Synthesis method of 9-(4-bromophenyl) carbazole by using carbazole and p-bromophenol as raw materials

A synthesis method and technology for p-bromophenol are applied in the field of synthesis of phenylcarbazole derivatives, can solve problems such as outstanding environmental protection problems, harsh reaction conditions, poor reaction selectivity, etc., and achieve low production cost, mild reaction conditions, and strong compounding. The effect of chelation

Pending Publication Date: 2022-08-05
SINOSTEEL NANJING NEW MATERIALS RES INST CO LTD
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0016] The object of the present invention is to provide a kind of synthetic method of 9-(4-bromophenyl) carbazole, which can solve the poor reaction selectivity and atom utilization in the existing 9-(4-bromophenyl) carbazole synthetic method. Low efficiency, harsh reaction conditions, high production costs, prominent environmental protection issues, and technical problems that are not conducive to mass production

Method used

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  • Synthesis method of 9-(4-bromophenyl) carbazole by using carbazole and p-bromophenol as raw materials
  • Synthesis method of 9-(4-bromophenyl) carbazole by using carbazole and p-bromophenol as raw materials
  • Synthesis method of 9-(4-bromophenyl) carbazole by using carbazole and p-bromophenol as raw materials

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Experimental program
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Effect test

Embodiment 1

[0052] Embodiment 1: a kind of synthetic method of 9-(4-bromophenyl) carbazole

[0053] The synthesis steps include: under nitrogen protection, add 83.6g carbazole (98%, 0.5mol), 86.6g p-bromophenol (98%, 0.5mol), 1.5g [Cp*RhCl] into a 1000mL reaction flask 2 ] 2 (98%, 2.5mmol), 1.1g imidazole nitrogen heterocyclic carbene ligand NHC1 (98%, 5.0mmol), 26.5g sodium carbonate (99%, 0.25mol) and 500mL n-heptane; ℃, stirring speed 500rpm, insulation reaction 8 hours; After the reaction, cooling at room temperature filtration, washing, extraction, organic layer precipitation recovery solvent, the crude product is crystallized through n-hexane to obtain 141.2g of 9-(4-bromophenyl)carbazone azole product, the yield is 87.6%.

[0054] The hydrogen nuclear magnetic resonance spectrum of the product prepared in this example is as follows figure 1 shown, 1 H NMR (400MHz, CDCl 3 )d=7.32(t,J=7.2Hz,2H),7.36-7.51(m,6H),7.74(d,J=8.5Hz,2H),8.16(d,J=7.7Hz,2H); NMR carbon spectrum as figu...

Embodiment 2

[0055] Embodiment 2: a kind of synthetic method of 9-(4-bromophenyl) carbazole

[0056] The synthesis steps include: under nitrogen protection, add 83.6g carbazole (98%, 0.5mol), 86.6g p-bromophenol (98%, 0.5mol), 1.5g [Cp*RhCl] into a 1000mL reaction flask 2 ] 2 (98%, 2.5mmol), 3.8g imidazole type azacyclic carbene ligand NHC2 (98%, 12.5mmol), 41.0g sodium acetate (99%, 0.5mol) and 500mL n-octane; ℃, stirring speed 500rpm, insulation reaction 6 hours; After the reaction finishes, cooling room temperature filtration, washing, extraction, organic layer precipitation reclaims solvent, crude product is through petroleum ether crystallization, obtains 149.0g of 9-(4-bromophenyl)carbazone azole product, the yield is 92.5%.

Embodiment 3

[0057] Embodiment 3: a kind of synthetic method of 9-(4-bromophenyl) carbazole

[0058] The synthesis steps include: under nitrogen protection, add 83.6g carbazole (98%, 0.5mol), 103.9g p-bromophenol (98%, 0.6mol), 4.6gRh (PPh) into a 1000mL reaction flask 3 ) 3 Cl (98%, 5.0 mmol), 8.3 g imidazole azacyclic carbene ligand NHC 3 (98%, 25.0mmol), 26.5g of sodium carbonate (99%, 0.25mol) and 700mL of n-nonane; after feeding, the temperature was raised to 110 ° C, the stirring speed was 500 rpm, and the reaction was incubated for 8 hours; Wash with water, extract, and desolvate the organic layer to recover the solvent. The crude product is crystallized from ethanol to obtain 153.5 g of 9-(4-bromophenyl)carbazole product with a yield of 95.3%.

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Abstract

The invention discloses a synthesis method of 9-(4-bromophenyl) carbazole, and belongs to the technical field of synthesis of phenylcarbazole derivatives. The method comprises the following steps: taking carbazole and p-bromophenol as initial reactants, and synthesizing 9-(4-bromophenyl) carbazole through dehydroxylation C-N coupling reaction under the action of a catalyst, a ligand, alkali and a solvent. An imidazole N-heterocyclic carbene ligand used in the synthesis method of 9-(4-bromophenyl) carbazole is a specific type of ligand aiming at the reaction system, the ligand has strong coordination chelation and large steric hindrance, carbazole N-H and p-bromophenol can be precisely coordinated in a targeted manner when the ligand is coordinated with rhodium salt, a stable rhodium ring intermediate is generated, and the 9-(4-bromophenyl) carbazole can be used for preparing the 9-(4-bromophenyl) carbazole. Therefore, the method disclosed by the invention is mild in reaction condition, good in selectivity, simple in post-treatment, high in yield, high in atom utilization rate, environment-friendly, economical and green.

Description

technical field [0001] The invention belongs to the technical field of synthesis of phenylcarbazole derivatives, in particular to a method for synthesizing 9-(4-bromophenyl)carbazole using carbazole and p-bromophenol as raw materials. Background technique [0002] Phenylcarbazoles are a class of important nitrogen-containing heterocyclic aromatic compounds with outstanding properties such as large π-conjugated electron systems, strong intramolecular electron transfer properties, and strong hole transport capabilities. They are used in medicine, dyes, pesticides and organic optoelectronics. Materials and other fields are widely used. 9-(4-Bromophenyl)carbazole is an important intermediate for the synthesis of compounds containing phenylcarbazole groups. It can synthesize 4-(9H-carbazol-9-yl)phenylboronic acid, 9-[4- (4,4,5,5-Tetramethyl-1,3,2-dioxaboran-2-yl)phenyl]-9H-carbazole, 3,6-dibromo-9-(4-bromo Phenyl)carbazole and other phenylcarbazole derivatives, and then synthes...

Claims

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Application Information

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IPC IPC(8): C07D209/86
CPCC07D209/86Y02E10/549Y02P20/584
Inventor 杨修光朱叶峰吴忠凯裴晓东王凡钱有军申保金张玲张倩倩
Owner SINOSTEEL NANJING NEW MATERIALS RES INST CO LTD
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