Dimethyl Sulfoxide → HCID 136337151, compound

HRID 520213Notes

Reaction equation

HRID 520213 reaction equation
[Cl-].[OH:2][NH3+:3].[C:4](=[O:7])([O-])O.[Na+].[CH3:9]S(C)=O.C([O:16][CH2:17][C:18]([O:21][C:22]1[CH:27]=[CH:26][C:25]([N:28]2[C:33](=[O:34])[C:32]([CH2:35][C:36]3[CH:41]=[CH:40][C:39]([C:42]4[CH:47]=[CH:46][CH:45]=[CH:44][C:43]=4[C:48]#[N:49])=[CH:38][CH:37]=3)=[C:31]([CH2:50][CH2:51][CH3:52])[N:30]3[N:53]=[CH:54]N=[C:29]23)=[CH:24][CH:23]=1)([CH3:20])[CH3:19])(=O)C>C(OCC)(=O)C>[OH:16][CH2:17][C:18]([CH3:19])([CH3:20])[O:21][C:22]1[CH:23]=[CH:24][C:25]([N:28]2[C:33](=[O:34])[C:32]([CH2:35][C:36]3[CH:41]=[CH:40][C:39]([C:42]4[CH:47]=[CH:46][CH:45]=[CH:44][C:43]=4[C:48]4[NH:49][C:4](=[O:7])[O:2][N:3]=4)=[CH:38][CH:37]=3)=[C:31]([CH2:50][CH2:51][CH3:52])[N:30]3[N:53]=[CH:54][CH:9]=[C:29]23)=[CH:26][CH:27]=1

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 21645Hydroxylamine HClHCID 516892Sodium BicarbonateHCID 67009234HCID 67009234, compound

Product 1

HCID 136337151HCID 136337151, compoundYield 28%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
40 °C

Procedure

A mixture of 4′-[(5-oxo-7-propyl-4,5-dihydro[1,2,4]triazolo[1,5-a]pyrimidin-6-yl)methyl]biphenyl-2-carbonitrile (0.68 g), {4-[2-(acetyloxy)-1,1-dimethylethoxy]phenyl}boronic acid (0.94 g), copper(II) acetate (0.68 g), pyridine (2.0 mL), triethylamine (1.0 mL), molecular sieves 4A (2.00 g) and tetrahydrofuran (20 mL) was stirred at room temperature for 1 day. To the reaction mixture was added ethyl acetate (100 mL), and the mixture was stirred at room temperature for 1 hr, and the insoluble material was filtered off. The filtrate was concentrated, and the residue was purified by silica gel column chromatography to give 2-(4-{6-[(2′-cyanobiphenyl-4-yl)methyl]-5-oxo-7-propyl[1,2,4]triazolo[1,5-a]pyrimidin-4(5H)-yl}phenoxy)-2-methylpropyl acetate as a colorless oil (0.85 g, 80%). A mixture of hydroxylammonium chloride (1.55 g), sodium hydrogen carbonate (2.50 g) and dimethyl sulfoxide (15 mL) was stirred at 40° C. for 30 min, 2-(4-{6-[(2′-cyanobiphenyl-4-yl)methyl]-5-oxo-7-propyl[1,2,4]triazolo[1,5-a]pyrimidin-4(5H)-yl}phenoxy)-2-methylpropyl acetate (0.85 g) was added, and the mixture was stirred at 90° C. for 18 hr. The reaction mixture was diluted with ethyl acetate, washed with water and then with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure, and the residue was dissolved in tetrahydrofuran (15 mL). N,N′-Carbonyldiimidazole (0.36 g) and then 1,8-diazabicyclo[5.4.0]undec-7-ene (0.33 mL) were added, and the mixture was stirred at room temperature for 2 hr. The reaction mixture was diluted with ethyl acetate, washed with saturated aqueous potassium hydrogensulfate solution and then with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography to give the title compound as a colorless solid (0.25 g, 28%).

Workup

  1. stirringthe mixture was stirred at 90° C. for 18 hr
  2. washwashed with water
  3. dry with materialwith saturated brine, and dried over anhydrous magnesium sulfate
  4. customThe solvent was evaporated under reduced pressure
  5. dissolutionthe residue was dissolved in tetrahydrofuran (15 mL)
  6. additionN,N′-Carbonyldiimidazole (0.36 g) and then 1,8-diazabicyclo[5.4.0]undec-7-ene (0.33 mL) were added
  7. stirringthe mixture was stirred at room temperature for 2 hr
  8. additionThe reaction mixture was diluted with ethyl acetate
  9. washwashed with saturated aqueous potassium hydrogensulfate solution
  10. dry with materialwith saturated brine, and dried over anhydrous magnesium sulfate
  11. customThe solvent was evaporated under reduced pressure
  12. customthe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-b915529c3e4343c49302e99370c4f482
Source dataset
uspto-grants-2015_08
Patent number
US09115136B2

Reaction notes

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