Photochromic compound containing polythiophene radicals
A photochromic and compound technology, applied in the direction of color-changing fluorescent materials, organic chemistry, chemical instruments and methods, etc., can solve the problems of difficult preparation of mixed crystal materials, difficult large-scale production, difficult optical information storage, etc., to achieve good Solubility, convenient bridging, good thermal stability
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Embodiment 1
[0044] Preparation of 2,3,4,5-tetrakis(2,,5,-dimethyl-3,-thiophene) thiophene (compound Ⅰ-1)
[0045]
[0046] In a 50ml two-necked bottle, add 1mmol of tetrabromothiophene (compound 3), Ni(dppp)Cl 2 and THF, evacuated, Ar 2 gas replacement, and then dropwise added 2,5-dimethyl-3-thiophene magnesium bromide (compound 2, which was prepared from 5 mmol 2,5-dimethyl-3-bromothiophene (compound 1) and 6 mmol magnesium chips ), and heated to 80°C for 12 hours under dark conditions. Cool to room temperature, spin off the solvent, and separate by silica gel column chromatography (petroleum ether) to obtain a light yellow solid product. Yield 33%.
[0047] 1 H NMR (400MHz, CDCl 3 ):δ2.04(s,3H,CH 3 ),2.06(s,3H,CH 3 ),2.10(s,3H,CH 3 ),2.34(s,3H,CH 3 ),2.37(s,6H,CH 3 ),2.41(s,3H,CH 3 ),2.54(s,3H,CH 3 ),6.45(s,1H,thiophene-H),6.50(s,1H,thiophene-H),6.81(s,1H,thiophene-H),6.99(s,1H,thiophene-H).MS(ESI) calcd for C 28 h 28 S 5 :524.08;Found:563.0[M+K] + .
Embodiment 2
[0049] Preparation of 2,3,4,5-tetrakis(2’,5’-dimethyl-3’-thiophene) thiophene (compound Ⅰ-1)
[0050]
[0051] In a 50ml two-necked flask, add 2.5mmol 2,5-dimethyl-3-thiophene boronic acid (compound 4), tetrabromothiophene (0.2g, 0.5mmol), tetrakis(triphenylphosphine) palladium (0.173g, 0.15mmol) , 1ml water, potassium carbonate (0.276g), 30ml toluene and 3ml ethanol, vacuum, Ar 2 Gas replacement, protected from light, heated to 80 ° C for 48 hours. Cool to room temperature, separate the layers, extract the aqueous phase with dichloromethane, combine the organic phases, spin off the solvent, and separate by silica gel column chromatography (petroleum ether) to obtain a yellow solid. Yield 40%. The structural characterization data are the same as in Example 1.
Embodiment 3
[0053] Preparation of 3,4-bis(5'-methyl-2'-thiophene)yl-2,5-bis(2',5'-dimethyl-3'-thiophene)ylthiophene (compound Ⅰ-2)
[0054]
[0055] 0.5 mmol of 3,4-bis(5'-methyl-2'-thiophene)-2,5-dibromothiophene (compound 5) and catalyst (Ni(dppp)Cl 2 ) were added together to 30 mL of diethyl ether, and a diethyl ether solution of a metal organic reagent (compound 2) prepared from 1.5 mmol of 2,5-dimethyl-3-bromothiophene and metal powder was added dropwise. After the dropwise addition was completed, the reaction was carried out overnight. Dilute hydrochloric acid was poured into the reaction mixture to terminate the reaction. The organic phase was separated and the aqueous phase was extracted three times with ether. The organic phases were combined and washed with water. After drying over anhydrous magnesium sulfate, diethyl ether was removed by rotary evaporation. The residue was separated by silica gel column (using petroleum ether as eluent) to obtain compound Ⅰ-2 with a yiel...
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