Water → HCID 86743584, compound

HRID 1074041Notes

Reaction equation

HRID 1074041 reaction equation
[C:1](Cl)(=[O:3])[CH3:2].[OH:5][C:6](=[CH:12][CH:13]=[C:14]([C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[C:15]([O:17][CH2:18][CH3:19])=[O:16])[C:7]([O:9][CH2:10][CH3:11])=[S:8].C(N(CC)CC)C.O>O1CCCC1.C1CCCCC1.C(OCC)(=O)C.ClCCl>[C:1]([O:5][C:6](=[CH:12][CH:13]=[C:14]([C:20]1[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=1)[C:15]([O:17][CH2:18][CH3:19])=[O:16])[C:7]([O:9][CH2:10][CH3:11])=[S:8])(=[O:3])[CH3:2]

Participants

9

Reactant 4

HCID 962WaterHCID 6367Acetyl chlorideHCID 8471TriethylamineHCID 86743585HCID 86743585, compound

Product 1

HCID 86743584HCID 86743584, compound

Reagents, catalysts & solvents 4

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolventHCID 8078CyclohexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

Acetyl chloride (1.2 cc) is added at a temperature of approximately 20° C., and in the course of 5 minutes, to a stirred solution, through which a stream of nitrogen is passed, of diethyl 2-hydroxy-5-phenylthio-2,4-hexadienedioate (5 g) and triethylamine (2.4 cc) in tetrahydrofuran (45 cc). Stirring is maintained for 2 hours at the same temperature. The mixture is taken up with water (100 cc) and dichloromethane (100 cc). The organic phase is separated off after settling has taken place, and the aqueous phase is extracted with dichloromethane (2×50 cc). The organic phases are combined, dried over anhydrous magnesium sulphate, filtered and concentrated to dryness at 40° C. under reduced pressure (20 mm Hg; 2.7 kPa). The oil obtained is dissolved in a mixture (10 cc) of cyclohexane and ethyl acetate (70:30 by volume), and poured onto silica (300 g) contained in a column 4 cm in diameter. Elution is performed with a mixture of cyclohexane and ethyl acetate (70:30 by volume), and the corresponding eluate is concentrated to dryness at 40° C. under reduced pressure (20 mm Hg; 2.7 kPa). Diethyl 2-acetoxy-5-phenylthio-2,4-hexadienedioate (4.5 g) is obtained in the form of an orange-coloured oil [Rf=0.50; thin layer chromatography on silica gel; eluent: cyclohexane/ethyl acetate (70:30 by volume)].

Workup

  1. customin the course of 5 minutes
  2. temperatureis maintained for 2 hours at the same temperature
  3. customThe organic phase is separated off after settling
  4. extractionthe aqueous phase is extracted with dichloromethane (2×50 cc)
  5. dry with materialdried over anhydrous magnesium sulphate
  6. filtrationfiltered
  7. concentrationconcentrated to dryness at 40° C. under reduced pressure (20 mm Hg; 2.7 kPa)
  8. customThe oil obtained
  9. additionpoured onto silica (300 g)
  10. washElution
  11. additionis performed with a mixture of cyclohexane and ethyl acetate (70:30 by volume)
  12. concentrationthe corresponding eluate is concentrated to dryness at 40° C. under reduced pressure (20 mm Hg; 2.7 kPa)

Sources & evidence

ORD record
ord-583f8bb26d22489682c0a2996aa38aa6
Source dataset
uspto-grants-1990_11
Patent number
US04971979

Reaction notes

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