Hydrochloric Acid → HCID 69671321, compound

HRID 1497581Notes

Reaction equation

HRID 1497581 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[C:7]([N+:9]([O-])=O)[CH:6]=[CH:5][C:4]=1[C:12]1[N:16]2[CH:17]=[C:18]([C:21]3[CH:26]=[CH:25][C:24]([O:27][CH3:28])=[CH:23][CH:22]=3)[CH:19]=[CH:20][C:15]2=[N:14][N:13]=1.[Cl:29][Sn]Cl.C([O-])([O-])=O.[Na+].[Na+].Cl>C(OCC)(=O)C.O>[ClH:29].[NH2:9][C:7]1[CH:6]=[CH:5][C:4]([C:12]2[N:16]3[CH:17]=[C:18]([C:21]4[CH:26]=[CH:25][C:24]([O:27][CH3:28])=[CH:23][CH:22]=4)[CH:19]=[CH:20][C:15]3=[N:14][N:13]=2)=[C:3]([O:2][CH3:1])[CH:8]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 10340Sodium CarbonateHCID 24479Stannous ChlorideHCID 69670985HCID 69670985, compound

Product 1

HCID 69671321HCID 69671321, compoundYield 32.1%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

A mixture of 3-(2-methoxy-4-nitrophenyl)-6-(4-methoxyphenyl)-[1,2,4]triazolo[4,3-a]pyridine (50 mg, 0.13 mmol) and SnCl2 (120 mg, 0.65 mmol) in ethyl acetate (25 mL) was heated to reflux for 6 h under Argon. The reaction mixture was cooled to room temperature and basified to pH=10 with saturated aqueous Na2CO3. The biphasic solution was separated and the aqueous layer was extracted with ethyl acetate (40 mL). The combined organic layers were washed with brine and concentrated. The residue was purified by flash column chromatography (petroleum ether:ethyl acetate=2:1 to 0:1) to give crude product as yellow oil. The oil was stirred in a solution of HCl in ethyl acetate (2M, 20 mL) at room temperature, and then was mixed with water (30 mL). The aqueous phase was washed with ethyl acetate (30 mL), basified with saturated aqueous Na2CO3 to pH>10 and extracted with ethyl acetate (30 mL). The organic phase was stirred with a solution of HCl in ethyl acetate (2M, 10 mL) at room temperature for 2 h and concentrated in vacuo to give the title compound as yellow solids (16 mg, 30% yield). 1H NMR (DMSO-d6): 8.32 (s, 1H), 8.19 (dd, J=9.6 and 1.2 Hz, 1H), 8.09 (d, J=9.6 Hz, 1H), 7.72 (d, J=8.7 Hz, 2H), 7.36 (d, J=8.4 Hz, 1H), 7.08 (d, J=8.7 Hz, 2H), 6.61 (d, J=1.5 Hz, 1H), 6.52 (dd, J=8.4 and 1.5 Hz, 1H), 3.82 (s, 3H), 3.79 (s, 3H). MS: m/z 347.1 [M+H+].

Workup

  1. temperaturewas heated
  2. temperatureto reflux for 6 h under Argon
  3. customThe biphasic solution was separated
  4. extractionthe aqueous layer was extracted with ethyl acetate (40 mL)
  5. washThe combined organic layers were washed with brine
  6. concentrationconcentrated
  7. customThe residue was purified by flash column chromatography (petroleum ether:ethyl acetate=2:1 to 0:1)
  8. customto give crude product as yellow oil
  9. washThe aqueous phase was washed with ethyl acetate (30 mL)
  10. extractionextracted with ethyl acetate (30 mL)
  11. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-88e4c3d2c153467baac4560b6b997e6a
Source dataset
uspto-grants-2015_12
Patent number
US09199983B2

Reaction notes

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