Green synthesis method for beta-carboline heterocyclic compounds

A heterocyclic compound and green synthesis technology, applied in the direction of organic chemistry, can solve the problems of heavy metal residues in products, limited synthetic applications, heavy toxicity of aldehyde odor, etc., and achieve the effects of easy operation, wide application range and low requirements

Active Publication Date: 2018-08-17
WENZHOU UNIVERSITY
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Problems solved by technology

Because the Pictet-Spengler reaction mainly uses aldehydes as raw materials, and the aldehydes have a heavy odor and are highly toxic, active and unstable, and difficult to store. They need to be purified before each use, and there are many shortcomings. In addition, some methods also use transition metal catalysts and ligands, resulting in product There are heavy metal residues in the method, which is not suitable for the synthesis of pharmaceutical intermediates with high requirements on metal residues, and also limits the further synthetic application of these methods

Method used

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  • Green synthesis method for beta-carboline heterocyclic compounds
  • Green synthesis method for beta-carboline heterocyclic compounds
  • Green synthesis method for beta-carboline heterocyclic compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Preparation of 1-phenyl-β-carboline from tryptamine and benzyl alcohol

[0022]

[0023] Add tryptamine (0.0801g, 0.5mmol), benzyl alcohol (0.0621ml, 1.2equiv.), TEMPO (0.0790g, 100mol%), TBN (0.0586ml, 100mol%) and glacial acetic acid (0.5 ml), pumping and exchanging the gas for three times, sealing the tube with oxygen, and then reacting at 80°C for 24h under stirring. After the completion of the reaction was monitored by TLC, the product was separated and purified by column chromatography, and the separation yield was 85%. 1 H NMR (500MHz, DMSO-d 6 ): δ11.54(br s,1H),8.48(d,J=5.0Hz,1H),8.27(d,J=8.0Hz,1H),8.13(d,J=5.0Hz,1H),8.06( d, J=7.5Hz, 2H), 7.68(d, J=8.0Hz, 1H), 7.63(t, J=7.5Hz, 2H), 7.58-7.52(m, 2H), 7.28(t, J=7.5 Hz,1H). 13 C NMR (125.4MHz, DMSO-d 6 ): δ142.1, 141.1, 138.3, 138.2, 132.9, 129.2, 128.7, 128.5, 128.3, 128.1, 121.5, 120.8, 119.5, 113.8, 112.4.

Embodiment 2

[0025] Preparation of 1-(4-methoxyphenyl)-β-carboline from tryptamine and 4-methoxybenzyl alcohol

[0026]

[0027] In the tubular reactor, add tryptamine (0.0801g, 0.5mmol), 4-methoxybenzyl alcohol (0.0745ml, 1.2equiv.), TEMPO (0.0790g, 100mol%), TBN (0.0586ml, 100mol%) and glacial acetic acid (0.5ml), pumped and ventilated three times and sealed with oxygen, then reacted at 80°C for 24h under stirring. After the complete reaction was monitored by TLC, the product was separated and purified by column chromatography, and the separation yield was 64%. 1 H NMR (500MHz, DMSO-d 6 ): δ11.51(br s,1H),8.43(d,J=5.0Hz,1H),8.26(d,J=8.0Hz,1H),8.07(d,J=5.0Hz,1H),8.01( d, J=8.5Hz, 2H), 7.67(d, J=8.5Hz, 1H), 7.56(t, J=7.5Hz, 1H), 7.27(t, J=7.5Hz, 1H), 7.18(d, J=8.0Hz,2H),3.88(s,3H). 13 CNMR (125.4MHz, DMSO-d 6 ): δ159.6, 142.1, 141.0, 138.2, 132.7, 130.9, 129.6, 128.9, 127.9, 121.5, 120.9, 119.4, 114.1, 113.2, 112.4, 55.3.

Embodiment 3

[0029] Preparation of 1-(4-methylphenyl)-β-carboline from tryptamine and 4-methylbenzyl alcohol

[0030]

[0031] Add tryptamine (0.0801g, 0.5mmol) successively in the tubular reactor, 4-methylbenzyl alcohol (0.0733g, 1.2equiv.), TEMPO (0.0790g, 100mol%), TBN (0.0586ml, 100mol%) and Glacial acetic acid (0.5ml) was pumped and ventilated three times to seal the oxygen, and then reacted at 80°C for 24h under stirring. After the complete reaction was monitored by TLC, the product was separated and purified by column chromatography, and the separation yield was 64%. 1 H NMR (500MHz, DMSO-d 6 ): δ11.51(br s,1H),8.46(d,J=5.0Hz,1H),8.26(d,J=7.5Hz,1H),8.10(d,J=5.0Hz,1H),7.96( d, J=7.5Hz, 2H), 7.67(d, J=8.0Hz, 1H), 7.56(t, J=7.5Hz, 1H), 7.43(d, J=7.5Hz, 2H), 7.27(t, J=7.5Hz,1H),2.44(s,3H). 13 CNMR (125.4MHz, DMSO-d 6 ): δ142.2, 141.0, 138.2, 137.9, 135.6, 132.9, 129.2, 129.0, 128.2, 128.0, 121.5, 120.8, 119.4, 113.6, 112.4, 20.9.

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Abstract

The invention discloses a green synthesis method for beta-carboline heterocyclic compounds. The green synthesis method includes that the beta-carboline heterocyclic compounds are made of alcohols compounds, oxidative condensation, cyclization and re-oxidation one-pot cascade reaction is carried out on tryptamines compounds and alcohol in oxygen under the catalytic effects of catalysts TEMPO and catalysts TBN to obtain the beta-carboline heterocyclic compounds, the reaction temperatures range from 40 DEG C to 120 DEG C, and the reaction time ranges from 6 hours to 48 hours. The green synthesismethod has the advantages that inexpensive, easily available, stable and low-toxicity alcohols which can come from wide sources are used as the raw materials for the beta-carboline heterocyclic compounds, the aerobic oxidative condensation, cyclization and re-oxidation cascade reaction is carried out on the tryptamines compounds and the alcohol under the synergistic catalytic effects of the catalysts TEMPO and the catalysts TBN and acetic acid solvent conditions to prepare the beta-carboline heterocyclic compounds, target products are high in selectivity, a byproduct is water, and accordinglythe green synthesis method is high in efficiency and free of pollution.

Description

technical field [0001] The invention relates to the technical field of chemical synthesis, in particular to a green synthesis method of β-carboline heterocyclic compounds. Background technique [0002] The β-carboline heterocyclic structure is the structural unit of many natural products and important drugs. Drug molecules with β-carboline heterocycle as the core structure include eudistomins U, canthine, manzamines, and several types of enzymes such as cholinesterases, tyrosine kinases, etc., and there are many kinds. Moreover, it is well known that many molecules with a β-carboline heterocycle as the core structure have biopharmaceutical activities such as anti-HIV, anti-tumor, anti-malarial, and anti-plasmodium. The search results of the World Drug Index also show that there are more than 200 reports on drug therapy research involving compounds with β-carboline heterocycle as the core structure. Therefore, the synthesis of β-carboline heterocyclic compounds has always b...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D471/04
Inventor 徐清刘海城
Owner WENZHOU UNIVERSITY
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