N,N'-bis(2-aminoethyl)propane-1,3-diamine

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: To a stirred solution of p-toluenesulfonyl chloride (262 g, 1.37 mole) in anhydrous pyridine (600 ml) at 5° C. was added a solution of 1,4,8,11-tetraazaundecane (49.1 g, 0.306 mole) in anhydrous pyridine (200 ml) under a dry argon atmosphere, maintaining the temperature <20° C. The addition required 1 h. The mixture was stirred overnight at room temperature. H2O (1.5 l) was slowly added to the cooled (ice bath) mixture. The resulting oil was dissolved in CH2Cl2, separated from the aqueous layer. The CH2Cl2 layer was washed with 5% HCl and H2O and dried (MgSO4). The solvent was removed in vacuo to give an oil which solidified on standing. The resulting solid was ground to a powder and dried in vacuo to give 186 g (78% yield) of the crude product: 1H NMR (CDCl3) δ1.98 (quint, J=7.3 Hz, 2 H), 2.40 (s, 6 H), 2.42 (s, 6 H), 3.11 (t, J=7.3 Hz, 4 H), 3.17 (s, 8 H), 5.76 (t, J=6.0 Hz, 2 H), 7.29 (m, 8 H), 7.64 (d, J=8.3 Hz, 4 H), 7.75 (d, J=8.3 Hz, 4 H). maintaining the temperature <20° C The addition required 1 h cooled (ice bath) mixture separated from the aqueous layer The CH2Cl2 layer was washed with 5% HCl and H2O dried (MgSO4) The solvent was removed in vacuo to give an oil which dried in vacuo

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

Procedure: To a stirred solution of p-toluenesulfonyl chloride (262 g, 1.37 mole) in anhydrous pyridine (600 ml) at 5° C. was added a solution of 1,4,8,11-tetraazaundecane (49.1 g, 0.306 mole) in anhydrous pyridine (200 ml) under a dry argon atmosphere, maintaining the temperature <20° C. The addition required 1 h. The mixture was stirred overnight at room temperature. H2O (1.5 1) was slowly added to the cooled (ice bath) mixture. The resulting oil was dissolved in CH2Cl2, separated from the aqueous layer. The CH2Cl2 layer was washed with 5% HCl and H2O and dried (MgSO4). The solvent was removed in vacuo to give an oil which solidified on standing. The resulting solid was ground to a powder and dried in vacuo to give 186 g (78% yield) of the crude product: 1H NMR (CDCl3) δ1.98 (quint, J=7.3 Hz, 2 H), 2.40 (s, 6 H), 2.42 (s, 6 H), 3.11 (t, J=7.3 Hz, 4 H), 3.17 (s, 8 H), 5.76 (t, J=6.0 Hz, 2 H), 7.29 (m, 8 H), 7.64 (d, J=8.3 Hz, 4 H), 7.75 (d, J=8.3 Hz, 4 H). maintaining the temperature <20° C The addition required 1 h cooled (ice bath) mixture separated from the aqueous layer The CH2Cl2 layer was washed with 5% HCl and H2O dried (MgSO4) The solvent was removed in vacuo to give an oil which dried in vacuo

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

Procedure: 9.04 g (62.4 mmol) of a 40% by weight aqueous glyoxal solution are slowly added dropwise to a solution of 10.00 g (62.4 mmol) of N,N′-bis(2-aminoethyl)-1,3-pro-panediamine in 30 ml of water at 0° C. The mixture is maintained at this temperature for 1 hour and then stirred at ambient temperature for 10 hours. After evaporation of the water, compound 12 is isolated quantitatively in the form of a pale yellow solid and is used for the following stage without subsequent purification. The mixture is maintained at this temperature for 1 hour After evaporation of the water

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

Procedure: A solution of 5.37 g (62.4 mmol) of butanedione in 30 ml of acetonitrile is slowly added dropwise to a solution of 10.00 g (62.4 mmol) of commercial N,N′-bis (2-aminoethyl)-1,3-propanediamine in 100 ml of acetonitrile at 0° C. The mixture is maintained at this temperature for two hours. After evaporating the solvent, compound 1 is isolated quantitatively in the form of a yellow solid and is used for the following stage without subsequent purification. The mixture is maintained at this temperature for two hours After evaporating the solvent

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

Procedure: To a stirred solution of p-toluenesulfonyl chloride (262 g, 1.37 mole) in anhydrous pyridine (600 ml) at 5° C. was added a solution of 1,4,8,11-tetraazaundecane (49.1 g, 0.306 mole) in anhydrous pyridine (200 ml) under a dry argon atmosphere, maintaining the temperature <20° C. The addition required 1 h. The mixture was stirred overnight at room temperature. H2O (1.5 l) was slowly added to the cooled (ice bath) mixture. The resulting oil was dissolved in CH2Cl2, separated from the aqueous layer. The CH2Cl2 layer was washed with 5% HCl and H2O and dried (MgSO4). The solvent was removed in vacuo to give an oil which solidified on standing. The resulting solid was ground to a powder and dried in vacuo to give 186 g (78% yield) of the crude product: 1H NMR (CDCl3) δ1.98 (quint, J=7.3 Hz, 2 H), 2.40 (s, 6 H), 2.42 (s, 6 H), 3.11 (t, J=7.3 Hz, 4 H), 3.17 (s, 8 H), 5.76 (t, J=6.0 Hz, 2 H), 7.29 (m, 8 H), 7.64 (d, J=8.3 Hz, 4 H), 7.75 (d, J=8.3 Hz, 4 H). maintaining the temperature <20° C The addition required 1 h cooled (ice bath) mixture separated from the aqueous layer The CH2Cl2 layer was washed with 5% HCl and H2O dried (MgSO4) The solvent was removed in vacuo to give an oil which dried in vacuo

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

Procedure: The procedure of (2) of Example 1 was repeated with the exception that N,N'-bis(2-aminoethyl)-1,3-propylenediamine was used in place of triethylenetetramine. Thus, 3-(3-cyanopropyl)-2,4-dioxo-1,5,8,12-tetraaza-cyclotetradecane (C-substituted cyclic diamide) was obtained in a yield of 30%.

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

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

Procedure: The procedure of (2) of Example 1 was repeated with the exception that N,N'-bis(2-aminoethyl)-1,3-propylenediamine was used in place of triethylenetetramine. Thus, 3-(3-cyanopropyl)-2,4-dioxo-1,5,8,12-tetraaza-cyclotetradecane (C-substituted cyclic diamide) was obtained in a yield of 30%.

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

Procedure: To a stirred solution of p-toluenesulfonyl chloride (262 g, 1.37 mole) in anhydrous pyridine (600 ml) at 5° C. was added a solution of 1,4,8,11-tetraazaundecane (49.1 g, 0.306 mole) in anhydrous pyridine (200 ml) under a dry argon atmosphere, maintaining the temperature <20° C. The addition required 1 h. The mixture was stirred overnight at room temperature. H2O (1.5 l) was slowly added to the cooled (ice bath) mixture. The resulting oil was dissolved in CH2Cl2, separated from the aqueous layer. The CH2Cl2 layer was washed with 5% HCl and H2O and dried (MgSO4) The solvent was removed in vacuo to give an oil which solidified on standing. The resulting solid was ground to a powder and dried in vacuo to give 186 g (78% yield) of the crude product: 1H NMR (CDCl3) δ 1.98 (quint, J=7.3 Hz, 2 H), 2.40 (s, 6 H), 2.42 (s, 6 H), 3.11 (t, J=7.3 Hz, 4 H), 3.17 (s, 8 H), 5.76 (t, J=6.0 Hz, 2 H), 7.29 (m, 8 H), 7.64 (d, J=8.3 Hz, 4 H), 7.75 (d, J=8.3 Hz, 4 H). maintaining the temperature <20° C The addition required 1 h cooled (ice bath) mixture separated from the aqueous layer The CH2Cl2 layer was washed with 5% HCl and H2O dried (MgSO4) The solvent was removed in vacuo to give an oil which dried in vacuo

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

Procedure: To a stirred solution of p-toluenesulfonyl chloride (262 g, 1.37 mole) in anhydrous pyridine (600 ml) at 5° C. was added a solution of 1,4,8,11-tetraazaundecane (49.1 g, 0.306 mole) in anhydrous pyridine (200 ml) under a dry argon atmosphere, maintaining the temperature <20° C. The addition required 1 h. The mixture was stirred overnight at room temperature. H2O (1.5 l) was slowly added to the cooled (ice bath) mixture. The resulting oil was dissolved in CH2Cl2, separated from the aqueous layer. The CH2Cl2 layer was washed with 5% HCl and H2O and dried (MgSO4) The solvent was removed in vacuo to give an oil which solidified on standing. The resulting solid was ground to a powder and dried in vacuo to give 186 g (78% yield) of the crude product: 1H NMR (CDCl3) δ 1.98 (quint, J=7.3 Hz, 2 H), 2.40 (s, 6 H), 2.42 (s, 6 H), 3.11 (t, J=7.3 Hz, 4 H), 3.17 (s, 8 H), 5.76 (t, J=6.0 Hz, 2 H), 7.29 (m, 8 H), 7.64 (d, J=8.3 Hz, 4 H), 7.75 (d, J=8.3 Hz, 4 H). maintaining the temperature <20° C The addition required 1 h cooled (ice bath) mixture separated from the aqueous layer The CH2Cl2 layer was washed with 5% HCl and H2O dried (MgSO4) The solvent was removed in vacuo to give an oil which dried in vacuo