Method for preparing 1-substituted-beta-carboline-3-carboxylic ester

A technology of carboxylate and carboxylate, applied in the field of preparation of 1-substituted-β-carboline-3-carboxylate, which can solve the problems of high toxicity of oxidant and solvent, high oxidation reaction temperature, unsatisfactory yield, etc. , to achieve the effect of simple preparation method, convenient post-processing and easy raw materials

Active Publication Date: 2016-08-24
SHAANXI UNIV OF SCI & TECH
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Problems solved by technology

β-carboline-3-carboxylate compound (shown in formula Ⅱ) is as a kind of important drug intermediate, and its synthesis has received extensive attention, and the synthesis of existing β-carboline-3-carboxylate compound is all Use 4-(H)-β-carboline-3-carboxylate as precursor to reflux oxidation in cumene or toluene to synthesize β-carboline compounds. The catalysts used are: palladium supported carbon catalyst, sulfur, SeO 2 or MnO 2 , tetrachlorobenzoquinone, dichlorodicyanobenzoquinone (DDQ), trichloroisocyanuric acid (TCCA), dimethyl phthalate (DMP), iodooxybenzoic acid (IBX), etc., these synthetic methods exist Catalysts, oxidants and solvents are highly toxic, the oxidation reaction temperature is high, the steps are complicated, and the yield is not ideal.

Method used

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  • Method for preparing 1-substituted-beta-carboline-3-carboxylic ester
  • Method for preparing 1-substituted-beta-carboline-3-carboxylic ester
  • Method for preparing 1-substituted-beta-carboline-3-carboxylic ester

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Experimental program
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Embodiment 1

[0058] Preparation of 1-(4'-methoxy)phenyl-β-carboline-3-carboxylic acid methyl ester

[0059] 2mmol of tryptophan methyl ester was dissolved in ethanol and water mixed liquid solvent with a volume ratio of 1:2, 2.1mmol of p-methoxybenzaldehyde was added, and 0.004mmol of nano-copper oxide and 0.004mmol of nano-ferric oxide were added. As a catalyst, it was heated under reflux at 75°C for 1 hour, and the progress of the reaction was monitored by TLC. After the reaction was complete, it was concentrated and separated by column chromatography to obtain 265 mg of a light yellow solid with a yield of 89%. The structural formula of the product obtained was as follows:

[0060]

[0061] Such as figure 1 and figure 2 Shown, product NMR characterization 1 H NMR (400MHz, CDCl 3 )δ8.99(s,1H),8.85(s,1H),8.23(d,J=7.9Hz,1H),7.87(d,J=8.6Hz,2H),7.61(t,J=11.8Hz, 2H),7.43–7.33(m,1H),7.01(d,J=8.6Hz,2H),4.07(s,3H),3.85(s,3H). 13 C NMR (101MHz, CDCl 3 )δ166.50, 159.83, 142.34, 140.11, 1...

Embodiment 2

[0063] Preparation of 1-(2'-pyridine)-β-carboline-3-carboxylic acid methyl ester

[0064] Dissolve 2mmol of tryptophan methyl ester in a methanol-water mixture solvent with a volume ratio of 5:1, add 2.4mmol of dipyridylbenzaldehyde, use 0.006mmol of nanometer ferric oxide as a catalyst, and heat at 40°C Reflux for 30 hours, monitor the progress of the reaction with TLC, concentrate after the reaction is complete, and separate through column chromatography to obtain 515 mg of a light yellow solid with a yield of 86%. The structural formula of the resulting product is as follows:

[0065]

[0066] Such as image 3 and Figure 4 Shown, product NMR characterization: 1 H NMR (400MHz, CDCl 3 )δ11.67(s,1H),8.96–8.91(m,2H),8.83(d,J=4.8Hz,1H),8.25(d,J=7.8Hz,1H),8.00–7.95(m,1H ), 7.71(d, J=8.2Hz, 1H), 7.65(t, J=7.3Hz, 1H), 7.44–7.38(m, 2H), 4.12(s, 3H). 13 C NMR (101MHz, CDCl 3 )δ166.24, 156.53, 147.72, 140.50, 137.07, 136.69, 136.15, 135.66, 130.18, 128.51, 123.10, 121.62, 12...

Embodiment 3

[0068] Preparation of 1-(4'-pyridine)-β-carboline-3-carboxylic acid methyl ester

[0069] Dissolve 2mmol of tryptophan methyl ester in ethanol and water mixture solvent with a volume ratio of 1:5, add 2.2mmol of dipyridylbenzaldehyde, use 0.008mmol of nano-cerium oxide as a catalyst, and heat to reflux at 50°C for 20 Hour, monitor the progress of reaction with TLC, concentrate after the reaction is complete, separate through column chromatography, obtain 500mg light yellow solid, productive rate is 84%, and gained product structural formula is as follows:

[0070]

[0071] Such as Figure 5 and Figure 6 As shown, the NMR characterization of the product: 1 H NMR (400MHz, CDCl 3 )δ9.74(s,1H),8.95(d,J=10.5Hz,1H),8.72(d,J=5.5Hz,2H),8.26(d,J=7.9Hz,1H),7.87(d, J=5.8Hz, 2H), 7.74–7.58(m, 2H), 7.47–7.39(m, 1H), 4.08(s, 3H). 13 C NMR (101MHz, CDCl 3 )δ166.04, 149.85, 145.12, 140.54, 139.19, 137.86, 134.81, 130.21, 129.02, 122.65, 121.60, 121.36, 121.01, 117.55, 111.68, 52.37....

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Abstract

The invention discloses a method for preparing 1-substituted-beta-carboline-3-carboxylic ester. Methyl tryptophan and aromatic aldehyde or a carbonyl containing cyclic compound and a catalyst are added into a solvent, separation and purification are carried out after a heating reaction, and 1-substituted-beta-carboline-3-carboxylic ester is obtained. A 1-substituted-beta-carboline-3-carboxylic ester derivative is synthesized through a one-step method with high yield. The defects that in a current synthesis reaction, a poisonous catalyst and a poisonous solvent are adopted, the reaction temperature is high, the steps are complex, and the yield is not ideal are avoided.

Description

technical field [0001] The invention belongs to the technical field of chemistry or medicinal chemistry, and in particular relates to a preparation method of 1-substituted-β-carboline-3-carboxylate. Background technique [0002] [0003] The β-carboline structure (shown in formula I) is a component of nitrogen-containing indole alkaloids and the basic unit of natural and synthetic medicines. Such compounds have a wide range of biochemical and pharmacological activities, such as anti-malarial, anti-tumor, anti-HIV, anxiolytic, sedative and so on. β-carboline-3-carboxylate compound (shown in formula Ⅱ) is as a kind of important drug intermediate, and its synthesis has received extensive attention, and the synthesis of existing β-carboline-3-carboxylate compound is all Use 4-(H)-β-carboline-3-carboxylate as precursor to reflux oxidation in cumene or toluene to synthesize β-carboline compounds. The catalysts used are: palladium supported carbon catalyst, sulfur, SeO 2 or Mn...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D471/04C07D471/10C07D471/20
CPCC07D471/04C07D471/10C07D471/20
Inventor 张金刘佳马养民程佩王伟涛
Owner SHAANXI UNIV OF SCI & TECH
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