Bromine → HCID 13784978, compound

Temperature

45 °C

To a mixture of 157.1 g (0.50 mol.) of methyl 2-phenylthio-5-propionylphenylacetate, 133.2 g (1.255 mol) of methyl orthoformate, 200 ml of methanol and 100 ml of ethylene tetrachloride was added 2.62 g (0.040 gram atom) of zinc powder, and the mixture was heated under stirring to a temperature of 40° to 45° C. To the solution was dropped 83.6 g (0.525 mol.) of bromine for 1 hour under stirring, and then the temperature was maintained at a temperature within 42° C. and 45° C. for 30 minutes. The reaction mixture was gradually heated to raise the external temperature to 120° C., under distilling off materials having a low boiling point (b.p. 32° to 65° C.). When almost all materials having a low boiling point were distilled off and the internal temperature almost lowered to approx. 80° C., to the reaction mixture was added 100 ml of ethylene tetrachloride. Then, the mixture was again heated to raise the internal temperature to a temperature of higher than 100° C., under distilling off remaining materials having a low boiling point. After the internal temperature was kept at a temperature of 100° to 110° C. for 1 hour, the reaction mixture was cooled to approx. 50° C. To the cooled reaction mixture was added 500 ml of water, and the mixture was stirred for a while. Insoluble materials were filtered off over a Celite and then was washed with three portions of 50 ml of 1,2-dichloroethane. The organic layer was separated from the filtrate and the washings. The aqueous layer was extracted with 150 ml of 1,2-dichloroethane. The extract was combined with the above-obtained organic layer and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and then the residue was distilled under reduced pressure to obtain 141 g of the desired product as a yellow oil (yield 82%).

1. temperaturethe mixture was heated
2. stirringunder stirring
3. temperatureThe reaction mixture was gradually heated
4. temperatureto raise the external temperature to 120° C.
5. distillationunder distilling off materials
6. distillationwere distilled off
7. customalmost lowered to approx. 80° C., to the reaction mixture
8. additionwas added 100 ml of ethylene tetrachloride
9. temperatureThen, the mixture was again heated
10. temperatureto raise the internal temperature to a temperature of higher than 100° C.
11. distillationunder distilling off
12. temperaturethe reaction mixture was cooled to approx. 50° C
13. customTo the cooled reaction mixture
14. stirringthe mixture was stirred for a while
15. filtrationInsoluble materials were filtered off over a Celite
16. washwas washed with three portions of 50 ml of 1,2-dichloroethane
17. customThe organic layer was separated from the filtrate
18. extractionThe aqueous layer was extracted with 150 ml of 1,2-dichloroethane
19. dry with materialdried over anhydrous sodium sulfate
20. distillationThe solvent was distilled off under reduced pressure
21. distillationthe residue was distilled under reduced pressure

ORD record

ord-d34072405fde408e9f00767eba94c1e4

Source dataset

uspto-grants-1990_01

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04891433