Sodium Hydroxide → HCID 178439631, compound

HRID 1067662Notes

Reaction equation

HRID 1067662 reaction equation
[F:1][C:2]([F:11])([F:10])[C:3]1[CH:4]=[C:5]([SH:9])[CH:6]=[CH:7][CH:8]=1.[H-].[Na+].CN(C)S([N:19]1[C:23]([CH2:24][CH:25](Cl)[CH3:26])=[CH:22][N:21]=[C:20]1[Si](C(C)(C)C)(C)C)(=O)=O.[OH-].[Na+].[C:38]([O-:43])(=[O:42])[C:39]([O-:41])=[O:40]>CN(C=O)C.[N+](CCCC)(CCCC)(CCCC)CCCC.[I-].Cl.C(OCC)(=O)C.CC(O)C.O>[C:38]([OH:43])(=[O:42])[C:39]([OH:41])=[O:40].[F:11][C:2]([F:1])([F:10])[C:3]1[CH:4]=[C:5]([S:9][CH:25]([CH3:26])[CH2:24][C:23]2[N:19]=[CH:20][NH:21][CH:22]=2)[CH:6]=[CH:7][CH:8]=1

Participants

12

Reactant 5

HCID 14798Sodium HydroxideHCID 24758Sodium hydrideHCID 71081OxalateHCID 1367513-(Trifluoromethyl)benzenethiolHCID 21193583HCID 21193583, compound

Product 1

HCID 178439631HCID 178439631, compound

Reagents, catalysts & solvents 6

HCID 67553Tetrabutylammonium IodideCatalystHCID 313Hydrochloric AcidSolventHCID 962WaterSolventHCID 3776IsopropanolSolventHCID 6228DimethylformamideSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

3-Trifluoromethylthiophenol (0.298 g; 1.67 mmol) is dissolved in 20 ml of anhydrous DMF and cooled to 0° C. under a nitrogen atmosphere, and NaH (60% dispersion in mineral oil; 0.0393 g; 1.638 mmol) is added in small portions. The reaction mixture is stirred at 0° C. for 15 min and then at 20° C. for a further 1.5 h, and 0.293 g (0.80 mmol) of 1-(N,N-dimethylsulphamoyl)-2-tert-butyldimethylsilyl-5-(2-chloropropyl) imidazole dissolved in 5 ml of DMF and 10 mg of n-Bu4NI are added and the mixture is heated at 80° C. for 3 days. The solvent is driven off under reduced pressure to yield a brown oil, which is treated with 100 ml of water and extracted 3 times with 40 ml of dichloromethane. The extracts are dried (MgSO4) and concentrated, and the oil obtained is subjected to column chromatography using 2:1 and 1:1 petroleum spirit/ethyl acetate, then dissolved in 10 ml of 2M HCl and heated at 100° C. under reflux for 3 hours. The reaction mixture is then alkalized by adding 10% NaOH (pH approximately 11) and is extracted 3 times with 40 ml of dichloromethane. The extracts are dried (MgSO4) and evaporated to form a clear oil, which is subjected to column chromatography with ethyl acetate as eluent and converted to the oxalate of the desired product in 2-propanol, m.p. 166-168° C.

Workup

  1. waitat 20° C. for a further 1.5 h
  2. temperaturethe mixture is heated at 80° C. for 3 days
  3. customto yield a brown oil, which
  4. extractionextracted 3 times with 40 ml of dichloromethane
  5. dry with materialThe extracts are dried (MgSO4)
  6. concentrationconcentrated
  7. customthe oil obtained
  8. temperatureheated at 100° C.
  9. temperatureunder reflux for 3 hours
  10. extractionis extracted 3 times with 40 ml of dichloromethane
  11. dry with materialThe extracts are dried (MgSO4)
  12. customevaporated
  13. customto form a clear oil, which

Sources & evidence

ORD record
ord-f07d8bff065a443c899ca89029955f28
Source dataset
uspto-grants-2001_06
Patent number
US06248765B1

Reaction notes

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