Hydroquinone → Methyl (1,2,3,4,5,6,7,8-octahydro-2,3-dimethylene-1,4-epoxynaphthalen-6-yl) ketone

HRID 1154772Notes

Reaction equation

HRID 1154772 reaction equation
[CH2:1]=[C:2]1[C:7](=[CH2:8])[CH:6]2[O:9][CH:3]1[C:4](=[CH2:11])[C:5]2=[CH2:10].[CH:12]([C:14]([CH3:16])=[O:15])=[CH2:13].C1(C=CC(O)=CC=1)O>[Cl-].[Zn+2].[Cl-].C(Cl)(Cl)Cl>[CH2:11]=[C:4]1[C:5](=[CH2:10])[CH:6]2[O:9][CH:3]1[C:2]1[CH2:1][CH2:13][CH:12]([C:14]([CH3:16])=[O:15])[CH2:8][C:7]=12

Participants

6

Reactant 3

HCID 785HydroquinoneHCID 6570Methyl vinyl ketoneHCID 1429962,3,5,6-Tetramethylidene-7-oxabicyclo[2.2.1]heptane

Product 1

HCID 54365753Methyl (1,2,3,4,5,6,7,8-octahydro-2,3-dimethylene-1,4-epoxynaphthalen-6-yl) ketoneYield 86%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 6212ChloroformSolvent

Procedure

A mixture of 11.4 g of 2,3,5,6-tetramethylene-7-oxabicyclo[2.2.1]heptane, 2 g of anhydrous zinc chloride, 30 ml of methyl vinyl ketone and 75 ml of chloroform, containing 10 mg of hydroquinone, was stirred at room temperature for 20 hours under nitrogen. The mixture was concentrated under reduced pressure (ca 15 mmHg, room temperature) and rapidly eluted with methylene chloride/ethyl acetate (2:1) on a short column filled with 18 g of SiO2 (70-230 mesh). The first fractions contained methyl (1,2,3,4,5,6,7,8-octahydro-2,3-dimethylene-1,4-epoxynaphthalene-6-yl) ketone and unreacted methyl vinyl ketone. After the addition of 5 mg of hydroquinone, the mixture was concentrated to dryness at room temperature under reduced pressure (1 mmHg) until the methyl vinyl ketone had been completely removed. There were obtained 14.5 g (86%) of methyl (1,2,3,4,5,6,7,8-octahydro-2,3-dimethylene-1,4-epoxynaphthalen-6-yl) ketone in sufficient purity for the next step.

Workup

  1. concentrationThe mixture was concentrated under reduced pressure (ca 15 mmHg, room temperature)
  2. washrapidly eluted with methylene chloride/ethyl acetate (2:1) on a short column
  3. additionfilled with 18 g of SiO2 (70-230 mesh)
  4. additionAfter the addition of 5 mg of hydroquinone
  5. concentrationthe mixture was concentrated to dryness at room temperature under reduced pressure (1 mmHg) until the methyl vinyl ketone
  6. customhad been completely removed

Sources & evidence

ORD record
ord-30f481953d0d4bb98130098ef8b67fe5
Source dataset
uspto-grants-1981_11
Patent number
US04298535

Reaction notes

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