Ethyl Acetate → HCID 178456786, compound

HRID 2261914Notes

Reaction equation

HRID 2261914 reaction equation
[C:1]([C:4]1[N:5]=[N:6][N:7]([C:9]2[CH:10]=[C:11]([CH:24]=[C:25]([N:27]([S:31]([CH3:34])(=[O:33])=[O:32])[CH2:28][CH2:29][CH3:30])[CH:26]=2)[C:12]([NH:14][C@@H:15]([C:17]2[CH:22]=[CH:21][C:20]([F:23])=[CH:19][CH:18]=2)[CH3:16])=[O:13])[CH:8]=1)(=O)[CH3:2].[CH3:35][C:36]([S:39]([NH2:41])=[O:40])([CH3:38])[CH3:37].CCOC(C)=O>C1COCC1.[Cl-].[Na+].O>[C:36]([S:39](/[N:41]=[C:1](/[C:4]1[N:5]=[N:6][N:7]([C:9]2[CH:10]=[C:11]([CH:24]=[C:25]([N:27]([S:31]([CH3:34])(=[O:33])=[O:32])[CH2:28][CH2:29][CH3:30])[CH:26]=2)[C:12]([NH:14][C@@H:15]([C:17]2[CH:22]=[CH:21][C:20]([F:23])=[CH:19][CH:18]=2)[CH3:16])=[O:13])[CH:8]=1)\[CH3:2])=[O:40])([CH3:38])([CH3:37])[CH3:35]

Participants

6

Reactant 3

HCID 8857Ethyl AcetateHCID 3382465Tert-Butanesulfinamide2×HCID 58990126HCID 58990126, compound

Product 1

HCID 178456786HCID 178456786, compoundYield 42.3%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

To a solution of 0.135 g (0.28 mmol) 3-(4-acetyl-1H-1,2,3-triazol-1-yl)-N-[(1R)-1-(4-fluorophenyl)ethyl]-5-[(methylsulfonyl)(propyl)amino]benzamide in 1 mL THF was added 0.18 mL (0.83 mmol) Ti(OEt)4 and 0.04 g (0.33 mmol) 2-methyl-2-propanesulfinamide. The mixture was stirred at rt for 1 hr then heated to reflux for 7 hours whereupon 40 mg more racemic 2-methyl-2-propanesulfinamide and 0.15 mL Ti(OEt)4 and were added and the mixture heated 2 more hr before cooling in an ice bath. To this was added 1 mL brine and 10 mL EtOAc and the mixture was stirred vigorously, breaking up clumps with a spatula. The mixture was filtered through celite and rinsed w. 50 mL EtOAc. The filtrate washed with 50 mL brine, dried over MgSO4, filtered, and concentrated to give 0.07 g 3-{4-[(1E)-N-(tert-butylsulfinyl)ethanimidoyl]-1H-1,2,3-triazol-1-yl}-N-[(1R)-1-(4-fluorophenyl)ethyl]-5-[(methylsulfonyl)(propyl)amino]benzamide as a white solid. 1H NMR (400 MHz, CDCl3) δ 8.53 (s, 1H), 8.14 (s, 1H), 7.96 (s, 1H), 7.87 (s, 1H), 7.39 (m, 2H) 7.07 (m, 2H), 6.51 (br d, J=7.33 Hz, 1H), 5.31 (quint, J=7.14 Hz, 1H), 3.74 (t, J=6.78 Hz, 2H), 2.94 (s, 3H), 2.92 (s, 3H), 1.65 (d, J=6.96 Hz, 3H), 1.54 (m, 2H), 1.33 (s, 9H), 0.93 (t, J=7.32 Hz, 3H). LCMS [M+H]+=591.2

Workup

  1. temperaturethen heated
  2. additionwere added
  3. temperaturethe mixture heated 2 more hr
  4. temperaturebefore cooling in an ice bath
  5. stirringthe mixture was stirred vigorously
  6. filtrationThe mixture was filtered through celite and
  7. washrinsed w
  8. washThe filtrate washed with 50 mL brine
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-a7a66119656d45e7aac9f072959e96ca
Source dataset
uspto-grants-2010_12
Patent number
US07847100B2

Reaction notes

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