bromo(trifluoro)methane

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: This example illustrates the preparation of several types of perfluoroalkylsulfonylphenyl ethers. Each of these illustrated ethers are produced in (a)-(e), below. Unless otherwise indicated, the reactions described below are performed in a 250 mL, 3-necked flask equipped with a mechanical stirrer, a reflux condenser topped with a nitrogen inlet tube, and a stopper. These illustrations utilize a starting material of 1-chloro-4-(trifluoromethylsulfonyl)benzene which may be prepared as described below. First, 1-chloro-4-trifluoromethylthiobenzene is prepared as follows: ##STR11## A mixture was formed in the flask from the following materials: 73 grams (g) of 4-chlorothiophenol, 400 milliliters (mL) of dimethyl formamide (DMF), and 70 g of potassium carbonate (K2CO3). This mixture was stirred at 60° C. for one hour and cooled to ice water bath temperatures (between about 0° C. and about 5° C.) and 100 g of bromotrifluoromethane (BrCF3) was bubbled into the mixture for two hours. The mixture was then stirred for two hours while warming to room temperature (about 23° C.) and then poured into 300 mL of water with stirring to form a product. The product was extracted with 300 mL of methylene chloride, separated, and washed with 250 mL of water. The product-containing, methylene chloride phase was separated and then dried by passing it through sodium sulfate. Low boiling point (up to 100° C., unless stated otherwise) components of the product phase ("low boilers") were then distilled off under reduced pressure (about 0.5 mm Hg) and the remaining product was then distilled over a short distillation column under reduced pressure to produce an 80% yield of an oily product. The identity of the product was confirmed by gas chromatography-mass spectroscopy (GC-MS) spectra to be 1-chloro-4-trifluoromethylthiobenzene. equipped with a mechanical stirrer, a reflux condenser topped with a nitrogen inlet tube may be prepared ##STR11## A mixture was formed in the flask from the following materials was bubbled into the mixture for two hours The mixture was then stirred for two hours while warming to room temperature (about 23° C.) poured into 300 mL of water with stirring to form a product The product was extracted with 300 mL of methylene chloride separated washed with 250 mL of water The product-containing, methylene chloride phase was separated dried up to 100° C. were then distilled off under reduced pressure (about 0.5 mm Hg) the remaining product was then distilled over a short distillation column under reduced pressure

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A flask equipped with a dry ice condenser was flame dried under a nitrogen sream, and charged with 5.0 g (20 mmol) of chlorotri-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 1N HCl (two 30 mL portions) washing, drying (MgSO4), and concentration afforded a residue which was short path distilled to give 3.6 g (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. A flask equipped with a dry ice condenser was flame dried under a nitrogen sream condensed into a graduated tube was warmed to room temperature to distill into the flask The cooling bath was removed to warm to the temperature of the refluxing Freon (-59°C.) To this cold solution was added at reflux for 1 hour Removal of the condenser continued stirring for 1 hour resulted in evaporation of excess Freon warming of the solution to room temperature Dilution with 30 mL of dichloromethane, water (three 30 mL portions) and 1N HCl (two 30 mL portions) washing drying (MgSO4), and concentration afforded a residue which distilled

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A flask equipped with a dry ice condenser was flame dried under a nitrogen stream, and charged with 25 g (0.17 mol) of chlorotriethylsilane and 40 mL of dichloromethane. After cooling the resulting solution to -78° C. and charging the condenser with dry ice and acetone, 40 mL (0.43 mol) 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 cold solution was treated dropwise with 66mL (0.24 mol) of hexaethylphosphorous triamide, allowed to stir at -78° C. for two hours, and allowed to stir at room temperature overnight. Low boiling components were then short path distilled into a cold (-78° C.) receiving flask at >1 torr with the pot temperature kept at <50° C. The distillate was further fractionated by removal of the dichloromethane (40°-45° C. at atmospheric pressure) and short path distillation to give 22.0 g of 98% pure (69% yield) triethyltrifluoromethylsilane: bp 52°-54° C. at 10 torr; 1H NMR (CDCl3) δ 0.59-1.16 (m); 19F NMR (CDCl3, relative to CFCl3) - 61.3 ppm (s); IR (neat) 2960, 2915, 2882, 1458, 1413, 1206, 1055, 1020, 734, 693 cm-1 ; mass spectrum (70 eV) m/z (relative intensity) 115 (66, M-CF3), 105 (46), 87 (85), 77 (100), 59 (56), 49 (41), 47 (37), 41 (38). Anal. Calcd. for C7H15F3Si: C, 45.62; H, 8.20. Found: C, 47.53; H, 8.56. A flask equipped with a dry ice condenser was flame dried under a nitrogen stream condensed into a graduated tube was warmed to room temperature to distill into the flask to stir at room temperature overnight short path distilled into a cold (-78° C.) kept at <50° C The distillate was further fractionated by removal of the dichloromethane (40°-45° C. at atmospheric pressure) and short path distillation

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 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. A flask equipped with a dry ice condenser was flame dried under a nitrogen sream condensed into a graduated tube was warmed to room temperature to distill into the flask The cooling bath was removed to warm to the temperature of the refluxing Freon (-59° C.) To this cold solution was added at reflux for 1 hour Removal of the condenser continued stirring for 1 hour resulted in evaporation of excess Freon 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 distilled

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 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. A flask equipped with a dry ice condenser was flame dried under a nitrogen sream condensed into a graduated tube was warmed to room temperature to distill into the flask The cooling bath was removed to warm to the temperature of the refluxing Freon (-59° C.) To this cold solution was added at reflux for 1 hour Removal of the condenser continued stirring for 1 hour resulted in evaporation of excess Freon 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 distilled

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A flask equipped with a dry ice condenser was flame dried under a nitrogen stream, and charged with 25g (0.17 mol) of chlorotriethylsilane and 40 mL of dichloromethane. After cooling the resulting solution to -78° C. and charging the condenser with dry ice and acetone, 40 mL (0.43 mol) 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 cold solution was treated dropwise with 66mL (0.24 mol) of hexaethylphosphorous triamide, allowed to stir at -78° C. for two hours, and allowed to stir at room temperature overnight. Low boiling components were then short path distilled into a cold (-78° C.) receiving flask at>1 torr with the pot temperature kept at<50° C. The distillate was further fractionated by removal of the dichloromethane (40-45° C. at atmospheric pressure) and short path distillation to give 22.0 g of 98% pure (69% yield) triethyltrifluoromethylsilane: bp 52-54° C. at 10 torr; 1H NMR (CDCl3) δ 0.59-1.16 (m); 19F NMR (CDCl3, relative to CFCl3) -61.3 ppm (s); IR (neat) 2960, 2915, 2882, 1458, 1413, 1206, 1055, 1020, 734, 693 cm-1; mass spectrum (70 eV) m/z (relative intensity) 115 (66, M-CF3), 105 (46), 87 (85), 77 (100), 59 (56), 49 (41), 47 (37), 41 (38). Anal. Calcd. for C7H15F3Si: C, 45.62; H, 8.20. Found: C, 47.53; H, 8.56. A flask equipped with a dry ice condenser was flame dried under a nitrogen stream condensed into a graduated tube was warmed to room temperature to distill into the flask to stir at room temperature overnight short path distilled into a cold (-78° C.) kept at<50° C The distillate was further fractionated by removal of the dichloromethane (40-45° C. at atmospheric pressure) and short path distillation

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A flask equipped with a dry ice condenser was flame dried under a nitrogen stream, and charged with 3.1 mL (17 mmol) of chlorodiphenylphosphine and 10 mL of dichloromethane. After cooling the resulting solution to -78° C. and charging the condenser with dry ice and acetone, 4 mL (43 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 cold solution was treated dropwise with 7 mL (26 mmol) of hexaethylphosphorous triamide, allowed to stir at "78° C. for 1 hour, and allowed to stir at room temperature overnight. Dilution with 50 mL of dichloromethane, water washing (three 50 mL portions), drying (MgSO4), and concentration afforded a brown liquid which was purified by flash chromatography on 50g of silica gel (230-400 mesh) eluted with petroleum ether to give 2.9g (68% yield) of diphenyltrifluoromethylphosphine as a colorless liquid. 19F NMR (CDCl3, relative to CFCl3) -55.60 ppm (d, JPF =73 Hz); 31P NMR (CDCl3, relative to H3PO4) 3.11 ppm (quartet of pentets, JPF =73 Hz, JPH =8 Hz); mass spectrum (70 eV) m/z (relative intensity) 254 (41, M+), 185 (74), 183 (100), 127 (23), 107 (40), 77 (26), 69 (65), 51 (54). A flask equipped with a dry ice condenser was flame dried under a nitrogen stream condensed into a graduated tube was warmed to room temperature to distill into the flask to stir at room temperature overnight Dilution with 50 mL of dichloromethane, water washing (three 50 mL portions), drying (MgSO4), and concentration afforded a brown liquid which was purified by flash chromatography on 50g of silica gel (230-400 mesh) eluted with petroleum ether

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A reaction tube in a photoreaction apparatus was charged with 50 ml of dimethylformamide (DMF) and 5.59 g (30 mmol) of 2-mercaptobiphenyl, and with ice cooling and stirring, 1.2 g (30 mmol) of sodium hydride (60% in oil) was added. When foaming ceased, trifluoromethyl bromide was introduced into the reaction solution. The atmosphere within the reaction system was replaced by gaseous trifluoromethyl bromide, and while irradiating light from a high-pressure mercury lamp, about 2 equivalents of trifluoromethyl bromide was passed into the reaction system over about 2 hours. Ice water (150 ml) was added to the resulting brown reaction solution, and it was extracted with pentane. The organic layer was washed with water and then with saturated aqueous sodium chloride solution, and then dried over anhydrous magnesium sulfate. The anhydrous magnesium sulfate was removed by filtration, and the filtrate was concentrated under reduced pressure to give 6.71 g (87.9%) of 2-(trifluoromethylthio)biphenyl as an oil. It was purified by silica gel column chromatography. The properties of the product were as shown below. while irradiating light from a high-pressure mercury lamp was extracted with pentane The organic layer was washed with water with saturated aqueous sodium chloride solution, and then dried over anhydrous magnesium sulfate The anhydrous magnesium sulfate was removed by filtration the filtrate was concentrated under reduced pressure

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: This example illustrates the preparation of several types of perfluoroalkylsulfonylphenyl ethers. Each of these illustrated ethers are produced in (a)-(e), below. Unless otherwise indicated, the reactions described below are performed in a 250 mL, 3-necked flask equipped with a mechanical stirrer, a reflux condenser topped with a nitrogen inlet tube, and a stopper. These illustrations utilize a starting material of 1-chloro-4-(trifluoromethylsulfonyl)benzene which may be prepared as described below. First, 1-chloro-4-trifluoromethylthiobenzene is prepared as follows: ##STR11## A mixture was formed in the flask from the following materials: 73 grams (g) of 4-chlorothiophenol, 400 milliliters (mL) of dimethyl formamide (DMF), and 70 g of potassium carbonate (K2CO3). This mixture was stirred at 60° C. for one hour and cooled to ice water bath temperatures (between about 0° C. and about 5° C.) and 100 g of bromotrifluoromethane (BrCF3) was bubbled into the mixture for two hours. The mixture was then stirred for two hours while warming to room temperature (about 23° C.) and then poured into 300 mL of water with stirring to form a product. The product was extracted with 300 mL of methylene chloride, separated, and washed with 250 mL of water. The product-containing, methylene chloride phase was separated and then dried by passing it through sodium sulfate. Low boiling point (up to 100° C., unless stated otherwise) components of the product phase ("low boilers") were then distilled off under reduced pressure (about 0.5 mm Hg) and the remaining product was then distilled over a short distillation column under reduced pressure to produce an 80% yield of an oily product. The identity of the product was confirmed by gas chromatography-mass spectroscopy (GC-MS) spectra to be 1-chloro-4-trifluoromethylthiobenzene. equipped with a mechanical stirrer, a reflux condenser topped with a nitrogen inlet tube may be prepared ##STR11## A mixture was formed in the flask from the following materials was bubbled into the mixture for two hours The mixture was then stirred for two hours while warming to room temperature (about 23° C.) poured into 300 mL of water with stirring to form a product The product was extracted with 300 mL of methylene chloride separated washed with 250 mL of water The product-containing, methylene chloride phase was separated dried up to 100° C. were then distilled off under reduced pressure (about 0.5 mm Hg) the remaining product was then distilled over a short distillation column under reduced pressure