Oxalyl chloride → HCID 67499273, compound

HRID 2408192Notes

Reaction equation

HRID 2408192 reaction equation
[CH3:1][CH:2]([CH:6]([S:8][CH3:9])[CH3:7])[C:3](O)=[O:4].C(Cl)(=O)C(Cl)=O.[Cl:16][C:17]1[C:21]([NH:22][CH2:23][CH3:24])=[CH:20][N:19]([C:25]2[CH:26]=[N:27][CH:28]=[C:29]([F:31])[CH:30]=2)[N:18]=1>ClCCl.CN(C)C=O.CN(C)C1C=CN=CC=1>[Cl:16][C:17]1[C:21]([N:22]([CH2:23][CH3:24])[C:3](=[O:4])[CH:2]([CH3:1])[CH:6]([S:8][CH3:9])[CH3:7])=[CH:20][N:19]([C:25]2[CH:26]=[N:27][CH:28]=[C:29]([F:31])[CH:30]=2)[N:18]=1.[Cl:16][C:17]1[C:21]([N:22]([CH2:23][CH3:24])[C:3](=[O:4])/[C:2](/[CH3:1])=[CH:6]\[CH3:7])=[CH:20][N:19]([C:25]2[CH:26]=[N:27][CH:28]=[C:29]([F:31])[CH:30]=2)[N:18]=1

Participants

8

Reactant 3

HCID 65578Oxalyl chlorideHCID 13952297HCID 13952297, compoundHCID 67499669HCID 67499669, compound

Product 2

HCID 67499273HCID 67499273, compoundYield 28.3%HCID 67499826HCID 67499826, compoundYield 22.06%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideCatalystHCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent2×

Procedure

To a solution 2-methyl-3-(methylthio)butanoic acid (0.154 g, 1.039 mmol) in dichloromethane (1 mL) at room temperature was added 1 drop of dimethylformamide. Oxalyl dichloride (0.178 ml, 2.078 mmol) was added dropwise and the reaction was stirred at room temperature overnight. The solvent was removed under reduced pressure. The residue was redissolved in dichloromethane (1 mL) and the solvent was removed under reduced pressure. The residue was redissolved in dichloromethane (0.5 mL) and the solution was added to a solution of 3-chloro-N-ethyl-1-(5-fluoropyridin-3-yl)-1H-pyrazol-4-amine (0.100 g, 0.416 mmol) and 4-dimethylaminopyridine (0.254 g, 2.078 mmol) in dichloromethane (1.5 mL) and stirred at room temperature overnight. The solvent was removed under reduced pressure and the residue was purify by chromatography (0-100% ethyl acetate/hexanes) to give N-(3-chloro-1-(5-fluoropyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-methyl-3-(methylthio)butanamide (34 mg, 0.092 mmol, 22.06%) as a faint yellow oil and (Z)-N-(3-chloro-1-(5-fluoropyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-methylbut-2-enamide (38 mg, 0.118 mmol, 28.3% yield) as a yellow oil.

Workup

  1. customThe solvent was removed under reduced pressure
  2. dissolutionThe residue was redissolved in dichloromethane (1 mL)
  3. customthe solvent was removed under reduced pressure
  4. dissolutionThe residue was redissolved in dichloromethane (0.5 mL)
  5. stirringstirred at room temperature overnight
  6. customThe solvent was removed under reduced pressure
  7. customthe residue was purify by chromatography (0-100% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-ab32920dca78431fa737b8f94a2b128b
Source dataset
uspto-grants-2014_08
Patent number
US08815271B2

Reaction notes

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