custombubbling in the presence of aqueous saturated sodium bicarbonate solution
22. filtrationThe solid collected by filtration from the original reaction mixture
23. dissolutionwas dissolved in 200 ml of ethyl acetate
24. washwashed with two portions of 100 ml each of water
25. dry with materialThe organic layer was dried with sodium sulfate
26. filtrationfiltered
27. customThe filtrate was evaporated under reduced pressure to a solid residue
28. customThe solid was recrystallized from toluene

ORD record

ord-ada208d62d204e5f9a5b808429152ec8

Source dataset

uspto-grants-1982_01

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04309566