Thiophenol → HCID 18755535, compound

HRID 1861613Notes

Reaction equation

HRID 1861613 reaction equation
O[C:2]1[CH2:7][CH2:6][CH2:5][C:4](=[O:8])[C:3]=1[C:9]([C:11]1[C:12]([CH3:21])=[N:13][C:14]([C:17]([F:20])([F:19])[F:18])=[CH:15][CH:16]=1)=[O:10].C(N(CC)CC)C.CN(C1C=CC=CN=1)C.[C:38]1([SH:44])[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1>C(Cl)(=O)C(Cl)=O.CN(C)C=O>[CH3:21][C:12]1[C:11]([C:9]([C:3]2[C:4](=[O:8])[CH2:5][CH2:6][CH2:7][C:2]=2[S:44][C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)=[O:10])=[CH:16][CH:15]=[C:14]([C:17]([F:20])([F:19])[F:18])[N:13]=1

Participants

7

Reactant 4

HCID 7969ThiophenolHCID 8471TriethylamineHCID 218852-DimethylaminopyridineHCID 178432827HCID 178432827, compound

Product 1

HCID 18755535HCID 18755535, compound

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 65578Oxalyl chlorideSolvent

Procedure

4.0 g (0.0134 mol) of 3-hydroxy-2-(2-methyl-6-trifluoromethylpyridine-3-carbonyl)cyclohex-2-enone (compound A2-B1) are suspended in 25 ml of oxalyl chloride, and 0.1 ml of dimethylformamide is subsequently added dropwise. After the vigorous evolution of gas has ceased, the mixture is held for 1.5 hours at a bath temperature of 45° C. and subsequently concentrated, and the residue (3-chloro-2-(2-methyl-6-trifluoromethylpyridine-3-carbonyl)-cyclohex-2-enone) is dissolved in 60 ml of methylene chloride. Triethylamine (3.7 ml, 0.0268 mol), dimethylaminopyridine (160 mg, 1.34 mmol) and 1.5 ml (0.0147 mol) of thiophenol are added at a temperature of 0-5° C. After 20 hours at a temperature of 22° C., the reaction mixture is concentrated and purified on silica gel (hexane/ethyl acetate 5:1). Trituration in hexane gives pure 2-(2-methyl-6-trifluoromethylpyridine-3-carbonyl)-3-phenylsulfanylcyclohex-2-enone in the form of white crystals of melting point 124-125° C. 1H-NMR (CDCl3): 1.99, m, 2H; 2.41, m 4H; 2.80, s, 3H; 2.60: 7.40-7.60, m, 6H; 7.80 ppm, d(J, 8.2 Hz), 1H.

Workup

  1. concentrationtemperature of 45° C. and subsequently concentrated
  2. dissolutionthe residue (3-chloro-2-(2-methyl-6-trifluoromethylpyridine-3-carbonyl)-cyclohex-2-enone) is dissolved in 60 ml of methylene chloride
  3. waitAfter 20 hours at a temperature of 22° C.
  4. concentrationthe reaction mixture is concentrated
  5. custompurified on silica gel (hexane/ethyl acetate 5:1)

Sources & evidence

ORD record
ord-33d5b6697fa44929af46b9ba51926edc
Source dataset
uspto-grants-2003_03
Patent number
US06534445B1

Reaction notes

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