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

HRID 2078274Notes

Reaction equation

HRID 2078274 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

6

Reactant 2

HCID 109209723,3,3-Triethoxyprop-1-yneHCID 510000721-Bromo-4-chloro-2-iodobenzene

Product 1

HCID 670999201-Bromo-4-chloro-2-(3,3,3-triethoxyprop-1-ynyl)benzeneYield 91%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6342AcetonitrileSolvent

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

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

Sources & evidence

ORD record
ord-ec212661b9774c72b6262e9d9d386b78
Source dataset
uspto-grants-2011_04
Patent number
US07928139B2

Reaction notes

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