Nitrogen → 2-(4-Bromophenyl)thiophene-3-carbonitrile

HRID 1990065Notes

Reaction equation

HRID 1990065 reaction equation
I[C:2]1[S:3][CH:4]=[CH:5][C:6]=1[C:7]#[N:8].[Br:9][C:10]1[CH:15]=[CH:14][C:13](B(O)O)=[CH:12][CH:11]=1.C(=O)([O-])[O-].[K+].[K+].N#N>[Pd].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.O.C(O)C.C(COC)OC>[Br:9][C:10]1[CH:15]=[CH:14][C:13]([C:2]2[S:3][CH:4]=[CH:5][C:6]=2[C:7]#[N:8])=[CH:12][CH:11]=1

Participants

9

Reactant 4

HCID 947NitrogenHCID 11430Potassium CarbonateHCID 79599(4-Bromophenyl)boronic acidHCID 109773992-Iodothiophene-3-carbonitrile

Product 1

HCID 579753192-(4-Bromophenyl)thiophene-3-carbonitrile

Reagents, catalysts & solvents 4

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 702EthanolSolventHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
80 °C

Procedure

Degass a solution of 2-iodo-thiophene-3-carbonitrile (20 g, 85 mmol), 4-bromobenzeneboronic acid (18.8 g, 94 mmol), potassium carbonate (26 g, 187 mmol) and tetrakis(triphenylphosphine)-palladium (0) (10 g, 8.5 mmol) in a mixture of anhydrous dimethoxyethane (300 mL) and absolute ethanol (150 mL) with Ar or N2 for 15 min and stir for 12 hours at 80° C. Cool the reaction mixture to room temperature, add water (100 ml) and extract the crude product dichloromethane (3×150 mL). Purification by chromatography (hexane-ethyl acetate 10/1) yields 16.3 g (72%) as a white solid: 1H NMR (CDCl3): δ 7.32 (m, 2H), 7.62 (m, 4H).

Workup

  1. temperatureCool the reaction mixture to room temperature
  2. extractionextract the crude product dichloromethane (3×150 mL)
  3. customPurification by chromatography (hexane-ethyl acetate 10/1)
  4. customyields 16.3 g (72%) as a white solid

Sources & evidence

ORD record
ord-3836629298ae4afa8cc807ef58348857
Source dataset
uspto-grants-2010_01
Patent number
US07642361B2

Reaction notes

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