Sodium Sulfite → 2-(5-ethylthio-1-methyl-3-trifluoromethyl-1H-pyrazol-4-yl)-6-trifluoromethylthiazolo[5,4-b]pyridine

HRID 2272910Notes

Reaction equation

HRID 2272910 reaction equation
[NH2:1][C:2]1[C:3]([SH:12])=[N:4][CH:5]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:7]=1.[CH2:13]([S:15][C:16]1[N:20]([CH3:21])[N:19]=[C:18]([C:22]([F:25])([F:24])[F:23])[C:17]=1[CH:26]=O)[CH3:14].S([O-])([O-])=O.[Na+].[Na+].C(=O)(O)[O-].[Na+]>[Cu](Cl)Cl.C(OCC)(=O)C.CN(C)C(=O)C>[CH2:13]([S:15][C:16]1[N:20]([CH3:21])[N:19]=[C:18]([C:22]([F:24])([F:25])[F:23])[C:17]=1[C:26]1[S:12][C:3]2[C:2]([N:1]=1)=[CH:7][C:6]([C:8]([F:9])([F:11])[F:10])=[CH:5][N:4]=2)[CH3:14]

Participants

8

Reactant 4

HCID 24437Sodium SulfiteHCID 516892Sodium BicarbonateHCID 57579702HCID 57579702, compoundHCID 178507667HCID 178507667, compound

Product 1

HCID 1179742782-(5-ethylthio-1-methyl-3-trifluoromethyl-1H-pyrazol-4-yl)-6-trifluoromethylthiazolo[5,4-b]pyridineYield 44.9%

Reagents, catalysts & solvents 3

HCID 24014Cupric ChlorideCatalystHCID 8857Ethyl AcetateSolventHCID 31374DimethylacetamideSolvent

Conditions

Temperature
150 °C

Procedure

A mixture of 0.24 g of 3-amino-5-(trifluoromethyl)pyridine-2-thiol, 0.27 g of 5-ethylthio-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboaldehyde, 0.19 g of sodium sulfite, 0.33 g of copper(II) chloride (anhydrous) and 2 ml of N,N-dimethylacetamide was stirred at 150° C. for 8 hours. Ethyl acetate and a saturated aqueous sodium bicarbonate solution were poured into the cooled reaction mixture, and the mixture was filtered. The aqueous layer of the filtrate was extracted with ethyl acetate and then combined with the organic layer of the filtrate, and the mixture was washed with water and dried over anhydrous magnesium sulfate. The mixture was concentrated under reduced pressure, then the resulting residue was applied to a silica gel column chromatography to obtain 0.21 g of 2-(5-ethylthio-1-methyl-3-trifluoromethyl-1H-pyrazol-4-yl)-6-trifluoromethylthiazolo[5,4-b]pyridine (Compound of Present Invention (27)).

Workup

  1. filtrationthe mixture was filtered
  2. extractionThe aqueous layer of the filtrate was extracted with ethyl acetate
  3. washthe mixture was washed with water
  4. dry with materialdried over anhydrous magnesium sulfate
  5. concentrationThe mixture was concentrated under reduced pressure

Sources & evidence

ORD record
ord-340dc02121174dc59712c588c68771a3
Source dataset
uspto-grants-2015_09
Patent number
US09120792B2

Reaction notes

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