Carbamate → HCID 21880483, compound

Temperature

55 °C

A Fischer Porter bottle was charged with 1.06 g (0.01 mol) diethylene glycol, 5.3 g (0.027 mol) N-cyclohexyl-N',N',N",N"-tetramethylguanidine, 154 mg biphenyl as G.C. internal standard and 20 mL CH3CN. The Fischer-Porter bottle was attached to a pressure head and at room temperature with stirring was added 80 psig carbon dioxide. Addition of CO2 resulted in an exothermic reaction with a rise in temperature to ca. 40° C. Into a second Fischer-Porter bottle was added 4.6 g (0.06 mol) allyl chloride in 10 mL CH3CN. This was attached to a pressure head and 80 psig carbon dioxide was added above the solution. After 1 h the allyl chloride solution was added all at once under 80 psig CO2 to the pre-formed carbamate anion solution generated in the first Fischer-Porter bottle. After addition the reaction mixture was warmed to 55° C. for 14 h. After this time the reaction mixture was allowed to cool to room temperature and then the pressure was released. An aliquot was taken, diluted with diethyl ether, Cl-+HCyTMG filtered off and by G.C. analysis a yield of 84% was calculated. The crude material was poured into 100 mL diethyl ether and was then extracted with 2×100 mL 0.5M aq. HCl and 100 mL brine. The ethereal layer was dried over Na2CO3, filtered and concentrated. The residue was chromatographed on silica gel using 100% hexane to remove internal standard and then CH2Cl2 giving 2.2 g (80%) of the di-carbonate 43. Oil 1H NMR (CDCl3) 5.91 (m, 2H), 5.35 (dq, J=17.2, 1.4 Hz, 2H), 5.25 (dq, J=10.4, 1.4 Hz, 2H), 4.62 (dt, J=5.8, 1.4 Hz, 4H), 4.28 (m, 4H), 3.72 (m, 4H). 13C{1H} NMR (CDCl3) 155.4, 132, 119.3, 69.4, 69.0, 67.3. IR (film) 1746, 1649, 1258.

1. customwas attached to a pressure head and at room temperature
2. customresulted in an exothermic reaction with a rise in temperature to ca. 40° C
3. additionwas added above the solution
4. additionAfter addition the reaction mixture
5. temperatureto cool to room temperature
6. filtrationfiltered off and by G.C
7. additionThe crude material was poured into 100 mL diethyl ether
8. extractionwas then extracted with 2×100 mL 0.5M aq. HCl and 100 mL brine
9. dry with materialThe ethereal layer was dried over Na2CO3
10. filtrationfiltered
11. concentrationconcentrated
12. customThe residue was chromatographed on silica gel using 100% hexane
13. customto remove internal standard

ORD record

ord-5eee2e64915b4b8fa6c46ca5992ddee2

Source dataset

uspto-grants-1994_12

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05371183