Allyl bromide → HCID 59315615, compound

To a stirred suspension of zinc (70.8 mmol, 4.63 g, <10 micron) in tetrahydrofuran (35 mL) under nitrogen was added allyl bromide (70.8 mmol, 6.16 mL, 8.57 g) over 1 minute at room temperature. There was a moderate exotherm and the resultant grey suspension was stirred for 1.5 h then cooled in an ice/brine bath. A solution of (S,E)-2-(2-bromobenzylideneamino)-2-phenylethanol (compound 1; 23.60 mmol, 7.18 g) in tetra-hydrofuran (20 mL) was added dropwise over 30 minutes and stirred 10 minutes at 0° C. The bath was replaced with a 25° C. water bath and the grey suspension was stirred for 30 minutes at room temperature then quenched by addition of water, in one portion (50 mL). Methylene chloride (100 mL) was added and the mixture stirred for 1 h then to this mixture was added saturated sodium hydrogen carbonate (50 mL). The mixture was filtered through dicalite and layers separated. The separated aqueous layer was extracted further with methylene chloride and the organic extracts dried over sodium sulfate and evaporated to a pale yellow oil which was purified on 200 g silica pad using ethyl acetate/heptane (10-30%) to give pure (S)-2-((S)-1-(2-bromophenyl)but-3-enylamino)-2-phenylethanol (4.52 g), MS (ES): m/z [M+H]+ 346 and 348.

1. temperaturethen cooled in an ice/brine bath
2. stirringstirred 10 minutes at 0° C
3. customwas replaced with a 25° C.
4. stirringthe grey suspension was stirred for 30 minutes at room temperature
5. customthen quenched by addition of water, in one portion (50 mL)
6. additionMethylene chloride (100 mL) was added
7. stirringthe mixture stirred for 1 h
8. additionto this mixture was added saturated sodium hydrogen carbonate (50 mL)
9. filtrationThe mixture was filtered through dicalite and layers
10. customseparated
11. extractionThe separated aqueous layer was extracted further with methylene chloride
12. dry with materialthe organic extracts dried over sodium sulfate
13. customevaporated to a pale yellow oil which
14. customwas purified on 200 g silica pad

ORD record

ord-04718edbf3224d409e89b16e32cec6b1

Source dataset

uspto-grants-2012_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08188123B2