1-Iodo-4-nitrobenzene → 1-(5-Chloropent-1-yn-1-yl)-4-nitrobenzene

HRID 385258Notes

Reaction equation

HRID 385258 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=1.[Cl:11][CH2:12][CH2:13][CH2:14][C:15]#[CH:16]>O1CCCC1.C(N(CC)CC)C.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.[Cu]I>[Cl:11][CH2:12][CH2:13][CH2:14][C:15]#[C:16][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=1

Participants

7

Reactant 2

HCID 124951-Iodo-4-nitrobenzeneHCID 843081-Pentyne, 5-chloro-2×

Product 1

HCID 547714241-(5-Chloropent-1-yn-1-yl)-4-nitrobenzene

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalyst2×HCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
55 °C

Procedure

A mixture of 4-iodonitrobenzene (25 g, 100 mmol), dichlorobis(triphenylphosphine)palladium(II) (0.30 g, 0.43 mmol) and copper (I) iodide (0.18 g, 0.95 mmol) in tetrahydrofuran (300 mL) and triethylamine (150 mL) was degassed under Argon for 10 minutes. The mixture was then heated to 55° C. and treated with 5-chloropentyne (12 mL, 110 mmol) via syringe. After 30 minutes of stirring, additional quantities of dichlorobis(triphenylphosphine)palladium(II) (0.10 g) and 5-chloropentyne (1 mL) were added. After another 30 minutes of stirring, the mixture was allowed to cool to room temperature and then was filtered through a pad of Celite diatomaceous earth. The filtrate was concentrated to dryness under reduced pressure to provide 1-(5-chloropent-1-ynyl)-4-nitrobenzene, which was carried on without further purification. ES/MS calcd. for C11H11ClNO2+ 224.1. found m/z=224.2 (M+1-1)+.

Workup

  1. customwas degassed under Argon for 10 minutes
  2. stirringAfter another 30 minutes of stirring
  3. temperatureto cool to room temperature
  4. filtrationwas filtered through a pad of Celite diatomaceous earth
  5. concentrationThe filtrate was concentrated to dryness under reduced pressure

Sources & evidence

ORD record
ord-a1619f377d3e480b98988f19557d7219
Source dataset
uspto-grants-2013_02
Patent number
US08367829B2

Reaction notes

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