ethene-1,1,2,2-tetracarbonitrile

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

Procedure: In an atmosphere of argon, 42.3 g (0.28 mol) of N,N-diethylaniline was dissolved in 570 ml of anhydrous DMF, and the solution obtained was cooled to 0° C., and then 46.3 g (1.25-fold equivalent weight) of tetracyanoethylene was added thereto. Then, the solution obtained was restored to room temperature, and stirred for 4.5 hours, which was thereafter poured in 1 liter of a saturated aqueous sodium hydrogencarbonate solution. The solid thus deposited was filtered to obtain a residue, and the residue was subjected to azeotropic distillation twice with 300 ml of toluene to remove the water content. Thereafter, 300 ml of ethyl acetate was added, and the atmosphere was replaced with argon, followed by heating at 80° C. for 1 hour to effect dissolution. To the mixture obtained, 800 ml of hexane was added with stirring, and the solution obtained was cooled to room temperature. The solid thus deposited was collected by filtration, and the residue obtained was vacuum-dried to obtain 51.7 g of N,N-diethyl-4-tricyanovinylaniline (yield: 74%). the solution obtained Then, the solution obtained was restored to room temperature The solid thus deposited was filtered to obtain a residue the residue was subjected to azeotropic distillation twice with 300 ml of toluene to remove the water content Thereafter, 300 ml of ethyl acetate was added by heating at 80° C. for 1 hour dissolution To the mixture obtained with stirring the solution obtained was cooled to room temperature The solid thus deposited was collected by filtration the residue obtained was vacuum-dried

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

Procedure: Tetracyanoethylene (1.9 g) and 2,6-dichloro-4-trifluoromethylphenylhydrazine (3.7 g) was added to a magnetically-stirred solution of sodium acetate (0.6 g) in glacial acetic acid (15 ml) at laboratory temperature. After stirring for 15 minutes, a colorless solid precipitated from the solution and stirring was continued overnight. The mixture was then filtered. The solid obtained was washed successively with acetic acid, water, aqueous sodium bicarbonate solution and water, to give 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3,4-dicyanopyrazole (2.5 g), as beige crystals, m.p. 221°-222° C. a colorless solid precipitated from the solution stirring was continued overnight The mixture was then filtered The solid obtained was washed successively with acetic acid, water, aqueous sodium bicarbonate solution and water

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

Procedure: A mixture of 2,4,6-trichlorophenylhydrazine (21.1 g) and tetracyanoethylene (13.3 g) in ethanol (100 ml) was heated at reflux for 15 minutes. The reaction mixture was cooled and the solid precipitate was filtered off and washed with diethyl ether to give 5-amino-3,4-dicyano-1-(2,4,6-trichlorophenyl)pyrazole (13 g), as a buff colored solid, m.p. 267°-271° C. was heated at reflux for 15 minutes The reaction mixture was cooled the solid precipitate was filtered off washed with diethyl ether

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

Procedure: A mixture of 2,4,6-trichlorophenylhydrazine (21.1 g) and tetracyanoethylene (13.3 g) in ethanol (100 ml) was heated at reflux for 15 minutes. The reaction mixture was cooled and the solid precipitate was filtered off and washed with diethyl ether to give 5-amino-3,4-dicyano-1-(2,4,6-trichlorophenyl)pyrazole (13 g), as a buff colored solid, m.p. 267°-271° C. was heated at reflux for 15 minutes The reaction mixture was cooled the solid precipitate was filtered off washed with diethyl ether

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 2-aminothiophenol (300 mg, 2.4 mmol) in DMA (3 mL) was added to resin-bound 4-carboxybenzaldehyde (subn. 0.60 mmol/g, 400 mg, 0.24 mmol), followed by TCNE (307 mg, 2.4 mmol). The suspension was shaken at 25° C. for 24h. The resin was filtered, washed with DMA and DCM, and dried under high vacuum. The resin-bound benzothiazole was cleaved from the solid support with 20% (v/v) TFA in DCM (2×5 mL, 15 min) and the combined filtrates were evaporated to give the title compound. 1H NMR (d6-DMSO) δ 7.52 (t, 1H, J=7.6 Hz), 7.60 (t, 1H, J=7.0 Hz), 8.12 (d, 2H, J=8.4 Hz), 8.23 (d, 2H, J=8.4 Hz), 8.00-8.40 (m, 2H). MS (API-ES+) m/z 256 (M+H). The resin was filtered washed with DMA and DCM dried under high vacuum was cleaved from the solid support with 20% (v/v) TFA in DCM (2×5 mL, 15 min) the combined filtrates were evaporated

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

Procedure: Resin-bound 4-carboxybenzaldehyde (subn. 0.60 mmol/g, 400 mg, 0.24 mmol) was treated with a solution of 2-aminophenol (262 mg, 2.4 mmol) in DMA (3 mL). The suspension was shaken at room temperature for 24 h. Tetracyanoethylene (307 mg, 2.4 mmol) was added, and the mixture stirred at room temperature for an additional 24 h. The resin was filtered, washed with DMA and DCM, and dried under high vacuum. The benzoxazole was cleaved from the solid support with 20% (v/v) TFA in DCM (2×5 mL, 15 min) and the combined filtrates were evaporated to give the title compound. 1H NMR (CD3OD) δ 7.36-7.45 (m, 2H), 7.62-7,67 (m, 111), 7.72-7.77 (m, 1H), 8.17 (d, 2H, J=8.3 Hz), 8.29 (d, 2H, J=8.3 Hz). MS (API-ES+) m/z 240 (M+H). the mixture stirred at room temperature for an additional 24 h The resin was filtered washed with DMA and DCM dried under high vacuum was cleaved from the solid support with 20% (v/v) TFA in DCM (2×5 mL, 15 min) the combined filtrates were evaporated

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

Procedure: Resin-bound 4-carboxybenzaldehyde (subn. 0.60 mmol/g, 400 mg, 0.24 mmol) was treated with a solution of 2-aminophenol (262 mg, 2.4 mmol) in DMA (3 mL). The suspension was shaken at room temperature for 24 h. Tetracyanoethylene (307 mg, 2.4 mmol) was added, and the mixture stirred at room temperature for an additional 24 h. The resin was filtered, washed with DMA and DCM, and dried under high vacuum. The benzoxazole was cleaved from the solid support with 20% (v/v) TFA in DCM (2×5 mL, 15 min) and the combined filtrates were evaporated to give the title compound. 1H NMR (CD3OD) δ 7.36-7.45 (m, 2H), 7.62-7,67 (m, 111), 7.72-7.77 (m, 1H), 8.17 (d, 2H, J=8.3 Hz), 8.29 (d, 2H, J=8.3 Hz). MS (API-ES+) m/z 240 (M+H). the mixture stirred at room temperature for an additional 24 h The resin was filtered washed with DMA and DCM dried under high vacuum was cleaved from the solid support with 20% (v/v) TFA in DCM (2×5 mL, 15 min) the combined filtrates were evaporated

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Resin-bound 4-carboxybenzaldehyde (subn. 0.65 mmol/g, 400 mg, 0.26 mmol) was suspended in DMA (3 mL) and treated with 1,2-phenylenediamine (2.6 mmol) and TCNE (2.6 mmol). The suspension was sonicated for 1 h and shaken at 25° C. for an additional 22 h. The resin was filtered, washed with DMA, DCM, and dried under high vacuum. The benzimidazole was cleaved from the solid support with 20% (v/v) TFA in DCM (2×5 mL, 15 min) and the combined filtrates were evaporated to give the title compound. 1H NMR (d6-DMSO) δ 7.35-7.43 (m, 2H), 7.69-7.78 (m, 2H), 8.19 (d, 2H, J=8.3 Hz), 8.26-8.34 (m, 2H), 12.50-14.20 (br s, CO2H). MS (API-ES+) m/z 239 (M+H). The suspension was sonicated for 1 h The resin was filtered washed with DMA, DCM dried under high vacuum was cleaved from the solid support with 20% (v/v) TFA in DCM (2×5 mL, 15 min) the combined filtrates were evaporated

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

Procedure: Trimethylsilyl cyanide (1.88 mL) and tetracyanoethylene (240 mg) were added to a solution of 5-[bis-(2-chloroethoxy)methyl]-2-chloropyridine (2.67 g) in acetonitrile (50 mL), and the reaction solution was heated under reflux for five hours. The reaction solution was left to cool to room temperature, and the solvent was evaporated under reduced pressure. Ethyl acetate was added to the resulting residue. The organic layer was washed with brine and then dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (carrier: Chromatorex NH; elution solvent: heptane:ethyl acetate=8:1) to obtain 2.04 g of the title compound. The property values of the compound are as follows. the reaction solution was heated under reflux for five hours The reaction solution was left the solvent was evaporated under reduced pressure Ethyl acetate was added to the resulting residue The organic layer was washed with brine dried over anhydrous magnesium sulfate concentrated under reduced pressure The residue was purified by silica gel column chromatography (carrier: Chromatorex NH; elution solvent: heptane:ethyl acetate=8:1)