Pyridine → HCID 13192517, compound

Under an argon atmosphere a stirred solution of 8.8 grams (0.044 mole) of N-(2-bromophenylmethyl)hydroxylamine and 12.0 grams (0.152 mole) of pyridine in 200 ml of methylene chloride was cooled to -10°. The reaction vessel was fitted with a septum and 5.2 grams (0.048 mole) of trimethylchlorosilane was added in small portions from a hypodermic syringe. Upon completion of addition the reaction mixture was stirred at -10° for 30 minutes, then allowed to warm to 0°. At this temperature a solution of 6.7 grams (0.044 mole) of 3-chloro-2,2-dimethylpropionyl chloride (prepared in the manner of Example 1, Step B) in 5 ml of methylene chloride was added dropwise over a 20-minute period. Upon completion of addition the reaction mixture was allowed to warm to ambient temperature where it was stirred for 18 hours. The reaction mixture was poured into a separatory funnel and diluted with 50 ml of methylene chloride. The mixture was washed with 50 ml of water, 50 ml of an aqueous solution saturated with sodium chloride, two portions of 100 ml each of a solution consisting of 1:1--aqueous saturated sodium chloride solution:aqueous 10% hydrochloric acid solution, and finally 50 ml of an aqueous solution saturated with sodium chloride. The organic layer was dried with magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to give a semi-solid residue. The semi-solid was slurried in 15 ml of hexane. The insoluble material was collected by filtration and recrystallized twice from hexane/ethyl acetate to give 5.7 grams of N-(2-bromophenyl)methyl-3-chloro-N-hydroxy-2,2-dimethylpropanamide; mp 119°-121°.

1. additionwas added in small portions from a hypodermic syringe
2. additionUpon completion of addition the reaction mixture
3. temperatureto warm to 0°
4. additionwas added dropwise over a 20-minute period
5. additionUpon completion of addition the reaction mixture
6. stirringwas stirred for 18 hours
7. additionThe reaction mixture was poured into a separatory funnel
8. washThe mixture was washed with 50 ml of water, 50 ml of an aqueous solution saturated with sodium chloride, two portions of 100 ml each of a solution
9. dry with materialThe organic layer was dried with magnesium sulfate
10. filtrationfiltered
11. concentrationThe filtrate was concentrated under reduced pressure
12. customto give a semi-solid residue
13. filtrationThe insoluble material was collected by filtration
14. customrecrystallized twice from hexane/ethyl acetate

ORD record

ord-b26090a8ccbf4e50bcd504879ea498aa

Source dataset

uspto-grants-1983_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04405357