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2,1,3-Benzothiadiazole-activated halogenation reaction method of aryl hydrocarbons
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A technology of benzothiadiazole and aryl hydrocarbon, which is applied in the direction of organic chemistry, can solve the problems of cumbersome steps, and achieve the effect of simple reaction system, simple substrate preparation and high yield
Active Publication Date: 2020-07-28
ZHEJIANG UNIV OF TECH
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[0007] In order to solve the problem of cumbersome steps for modifying benzothiadiazole molecules in the past, the present invention provides a method for arylhydrocarbon activated halogenation reaction using 2,1,3-benzothiadiazole as a guiding group. Concise and efficient site-specific introduction of chlorine and iodine
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Embodiment 1
[0025]
[0026] 4-methyl-7-phenyl-2,1,3-benzothiadiazole (45mg, 0.2mmol), sodiumchloride (14mg, 0.24mmol), iodobenzenediethyl ester (77mg, 0.24mmol) , palladium acetate (2.2mg, 0.01mmol), dissolved in 2ml of acetic acidsolvent, heated to 100 ° C and stirred for 12 hours, extracted with ethyl acetate, washed with saturated sodiumchloride solution, dried over anhydroussodium sulfate, filtered, concentrated, Through column chromatography, 46 mg of the product 4-methyl-7-(2-chloro)phenyl-2,1,3-benzothiadiazole was obtained with a yield of 88%. The product was a yellow solid. m.p.:98-99℃ 1 H NMR (500MHz, CDCl 3 )δ7.59–7.55(m,1H),7.54–7.49(m,2H),7.46(dd,J=6.9,1.0Hz,1H),7.42–7.39(m,2H),2.82(d,J= 0.7Hz, 3H)ppm. 13 C NMR (126MHz, CDCl 3 )δ155.41, 153.66, 136.56, 133.50, 131.91, 131.51, 130.04, 129.98, 129.95, 129.43, 127.80, 126.68, 17.98ppm.
Embodiment 2
[0028]
[0029] 4-methyl-7-phenyl-2,1,3-benzothiadiazole (45mg, 0.2mmol), sodium iodide (36mg, 0.24mmol), iodobenzenediethyl ester (77mg, 0.24mmol) , palladium acetate (2.2mg, 0.01mmol), dissolved in 2ml of acetic acidsolvent, heated to 100 ° C and stirred for 12 hours, extracted with ethyl acetate, washed with saturated sodium chloride solution, dried over anhydroussodium sulfate, filtered, concentrated, Through column chromatography, 66 mg of the product 4-methyl-7-(2-iodo)phenyl-2,1,3-benzothiadiazole was obtained with a yield of 94%. The product was a yellow solid. m.p.:81-83℃ 1 H NMR (500MHz, CDCl 3 )δ8.03(dd, J=8.0,0.9Hz,1H),7.49–7.41(m,4H),7.15(td,J=7.8,1.8Hz,1H),2.85–2.80(m,3H)ppm. 13 C NMR (126MHz, CDCl 3 )δ155.43, 153.40, 142.76, 139.52, 134.72, 131.51, 130.84, 129.83, 129.65, 128.09, 127.80, 99.44, 18.10ppm.
Embodiment 3
[0031]
[0032] According to the method described in Example 1, the difference is that the substrate used is: 4-methyl-7-(4-methyl)phenyl-2,1,3-benzothiadiazole (48mg, 0.2mmol) 49 mg of the product 4-methyl-7-(2-chloro-4-methyl)phenyl-2,1,3-benzothiadiazole was obtained, the yield was 80%, and the product was a yellow solid. m.p.:103-105℃ 1 H NMR (500MHz, CDCl 3 )δ7.51(d,J=6.9Hz,1H),7.45 (dd,J=7.0,1.2Hz,1H),7.41–7.37(m,2H),7.21(dt,J=7.8,1.2Hz,1H ), 2.81(d,J=1.1Hz,3H), 2.43(s,3H)ppm. 13 C NMR (126MHz, CDCl 3 )δ155.41, 153.85, 139.73, 133.51, 133.10, 131.62, 131.24, 130.40, 129.98, 128.75, 127.81, 127.52, 20.99, 17.96ppm.
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Abstract
Provided is an aryl carbon hydrogen activation halogenating reaction method using 2,1,3-diazosulfide as an orienting group. The method comprises the steps that a compound shown in a formula (I), sodium salt, palladium acetate and iodobenzenediethyl ester are dissolved in acetic acid, heating is performed to 90-110 DEG C, stirring reaction is performed for 10-14 hours, treatment is performed afterreaction liquid, and a compound shown in a formula (II) is obtained. A reaction system is simple, and the used solvent is cheap and easy to obtain. A substrate is simple to prepare and high in yield,so that the yield of the reaction is higher. The method is characterized in that under the effect of the orienting group, fixed-point modification can be conducted on 2,1,3-diazosulfide conjugated molecules through one step to introduce chlorine and iodine, so that a reaction route is greatly shortened. The highest yield of an obtained corresponding product is 95%.
Description
[0001] (1) Technical field [0002] The invention relates to a method for the fixed-point modification of 2,1,3-benzothiadiazole conjugated molecules, in particular to a method for activating aryl hydrocarbons with 2,1,3-benzothiadiazole as a guiding group Halogenation method. [0003] (2) Background technology [0004] 2,1,3-Benzothiadiazole (BTD) is widely used in the construction of conjugated organic molecules, and its conjugated molecules can be used as liquid crystal materials with special optoelectronic properties. It is also a new type of organic optoelectronic material that can be used in Optoelectronic devices are widely used in photovoltaic solar cells, ion recognition materials, fluorescent probes and light-emitting diodes. Therefore, it has great development and utilization value in materials (Chem.Rev., 2004,104(3):1687-1716; J.Am.Chem.Soc., 2000,122(37):8956-8967; Eur .J.Org.Chem., 2013(2):228-255.). [0005] Currently, using the Suzuki reaction is the most co...
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