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Method for selectively synthesizing dihydrophenanthridine or phenanthridine compound

A technique for dihydrophenanthridine and compounds, which is applied in the field of selective synthesis of dihydrophenanthridine or phenanthridine compounds, can solve problems such as lack of universal applicability, single product structure, and difficult acquisition of raw materials, and achieve cheap raw materials, The synthesis process is simple and the effect of a wide range of applications

Active Publication Date: 2021-06-29
HENAN NORMAL UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] At present, there are some reports on the synthesis methods of dihydrophenanthridine and phenanthridine compounds, but these literature methods still have certain limitations: such as raw materials are not easy to obtain, harsh reaction conditions, long synthetic routes, single product structure and no issues of universal applicability

Method used

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  • Method for selectively synthesizing dihydrophenanthridine or phenanthridine compound
  • Method for selectively synthesizing dihydrophenanthridine or phenanthridine compound
  • Method for selectively synthesizing dihydrophenanthridine or phenanthridine compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021]

[0022] Add 1a (50.8mg, 0.3mmol), 2a (44.1mg, 0.45mmol), solvent (2mL), ruthenium catalyst (0.015mmol), additive (0.06mmol), acid (0.6mmol) and Molecular sieves (50mg), under the protection of argon, seal the pressure tube, and stir the reaction at a certain temperature. After the reaction is over, use saturated NaHCO 3 The solution was quenched, filtered with suction, extracted with ethyl acetate (10mL×3), the organic phases were combined and washed with water and saturated sodium chloride solution successively, anhydrous Na 2 SO 4 Dried, spin-dried, and separated by silica gel column (petroleum ether / ethyl acetate=20 / 1 to petroleum ether / ethyl acetate=10 / 1) to obtain product 3a and / or 4a.

[0023] A series of reaction results are obtained by changing reaction conditions such as catalyst, additive, acid type, solvent, temperature and the equivalent ratio between reactants, as shown in Table 1.

[0024] Synthesis of 3a and 4a under different reaction conditions ...

Embodiment 2

[0028] Add 1a (50.8mg, 0.3mmol), 2a (44.1mg, 0.45mmol), tetrahydrofuran (2mL), dichlorobis(4-methylisopropylphenyl) ruthenium (II) to a 15mL pressure-resistant tube sequentially ( [Ru(p-cymene)Cl 2 ] 2 ,9.2mg, 0.015mmol), silver trifluoromethanesulfonate (15.4mg, 0.06mmol), acetic acid (34.3μL, 0.6mmol) and MS (50mg), and then the pressure tube was sealed under the protection of argon, and placed in a 60°C oil bath to stir for 24 hours. After the reaction is over, use saturated NaHCO 3 The solution was quenched, suction filtered, extracted with ethyl acetate (10mL × 3), the organic phases were combined and washed with water and saturated sodium chloride solution successively, anhydrous Na 2 SO 4 Drying, spin-drying, and silica gel column separation (petroleum ether / ethyl acetate=20 / 1) gave white solid product 3a (50.5 mg, 63%). The characterization data of this compound are: 1 H NMR (CDCl 3 ,400MHz):δ7.73(d,J=8.0Hz,1H),7.68(d,J=7.6Hz,1H),7.32-7.23(m,3H),7.12(t,J=7.2Hz,...

Embodiment 3

[0030] According to the method and steps of Example 2, by changing reactants 1 and 2, multiple dihydrophenanthridine compounds 3 were synthesized, and the specific results are shown in Table 2.

[0031] The synthesis of various dihydrophenanthridine compounds 3 of table 2 a,b

[0032]

[0033] a Reaction conditions: 1(0.3mmol), 2(0.45mmol), [Ru(p-cymene)Cl 2 ] 2 (0.015mmol), AgOTf (0.06mmol), AcOH (0.6mmol), MS (50mg), THF (2mL), argon atmosphere, 60°C, 24 h.b Separation yield.

[0034] Representative product characterization data are as follows:

[0035] Methyl 2-(8-methoxy-6-methyl-5,6-dihydrophenanthridin-6-yl)acetate(3d)

[0036] Yellowish solid (58.0mg, 65%). 1 H NMR (CDCl 3 ,400MHz): δ7.74(d,J=8.4Hz,1H),7.67(dd,J 1 =7.6Hz,J 2 =0.8Hz,1H),7.15(td,J 1 =7.6Hz,J 2 =1.2Hz,1H), 6.94(dd,J 1 =8.4 Hz,J 2 =2.4 Hz,1H),6.90(td,J 1 =7.6 Hz,J 2 =0.8 Hz, 1H), 6.86(d, J=2.4 Hz, 1H), 6.78(dd, J 1 =8.0 Hz,J 2 =0.8 Hz, 1H), 4.95(s, 1H), 3.89(s, 3H), 3.70(s, 3H), 2.90...

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Abstract

The invention discloses a method for selectively synthesizing a dihydrophenanthridine compound 3 or a phenanthridine compound 4, and belongs to the technical field of organic synthesis. An o-aryl aniline compound 1 and an acetylenic acid ester compound 2 are used as raw materials, and in the presence of a ruthenium catalyst, an additive and acid, a heating reaction is performed in an organic solvent to obtain a dihydrophenanthridine compound 3 or a phenanthridine compound 4. The method has the following advantages: (1) the synthesis process is simple, and the dihydrophenanthridine or phenanthridine compound can be synthesized with high selectivity by starting from the o-aryl aniline compound and the acetylenic acid ester compound under the catalysis of the ruthenium catalyst and changing the reaction temperature; and (2) the raw materials are cheap and easy to obtain, the reaction conditions are mild, the operation is easy and convenient, and the application range of the substrate is wide.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, in particular to a method for selectively synthesizing dihydrophenanthridine or phenanthridine compounds. Background technique [0002] As an important class of nitrogen-containing fused heterocycles, phenanthridine structural units widely exist in molecules of natural products, drugs and functional materials. For example, chelerythrine, lianthine, and xanthoningine all belong to the phenanthridine alkaloids. Among them, chelerythrine has anti-cytotoxic, antibacterial and other activities, while limianine and xanthoningine have Significant anticancer activity. [0003] In addition, dihydrophenanthridine and its derivatives are not only an important class of organic synthesis intermediates, but also important components of biologically active natural products such as lycorine and chelidonine, which can be used clinically for emetic, anticancer And the treatment of gastrointestinal coli...

Claims

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Application Information

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IPC IPC(8): C07D221/12C07D221/18C07D491/107
CPCC07D221/12C07D221/18C07D491/107
Inventor 张新迎于彩云徐园双范学森
Owner HENAN NORMAL UNIV
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