Hydrochloric Acid → HCID 13290066, compound

HRID 371002Notes

Reaction equation

HRID 371002 reaction equation
[Cl:1][C:2]1[C:7]([Cl:8])=[C:6]([O:9][CH3:10])[CH:5]=[CH:4][C:3]=1[S:11][CH2:12][C:13]1[C:18]([F:19])=[CH:17][CH:16]=[CH:15][C:14]=1[F:20].[CH2:21]([Li])CCC.C(OC)=O.Cl>O1CCCC1>[Cl:8][C:7]1[C:6]([O:9][CH3:10])=[CH:5][C:4]2[CH:21]=[C:12]([C:13]3[C:14]([F:20])=[CH:15][CH:16]=[CH:17][C:18]=3[F:19])[S:11][C:3]=2[C:2]=1[Cl:1]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 7865Methyl formateHCID 13290202HCID 13290202, compoundHCID 178418339Butyllithium

Product 1

HCID 13290066HCID 13290066, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To 15 g of (2,3-dichloro-4-methoxyphenyl)(2',6'-difluorobenzyl)sulfide in 140 ml of dry tetrahydrofuran at -75° is added dropwise 25 ml of 2.2M n-butyllithium over a period of 20 mins, maintaining the temperature below -65°. After stirring at this temperature for 1 hr, 10 ml of dried methyl formate is added dropwise, maintaining the temperature below -60°. The reaction mixture is poured onto 100 ml of 10N hydrochloric acid. The mixture is extracted with ethyl ether. The ether extract is dried over anhydrous magnesium sulfate, filtered and the solvent is removed to give an oil. The oil is heated to 120° and 240 g of warm polyphosphoric acid is added. The reaction mixture is warmed at 130° for 20 mins. The mixture is allowed to cool and to the mixture is added 400 ml of ice water. The aqueous solution is extracted with ethyl ether. The ether extract is washed, dried over anhydrous magnesium sulfate, filtered and the solvent is removed to give an oil. Crystallization from hexane, followed by recrystallization from acetone-hexane, gives 7 g of 6,7-dichloro-2-(2',6'-difluorophenyl)-5-methoxybenzo[b]thiophene.

Workup

  1. temperaturemaintaining the temperature below -65°
  2. temperaturemaintaining the temperature below -60°
  3. extractionThe mixture is extracted with ethyl ether
  4. extractionThe ether extract
  5. dry with materialis dried over anhydrous magnesium sulfate
  6. filtrationfiltered
  7. customthe solvent is removed
  8. customto give an oil
  9. temperatureThe oil is heated to 120°
  10. temperatureThe reaction mixture is warmed at 130° for 20 mins
  11. temperatureto cool and to the mixture
  12. extractionThe aqueous solution is extracted with ethyl ether
  13. extractionThe ether extract
  14. washis washed
  15. dry with materialdried over anhydrous magnesium sulfate
  16. filtrationfiltered
  17. customthe solvent is removed
  18. customto give an oil
  19. customCrystallization from hexane
  20. customfollowed by recrystallization from acetone-hexane

Sources & evidence

ORD record
ord-8b1acffd868b45bf88ee2cd0fa36cba4
Source dataset
uspto-grants-1985_07
Patent number
US04528399

Reaction notes

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