difluoro(trimethyl)silanuide;tris(dimethylamino)sulfanium

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

Procedure: To a solution of 2.12 mL (20 mmol) of 4-fluoronitrobenzene and 4.12 mL (21 mmol) of [(1-phenyl-1-ethenyl)oxy]trimethylsilane in 30 mL of THF at -78° C. was added 5.502 g (20 mmol) of TASF dissolved in 6 mL of acetonitrile and 5 mL of THF. After stirring for 3 hrs at -78° C., 1.00 mL (19.50 mmol) of bromine in 5 mL of cyclohexane was added dropwise. After being stirred for 15 min at -78° C., the mixture was warmed to room temperature and stirred further for 30 min. Thirty mL of saturated sodium bisulfite was added, and the product was extracted into four 60 mL portions of ether. The organic phase was washed with saturated sodium chloride, dried, and concentrated. Chromatography on silica using 30% ether/hexanes yielded the expected product. The yield was 1.660 g (38%) of product, which was an oil. The product material was analyzed by infrared spectroscopy, nuclear magnetic resonance spectroscopy, and mass spectrometry. After being stirred for 15 min at -78° C. the mixture was warmed to room temperature stirred further for 30 min the product was extracted into four 60 mL portions of ether The organic phase was washed with saturated sodium chloride dried concentrated

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

Procedure: To a solution of 1.576 g (10 mmol) of 4-chloronitrobenzene and 1.68 mL (10.22 mmol) of carbomethyoxymethyltrimethylsilane in anhydrous THF was added 2.751 g (10 mmol) of TASF in 5 mL of acetonitrile at -78° C. The mixture was stirred for 7 hrs at that temperature, and 0.50 mL (9.70 mmol) of bromine was added dropwise. Stirring was continued for 1 hr, and saturated sodium bisulfite was added. The product was extracted into ether and isolated by chromatography on silica using 30% ether/hexane as solvent. The yield was 1.15 g (50%) product, which was an oil. The product was analyzed by infrared spectroscopy and nuclear magnetic resonance spectroscopy. was added dropwise The product was extracted into ether isolated by chromatography on silica using 30% ether/hexane as solvent

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

Procedure: A solution of 2.75 g (10 mmol) of TASF in 3 mL of acetonitrile and 3 mL of THF was added to a solution of 1.02 mL (10 mmol) of nitrobenzene and 1.93 mL (10.50 mmol) of [(oxacyclopent-2-ene-2-yl)oxy]trimethylsilane (OCS) in 12 mL of anhydrous THF at -78° C. over 10 min. The last traces of TASF from the dropping funnel were washed down with additional 5 mL of THF. The mixture was stirred for 20 hrs. at -78° C. Then, 0.460 mL (8.98 mmol) of bromine was added from a dropping funnel. The mixture was stirred at -78° C. for 15 min, and then the cold bath was removed. Stirring was continued for 1 hr. Thirty mL of freshly prepared saturated sodium bisulfite was added, and the product was extracted into four 60 mL portions of ether. Combined ether extracts were washed with saturated potassium hydrogen phosphate and sodium chloride. Concentration and chromatography on silica yielded two products identified as the ortho and para addition products. The ortho-adduct yielded 0.660 g (32%) of product which had a melting point of 112°-117° C. (dec). The para-adduct yielded 0.282 g (14%) of product which had a melting point of 76° to 78° C. Both the o- and p-products were analyzed by ultraviolet absorption, infrared spectroscopy, nuclear magnetic resonance spectroscopy, and mass spectrometry. The last traces of TASF from the dropping funnel were washed down with additional 5 mL of THF at -78° C The mixture was stirred at -78° C. for 15 min the cold bath was removed Stirring was continued for 1 hr Thirty mL of freshly prepared saturated sodium bisulfite was added the product was extracted into four 60 mL portions of ether Combined ether extracts were washed with saturated potassium hydrogen phosphate and sodium chloride Concentration and chromatography on silica yielded two products identified as the ortho and para addition products

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

Procedure: To a solution of 0.757 g (3.39 mmol) of 9-nitroanthracene and 0.663 mL (3.56 mmol) of MTS in 20 mL of anhydrous THF was added 0.941 g (3.42 mmol) of TASF in 2 mL of anhydrous acetonitrile at -78° C. The mixture was stirred for 24 hr. at -78° C. Then, ten mL of saturated KH2PO4 and 20 mL of water were added, the mixture was warmed to room temperature, and the product was extracted into ether. The combined ether extract was washed with water, dried, and concentrated. The major product, 0.491 g (56%), was isolated by column chromatography on silica using 20° ether/hexane as the solvent. Addition of small amount of ether to the major fraction yielded a light yellow solid. The product was analyzed by ultraviolet absorption, infrared spectroscopy, nuclear magnetic resonance spectroscopy, and mass spectrometry. at -78° C the product was extracted into ether The combined ether extract was washed with water dried concentrated The major product, 0.491 g (56%), was isolated by column chromatography on silica using 20° ether/hexane as the solvent yielded a light yellow solid The product was analyzed by ultraviolet absorption

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

Procedure: A solution of 1.115 g (5 mmol) of 9-nitroanthracene and 1.01 mL (5 mmol) of MMTS in 20 mL of anhydrous THF was treated with 1.375 g (5 mmol) of TASF dissolved in 3 mL of acetonitrile at -78° C. After addition of TASF had been completed, the reaction mixture was brought to -10° C. and stirred for 1 hr. Ten mL of water was then added, the mixture was warmed to room temperature, and the product was extracted into ether. The organic layer was washed with saturated sodium chloride solution, dried and concentrated. The melting point was 159° to 163° C. (dec). The product material was analyzed by ultraviolet absorption, infrared spectroscopy, nuclear magnetic resonance spectroscopy, and mass spectrometry. was brought to -10° C. the product was extracted into ether The organic layer was washed with saturated sodium chloride solution dried concentrated The product material was analyzed by ultraviolet absorption

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

Procedure: A flame dried 50 mL flask fitted with an addition funnel was charged with 0.872 g (500 mmol) of 5-nitroisoquinoline and 0.95 mL (5.1 mmol) of MTS. An acetonitrile solution of 1.40 g (5.09 mmol) of TASF was slowly added to the reaction mixture in 15 min at -78° C. The mixture was stirred for 22 h at that temperature. One mL of acetic acid in 5 mL of hexane was added, and reaction was warmed to room temperature. After 30 min, 40 mL of water was added. The solid which precipitated out was collected and analyzed. The product yield was 0.972 g (74%). The product material was analyzed by infrared spectroscopy, nuclear magnetic resonance spectroscopy, and mass spectrometry. A flame dried 50 mL flask fitted with an addition funnel reaction After 30 min The solid which precipitated out was collected

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

Procedure: To a solution of 2.12 mL (20 mmol) of 4-fluoronitrobenzene and 4.12 mL (21 mmol) of [(1-phenyl-1-ethenyl)oxy]trimethylsilane in 30 mL of THF at -78° C. was added 5.502 g (20 mmol) of TASF dissolved in 6 mL of acetonitrile and 5 mL of THF. After stirring for 3 hrs at -78° C., 1.00 mL (19.50 mmol) of bromine in 5 mL of cyclohexane was added dropwise. After being stirred for 15 min at -78° C., the mixture was warmed to room temperature and stirred further for 30 min. Thirty mL of saturated sodium bisulfite was added, and the product was extracted into four 60 mL portions of ether. The organic phase was washed with saturated sodium chloride, dried, and concentrated. Chromatography on silica using 30% ether/hexanes yielded the expected product. The yield was 1.660 g (38%) of product, which was an oil. The product material was analyzed by infrared spectroscopy, nuclear magnetic resonance spectroscopy, and mass spectrometry. After being stirred for 15 min at -78° C. the mixture was warmed to room temperature stirred further for 30 min the product was extracted into four 60 mL portions of ether The organic phase was washed with saturated sodium chloride dried concentrated

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

Procedure: To a solution of 1.576 g (10 mmol) of 4-chloronitrobenzene and 1.68 mL (10.22 mmol) of carbomethyloxymethyltrimethylsilane in anhydrous THF was added 2.751 g (10 mmol) of TASF in 5 mL of acetonitrile at -78° C. The mixture was stirred for 7 hrs at that temperature, and 0.50 mL (9.70 mmol) of bromine was added dropwise. Stirring was continued for 1 hr, and saturated sodium bisulfite was added. The product was extracted into ether and isolated by chromatography on silica using 30% ether/hexane as solvent. The yield was 1.15 g (50%) product, which was an oil. The product was analyzed by infrared spectroscopy and nuclear magnetic resonance spectroscopy. was added dropwise The product was extracted into ether isolated by chromatography on silica using 30% ether/hexane as solvent

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

Procedure: To a solution of 0.757 g (3.39 mmol) of 9-nitroanthracene and 0.663 mL (3.56 mmol) of MTS in 20 mL of anhydrous THF was added 0.941 g (3.42 mmol) of TASF in 2 mL of anhydrous acetonitrile at -78° C. The mixture was stirred for 24 hr. at -78° C. Then, ten mL of saturated KH2PO4 and 20 mL of water were added, the mixture was warmed to room temperature, and the product was extracted into ether. The combined ether extract was washed with water, dried, and concentrated. The major product, 0.491 g (56%), was isolated by column chromatography on silica using 20° ether/hexane as the solvent. Addition of small amount of ether to the major fraction yielded a light yellow solid. The product was analyzed by ultraviolet absorption, infrared spectroscopy, nuclear magnetic resonance spectroscopy, and mass spectrometry. at -78° C the product was extracted into ether The combined ether extract was washed with water dried concentrated The major product, 0.491 g (56%), was isolated by column chromatography on silica using 20° ether/hexane as the solvent yielded a light yellow solid The product was analyzed by ultraviolet absorption

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

Procedure: To a solution of 0.757 g (3.39 mmol) of 9-nitroanthracene and 0.663 mL (3.56 mmol) of MTS in 20 mL of anhydrous THF was added 0.941 g (3.42 mmol) of TASF in 2 mL of anhydrous acetonitrile at -78° C. The mixture was stirred for 24 hr. at -78° C. Then, ten mL of saturated KH2PO4 and 20 mL of water were added, the mixture was warmed to room temperature, and the product was extracted into ether. The combined ether extract was washed with water, dried, and concentrated. The major product, 0.491 g (56%), was isolated by column chromatography on silica using 20° ether/hexane as the solvent. Addition of small amount of ether to the major fraction yielded a light yellow solid. The product was analyzed by ultraviolet absorption, infrared spectroscopy, nuclear magnetic resonance spectroscopy, and mass spectrometry. at -78° C the product was extracted into ether The combined ether extract was washed with water dried concentrated The major product, 0.491 g (56%), was isolated by column chromatography on silica using 20° ether/hexane as the solvent yielded a light yellow solid The product was analyzed by ultraviolet absorption

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

Procedure: A solution of 1.115 g (5 mmol) of 9-nitroanthracene and 1.01 mL (5 mmol) of MMTS in 20 mL of anhydrous THF was treated with 1.375 g (5 mmol) of TASF dissolved in 3 mL of acetonitrile at -78° C. After addition of TASF had been completed, the reaction mixture was brought to -10° C. and stirred for 1 hr. Ten mL of water was then added, the mixture was warmed to room temperature, and the product was extracted into ether. The organic layer was washed with saturated sodium chloride solution, dried and concentrated. The melting point was 159° to 163° C. (dec). The product material was analyzed by ultraviolet absorption, infrared spectroscopy, nuclear magnetic resonance spectroscopy, and mass spectrometry. was brought to -10° C. the product was extracted into ether The organic layer was washed with saturated sodium chloride solution dried concentrated The product material was analyzed by ultraviolet absorption

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

Procedure: A flame dried 50 mL flask fitted with an addition funnel was charged with 0.872 g (500 mmol) of 5-nitroisoquinoline and 0.95 mL (5.1 mmol) of MTS. An acetonitrile solution of 1.40 g (5.09 mmol) of TASF was slowly added to the reaction mixture in 15 min at -78° C. The mixture was stirred for 22 h at that temperature. One mL of acetic acid in 5 mL of hexane was added, and reaction was warmed to room temperature. After 30 min, 40 mL of water was added. The solid which precipitated out was collected and analyzed. The product yield was 0.972 g (74%). The product material was analyzed by infrared spectroscopy, nuclear magnetic resonance spectroscopy, and mass spectrometry. A flame dried 50 mL flask fitted with an addition funnel reaction After 30 min The solid which precipitated out was collected