1-azido-4-chlorobenzene

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

Procedure: Reaction of p-chlorophenyl azide (7.48 g; 0.0487 mole) with ethyl cyanoacetate (5.5 g; 0.0487 mole) as described in example 1a gave 10.057 g (81%) of the triazole of mp (ethanol) 162-164° C. (lit mp 165-167° C.; Ger Offen No. 2,009,134[1970]) (Found; C, 49.78; H, 4.31; N, 21.15; C11H11CIN4O2 requires; C, 49.54; H, 4.16; N, 21.01%).

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

Procedure: A solution of (S)-tert-butyl but-3-yn-2-ylcarbamate (250 mg, 1.48 mmol), 1-azido-4-chlorobenzene (227 mg, 1.48 mmol, 1.0 equiv), and N-ethyl-N-isopropylpropan-2-amine (0.77 mL, 4.43 mmol, 3.0 equiv) in anhydrous acetonitrile (14.8 mL) was stirred at room temperature for 10 min. Copper(I) iodide (563 mg, 2.95 mmol, 2.0 equiv) was then added in portions. The mixture was stirred at room temperature for 30 min. The reaction was quenched with saturated aqueous ammonium chloride (50 mL) and diluted with water (50 mL). The mixture was extracted with ethyl acetate (3×30 mL) and the combined organic extracts were washed with water (30 mL), saturated aqueous sodium chloride (30 mL), dried over Na2SO4, filtered and concentrated. Silica gel column chromatography (EtOAc/Heptane) provided (S)-tert-butyl(1-(1-(4-chlorophenyl)-1H-1,2,3-triazol-4-yl)ethyl)carbamate (0.428 g, white solid) in 90% yield. 1H NMR (400 MHz, CDCl3) δ 7.86 (s, 1H), 7.68 (d, J=8.8 Hz, 2H), 7.50 (d, J=8.8 Hz, 2H), 5.02 (m, 1H), 1.63 (d, J=6.8 Hz, 3H), 1.46 (s, 9H). MS m/z 323.1 (M+H)+; Rt-0.92 min. The reaction was quenched with saturated aqueous ammonium chloride (50 mL) diluted with water (50 mL) The mixture was extracted with ethyl acetate (3×30 mL) the combined organic extracts were washed with water (30 mL), saturated aqueous sodium chloride (30 mL) dried over Na2SO4 filtered concentrated

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

Procedure: Reaction of p-chlorophenyl azide (7.48 g; 0.0487 mole) with ethyl cyanoacetate (5.5 g; 0.0487 mole) as described in example 1a gave 10.057 g (81%) of the triazole of mp (ethanol) 162-164° C. (lit mp 165-167° C.; Ger Offen No. 2,009,134[1970]) (Found; C, 49.78; H, 4.31; N, 21.15; C11H11CIN4O2 requires; C, 49.54; H, 4.16; N, 21.01%).

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

Procedure: A solution of (S)-tert-butyl but-3-yn-2-ylcarbamate (250 mg, 1.48 mmol), 1-azido-4-chlorobenzene (227 mg, 1.48 mmol, 1.0 equiv), and N-ethyl-N-isopropylpropan-2-amine (0.77 mL, 4.43 mmol, 3.0 equiv) in anhydrous acetonitrile (14.8 mL) was stirred at room temperature for 10 min. Copper(I) iodide (563 mg, 2.95 mmol, 2.0 equiv) was then added in portions. The mixture was stirred at room temperature for 30 min. The reaction was quenched with saturated aqueous ammonium chloride (50 mL) and diluted with water (50 mL). The mixture was extracted with ethyl acetate (3×30 mL) and the combined organic extracts were washed with water (30 mL), saturated aqueous sodium chloride (30 mL), dried over Na2SO4, filtered and concentrated. Silica gel column chromatography (EtOAc/Heptane) provided (S)-tert-butyl(1-(1-(4-chlorophenyl)-1H-1,2,3-triazol-4-yl)ethyl)carbamate (0.428 g, white solid) in 90% yield. 1H NMR (400 MHz, CDCl3) δ 7.86 (s, 1H), 7.68 (d, J=8.8 Hz, 2H), 7.50 (d, J=8.8 Hz, 2H), 5.02 (m, 1H), 1.63 (d, J=6.8 Hz, 3H), 1.46 (s, 9H). MS m/z 323.1 (M+H)+; Rt-0.92 min. The reaction was quenched with saturated aqueous ammonium chloride (50 mL) diluted with water (50 mL) The mixture was extracted with ethyl acetate (3×30 mL) the combined organic extracts were washed with water (30 mL), saturated aqueous sodium chloride (30 mL) dried over Na2SO4 filtered concentrated

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

Procedure: Reaction of p-chlorophenyl azide (7.48 g; 0.0487 mole) with ethyl cyanoacetate (5.5 g; 0.0487 mole) as described in example 1a gave 10.057 g (81%) of the triazole of mp (ethanol) 162-164° C. (lit mp 165-167° C.; Ger Offen No. 2,009,134[1970]) (Found; C, 49.78; H, 4.31; N, 21.15; C11H11CIN4O2 requires; C, 49.54; H, 4.16; N, 21.01%).

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

Procedure: 30 parts of 9-hydroxy-3,4-diazatricyclo[4,2,1,02,5 ]-nona-3,7-diene and 34 parts of p-chlorophenyl azide in 100 parts of toluene were heated at 80° C. for 3 hours, while stirring. The mixture was evaporated down in a rotary evaporator at from 20° to 40° C. and under 20 mbar, after which the residue was digested successively with 100 parts of diethyl ether and 100 parts of petroleum ether, and the product was dried at 20° C. under 1 mbar. 59 parts (92 mole %) of 8-(4-chlorophenyl)-12-hydroxy-3,4,8,9,10-pentazatetracyclo[5,4,1,02,5,07,11 ]dodeca-3,9-diene of melting point 178° C. (decomposition) were obtained (Command No. 1). ##STR20## The mixture was evaporated down in a rotary evaporator at from 20° to 40° C. and under 20 mbar the product was dried at 20° C. under 1 mbar

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

Procedure: The title compound was prepared analogously to 1-(2-chloro-4-methoxyphenyl)-5-methyl-1H-1,2,3-triazole-4-carboxylic acid (Example 1 step 2) by replacing 1-azido-2-chloro-4-methoxybenzene with 1-azido-4-chlorobenzene in (0.5 M in TBME).

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

Procedure: A solution of (S)-tert-butyl but-3-yn-2-ylcarbamate (250 mg, 1.48 mmol), 1-azido-4-chlorobenzene (227 mg, 1.48 mmol, 1.0 equiv), and N-ethyl-N-isopropylpropan-2-amine (0.77 mL, 4.43 mmol, 3.0 equiv) in anhydrous acetonitrile (14.8 mL) was stirred at room temperature for 10 min. Copper(I) iodide (563 mg, 2.95 mmol, 2.0 equiv) was then added in portions. The mixture was stirred at room temperature for 30 min. The reaction was quenched with saturated aqueous ammonium chloride (50 mL) and diluted with water (50 mL). The mixture was extracted with ethyl acetate (3×30 mL) and the combined organic extracts were washed with water (30 mL), saturated aqueous sodium chloride (30 mL), dried over Na2SO4, filtered and concentrated. Silica gel column chromatography (EtOAc/Heptane) provided (S)-tert-butyl(1-(1-(4-chlorophenyl)-1H-1,2,3-triazol-4-yl)ethyl)carbamate (0.428 g, white solid) in 90% yield. 1H NMR (400 MHz, CDCl3) δ 7.86 (s, 1H), 7.68 (d, J=8.8 Hz, 2H), 7.50 (d, J=8.8 Hz, 2H), 5.02 (m, 1H), 1.63 (d, J=6.8 Hz, 3H), 1.46 (s, 9H). MS m/z 323.1 (M+H)+; Rt-0.92 min. The reaction was quenched with saturated aqueous ammonium chloride (50 mL) diluted with water (50 mL) The mixture was extracted with ethyl acetate (3×30 mL) the combined organic extracts were washed with water (30 mL), saturated aqueous sodium chloride (30 mL) dried over Na2SO4 filtered concentrated