Methanol → HCID 86755383, compound

HRID 1107122Notes

Reaction equation

HRID 1107122 reaction equation
O=[C:2]([CH:8]=[CH:9][CH2:10][CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[CH2:3][C:4]([O:6][CH3:7])=[O:5].P(Cl)(Cl)(Cl)(Cl)[Cl:19].CO.O>CCCCCC>[Cl:19]/[C:2](/[CH2:8][CH2:9][CH2:10][CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)=[CH:3]/[C:4]([O:6][CH3:7])=[O:5].[Cl:19]/[C:2](/[CH2:8][CH2:9][CH2:10][CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)=[CH:3]\[C:4]([O:6][CH3:7])=[O:5]

Participants

7

Reactant 4

HCID 887MethanolHCID 962WaterHCID 24819Phosphorus pentachlorideHCID 57219343HCID 57219343, compound

Product 2

HCID 86755383HCID 86755383, compoundYield 25%HCID 86755384HCID 86755384, compoundYield 17%

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Procedure

A mixture of methyl 3-keto-7-phenylheptenoate (8 g, 34 mmol) and phosphorus pentachloride (14.1 g, 68 mmol) in hexane (60 mL) is heated under reflux for 2 hours. The solution is cooled in ice and methanol (5 mL) is added slowly. The mixture is stirred at room temperature for 10 minutes and is added to water and is extracted with hexane. The organic layer is dried over MgSO4 and the solvent is removed in vacuo. The residue is dissolved in dichloromethane (70 mL) and 17 mL of 2 M oxalyl chloride is added. The solution is stirred for 2 hours and the solvent is removed in vacuo. The residue is dissolved in dichloromethane and some methanol is added. After stirring for 30 minutes the solvent is removed in vacuo. The residue is chromatographed on silica gel (20:1 hexane:ethyl acetate) to give methyl (E)-3-chloro-7-phenyl-2-heptenoate (2.1 g, 25%) as the first component off the column and methyl (Z)-3-chloro-7-phenyl-2-heptenoate (1.4 g, 17%) as the second component off the column: methyl (E)-3-chloro-7-phenyl-2-heptenoate, 1H-NMR (300 MHz, CDCl3) δ (TMS) 1.58-1.69 (m, 4H), 2.57-2.60 (m, 2H), 2.92-3.04 (m, 2H), 3.68 (s, 3H), 6.06 (s, 1H), 7.12-7.22 (m, 3H), 7.22-7.45 (m, 2H); methyl (Z)-3-chloro-7-phenyl-2-heptenoate, 1H-NMR (300 MHz, CDCl3) δ (TMS) 1.58-1.78 (m, 4H), 2.38-2.50 (m, 2H), 2.57-2.62 (m, 2H), 3.72 (s, 3H), 6.00 (s, 1H), 7.12-7.27 (m, 3H), 7.27-7.38(m, 2H).

Workup

  1. temperatureis heated
  2. temperatureunder reflux for 2 hours
  3. temperatureThe solution is cooled in ice
  4. extractionis extracted with hexane
  5. dry with materialThe organic layer is dried over MgSO4
  6. customthe solvent is removed in vacuo
  7. dissolutionThe residue is dissolved in dichloromethane (70 mL)
  8. addition17 mL of 2 M oxalyl chloride is added
  9. stirringThe solution is stirred for 2 hours
  10. customthe solvent is removed in vacuo
  11. dissolutionThe residue is dissolved in dichloromethane
  12. additionsome methanol is added
  13. stirringAfter stirring for 30 minutes the solvent
  14. customis removed in vacuo
  15. customThe residue is chromatographed on silica gel (20:1 hexane:ethyl acetate)

Sources & evidence

ORD record
ord-5520e4c4f0984895b1bffddd62d11d35
Source dataset
uspto-grants-2000_05
Patent number
US06057369

Reaction notes

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