Potassium Carbonate → HCID 66745967, compound

HRID 1467003Notes

Reaction equation

HRID 1467003 reaction equation
[NH2:1][C:2]1[CH:9]=[CH:8][CH:7]=[C:6](Br)[C:3]=1[C:4]#[N:5].[CH3:11][C:12]([CH3:16])([CH3:15])[C:13]#[CH:14].C([O-])([O-])=O.[K+].[K+]>COCCOC.O.[Cu]I.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[NH2:1][C:2]1[CH:9]=[CH:8][CH:7]=[C:6]([C:14]#[C:13][C:12]([CH3:16])([CH3:15])[CH3:11])[C:3]=1[C:4]#[N:5]

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 135123,3-Dimethyl-1-butyneHCID 98130382-Amino-6-bromobenzonitrile

Product 1

HCID 66745967HCID 66745967, compoundYield 93%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 18180031Water 1,2-dimethoxyethaneSolvent

Procedure

To a solution of 2-amino-6-bromobenzonitrile (1.97 g, 10.0 mmol), 3,3-dimethylbut-1-yne (2.46 g, 30 mmol), K2CO3 (2.76 g, 20.0 mmol), and CuI (191 mg, 0.1 mmol) in DME/H2O (4:1, 50 mL) was added Pd(PPh3)4 (1.16 g, 0.1 mmol) at room temperature under nitrogen. The reaction mixture was refluxed under nitrogen overnight. After it was cooled down to room temperature, the reaction was quenched with brine, extracted with EtOAc. The organic layer was washed with brine, dried over Na2SO4, and concentrated. The residue was purified by chromatography on silica gel eluting with 20% EtOAc in hexanes to give the title compound as a light brown oil (1.84 g, 93%). 1H NMR (400 MHz, DMSO-d6) δ 1.27 (s, 9H), 6.10 (s, 2H), 6.59 (d, J=7.2 Hz, 1H), 6.71 (d, J=8.0 Hz, 1H), 7.18-7.22 (m, 1H). MS 199 (MH+).

Workup

  1. temperatureThe reaction mixture was refluxed under nitrogen overnight
  2. customthe reaction was quenched with brine
  3. extractionextracted with EtOAc
  4. washThe organic layer was washed with brine
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated
  7. customThe residue was purified by chromatography on silica gel eluting with 20% EtOAc in hexanes

Sources & evidence

ORD record
ord-cf8c7596f8b64113ac056c5175adc74d
Source dataset
uspto-grants-2015_04
Patent number
US09000054B2

Reaction notes

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