(Aminomethyl)phosphonic acid → Prop-2-en-1-yl 7-oxabicyclo[4.1.0]heptane-3-carboxylate

HRID 1970082Notes

Reaction equation

HRID 1970082 reaction equation
[CH:1]1([C:7]([O:9][CH2:10][CH:11]=[CH2:12])=[O:8])[CH2:6][CH2:5][CH:4]=[CH:3][CH2:2]1.C([NH+](CCCCCCCC)CCCCCCCC)CCCCCCC.S(OC)(O)(=O)=[O:39].NCP(=O)(O)O>O.O.[O-][W]([O-])(=O)=O.[Na+].[Na+].OO>[O:39]1[CH:4]2[CH:3]1[CH2:2][CH:1]([C:7]([O:9][CH2:10][CH:11]=[CH2:12])=[O:8])[CH2:6][CH2:5]2

Participants

6

Reactant 3

HCID 14017(Aminomethyl)phosphonic acidHCID 12640054Allyl 3-cyclohexene-1-carboxylateHCID 86650352Methyl hydrogensulfate trioctylammonium

Product 1

HCID 235353Prop-2-en-1-yl 7-oxabicyclo[4.1.0]heptane-3-carboxylateYield 8,714.1%

Reagents, catalysts & solvents 2

HCID 150191Sodium Tungstate DihydrateCatalystHCID 784Hydrogen PeroxideSolvent

Conditions

Temperature
90 °C

Procedure

A three neck flask of 500 mL equipped with a reflux condenser, a thermometer, a stirring device, a dropping funnel and an oil bath was charged with 100.0 g of allyl 3-cyclohexene-1-carboxylate, 2.34 g of methyl hydrogensulfate trioctylammonium, 3.96 g of sodium tungstate dihydrate and 0.45 g of aminomethylphosphonic acid. The flask was heated on the oil bath maintained at 90° C., and 80 ml of 30% aqueous hydrogen peroxide was dropwise added thereto through the dropping funnel in 180 minutes to ripen the solution as it was for 4 hours. The flask was cooled on an ice bath, and surplus hydrogen peroxide was removed by 300 ml of a saturated sodium thiosulfate aqueous solution. Then, the solution was extracted twice with 200 ml of ethyl acetate. The ethyl acetate solution thus obtained was dried on anhydrous sodium sulfate for a night, and ethyl acetate which was the solvent was removed by means of a rotary evaporator. Then, the residue was refined by a silica gel chromatography filled with 25% hydrous silica gel to obtain 79.6 g of allyl 3,4-epoxycyclohexane-1-carboxylate.

Workup

  1. customA three neck flask of 500 mL equipped with a reflux condenser
  2. temperatureThe flask was heated on the oil bath
  3. waitthe solution as it was for 4 hours
  4. temperatureThe flask was cooled on an ice bath
  5. customsurplus hydrogen peroxide was removed by 300 ml of a saturated sodium thiosulfate aqueous solution
  6. extractionThen, the solution was extracted twice with 200 ml of ethyl acetate
  7. customThe ethyl acetate solution thus obtained
  8. dry with materialwas dried on anhydrous sodium sulfate for a night
  9. customwas removed by means of a rotary evaporator
  10. additionfilled with 25% hydrous silica gel

Sources & evidence

ORD record
ord-d6ea682afd904ab9b21c571aa0ec097b
Source dataset
uspto-grants-2013_04
Patent number
US08426614B2

Reaction notes

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