Formaldehyde → 2-(Methoxymethyl)-1,3-dimethylcyclopenta-1,3-diene

121.7 ml of 1.1 equivalents of methyl lithium solution was slowly added to 300 ml of tetrahydrofuran solution in which 29 g (166 mmol) of 2-bromo-3-methyl-2-cyclopentene-1-one [Formula I (R2═CH3, X═Br)] compound are dissolved at −78° C. nitrogen state, and then the mixture was reacted for 2 hours. 195.3 ml of 2.0 equivalents of tertiary butyl lithium solution was slowly added at the same temperature, and then the mixture was reacted for 2 hours. 3 equivalents of paraformaldehyde and the catalytic amount of paratoluenesulfonic anhydride were reacted at 100° C., and then the resulting formaldehyde gas was introduced in a reaction flask. After the completion of introducing the formaldehyde gas, the solvent was removed under reduced pressure while slowly elevating the temperature to a room temperature. After the removal of the solvent, 250 ml of dimethylformamide was injected into the reaction vessel using a cannula. 2 equivalents of methyl iodide were added thereto and the mixture was reacted for 15 hours. Then one equivalent of sodium hydride and the same equivalents of methyl iodide were added, and the mixture was reacted for a day. After the completion of the reaction, 300 ml of water and 300 ml of a sodium chloride solution were added and the mixture was extracted with 600 ml of hexane and once again with 200 ml of hexane. An organic layer was washed three times with 200 ml of a sodium chloride solution and the solvent was removed with a rotatory evaporator, and then 300 ml of ethyl acetate was added. 200 ml of 2N HCl solution was added to the extracted organic layer, and the resulting mixture was vigorously shaked for 2 minutes. Water layer was removed and the organic layer was neutralized with 200 ml of a saturated sodium bicarbonate solution. Isolated organic layer was treated with magnesium sulfate to remove water, and then vacuum-distillated to give 14.2 g of white 2-methoxymethyl-1,3-dimethyl-cyclopenta-1,3-diene. Yield: 62%.

1. dissolutionare dissolved at −78° C. nitrogen state
2. customthe mixture was reacted for 2 hours
3. customthe mixture was reacted for 2 hours
4. customthe solvent was removed under reduced pressure
5. customto a room temperature
6. customAfter the removal of the solvent, 250 ml of dimethylformamide
7. customthe mixture was reacted for 15 hours
8. customthe mixture was reacted for a day
9. additionwere added
10. extractionthe mixture was extracted with 600 ml of hexane and once again with 200 ml of hexane
11. washAn organic layer was washed three times with 200 ml of a sodium chloride solution
12. customthe solvent was removed with a rotatory evaporator
13. addition300 ml of ethyl acetate was added
14. addition200 ml of 2N HCl solution was added to the extracted organic layer
15. customWater layer was removed
16. additionIsolated organic layer was treated with magnesium sulfate
17. customto remove water

ORD record

ord-0ded527c441b405da322c083c1c69902

Source dataset

uspto-grants-2007_01

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07166731B2