Solid acid catalyst and method for catalytic synthesis of 5-substituted tetrazole by solid acid catalyst

A technology of solid acid catalyst and tetrazolium, which is applied in the direction of organic chemistry, can solve the problems of cumbersome post-processing, slow reaction speed, and many by-products, and achieve the effect of simple and safe synthesis process, mild use conditions, and easy operation

Inactive Publication Date: 2011-08-10
ZHEJIANG KINGLYUAN PHARMA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] The synthetic method of 5-substituted tetrazole has a lot, utilizes nitrile compound and sodium azide to make tetrazole under the condition that alcohol (such as n-butanol, Virahol) is made solvent, acid (such as glacial acetic acid) is made catalyst. Azole compounds are the most classic method, but this method is only suitable for the synthesis of simple tetrazole
Change the solvent to an aprotic solvent (such as DMF, DMAC), use an inorganic salt or an organic salt (such as NH 4 Cl, ZnCl 2 、Et 3 N HCl) as catalyzer, nitrile compound and sodium azide reaction can prepare tetrazole derivatives with aromatic group with complex structure, but same as above-mentioned reaction, this reaction speed is slower, and the reaction time is long ( It takes a few days), and it is easy to produce toxic and explosive HN 3 , NH 4 N 3 Wait
There are also reports in the literature that organotin catalysis is used to synthesize tetrazole derivatives containing multifunctional groups in aromatic hydrocarbon solvents, but there are many by-products, the target product is difficult to completely separate, the yield is low, the post-treatment is cumbersome, and the price of tin compounds is high. Toxic

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] 10g SiO 2 The carrier was calcined at 500°C for 4h to obtain a pretreated carrier, and the pretreated carrier was added to 15.6mL of 6.89% ammonium bisulfate aqueous solution, immersed at 20°C for 6h, stirred at 80°C for 2h, and then dried at 120°C for 24h to obtain Ammonium bisulfate catalyst 10.88g (NH 4 HSO 4 / SiO 2 ) (ammonium bisulfate weight is 10wt.%).

[0027] Dissolve 27.2g (0.10mol) of 4'-bromomethyl-2-cyanobiphenyl in 150mL N,N-dimethylformamide, add 7.8g (0.12mol) sodium azide, 2.63g ( 0.015mol)NH 4 HSO 4 / SiO 2 Catalyst, reacted at 120°C for 15h, thin-layer chromatography (TLC) tracked the reaction, after the reaction was complete, the reaction solution was cooled to room temperature, filtered to remove insoluble matter, the filtrate was added with 100mL of ethyl acetate and 20mL of 4mol / L hydrochloric acid and stirred vigorously for 30min, and then used 150 mL of ethyl acetate was extracted three times, the organic phase was washed twice with satura...

Embodiment 2

[0029] 10g SiO 2 The carrier was calcined at 500°C for 4h to obtain a pretreated carrier, and the pretreated carrier was added to 15.5mL of 6.89% sodium bisulfate aqueous solution, immersed at 20°C for 6h, stirred at 80°C for 2h, and then dried at 120°C for 24h to obtain Sodium bisulfate catalyst 10.90g (NaHSO 4 / SiO 2 ) (sodium bisulfate weight is 10wt.%).

[0030] Dissolve 27.2g (0.10mol) of 4'-bromomethyl-2-cyanobiphenyl in 150mL N,N-dimethylformamide, add 7.8g (0.12mol) sodium azide, 2.70g ( 0.015mol) NaHSO 4 / SiO 2 Catalyst, reacted at 120°C for 15h, thin-layer chromatography (TLC) tracked the reaction, after the reaction was complete, the reaction solution was cooled to room temperature, filtered to remove insoluble matter, the filtrate was added with 100mL of ethyl acetate and 20mL of 4mol / L hydrochloric acid and stirred vigorously for 30min, and then used 150 mL of ethyl acetate was extracted three times, the organic phase was washed twice with saturated brine and...

Embodiment 3

[0032] 10g SiO 2The carrier was calcined at 500°C for 4 hours to obtain a pretreated carrier, and the pretreated carrier was added to 15.5mL of 6.89% potassium bisulfate aqueous solution, immersed at 20°C for 6h, stirred at 80°C for 2h, and then dried at 120°C for 24h to obtain 10.90 g (KHSO 4 / SiO 2 ) (potassium bisulfate weight is 10wt.%).

[0033] Dissolve 27.2g (0.10mol) of 4'-bromomethyl-2-cyanobiphenyl in 150mL N,N-dimethylformamide, add 7.8g (0.12mol) sodium azide, 2.94g ( 0.015mol)KHSO 4 / SiO 2 Catalyst, reacted at 120°C for 15h, thin-layer chromatography (TLC) tracked the reaction, after the reaction was complete, the reaction solution was cooled to room temperature, filtered to remove insoluble matter, the filtrate was added with 100mL of ethyl acetate and 20mL of 4mol / L hydrochloric acid and stirred vigorously for 30min, and then used 150 mL of ethyl acetate was extracted three times, the organic phase was washed twice with saturated brine and once with tap wat...

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PUM

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Abstract

The invention discloses a solid acid catalyst, which is characterized by taking bisulfate as an active ingredient and SiO2, ZnO, TiO2, ZrO2, Fe2O3, diatomite or active carbon as a carrier, wherein the loading amount of the active ingredients of the solid acid catalyst is 5 to 50wt%; and the bisulfate is ammonium bisulfate, sodium bisulfate or potassium bisulfate; the method of solid acid for the catalytic synthesis of 5-substituted tetrazole comprises the steps of: using nitrile compound and sodium azide as raw material and solid acid as catalyst, reacting for 8 to 72 hours in organic solvent at 120 to 160 DEG C, post-treating the reaction liquid to obtain the 5-substituted tetrazole; the solid acid catalyst of the invention has the advantages of moderate application conditions, high activity, simple preparation and no environmental pollution; and the process of the invention for synthesizing the 5-substituted tetrazole is simple and safe, easy in operation, high in yield, environmentally-friendly and suitable for industrial production.

Description

(1) Technical field [0001] The invention relates to a method for synthesizing 5-substituted tetrazole, in particular to a method for catalyzing and synthesizing 5-substituted tetrazole with a solid acid catalyst. (2) Background technology [0002] Tetrazolium compounds are important intermediates in organic synthesis, which can be used to synthesize medicines, pesticides, photosensitive materials and industrial foaming agents and other products. 5-Substituted tetrazole has significant biological activity and is often used in the modification of cephalosporin antibiotics, angiotensin receptor inhibitors and anti-tumor drugs. In recent years, tetrazole compounds have been used more and more in the field of medicine. More and more, and has a good development prospect. [0003] The synthetic method of 5-substituted tetrazole has a lot, utilizes nitrile compound and sodium azide to make tetrazole under the condition that alcohol (such as n-butanol, Virahol) is made solvent, acid...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J27/24B01J27/055C07D257/04
Inventor 范青明赵海龙方建兵李细英盛金火
Owner ZHEJIANG KINGLYUAN PHARMA
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