N',N'-bis(2-aminoethyl)ethane-1,2-diamine

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Following the general procedure of Example 33, but starting with tris-(2-aminoethyl)amine and cyclopentadecanone, the title compound is produced; IR (liquid film) 3361, 3287, 2928, 2857, 2810, 1460, 1350, 1282, 1116, 1043, 893, 843, 711, (PLA2)

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In accord with the procedure of H. Schmidt et al., Z. anoro. allq. Chem., 578, 75 (1989), ethylchloroformate (33.4 g, 0.310 mol) was added dropwise to a solution of tris(2-aminoethyl)amine (TREN) (29.2 g, 0.20 mol) dissolved in a mixture of benzene (225 mL) and water (100 mL) cooled to 5° C. After the addition was completed, KOH (36.4 g, 0.650 mol) dissolved in water (35 mL) was added dropwise simultaneously with more ethylchloroformate (33.4 g, 0.310 mol). The reaction mixture was stirred for 2 hr. at 5° C. and then for 8 hr. at room temperature. The benzene layer was separated and the water layer extracted with chloroform (2×100 mL). The combined organic fractions were dried over MgSO4, decanted and the decantate evaporated to dryness to give the intermediate tris(2-carbethoxyaminoethyl)amine (5) in 85% yield as a thick oil which was used in subsequent reactions without further purification (1H NMR (CDCl3)δ1.27 (9H, t, 3JHH =7.1 Hz), δ2.60 (6H, t, 3JHH =5.7 Hz), δ3.23 (6H, br), δ4.10 (6H, q, 3J=7.1 5.50 (3H, br); IR 3300, 1720, 1530, 1250 cm-1). After the addition at 5° C. and then for 8 hr at room temperature The benzene layer was separated the water layer extracted with chloroform (2×100 mL) The combined organic fractions were dried over MgSO4 decanted the decantate evaporated to dryness

反応条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In accord with the procedure of H. Schmidt et al., Z. anoro. allq. Chem., 578, 75 (1989), ethylchloroformate (33.4 g, 0.310 mol) was added dropwise to a solution of tris(2-aminoethyl)amine (TREN) (29.2 g, 0.20 mol) dissolved in a mixture of benzene (225 mL) and water (100 mL) cooled to 5° C. After the addition was completed, KOH (36.4 g, 0.650 mol) dissolved in water (35 mL) was added dropwise simultaneously with more ethylchloroformate (33.4 g, 0.310 mol). The reaction mixture was stirred for 2 hr. at 5° C. and then for 8 hr. at room temperature. The benzene layer was separated and the water layer extracted with chloroform (2×100 mL). The combined organic fractions were dried over MgSO4, decanted and the decantate evaporated to dryness to give the intermediate tris(2-carbethoxyaminoethyl)amine (5) in 85% yield as a thick oil which was used in subsequent reactions without further purification (1H NMR (CDCl3)δ1.27 (9H, t, 3JHH =7.1 Hz), δ2.60 (6H, t, 3JHH =5.7 Hz), δ3.23 (6H, br), δ4.10 (6H, q, 3J=7.1 5.50 (3H, br); IR 3300, 1720, 1530, 1250 cm-1). After the addition at 5° C. and then for 8 hr at room temperature The benzene layer was separated the water layer extracted with chloroform (2×100 mL) The combined organic fractions were dried over MgSO4 decanted the decantate evaporated to dryness

反応条件: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 14.69 g (0.100 mol) of tris-(2-aminoethyl)-amine, dissolved in 20 ml of methanol, is instilled in 103.3 g (1.20 mol) of methyl acrylate with stirring at 20° C. The batch is stirred under argon atmosphere for 5 days at room temperature and for 2 days at 50° C. Then, it is concentrated by evaporation in a vacuum and excess methyl acrylate is removed by azeotropic distillation with toluene. The residue is taken up in 150 ml of methanol and 30 ml of diethyl ether, absorptively precipitated with 150 ml of hexane and, after separation of the hexane phase, concentrated by evaporation in a vacuum. The product is obtained as yellowish liquid, which is further reacted without purification. The batch is stirred under argon atmosphere for 5 days at room temperature and for 2 days at 50° C Then, it is concentrated by evaporation in a vacuum and excess methyl acrylate is removed by azeotropic distillation with toluene 30 ml of diethyl ether, absorptively precipitated with 150 ml of hexane after separation of the hexane phase concentrated by evaporation in a vacuum The product is obtained as yellowish liquid, which is further reacted without purification

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 8 mL vial was charged with 2-morpholinoethanol (200 μL, 1.63 mmol), dichloromethane (5 mL), polystyrene-linked diisopropylamine (4.90 mmol), and 4-iodobenzoyl chloride (479 mg, 1.80 mmol), and the reaction mixture was shaken at room temperature. After 16 hours, the reaction mixture was charged with polystyrene-linked tris(2-aminoethyl)-amine (1.63 mmol), and shaken at room temperature for 2 hours. The reaction was filtered, and the resin was washed with dichloromethane (3×10 mL), tetrahydrofuran (2×10 mL), and diethyl ether (2×10 mL). The combined filtrates were concentrated in vacuo to give 2-morpholinoethyl 4-iodobenzoate (434 mg, 1.19 mmol) as a white solid. shaken at room temperature for 2 hours The reaction was filtered the resin was washed with dichloromethane (3×10 mL), tetrahydrofuran (2×10 mL), and diethyl ether (2×10 mL) The combined filtrates were concentrated in vacuo

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: According to the general procedure for Fmoc-cleavage, 9 g Fmoc-Ser(tBu)-Tyr(tBu)-OMe, 22 ml TAEA in ethyl acetate yielded 4.7 g of crude product (yield based on HPLC: 88%).

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The ligand [(((pyrrole-2-yl)methylidene)amino)ethyl]amine was prepared by adding a methanolic solution of pyrrole-2-carboxaldehyde (1.430 g, 15 mmol, 100 mL) to a methanolic solution of tris(2-aminoethyl)amine (0.720 g, 5 mmol, 10 mL). The resulting yellow solution was stirred at room temperature for 30 min. A methanolic solution of gallium(III) nitrate hydrate (1.280 g, 5 mmol, 150 mL) was added to the ligand solution and stirred at room temperature for 30 min. The solution was filtered and left to stand at ambient temperature until crystallization occurred. The crude material was then sublimed at 235° C. stirred at room temperature for 30 min The solution was filtered left to stand at ambient temperature until crystallization was then sublimed at 235° C.