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Preparation method of monosubstituted benzotriazole small molecule

A small benzotriazole and benzotriazole technology, which is applied in the field of preparation of monosubstituted benzotriazole small molecules, can solve problems such as the inability to achieve 5-position mononitro substitution, and achieve changes in optical and electrical properties, reaction Mild conditions, range-extending effects

Inactive Publication Date: 2018-06-22
GUILIN UNIVERSITY OF TECHNOLOGY
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Problems solved by technology

At present, the modification of this kind of benzotriazole compounds mainly focuses on the substituents on the N of the five-membered heterocyclic ring, while the modification of the benzene ring structure is rarely involved. It can be found in the literature that the 5 and 6 positions are dinitrogen group, difluoro group and dicyano group, and only one article (Org. Lett., 2011, 13, 2338-2341) reported that there is a by-product in the process of double nitration - 5-position single Nitro-substituted benzotriazole is generated, but it is still impossible to achieve the 5-position mononitro substitution of a single university

Method used

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  • Preparation method of monosubstituted benzotriazole small molecule
  • Preparation method of monosubstituted benzotriazole small molecule
  • Preparation method of monosubstituted benzotriazole small molecule

Examples

Experimental program
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Effect test

Embodiment 1

[0022] Example 1: Preparation of 2-(2-ethylhexyl)-4,7-dibromo-5-nitro-benzotriazole (1)

[0023]

[0024] Add 110mL of sulfuric acid / dichloromethane mixed solution with a volume ratio of 1:5 into the two-necked flask, and after the solution is cooled to 0°C, add 2-(2-ethylhexyl)-4 with a molar ratio of 1:1, 7-Dibromo-benzotriazole (4.0g, 5.14mmol) and ammonium cerium nitrate (5.63g, 5.14mmol), stirred for one hour; the reaction was stopped, and the reaction dichloromethane solution was washed with deionized water and saturated brine in turn , and then add anhydrous magnesium sulfate to dry the dichloromethane solution, filter and concentrate the dichloromethane solution, the concentrated product is separated by silica gel chromatography, and vacuum-dried to obtain a light yellow solid product 2-(2-ethylhexyl)-4, 7-Dibromo-5-nitro-benzotriazole (1) (4.0 g, 9.21 mmol), 90% yield. 1 H NMR (500MHz, CDCl 3 ,ppm)δ8.10(s,1H),4.74(d,J=7.2Hz,2H),2.32(dt,J=12.8,6.4Hz,1H),1.41-1.26(...

Embodiment 2

[0025] Example 2: Preparation of 2-(2-ethylhexyl)-4,7-dibromo-5-amino-benzotriazole (2)

[0026]

[0027] Dissolve 2-(2-ethylhexyl)-4,7-dibromo-5-nitro-benzotriazole (1) (3.6g, 8.29mmol) in 50mL glacial acetic acid solution, add iron powder (6.95 g, 124.39mmol), heated to 70°C and stirred at constant temperature for 3 hours; stopped the reaction, poured the reaction solution into 50mL deionized aqueous solution, extracted the aqueous solution with dichloromethane solution, combined the obtained dichloromethane solution with deionized water Wash with saturated brine, then add anhydrous magnesium sulfate to dry the dichloromethane solution, filter and concentrate the dichloromethane solution, the concentrated product is separated by silica gel chromatography, and vacuum-dried to obtain a yellow-brown liquid product 2-(2-ethyl Hexyl)-4,7-dibromo-5-amino-benzotriazole (2) (3.0 g, 7.42 mmol) in 90% yield. 1 H NMR (500MHz, CDCl 3 ,ppm)δ7.16(s,1H),4.59(d,J=7.4Hz,2H),4.31(s,2H),2...

Embodiment 3

[0028] Example 3: Preparation of 2-(2-ethylhexyl)-4,7-dibromo-5-formamido-benzotriazole (3)

[0029]

[0030] Dissolve 2-(2-ethylhexyl)-4,7-dibromo-5-amino-benzotriazole (2) (2.2g, 5.44mmol) in 50mL of anhydrous formic acid solution, heat up to 110°C Reflux and stir for 12 hours; stop the reaction, remove the formic acid in the reaction solution by rotary evaporation, dissolve the crude product in dichloromethane solution, wash the combined dichloromethane solution with deionized water and saturated brine in turn, add anhydrous magnesium sulfate Dry the dichloromethane solution, filter and concentrate the dichloromethane solution. The concentrated product is separated by silica gel chromatography and dried in vacuo to obtain a light gray solid product 2-(2-ethylhexyl)-4,7-dibromo-5- Formamido-benzotriazole (3) (2.0 g, 4.63 mmol), the yield was 85%. 1 H NMR (500MHz, CDCl 3 ,ppm)δ8.73(s,1H),8.56(s,1H),7.77(s,1H),4.66(d,J=7.2Hz,2H),2.30(m,1H),1.41-1.24(m ,8H), 0.93(t, J=7.4Hz...

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Abstract

The invention discloses a preparation method of a monosubstituted benzotriazole small molecule. The preparation method comprises the following steps: 2-(2-ethylhexyl)-4,7-dibromo-benzotriazole is usedas a raw material to react with ceric ammonium nitrate in a mixed solution of sulfuric acid and dichloromethane, so that a mono-nitro-substituted product 2-(2-ethylhexyl)-4,7-dibromo-5-nitro-benzotriazole with a high nitration yield is obtained; and then the nitro groups are smoothly converted into amino groups, formamido groups and isocyano groups. The synthesis method provided by the inventionhas easily obtained raw materials, low cost and mild reaction conditions, and the introduction of a series of different substituent groups into the fifth position of benzotriazole is realized for thefirst time, so that the range of benzotriazole derivatives is greatly expanded.

Description

technical field [0001] The invention belongs to the technical field of chemical intermediate synthesis, and in particular relates to a preparation method of a class of monosubstituted benzotriazole small molecules. Background technique [0002] Benzotriazole derivatives are a good class of electron acceptor units. Their unique photoelectric properties make them widely used in photoelectric materials, such as field effect transistors, organic solar cells, organic light-emitting diodes, etc. At present, the modification of this kind of benzotriazole compounds mainly focuses on the substituents on the N of the five-membered heterocyclic ring, while the modification of the benzene ring structure is rarely involved. It can be found in the literature that the 5 and 6 positions are dinitrogen group, difluoro group and dicyano group substitution, and only one article (Org. Lett., 2011, 13, 2338-2341) reported a synthesis method which mentioned that there was a by-product in the doub...

Claims

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Application Information

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IPC IPC(8): C07D249/18
CPCC07D249/18
Inventor 海杰峰李玲林芝官韦刚张在驰
Owner GUILIN UNIVERSITY OF TECHNOLOGY
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