4-Iodoaniline → HCID 15515315, compound

HRID 1944864Notes

Reaction equation

HRID 1944864 reaction equation
I[C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][CH:3]=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C([O-])([O-])=O.[K+].[K+].[CH2:34]([OH:39])[CH2:35][CH2:36][C:37]#[CH:38]>[Pd].[Cu]I.CCOC(C)=O.O.COCCOC>[NH2:6][C:5]1[CH:7]=[CH:8][C:2]([C:38]#[C:37][CH2:36][CH2:35][CH2:34][OH:39])=[CH:3][CH:4]=1

Participants

10

Reactant 4

HCID 108934-IodoanilineHCID 11430Potassium CarbonateHCID 11776TriphenylphosphineHCID 793464-Pentyn-1-ol

Product 1

HCID 15515315HCID 15515315, compoundYield 76.1%

Reagents, catalysts & solvents 5

HCID 23938PalladiumCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 962WaterSolvent2×HCID 80711,2-DimethoxyethaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
85 °C

Procedure

4-Iodoaniline (10 g, 45 mmol), palladium on carbon (2.86 g, 1.35 mmol, 5% w/w), PPh3 (1.4 g, 5.4 mmol), CuI (513 mg, 2.7 mmol), and K2CO3 (15 g, 5.4 mmol) were added to DME (50 mL) and H2O (50 mL). The mixture is degassed while stirring by bubbling nitrogen vigorously into the solution. Pent-4-yn-1-ol (10.5 mL, 114 mmol) was added by syringe. The mixture was heated at 85° C. After cooling, water (100 mL) and EtOAc (200 mL) were added. The mixture was extracted with EtOAc. The organic layer and the water layer were independently neutralized with 1N HCl. The aqueous layer was extracted with EtOAc and the combined organic layers dried over MgSO4. The material was concentrated by rotary evaporation and the oil was purified by chromatography (gradient 10-100% EtOAc/Hex) to give the title compound as a dark oil (6 g, 76%). 1H NMR (400 MHz, CDCl3) δ 7.19 (dd, 2H, J=8.9, 1.5 Hz), 6.58 (dd, 2H, J=8.9, 1.5 Hz), 3.85 (t, 2H, J=8.0 Hz), 3.75 (brs, 2H), 2.55 (t, 2H, J=8.0 Hz), 1.86 (m, 2H); ES/MS calcd. for C11H14NO+ 176.1. Found m/z=176.1 (M+H)+.

Workup

  1. customThe mixture is degassed
  2. customby bubbling nitrogen vigorously into the solution
  3. temperatureAfter cooling
  4. extractionThe mixture was extracted with EtOAc
  5. extractionThe aqueous layer was extracted with EtOAc
  6. dry with materialthe combined organic layers dried over MgSO4
  7. concentrationThe material was concentrated by rotary evaporation
  8. customthe oil was purified by chromatography (gradient 10-100% EtOAc/Hex)

Sources & evidence

ORD record
ord-ff149ab1188b4ea39c88f7733c10b4b2
Source dataset
uspto-grants-2013_03
Patent number
US08394829B2

Reaction notes

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