CN111303127B - (E)2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole and preparation method thereof - Google Patents

(E)2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole and preparation method thereof Download PDF

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CN111303127B
CN111303127B CN202010121201.2A CN202010121201A CN111303127B CN 111303127 B CN111303127 B CN 111303127B CN 202010121201 A CN202010121201 A CN 202010121201A CN 111303127 B CN111303127 B CN 111303127B
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刘玉婷
杨岚
尹大伟
孙嘉希
李洁
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Shaanxi University of Science and Technology
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Abstract

The invention provides (E)2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole and a preparation method thereof. Adding A mol of N-alkyl-3-carbazole acrylic acid and B mol of o-phenylenediamine into a dry three-neck flask, adding C mL of phosphorus oxychloride (concentrated hydrochloric acid), reacting at 80-105 ℃, and monitoring by TLC until the reaction is complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring for 10min at the temperature of 80-105 ℃, then carrying out suction filtration while the solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole. The method has the advantages of simple operation, convenient post-treatment, short reaction time and high efficiency, and has important significance for the synthesis and development of the compounds.

Description

(E)2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole and preparation method thereof
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a preparation method of (E)2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole.
Background
Carbazole has relatively strong intramolecular transfer capability, and is a large conjugated system molecule. The carbazole molecule can be used for synthesizing a plurality of fine chemicals, can be used for producing dyes, pigments, photoconductors, photosensitive materials, special inks and the like, and has excellent thermal and optical properties. Carbazole molecules are chemically modified, and specific substituent groups or functional groups are introduced to obtain carbazole derivatives with various structures, so that the carbazole derivatives meet the requirements of people in many aspects of production and life.
Benzimidazole is a heterocyclic compound containing 2 nitrogen atoms, and the unique electronic structure and photoelectric properties of benzimidazole lead the benzimidazole complex to have good fluorescence and conductivity. In addition, benzimidazole and its derivatives are important pharmaceutical and dye intermediates. It is mainly used as insect repellent and bactericide, and can also be used as metal anticorrosive, surfactant, fluorescent whitening agent and photosensitive dye, etc.
The benzimidazole ring is introduced into the carbazolyl to form a large conjugated compound, so that a novel compound with special photoelectric activity and other special properties can be generated. Therefore, a series of compounds with special activity can be obtained by developing a method for efficiently and simply preparing the benzimidazole containing carbazolyl, and the method has important significance.
Disclosure of Invention
The invention aims to provide a preparation method of (E)2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole, which has the advantages of simple operation, convenient post-treatment, short reaction time and high efficiency.
In order to achieve the purpose, the invention adopts the technical scheme that:
(E)2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole with the structural general formula:
Figure BDA0002393017810000011
wherein R is-CH3，-C2H5，-CH2-Ph，-C3H7-n，-C3H7-i，-C4H9-n，C5H11-n，-C6H13-n，-C8H17-n，-C10H23-n，-C12H25-n，-C14H29-n，-C16H33-n.
(E) The preparation method of 2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole comprises the following steps:
adding A mol of N-alkyl-3-carbazole acrylic acid and B mol of o-phenylenediamine into a dry three-neck flask, adding C mL of phosphorus oxychloride (concentrated hydrochloric acid), reacting at 80-105 ℃, and monitoring by TLC until the reaction is complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring for 10min at the temperature of 80-105 ℃, then carrying out suction filtration while the solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole.
The structural general formula of the N-alkyl-3-carbazole acrylic acid is shown as follows:
Figure BDA0002393017810000021
wherein R is-CH3，-C2H5，-CH2-Ph，-C3H7-n，-C3H7-i，-C4H9-n，C5H11-n，-C6H13-n，-C8H17-n，-C10H23-n，-C12H25-n，-C14H29-n，-C16H33-n.
The N-alkyl-3-carbazole acrylic acid can be obtained by a scheme comprising the following steps: the (E)1- (9-alkyl-carbazole-3-) -acrylic acid is prepared by taking 3-formyl-9-alkyl carbazole and malonic acid as raw materials and taking choline chloride-urea as a eutectic solvent as a solvent and a catalyst. The reaction formula is as follows:
Figure BDA0002393017810000022
wherein R is-CH3，-C2H5，-C3H7-n，-C3H7-i,-C4H9-n,-C5H11-n,-C6H13-n，-CH2ph，-C8H17-n，-C10H23-n，-C12H25-n，-C14H29-n，-C16H33-n.
And (3) monitoring by TLC, wherein the developing solvent used is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 1: 1.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of (E)2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole provided by the invention takes N-alkyl-3-carbazole acrylic acid and o-phenylenediamine as raw materials, and phosphorus oxychloride (concentrated hydrochloric acid) as a solvent and a catalyst, so that the (E)2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole can be prepared with high yield. The method has the advantages of simple operation, convenient post-treatment, short reaction time, high efficiency and great application prospect.
The product (E)2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole is an important medical compound intermediate, and can be further reacted to obtain (E) 1-acyl-2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole, wherein the reaction equation is as follows:
Figure BDA0002393017810000031
drawings
FIG. 1 shows the IR spectrum of (E)2- (2- (9-methyl) carbazole-3-) vinyl-benzimidazole prepared in example 1
FIG. 2 shows the IR spectrum of (E)2- (2- (9-ethyl) carbazole-3-) vinyl-benzimidazole prepared in example 2
FIG. 3 is an IR spectrum of (E)2- (2- (9-propyl) carbazole-3-) vinyl-benzimidazole prepared in example 3
FIG. 4 is an IR spectrum of (E)2- (2- (9-butyl) carbazole-3-) vinyl-benzimidazole prepared in example 4
FIG. 5 is an IR spectrum of (E)2- (2- (9-benzyl) carbazole-3-) vinyl-benzimidazole prepared in example 5
FIG. 6 is an IR spectrum of (E)2- (2- (9-dodecyl) carbazole-3-) vinyl-benzimidazole prepared in example 6
FIG. 7 is an IR spectrum of (E)2- (2- (9-tetradecyl) carbazole-3-) vinyl-benzimidazole prepared in example 7
FIG. 8 is an IR spectrum of (E)2- (2- (9-hexadecyl) carbazole-3-) vinyl-benzimidazole prepared in example 8
FIG. 9 is a photograph of (E)2- (2- (9-ethyl) carbazole-3-) vinyl-benzimidazole prepared in example 21H NMR spectrum
Detailed Description
The following is a further detailed description of the invention with reference to examples:
the invention takes N-alkyl-3-carbazole acrylic acid and o-phenylenediamine as raw materials, and phosphorus oxychloride (concentrated hydrochloric acid) as a solvent and a catalyst to prepare a series of (E)2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole. The reaction equation is as follows:
Figure BDA0002393017810000032
wherein R is-CH3，-C2H5，-CH2-Ph，-C3H7-n，-C3H7-i，-C4H9-n，C5H11-n，-C6H13-n，-C8H17-n，-C10H23-n，-C12H25-n，-C14H29-n，-C16H33-n.
Wherein the N-alkyl-3-carbazole acrylic acid is obtained by a scheme comprising the following steps: 3-formyl-9-alkyl carbazole and malonic acid are used as raw materials, a eutectic solvent choline chloride-urea is used as a solvent and a catalyst, and the (E)1- (9-alkyl-carbazole-3-) -acrylic acid is prepared at the reaction temperature of about 50 ℃. The reaction formula is as follows:
Figure BDA0002393017810000041
wherein R is-CH3，-C2H5，-C3H7-n，-C3H7-i,-C4H9-n,-C5H11-n,-C6H13-n，-CH2ph，-C8H17-n，-C10H23-n，-C12H25-n，-C14H29-n，-C16H33-n。
Example 1(E) preparation of 2- (2- (9-methyl) carbazole-3-) vinyl-benzimidazole
(1) To a dry three-necked flask, 500mg (0.002mol) of N-methyl-3-carbazole acrylic acid, 195.6(0.0018mol) of o-phenylenediamine and 5mL of phosphorus oxychloride were added, and the reaction was carried out at 80 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 80 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-methyl) carbazole-3-) vinyl-benzimidazole. The yield was 91.2%. The melting point is greater than 260 ℃.
(2) To a dry three-neck flask, 500mg (0.002mol) of N-methyl-3-carbazole acrylic acid, 195.6(0.0018mol) of o-phenylenediamine, and 5mL of phosphorus oxychloride were added, and the reaction was carried out at 100 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 100 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-methyl) carbazole-3-) vinyl-benzimidazole. The yield was 88.3%. The melting point is greater than 260 ℃.
(3) To a dry three-necked flask, 500mg (0.002mol) of N-methyl-3-carbazole acrylic acid, 195.6(0.0018mol) of o-phenylenediamine and 5mL of concentrated hydrochloric acid were added, and the reaction was carried out at 80 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 80 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-methyl) carbazole-3-) vinyl-benzimidazole. The yield was 70.1%. The melting point is greater than 260 ℃.
Ir (kbr) v: 3413(N-H),3051(C ═ C),2914,2844 (saturated C-H),1631(C ═ N),1492 (vibration of benzene ring skeleton), 1363 (CH)3) 1319(C-N),759 (ortho-disubstituted phenyl rings).
Example 2(E) preparation of 2- (2- (9-ethyl) carbazole-3-) vinyl-benzimidazole
(1) To a dry three-necked flask, 500mg (0.0019mol) of N-ethyl-3-carbazole acrylic acid, 185.3(0.0017mol) of o-phenylenediamine and 5mL of phosphorus oxychloride were added, and the reaction was carried out at 80 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 80 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-ethyl) carbazole-3-) vinyl-benzimidazole. The yield was 90.8%. The melting point is greater than 260 ℃.
(2) To a dry three-necked flask, 500mg (0.0019mol) of N-ethyl-3-carbazole acrylic acid, 185.3(0.0017mol) of o-phenylenediamine and 5mL of phosphorus oxychloride were added, and the reaction was carried out at 100 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 100 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-ethyl) carbazole-3-) vinyl-benzimidazole. The yield was 85.1%. The melting point is greater than 260 ℃.
(3) To a dry three-necked flask, 500mg (0.0019mol) of N-ethyl-3-carbazole acrylic acid, 185.3(0.0017mol) of o-phenylenediamine and 5mL of concentrated hydrochloric acid were added, and the reaction was carried out at 80 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 80 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-ethyl) carbazole-3-) vinyl-benzimidazole. The yield was 74.5%. The melting point is greater than 260 ℃.
Ir (kbr) v 3404(N-H),3051(C ═ C),2970,2873 (saturated C-H),1600(C ═ N),1485 (vibration of benzene ring skeleton), 1384 (CH) (CH ═ N), and so on3) 1338(C-N),746 (ortho-disubstituted benzene rings).
1H NMR(400MHz,DMSO-d6)δ:12.84(s,1H,-N-H),8.98(s,1H,-Ar-H),8.23-8.29(m,2H,-Ar-H),7.28-7.79(m,7H,-Ar-H),7.19(d,2H,-CH＝CH-),4.43(q,2H,-N-CH2),0.91(t,3H,-CH2-CH3)。
Example 3(E) preparation of 2- (2- (9-propyl) carbazole-3-) vinyl-benzimidazole
(1) To a dry three-neck flask was added 500mg (0.0019mol) of N-propyl-3-carbazole acrylic acid, 176.0(0.0018mol) o-phenylenediamine, and 5mL of phosphorus oxychloride, and the reaction was carried out at 80 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 80 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-propyl) carbazole-3-) vinyl-benzimidazole. The yield was 90.3%. The melting point is greater than 260 ℃.
(2) To a dry three-neck flask was added 500mg (0.0019mol) of N-propyl-3-carbazole acrylic acid, 176.0(0.0018mol) o-phenylenediamine, and 5mL of phosphorus oxychloride, and the reaction was carried out at 100 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 100 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-propyl) carbazole-3-) vinyl-benzimidazole. The yield was 83.9%. The melting point is greater than 260 ℃.
(3) To a dry three-necked flask, 500mg (0.0019mol) of N-propyl-3-carbazole acrylic acid, 176.0(0.0018mol) o-phenylenediamine and 5mL of concentrated hydrochloric acid were added, and the reaction was carried out at 80 ℃ and monitored by TLC until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 80 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-propyl) carbazole-3-) vinyl-benzimidazole. The yield was 70.2%. The melting point is greater than 260 ℃.
Ir (kbr) ν 3396(N-H),3055(C ═ C),2970,2869 (saturated C-H),1593(C ═ N),1487 (vibration of benzene ring skeleton), 1348 (CH) (CH ═ C), and methods for their preparation3) 1330(C-N),748 (ortho-disubstituted phenyl).
Example 4(E) preparation of 2- (2- (9-butyl) carbazole-3-) vinyl-benzimidazole
(1) To a dry three-necked flask, 500mg (0.0017mol) of N-butyl-3-carbazole acrylic acid, 167.6(0.0015mol) of o-phenylenediamine and 5mL of phosphorus oxychloride were added, and the reaction was carried out at 80 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 80 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-butyl) carbazole-3-) vinyl-benzimidazole. The yield was 88.6%. The melting point is greater than 260 ℃.
(2) To a dry three-necked flask, 500mg (0.0017mol) of N-butyl-3-carbazole acrylic acid, 167.6(0.0015mol) of o-phenylenediamine and 5mL of phosphorus oxychloride were added, and the reaction was carried out at 100 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 100 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-butyl) carbazole-3-) vinyl-benzimidazole. The yield was 80.9%. The melting point is greater than 260 ℃.
(3) To a dry three-necked flask, 500mg (0.0017mol) of N-butyl-3-carbazole acrylic acid, 167.6(0.0015mol) of o-phenylenediamine and 5mL of concentrated hydrochloric acid were added, and the reaction was carried out at 80 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 80 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-butyl) carbazole-3-) vinyl-benzimidazole. The yield was 66.1%. The melting point is greater than 260 ℃.
Ir (kbr) ν 3429(N-H),3051(C ═ C),2956,2875 (saturated C-H),1596(C ═ N),1485 (vibration of benzene ring skeleton), 1387 (CH) (CH ═ C), and so on3) 1334(C-N),746 (ortho-disubstituted benzene rings).
Example 5(E) preparation of 2- (2- (9-benzyl) carbazole-3-) vinyl-benzimidazole
(1) To a dry three-neck flask, 500mg (0.0015mol) of N-benzyl-3-carbazole acrylic acid, 150.1(0.0014mol) of o-phenylenediamine, and 5mL of phosphorus oxychloride were added, and the reaction was carried out at 80 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 80 ℃ for 10min, then carrying out suction filtration while the solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-benzyl) carbazole-3-) vinyl-benzimidazole. The yield was 93.1%. The melting point is greater than 260 ℃.
(2) To a dry three-neck flask, 500mg (0.0015mol) of N-benzyl-3-carbazole acrylic acid, 150.1(0.0014mol) of o-phenylenediamine, and 5mL of phosphorus oxychloride were added, and the reaction was carried out at 100 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 100 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-benzyl) carbazole-3-) vinyl-benzimidazole. The yield was 82.7%. The melting point is greater than 260 ℃.
(3) To a dry three-necked flask, 500mg (0.0015mol) of N-benzyl-3-carbazole acrylic acid, 150.1(0.0014mol) of o-phenylenediamine and 5mL of concentrated hydrochloric acid were added, and the reaction was carried out at 80 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 80 ℃ for 10min, then carrying out suction filtration while the solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-benzyl) carbazole-3-) vinyl-benzimidazole. The yield was 70.7%. The melting point is greater than 260 ℃.
Ir (kbr) ν 3649(N-H),3057(C ═ C),2931 (saturated C-H),1595(C ═ N),1490,1461 (shaking of the benzene ring skeleton), 1290(C-N),750 (ortho-disubstituted benzene rings).
Example 6(E) preparation of 2- (2- (9-dodecyl) carbazole-3-) vinyl-benzimidazole
(1) To a dry three-neck flask, 500mg (0.0012mol) of N-dodecyl-3-carbazole acrylic acid, 121.2(0.0011mol) of o-phenylenediamine, and 5mL of phosphorus oxychloride were added, and the reaction was carried out at 80 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 80 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-dodecyl) carbazole-3-) vinyl-benzimidazole. The yield was 78.9%. The melting point is greater than 260 ℃.
(2) To a dry three-neck flask, 500mg (0.0012mol) of N-dodecyl-3-carbazole acrylic acid, 121.2(0.0011mol) of o-phenylenediamine, and 5mL of phosphorus oxychloride were added, and the reaction was carried out at 105 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 105 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-dodecyl) carbazole-3-) vinyl-benzimidazole. The yield was 85.2%. The melting point is greater than 260 ℃.
(3) To a dry three-necked flask, 500mg (0.0012mol) of N-dodecyl-3-carbazole acrylic acid, 121.2(0.0011mol) of o-phenylenediamine and 5mL of concentrated hydrochloric acid were added, and the reaction was carried out at 80 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 80 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-dodecyl) carbazole-3-) vinyl-benzimidazole. The yield was 61.7%. The melting point is greater than 260 ℃.
Ir (kbr) v 3423(N-H),3053(C ═ C),2923,2853 (saturated C-H),1598(C ═ N),1487,1458 (vibration of benzene ring skeleton), 1346 (CH)3) 1240(C-N),742 (ortho-disubstituted phenyl rings).
Example 7(E) preparation of 2- (2- (9-tetradecyl) carbazole-3-) vinyl-benzimidazole
(1) To a dry three-necked flask, 500mg (0.00115mol) of N-tetradecyl-3-carbazole acrylic acid, 113.4(0.00105mol) of o-phenylenediamine and 5mL of phosphorus oxychloride were added, and the reaction was carried out at 80 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 80 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-tetradecyl) carbazole-3-) vinyl-benzimidazole. The yield was 75.8%. The melting point is greater than 260 ℃.
(2) To a dry three-necked flask, 500mg (0.00115mol) of N-tetradecyl-3-carbazole acrylic acid, 113.4(0.00105mol) of o-phenylenediamine and 5mL of phosphorus oxychloride were added, and the reaction was carried out at 105 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 105 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-tetradecyl) carbazole-3-) vinyl-benzimidazole. The yield was 82.1%. The melting point is greater than 260 ℃.
(3) To a dry three-necked flask, 500mg (0.00115mol) of N-tetradecyl-3-carbazole acrylic acid, 113.4(0.00105mol) of o-phenylenediamine and 5mL of concentrated hydrochloric acid were added, and the reaction was carried out at 80 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 80 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-tetradecyl) carbazole-3-) vinyl-benzimidazole. The yield was 58.4%. The melting point is greater than 260 ℃.
Ir (kbr) v 3409(N-H),3053(C ═ C),2923,2852 (saturated C-H),1600(C ═ N),1487,1460 (vibration of benzene ring skeleton), 1348 (CH) (CH ═ C)3) 1271(C-N),748 (ortho-position to the phenyl ring)Disubstituted).
Example 8(E) preparation of 2- (2- (9-hexadecyl) carbazole-3-) vinyl-benzimidazole
(1) To a dry three-necked flask, 500mg (0.0011mol) of N-hexadecyl-3-carbazole acrylic acid, 106.5(0.001mol) of o-phenylenediamine and 5mL of phosphorus oxychloride were added, and the reaction was carried out at 80 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 80 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-hexadecyl) carbazole-3-) vinyl-benzimidazole. The yield was 69.5%. The melting point is greater than 260 ℃.
(2) To a dry three-necked flask, 500mg (0.0011mol) of N-hexadecyl-3-carbazole acrylic acid, 106.5(0.001mol) of o-phenylenediamine and 5mL of phosphorus oxychloride were added, and the reaction was carried out at 105 ℃ with TLC monitoring until the reaction was complete. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 105 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-hexadecyl) carbazole-3-) vinyl-benzimidazole. The yield was 80.8%. The melting point is greater than 260 ℃.
(3) To a dry three-necked flask, 500mg (0.0011mol) of N-hexadecyl-3-carbazole acrylic acid, 106.5(0.001mol) of o-phenylenediamine and 5mL of concentrated hydrochloric acid were added, and the reaction was carried out at 80 ℃ with TLC monitoring until the reaction was completed. After the reaction is finished, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 80 ℃ for 10min, then carrying out suction filtration while the reaction solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-hexadecyl) carbazole-3-) vinyl-benzimidazole. The yield was 52.1%. The melting point is greater than 260 ℃.
Ir (kbr) v: 3417(N-H),3051(C ═ C),2923,2850 (saturated C-H),1606(C ═ N),1483 (vibration of benzene ring skeleton), 1346(CH ═ C)3) 1271(C-N),740 (ortho-disubstituted phenyl rings).
Testing
Figure BDA0002393017810000101
(E)2- (2- (9-hexadecyl) carbazole-3-) vinyl-benzimidazole A
TABLE 1 antibacterial Activity of carbazolyl-containing benzimidazole derivatives (mm)
Figure BDA0002393017810000102
Bacteriostatic activity is expressed by the size of the zone of inhibition, unit: mm. DMSO was used as a blank control.
The invention mainly aims at gram-negative bacteria and gram-positive bacteria to carry out the bacteriostasis test of (E)2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole, and the result shows that the target compound has certain bacteriostasis effect. The results of the bacteriostatic test of all the compounds are shown in the attached table 1, and all the compounds have obvious inhibitory effect on gram-positive bacteria and gram-negative bacteria.

Claims (7)

1. A (E)2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole having the structural formula:
Figure DEST_PATH_IMAGE001
（1）；
wherein R is-CH2-Ph。
2. A preparation method of (E)2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole is characterized by comprising the following steps:
reacting N-alkyl-3-carbazole acrylic acid with o-phenylenediamine in phosphorus oxychloride and/or concentrated hydrochloric acid to obtain (E)2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole;
the structural formula of the N-alkyl-3-carbazole acrylic acid is as follows:
Figure DEST_PATH_IMAGE003
（2）；
wherein R is-CH2-Ph。
3. The method of claim 2, wherein the reaction of N-alkyl-3-carbazole acrylic acid with o-phenylenediamine is carried out at a temperature of from 80 ℃ to 105 ℃.
4. The method as claimed in claim 2, wherein after the reaction is completed, the reaction solution is cooled, a small amount of activated carbon is added, the reaction solution is continuously stirred at 80-105 ℃ for 10min, then the hot reaction solution is subjected to suction filtration, the pH of the filtrate is adjusted to be alkaline in an ice bath, and a large amount of solid is separated out, so that the (E)2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole is obtained.
5. The method of claim 2, comprising the steps of:
reacting A mol of N-alkyl-3-carbazole acrylic acid and B mol of o-phenylenediamine in C mL of phosphorus oxychloride and/or concentrated hydrochloric acid at 80-105 ℃, monitoring by TLC until the reaction is complete, cooling the reaction solution, adding a small amount of activated carbon, continuously stirring at 80-105 ℃ for 10min, carrying out suction filtration while the solution is hot, adjusting the pH of the filtrate in an ice bath by using ammonia water to be alkaline, separating out a large amount of solids, carrying out suction filtration, washing with water, and drying to obtain (E)2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole;
a mol of N-alkyl-3-carbazole acrylic acid and B mol of o-phenylenediamine, wherein A: B = (1-1.1): 1;
c mL of phosphorus oxychloride and/or concentrated hydrochloric acid, wherein the C mL = 5-10 mL.
6. The method of claim 5, wherein the phosphorus oxychloride and/or concentrated hydrochloric acid serves as both a catalyst and a solvent in the reaction.
7. The method of claim 5, wherein the TLC monitors the reaction and is complete when the starting material spot disappears; the developing solvent used for TLC monitoring is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 1: 1.
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