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A kind of preparation method of hydroxyl and methoxycarbonyl substituted triarylamine compounds

A technology of methoxycarbonyl and triarylamine, which is applied in the field of preparation of triarylamine compounds, can solve problems such as harsh reaction conditions, difficulties, and narrow substrate adaptability, and achieves short reaction time, simple operation and convenient post-processing. Effect

Inactive Publication Date: 2016-04-13
GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI
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  • Abstract
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Problems solved by technology

[0004] At present, the preparation methods of triarylamines mainly contain the following two types: (1) the N-arylation reaction of non-metallic catalyzed diarylamines, such methods require harsh reaction conditions and substrate adaptability Narrow (Organic Chemistry, 2011,31(11):1799-1810)
(2) metal-catalyzed N-arylation of diarylamines, such reactions mainly include copper-catalyzed Ullmann cross-coupling reactions between diarylamines and aryl halides (TetrahedronLett., 2006, 47( 52):9275–9278) and palladium-catalyzed Buchwald-Hartwig cross-coupling reaction (Adv.Synth.Catal., 2008,350(5):652-656), because the functional group has a relatively large effect on the reactivity and the selectivity of the reaction There are still difficulties in the synthesis of structures containing active groups such as hydroxyl and carboxyl in this type of reaction.

Method used

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  • A kind of preparation method of hydroxyl and methoxycarbonyl substituted triarylamine compounds
  • A kind of preparation method of hydroxyl and methoxycarbonyl substituted triarylamine compounds

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Embodiment 1

[0024] Embodiment 1: Preparation of N-phenyl-N-(2-carboxyphenyl)-2-hydroxyl-5-methoxycarbonylaniline

[0025] Methyl 3-dehydroshikimate (0.41g, 2.2mmol), aniline (0.19g, 2.0mmol), p-toluenesulfonic acid (19.0mg, 0.1mmol), and 5ml N,N-dimethylformamide were added to the microwave at one time in the reaction vial. The reaction system was reacted at 130° C. for 8 min in a microwave reactor. TLC monitors the reaction. After the reaction is completed, potassium carbonate (0.83g, 6mmol), cuprous oxide (0.27g, 2mmol), o-iodobenzoic acid (0.50g, 2mmol) are added to the above system, and the system is placed in a microwave reactor for 130 Reaction at ℃ for 5min. The reaction was monitored by TLC. After the reaction was completed, it was cooled and filtered with suction. The filtrate was poured into 100ml of ice water and acidified with dilute hydrochloric acid. A large amount of off-white solids were precipitated, filtered with suction, dried, and recrystallized with ethyl acetate-pe...

Embodiment 2

[0027] Embodiment 2: Preparation of N-(4-methylphenyl)-N-(2-carboxyphenyl)-2-hydroxyl-5-methoxycarbonylaniline

[0028] Methyl 3-dehydroshikimate (0.37g, 2.0mmol), p-methylaniline (0.22g, 2.0mmol), formic acid (4.6mg, 0.1mmol), and 5ml N,N-dimethylformamide were added to the microwave at one time in the reaction vial. The reaction system was reacted at 130° C. for 6 min in a microwave reactor. The reaction was monitored by TLC. After the reaction was completed, potassium carbonate (0.83g, 6mmol), cuprous oxide (0.27g, 2mmol), and o-iodobenzoic acid (0.50g, 2mmol) were added to the above system in a microwave reactor at 130°C. React for 5 minutes. The reaction was monitored by TLC. After the reaction was completed, it was cooled and filtered with suction. The filtrate was poured into 100ml of ice water and acidified with dilute hydrochloric acid. A large amount of off-white solid precipitated, filtered with suction, dried, and recrystallized with ethyl acetate-ethanol to obta...

Embodiment 3

[0030] Example 3: Preparation of N-(4-bromophenyl)-N-(2-carboxyphenyl)-2-hydroxyl-5-methoxycarbonylaniline:

[0031]Methyl 3-dehydroshikimate (0.45g, 2.5mmol), p-bromoaniline (0.35g, 2.0mmol), p-toluenesulfonic acid (28.5mg, 0.15mmol), 5ml N,N-dimethylacetamide in one go Add to microwave reaction vial. The reaction system was reacted at 130° C. for 8 min in a microwave reactor. The reaction was monitored by TLC. After the reaction was completed, potassium carbonate (0.83g, 6mmol), cuprous chloride (0.20g, 2mmol), and o-iodobenzoic acid (0.50g, 2mmol) were added to the above system at 110°C in a microwave reactor. Under reaction 8min. The reaction was monitored by TLC, after the reaction was completed, suction filtered after cooling, the filtrate was poured into 100ml of ice water, acidified with dilute hydrochloric acid, a large amount of off-white solid was precipitated, filtered with suction, dried, and recrystallized with ethanol-water to obtain white crystal N-(4 -Bromo...

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Abstract

The invention discloses a preparation method for hydroxyl- and methoxycarbonyl-substituted triarylamine compounds. The preparation method comprises the following steps: subjecting 3-methyl dehydroshikimate and arylamine compounds to condensation, isomerization and dehydration in the presence of an organic solvent and a catalyst and under microwave conditions; and continuing to add aryl halide, alkali and the catalyst, carrying out a reaction under microwave conditions and then carrying out cooling, pumping filtration and recrystallization so as to obtain the hydroxyl- and methoxycarbonyl-substituted triarylamine compounds. According to the invention, through a microwave-assisted process, synthesis of the hydroxyl- and methoxycarbonyl-substituted triarylamine compounds can be realized, and the preparation method has the advantages of simple operation, short reaction time and convenient after-treatment.

Description

technical field [0001] The invention relates to the field of chemical industry, in particular to a preparation method of triarylamine compounds substituted by hydroxyl and methoxycarbonyl groups. Background technique [0002] Triarylamine compounds are an important class of organic compounds, and related structural compounds are widely used in the fields of dye chemical industry and organic materials. For example: hexaethyltriindenylamine epoxythiophene rhodanine acetic acid (MXD9) is a three polyindenyltriarylamine photosensitive dyes, optical tests show that this type of dye has a wide spectral response range and high molar absorptivity (application Chemistry, 2011, 28(12):1388-1392). N,N'-diphenyl-N,N'-di-m-cresyl-1,1'-biphenyl-4,4'-diamine (TPD) and its similar structures are widely used in electroluminescent devices and Preparation of Light Emitting Diodes (J.Org.Chem., 2000, 65(17):5327-5333). All of the above molecular structures have structural units of triarylami...

Claims

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Application Information

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IPC IPC(8): C07C229/64C07C227/18
Inventor 邹永张恩生徐田龙王德建黄桐堃陈爱民
Owner GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI
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