1,4,7-triazonane

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

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

Procedure: 1,4,7-tris(pyrrole-2ylmethyl)-1,4,7-triazacyclononane was prepared according to procedure B using TACN and pyrrole-2-carboxaldehyde as starting material.

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

Procedure: L4: 1,4,7-tris(4-bromo-pyrazol-3-ylmethyl)-1,4,7-triazacyclononane was prepared by procedure B using TACN and 4-bromo-pyrazole-3-carboxaldehyde.

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

Procedure: N,N'-bis(p-toluenesulfonyl)-1,4,7-triazacyclononane (1.1.20) was prepared by reacting (1.1.3) with two equivalents of p-toluenesulfonyl chloride. Two equivalents of N,N'-bis(p-toluenesulfonyl)-1,4,7-triazacyclononane (1.1.20) hydrobromide were reacted with one equivalent of 1,3-diiodopropane in acetonitrile with excess potassium carbonate. 1,3-Bis[N,N'-bis(p-toluenesulfonyl)-1,4,7-triazacyclononane propane (1.1.21) was isolated and purified by chromatography. The p-toluenesulfonyl groups were removed using sulfuric acid and HBr to yield the title compound (1.1.19). ##STR8## 1.1.22 1,4,7,10-Tetraazabicyclo[5.5.2]tetradecane

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

Procedure: 1,4,7-triazacyclononane (31.5 mg) and compound 14 (0.3 g, 0.76 mmol) were dissolved in dry acetonitrile (20 mL) Potassium carbonate (0.17 g) was added and the mixture was refluxed overnight. The mixture was allowed to cool to room temperature, filtered and concentrated. Purification on silica gel (eluent CH2Cl2:EtOH:HOAc; 80:20:1, v/v/v) yielded the title compound (0.17 g, 62%). ESI-MS: [M+H]+ 1117.5 calc. for C60H73N6O15+ 1117.5 was added the mixture was refluxed overnight filtered concentrated Purification on silica gel (eluent CH2Cl2:EtOH:HOAc; 80:20:1, v/v/v)

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

Procedure: 1,4,7-triazacyclononane (31.5 mg) and compound 14 (0.3 g, 0.76 mmol) were dissolved in dry acetonitrile (20 mL) Potassium carbonate (0.17 g) was added and the mixture was refluxed overnight. The mixture was allowed to cool to room temperature, filtered and concentrated. Purification on silica gel (eluent CH2Cl2:EtOH:HOAc; 80:20:1, v/v/v) yielded the title compound (0.17 g, 62%). ESI-MS: [M+H]+ 1117.5 calc. for C60H73N6O15+ 1117.5 was added the mixture was refluxed overnight filtered concentrated Purification on silica gel (eluent CH2Cl2:EtOH:HOAc; 80:20:1, v/v/v)

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

Procedure: It appears however that the HI3 salts of the monomethylenesulfonic acids of [9]aneN3 and [12]aneN3 can be used directly. When these triiodide salts are added to melted phosphorous acid at 80° C., at 25° C., HP(=O)Et(OEt), or HP(=O)(OEt)2, a very exothermic reaction occurs whereby the respective monomethylenephosphonate, the monomethylene(ethyl)- phosphinate ethyl ester and the monomethylenephosphonate diethyl ester of [9]aneN3 (FIGS. 31A, 31B, and 31C) and the monomethylenephosphonate diethyl ester and the monomethylene(ethyl)-phosphinate ethyl ester of [12]aneN3 (FIGS. 32A and 32B) are formed almost quantitatively within a few seconds. at 80° C. at 25° C., HP(=O)Et(OEt), or HP(=O)(OEt)2, a very exothermic reaction

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

Procedure: 1,4,7-triazacyclononane (31.5 mg) and compound 14 (0.3 g, 0.76 mmol) were dissolved in dry acetonitrile (20 mL) Potassium carbonate (0.17 g) was added and the mixture was refluxed overnight. The mixture was allowed to cool to room temperature, filtered and concentrated. Purification on silica gel (eluent CH2Cl2:EtOH: HOAc; 80:20:1, v/v/v) yielded the title compound (0.17 g, 62%). ESI-MS: [M+H]+ 1117.5 calc. for C60H73N6O15+1117.5. was added the mixture was refluxed overnight filtered concentrated Purification on silica gel (eluent CH2Cl2:EtOH: HOAc; 80:20:1, v/v/v)

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

Procedure: 1,4,7-triazacyclononane (31.5 mg) and compound 14 (0.3 g, 0.76 mmol) were dissolved in dry acetonitrile (20 mL) Potassium carbonate (0.17 g) was added and the mixture was refluxed overnight. The mixture was allowed to cool to room temperature, filtered and concentrated. Purification on silica gel (eluent CH2Cl2:EtOH: HOAc; 80:20:1, v/v/v) yielded the title compound (0.17 g, 62%). ESI-MS: [M+H]+ 1117.5 calc. for C60H73N6O15+1117.5. was added the mixture was refluxed overnight filtered concentrated Purification on silica gel (eluent CH2Cl2:EtOH: HOAc; 80:20:1, v/v/v)

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

Procedure: 1,4,7-tris(pyrrole-2ylmethyl)-1,4,7-triazacyclononane was prepared according to procedure B using TACN and pyrrole-2-carboxaldehyde as starting material.

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

Procedure: 1,4,7-tris(pyrrole-2ylmethyl)-1,4,7-triazacyclononane was prepared according to procedure B using TACN and pyrrole-2-carboxaldehyde as starting material.

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

Procedure: L4: 1,4,7-tris(4-bromo-pyrazol-3-ylmethyl)-1,4,7-triazacyclononane was prepared by procedure B using TACN and 4-bromo-pyrazole-3-carboxaldehyde.