Ammonium Hydroxide → 2-Amino-6-(4,5-dihydrofuran-2-yl)benzonitrile

HRID 471668Notes

Reaction equation

HRID 471668 reaction equation
[NH2:1][C:2]1[CH:9]=[CH:8][CH:7]=[C:6](Br)[C:3]=1[C:4]#[N:5].[O:11]1[CH2:15][CH2:14][CH:13]=[C:12]1[Sn](C)(C)C.[Cl-].[NH4+].[OH-].[NH4+]>C1(C)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd]>[NH2:1][C:2]1[CH:9]=[CH:8][CH:7]=[C:6]([C:12]2[O:11][CH2:15][CH2:14][CH:13]=2)[C:3]=1[C:4]#[N:5]

Participants

7

Reactant 4

HCID 14923Ammonium HydroxideHCID 25517Ammonium ChlorideHCID 98130382-Amino-6-bromobenzonitrileHCID 10243055(4,5-Dihydrofuran-2-yl)trimethylstannane

Product 1

HCID 667461322-Amino-6-(4,5-dihydrofuran-2-yl)benzonitrileYield 68%

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 1140TolueneSolvent

Procedure

2-Amino-6-bromobenzonitrile (0.75 g, 3.81 mmol), (4,5-dihydrofuran-2-yl)trimethylstannane (Menez, P.; Fargeas, V.; Poisson, J.; Ardisson, J.; Lallemand, J.-Y.; Pancrazi, A. Tetrahedron Letters 1994, 35(42), 7767) (1.02 g, 4.38 mmol), and palladium tetrakis(triphenylphosphine) (0.33 g, 0.28 mmol) were refluxed in toluene (10.0 mL) under nitrogen for 1.5 h. Saturated ammonium chloride (12 mL) and ammonium hydroxide (4 mL) were added, and the mixture was extracted with EtOAc. The organic layer was concentrated under vacuum and the residue was purified by chromatography on silica using 35% EtOAc/hexanes to give 0.48 g (68%) of the title compound as yellow oil. 1H NMR (400 MHz, Acetone-d6) δ 2.78-2.83 (m, 2H), 4.40 (t, J=9.2 Hz, 2H), 5.76 (t, J=3.2 Hz, 1H), 6.04 (s, 2H), 6.77-6.80 (m, 2H), 7.28 (t, J=8.0 Hz, 1H). MS 187 (MH+).

Workup

  1. extractionthe mixture was extracted with EtOAc
  2. concentrationThe organic layer was concentrated under vacuum
  3. customthe residue was purified by chromatography on silica using 35% EtOAc/hexanes

Sources & evidence

ORD record
ord-7b08581b4034451f9de06ddc8a4964a4
Source dataset
uspto-grants-2014_01
Patent number
US08633186B2

Reaction notes

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