3-O5 atom bridged binuclear metallocene complex and its application
A metallocene complex and atomic bridge technology, applied in the field of binuclear metallocene complexes, can solve problems such as poor processing performance and unfavorable industrialized production.
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Embodiment 1
[0052] [C 5 h 5 (CH 2 ) 2 O(CH 2 ) 2 C 5 h 5 ]Synthesis
[0053]
[0054] At 0°C, the C 5 h 5 Na (20.0ml, 1.00mol / l) was slowly dropped into (Cl(CH 2 ) 2 ) 2 O (1.43g, 10.00mmol) in THF (50.0ml) solution. After naturally rising to room temperature (25° C.), a white precipitate gradually appeared, and the mixture was stirred for 5 hours. Add saturated NH 4 Cl aqueous solution, ether extraction separation, organic phase solution with anhydrous MgSO 4 dry. TLC finds that by-products are produced, and attempts to distill under reduced pressure fail, (1) easily polymerized at high temperature. Finally adopt column chromatography to separate, eluent sherwood oil: ethyl acetate=10:1, Rf 1 =0.56, Rf 2 =0.32, Rf 3 =0.21, respectively collect 1, 2, 3 fractions and send them to GC-MS analysis, the result 2 is the target product. 1.51 g of a light yellow transparent liquid was obtained (60% yield).
[0055] GC-MS m / z (%): 202 (M + , 0.3%), 123 (M + -CH 2 C 5 h ...
Embodiment 2
[0057] [(CpTiCl 2 ) 2 (η5-η5-C 5 h 4 (CH 2 ) 2 O(CH 2 ) 2 C 5 h 4 )] Synthesis of (2)
[0058]
[0059] A solution of (1) (1.51 g, 6.00 mmol) in THF (20 ml) was slowly dropped into a suspension of NaH (0.30 g, 12.50 mmol) in THF (100 ml) at 0°C. Immediately there are bubbles generated, naturally rise to room temperature, stop the reaction when the bubbles are no longer generated. After centrifugation, standard hydrochloric acid solution is used to calibrate the concentration of bis-sodium salt, C=0.049mol / l.
[0060] At 0°C, slowly drop bis-sodium salt (102.0ml, 0.049mol / l) into C 5 h 5 TiCl 3 (2.20g, 10.00mmol) in THF (50ml). The solution turned from yellow to dark red and became cloudy. Naturally rise to room temperature and react for 4 hours. The solution was dried in vacuum, washed with petroleum ether (20ml×2), precipitated with CH 2 Cl 2 Extract (30ml×3), combine the supernatants, concentrate the solution to about 20ml, and crystallize at -5°C. The ...
Embodiment 3
[0063] [(CpZrCl 2 ) 2 (η5-η5-C 5 h 4 (CH 2 ) 2 O(CH 2 ) 2 C 5 h 4 )] Synthesis of (3)
[0064]
[0065] At 0°C, slowly drop bis-sodium salt (102.0ml, 0.049mol / l) into C 5 h 5 ZrCl 3 - DME (3.52g, 10.00mmol) in THF (50ml) suspension. The solution turned from white to light yellow. Naturally raised to room temperature, reacted for 24 hours. The solution was dried in vacuum, washed with petroleum ether (20ml×2), precipitated with CH 2 Cl 2 Extract (30ml×3), combine the supernatants, concentrate the solution to about 20ml, and crystallize at -5°C. The obtained white solid powder was 1.47 g of the complex (yield 45%).
[0066] 1 H-NMR (CDCl 3 , 20°C, δppm): 6.46(s, 10H, 2×C 5 h 5 ), 6.32(t, 3 J=2.5Hz, 4H, 2×C 5 h 4 ), 6.25(t, 3 J=2.5Hz, 4H, 2×C 5 h 4 ), 3.62(t, 3 J=6.0Hz, 4H, 2×CH 2 ), 2.89(t, 3 J=6.0Hz, 4H, 2×CH 2 ).IR(KBr, cm -1 ): 3104, 2956, 2867, 1653, 1437, 1255, 1104, 1018, 815, 495.
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