1-chloro-4-(trifluoromethylsulfanyl)benzene

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

Procedure: Then, 1-chloro-4-(trifluoromethylsulfonyl)benzene was prepared as follows: ##STR12## 74 g of the 1-chloro-4-trifluoromethylthiobenzene was placed into a flask with 500 mL of glacial acetic acid and stirred to form a mixture. While stirring, 300 mL of a 30% hydrogen peroxided (H2O2)/water solution was added dropwise. After this addition, the mixture was stirred at reflux for several hours then cooled to room temperature. After cooling, the solids were filtered off and dried to produce 37 g of a product ("first product solids") having a melting point of 56°-57° C. GC-MS spectra confirmed a product of -chloro-4-(trifluoromethyl-sulfonyl)-benzene. The liltrate from filtering the solids was stirred with 300 mL of water and the product was extracted with 250 mL of methylene chloride to form an aqueous phase and a product-containing methylene chloride phase. The product-containing phase was separated, dried by passing it through sodium sulfate, low boilers were distilled off, and the remaining product was distilled to produce 15 g of product. This 15 g of product was then combined with the first product solids for a total yield of 57%. ##STR13## 6.1 g Of the 1-chloro-4-(trifluoromethylsulfonyl)benzene was placed into a flask with 5 g of potassium carbonate, 10 g of 3-phenoxyphenol (Eastman Kodak, now Eastman Chemical Company), 100 mL of dimethyl sulfoxide (DMSO), and stirred to form a mixture. While stirring, this mixture was heated to 120° C. and an exotherm occurred. The product was stirred at 120° C. for a total of two hours. Gas chromatography (GC) analysis showed complete reaction. After cooling to room temperature, the reaction mixture was poured into 400 mL of water and the product was extracted with 200 mL of methylene chloride to form a product phase. The product phase was separated, dried by passing through sodium sulfate, low boilers were distilled off, and the remaining product distilled. The product distilled at 180°-190° C. at 0.5 mm Hg to produce an oil in 64% yield. The identity of the product was confirmed by GC-MS analysis as 1-(3-phenoxyphenoxy)-4-(trifluoromethylsulfonyl)benzene. PDSC of the product indicated an oxidative stability up to 349° C. under 200 psi oxygen pressure, suggesting a high degree of thermo-oxidative stability. ##STR14## 100 mL of methanol and 10 g of sodium were placed into a pre-dried (under nitrogen), 500 mL 3-necked flask equipped with a mechanical stirrer, a reflux condenser topped with a nitrogen inlet tube, and a stopper. After all of the sodium had been consumed, the methanol was distilled from the flask, and the last traces were removed by azeotropic distillation with benzene. Anhydrous pyridine (250 mL) and resorcinol (35 g) were added, followed by 3-bromobenzotrifluoride (50 g) and cuprous chloride (20 g), and the mixture was left to stir at reflux for 24 hours. The mixture was cooled and filtered with the aid of ether (200 mL). The ether-containing phase was washed successively with water (250 mL), 5% hydrochloric acid (2×500 mL), saturated sodium bicarbonate (200 mL), and saturated sodium chloride (200 mL). Then it was dried with magnesium sulfate, filtered, and solvent was removed on a rotary evaporator to leave 38 g of a dark oily residue. Fractional distillation in vacuo afforded 25.2 g (45% yield) of 3-(3-trifluoromethylphenoxy)phenol as a faintly yellowish oil distilling at 132° C. and 1.5 mm Hg. The identity of the product was confirmed by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopies. to form a mixture While stirring was added dropwise After this addition the mixture was stirred at reflux for several hours After cooling the solids were filtered off dried

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

Procedure: Then, 1-chloro-4-(trifluoromethylsulfonyl)benzene was prepared as follows: ##STR12## 74 g of the 1-chloro-4-trifluoromethylthiobenzene was placed into a flask with 500 mL of glacial acetic acid and stirred to form a mixture. While stirring, 300 mL of a 30% hydrogen peroxided (H2O2)/water solution was added dropwise. After this addition, the mixture was stirred at reflux for several hours then cooled to room temperature. After cooling, the solids were filtered off and dried to produce 37 g of a product ("first product solids") having a melting point of 56°-57° C. GC-MS spectra confirmed a product of -chloro-4-(trifluoromethyl-sulfonyl)-benzene. The liltrate from filtering the solids was stirred with 300 mL of water and the product was extracted with 250 mL of methylene chloride to form an aqueous phase and a product-containing methylene chloride phase. The product-containing phase was separated, dried by passing it through sodium sulfate, low boilers were distilled off, and the remaining product was distilled to produce 15 g of product. This 15 g of product was then combined with the first product solids for a total yield of 57%. ##STR13## 6.1 g Of the 1-chloro-4-(trifluoromethylsulfonyl)benzene was placed into a flask with 5 g of potassium carbonate, 10 g of 3-phenoxyphenol (Eastman Kodak, now Eastman Chemical Company), 100 mL of dimethyl sulfoxide (DMSO), and stirred to form a mixture. While stirring, this mixture was heated to 120° C. and an exotherm occurred. The product was stirred at 120° C. for a total of two hours. Gas chromatography (GC) analysis showed complete reaction. After cooling to room temperature, the reaction mixture was poured into 400 mL of water and the product was extracted with 200 mL of methylene chloride to form a product phase. The product phase was separated, dried by passing through sodium sulfate, low boilers were distilled off, and the remaining product distilled. The product distilled at 180°-190° C. at 0.5 mm Hg to produce an oil in 64% yield. The identity of the product was confirmed by GC-MS analysis as 1-(3-phenoxyphenoxy)-4-(trifluoromethylsulfonyl)benzene. PDSC of the product indicated an oxidative stability up to 349° C. under 200 psi oxygen pressure, suggesting a high degree of thermo-oxidative stability. ##STR14## 100 mL of methanol and 10 g of sodium were placed into a pre-dried (under nitrogen), 500 mL 3-necked flask equipped with a mechanical stirrer, a reflux condenser topped with a nitrogen inlet tube, and a stopper. After all of the sodium had been consumed, the methanol was distilled from the flask, and the last traces were removed by azeotropic distillation with benzene. Anhydrous pyridine (250 mL) and resorcinol (35 g) were added, followed by 3-bromobenzotrifluoride (50 g) and cuprous chloride (20 g), and the mixture was left to stir at reflux for 24 hours. The mixture was cooled and filtered with the aid of ether (200 mL). The ether-containing phase was washed successively with water (250 mL), 5% hydrochloric acid (2×500 mL), saturated sodium bicarbonate (200 mL), and saturated sodium chloride (200 mL). Then it was dried with magnesium sulfate, filtered, and solvent was removed on a rotary evaporator to leave 38 g of a dark oily residue. Fractional distillation in vacuo afforded 25.2 g (45% yield) of 3-(3-trifluoromethylphenoxy)phenol as a faintly yellowish oil distilling at 132° C. and 1.5 mm Hg. The identity of the product was confirmed by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopies. to form a mixture While stirring was added dropwise After this addition the mixture was stirred at reflux for several hours After cooling the solids were filtered off dried

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

Procedure: Then, 1-chloro-4-(trifluoromethylsulfonyl)benzene was prepared as follows: ##STR12## 74 g of the 1-chloro-4-trifluoromethylthiobenzene was placed into a flask with 500 mL of glacial acetic acid and stirred to form a mixture. While stirring, 300 mL of a 30% hydrogen peroxided (H2O2)/water solution was added dropwise. After this addition, the mixture was stirred at reflux for several hours then cooled to room temperature. After cooling, the solids were filtered off and dried to produce 37 g of a product ("first product solids") having a melting point of 56°-57° C. GC-MS spectra confirmed a product of -chloro-4-(trifluoromethyl-sulfonyl)-benzene. The liltrate from filtering the solids was stirred with 300 mL of water and the product was extracted with 250 mL of methylene chloride to form an aqueous phase and a product-containing methylene chloride phase. The product-containing phase was separated, dried by passing it through sodium sulfate, low boilers were distilled off, and the remaining product was distilled to produce 15 g of product. This 15 g of product was then combined with the first product solids for a total yield of 57%. ##STR13## 6.1 g Of the 1-chloro-4-(trifluoromethylsulfonyl)benzene was placed into a flask with 5 g of potassium carbonate, 10 g of 3-phenoxyphenol (Eastman Kodak, now Eastman Chemical Company), 100 mL of dimethyl sulfoxide (DMSO), and stirred to form a mixture. While stirring, this mixture was heated to 120° C. and an exotherm occurred. The product was stirred at 120° C. for a total of two hours. Gas chromatography (GC) analysis showed complete reaction. After cooling to room temperature, the reaction mixture was poured into 400 mL of water and the product was extracted with 200 mL of methylene chloride to form a product phase. The product phase was separated, dried by passing through sodium sulfate, low boilers were distilled off, and the remaining product distilled. The product distilled at 180°-190° C. at 0.5 mm Hg to produce an oil in 64% yield. The identity of the product was confirmed by GC-MS analysis as 1-(3-phenoxyphenoxy)-4-(trifluoromethylsulfonyl)benzene. PDSC of the product indicated an oxidative stability up to 349° C. under 200 psi oxygen pressure, suggesting a high degree of thermo-oxidative stability. ##STR14## 100 mL of methanol and 10 g of sodium were placed into a pre-dried (under nitrogen), 500 mL 3-necked flask equipped with a mechanical stirrer, a reflux condenser topped with a nitrogen inlet tube, and a stopper. After all of the sodium had been consumed, the methanol was distilled from the flask, and the last traces were removed by azeotropic distillation with benzene. Anhydrous pyridine (250 mL) and resorcinol (35 g) were added, followed by 3-bromobenzotrifluoride (50 g) and cuprous chloride (20 g), and the mixture was left to stir at reflux for 24 hours. The mixture was cooled and filtered with the aid of ether (200 mL). The ether-containing phase was washed successively with water (250 mL), 5% hydrochloric acid (2×500 mL), saturated sodium bicarbonate (200 mL), and saturated sodium chloride (200 mL). Then it was dried with magnesium sulfate, filtered, and solvent was removed on a rotary evaporator to leave 38 g of a dark oily residue. Fractional distillation in vacuo afforded 25.2 g (45% yield) of 3-(3-trifluoromethylphenoxy)phenol as a faintly yellowish oil distilling at 132° C. and 1.5 mm Hg. The identity of the product was confirmed by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopies. to form a mixture While stirring was added dropwise After this addition the mixture was stirred at reflux for several hours After cooling the solids were filtered off dried

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