Method for synthesizing 3,4-dihydroisoquinoline by semi-dehydrogenation oxidation of 1,2,3,4-tetrahydroisoquinoline

A technology of tetrahydroisoquinoline and dihydroisoquinoline, which is applied in chemical instruments and methods, organic chemistry, chemical/physical processes, etc., can solve the problems of high synthesis cost, limited production, etc., and achieves high selectivity and preparation. The method is simple and easy to implement, and it is beneficial to the effect of large-scale industrial production

Active Publication Date: 2019-01-04
FUZHOU UNIVERSITY
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, it is currently only limited to 1,2,3,4-tetrahydroisoquinoline dehydrogenation to generate isoquinoline, and there are few relevant reports on partial dehydrogenation to generate 3,4-dihydroisoquinoline. Moreover, in 1,2 , The photocatalyst used in the photocatalytic dehydrogenation process of 3,4-tetrahydroisoquinoline is generally a complex formed by noble metals Ru and Ir with strong absorption under visible light combined with ligands of pyridine analogs, but due to the The high cost of synthesis and its ligands limits large-scale production

Method used

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  • Method for synthesizing 3,4-dihydroisoquinoline by semi-dehydrogenation oxidation of 1,2,3,4-tetrahydroisoquinoline
  • Method for synthesizing 3,4-dihydroisoquinoline by semi-dehydrogenation oxidation of 1,2,3,4-tetrahydroisoquinoline

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preparation example Construction

[0017] (1) [(NH 4 ) 2 MoS 4 ] Preparation: 7.5g (NH 4 ) 6 Mo 7 o 24 • 4H 2 Add O into 50ml of concentrated ammonia water, stir until dissolved, then add 50ml of ammonium sulfide solution with a mass fraction of 20%, keep the temperature at 80°C for 1 hour, cool the reaction system to 0°C, wash with water and ethanol, and dry After obtaining the compound [(NH 4 ) 2 MoS 4 ];

[0018] (2) MoS 2 / ZnIn 2 S 4 Preparation: 200mg ZnIn 2 S 4 Solid powder and [(NH 4 ) 2 MoS 4 ] into a dry schlenk tube and replace with N 2 Wash the air three times, then add 3ml of methanol solution to remove oxygen, and then use a 300W xenon lamp to illuminate under visible light for 3h, after washing and drying, dark yellow solid powder MoS 2 / ZnIn 2 S 4 , where MoS 2 The loading amount is 1.0 wt%.

Embodiment 1

[0020] With 1,2,3,4-tetrahydroisoquinoline as substrate, MoS 2 / ZnIn 2 S 4 as a photocatalyst, in N 2 Atmosphere, with acetonitrile (CH 3 CN), water (H 2O), a mixed solution of acetonitrile and water, a mixed solution of DMSO and water, and a mixed solution of EtOH and water were used as solvents, and were illuminated for 12 hours under visible light. The reaction results are shown in the table below, where when the volume ratio of acetonitrile to water is 2:1, the conversion rate and selectivity are higher than other solvents as a whole.

[0021] Table 1 Reaction solvent to MoS 2 / ZnIn 2 S 4 Influence of photocatalytic semidehydrogenation performance of 1,2,3,4-tetrahydroisoquinoline

[0022]

[0023] Note: The solvent ratios in Table 1 are volume ratios.

Embodiment 2

[0025] With 1,2,3,4-tetrahydroisoquinoline as substrate, MoS 2 / ZnIn 2 S 4 as a photocatalyst, in N 2 Under the atmosphere, using the mixed solution of acetonitrile and water with a volume ratio of 2:1 as the solvent, the trend chart of the change of different products over time was made. The result of the reaction is as figure 1 shown by figure 1 It can be seen that with the increase of time, the conversion rate of the substrate 1,2,3,4-tetrahydroisoquinoline is constantly increasing, and the conversion rate can reach 94% after 12 hours of reaction, and the yield of the main product 3.4-dihydroisoquinoline Decrease slowly with the increase of reaction time, and the productive rate reaches 90% after 12 hours of reaction, and the productive rate of by-product isoquinoline increases slowly with the increase of reaction time, and the productive rate reaches 10% after 12 hours of reaction, shows that with the prolongation of time, A small amount of 3,4-dihydroisoquinoline con...

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Abstract

The invention belongs to the technical field of organic chemistry and photocatalysis and discloses a method for synthesizing 3,4-dihydroisoquinoline by semi-dehydrogenation oxidation of 1,2,3,4-tetrahydroisoquinoline. According to the method, by adoption of MoS2 / ZnIn2S4 as a photocatalyst, semi-dehydrogenation oxidation of 1,2,3,4-tetrahydroisoquinoline is realized in an N2 atmosphere under the visible light condition to obtain a product namely 3,4-dihydroisoquinoline, and high conversion rate and selectivity are achieved. In addition, the method is simple, convenient and feasible and is beneficial to large-scale industrial popularization.

Description

technical field [0001] The invention belongs to the field of organic chemistry and photocatalysis, and specifically relates to a method for synthesizing 3,4-dihydroisoquinoline by semi-dehydrogenation oxidation of 1,2,3,4-tetrahydroisoquinoline. Background technique [0002] 1,2,3,4-Tetrahydroisoquinoline is a class of alkaloids widely distributed in nature, and its dehydrogenation product isoquinoline compounds are an important class of chemical intermediates, widely used in organic conductors, In the synthesis of dyes, photosensitive pigments, insecticides, alkaloids, medicines and fungicides, rubber vulcanization accelerators and other compounds, among them, the semi-dehydrogenated product 3,4-dihydroisoquinoline is an important factor for the synthesis of many morphinan compounds Intermediates, morphinans are widely used in the field of medicine for pain relief. Therefore, in the synthetic research of organic chemistry, it is of great significance to develop a method fo...

Claims

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Application Information

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IPC IPC(8): C07D217/02B01J27/051
CPCC07D217/02B01J27/051B01J35/39
Inventor 李朝晖郝明明徐丽芝
Owner FUZHOU UNIVERSITY
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