2-Bromobenzonitrile → HCID 18963827, compound

HRID 2226840Notes

Reaction equation

[CH2:1]([Li])[CH2:2][CH2:3][CH3:4].Br[C:7]1[CH:14]=[CH:13][CH:12]=[CH:11][C:8]=1[C:9]#[N:10]>O1CCCC1.[Cl-].[Zn+2].[Cl-].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Pd]>[CH3:4][C:3]1[CH:13]=[CH:12][CH:11]=[C:1]2[C:2]=1[CH:14]=[CH:7][CH:8]=[C:9]2[C:7]1[CH:14]=[CH:13][CH:12]=[CH:11][C:8]=1[C:9]#[N:10]

Participants

Conditions

Temperature: -78 °C

Procedure

The title D compound (1.99 g, 9.00 mmol) was dissolved in 10 mL of freshly distilled tetrahydrofuran, cooled to -78° C. and n-butyllithium (2.23M in hexane, 4.24 mL, 9.45 mmol) was added dropwise over 10 minutes. Upon complete addition the reaction was cloudy, bright yellow. After stirring 40 minutes, zinc chloride (1.0M in ether, 9.45 mL, 9.45 mmol) was added and the reaction mixture turned to clear pale yellow. The reaction was stirred 30 minutes, then the cold bath was removed and the reaction stirred an additional 30 minutes before 2-bromobenzonitrile (1.64 g, 9.45 mmol) and tetrakis(triphenylphosphine)palladium(O) (520 mg, 0.45 mmol) were added. After stirring 22 hours at 55° C., the reaction mixture was adsorbed on 10 g of silica gel and purified by flash chromatography (170 g silica gel; 30% toluene, hexane) to yield 1.31 g (60%) of the product as a white solid.

Workup

additionUpon complete addition the reaction
stirringThe reaction was stirred 30 minutes
customthe cold bath was removed
additionwere added
stirringAfter stirring 22 hours at 55° C.
custompurified by flash chromatography (170 g silica gel; 30% toluene, hexane)

Sources & evidence

ORD record: ord-700b42dd6ae54680b2dccba366454f52
Source dataset: uspto-grants-1994_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05350752

Reaction notes

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