Potassium Carbonate → HCID 66929695, compound

HRID 1942566Notes

Reaction equation

HRID 1942566 reaction equation
[NH2:1][C:2]1[N:6]([C:7]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=2[CH3:15])=[O:8])[N:5]=[C:4]([NH:16][C:17]2[CH:22]=[CH:21][CH:20]=[C:19]([OH:23])[CH:18]=2)[N:3]=1.C([O-])([O-])=O.[K+].[K+].Br[CH2:31][C:32]#[N:33]>CC(=O)CC>[NH2:1][C:2]1[N:6]([C:7]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=2[CH3:15])=[O:8])[N:5]=[C:4]([NH:16][C:17]2[CH:22]=[CH:21][CH:20]=[C:19]([O:23][CH2:31][C:32]#[N:33])[CH:18]=2)[N:3]=1

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 11534BromoacetonitrileHCID 16051417HCID 16051417, compound

Product 1

HCID 66929695HCID 66929695, compoundYield 35%

Reagents, catalysts & solvents 1

HCID 6569Methyl Ethyl KetoneSolvent

Conditions

Temperature
75 °C

Procedure

In particular, to a solution of 5-amino-3-[3-(hydroxy)phenylamino]-1-(2-(methyl)phenyl)carbonyl-1H-1,2,4-triazole (Ia-6) (0.23 g, 0.75 mmol) in 2-butanone (3 mL) was added K2CO3 (0.11 g, 0.83 mmol) and BrCH2CN (0.10 g, 0.83 mmol). After stirring the mixture at 75° C. for 20 h, the 2-butanone was removed under reduced pressure. The residue was dissolved in EtOAc (50 mL), washed with water (50 mL), brine (30 mL), dried (Na2SO4) and concentrated to afford the crude product. Purification by flash chromatography (1:1 hexanes/EtOAc) gave 5-amino-3-[3-(cyanomethoxy)phenylamino]-1-(2-(methyl)phenyl)carbonyl-1H-1,2,4-triazole (Ia-8) (0.09 g, 35%) as a white solid: Rf 0.29 (1:1 hexanes/ethyl acetate); mp (DSC) 204.5-207.9° C.; 1H NMR (300 MHz, DMSO-d6) δ 9.43 (s, 1H), 7.84 (s, 2H), 7.56 (d, J=7.6 Hz, 1H), 7.46-7.41 (m, 1H), 7.35-7.22 (m, 3H), 7.11 (t, J=8.1 Hz, 1H), 6.96-6.93 (m, 1H), 6.48 (dd, J=8.0, 2.2 Hz, 1H), 4.80 (s, 2H), 2.31 (s, 3H); 13C NMR (75 MHz, DMSO-d6) δ 168.8, 158.5, 157.0, 156.9, 142.7, 135.5, 134.7, 130.5, 130.4, 129.8, 128.1, 125.5, 116.7, 111.2, 106.3, 103.3, 53.3, 19.5; IR (ATR) 3448, 3368, 2325, 1689 cm−1; APCI MS m/z 349 [C18H16N6O2+H]+; HPLC (Method A) 91.3% (AUC), tR=12.46 min.

Workup

  1. customthe 2-butanone was removed under reduced pressure
  2. dissolutionThe residue was dissolved in EtOAc (50 mL)
  3. washwashed with water (50 mL), brine (30 mL)
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated
  6. customto afford the crude product
  7. customPurification by flash chromatography (1:1 hexanes/EtOAc)

Sources & evidence

ORD record
ord-268a3934aa0b40f5bc12501095aeb97c
Source dataset
uspto-grants-2013_03
Patent number
US08389557B2

Reaction notes

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