Hydrochloric Acid → 3-(benzyloxy)-5-(methylsulfinyl)-N-(4-methylthiazol-2-yl)pyridin-2-amine hydrochloride

HRID 1426092Notes

Reaction equation

HRID 1426092 reaction equation
[CH2:1]([O:8][C:9]1[C:10]([NH:17][C:18]2[S:19][CH:20]=[C:21]([CH3:23])[N:22]=2)=[N:11][CH:12]=[C:13]([S:15][CH3:16])[CH:14]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1C=C([Cl:30])C=C(C(OO)=[O:32])C=1.Cl>C(Cl)Cl.CCOCC>[ClH:30].[CH2:1]([O:8][C:9]1[C:10]([NH:17][C:18]2[S:19][CH:20]=[C:21]([CH3:23])[N:22]=2)=[N:11][CH:12]=[C:13]([S:15]([CH3:16])=[O:32])[CH:14]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 70297m-Chloroperbenzoic acidHCID 592256943-(benzyloxy)-N-(4-methylthiazol-2-yl)-5-(methylthio)pyridin-2-amine

Product 1

HCID 866396513-(benzyloxy)-5-(methylsulfinyl)-N-(4-methylthiazol-2-yl)pyridin-2-amine hydrochlorideYield 56.3%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

3-(Benzyloxy)-N-(4-methylthiazol-2-yl)-5-(methylthio)pyridin-2-amine (prepared according to Example 7; 0.057 g, 0.166 mmol) was placed in CH2Cl2 (5 mL) and cooled to 0° C. MCPBA (0.0398 g, 0.166 mmol) was added, and the reaction mixture was stirred at room temperature for 2 hours, then quenched with sodium bisulfite and extracted with CH2Cl2. The organic layer was washed with saturated sodium bicarbonate, dried, filtered, and concentrated. The residue was purified by silica gel (40-80% EtOAc in hexanes) to give the free base. The free base was dissolved in CH2Cl2, and 2M HCl in ether was added. The solution was concentrated to give 3-(benzyloxy)-5-(methylsulfinyl)-N-(4-methylthiazol-2-yl)pyridin-2-amine hydrochloride (0.037 g, 56.3% yield). 1H NMR (DMSO-d6) δ 8.18 (d, 1H), 7.81 (d, 1H), 7.62 (m, 2H), 7.43 (m, 2H), 7.37 (m, 1H), 6.83 (s, 1H), 5.39 (d, 2H), 2.82 (s, 3H), 2.30 (s, 3H). Mass spectrum (apci) m/z=360.0 (M+H-HCl).

Workup

  1. customquenched with sodium bisulfite
  2. extractionextracted with CH2Cl2
  3. washThe organic layer was washed with saturated sodium bicarbonate
  4. customdried
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe residue was purified by silica gel (40-80% EtOAc in hexanes)
  8. customto give the free base
  9. concentrationThe solution was concentrated

Sources & evidence

ORD record
ord-396e6b12d9194b7a834f7db2d62e9124
Source dataset
uspto-grants-2015_01
Patent number
US08933077B2

Reaction notes

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