benzyl N-(3-aminopropyl)carbamate

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:0.00; pressure:0.00; stir:

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

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

Procedure: 0.19 g (0.768 mmol) of 2,4-dichloro-3-nitroquinoline and 0.16 g (0.768 mmol) of N-(benzyloxycarbonyl)-1,3-propanediamine was heated at 70° C. in 5 ml of triethylamine for one hour with stirring. After triethylamine was distilled off under reduced pressure, the residue was dissolved in methylene chloride, washed with water, and dried (MgSO4). The solvent was distilled off under reduced pressure and the residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=2:1 (v/v)) to obtain 0.27 g (0.651 mmol) of 4-[3-(benzyloxycarbonylamino)propylamino]-2-chloro-3-nitroquinoline shown below as yellow powder. ##STR29## Its spectroscopic data are as follows: 1H-NMR (CDCl3) δ (ppm) :1.79 (2H, m), 3.35 (4H, m), 5.02 (1H, br), 5.18 (2H, s), 7.15 (1H, br), 7.37 (5H, m), 7.57 (1H, t, J=8.0 Hz), 7.73 (1H, t, J=7.8 Hz), 7.90 (1H, d, J=8.4 Hz), 8.21 (1H, d, J=8.0 Hz). After triethylamine was distilled off under reduced pressure the residue was dissolved in methylene chloride washed with water dried (MgSO4) The solvent was distilled off under reduced pressure the residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=2:1 (v/v))

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

Procedure: 0.19 g (0.768 mmol) of 2,4-dichloro-3-nitroquinoline and 0.16 g (0.768 mmol) of N-(benzyloxycarbonyl)-1,3-propanediamine was heated at 70° C. in 5 ml of triethylamine for one hour with stirring. After triethylamine was distilled off under reduced pressure, the residue was dissolved in methylene chloride, washed with water, and dried (MgSO4). The solvent was distilled off under reduced pressure and the residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=2:1 (v/v)) to obtain 0.27 g (0.651 mmol) of 4-[3-(benzyloxycarbonylamino)propylamino]-2-chloro-3-nitroquinoline shown below as yellow powder. ##STR29## Its spectroscopic data are as follows: 1H-NMR (CDCl3) δ (ppm) :1.79 (2H, m), 3.35 (4H, m), 5.02 (1H, br), 5.18 (2H, s), 7.15 (1H, br), 7.37 (5H, m), 7.57 (1H, t, J=8.0 Hz), 7.73 (1H, t, J=7.8 Hz), 7.90 (1H, d, J=8.4 Hz), 8.21 (1H, d, J=8.0 Hz). After triethylamine was distilled off under reduced pressure the residue was dissolved in methylene chloride washed with water dried (MgSO4) The solvent was distilled off under reduced pressure the residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=2:1 (v/v))

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

Procedure: Benzyl 3-aminopropylcarbamate 12 (8.00 g, 36.0 mmol) was dissolved in 250 mL of ethyl formate. The solution was refluxed for 4 h. Following complete conversion of the amine, the solution was concentrated to dryness in a rotary evaporator to obtain the formamide as a colorless oil (8.90 g, 99%). The solution was refluxed for 4 h the solution was concentrated to dryness in a rotary evaporator

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

Procedure: Benzyl 3-aminopropylcarbamate 12 (8.00 g, 36.0 mmol) was dissolved in 250 mL of ethyl formate. The solution was refluxed for 4 h. Following complete conversion of the amine, the solution was concentrated to dryness in a rotary evaporator to obtain the formamide as a colorless oil (8.90 g, 99%). The solution was refluxed for 4 h the solution was concentrated to dryness in a rotary evaporator

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

Procedure: To a solution of 1,3-propanediamine (6.50 g, 87.0 mol) in 250 mL of abs. EtOH was added benzyl phenyl carbonate (20.0 g, 87.0 mmol). The solution was stirred overnight. A white precipitate formed. The solvent was removed in a rotary evaporator, and the residue was taken up with 100 ml of distilled H2O. This was followed by acidification with 2M HCl to pH 1-2, and 4× extracting with 250 mL of CH2Cl2 each time. The aqueous phase was rendered strongly alkaline with 2M NaOH and extracted 4× with 250 mL of CH2Cl2 each time. The combined organic phases were dried over Na2SO4, subsequently the solvent was removed in a rotary evaporator to obtain the product as a viscid white mass (4.70 g, 26%). A white precipitate formed The solvent was removed in a rotary evaporator extracting with 250 mL of CH2Cl2 each time extracted 4× with 250 mL of CH2Cl2 each time The combined organic phases were dried over Na2SO4 subsequently the solvent was removed in a rotary evaporator to obtain the product as a viscid white mass (4.70 g, 26%)

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

Procedure: 1,3-Diaminopropane (35.5 g, 0.48 mol) was dissolved in 300 mL CHCl3, and the solution was cooled to 0° C. A solution of N-(benzyloxycarbonyloxy)succinimide (4.5 g, 0.018 mol) in 150 mL CHCl3 was added dropwise over 6 h, with the internal temperature maintained below 10° C. After addition was complete, the reaction solution was stirred at room temperature overnight. The solution was washed with water, dried (Na2SO4), filtered and concentrated in vacuo to provide 3.0 g (80%) of the title compound as a low melting solid: 1H NMR (CDCl3) δ 1.25 (bs, 2 H), 1.63 (quintet, 2 H), 2.77 (t, 2 H), 3.2-3.34 (bm, 2 H), 5.09 (s, 2 H), 5.37 (bm, 1 H), 7.28-7.40 (m, 5 H); MS, m/e 209 ((M+H)+). maintained below 10° C After addition The solution was washed with water dried (Na2SO4) filtered concentrated in vacuo

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

Procedure: 1,3-Diaminopropane (35.5 g, 0.48 mol) was dissolved in 300 mL CHCl3, and the solution was cooled to 0° C. A solution of N-(benzyloxycarbonyloxy)succinimide (4.5 g, 0.018 mol) in 150 mL CHCl3 was added dropwise over 6 h, with the internal temperature maintained below 10° C. After addition was complete, the reaction solution was stirred at room temperature overnight. The solution was washed with water, dried (Na2SO4), filtered and concentrated in vacuo to provide 3.0 g (80%) of the title compound as a low melting solid: 1H NMR (CDCl3) δ 1.25 (bs, 2 H), 1.63 (quintet, 2 H), 2.77 (t, 2 H), 3.2-3.34 (bm, 2 H), 5.09 (s, 2 H), 5.37 (bm, 1 H), 7.28-7.40 (m, 5 H); MS, m/e 209 ((M+H)+). maintained below 10° C After addition The solution was washed with water dried (Na2SO4) filtered concentrated in vacuo