Methanol → HCID 72956942, compound

HRID 1167147Notes

Reaction equation

HRID 1167147 reaction equation
[CH2:1]([O:8][CH2:9][CH2:10][CH:11]1[CH2:13][C:12]1(Cl)[C:14]([Cl:18])=[C:15](Cl)Cl)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Na].[OH2:21].[CH3:22][OH:23]>>[CH2:1]([O:8][CH2:9][CH2:10][CH:11]1[CH2:13][C:12]1=[C:14]([Cl:18])[C:15]([O:23][CH3:22])=[O:21])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 4

HCID 887Methanol2×HCID 962WaterHCID 5360545SodiumHCID 12165826HCID 12165826, compound

Product 1

HCID 72956942HCID 72956942, compound

Procedure

At 0° C., a solution of 62.9 g (185 mmol) of J, 2-(2-benzyloxyethyl)-1-chloro-1-(1,2,2-trichlorovinyl)cyclopropane, in 50 ml of anhydrous methanol is slowly added dropwise with stirring to a freshly prepared solution of 34.0 g of sodium (1.48 mol, 8 equivalents) in 250 ml of methanol. The mixture is then heated at reflux for 2 d. After cooling to room temperature, the mixture is admixed with 700 ml of water and extracted with diethyl ether. The combined organic phases are concentrated under reduced pressure and the residue is taken up in 300 ml of methanol. 25 ml of 10 per cent hydrochloric acid are added and the reaction mixture is stirred for 45 min. The mixture is then admixed with 300 ml of saturated sodium bicarbonate solution and extracted with diethyl ether. The ether extracts are dried over calcium chloride. Removal of the solvent under reduced pressure gives a dark-brown oil. Filtration through 300 g of silica gel (PE:diethyl ether 10:1) gives 24.4 g (47%) of K methyl [2-(2-benzyloxyethyl)cyclo-propylidene]chloroacetate in the form of a pale yellow liquid as a mixture of two diastereomers in the ratio of 1:1.6.-13C-NMR (62.9 MHz, CDCl3, additionally DEPT), isomer A: δ=11.6 (−), 20.3 (+), 31.6 (−), 52.8 (+), 68.8 (−), 72.9 (−), 115.3 (Cquart), 127.49 (+), 127.53 (+), 128.3 (+), 138.3 (Cquart), 143.8 (Cquart), 162.4 (Cquart). -isomer B: δ=15.6 (−), 16.1 (+), 31.5 (−), 52.8 (+), 69.3 (−), 73.0 (−), 114.6 (Cquart), 127.49 (+), 127.53 (+), 128.3 (+), 143.3 (Cquart), 162-7 (Cquart). MS (70 eV), m/z (%): 280 (<1) [M+], 245 (1) [M+—Cl], 189 (2) [M+—CH2Ph], 91 (100) [CH2Ph+]. —C15H17ClO3 (280.8): calc. C, 64.17 H, 6.10; found C, 63.24, H, 5.97.

Workup

  1. temperatureThe mixture is then heated
  2. temperatureat reflux for 2 d
  3. extractionextracted with diethyl ether
  4. concentrationThe combined organic phases are concentrated under reduced pressure
  5. addition25 ml of 10 per cent hydrochloric acid are added
  6. extractionextracted with diethyl ether
  7. dry with materialThe ether extracts are dried over calcium chloride
  8. customRemoval of the solvent under reduced pressure
  9. customgives a dark-brown oil
  10. filtrationFiltration through 300 g of silica gel (PE:diethyl ether 10:1)

Sources & evidence

ORD record
ord-7fa97cb90c364d20bd3d177576d3f52e
Source dataset
uspto-grants-2003_09
Patent number
US06617332B1

Reaction notes

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