Multi-cyano substituted triphenylamine derivatives and synthesis method and use thereof
A cyano-substituted, triphenylamine technology, applied in a class of polycyano-substituted triphenylamine derivatives and its synthesis and application, can solve the problem of low efficiency of organic solar cells
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Embodiment 1
[0046] Example 1. Preparation of 2-(4-(diphenylamino)phenyl)-1,1,4,4-tetracyano-1,3-butadiene (MTCBD)
[0047]
[0048] (1). Under nitrogen protection, p-iodotriphenylamine is mixed with acetylene, wherein the molar ratio of p-iodotriphenylamine to acetylene is 2: 3; add catalyst amount of bistriphenylphosphine palladium dichloride and catalyst amount Cuprous iodide, then the mixture is mixed with triethylamine, and refluxed under stirring; the crude product is obtained by filtration, and through silica gel column chromatography, p-ethynyl triphenylamine is obtained, and the productive rate is about 90%;
[0049] (2). Under nitrogen protection, the p-ethynyltriphenylamine obtained in step (1) is mixed with tetracyanoethylene in a molar ratio of 1:1, and then the mixture is stirred at room temperature in dichloromethane for 16 hours, After recrystallization from its n-hexane solution, the target product was obtained with a yield of about 95%.
[0050] m / z: 397.13 (100.0%), ...
Embodiment 2
[0056] Example 2. 2-(4-(Diphenylamino)phenyl)-1,1,3,4,4-pentacyano-1,3-butadiene (MPCBD)
[0057]
[0058] (1). Under the protection of nitrogen, mix 4-iodo-triphenylamine and propionitrile, wherein, the molar ratio of 4-iodo-triphenylamine and propionitrile is 2:3; Phosphorous palladium dichloride and cuprous iodide of catalytic amount, then the mixture is mixed with triethylamine, and refluxed under stirring; the crude product is obtained by filtration, recrystallized through its petroleum ether solution, to obtain the target product, and the yield is about 80%;
[0059] (2). Under the protection of nitrogen, the product obtained in step (1) is mixed with tetracyanoethylene in a molar ratio of 1:1, and then the mixture is stirred at room temperature in dichloromethane for 20 hours, and first passed through a silica gel column Chromatography gave the target product with a yield of about 85%.
[0060] m / z: 422.13 (100.0%), 423.13 (31.6%), 424.13 (4.8%).
[0061] Preparat...
Embodiment 3
[0066] Example 3. 2-(4-(Di-p-toluidyl)phenyl)-1,1,4,4-tetracyano-1,3-butadiene (DTMTCBD)
[0067]
[0068](1). Under nitrogen protection, mix 4-iodo-N, N-di-p-toluidine and acetylene, wherein the molar ratio of 4-iodo-N, N-di-p-toluidine to acetylene is 2:3; Add a catalytic amount of bistriphenylphosphine palladium dichloride and a catalytic amount of cuprous iodide, then mix the mixture with triethylamine, and reflux under stirring; filter to obtain a crude product, which is subjected to silica gel column chromatography to obtain The target product, the yield is about 83%;
[0069] (2). Under nitrogen protection, the product obtained in step (1) is mixed with tetracyanoethylene in a molar ratio of 1:1, and then the mixture is stirred at room temperature in dichloromethane for 18 hours, and then the mixture is stirred with normal hexane The solution was recrystallized to obtain the target product with a yield of about 80%.
[0070] m / z: 425.16 (100.0%), 426.17 (30.5%), 42...
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