Cyclohexene → HCID 16051413, compound

HRID 1942568Notes

Reaction equation

HRID 1942568 reaction equation
[NH2:1][C:2]1[N:6]([C:7]([C:9]2[CH:14]=[CH:13][C:12]([CH3:15])=[CH:11][CH:10]=2)=[O:8])[N:5]=[C:4]([NH:16][C:17]2[CH:22]=[CH:21][CH:20]=[C:19]([O:23]CC3C=CC=CC=3)[CH:18]=2)[N:3]=1.C1CCCCC=1>C1COCC1.[Pd]>[NH2:1][C:2]1[N:6]([C:7]([C:9]2[CH:14]=[CH:13][C:12]([CH3:15])=[CH:11][CH:10]=2)=[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

Participants

5

Reactant 2

HCID 8079CyclohexeneHCID 16051414HCID 16051414, compound

Product 1

HCID 16051413HCID 16051413, compoundYield 14%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
90 °C

Procedure

To a solution of 5-amino-3-[3-(benzyloxy)phenylamino]-1-(4-(methyl)phenyl)carbonyl-1H-1,2,4-triazole (Ia-14) (0.50 g, 1.3 mmol) in THF (20 mL) was added cyclohexene (10 mL) and 10% Pd/C (0.10 g). The reaction was stirred at 90° C. under N2 for 48 h, then filtered through diatomaceous earth, washing with THF, and concentrated to give a yellow-orange solid. Purification by flash chromatography (95:5 CH2Cl2/CH3OH) followed by triturated in CH2Cl2 afforded 5-amino-3-[3-(hydroxy)phenylamino]-1-(4-(methyl)phenyl)carbonyl-1H-1,2,4-triazole (Ia-15) (0.05 g, 14%) as a yellow solid: Rf 0.22 (95:5 CH2Cl2/CH3OH); mp (DSC) 2 endothermic events, 214.7-217.5° C., 322.1-329.8° C., 1 exothermic event, 226.8-228.8° C.; 1H NMR (300 MHz, DMSO-d6) δ 9.14 (d, J=8.1 Hz, 2H), 8.13 (d, J=8.2 Hz, 2H), 7.77 (s, 2H), 7.36 (d, J=8.1 Hz, 2H), 6.99-6.94 (m, 3H), 6.29-6.25 (m, 1H), 2.45 (s, 3H); 13C NMR (75 MHz, DMSO-d6) δ 166.2, 158.2, 157.6, 157.3, 142.9, 142.0, 130.6, 129.7, 129.1, 128.5, 107.8, 107.4, 104.0, 21.0; IR (ATR) 3363, 1668 cm−1; APCI MS m/z 310 [C16H15N5O2+H]+; HPLC (Method A) 96.9% (AUC), tR=11.5 min. Anal. Calcd for C16H16N6O2.0.50H2O: C, 60.47; H, 4.92; N, 22.03. Found: C, 60.87; H, 4.65; N, 21.75.

Workup

  1. filtrationfiltered through diatomaceous earth
  2. washwashing with THF
  3. concentrationconcentrated
  4. customto give a yellow-orange solid
  5. customPurification by flash chromatography (95:5 CH2Cl2/CH3OH)
  6. customby triturated in CH2Cl2

Sources & evidence

ORD record
ord-bf39c387cce94185bd4697683989b8be
Source dataset
uspto-grants-2013_03
Patent number
US08389557B2

Reaction notes

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