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A method for synthesizing benzothiazol-2-one derivatives using carbonyl sulfide and disulfide as raw materials

A technology for disulfide and benzothiazole, which is applied in the field of synthesizing benzothiazol-2-one derivatives, can solve the problem of long synthesis steps of o-nitrochlorobenzene, unstable o-aminothiophenol, and 2-chlorobenzene. The problem of high preparation cost of benzothiazole raw materials, to achieve the effects of low price, improved atom economy, and short reaction time

Active Publication Date: 2022-01-25
INNER MONGOLIA UNIV OF TECH
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  • 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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  • A method for synthesizing benzothiazol-2-one derivatives using carbonyl sulfide and disulfide as raw materials
  • A method for synthesizing benzothiazol-2-one derivatives using carbonyl sulfide and disulfide as raw materials
  • A method for synthesizing benzothiazol-2-one derivatives using carbonyl sulfide and disulfide as raw materials

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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 and react for 1.5h, 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 go through column ch...

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 benzothiazole-2-ketone derivatives by using carbonyl sulfide and disulfide as raw materials. The method comprises mixing disulfides, inorganic sulfides and organic solvents, introducing a sufficient amount of COS for reaction, concentrating and purifying the reaction solution to obtain the benzothiazol-2-ketone derivatives. The activated catalyst involved in the present invention is an inorganic sulfide, which is cheap and easy to obtain; the catalytic system is relatively simple, and no other co-catalysts are added except the reactant and the inorganic sulfide; direct dehydration in the reaction process does not need to add other dehydrating agents, improving Atom economy is guaranteed; the catalytic system has wide adaptability and is suitable for the synthesis of a variety of high value-added fine chemicals, and has strong substrate applicability for each high value-added fine chemical; the reaction is normal temperature and normal pressure Or low pressure, reduce the risk factor; short reaction time, improve efficiency.

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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Patent Type & Authority Patents(China)
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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