Methyl iodide → 1,3-Cyclopentanedione, 2,2-dimethyl-

Synthesized according to Agosta and Smith, J. Org. Chem., 35: 3856 (1970). A mixture of 2-methyl-1,3-cyclopentanedione (10.025 g, 89.4 mmol, Aldrich), methyl iodide (6.0 mL, 96.4 mmol, Aldrich), and KOH (5.097 g, 90.8 mmol) in water (25 mL)/dioxane (75 mL) was heated at reflux. After 5 hours, a solution of KOH (2 g) and MeI (2.4 mL) in water (5 mL)/dioxane (15 mL) was added and after another 3 hours at reflux, the solution was stirred at room temperature overnight. A solution of KOH (2 g) and MeI (2.4 mL) in water (5 mL)/dioxane (15 mL) was added to the overnight reaction and heating at reflux. After 4 hours, the mixture was cooled to room temperature and extracted with ether (1×100 mL, 3×75 mL). The combined ether extracts were evaporated, the residue combined with 10% HCl (50 mL), and the resulting mixture placed in a 120° C. oil bath until it began boiling (ca. 15 minutes). The mixture was cooled to room temperature, neutralized by addition of saturated NaHCO3 solution (150 mL) and the resulting mixture extracted with CH2Cl2 (4×75 mL). The combined CH2Cl2 solution was dried (MgSO4), filtered and evaporated to leave a brown oil (10.474 g, 83 mmol, 93%) which was used directly in the next step.

1. customSynthesized
2. temperaturewas heated
3. temperatureat reflux
4. temperatureat reflux
5. temperatureheating
6. temperatureat reflux
7. waitAfter 4 hours
8. temperaturethe mixture was cooled to room temperature
9. extractionextracted with ether (1×100 mL, 3×75 mL)
10. customThe combined ether extracts were evaporated
11. customplaced in a 120° C.
12. custom(ca. 15 minutes)
13. temperatureThe mixture was cooled to room temperature
14. additionneutralized by addition of saturated NaHCO3 solution (150 mL)
15. extractionthe resulting mixture extracted with CH2Cl2 (4×75 mL)
16. dry with materialThe combined CH2Cl2 solution was dried (MgSO4)
17. filtrationfiltered
18. customevaporated

ORD-Eintrag

ord-093c570a32174974a56db476e33f4927

Quelldatensatz

uspto-grants-2014_11

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US08883139B2