Synthesis method of 2-aldehyde thiochromone compound

A technology for the synthesis of aldehyde thiochromones and methods, which is applied in the field of synthesis of organic compounds, can solve the problems of unstable yield, cumbersome separation of by-products, and poor repeatability, and achieve simple post-processing operations and a wide range of substrates , good repeatability

Inactive Publication Date: 2021-04-02
SHAANXI NORMAL UNIV
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  • Abstract
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  • Application Information

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Problems solved by technology

[0004] The preparation of 2-aldehyde thiochromones has been previously reported. US Patent US20110028738A1 uses 2-methylthiochromone as a raw material and refluxes for 12 hours under the condition of selenium dioxide as an oxidant and chlorobenzene as a solvent to obtain 2-aldehydes Based on thiochromone compounds, the product yield obtained by this method is low, and the separation of a large amount of by-product selenium is relatively cumbersome, and additional recrystallization separation is required
The Zhang group (Heterocycles, 2011, 85, 2337-2342.) further improved the aforementioned method, still using 2-methylthiochromone as a raw material, using selenium dioxide as an oxidant, and o-dichlorobenzene as a solvent for reflux reaction , under this condition, the product is prone to intramolecular Friedel-Crafts side reactions, the experimental reproducibility is poor, and a large amount of by-product selenium is still difficult to separate
[0005] In summary, the reported methods for the synthesis of 2-formylthiochromones still have some shortcomings, such as the separation of by-products is cumbersome and the yield is unstable.

Method used

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  • Synthesis method of 2-aldehyde thiochromone compound
  • Synthesis method of 2-aldehyde thiochromone compound
  • Synthesis method of 2-aldehyde thiochromone compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Preparation of 2-aldehydethiochromone

[0028]

[0029] 150mg (0.85mmol) of 2-methylthiochromone shown in formula I-1 was added to a 25mL round bottom flask, and 4.3mL of N,N-dimethylformamide was added to dissolve 2-methylthiochromone, and then Add 0.23mL (1.70mmol) N,N-dimethylformamide dimethyl acetal, reflux reaction at 150°C for 4h, cool down to room temperature after the reaction, add water to the reaction solution, and then add dichloromethane for separation and extraction Three times, the organic phases were combined, dried with anhydrous magnesium sulfate, suction filtered with a sand core funnel, and the solvent was evaporated under reduced pressure to obtain the enamine intermediate shown in formula II-1. Add the enamine intermediate shown in formula II-1 and 546mg (2.55mmol) sodium periodate into a 25mL round bottom flask, add 2.8mL tetrahydrofuran and 2.8mL water, and react at room temperature for 2h. Add saturated aqueous sodium thiosulfate solution to...

Embodiment 2

[0031] Preparation of 2-formyl-3-iodothiochromone

[0032]

[0033] Add 75mg (0.25mmol) of 2-methyl-3-iodothiochromone represented by formula I-2 into a 10mL round bottom flask, add 2.5mL N,N-dimethylformamide to dissolve 2-methyl- 3-iodothiochromone, then add 66 μL (0.5 mmol) N,N-dimethylformamide dimethyl acetal, 150 ° C reflux reaction for 4 hours, after the reaction is completed, cool down to room temperature, add water to the reaction solution, and then Dichloromethane was added for liquid separation and extraction three times, the organic phases were combined, dried over anhydrous magnesium sulfate, filtered through a sand core funnel, and the solvent was evaporated under reduced pressure to obtain the enamine intermediate of formula II-2. Add the enamine intermediate shown in formula II-2 and 159mg (0.74mmol) sodium periodate into a 10mL round-bottomed flask, add 1.3mL tetrahydrofuran and 1.3mL water, and react at room temperature for 2h. Add saturated aqueous sodiu...

Embodiment 3

[0035] Preparation of 2-aldehyde-3-phenylthiochromone

[0036]

[0037] Add 250 mg (0.98 mmol) of 2-methyl-3-phenylthiochromone shown in formula I-3 into a 25 mL round bottom flask, add 4.0 mL of N,N-dimethylformamide to dissolve 2-methyl-3- 3-Phenylthiochromone, then add 0.26mL (1.96mmol) N,N-dimethylformamide dimethyl acetal, reflux reaction at 150°C for 6h, cool down to room temperature after the reaction, add water to the reaction solution , and dichloromethane was added for liquid separation and extraction three times, the organic phases were combined, dried with anhydrous magnesium sulfate, suction filtered with a sand core funnel, and the solvent was evaporated under reduced pressure to obtain the enamine intermediate of formula II-3. Add the enamine intermediate shown in formula II-3 and 631mg (2.95mmol) sodium periodate into a 25mL round-bottomed flask, add 2.3mL tetrahydrofuran and 2.3mL water, and react at room temperature for 1 h. Add saturated aqueous sodium t...

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Abstract

The invention discloses a synthesis method of 2-aldehyde thiochromone, which comprises the following steps: by using a 2-methyl thiochromone compound as a raw material, reacting with N, N-dimethylformamide dimethyl acetal to generate an enamine intermediate, and carrying out simple post-treatment on the reaction system, and directly adding a high-iodine compound for oxidation-reduction reaction toobtain the 2-aldehyde thiochromone compound. According to the synthesis method, the post-treatment operation is simpler, the product yield is higher, the repeatability is good, the substrate application range is wide, the used N, N-dimethylformamide dimethyl acetal and high-iodine compounds are relatively safe, and the method is simpler, more convenient and more efficient.

Description

technical field [0001] The invention belongs to the technical field of synthesis of organic compounds, and in particular relates to a synthesis method of 2-formylthiochromone compounds. Background technique [0002] According to the report of Kakiuchi group (Chemical Communications, 2008, 2013-2015) and Zhang group (Tetrahedron Letters, 2016, 57, 5179-5184.), the thiochromone compound shown in the following formula IV can protect hydroxyl, amino and carboxyl groups , the thiochromone dioxide compound shown in formula V can protect phosphoric acid and sulfonic acid groups, and under certain conditions can obtain photoremoval products in higher yields. Therefore, the thiochromone photoprotecting group is used in organic synthesis with broadly application foreground. 2-formyl thiochromones are necessary intermediates for the synthesis of the two S, S-thiochromone photoprotective groups of formula IV and formula V (the following is the synthesis of S, S-sulfur dioxide by 2-form...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D335/06
CPCC07D335/06
Inventor 柴永海孙陶陶张琦王荣欣
Owner SHAANXI NORMAL UNIV
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