3,3,3-Triethoxyprop-1-yne → 1-Bromo-4-chloro-2-(3,3,3-triethoxyprop-1-ynyl)benzene

HRID 1868866Notes

Reaction equation

[Br:1][C:2]1[CH:7]=[CH:6][C:5]([Cl:8])=[CH:4][C:3]=1I.[CH2:10]([O:12][C:13]([O:19][CH2:20][CH3:21])([O:16][CH2:17][CH3:18])[C:14]#[CH:15])[CH3:11]>[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C(#N)C>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([Cl:8])=[CH:4][C:3]=1[C:15]#[C:14][C:13]([O:16][CH2:17][CH3:18])([O:12][CH2:10][CH3:11])[O:19][CH2:20][CH3:21]

Participants

Conditions

Temperature: 23 °C

Procedure

A suspension of 1-bromo-4-chloro-2-iodobenzene (2.5 g, 7.9 mmol), 3,3,3-triethoxyprop-1-yne (2.4 g, 13.9 mmol), copper(I) iodide, (455 mg, 2.3 mmol), and trans-dichlorobis(triphenylphosphine)palladium(II) (559 mg, 0.79 mmol) was treated with ACN (30 mL). The reaction was capped, evacuated under vacuum, backfilled with argon, and treated with TEA (9.9 mL, 71.6 mmol). The reaction was stirred at 23° C. After 2 hours, the reaction mixture was concentrated in vacuo to remove all solvents, diluted with EtOAc (250 mL), and washed with brine (150 mL). The organic layer was dried over MgSO4, concentrated in vacuo, and purified by silica gel chromatography (eluant: 4% EtOAc/hexane+1% TEA) affording 2.6 g of 1-bromo-4-chloro-2-(3,3,3-triethoxyprop-1-ynyl)benzene.

Workup

customThe reaction was capped
customevacuated under vacuum
concentrationthe reaction mixture was concentrated in vacuo
customto remove all solvents
additiondiluted with EtOAc (250 mL)
washwashed with brine (150 mL)
dry with materialThe organic layer was dried over MgSO4
concentrationconcentrated in vacuo
custompurified by silica gel chromatography (eluant: 4% EtOAc/hexane+1% TEA)

Sources & evidence

ORD record: ord-e096124bce1a49d9ac2fb641275d2650
Source dataset: uspto-grants-2009_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07635715B2

Reaction notes

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