Carbon Dioxide → Tri-n-butyltrifluoromethylsilane

温度

-78 °C

A flask equipped with a dry ice condenser was flame dried under a nitrogen sream, and charged with 5.0g (20 mmol) of chloro -tri-n-butylsilane and 10 mL of dichloromethane. After cooling the resulting solution to -78° C. and charging the condenser with dry ice and acetone, 6.2 mL (66 mmol) of bromotrifluoromethane (Freon 13B1) that had been condensed into a graduated tube was warmed to room temperature and allowed to distill into the flask. The cooling bath was removed and the mixture was allowed to warm to the temperature of the refluxing Freon (-59° C.). To this cold solution was added, dropwise, 8.0 mL (29 mmol) of hexaethylphosphorous triamide. The resulting solution was stirred at reflux for 1 hour. Removal of the condenser and continued stirring for 1 hour resulted in evaporation of excess Freon and warming of the solution to room temperature. Dilution with 30 mL of dichloromethane, water (three 30 mL portions) and lN HCl (two 30 mL portions) washing, drying (MgSO4), and concentration afforded a residue which was short path distilled to give 3.6g (64% yield) of tri-n-butyltrifluoromethylsilane: bp 53-58° C. at 0.5 torr; 1H NMR (CDCl3) δ 0.60-1.10 (m, 5H), 1.10-1.56 (m, 4H); 19F NMR (CDCl3, relative to CFCl3) -61.6 ppm (s); IR (neat) 2956, 2925, 2872, 1214, 1058 cm-1; mass spectrum (70 eV) m/z (relatiVe intensity) 199 (30, M-CF3), 143 (80), 105 (30), 101 (27), 87 (30), 77 (66), 63 (43), 59 (41), 55 (54), 47 (25), 43 (20), 41 (100). Anal. Calcd. for C13H27F3Si: C, 58.16; H, 10.14. Found: C, 58.26; H, 10.09.

1. customA flask equipped with a dry ice condenser
2. temperaturewas flame
3. customdried under a nitrogen sream
4. customcondensed into a graduated tube
5. temperaturewas warmed to room temperature
6. distillationto distill into the flask
7. customThe cooling bath was removed
8. temperatureto warm to the temperature of the refluxing Freon (-59° C.)
9. additionTo this cold solution was added
10. temperatureat reflux for 1 hour
11. customRemoval of the condenser
12. stirringcontinued stirring for 1 hour
13. customresulted in evaporation of excess Freon
14. temperaturewarming of the solution to room temperature
15. washDilution with 30 mL of dichloromethane, water (three 30 mL portions) and lN HCl (two 30 mL portions) washing
16. customdrying
17. concentration(MgSO4), and concentration
18. customafforded a residue which
19. distillationdistilled

ORDレコード

ord-5445f077b1b24c91bdc46316f4ecd27d

出典データセット

uspto-grants-1991_04

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US05008425