CN102108069B - Method for preparing 6-benzothiazole sulfonyl chloride - Google Patents
Method for preparing 6-benzothiazole sulfonyl chloride Download PDFInfo
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- CN102108069B CN102108069B CN201110003115A CN201110003115A CN102108069B CN 102108069 B CN102108069 B CN 102108069B CN 201110003115 A CN201110003115 A CN 201110003115A CN 201110003115 A CN201110003115 A CN 201110003115A CN 102108069 B CN102108069 B CN 102108069B
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- GPNAVOJCQIEKQF-UHFFFAOYSA-N Nc([s]c1c2)nc1ccc2[N+]([O-])=O Chemical compound Nc([s]c1c2)nc1ccc2[N+]([O-])=O GPNAVOJCQIEKQF-UHFFFAOYSA-N 0.000 description 1
- GPNAVOJCQIEKQF-UHFFFAOYSA-O [NH3+]c([s]c1c2)nc1ccc2[N+]([O-])=O Chemical compound [NH3+]c([s]c1c2)nc1ccc2[N+]([O-])=O GPNAVOJCQIEKQF-UHFFFAOYSA-O 0.000 description 1
- QLUFBCVWKTWKBF-UHFFFAOYSA-N [O-][N+](c1ccc2nc[s]c2c1)=O Chemical compound [O-][N+](c1ccc2nc[s]c2c1)=O QLUFBCVWKTWKBF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for preparing 6-benzothiazole sulfonyl chloride. In the method, the raw materials are cheap and readily available, the reaction conditions are mild, the operation is simple, and the synthesis efficiency is high. The method is favorable for industrial production and provides a new approach for preparing benzothiazole derivatives with human immunodeficiency virus resisting activity.
Description
Technical field
The present invention relates to a kind of preparation method of 6-benzothiazole SULPHURYL CHLORIDE.
Background technology
6-benzothiazole SULPHURYL CHLORIDE is the important intermediate of preparation benzothiazole derivant; A lot of benzothiazole derivants have the activity of anti-human immunodeficiency virus (HIV); Therefore, the compound method of research 6-benzothiazole SULPHURYL CHLORIDE is significant for the medicine that research and development are used to treat the human immunodeficiency syndrome.
U.S. Pat 6140505 discloses a series of benzothiazole derivants with HIV-resistant activity, and discloses the compound method of key intermediate 6-benzothiazole SULPHURYL CHLORIDE, is shown below:
This method comprises the following steps: at first sulfanilic amide and ammonium thiocyanide reaction to be made N-(4-sulfanilamide (SN) phenyl) thiocarbamide; Make 2-amino-6-sulfahydantoin benzothiazole with bromine reaction cyclization then; Carry out diazotization reaction with Isopentyl nitrite subsequently and obtain 6-sulfonic acid benzothiazole, make 6-benzothiazole SULPHURYL CHLORIDE with the sulfur oxychloride chlorination at last.
This route is repeatable poor, to the corrosion of conversion unit and comparatively serious to the pollution of environment, is unfavorable for scale operation in the industry.
Summary of the invention
Technical problem to be solved by this invention is that to have overcome the compound method of 6-benzothiazole SULPHURYL CHLORIDE in the prior art repeatable poor; To corrosion on Equipment and seriously polluted to environment; Be unfavorable for the upward defective of scale operation of industry; A kind of new method for preparing 6-benzothiazole SULPHURYL CHLORIDE is provided, and this method low in raw material cost is easy to get, reaction conditions is gentle, easy and simple to handle, combined coefficient is high, help suitability for industrialized production.
Therefore, the present invention relates to a kind of preparation method of 6-benzothiazole SULPHURYL CHLORIDE, it comprises the following steps:
Step (1) in the organic solvent, under the effect of hydrogenation catalyst, is carried out reduction reaction with compound and hydrogen shown in formula III, makes compound I I;
Step (2), I carries out diazotization reaction with step (1) gained compound I, makes diazonium salt V;
Step (3) in the organic solvent, in the presence of copper sulfate, is reacted step (2) gained diazonium salt V and sulfurous gas and chlorine, gets final product.
Wherein, in the step (1), described organic solvent can be the conventional solvent of this type of reaction of this area, one or more that preferable is in ethanol, methyl alcohol, Virahol and the trimethyl carbinol; Better is methyl alcohol.The volume mass of described organic solvent and compound III than preferable be 5.0～50.0ml/g; That better is 15.0ml/g.Described hydrogenation catalyst can be the catalyzer that this area routine is used for catalytic hydrogenation.The preferred especially following hydrogenation catalyst of the present invention: one or more in Raney's nickel, palladium carbon and the platinum carbon; Better is palladium carbon.What the consumption of described hydrogenation catalyst was preferable is 0.1～20.0% of compound III quality, and better is 10%.That the pressure of described hydrogen is preferable is 0.1～1MPa; That better is 0.5MPa.What the temperature of described reaction was preferable is 20 ℃ of reflux temperatures to organic solvent, and better is 50 ℃.The time of described reaction preferable with detection reaction fully till.
In the step (2), the method for described diazotization reaction and condition all can be the ordinary method and the condition of this type of reaction of this area, preferred especially following method of the present invention and condition: in the water, compound I I and mineral acid and Sodium Nitrite are reacted, get final product.
Wherein, the volume mass of described water and compound I I than preferable be 1.0～20.0ml/g; That better is 1.5ml/g.Described mineral acid is preferable is in hydrochloric acid, sulfuric acid and the phosphoric acid one or more.The consumption of described mineral acid is preferable is 1.5～10.0 times of compound I I molar weight; Better is 4.0 times.The consumption of described Sodium Nitrite is preferable is 1.0～1.5 times of compound I I molar weight; Better is 1.0 times.What the temperature of described reaction was preferable is-20～30 ℃; Better is 10 ℃.The time of described reaction is preferable accomplish with detection reaction till.
In the step (3), described organic solvent can be the conventional solvent of this type of reaction of this area, one or more that preferable is in toluene, YLENE, methylene dichloride, ethylene dichloride, chloroform and the tetracol phenixin, and better is toluene.The volume mass of described organic solvent and compound V than preferable be 5.0～50.0ml/g; That better is 10.0ml/g.The consumption of described copper sulfate is preferable is 1.0～3.0 times of compound V molar weight; Better is 1.0 times.What the temperature of described reaction was preferable is 0～115 ℃; Better is 45～50 ℃.The time of described reaction is preferable accomplish with detection reaction till.
Among the present invention, described compound III can be made by following method:
Step (1) will be carried out diazotization reaction suc as formula the compound shown in the IV, make diazonium salt VI;
Step (2), in the organic solvent, VI reacts under 0～100 ℃ with step (1) gained diazonium salt, gets final product.
Wherein, The method of the diazotization reaction described in the step (1) and condition all can be the ordinary method and the condition of this type of reaction of this area; Preferred especially following method of the present invention and condition: in the organic solvent, compound IV and mineral acid and Sodium Nitrite are reacted, get final product.
Wherein, described organic solvent is preferable is in methyl alcohol, ethanol, Virahol and the benzene one or more, better for volume ratio be 4: 1 95% the ethanol and the mixed solvent of benzene.The volume mass of described organic solvent and compound IV than preferable be 5.0～30.0ml/g; That better is 15.0ml/g.Described mineral acid is preferable is in hydrochloric acid, sulfuric acid and the phosphoric acid one or more.The consumption of described mineral acid is preferable is 1.0～5.0 times of compound IV molar weight; Better is 2.5 times.The consumption of described Sodium Nitrite is preferable is 1.0～5.0 times of compound IV molar weight; Better is 2.0 times.What the temperature of described reaction was preferable is 0～100 ℃; Better is 25 ℃.The time of described reaction is preferable accomplish with detection reaction till.
In the step (2), described organic solvent can be the conventional solvent of this type of reaction of this area.One or more that preferable is in methyl alcohol, ethanol, Virahol and the benzene, better for volume ratio be 4: 1 95% the ethanol and the mixed solvent of benzene.The volume mass of described organic solvent and compound IV than preferable be 5.0～30.0ml/g; That better is 15.0ml/g.The time of described reaction is preferable accomplish with detection reaction till, be generally 3～5 hours.
On the basis of this area general knowledge, but above-mentioned each preferred feature arbitrary combination among the present invention promptly gets each preferred embodiments of the present invention.
Raw material described in the present invention or reagent except that specifying, all commercially available getting.
Positive progressive effect of the present invention is: the compound method low in raw material cost of 6-benzothiazole SULPHURYL CHLORIDE of the present invention is easy to get, reaction conditions is gentle, easy and simple to handle, combined coefficient is high, help suitability for industrialized production, for preparation has the active benzothiazole derivant of anti-human immunodeficiency virus a new approach is provided.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.
Used raw material or reagent is except that specifying among the embodiment, all commercially available getting.
Room temperature described in the embodiment all refers to 20～35 ℃.
The preparation of embodiment 1 compound III
Under 25 ℃, 19.5g (0.1mol) compound IV is dissolved in the mixed solvent of ethanol and 50ml benzene of 200ml 95%, adds the 14ml vitriol oil, add 14g (0.2mol) Sodium Nitrite under the vigorous stirring rapidly, keeps 25 ℃ to react 1 hour.Slowly be heated to backflow, reacted 3～5 hours, cooling is filtered, and filter cake is with the washing with alcohol of 50ml 95%, merging filtrate, and concentrating under reduced pressure obtains light yellow solid 12.6g, yield 70%, HPLC purity is 98%, fusing point: 174～176 ℃.
Its structure appraising datum is following:
1H?NMR(CDCl
3)：δ8.25～8.27(d，1H)，8.40～8.43(d，1H)，8.92～8.93(s，1H)，9.28(s，1H)。
The preparation of embodiment 2 compound I I
10g (0.056mol) compound III is dissolved in the 150ml methyl alcohol, adds the palladium carbon of 1.0g 10%, 50 ℃, logical hydrogen; Pressure 0.5MPa no longer inhales hydrogen up to system, and cooling is filtered; Filter cake is used the 10ml methanol wash, merging filtrate, and concentrating under reduced pressure obtains brown solid 7.5g; Yield 90%, HPLC purity are 98%, fusing point: 84～86 ℃.
Its structure appraising datum is following:
1H?NMR(CDCl
3)：δ3.87(br.s，2H)，6.86～6.88(d，1H)，7.16～7.17(s，1H)，7.88～7.92(d，1H)，8.66～8.73(s，1H)。
The preparation of embodiment 3 compound I
With 10g (0.067mol) compound I I, 4.8g (0.07mol) Sodium Nitrite and 15g water uniform mixing.Aqueous sulfuric acid and 22ml concentrated hydrochloric acid with 10.4g 50% is mixed into nitration mixture in addition, is cooled to 10 ℃, drips above-mentioned mixed solution.Drip off the back and keep 10 ℃ of reactions 8 hours, add 10g copper sulfate, feed sulfur dioxide gas, about 5 hours.Add toluene 50ml, be warming up to 45～50 ℃, logical chlorine cools off to reaction end.Separatory, water are used the 50ml extracted in toluene, merge organic phase, anhydrous sodium sulfate drying, and activated carbon decolorizing, concentrating under reduced pressure obtains light yellow solid 10.2g, yield 65%, HPLC purity 98%, fusing point: 116～118 ℃.
Its structure appraising datum is following:
1H?NMR(CDCl
3)：δ8.18～8.20(d，1H)，8.35～8.37(d，1H)，8.73(s，1H)，9.33～9.34(s，1H)。
The preparation of embodiment 4 compound III
Under 25 ℃, 19.5g (0.1mol) compound IV is dissolved in the 200ml Virahol, adds 0.1mol hydrochloric acid; Add 7g (0.1mol) Sodium Nitrite under the vigorous stirring rapidly, keep 0 ℃ of reaction, filter; Filter cake is with the washing with alcohol of 50ml 95%, merging filtrate, concentrating under reduced pressure; Obtain light yellow solid 12.2g, yield 68%.
The preparation of embodiment 5 compound III
Under 25 ℃, 19.5g (0.1mol) compound IV is dissolved in 200ml methyl alcohol, adds 0.5mol phosphoric acid, under the vigorous stirring; Add 35g (0.5mol) Sodium Nitrite rapidly, keep 25 ℃ of reactions 1 hour, slowly be heated to 100 ℃, cooling; Filter, filter cake is used 50ml methanol wash, merging filtrate; Concentrating under reduced pressure obtains light yellow solid 11.9g, yield 66%.
The preparation of embodiment 6 compound I I
10g (0.056mol) compound III is dissolved in the 150ml trimethyl carbinol, adds the 2.0g Raney's nickel, 20 ℃, logical hydrogen, pressure 0.1MPa no longer inhales hydrogen up to system.Cooling is filtered, and filter cake washs with the 10ml trimethyl carbinol, merging filtrate, and concentrating under reduced pressure obtains brown solid 7.2g, yield 86%.
The preparation of embodiment 7 compound I I
10g (0.056mol) compound III is dissolved in the 150ml Virahol, adds 0.01g platinum carbon, be warming up to backflow, logical hydrogen, pressure 1MPa no longer inhales hydrogen up to system.Cooling is filtered, and filter cake is used the 10ml washed with isopropyl alcohol, merging filtrate, and concentrating under reduced pressure obtains brown solid 7.1g, yield 85%.
The preparation of embodiment 8 compound I
With 10g (0.067mol) compound I I, 6.9g (0.10.07mol) Sodium Nitrite and 15g water uniform mixing.Aqueous sulfuric acid and 47ml concentrated hydrochloric acid with 22.3g 50% is mixed into nitration mixture in addition, is cooled to-20 ℃, drips above-mentioned mixed solution.Drip off the back and keep-20 ℃ of reactions 8 hours, add 30g copper sulfate, feed sulfur dioxide gas, about 5 hours.Add YLENE 50ml, be warming up to 115 ℃, logical chlorine cools off to reaction end.Separatory, water are used the 50ml extracted in toluene, merge organic phase, anhydrous sodium sulfate drying, and activated carbon decolorizing, concentrating under reduced pressure obtains light yellow solid 10.6g, yield 67.5%.
The preparation of embodiment 9 compound I
With 10g (0.067mol) compound I I, 5.5g (0.08mol) Sodium Nitrite and 15g water uniform mixing.Aqueous sulfuric acid and 7ml concentrated hydrochloric acid with 3.4g 50% is mixed into nitration mixture in addition, is cooled to 10 ℃, drips above-mentioned mixed solution.Drip off the back in 30 ℃ of reactions 8 hours, add 15g copper sulfate, feed sulfur dioxide gas, about 5 hours.Add tetracol phenixin 50ml, be warming up to backflow, logical chlorine cools off to reaction end.Separatory, water are used the 50ml carbon tetrachloride extraction, merge organic phase, anhydrous sodium sulfate drying, and activated carbon decolorizing, concentrating under reduced pressure obtains light yellow solid 9.8g, yield 62%.
The preparation of embodiment 10 compound I
With 10g (0.067mol) compound I I, 4.8g (0.07mol) Sodium Nitrite and 15g water uniform mixing.In addition 66g phosphoric acid is cooled to 10 ℃, drips above-mentioned mixed solution.Drip off the back and keep 10 ℃ of reactions 8 hours, add 10g copper sulfate, feed sulfur dioxide gas, about 5 hours.Add ethylene dichloride 50ml, under 0 ℃, logical chlorine is to reaction end, cooling.Separatory, water are used the 50ml extracted in toluene, merge organic phase, anhydrous sodium sulfate drying, and activated carbon decolorizing, concentrating under reduced pressure obtains light yellow solid 10.3g, yield 66%.
Claims (9)
1. the preparation method suc as formula the 6-benzothiazole SULPHURYL CHLORIDE shown in the I is characterized in that comprising the following steps:
Step (1) in the organic solvent, under the effect of hydrogenation catalyst, will be carried out reduction reaction suc as formula compound shown in the III and hydrogen, make compound ii;
Step (2) is carried out diazotization reaction with step (1) gained compound ii, makes the diazonium salt V;
Step (3) in the organic solvent, in the presence of copper sulfate, is reacted step (2) gained diazonium salt V and sulfurous gas and chlorine, gets final product;
2. preparation method as claimed in claim 1 is characterized in that: in the step (1), described organic solvent is one or more in ethanol, methyl alcohol, Virahol and the trimethyl carbinol; Described hydrogenation catalyst is one or more in Raney's nickel, palladium carbon and the platinum carbon; The consumption of described hydrogenation catalyst is 0.1 ~ 20.0% of a compound III quality; The pressure of described hydrogen is 0.1 ~ 1MPa; The temperature of described reaction is 20 ℃ of reflux temperatures to organic solvent; The time of described reaction with detection reaction fully till.
3. preparation method as claimed in claim 1 is characterized in that: in the step (2), described diazotization reaction comprises the following steps: in the water, and compound ii and mineral acid and Sodium Nitrite are reacted, and gets final product.
4. preparation method as claimed in claim 3 is characterized in that: in the diazotization reaction, described mineral acid is one or more in hydrochloric acid, sulfuric acid and the phosphoric acid; The consumption of described mineral acid is 1.5 ~ 10.0 times of compound ii molar weight; The consumption of described Sodium Nitrite is 1.0 ~ 1.5 times of compound ii molar weight; The temperature of described reaction is-20 ~ 30 ℃; Till the time of described reaction accomplishes with detection reaction.
5. preparation method as claimed in claim 1 is characterized in that: in the step (3), described organic solvent is one or more in toluene, YLENE, methylene dichloride, ethylene dichloride, chloroform and the tetracol phenixin; The consumption of described copper sulfate is 1.0 ~ 3.0 times of compound V molar weight; The temperature of described reaction is 0 ~ 115 ℃; Till the time of described reaction accomplishes with detection reaction.
6. like each described preparation method of claim 1 ~ 5, it is characterized in that: described compound III is made by following method:
Step (1) will be carried out diazotization reaction suc as formula the compound shown in the IV, make the diazonium salt VI;
Step (2) in the organic solvent, is reacted step (1) gained diazonium salt VI under 0 ~ 100 ℃, get final product;
7. preparation method as claimed in claim 6 is characterized in that: the diazotization reaction described in the step (1) comprises the following steps: in the organic solvent, and compound IV and mineral acid and Sodium Nitrite are reacted, and gets final product.
8. preparation method as claimed in claim 7 is characterized in that: in the diazotization reaction in the preparation compound III, described organic solvent is one or more in methyl alcohol, ethanol, Virahol and the benzene; Described mineral acid is one or more in hydrochloric acid, sulfuric acid and the phosphoric acid; The consumption of described mineral acid is 1.0 ~ 5.0 times of compound IV molar weight; The consumption of described Sodium Nitrite is 1.0 ~ 5.0 times of compound IV molar weight; The temperature of described reaction is 0 ~ 100 ℃; Till the time of described reaction accomplishes with detection reaction.
9. preparation method as claimed in claim 6 is characterized in that: in the step (2) in the preparation compound III, described organic solvent is one or more in methyl alcohol, ethanol and the Virahol, or the mixed solvent of ethanol and benzene; Till the time of described reaction accomplishes with detection reaction.
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| CN201110003115A CN102108069B (en) | 2011-01-07 | 2011-01-07 | Method for preparing 6-benzothiazole sulfonyl chloride |
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| CN102603582A (en) * | 2012-02-28 | 2012-07-25 | 王继龙 | Method for synthesizing o-methyl formate benzene sulfonamide |
| CN105037294B (en) * | 2015-06-15 | 2018-02-06 | 南京哈柏医药科技有限公司 | A kind of synthetic method of the aryl benzothiazole compound of medicine intermediate 2 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6140505A (en) * | 1995-03-10 | 2000-10-31 | G. D. Searle & Co. | Synthesis of benzo fused heterocyclic sulfonyl chlorides |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6140505A (en) * | 1995-03-10 | 2000-10-31 | G. D. Searle & Co. | Synthesis of benzo fused heterocyclic sulfonyl chlorides |
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