Allyl bromide → 2,4-Dichlorobenzoyl chloride

To the suspension of Intermediate 233 (138 mg, 0.5 mmol, 1.0 equiv), tetrazolo[1,5-a]pyrimidine (Intermediate 234) (67 mg, 0.55 mmol, 1.1 equiv.), allyl bromide (73 mg, 0.6 mmol, 1.2 equiv.) and Cs2CO3(0.49 g, 1.5 mmol, 3.0 equiv.) in THF (2 mL), CuI (48 mg, 0.25 mmol, 0.5 equiv.) was added at room temperature in one portion under N2. The reaction mixture was then stirred at room temperature under N2 for 16 hours. Celite and EtOAc (5 mL) were added and the suspension was stirred for 20 minutes. The insoluble solid was filtered off and washed with EtOAc. The filtrate solution was washed with brine, dried over Na2SO4 and concentrated. The crude product was purified by column chromatography with EtOAc/hexanes as eluents to afford compound Intermediate 235 (146 mg, 0.34 mmol, 67% yield) as a white solid. Byproducts Intermediate 236 (30 mg, 0.075 mmol, 15% yield) and Intermediate 237 (2% yield) were also isolated.

1. additionwas added at room temperature in one portion under N2
2. stirringthe suspension was stirred for 20 minutes
3. filtrationThe insoluble solid was filtered off
4. washwashed with EtOAc
5. washThe filtrate solution was washed with brine
6. dry with materialdried over Na2SO4
7. concentrationconcentrated
8. customThe crude product was purified by column chromatography with EtOAc/hexanes as eluents

ORD-Eintrag

ord-e1f57e29d387476b8162e80b6fcab2a0

Quelldatensatz

uspto-grants-2015_06

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US09066946B2