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

HRID 2078234Notes

Reaction equation

HRID 2078234 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 65.7%

Reagents, catalysts & solvents 3

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

Procedure

A mixture of 1-bromo-4-chloro-2-iodobenzene (10 g, 32 mmol) in 100 mL degassed ACN and TEA (29 g, 284 mmol), was treated with 3,3,3-triethoxyprop-1-yne (6.0 g, 35 mmol), copper(I) iodide (0.60 g, 3.2 mmol), and dichlorobis(triphenylphosphine)palladium(II) (1.1 g, 1.6 mmol). The mixture was stirred at room temperature for 2 hours at room temperature (the mixture turned dark green after 5 minutes). TLC showed that all starting material was converted, and a new spot was produced. The mixture was concentrated in vacuo. The residue was diluted with 100 mL ether, washed with H2O (2×20 mL), 5% ammonia water (2×20 mL), brine (20 mL), dried over anhydrous Na2SO4, and concentrated in vacuo. The crude product was purified by column chromatography pretreated with TEA and eluted with 0-15% EtOAc/hexane to give 7.6 g of the product as a pale yellow oil. The oil solidified after it was stored in the refrigerator.

Workup

  1. waitturned dark green after 5 minutes
  2. customa new spot was produced
  3. concentrationThe mixture was concentrated in vacuo
  4. additionThe residue was diluted with 100 mL ether
  5. washwashed with H2O (2×20 mL), 5% ammonia water (2×20 mL), brine (20 mL)
  6. dry with materialdried over anhydrous Na2SO4
  7. concentrationconcentrated in vacuo
  8. customThe crude product was purified by column chromatography
  9. washeluted with 0-15% EtOAc/hexane

Sources & evidence

ORD record
ord-1de7f479e06f433a9dca27d3362fa019
Source dataset
uspto-grants-2011_04
Patent number
US07928139B2

Reaction notes

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