Chiral glucose bidentate N-heterocyclic carbene precursor salt as well as preparation method and purpose thereof
A technology of heterocyclic carbene and bidentate nitrogen, which is applied in the field of chiral glucose bidentate nitrogen heterocyclic carbene precursor salt and its preparation, can solve the problem of difficult hyperbranched polymerization, degree of polymerization and branching, and low catalytic activity , poor stereoselectivity and other issues, to avoid side reactions, high catalytic activity, high conversion effect
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Embodiment 1
[0031] This embodiment relates to a preparation method of a chiral glucose bidentate azacyclic carbene precursor salt, which comprises the following steps:
[0032] 1. Add 1.0mmol of 1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)imidazole 1 and 3.0mmol of 1 in a 50mL double-necked round bottom flask successively, 3-Dibromopropane was reacted vigorously under reflux in 10 mL of dry THF for 12 hours. After the reaction was complete, the reaction was stopped, post-processing, and purified by column chromatography to obtain a colorless viscous compound II with a yield of 96%. 1 H NMR (400MHz, CDCl 3 ):δ=1.97(s,3H),2.02(s,3H),2.04(s,3H),2.06(s,3H),2.55(m,2H),3.44(m,2H),4.15(d, 1H, J=11Hz), 4.30(m, 1H), 4.34(m, 1H), 4.65(t, 2H, J=6.8Hz), 5.23(dd, 1H, J=9.5Hz), 5.21(t, 1H ,J=2.5Hz),5.48(t,1H,J=9.5Hz),6.51(d,1H,J=9.2Hz),7.68(s,1H,4-Im),7.77(s,1H),11.60 (s,1H); 13 C NMR (100MHz, CDCl 3 ): δ=20.47, 20.54, 20.71, 20.79, 28.96, 32.51, 48.79, 61.36, 67.42, 70.86, 72.06, 74.84, 84.00, 1...
Embodiment 2
[0035]This embodiment relates to a preparation method of a chiral glucose bidentate azacyclic carbene precursor salt, which comprises the following steps:
[0036] 1. Add 1.0mmol of N-benzyl imidazole and 3.0mmol of 1,3-dibromopropane in sequence in a 50mL double-necked round bottom flask, and react in 10mL of dry THF for 12 hours. After the reaction is complete, stop the reaction and perform post-treatment , and purified by column chromatography to obtain compound III. 1 H NMR (400MHz, CDCl 3 )δ9.98(s,1H),7.52(s,1H),7.32(s,1H),7.25(m,2H),7.06(m,3H),5.34(s,2H),4.27(t,J =8.0Hz, 2H), 3.18(t, J=8.0Hz, 2H), 2.22(m, 2H). 13 C NMR (101MHz, CDCl 3 )δ136.17, 132.92, 129.11, 129.05, 128.72, 122.78, 122.07, 52.86, 48.07, 32.29, 29.12;
[0037] 2. Add 1.0 mmol of compound III and 1.5 mmol of 1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl) imidazole in sequence in a 50 mL double-necked round bottom flask, React in 10 mL of dry THF for 12 hours. After the reaction is complete, stop the ...
Embodiment 3
[0039] This embodiment relates to a method for preparing a hyperbranched polymer catalyzed by the chiral glucose bidentate nitrogen heterocyclic carbene precursor salt obtained in Example 1, which specifically includes the following steps:
[0040] Chiral glucose bidentate nitrogen heterocyclic carbene precursor salt (1.1mmol%), PdCl 2 (1mmol%), base additive K 2 CO 3 (6.0mmol), 3,6-dibromo-9-(4-bromophenyl)-9H-carbazole (2.0mmol) and 2,7-bis(4,4,5,5-tetramethyl-1 , 3,2-dioxaborolane-2-yl)-9-(undecyl-5-yl)-9H-carbazole (3.0mmol) was placed in a 50mL double-necked round bottom flask, and by replacement, Fill the system with nitrogen, then add 10 mL of deoxygenated acetone / water (V / V=3 / 1), heat to 110°C and keep for 1.5h, then add the capping agent 4-methylphenylboronic acid, and continue to react at 110°C for 4h. The reaction mixture was poured into dry methanol, a solid precipitated and was filtered. Continue to dissolve the solid in anhydrous THF, remove the insoluble mat...
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