Allyl bromide → 2,4-Dichlorobenzoyl chloride

Participants

Role	Name	HCID	Charge
Reactant	Allyl bromide	HCID 7841	—
Reactant	Cesium carbonate	HCID 10796	—
Reactant	Tetrazolo(1,5-a)pyrimidine	HCID 349391	—
Reactant	2-Chloro-4-fluorobenzoyl chloride	HCID 2736546	—
Reactant	N-(1-Methylpropargyl)-2-chloro-3-(trifluoromethyl)benzamide	HCID 90409423	—
Catalyst	Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)	HCID 24350	—
Solvent	Tetrahydrofuran	HCID 8028	—
Solvent	Ethyl Acetate	HCID 8857	—
Product	2,4-Dichlorobenzoyl chloride	HCID 66645	67%

Reaction Steps

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.

Provenance & Evidence

DOI	10.6084/m9.figshare.5104873.v1
Patent number	US09066946B2
Source dataset	uspto-grants-2015_06
ORD ID	ord-e1f57e29d387476b8162e80b6fcab2a0
Source note	uspto-grants-2015_06