Pyridine → S-(4-methylphenyl) 2-methyl-5-phenylpyridine-3-carbothioate

HRID 1987083Notes

Reaction equation

HRID 1987083 reaction equation
[CH3:1][C:2]1[N:10]=[CH:9][C:8]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[CH:7][C:3]=1[C:4]([OH:6])=O.C(Cl)(=O)C(Cl)=O.N1C=CC=CC=1.[CH3:29][C:30]1[CH:35]=[CH:34][C:33]([SH:36])=[CH:32][CH:31]=1>C(Cl)Cl.CN(C)C1C=CN=CC=1.CCOC(C)=O>[CH3:1][C:2]1[C:3]([C:4](=[O:6])[S:36][C:33]2[CH:34]=[CH:35][C:30]([CH3:29])=[CH:31][CH:32]=2)=[CH:7][C:8]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[CH:9][N:10]=1

Participants

8

Reactant 4

HCID 1049PyridineHCID 78114-MethylbenzenethiolHCID 65578Oxalyl chlorideHCID 579000812-Methyl-5-phenylnicotinic acid

Product 1

HCID 57722887S-(4-methylphenyl) 2-methyl-5-phenylpyridine-3-carbothioate

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
40 °C

Procedure

To a 0° C. solution of 2-methyl-5-phenylnicotinic acid (100 mg, 0.40 mmol) in CH2Cl2 (4 mL) was added oxalyl chloride (344 μL, 4.0 mmol). The mixture was stirred at 40° C. After 3 hours, the mixture was concentrated to dryness, dissolved in benzene (2×5 mL) and concentrated again. After dissolving the crude residue in CH2Cl2 (2 mL) at 0° C., pyridine (1 mL, 0.92 M in CH2Cl2), 4-dimethylaminopyridine (10 mg, 0.08 mmol) and 4-methylthiophenol (60 mg, 0.48 mmol) were added. The mixture was then allowed to warm to room temperature. After stirring for 2 hours, the mixture was diluted with EtOAc, washed with 1N HCl, brine, dried over sodium sulfate, filtered, and concentrated. The crude residue was purified by flash chromatography (100-80% hexanes/EtOAc gradient) to afford the title compound. LRMS (APCI) calculated for C20H18NOS [M+H]+, 320.1; found 320.1

Workup

  1. concentrationthe mixture was concentrated to dryness
  2. dissolutiondissolved in benzene (2×5 mL)
  3. concentrationconcentrated again
  4. dissolutionAfter dissolving the crude residue in CH2Cl2 (2 mL) at 0° C.
  5. temperatureto warm to room temperature
  6. stirringAfter stirring for 2 hours
  7. washwashed with 1N HCl, brine
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe crude residue was purified by flash chromatography (100-80% hexanes/EtOAc gradient)

Sources & evidence

ORD record
ord-ef98187da3914b7c8f78a82f2170b913
Source dataset
uspto-grants-2009_06
Patent number
US07550478B2

Reaction notes

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