Ammonia → 1-(2-Bromo-4-chlorophenyl)ethanamine

Stir a mixture of 1-(2-bromo-4-chlorophenyl)ethanol (2.33 g, 10 mmol), titanium isopropoxide (6 mL, 20 mmol) and ammonia in ethanol (25 mL, 50 mmol) under N2 at ambient temperature for 6 h. Add sodium tetrahydroborate (0.6 g, 15 mmol) and stir the mixture for 3 h. Quench the reaction with ammonia hydroxide (2 N, 25 mL). Remove the insolubles by filtration. Extract the aqueous layer with ethyl acetate. Combine the organic layers and extract with an HCl solution (1 N, 30 mL). Wash the aqueous layer with ethyl acetate and then treat with a NaOH (2 N) solution to pH 10-12. Extract the aqueous layer with ethyl acetate (50 mL×3). Combine the organic layers and wash with aqueous saturated sodium chloride. Dry over magnesium sulfate. Remove the organic solvent to give the title compound (1.5 g, 64%). MS (ES) m/z 236 [M+1]+.

1. customQuench
2. customthe reaction with ammonia hydroxide (2 N, 25 mL)
3. customRemove the insolubles
4. filtrationby filtration
5. extractionExtract the aqueous layer with ethyl acetate
6. extractionextract with an HCl solution (1 N, 30 mL)
7. washWash the aqueous layer with ethyl acetate
8. additiontreat with a NaOH (2 N) solution to pH 10-12
9. extractionExtract the aqueous layer with ethyl acetate (50 mL×3)
10. washCombine the organic layers and wash with aqueous saturated sodium chloride
11. dry with materialDry over magnesium sulfate
12. customRemove the organic solvent

ORD record

ord-e6ae771da49b4965b279102c9fa0442c

Source dataset

uspto-grants-2011_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08063035B2