CN108101863B - Method for synthesizing benzothiazole-2-ketone derivative by using carbonyl sulfide and disulfide as raw materials - Google Patents
Method for synthesizing benzothiazole-2-ketone derivative by using carbonyl sulfide and disulfide as raw materials Download PDFInfo
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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 the steps of mixing disulfide, inorganic sulfide and an organic solvent, introducing sufficient COS for reaction, and concentrating and purifying reaction liquid to obtain the benzothiazole-2-ketone derivative. The activating catalyst is inorganic sulfide, and is low in price and easy to obtain; the catalytic system is relatively simple, and no other cocatalyst is added except for reactants and inorganic sulfide; the reaction process is directly dehydrated without adding other dehydrating agents, so that the atom economy is improved; the catalytic system has wide adaptability, is suitable for synthesizing various fine chemicals with high added values, and has strong substrate applicability to each fine chemical with high added value; the reaction is at normal temperature, normal pressure or low pressure, so that the risk coefficient is reduced; the reaction time is short, and the efficiency is improved.
Description
Technical Field
The invention relates to the technical field of industry, medicine and agriculture, in particular to a method for synthesizing benzothiazole-2-ketone derivatives by using carbonyl sulfide and disulfide as raw materials.
Background
The benzothiazole-2-ketone derivative is a very important heterocyclic compound and has wide application prospect in the fields of industry, medicine, agriculture and the like. The thiazole ring of the benzothiazole-2-ketone contains S, N element and many functional groups which are mutually in a bioisostere structure, and the benzothiazole-2-ketone is used as an intermediate with excellent performance in the aspect of medicine and can achieve different expected drug effects by changing a side chain. In agriculture, the compound containing the benzothiazole-2-ketone mother ring structure has good biological activities of sterilization, plant virus resistance, insect killing, weeding, mite removal and the like, and due to the characteristics of low toxicity, excellent biological activity and the like, the application of the benzothiazole-ketone compound also becomes a hotspot in the research field of pesticides, and a large number of benzothiazole-2-ketone pesticides are successfully applied to agriculture, such as chlobenzhiazone and Benazolin. Because the application of the benzothiazole-2-ketone is wide, the research and development of a synthetic method thereof are strived at home and abroad, at present, the benzothiazole-2-ketone derivative is mainly synthesized by taking o-aminothiophenol, o-nitrochlorobenzene, 2-chlorobenzothiazole and the like as raw materials; wherein the synthesis steps of the o-nitrochlorobenzene are longer, and the preparation cost of the 2-chlorobenzothiazole raw material is higher. Thus, benzothiazol-2-ones are generally synthesized using o-aminothiophenols as starting materials by reaction with a carbonyl reagent, but o-aminothiophenols are unstable and readily undergo oxidative dimerization to form disulfides.
Disclosure of Invention
The invention aims to provide a novel method for synthesizing benzothiazole-2-ketone derivatives, which takes stable and easily obtained disulfide and COS as raw materials, and has the advantages of rapidness, convenience, mild conditions and high yield.
According to the invention, stable disulfide is selected to react with a carbonyl reagent to synthesize benzothiazole-2-ketone, but an S-S bond needs to be broken, so that the disulfide bond is broken by using a method for breaking the disulfide bond of metal sulfide-disulfide dynamic exchange reaction found in the subject group, and the carbonyl reagent is searched after the problem of disulfide bond breakage is solved. The o-aminothiophenol can react with a plurality of carbonyl reagents to synthesize benzothiazolone, such as urea, phosgene, ethyl chloroformate, carbonyl diimidazole, isocyanate and the like, and in recent years, with the annual rise of global temperature, the greenhouse effect is increasingly serious, and CO is generated2As a main substance causing the greenhouse effect, CO has been widely noticed2Reduction of atmospheric CO by chemical conversion to high value-added chemicals2One of the content routes. CO 22Is a carbonyl reagent with simple structure, and the carbonyl reagent is used as the carbonyl reagent to accord with the concept of atom economy. CO 22Is composed of two C ═ O bonds of about 116pm length, due to CO2Has a relatively short bond length, so that it exhibits thermodynamic stability and kinetic inertness, thereby activating CO2The conditions of (A) are relatively harsh, and an active property and CO are needed2As well as carbonyl reagents with atomic economy. Carbonyl sulfide (COS) is a sulfur compound with CO2Carbonyl reagents of similar structure consisting ofThe chemical activity of COS is relatively high because COS is composed of one C ═ O bond (116pm) and one C ═ S bond (156pm), which are relatively easily broken. According to COS structure analysis, C-S bonds formed after C ═ S bond breakage can also be used as sulfide to participate in the reaction with disulfide bond dynamic exchange, and further the reaction speed is accelerated. Therefore, the invention provides a novel method for preparing benzothiazole-2-ketone derivatives by using stable and easily obtained disulfide and carbonyl sulfide.
The method comprises the steps of mixing disulfide, inorganic sulfide and an organic solvent, introducing sufficient COS for reaction, concentrating and purifying reaction liquid to obtain the benzothiazole-2-ketone derivative shown in a formula 1.
According to a preferred embodiment of the present invention, the specific method for synthesizing benzothiazole-2-one derivatives provided by the present invention is to add the raw material disulfide to the solvent, and then add a certain amount of sulfide, such as NaHS and K, to the mixed solution2S or Na2S·9H2And O, introducing sufficient COS, reacting for 1-2 hours at normal temperature, and treating the reaction liquid to obtain the product.
After the reaction is completed, the product is generally obtained through concentration and purification processes. The concentration process adopts methods such as atmospheric distillation, reduced pressure distillation and the like, such as vacuum concentration by a rotary evaporator. The purification process refers to column chromatography or recrystallization separation and purification technology.
According to the invention, the disulfide is preferably an o-amino aromatic disulfide, and the substituent on the o-amino aromatic disulfide is preferably H, F, Cl, Br, I, CF which is mono-or polysubstituted at the ortho-, meta-or para-position of the disulfide bond3、OCF3、C1-C8Alkyl of (C)1-C8Alkoxy or C1-C8The o-amine of (a)The aromatic disulfide is represented by formula 2.
According to the invention, the disulphide is not disposed of before use.
According to the invention, the molar ratio of the disulfide to the inorganic sulfide can be adjusted as desired, preferably 1: 0.1 to 1, and more preferably 1: 0.5-1.
According to the invention, the inorganic sulfide is preferably NaHS, K2S and Na2S·9H2At least one of O. The NaHS is an inorganic sulfur reagent and is directly used without being treated after purchase.
According to the present invention, the organic solvent is preferably at least one of methanol, ethanol, THF, DMF and 1, 4-dioxane. Preferably, the organic solvent does not require anhydrous treatment prior to use.
According to the invention, the solvent is preferably subjected to an anhydrous treatment before use.
According to the invention, the temperature of the reaction is preferably between 5 ℃ and 50 ℃.
According to the invention, the pressure of COS is preferably 0.1-1 MPa.
According to the invention, the reaction time is preferably 1-2 h.
According to the invention, when the disulfide: the molar ratio of the inorganic sulfide is 1: 0.5-1, COS pressure of 0.5-0.8MPa, reaction temperature of 5-25 deg.c and DMF or THF as solvent, and the reaction under the said conditions can obtain high yield.
According to a preferred embodiment of the present invention, the reaction equation is as follows:
under the action of NaHS, the invention utilizes the reaction of aromatic o-amino disulfide and COS to quickly and efficiently synthesize the benzothiazole-2-ketone derivative. The disulfide of the invention is stable and easy to obtain, and the synthesis method has the advantages of simple operation, mild condition, short steps, high yield, easy purification of products and the like.
Compared with the traditional catalyst and reaction process, the invention has the following advantages:
1. the related activating catalyst is inorganic sulfide, and is low in price and easy to obtain.
2. The catalytic system is relatively simple and does not add any co-catalyst other than the reactants and inorganic sulphide.
3. The reaction process is directly dehydrated without adding other dehydrating agents, so that the atom economy is improved.
4. The catalytic system has wide adaptability, is suitable for synthesizing various fine chemicals with high added values, and has strong substrate applicability for each fine chemical with high added value.
5. The reaction is at normal temperature, normal pressure or low pressure, so that the risk coefficient is reduced; the reaction time is short, and the efficiency is improved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The reagents involved in the examples are all commonly available commercial products, and the NMR spectrometer model used is Agilent 500MHz DD 2.
Examples 1 to 12
Different kinds of inorganic sulfides catalyze carbonyl sulfide to synthesize benzothiazolone compounds.
A magneton is put into a 12mL stainless steel high-pressure reaction kettle, 0.5mmol of o-amino aromatic disulfide, inorganic sulfide and 1mL of solvent are sequentially added, and the reaction kettle is screwed down. And (3) filling a proper amount of COS into the reaction kettle, stirring for reaction for 1.5h, stopping the reaction, slowly exhausting the gas in the reaction kettle, unscrewing the reaction kettle, and transferring the solution in the reaction kettle to a 50mL conical flask. Extracted with ethyl acetate and washed 3 times with saturated brine, and the organic phases were combined and dried over anhydrous magnesium sulfate for 30 minutes. The anhydrous magnesium sulfate was removed by filtration, and the residue was distilled under reduced pressure to obtain a crude product. Using mixed solvent of dichloromethane and ethyl acetate as eluent, loading the mixture into a column by a dry method, carrying out column chromatography (200-300 mesh silica gel) to respectively obtain solutions containing two products, and carrying out reduced pressure distillation to remove the solvent.
TABLE 1 Experimental results of the synthesis of benzothiazolone compounds from COS and 2, 2' -dithiodiphenylamine catalyzed by inorganic sulfides
Structural identification of benzothiazolones
Characterization data for benzothiazol-2-one: 1H NMR (CDCl)3,500MHz):δ(ppm)10.01(brs,1H),7.41(d,1H,J＝7.5Hz),7.30-7.26(m,1H),7.17-7.14(m,2H).13C NMR(CDCl3,125MHz):δ(ppm)172.8,135.3,126.5,123.9,123.3,122.6,111.7；MS(EI):m/z calcd for C7H5NOS[M]+151.0, found 151.0, melting point 139-.
The analysis result shows that the obtained target product has a correct structure.
Examples 13 to 21
Synthesis of benzothiazolone derivatives.
A12 mL stainless steel autoclave was charged with magnetons, and 0.5mmol aromatic disulfide, 0.25mmol sodium hydrosulfide and 1mL DMF were added in this order, and the autoclave was screwed down. And (3) filling 0.5MPa COS into the reaction kettle, stirring for reaction for 1.5h, stopping the reaction, slowly exhausting the gas in the reaction kettle, unscrewing the reaction kettle, and transferring the solution in the reaction kettle to a 50mL conical flask. Extracted with ethyl acetate and washed 3 times with saturated brine, and the organic phases were combined and dried over anhydrous magnesium sulfate for 30 minutes. The anhydrous magnesium sulfate was removed by filtration, and the residue was distilled under reduced pressure to obtain a crude product. Using mixed solvent of dichloromethane and ethyl acetate as eluent, loading the mixture into a column by a dry method, carrying out column chromatography (200-300 mesh silica gel) to respectively obtain solutions containing two products, and carrying out reduced pressure distillation to remove the solvent.
Example 13
(1) Synthesizing 6-methoxybenzothiazole-2-ketone from 4,4 '-dimethoxy-2, 2' -dithio diphenylamine.
Dry-method column filling and dry-method column chromatography (200-300 mesh silica gel) separation: gradient elution is adopted, ethyl acetate and dichloromethane are used as eluent, and the ratio of dichloromethane: ethyl acetate (V/V) ═ 100: 1, increasing the polarity to 20: 163mg of 6-methoxybenzothiazol-2-one as a white solid was obtained after separation, and the yield by column chromatography was 90%.
(2) Structure identification of 6-methoxybenzothiazol-2-one
Characterization data for 6-methoxybenzothiazol-2-one: 1H NMR (DMSO-d6,500mhz) δ (ppm)11.658(brs,1H),7.23(d,1H, J2.5 Hz),7.02(d,1H, J8.5 Hz),6.86(dd,1H, J1 8.5Hz, J2 2.5Hz),3.73(s, 3H); 13C NMR (DMSO-d6,125MHz) delta (ppm)169.8,155.2,129.9,124.3,113.2,112.1,107.8, 55.6; MS (EI) m/z calcd for C8H7NO2S[M]+180.9, found 181.0, melting point 161 and 163 ℃.
The analysis result shows that the obtained target product has a correct structure.
Example 14
6,6 '-dimethyl-2, 2' -dithio diphenylamine is used as a raw material to synthesize 6-methylbenzothiazole-2-ketone.
(1) Synthesis of 6-methylbenzothiazol-2-one
Dry-method column filling and dry-method column chromatography (200-300 mesh silica gel) separation: gradient elution is adopted, ethyl acetate and dichloromethane are used as eluent, and the ratio of dichloromethane: ethyl acetate (V/V) ═ 100: 1, increasing the polarity to 20: 1, obtaining white solid 6-methylbenzothiazole-2-ketone 126mg after separation, and the separation yield of column chromatography is 76%.
(2) Structural identification of 6-methylbenzothiazol-2-one
Characterization data for 6-methylbenzothiazol-2-one: 1H NMR (DMSO-d6,500mhz): δ (ppm)11.75(brs,1H),7.36(s,1H),7.07-7.09(m,1H),7.00(d,1H, J ═ 8Hz),2.30(s, 3H); 13C NMR (DMSO-d6,125MHz) delta (ppm)169.8,133.9,131.7,127.0,123.2,122.5,111.1, 20.5; MS (EI), M/z calcd for C8H7NOS [ M ] +, 165.0, found 165.0, melting point 170-171 ℃.
The analysis result shows that the obtained target product has a correct structure.
Example 15
4,4 '-dimethoxy-2, 2' -dithio diphenylamine is used as a raw material to synthesize 4-methylbenzothiazole-2-ketone.
(1) Synthesis of 4-methylbenzothiazol-2-one
Dry-method column filling and dry-method column chromatography (200-300 mesh silica gel) separation: gradient elution is adopted, ethyl acetate and dichloromethane are used as eluent, and the ratio of dichloromethane: ethyl acetate (V/V) ═ 100: 1, increasing the polarity to 20: 1, obtaining 149mg of white solid 4-methylbenzothiazole-2-ketone after separation, and the separation yield of column chromatography is 90%.
(2) Structural identification of 4-methylbenzothiazol-2-one
Characterization data for 4-methylbenzothiazol-2-one: 1H NMR (DMSO-d6,500mhz): δ (ppm)11.73(brs,1H),7.37(dd,1H, J1 ═ 7.5, J2 ═ 0.5Hz),7.08-7.09(m,1H),7.03(t,1H, J ═ 7.5Hz),2.32(s, 3H); 13C NMR (DMSO-d6,125MHz) delta (ppm)170.4,135.0,127.6,122.8,122.5,121.3,120.0, 17.4; MS (EI) M/z calcd for C8H7NOS [ M ]]+165.1, found 165.0, melting point 211-212 DEG C
The analysis result shows that the obtained target product has a correct structure.
Example 16
4,4 '-dibromo-2, 2' -dithio diphenylamine is used as a raw material to synthesize the 6-bromobenzothiazole-2-ketone.
(1) Synthesis of 6-bromobenzothiazole-2-ketone
Dry-method column filling and dry-method column chromatography (200-300 mesh silica gel) separation: gradient elution is adopted, ethyl acetate and dichloromethane are used as eluent, and the ratio of dichloromethane to ethyl acetate (V/V) is 100: 1, increasing the polarity to 20: 1, obtaining 189mg of white solid 6-bromobenzothiazole-2-ketone after separation, and the separation yield of column chromatography is 82 percent
(2) Structure identification of 6-bromobenzothiazole-2-ketone
Characterization data for 6-bromobenzothiazole-2-one: 1H NMR (DMSO-d6,500mhz): δ (ppm)12.02(brs,1H),7.86(d,1H, J ═ 2.0Hz),7.44(dd,1H, J1 ═ 8.5, J2 ═ 2.5Hz),7.05(d,1H, J ═ 8.5 Hz); 13C NMR (DMSO-d6,125MHz) delta (ppm)169.7,135.6,129.2,125.6,125.0,114.0,113.1; MS (EI) M/z calcd for C7H4BrNOS [ M ]]+228.9, found 228.9, a melting point of 231-.
The analysis result shows that the obtained target product has a correct structure.
Example 17
4,4 '-dichloro-2, 2' -dithio diphenylamine is used as a raw material to synthesize the 6-chlorobenzothiazole-2-ketone.
(1) Synthesis of 6-chlorobenzothiazol-2-one
Dry-method column filling and dry-method column chromatography (200-300 mesh silica gel) separation: gradient elution is adopted, ethyl acetate and dichloromethane are used as eluent, and the ratio of dichloromethane: ethyl acetate (V/V) ═ 100: 1, increasing the polarity to 20: 1, obtaining 156mg of white solid 6-chlorobenzothiazol-2-ketone after separation, and the separation yield of column chromatography is 84 percent.
(2) Structural identification of 6-chlorobenzothiazol-2-one
Characterization data for 6-chlorobenzothiazol-2-one: 1H NMR (DMSO-d6,500mhz) δ (ppm)12.02(brs,1H),7.74(d,1H, J ═ 2.0Hz),7.32(dd,1H, J1 ═ 8.5, J2 ═ 2.5Hz),7.11(d,1H, J ═ 8.5 Hz); 13C NMR (DMSO-d6,125MHz) delta (ppm)169.7,135.3,126.4,125.2,122.4,112.7; MS (EI) M/z calcd for C7H4ClNOS [ M ]]+185.1, found 185.0, melting point 212-.
The analysis result shows that the obtained target product has a correct structure.
Example 18
5,5 '-dichloro-2, 2' -dithio diphenylamine is used as a raw material to synthesize 5-chlorobenzothiazole-2-ketone.
(1) Synthesis of 5-chlorobenzothiazol-2-one
Dry-method column filling and dry-method column chromatography (200-300 mesh silica gel) separation: gradient elution is adopted, ethyl acetate and dichloromethane are used as eluent, and the ratio of dichloromethane: ethyl acetate (V/V) ═ 100: 1, increasing the polarity to 20: 1, obtaining 156mg of white solid 5-chlorobenzothiazol-2-ketone after separation, and the separation yield of column chromatography is 84 percent.
(2) Structure identification of 5-chlorobenzothiazol-2-one
Characterization data for 5-chlorobenzothiazol-2-one: 1H NMR (DMSO-d6,500mhz): δ (ppm)12.04(brs,1H),7.61(d,1H, J ═ 8.5Hz),7.19(dd,1H, J1 ═ 8.5, J2 ═ 2.5Hz),7.12(d,1H, J ═ 2.0 Hz); 13C NMR (DMSO-d6,125MHz): delta (ppm)170.0,137.4,130.8,124.3,122.4,122.2,111.2；MS(EI):m/z calcd for C7H4ClNOS[M]+184.9, found 185.0, melting point 224-.
The analysis result shows that the obtained target product has a correct structure.
Example 19
6, 6' -dithiobis (2-fluoroaniline) is used as a raw material to synthesize the 5-fluorobenzothiazole-2-ketone.
(1) Synthesis of 5-fluorobenzothiazol-2-one
Dry-method column filling and dry-method column chromatography (200-300 mesh silica gel) separation: gradient elution is adopted, ethyl acetate and dichloromethane are used as eluent, and the ratio of dichloromethane: ethyl acetate (V/V) ═ 100: 1, increasing the polarity to 20: 1, obtaining 129mg of white solid 5-fluorobenzothiazole-2-ketone after separation, and the separation yield of column chromatography is 76%.
(2) Structure identification of 5-fluorobenzothiazole-2-one
Characterization data for 5-fluorobenzothiazol-2-one: 1H NMR (DMSO-d6,500MHz) Δ (ppm)12.39(brs,1H),7.43(d,1H, J ═ 7.5Hz),7.12-7.22(m, 2H); 13C NMR (DMSO-d6,125mhz) δ (ppm)169.7,147.1(d, J ═ 243.8Hz),125.5(d, J ═ 3.8Hz),124.3(d, J ═ 14.6Hz),123.0(d, J ═ 6.5Hz),118.6(d, J ═ 6.0Hz),112.7(d, J ═ 16.9 Hz); MS (EI) m/z calcd for C7H4FNOS[M]+169.0, found 169.0, melting point 172-.
The analysis result shows that the obtained target product has a correct structure.
Example 20
5,5 '-bis (trifluoromethyl) -2, 2' -dithio diphenylamine is used as a raw material to synthesize the 6-trifluoromethyl benzothiazole-2-ketone.
(1) Synthesis of 6-trifluoromethylbenzothiazol-2-one
Dry-method column filling and dry-method column chromatography (200-300 mesh silica gel) separation: gradient elution is adopted, ethyl acetate and dichloromethane are used as eluent, and the ratio of dichloromethane: ethyl acetate (V/V) ═ 100: 1, increasing the polarity to 20: 1, obtaining 167mg of white solid 6-trifluoromethyl benzothiazole-2-ketone after separation, and the separation yield of column chromatography is 76%.
(2) Structure identification of 6-trifluoromethylbenzothiazole-2-ketone
Characterization data for 6-trifluoromethylbenzothiazol-2-one: 1H NMR (DMSO-d6,500mhz): δ (ppm)12.22(brs,1H),7.85(d,1H, J ═ 8.5Hz),7.48(dd,1H, J1 ═ 8.0Hz, J2 ═ 1.0Hz),7.33(d,1H, J ═ 1.5 Hz); 13C NMR (DMSO-d6,125mhz) δ (ppm)169.7,136.7,128.4(d, J ═ 1.25Hz),126.9(q, J ═ 31.9.5Hz),124.0(q, J ═ 270.5Hz),123.8,119.0(q, J ═ 3.9Hz),107.6(q, J ═ 4.1 Hz); MS (EI) m/z calcd for C8H4F3NOS[M]+219.2, found 219.0, melting point 216 and 218 ℃. The analysis result shows that the obtained target product has a correct structure.
Example 21
6-methylsulfonyl benzothiazole-2-ketone is synthesized by taking 6,6 '-dimethylsulfonyl-2, 2' -dithio diphenylamine as a raw material.
(1) Synthesis of 6-methylsulfonyl benzothiazole-2-ketone
Dry-method column filling and dry-method column chromatography (200-300 mesh silica gel) separation: gradient elution is adopted, ethyl acetate and dichloromethane are used as eluent, and the ratio of dichloromethane: ethyl acetate (V/V) ═ 100: 1, increasing the polarity to 20: 1, obtaining 149mg of white solid 6-methylsulfonyl benzothiazole-2-ketone after separation, and the separation yield of column chromatography is 65%.
(2) Structure identification of 6-methylsulfonyl benzothiazole-2-ketone
Characterization data for 6-methylsulfonylbenzothiazol-2-one: 1H NMR (DMSO-d6,500mhz) δ (ppm)12.41(brs,1H),8.22(d,1H, J ═ 7.0Hz),7.812(dd,1H, J ═ 7.5Hz, J ═ 2.0Hz),7.31(d,1H, J ═ 8.0Hz),3.20(s, 3H); 13C NMR (DMSO-d6,125MHz): delta (ppm)170.2,140.4,134.6,125.6,124.2,122.2,111.5,43.9；MS(EI):m/z calcd for C8H7NO3S2[M]+229.0, found 228.8, melting point 241-244 ℃.
The analysis result shows that the obtained target product has a correct structure.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (6)
1. A method for synthesizing benzothiazole-2-ketone derivatives by using carbonyl sulfide and disulfide as raw materials is characterized by comprising the steps of mixing disulfide, inorganic sulfide and an organic solvent, introducing sufficient COS for reaction for 1-2 hours at the reaction temperature of 25 ℃, and concentrating and purifying reaction liquid to obtain the benzothiazole-2-ketone derivatives shown in formula 1;
the disulfide is o-amino aromatic disulfide;
the o-amino aromatic disulfide is shown as a formula 2:
wherein, the substituent R on the o-amino aromatic disulfide is H, F, Cl, Br, I and CF mono-substituted at ortho-position, meta-position and para-position of the disulfide bond3、OCF3、C1-C8Alkyl of (C)1-C8Alkoxy or C1-C8A sulfonyl group of (a).
2. The method of claim 1, wherein the molar ratio of disulfide to inorganic sulfide is 1: 0.1 to 1.
3. The process according to claim 1, wherein the inorganic sulfide is NaHS, K2S and Na2S·9H2At least one of O.
4. The method of claim 1, wherein the organic solvent is at least one of methanol, ethanol, THF, DMF, and 1, 4-dioxane.
5. The method of claim 4, wherein the organic solvent does not require anhydrous treatment prior to use.
6. The method as claimed in claim 1, wherein the pressure of COS is 0.1 to 1 MPa.
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|---|---|---|---|---|
| US4150027A (en) * | 1977-03-28 | 1979-04-17 | Monsanto Company | Process for preparing 2-hydroxybenzothiazole compounds |
| CN105884714A (en) * | 2016-05-03 | 2016-08-24 | 内蒙古工业大学 | Method for realizing green synthesis of 2-substituted benzothiazole derivatives |
| CN105949147A (en) * | 2016-05-26 | 2016-09-21 | 内蒙古工业大学 | Green synthesis method of 2-mercaptobenzothiazoles derivatives |
-
2017
- 2017-12-12 CN CN201711318196.9A patent/CN108101863B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4150027A (en) * | 1977-03-28 | 1979-04-17 | Monsanto Company | Process for preparing 2-hydroxybenzothiazole compounds |
| CN105884714A (en) * | 2016-05-03 | 2016-08-24 | 内蒙古工业大学 | Method for realizing green synthesis of 2-substituted benzothiazole derivatives |
| CN105949147A (en) * | 2016-05-26 | 2016-09-21 | 内蒙古工业大学 | Green synthesis method of 2-mercaptobenzothiazoles derivatives |
Non-Patent Citations (3)
| Title |
|---|
| 1,3-苯并噻嗪酮类衍生物合成方法的研究进展;李闪闪 等;《有机化学》;20161231;第36卷;第2024-2038页 * |
| A Facile One-Pot Synthesis of Benzothiazolones from 2-Halonitrobenzenes;Ken-ichi KONISHI et al.;《Synthesis》;19840331(第3期);第254-255页 * |
| Highly efficient synthesis of 2-mercaptobenzothiazole derivatives in water: metal sulfide–disulfide dynamic interchange reaction;Chunqing Lou et al.;《Green Chem.》;20170103;第19卷;第1102-1108页 * |
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