Fullerene mono-macrocyclic polyamine derivative intermediate and preparation method thereof
A macrocyclic polyamine and fullerene single technology is applied in the field of fullerene single macrocyclic polyamine derivative intermediates and their preparation, and can solve problems such as changing toxic effects
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Embodiment 1
[0059] 1) Preparation of N,N′,N″-tri-p-toluenesulfonyldiethylenetriamine compound (1):
[0060] Under an ice bath, a solution of 126 g p-toluenesulfonyl chloride dissolved in 300 mL acetone and a solution of 91.2 g anhydrous potassium carbonate dissolved in 200 mL water were added dropwise to 20.6 g (0.20 mol) of diethylenetriamine, The dropping time is about 1.5 h. Stir again at room temperature for 4 h. Then the reactant was poured into ice water, then poured into water under stirring, filtered, the filter cake was washed with methanol, suction filtered, and dried in vacuum to obtain N,N',N"-tri-p-toluenesulfonyldiethylenetri The white solid of amine compound (1) was 103.2 g, and the yield was 91%.
[0061] 2) Preparation of N,O,O′-tri-p-toluenesulfonylbis(2-hydroxyethyl)amine compound (2)
[0062] Under ice bath, add 300 mL of dichloromethane solution with 126 g (0.66 mol) of p-toluenesulfonyl chloride dropwise into the reaction flask containing 21.0 g (0.2 mol) of dieth...
Embodiment 2
[0080] Compounds (1) to (4) were prepared according to the preparation methods 1) to 4) in Example 1
[0081] 5) Preparation of N,N′,N″-tri-tert-butoxyformyl-1,4,7,10-tetraazacyclododecane compound (5)
[0082] 5.0 g (29.0 mmol) of 1,4,7,10-tetraazacyclododecane compound (4) and 12.4 mL (89.3 mmol) of triethylamine were dissolved in 150 mL of dichloromethane, and slowly added dropwise at room temperature (Boc ) 2 O 17.72 g (81.2 mmol) of dichloromethane 120 mL solution, added dropwise within 3 h. Stir at room temperature for 24-25 h, remove the solvent under reduced pressure, and perform column chromatography (petroleum ether: ethyl acetate = 1:1) to obtain N,N′,N″-tri-tert-butoxyformyl-1,4 , 10.50 g of white solid of 7,10-tetraazacyclododecane compound (5), yield: 76.8 %. 1 H NMR (400 MHz, CDCl 3 ): δ = 3.60 (s, 4H), 3.37(s, 4H), 3.28 (s, 4H), 2.86 (s, 4H), 1.45 (s, 9H), 1.44 (s, 18H) ppm.
[0083] 6) Preparation of 10-cyano-N,N′,N″-tri-tert-butoxycarbonyl-1,4,7,10-tetra...
Embodiment 3
[0094] Compounds (1) to (4) were prepared according to the preparation methods 1) to 4) in Example 1
[0095]5) Preparation of N,N′,N″-tri-tert-butoxyformyl-1,4,7,10-tetraazacyclododecane compound (5)
[0096] 6.0 g (34.8 mmol) of 1,4,7,10-tetraazacyclododecane (4) and 15 mL (108.0 mmol) of triethylamine were dissolved in 160 mL of dichloromethane, and slowly added dropwise at room temperature (Boc) 2 O 20.42 g (93.6 mmol) in dichloromethane 130 mL solution, added dropwise within 3 h. Stir at room temperature for 24-25 h, remove the solvent under reduced pressure, and perform column chromatography (petroleum ether: ethyl acetate = 1:1) to obtain N,N′,N″-tri-tert-butoxyformyl-1,4 , 11.72 g of white solid of 7,10-tetraazacyclododecane compound (5), yield: 74.3%. 1 H NMR (400 MHz, CDCl 3 ): δ = 3.61 (s, 4H), 3.36 (s, 4H), 3.27 (s, 4H), 2.85 (s, 4H), 1.46 (s, 9H), 1.44 (s, 18H) ppm.
[0097] 6) Preparation of 10-cyano-N,N′,N″-tri-tert-butoxycarbonyl-1,4,7,10-tetraazacyclododec...
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