Porphyrin molecule for fluorenyl Friedel-Crafts reaction modification, post-modification material, preparation method and application thereof
A technology for modifying materials and molecules, which is applied in semiconductor/solid-state device manufacturing, electrical components, circuits, etc., can solve problems that have not been reported before, and achieve the effects of accelerated fusion, wide range of raw materials, and low material loss
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Embodiment 1
[0060] When Ar in the general formula molecule 1 1 、Ar 2 、Ar 3 is 4-butoxyphenyl, Ar 4 is thienyl, M is replaced by H ion, W in the general formula molecule 2 is C, X 1 、X 2 for Hr, R 1 , R 2 Be H, when Ar is bromobenzene, its specific reaction scheme is as follows:
[0061]
[0062] The synthetic steps of 4-butoxybenzaldehyde (2) are as follows: get p-hydroxybenzaldehyde (1) (50g, 0.409mol), bromobutane (72.93g, 0.532mol), anhydrous potassium carbonate (84.79g , 0.614mol), the catalyst potassium iodide (4.07g, 0.025mol), and the solvent N,N-dimethylformamide 600mL were added to the dried reaction flask, and reacted at 90°C in the dark for 24 hours. Extract with ethyl acetate and water, spin dry after anhydrous sodium sulfate drying, sherwood oil / methylene chloride 1 / 1 pass through silica gel column to separate, obtain light yellow oily matter target product 4-butoxybenzaldehyde (67g, 92%). 1H NMR (400MHz, CDCl3) δ9.87(s, 1H), 7.82(d, J=8.7Hz, 2H), 6.98(d, J=8.7Hz,...
Embodiment 2
[0067] When Ar 1 、Ar 2 、Ar 3 、Ar 4 Be phenyl and thienyl, when M is replaced by H ion, the specific reaction scheme is as follows:
[0068]
[0069] The synthesis steps are as follows: dissolve benzaldehyde (5g, 47.15mmol), 2-thiophenecarbaldehyde (5.29g, 47.15mmol) and pyrrole (6.32g, 94.3mol) in dried 800ml dichloromethane, avoid light and nitrogen bubble After 2h, after stirring for 5min, the catalyst trifluoroacetic acid (3.2g, 28.29mmol) was added. After reacting for 4h at room temperature, 1g of chloranil was added as an oxidizing agent. After reacting for 2h, 4ml of triethylamine was added to quench. After being spin-dried, it was separated by a 100-200 mesh silica gel column, the volume ratio of petroleum ether / dichloromethane was 2 / 1, and recrystallized by methanol to obtain a purple-red solid (0.84 g).
[0070] Yet the defect that the method for this kind of Lindsey porphyrin synthesis exists is that target product is not single, the present situation of rever...
Embodiment 3
[0081] After the Friedel-Crafts modification, metal coordination is carried out. When M in the general formula molecule 1 is Zn, the reaction route is as follows:
[0082]
[0083] Take the molecular compound (7) (0.1g, 0.09mmol) modified by porphyrin Friedel-Crafts and dissolve it in 100ml of dichloromethane, then take zinc acetate (0.05g, 0.28mmol) and dissolve it in methanol solution and add the above-mentioned porphyrin dichloride In the methane solution, fully stirred for 5 h, extracted and filtered, and recrystallized from methanol to obtain a purple solid (0.19 g, 98%). MALDI-TOF-MS(m / z):calcd.Formula:C 73 h 62 N 4 o 3 S 1 Zn 1 ; Exact Mass: 1138.383 [M+]; Found: 1138.565. 1 H NMR (400MHz, CDCl 3 )δ9.26(d, J=4.6Hz, 2H), 9.02(d, J=7.2Hz, 6H), 8.12(d, J=8.3Hz, 6H), 7.90(d, J=7.4Hz, 2H) ,7.84(d,J=7.3Hz,2H),7.73(d,J=3.4Hz,1H),7.58(d,J=7.5Hz,2H),7.49(t,J=7.3Hz,2H),7.84 (d, J=7.3Hz, 2H), 7.46-7.41(m, 2H), 7.41-7.37(m, 2H), 7.35-7.26(m, 2H), 7.26-7.23(m, 4H), 4.22(...
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