Sodium Thiosulfate → 4-(2-fluoro-5-(1-(4-(methylsulfonyl)phenyl)ethyl)pyridin-3-yl)-N,N-bis(4-methoxybenzyl)-6-methyl-1,3,5-triazin-2-amine

HRID 1621588Notes

Reaction equation

HRID 1621588 reaction equation
[F:1][C:2]1[C:7]([C:8]2[N:13]=[C:12]([CH3:14])[N:11]=[C:10]([N:15]([CH2:25][C:26]3[CH:31]=[CH:30][C:29]([O:32][CH3:33])=[CH:28][CH:27]=3)[CH2:16][C:17]3[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[CH:19][CH:18]=3)[N:9]=2)=[CH:6][C:5]([CH:34]([C:36]2[CH:41]=[CH:40][C:39](SC)=[CH:38][CH:37]=2)[CH3:35])=[CH:4][N:3]=1.Cl[C:45]1C=C(C=CC=1)C(OO)=O.C(=O)(O)[O-].[Na+].[S:60]([O-:64])([O-])(=[O:62])=S.[Na+].[Na+]>C(Cl)Cl>[F:1][C:2]1[C:7]([C:8]2[N:13]=[C:12]([CH3:14])[N:11]=[C:10]([N:15]([CH2:16][C:17]3[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[CH:19][CH:18]=3)[CH2:25][C:26]3[CH:27]=[CH:28][C:29]([O:32][CH3:33])=[CH:30][CH:31]=3)[N:9]=2)=[CH:6][C:5]([CH:34]([C:36]2[CH:37]=[CH:38][C:39]([S:60]([CH3:45])(=[O:64])=[O:62])=[CH:40][CH:41]=2)[CH3:35])=[CH:4][N:3]=1

Participants

6

Reactant 4

HCID 24477Sodium ThiosulfateHCID 70297m-Chloroperbenzoic acidHCID 516892Sodium BicarbonateHCID 666112674-(2-fluoro-5-(1-(4-(methylthio)phenyl)ethyl)pyridin-3-yl)-N,N-bis(4-methoxybenzyl)-6-methyl-1,3,5-triazin-2-amine

Product 1

HCID 666112714-(2-fluoro-5-(1-(4-(methylsulfonyl)phenyl)ethyl)pyridin-3-yl)-N,N-bis(4-methoxybenzyl)-6-methyl-1,3,5-triazin-2-amine

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

4-(2-Fluoro-5-(1-(4-(methylthio)phenyl)ethyl)pyridin-3-yl)-N,N-bis(4-methoxybenzyl)-6-methyl-1,3,5-triazin-2-amine (1.797 g, 3.016 mmol) was dissolved in DCM (30 mL) and the reaction flask was cooled in an ice water bath under nitrogen. Then, 3-chlorobenzoperoxoic acid (1.668 g, 9.666 mmol) was added as a solution in DCM (52 mL), and the reaction was warmed to room temperature and stirred. After 30 min, the reaction was cooled in an ice water bath and treated with a mixture of saturated sodium bicarbonate (50 mL) and saturated sodium thiosulfate (15 mL). The biphasic mixture was warmed to room temperature and stirred. After 1 h, the layers were separated, and the aqueous phase was extracted with DCM. The organic phases were combined, dried over sodium sulfate, filtered, concentrated, and purified on a silica gel filter (150 mL fritted filter with about 2 inches of silica gel; DCM to 100:1 DCM/MeOH to 50:1 DCM/MeOH). The fractions with product were collected, concentrated, and dried under high vacuum to give 4-(2-fluoro-5-(1-(4-(methylsulfonyl)phenyl)ethyl)pyridin-3-yl)-N,N-bis(4-methoxybenzyl)-6-methyl-1,3,5-triazin-2-amine (1.517 g). 1H NMR (CDCl3, 400 MHz) δ 8.34 (dd, J=8.90 Hz, 2.45 Hz, 1H), 8.17 (s, 1H), 7.88 (d, J=8.41 Hz, 2H), 7.42 (d, J=8.22 Hz, 2H), 7.21 (d, J=8.02 Hz, 4H), 6.86 (t, J=8.90 Hz, 4H), 4.82 (s, 2H), 4.78 (s, 2H), 4.34 (q, J=7.69 Hz, 1H), 3.82 (s, 3H), 3.81 (s, 3H), 3.02 (s, 3H), 2.54 (s, 3H), 1.74 (d, J=7.24 Hz, 3H). m/z (ESI, pos. ion) 628 (M+H)+.

Workup

  1. temperaturethe reaction flask was cooled in an ice water bath under nitrogen
  2. temperaturethe reaction was cooled in an ice water bath
  3. temperatureThe biphasic mixture was warmed to room temperature
  4. stirringstirred
  5. waitAfter 1 h
  6. customthe layers were separated
  7. extractionthe aqueous phase was extracted with DCM
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated
  11. custompurified on a silica gel
  12. filtrationfilter (150 mL fritted filter with about 2 inches of silica gel; DCM to 100:1 DCM/MeOH to 50:1 DCM/MeOH)
  13. customThe fractions with product were collected
  14. concentrationconcentrated
  15. customdried under high vacuum

Sources & evidence

ORD record
ord-dbc2145d4ae64f94b0155494b24da01a
Source dataset
uspto-grants-2014_07
Patent number
US08772480B2

Reaction notes

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