A kind of ruthenium catalysis prepares the method for many substituted 1-naphthoic acid compounds

A compound and multi-substitution technology, which is applied in the field of ruthenium-catalyzed preparation of multi-substituted 1-naphthoic acid compounds, can solve the problems that the product cannot be separated and cannot be used to prepare multi-substituted 1-naphthoic acid, and achieves high yield, The reaction operation is simple and the selectivity is good

Active Publication Date: 2021-05-11
GUANGZHOU UNIVERSITY
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Problems solved by technology

This by-product is generated by the cyclization reaction of benzoic acid and two molecules of alkynes, and the highest yield is only 8% (GC yield), and the product cannot be separated, and only one carboxyl group in the substrate is removed, so it cannot be used for the preparation of polysubstituted 1-naphthoic acids

Method used

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  • A kind of ruthenium catalysis prepares the method for many substituted 1-naphthoic acid compounds
  • A kind of ruthenium catalysis prepares the method for many substituted 1-naphthoic acid compounds
  • A kind of ruthenium catalysis prepares the method for many substituted 1-naphthoic acid compounds

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] Add p-cymene dichloride ruthenium dimer (0.01mmol, 6.1mg), toluene (0.4mmol, 71.3mg), phthalic acid (0.3mmol, 49.8 mg), tetrabutylammonium bromide (0.04mmol, 12.9mg) and a magnetic stirrer, add 900μL GVL and 100μL DMF with a pipette gun, cover the upper opening of the reaction tube and leave its branch open to the air, then put Stir in a metal heating block at 100°C for 12 hours. After the reaction was completed, ethyl acetate was added, washed with water, separated, the organic phase was concentrated and then separated by silica gel column chromatography to obtain a light yellow solid which was the product 5,6,7,8-tetraphenyl-1-naphthoic acid, the yield 81%.

[0044] The structure of the obtained product was confirmed by high-resolution mass spectrum, hydrogen nuclear magnetic spectrum and carbon spectrum. HRMS (ESI) calcd for C 35 h 24 o 2 [M–H] – 475.1704, found 475.1712. The H NMR and C NMR spectra of the product are shown as figure 1 and figure 2 shown. ...

Embodiment 2

[0046] Add ruthenium trichloride trihydrate (0.024mmol, 6.3mg), diphenylacetylene (0.4mmol, 71.3mg), phthalic anhydride (0.3mmol, 44.4mg) and tetrabutyl bromide successively into a 10mL reaction tube with a branch Ammonium (0.05mmol, 16.1mg) and a magnetic stirring bar were added to 1mL of GVL, the upper opening of the reaction tube was covered and its branch was connected to the oxygen bulb, and then placed in a metal heating module at 100°C and stirred for 20 hours. After the reaction was completed, ethyl acetate was added, washed with water, separated, the organic phase was concentrated and then separated by silica gel column chromatography to obtain a light yellow solid which was the product 5,6,7,8-tetraphenyl-1-naphthoic acid, the yield 68%.

Embodiment 3

[0048] Add p-cymene dichloride ruthenium dimer (0.01mmol, 6.1mg), toluene (0.4mmol, 71.3mg), 4-methylphthalic anhydride (0.3mmol, 48.6mg), tetrabutylammonium bromide (0.04mmol, 12.9mg) and a magnetic stirrer, add 900μL GVL, 100μL DMF and 20μL water with a pipette gun, cover the upper opening of the reaction tube and leave its branch open to the air , and then placed in a metal heating block at 100°C and stirred for 20 hours. After the reaction was completed, ethyl acetate was added, washed with water, separated, the organic phase was concentrated and separated by silica gel column chromatography to obtain a light yellow solid which was the product 3-methyl-5,6,7,8-tetraphenyl-1- Naphthoic acid, yield 82%.

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Abstract

The invention belongs to the technical field of organic synthesis and discloses a ruthenium-catalyzed method for preparing multi-substituted 1-naphthoic acid compounds. Heat reaction of phthalic acid (I) or phthalic anhydride compound (II) with diaryl-substituted symmetrical alkyne compound (III), ruthenium catalyst, additive and solvent in air or oxygen environment, and the reaction product is separated and purified , to obtain many substituted 1-naphthoic acid compounds (IV). The method of the present invention uses easy-to-obtain phthalic acid or phthalic anhydride compounds and alkynes as raw materials, and the high catalytic activity of the ruthenium catalyst system used enables the reaction to use air or oxygen as a green oxidant, avoiding the use of toxic, dangerous or expensive The oxidizing agent, the reaction operation is simple and safe, and it is easy to realize industrialization.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for preparing multi-substituted 1-naphthoic acid compounds by ruthenium catalysis. Background technique [0002] In the context of the increasing demand for multi-substituted small molecules in drug screening and organic material development, the efficient preparation of functionalized carbocyclic compounds has become an important research direction in the field of organic synthesis in recent years. Multi-substituted 1-naphthoic acids and their derivatives exist in some natural products and bioactive molecules, such as neocarzinostatin and azinomycin B with anticancer activity (Zhang Q., Pang B., Liu W, et al.ACS Catal. 2013,3,1439) and a class of bile acid receptor agonists (Akwabi-Ameyaw A., Bass J.Y., Deaton D.N., et al.Bioorg.Med.Chem.Lett.2008,18,4339). In addition, the carboxyl group in the multi-substituted 1-naphthoic acid can be further tr...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C51/353C07C63/44C07C65/24C07C63/72C07C63/49C07D333/24C07C201/12C07C205/57C07C61/39
CPCC07C51/353C07C201/12C07D333/24C07C2603/26C07C2603/74C07C63/44C07C65/24C07C63/72C07C63/49C07C205/57C07C61/39
Inventor 郑李垚陈弘浩欧阳禄锋刘吉旦
Owner GUANGZHOU UNIVERSITY
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