CN102040563B - Preparation method for 3-aryl benzo [d] isothiazole - Google Patents
Preparation method for 3-aryl benzo [d] isothiazole Download PDFInfo
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- CN102040563B CN102040563B CN200910197259.9A CN200910197259A CN102040563B CN 102040563 B CN102040563 B CN 102040563B CN 200910197259 A CN200910197259 A CN 200910197259A CN 102040563 B CN102040563 B CN 102040563B
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Abstract
The invention provides a preparation method for 3-aryl benzo [d] isothiazole shown in formula I. The method comprises the following step: subjecting a compound II and a compound III to coupling reaction to obtain the compound I. In formula I, R1, R2, R3, R4, R5 are separately C1 to C3 alkyl, C1 to C3 alkyloxy, amino substituted by one or two C1-C4 alkyls, amino, hydroxyl, nitro or carbonyl connecting C1 to C3 alkyloxy. The preparation method provided by the invention has the advantages that: the raw material is cheap and easily available, the step is simple, the condition is mild, and the yield is high generally which can reach 70% to 80%.
Description
Technical field
The present invention relates to a kind of preparation method of pharmaceutical intermediate, be specifically related to the preparation method of a kind of 3-aryl benzo [d] isothiazole.
Background technology
3-aryl benzo [d] isothiazole (I), structural formula specific as follows:
The type compound is a kind of important medicine and chemical intermediate.
In existing synthetic method, (as shown below, Chemische Berichte 1979,112,3286-3292), independently react through three steps, and use the acute product such as phosphorus oxychloride, and environmental pollution is serious; Temperature of reaction is very high, dangerous large; Aftertreatment complexity.So need development step brief, environmental friendliness, and lower-cost method.
Summary of the invention
Technical problem to be solved by this invention is in the method in order to overcome the existing 3-of preparation aryl benzo [d] isothiazole, reactions steps is long, and use the highly toxic product such as phosphorus oxychloride, environmental pollution is serious, temperature of reaction is very high, dangerous large, and the defect such as aftertreatment complexity, and the preparation method of a kind of 3-aryl benzo [d] isothiazole is provided.Preparation method's raw material of the present invention is cheap and easy to get, and step is simple, mild condition, and product yield is higher, generally can reach 70%-80%.
The present invention relates to a kind of preparation method suc as formula 3-aryl benzo [d] isothiazole shown in I, it comprises the following step: in solvent, Compound I I and compound III are carried out linked reaction, make Compound I;
Wherein, R
1, R
2, R
3, R
4and R
5alone be C
1～C
3alkyl, C
1～C
3alkoxyl group, by 1 or 2 C
1～C
4amino, amino, hydroxyl, nitro or connection C that alkyl replaces
1～C
3the carbonyl of alkoxyl group.
Preferably, compound III is to methylphenylboronic acid, a methylphenylboronic acid, to methoxyphenylboronic acid, meta-methoxy phenylo boric acid, to dimethylin phenylo boric acid, a dimethylin phenylo boric acid, to diethylin phenylo boric acid, a diethylin phenylo boric acid, to methylamino phenylo boric acid, a methylamino phenylo boric acid, to ethylamino-phenylo boric acid, an ethylamino-phenylo boric acid, p-aminophenyl boric acid, m-aminophenyl boric acid, para hydroxybenzene boric acid, a hydroxybenzene boric acid, p-nitrophenyl boric acid, m-nitro boric acid or to ethoxycarbonyl phenylo boric acid.
Wherein, the method for described reaction and condition all can be method and the condition of this area microcosmic salt linked reaction, and preferred method and condition are as follows:
(1) in polar aprotic solvent, under protection of inert gas, Compound I I and microcosmic salt and alkali effect;
(2), under protection of inert gas, product and compound III that step (1) is obtained are carried out linked reaction.
Wherein, described microcosmic salt is preferably tripyrrole alkyl bromide phosphine hexafluoro microcosmic salt (PyBroP) and/or phosphofluoric acid benzotriazole-1-base-oxygen base tripyrrole alkyl phosphorus (PyBOP), preferably PyBroP; Described alkali can be mineral alkali and/or organic bases, preferably organic bases; Mineral alkali is preferably sodium tert-butoxide, and organic bases is preferably triethylamine and/or diethyl propyl group ethylamine, preferably triethylamine; The mol ratio of described Compound I I and microcosmic salt, alkali is preferably 1: 1: 1～1: 2: 10, and better is 1: 1.1: 2.5～1: 1.5: 6; The mol ratio of compound III and Compound I I is preferably 0.8: 1～2: 1, and better is 1: 1～1.2: 1; Described polar aprotic solvent is preferably one or more in Isosorbide-5-Nitrae-dioxane, tetrahydrofuran (THF), acetonitrile and glycol dimethyl ether, preferably Isosorbide-5-Nitrae-dioxane; Described Compound I I is 0.01～1mol/L with the molecular volume of solvent than preferably, and that better is 0.05～0.5mol/L.
In described step (1), the temperature of effect is preferably 0～50 ℃, and better is 10～30 ℃, in step (1) time of effect preferably with detection effect completely till, preferably 0.5～4 hour, better was 1.5～2.5 hours;
The method of the linked reaction in described step (2) and condition can be ordinary method and the condition of this area Suzuki linked reaction; particularly preferably following method and condition: in solvent; under protection of inert gas; under the effect of palladium catalyst and alkali; step (1) products therefrom and compound III are reacted.Wherein, described palladium catalyst is preferably tetrakis triphenylphosphine palladium, two (triphenylphosphine) Palladium Diacetate and two (triphenylphosphine) palladium chloride [Pd (PPh
3)
2cl
2] in one or more, preferably Pd (PPh
3)
2cl
2; The consumption of palladium catalyst is preferably 0.1～20mol% of Compound I I, and that better is 1～10mol%; Described alkali is preferably mineral alkali, as one or more in sodium carbonate, salt of wormwood and cesium carbonate, and preferably sodium carbonate; The consumption of alkali is preferably 1～10 equivalent of Compound I I, and better is 3～5 equivalents; In step (2), can continue to use the solvent in step (1), also can be with an organic solvent and the mixed solvent of water, preferably mixed solvent, the preferred Isosorbide-5-Nitrae-dioxane of organic solvent in mixed solvent; Compound I I is 0.01～1mol/L with the molecular volume of solvent than preferably, and that better is 0.05～0.5mol/L; The temperature of described reaction is preferably 50～150 ℃, and better is 80～110 ℃; The time of reaction preferably with detection reaction completely till, preferably 4～8 hours.
In preparation method of the present invention, the optimum condition of above-mentioned each processing step can arbitrary combination, obtains each preferred embodiments of the present invention.
Except specified otherwise, the raw material the present invention relates to and reagent is commercially available obtaining all.
Positively effect of the present invention is:
(1) in preparation method of the present invention, raw material is all cheap and easy to get, and does not use and poison large raw material reagent.
(2) preparation method's reactions steps of the present invention is simple, easily operation, and mild condition, aftertreatment is also simpler, and cost is lower, and the total recovery of product is higher, reaches 70～80%, and product purity is also higher, is easy to realize suitability for industrialized production.
Embodiment
With embodiment, further illustrate the present invention below, but the present invention is not limited.
In following embodiment, " equivalent " of correlated response thing is all the equivalents with respect to Compound I I.
Embodiment 1
By benzisothia oxazolone (II) (0.5mmol); PyBroP (1.2 equivalent) and triethylamine (3.0 equivalent) join 1; in 4-dioxane (4mL), room temperature under nitrogen protection (25 ℃) stirs 2 hours.Then add to methylphenylboronic acid (2.0 equivalent) two (triphenylphosphine) palladium chloride (Pd (PPh
3)
2cl
2) (5% equivalent), sodium carbonate (5.0 equivalent) and water (1 milliliter).Reaction mixture is heated to 100 ℃, stirs 4 hours.Cool to room temperature, adds ethyl acetate dilution, water, saturated common salt water washing successively, anhydrous sodium sulfate drying.Be concentrated into dryly, column chromatography obtains compound 3-tolyl benzo [d] isothiazole, yield: 78%.Nuclear magnetic resonance data is consistent with bibliographical information, and HPLC purity assay is 92%.
Embodiment 2
By benzisothia oxazolone (II) (0.5mmol); PyBroP (1.2 equivalent) and triethylamine (3.0 equivalent) join 1; in 4-dioxane (4mL), room temperature under nitrogen protection (25 ℃) stirs 2 hours.Then add to dimethylin phenylo boric acid (2.0 equivalent) two (triphenylphosphine) palladium chloride (Pd (PPh
3)
2cl
2) (5% equivalent), sodium carbonate (5.0 equivalent) and water (1 milliliter).Reaction mixture is heated to 100 ℃, stirs 4 hours.Cool to room temperature, adds ethyl acetate dilution, water, saturated common salt water washing successively, anhydrous sodium sulfate drying.Be concentrated into dryly, column chromatography obtains 3-(to dimethylamine phenyl) benzo [d] isothiazole, yield: 70%.Nuclear magnetic resonance data is consistent with bibliographical information, and HPLC purity assay is 95%.
Embodiment 3
By benzisothia oxazolone (II) (0.5mmol); PyBroP (1.2 equivalent) and triethylamine (3.0 equivalent) join 1; in 4-dioxane (4mL), room temperature under nitrogen protection (25 ℃) stirs 2 hours.Then add to methoxyphenylboronic acid (2.0 equivalent) two (triphenylphosphine) palladium chloride (Pd (PPh
3)
2cl
2) (5% equivalent), sodium carbonate (5.0 equivalent) and water (1 milliliter).Reaction mixture is heated to 100 ℃, stirs 4 hours.Cool to room temperature, adds ethyl acetate dilution, water, saturated common salt water washing successively, anhydrous sodium sulfate drying.Be concentrated into dryly, column chromatography obtains 3-(p-methoxyphenyl) benzo [d] isothiazole, yield: 68%.Nuclear magnetic resonance data is consistent with bibliographical information, and HPLC purity assay is 90%.
Embodiment 4
By benzisothia oxazolone (II) (0.5mmol); PyBroP (1.2 equivalent) and triethylamine (3.0 equivalent) join 1; in 4-dioxane (4mL), room temperature under nitrogen protection (25 ℃) stirs 2 hours.Then add to ethoxycarbonyl phenylo boric acid (2.0 equivalent) two (triphenylphosphine) palladium chloride (Pd (PPh
3)
2cl
2) (5% equivalent), sodium carbonate (5.0 equivalent) and water (1 milliliter).Reaction mixture is heated to 100 ℃, stirs 4 hours.Cool to room temperature, adds ethyl acetate dilution, water, saturated common salt water washing successively, anhydrous sodium sulfate drying.Be concentrated into dryly, column chromatography obtains 3-(to carbethoxy phenyl) benzo [d] isothiazole, yield: 72%.Nuclear magnetic resonance data is consistent with bibliographical information, and HPLC purity assay is 94%.
Embodiment 5
By benzisothia oxazolone (II) (0.5mmol), PyBoP (1 equivalent) and sodium tert-butoxide (1.0 equivalent) join in tetrahydrofuran (THF) (4mL), the lower 0 ℃ of stirring of nitrogen protection 2 hours.Then add to methylphenylboronic acid (0.8 equivalent) tetrakis triphenylphosphine palladium (0.1% equivalent), cesium carbonate (1.0 equivalent) and water (1 milliliter).Reaction mixture is heated to 80 ℃, stirs 4 hours.Cool to room temperature, adds ethyl acetate dilution, water, saturated common salt water washing successively, anhydrous sodium sulfate drying.Be concentrated into dryly, column chromatography obtains compound 3-tolyl benzo [d] isothiazole, yield: 76%.Nuclear magnetic resonance data is consistent with bibliographical information, and HPLC purity assay is 93%.
Embodiment 6
By benzisothia oxazolone (II) (0.5mmol), PyBroP (2 equivalent) and diethyl propyl group ethylamine (10 equivalent) join in acetonitrile (4mL), the lower 50 ℃ of stirrings of nitrogen protection 2 hours.Then add to methylphenylboronic acid (1 equivalent) two (triphenylphosphine) palladium chloride (Pd (PPh
3)
2cl
2) (20% equivalent), salt of wormwood (3 equivalent) and water (1 milliliter).Reaction mixture is heated to 150 ℃, stirs 4 hours.Cool to room temperature, adds ethyl acetate dilution, water, saturated common salt water washing successively, anhydrous sodium sulfate drying.Be concentrated into dryly, column chromatography obtains compound 3-tolyl benzo [d] isothiazole, yield: 75%.Nuclear magnetic resonance data is consistent with bibliographical information, and HPLC purity assay is 92%.
Embodiment 7
By benzisothia oxazolone (II) (0.5mmol); PyBroP (1.5 equivalent) and diethyl propyl group ethylamine (6 equivalent) join in glycol dimethyl ether (4mL), the lower 30 ℃ of stirrings of nitrogen protection 2 hours.Then add to methylphenylboronic acid (1.2 equivalent) two (triphenylphosphine) Palladium Diacetate (1% equivalent), sodium carbonate (1 equivalent) and water (1 milliliter).Reaction mixture, at 50 ℃, stirs 10 hours.Cool to room temperature, adds ethyl acetate dilution, water, saturated common salt water washing successively, anhydrous sodium sulfate drying.Be concentrated into dryly, column chromatography obtains compound 3-tolyl benzo [d] isothiazole, yield: 71%.Nuclear magnetic resonance data is consistent with bibliographical information, and HPLC purity assay is 90%.
Embodiment 8
By benzisothia oxazolone (II) (0.5mmol); PyBroP (1.1 equivalent) and triethylamine (2.5 equivalent) join 1; in 4-dioxane (4mL), room temperature under nitrogen protection (25 ℃) stirs 2 hours.Then add to methoxyphenylboronic acid (2.0 equivalent) two (triphenylphosphine) palladium chloride [Pd (PPh
3)
2cl
2] (10% equivalent), sodium carbonate (10 equivalent) and water (1 milliliter).Reaction mixture is heated to 100 ℃, stirs 4 hours.Cool to room temperature, adds ethyl acetate dilution, water, saturated common salt water washing successively, anhydrous sodium sulfate drying.Be concentrated into dryly, column chromatography obtains 3-(p-methoxyphenyl) benzo [d] isothiazole, yield: 67%.Nuclear magnetic resonance data is consistent with bibliographical information, and HPLC purity assay is 90%.
Claims (8)
1. suc as formula a preparation method for 3-aryl benzo [d] isothiazole shown in I, it is characterized in that comprising the following step:
(1) in polar aprotic solvent, under protection of inert gas, Compound I I and microcosmic salt and alkali effect; Described microcosmic salt is tripyrrole Wan base phosphonium bromide hexafluorophosphate and/or phosphofluoric acid benzotriazole-1-base-oxygen base tripyrrole alkyl phosphorus; Described alkali is sodium tert-butoxide and/or triethylamine;
(2), under protection of inert gas, product and compound III that step (1) is obtained are carried out linked reaction;
Wherein, R
1, R
2, R
3, R
4and R
5alone be C
1～C
3alkyl, C
1～C
3alkoxyl group, by 1 or 2 C
1～C
4amino, amino, hydroxyl, nitro or connection C that alkyl replaces
1～C
3the carbonyl of alkoxyl group.
2. suc as formula a preparation method for 3-aryl benzo [d] isothiazole shown in I, it is characterized in that comprising the following step:
(1) in polar aprotic solvent, under protection of inert gas, Compound I I and microcosmic salt and alkali effect; Described microcosmic salt is tripyrrole Wan base phosphonium bromide hexafluorophosphate and/or phosphofluoric acid benzotriazole-1-base-oxygen base tripyrrole alkyl phosphorus; Described alkali is sodium tert-butoxide and/or triethylamine;
(2), under protection of inert gas, product and compound III that step (1) is obtained are carried out linked reaction;
Described compound III is to methylphenylboronic acid, between methylphenylboronic acid, to methoxyphenylboronic acid, meta-methoxy phenylo boric acid, to dimethylin phenylo boric acid, between dimethylin phenylo boric acid, to diethylin phenylo boric acid, between diethylin phenylo boric acid, to methylamino phenylo boric acid, between methylamino phenylo boric acid, to ethylamino-phenylo boric acid, between ethylamino-phenylo boric acid, p-aminophenyl boric acid, m-aminophenyl boric acid, para hydroxybenzene boric acid, between hydroxybenzene boric acid, p-nitrophenyl boric acid, m-nitro boric acid, or to ethoxycarbonyl phenylo boric acid.
3. preparation method as claimed in claim 1 or 2, is characterized in that: the mol ratio of described Compound I I and microcosmic salt, alkali is 1:1:1 ~ 1:2:10; The mol ratio of described compound III and Compound I I is 0.8:1 ~ 2: 1.
4. preparation method as claimed in claim 3, is characterized in that: the mol ratio of described Compound I I and microcosmic salt, alkali is 1:1.1:2.5 ~ 1:1.5:6; The mol ratio of described compound III and Compound I I is 1:1 ~ 1.2: 1.
5. preparation method as claimed in claim 1 or 2, is characterized in that: described polar aprotic solvent is one or more in Isosorbide-5-Nitrae-dioxane, tetrahydrofuran (THF), acetonitrile and glycol dimethyl ether; In described step (1), the temperature of effect is 0 ~ 50 ℃; Till the time acting in described step (1) is complete with detection effect.
6. preparation method as claimed in claim 1 or 2; it is characterized in that: the method for the linked reaction in described step (2) comprises the following step: in solvent, under protection of inert gas, under the effect of palladium catalyst and alkali; step (1) products therefrom and compound III are reacted.
7. preparation method as claimed in claim 6, is characterized in that: described palladium catalyst is one or more in tetrakis triphenylphosphine palladium, two (triphenylphosphine) Palladium Diacetate and two (triphenylphosphine) palladium chloride; The consumption of described palladium catalyst is 0.1 ~ 20 mol% of Compound I I; Described alkali is one or more in sodium carbonate, salt of wormwood and cesium carbonate; The consumption of described alkali is 1 ~ 10 equivalent of Compound I I; Solvent in described step (2) is the solvent in step (1), or is the mixed solvent of organic solvent and water; The temperature of described reaction is 50 ~ 150 ℃; Till the time of reaction is complete with detection reaction.
8. preparation method as claimed in claim 7, is characterized in that: the consumption of described palladium catalyst is 1 ~ 10 mol % of Compound I I; The consumption of described alkali is 3 ~ 5 equivalents of Compound I I; Described organic solvent is Isosorbide-5-Nitrae-dioxane; The temperature of described reaction is 80 ~ 110 ℃.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4590196A (en) * | 1984-08-23 | 1986-05-20 | Bristol-Myers Company | Analgesic 1,2-benzisothiazol-3-ylpiperazine derivatives |
| CN1246114A (en) * | 1996-12-20 | 2000-03-01 | 曾尼卡有限公司 | Process for making benzisothiazolin-3-ones |
-
2009
- 2009-10-16 CN CN200910197259.9A patent/CN102040563B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4590196A (en) * | 1984-08-23 | 1986-05-20 | Bristol-Myers Company | Analgesic 1,2-benzisothiazol-3-ylpiperazine derivatives |
| CN1246114A (en) * | 1996-12-20 | 2000-03-01 | 曾尼卡有限公司 | Process for making benzisothiazolin-3-ones |
Non-Patent Citations (2)
| Title |
|---|
| Horst Boshagen et al..Uber die Umsetzung von 3-Chlor-l,2-benzisothiazolium-chloriden mit N-Mono- und N,N-Dialkylanilinen.《Chem. Ber.》.1979,第112卷3286-3292. |
| Uber die Umsetzung von 3-Chlor-l,2-benzisothiazolium-chloriden mit N-Mono- und N,N-Dialkylanilinen;Horst Boshagen et al.;《Chem. Ber.》;19791231;第112卷;3286-3292 * |
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