2-[N-(2-hydroxyethyl)anilino]ethanol

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

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

Procedure: A stirred solution of 2-(6-bromopyridin-2-yl)-2-methylpropanenitrile (1 g, 4.44 mmol) and triisopropylborate (1.23 ml, 5.33 mmol) in tetrahydrofuran (10 ml) was cooled down to −75° C. A 2.5 M solution of n-BuLi in hexanes (2.31 ml, 5.77 mmol) was added at such a rate that the temperature did not exceed −67° C. After complete addition, the reaction was allowed to warm to room temperature and was stirred at this temperature for 16 hours. After this time, a solution of N-phenyldiethanolamine (805 mg, 4.44 mmol) in THF (8 ml) was added and the resulting mixture was heated at reflux for 4 hours. The mixture was concentrated in vacuo, diluted with isopropanol (18 ml) and refluxed for 1 hour. The reaction mixture was cooled down to room temperature and stirred for 18 hours. The newly formed solid was filtered off and dried under vacuo at 40° C. to afford the title compound as a white solid (880 mg, 59% yield). did not exceed −67° C After complete addition the resulting mixture was heated at reflux for 4 hours The mixture was concentrated in vacuo diluted with isopropanol (18 ml) refluxed for 1 hour The reaction mixture was cooled down to room temperature stirred for 18 hours The newly formed solid was filtered off dried under vacuo at 40° C.

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

Procedure: 4-[[4-[N,N-Bis(hydroxylethyl)amino]phenyl]azo]pyridine (1) was prepared according to procedures described in Lin et al., J. Am. Chem. Soc., 118: 8034 (1996). Specifically, pyridin-4-amine was reacted with a mixture of sodium nitrate and sulfuric acid, followed by reaction with 2,2′-(phenylazanediyl)diethanol.

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

Procedure: 4-[[4-[N,N-Bis(hydroxylethyl)amino]phenyl]azo]pyridine (1) was prepared according to procedures described in Lin et al., J. Am. Chem. Soc., 118: 8034 (1996). Specifically, pyridin-4-amine was reacted with a mixture of sodium nitrate and sulfuric acid, followed by reaction with 2,2′-(phenylazanediyl)diethanol.

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

Procedure: 4-[[4-[N,N-Bis(hydroxylethyl)amino]phenyl]azo]pyridine (1) was prepared according to procedures described in Lin et al., J. Am. Chem. Soc., 118: 8034 (1996). Specifically, pyridin-4-amine was reacted with a mixture of sodium nitrate and sulfuric acid, followed by reaction with 2,2′-(phenylazanediyl)diethanol.

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

Procedure: 4-[[4-[N,N-Bis(hydroxylethyl)amino]phenyl]azo]pyridine (1) was prepared according to procedures described in Lin et al., J. Am. Chem. Soc., 118: 8034 (1996). Specifically, pyridin-4-amine was reacted with a mixture of sodium nitrate and sulfuric acid, followed by reaction with 2,2′-(phenylazanediyl)diethanol.

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

Procedure: 23.9 g of N-phenyldiethanol amine were ground in a mortar and dissolved in 50 ml conc. HCl. The solution was then cooled to 0°C and 10 g NaNO2 in 25 ml of water were added over a period of one hour with stirring. The temperature was maintained between 0°-5°C. After the addition was complete, the mixture was stirred one hour more and then filtered. The orange precipitate of 4-nitroso-N,N-bis-(β-hydroxyethyl) aniline formed was dried in a vacuum desiccator overnight. The dried product, amounting to 25.0 g was suspended in 150 ml. isopropanol and reduced on a Parr hydrogenator over Pt/C. When the loss in pressure approached theoretical, the mixture was filtered into a flask containing 200 ml. isopropanol saturated with HCl gas. A stream of HCl gas was passed through the filtrate during the filtration and for about 20 minutes after the filtration was complete. The white precipitate of N,N-bis-(β-hydroxyethyl)-p-phenylenediamine hydrochloride was collected and weighed. Yield 19.8 g. The temperature was maintained between 0°-5°C After the addition the mixture was stirred one hour more filtered

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

Procedure: 23.9 g of N-phenyldiethanol amine were ground in a mortar and dissolved in 50 ml conc. HCl. The solution was then cooled to 0°C and 10 g NaNO2 in 25 ml of water were added over a period of one hour with stirring. The temperature was maintained between 0°-5°C. After the addition was complete, the mixture was stirred one hour more and then filtered. The orange precipitate of 4-nitroso-N,N-bis-(β-hydroxyethyl) aniline formed was dried in a vacuum desiccator overnight. The dried product, amounting to 25.0 g was suspended in 150 ml. isopropanol and reduced on a Parr hydrogenator over Pt/C. When the loss in pressure approached theoretical, the mixture was filtered into a flask containing 200 ml. isopropanol saturated with HCl gas. A stream of HCl gas was passed through the filtrate during the filtration and for about 20 minutes after the filtration was complete. The white precipitate of N,N-bis-(β-hydroxyethyl)-p-phenylenediamine hydrochloride was collected and weighed. Yield 19.8 g. The temperature was maintained between 0°-5°C After the addition the mixture was stirred one hour more filtered

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

Procedure: 4-[[4-[N,N-Bis(hydroxylethyl)amino]phenyl]azo]pyridine (1) was prepared according to procedures described in Lin et al., J. Am. Chem. Soc., 118: 8034 (1996). Specifically, pyridin-4-amine was reacted with a mixture of sodium nitrate and sulfuric acid, followed by reaction with 2,2′-(phenylazanediyl)diethanol.

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

Procedure: A stirred solution of 2-(6-bromopyridin-2-yl)-2-methylpropanenitrile (1 g, 4.44 mmol) and triisopropylborate (1.23 ml, 5.33 mmol) in tetrahydrofuran (10 ml) was cooled down to −75° C. A 2.5 M solution of n-BuLi in hexanes (2.31 ml, 5.77 mmol) was added at such a rate that the temperature did not exceed −67° C. After complete addition, the reaction was allowed to warm to room temperature and was stirred at this temperature for 16 hours. After this time, a solution of N-phenyldiethanolamine (805 mg, 4.44 mmol) in THF (8 ml) was added and the resulting mixture was heated at reflux for 4 hours. The mixture was concentrated in vacuo, diluted with isopropanol (18 ml) and refluxed for 1 hour. The reaction mixture was cooled down to room temperature and stirred for 18 hours. The newly formed solid was filtered off and dried under vacuo at 40° C. to afford the title compound as a white solid (880 mg, 59% yield). did not exceed −67° C After complete addition the resulting mixture was heated at reflux for 4 hours The mixture was concentrated in vacuo diluted with isopropanol (18 ml) refluxed for 1 hour The reaction mixture was cooled down to room temperature stirred for 18 hours The newly formed solid was filtered off dried under vacuo at 40° C.

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

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

Procedure: A procedure analogous to that used for 1a was used with the following materials: 2,2'-(phenylimino)diethanol (9.0 g, 50 mmol), t-butyldimethylsilyl chloride (18.1 g, 0.12 mol), imidazole (17.0 g, 0.25 mol), and dimethylformamide (50 mL). The reaction was stirred overnight for convenience. Workup as in 1a gave 3a as a pale oil (21.6 g, >100%). 1H NMR (CDCl3) δ7.21 (2H, d, J=8.4), 6.68 (3H, overlapping d, t), 3.77 (4H, d, J=6.6), 3.52 (4H, d, J=6.6), 0.92 (18H, s), 0.06 (12H, s). 13C NMR (CDCl3) δ147.8, 129.2, 115.7, 111.4, 60.3, 53.5, 25.9, 18.3, -5.3. FDMS (m/e) 409 (M+). It was used as 100% without purification.