Potassium Phosphate, Tribasic → 4-(5-Amino-pyridin-3-yl)-2-chloro-benzonitrile

HRID 1897750Notes

Reaction equation

HRID 1897750 reaction equation
[Cl:1][C:2]1[CH:9]=[C:8](B2OC(C)(C)C(C)(C)O2)[CH:7]=[CH:6][C:3]=1[C:4]#[N:5].Br[C:20]1[CH:21]=[C:22]([NH2:26])[CH:23]=[N:24][CH:25]=1.COC1C=CC=C(OC)C=1C1C=CC=CC=1P(C1CCCCC1)C1CCCCC1.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[NH2:26][C:22]1[CH:21]=[C:20]([C:8]2[CH:7]=[CH:6][C:3]([C:4]#[N:5])=[C:2]([Cl:1])[CH:9]=2)[CH:25]=[N:24][CH:23]=1

Participants

7

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 8176813-Amino-5-bromopyridineHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylHCID 579261132-Chloro-4-(tetramethyl-1,3,2-dioxaborolan-2-yl)benzonitrile

Product 1

HCID 595783904-(5-Amino-pyridin-3-yl)-2-chloro-benzonitrileYield 43.5%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
95 °C

Procedure

(General Suzuki reaction procedure 1) A mixture of 2-chloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzonitrile (1.32 g, 5 mmol), 5-Bromo-pyridin-3-ylamine (865 mg, 5 mmol), s-PHOS (103 mg, 0.25 mmol), potassium phosphate (2.12 g, 10 mmol) and Pd2(dba)3 (41.2 mg, 0.1 mmol) in toluene (20 mL) was heated to 95° C. overnight (18 h). After filtration and concentration, the residue was dissolved into CH2Cl2 and mixed with celite. After concentration, the residue was loaded to column (MeOH—CH2Cl2, v/v, 1%-3.5%) and resulted in a light brown solid (500 mg). 1HNMR (400 MHz, CDCl3): δ 4.82 (brs, 2H), 7.11 (t, J=2 Hz, 1H), 7.55 (dd, J=2 Hz, 8 Hz, 1H), 7.69 (d, J=2 Hz, 1H), 7.75 (d, J=8 Hz, 1H), 8.16 (d, J=2 Hz, 1H), 8.22 (d, J=2 Hz, 1H).

Workup

  1. custom(General Suzuki reaction procedure 1)
  2. filtrationAfter filtration and concentration
  3. dissolutionthe residue was dissolved into CH2Cl2
  4. additionmixed with celite
  5. concentrationAfter concentration

Sources & evidence

ORD record
ord-c5811addf95b49e5a44a0fc7751d2929
Source dataset
uspto-grants-2013_08
Patent number
US08519142B2

Reaction notes

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