Sodium Chloride → 1-[2-Chloro-4-(methylsulphenyl)phenyl]-3-cyclopropylprop-1-yn-3-one

HRID 21456Notes

Reaction equation

HRID 21456 reaction equation
C([Li])CCC.[Cl:6][C:7]1[CH:12]=[C:11]([S:13][CH3:14])[CH:10]=[CH:9][C:8]=1[C:15]#[CH:16].[CH:17]1([C:20](Cl)=[O:21])[CH2:19][CH2:18]1.[Cl-].[Na+]>CCCCCC.C1COCC1>[Cl:6][C:7]1[CH:12]=[C:11]([S:13][CH3:14])[CH:10]=[CH:9][C:8]=1[C:15]#[C:16][C:20]([CH:17]1[CH2:19][CH2:18]1)=[O:21]

Participants

7

Reactant 4

HCID 5234Sodium ChlorideHCID 77637Cyclopropanecarbonyl chlorideHCID 19931759[2-Chloro-4-(methylsulphenyl)phenyl]acetyleneHCID 178418339Butyllithium

Product 1

HCID 199317691-[2-Chloro-4-(methylsulphenyl)phenyl]-3-cyclopropylprop-1-yn-3-one

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

A solution of n-butyllithium in hexane (4.4 ml) was added to a stirred solution of [2-chloro-4-(methylsulphenyl)phenyl]acetylene (2.0 g) in THF while maintaining the temperature below -70° C. The mixture was stirred for 5 minutes and cyclopropanecarbonyl chloride (2.4 g) was added. The mixture was warmed to room temperature and poured onto aqueous sodium chloride solution. The aqueous layer was extracted with ether and combined organic layers dried (MgSO4) and filtered. The filtrate was evaporated to dryness and the residue was dissolved in methanol and heated at reflux for 5 minutes. Toluene was added and the mixture was evaporated to dryness. The residue was purified by chromatography eluted with a mixture of hexane and ether to give 1-[2-chloro-4-(methylsulphenyl)phenyl]-3-cyclopropylprop-1-yn-3-one as yellow oil which crystallized on standing, m.p. 46°-50° C. [2-Chloro-4-(methylsulphenyl)phenyl]acetylene was prepared by the reaction of 1-bromo-2-[2-chloro-4-(methylsulphenyl)phenyl]acetylene with n-butyllithium and wet zinc chloride in THF at -70° C.

Workup

  1. temperaturewhile maintaining the temperature below -70° C
  2. extractionThe aqueous layer was extracted with ether
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. customThe filtrate was evaporated to dryness
  6. dissolutionthe residue was dissolved in methanol
  7. temperatureheated
  8. temperatureat reflux for 5 minutes
  9. additionToluene was added
  10. customthe mixture was evaporated to dryness
  11. customThe residue was purified by chromatography
  12. washeluted with a mixture of hexane and ether

Sources & evidence

ORD record
ord-4ed8c0a00f4944238bf534ab24c818ea
Source dataset
uspto-grants-1995_06
Patent number
US05424276

Reaction notes

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