Acetate → HCID 12811936, Verbindung

Temperatur

55 °C

A 3 neck 2 L round bottom flask equipped with dropping funnel, temperature controller, nitrogen outlet, stir bar and condenser is charged with 71 g (1.27 mols) of potassium hydroxide (KOH), 300 mL of methanol and 300 mL of isopropanol. The addition takes place at room temperature, however, while the base is dissolving in the solvent there is approximately 30° C. increase in temperature. The base solution is allowed to stir under nitrogen for 20 minutes. During this time, the temperature of the flask goes down to 44.7° C. To the above base solution, 156 g of nitrocyclohexane (“NCyHex”) (1.16 mols) is added slowly with vigorous stirring. The mixture stirred for 10 minutes, and palladium acetate (0.56 mmol)/triphenyl phosphine (1.7 mmol) added as catalyst. The resulting yellow solution stirred under nitrogen for another 5 minutes and 139.5 mL (1.06 mols) of allyl acetate added drop-wise to the mixture via the dropping funnel. During the addition of the acetate, the reaction mixture turns brown but transparent. During the addition, the temperature rises. At this point, heat is switched on and the mixture stirred for 8 h at 55° C. followed by overnight stiffing at room temperature. The next day the mixture is heated again to 55° C. followed by room temperature stirring overnight. After the reaction is complete, the contents of the flask are poured into a separatory funnel containing 600 mL of water. The organic layer is extracted with pentane (3×200 mL) and dried under MgSO4. Excess solvent is removed under a rotary evaporator and 167 g (93.5%) of deep brown solution of the desired 1-allyl-1-nitrocyclohexane (11) obtained at 90.7% purity. GC/MS analysis shows [MH]+ m/z 123.

1. customA 3 neck 2 L round bottom flask equipped
2. additionThe addition
3. customat room temperature
4. dissolutionhowever, while the base is dissolving in the solvent there
5. customis approximately 30° C.
6. temperatureincrease in temperature
7. stirringto stir under nitrogen for 20 minutes
8. customgoes down to 44.7° C
9. stirringThe mixture stirred for 10 minutes
10. stirringThe resulting yellow solution stirred under nitrogen for another 5 minutes
11. additionDuring the addition
12. temperatureAt this point, heat
13. stirringstirred for 8 h at 55° C.
14. customstiffing at room temperature
15. customfollowed by room temperature
16. stirringstirring overnight
17. additionthe contents of the flask are poured into a separatory funnel
18. extractionThe organic layer is extracted with pentane (3×200 mL)
19. customdried under MgSO4
20. customExcess solvent is removed under a rotary evaporator and 167 g (93.5%) of deep brown solution of the desired 1-allyl-1-nitrocyclohexane (11)
21. customobtained at 90.7% purity

ORD-Eintrag

ord-8cebf3388ce54654bd1b89a77e308c42

Quelldatensatz

uspto-grants-2013_07

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US08480800B2