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Method for synthesizing benzothiazole-2-ketone derivative from carbonyl sulfide and disulfide as raw materials

A disulfide and benzothiazole technology, which is applied in the field of synthesizing benzothiazol-2-one derivatives, can solve the problem of high cost of raw material preparation of 2-chlorobenzothiazole, long synthesis steps of o-nitrochlorobenzene, O-aminothiophenol instability and other problems, to achieve the effect of improving atom economy, low price, and short reaction time

Active Publication Date: 2018-06-01
INNER MONGOLIA UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Due to the wide application of benzothiazol-2-one, efforts are being made to develop its synthetic method at home and abroad. At present, benzothiazole is mainly synthesized from o-aminothiophenol, o-nitrochlorobenzene, 2-chlorobenzothiazole, etc. -2-ketone derivatives; wherein the synthesis steps of o-nitrochlorobenzene are relatively long, and the raw material preparation cost of 2-chlorobenzothiazole is relatively high
Therefore, o-aminothiophenol is usually used as a raw material to react with a carbonyl reagent to synthesize benzothiazol-2-one, but o-aminothiophenol is unstable and is easily oxidized and dimerized to form a disulfide

Method used

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  • Method for synthesizing benzothiazole-2-ketone derivative from carbonyl sulfide and disulfide as raw materials
  • Method for synthesizing benzothiazole-2-ketone derivative from carbonyl sulfide and disulfide as raw materials
  • Method for synthesizing benzothiazole-2-ketone derivative from carbonyl sulfide and disulfide as raw materials

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1-12

[0033] Synthesis of benzothiazolones from carbonyl sulfide catalyzed by different kinds of inorganic sulfides.

[0034] Put a magnet into a 12mL stainless steel autoclave, and add 0.5mmol o-aminoaromatic disulfide, inorganic sulfide and 1ml solvent in sequence, and tighten the autoclave. Fill the reaction kettle with an appropriate amount of COS, stir for 1.5 hours, stop the reaction, slowly exhaust the gas in the reaction kettle, unscrew the reaction kettle, and transfer the solution in the reaction kettle to a 50mL Erlenmeyer flask. It was extracted with ethyl acetate and washed with saturated brine three times. The organic phases were combined and dried over anhydrous magnesium sulfate for 30 minutes. Anhydrous magnesium sulfate was removed by filtration, and the crude product was obtained by distillation under reduced pressure. Use a mixed solvent of dichloromethane and ethyl acetate as the eluent, dry-pack the column and dry-load the sample, and through column chromatogr...

Embodiment 13-21

[0044] Synthesis of benzothiazolone derivatives.

[0045] Put a magnet into a 12mL stainless steel autoclave, and add 0.5mmol aromatic disulfide, 0.25mmol sodium hydrosulfide and 1ml DMF in sequence, and tighten the autoclave. Fill the reactor with 0.5MPa COS, stir the reaction for 1.5h, stop the reaction, slowly exhaust the gas in the reactor, unscrew the reactor, and transfer the solution in the reactor to a 50mL Erlenmeyer flask. It was extracted with ethyl acetate and washed with saturated brine three times. The organic phases were combined and dried over anhydrous magnesium sulfate for 30 minutes. Anhydrous magnesium sulfate was removed by filtration, and the crude product was obtained by distillation under reduced pressure. Use a mixed solvent of dichloromethane and ethyl acetate as the eluent, dry-pack the column and dry-load the sample, and through column chromatography (200-300 mesh silica gel), obtain solutions containing the two products respectively, and distill u...

Embodiment 13

[0047] (1) Synthesis of 6-methoxybenzothiazol-2-one from 4,4'-dimethoxy-2,2'-dithiodianiline.

[0048] Dry packing Dry loading column chromatography (200-300 mesh silica gel) separation: using gradient elution, ethyl acetate and dichloromethane as eluent, dichloromethane: ethyl acetate (V / V) = 100:1, and then increase the polarity to 20:1, after separation, 163 mg of 6-methoxybenzothiazol-2-one was obtained as a white solid, and the separation yield by column chromatography was 90%.

[0049] (2) Structural identification of 6-methoxybenzothiazol-2-one

[0050]

[0051] Characterization data of 6-methoxybenzothiazol-2-one: 1H NMR (DMSO-d6, 500MHz): δ (ppm) 11.658 (brs, 1H), 7.23 (d, 1H, J=2.5Hz), 7.02 (d, 1H, J = 8.5Hz), 6.86 (dd, 1H, J1 = 8.5Hz, J2 = 2.5Hz), 3.73 (s, 3H); 13C NMR (DMSO-d6, 125MHz): δ (ppm) 169.8 ,155.2,129.9,124.3,113.2,112.1,107.8,55.6; MS(EI):m / z calcd for C 8 h 7 NO 2 S[M] + : 180.9, found 181.0. The melting point is 161-163°C.

[0052] The analys...

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Abstract

The invention discloses a method for synthesizing a benzothiazole-2-ketone derivative from carbonyl sulfide and disulfide as raw materials. The method comprises the following steps: mixing disulfide,inorganic sulfide and an organic solvent, introducing sufficient COS to implement a reaction, and concentrating and purifying a reaction liquid, thereby obtaining the benzothiazole-2-ketone derivative. The inorganic sulfide used in the method is adopted as an activation catalyst and is low in price and easy to obtain; a catalysis system is relatively simple, and no other catalyst promoter is addedexcept reactants and inorganic sulfide; direct dehydration is implemented in the reaction process, no other dehydration agent is used, and thus the atom economy is improved; the catalysis system is good in applicability, is applicable to synthesis of fine chemicals with high additional values, and is very good in substrate applicability to each fine chemical with high additional values; reactionsare implemented at normal temperatures, normal pressure or low pressure, and thus danger coefficients can be reduced; the reaction time is short, and the efficiency can be improved.

Description

technical field [0001] The invention relates to the technical fields of industry, medicine and agriculture, and more specifically relates to a method for synthesizing benzothiazol-2-one derivatives by using carbonyl sulfide and disulfide as raw materials. Background technique [0002] Benzothiazol-2-one derivatives are a very important class of heterocyclic compounds, which have broad application prospects in the fields of industry, medicine and agriculture. The thiazole ring of benzothiazol-2-one contains S and N elements and many functional groups are bioelectronic isosteres. As an intermediate with excellent performance in medicine, it can also achieve different expected efficacy. In agriculture, compounds containing the parent ring structure of benzothiazol-2-one have good biological activities such as sterilization, anti-plant virus, insecticide, herbicide, and acaricide. Due to its low toxicity and excellent biological activity, benzene The application of thiazolone ...

Claims

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Application Information

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IPC IPC(8): C07D277/68
CPCC07D277/68
Inventor 洪海龙周博浩竺宁韩利民
Owner INNER MONGOLIA UNIV OF TECH
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