CN101774981A - Method for preparation of 6-methoxybenzothiazole - Google Patents
Method for preparation of 6-methoxybenzothiazole Download PDFInfo
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- CN101774981A CN101774981A CN201010100973A CN201010100973A CN101774981A CN 101774981 A CN101774981 A CN 101774981A CN 201010100973 A CN201010100973 A CN 201010100973A CN 201010100973 A CN201010100973 A CN 201010100973A CN 101774981 A CN101774981 A CN 101774981A
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- methoxyl group
- group benzo
- benzo thiazole
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- Thiazole And Isothizaole Compounds (AREA)
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Abstract
The invention discloses a method for the preparation of 6-methoxybenzothiazole, comprising the steps: evenly mixing 2-amino-6-methoxybenzothiazole, 20-50wt% of hypophosphorous acid solution and cuprous oxide as much as the amount of catalyst, then slowly, proportionally and dropwise adding 25-35wt% of sodium nitrite solution for reacting for 2 to 6 hours at the temperature from -10 to 15 DEG C; diluting and then neutralizing the resultant reaction liquid with saturated sodium carbonate solution, and implementing the operations including extraction, combination of organic phase, washing, drying, and concentrated crystallization to result in 6-methoxybenzothiazole. The method according to the invention has the advantages of mild reaction conditions, easy control, simple technology and great easiness for large-scale production.
Description
Technical field
The present invention relates to a kind of preparation method of 6-methoxyl group benzo thiazole, belong to organic chemistry filed.
Background technology
Benzothiazole compound has unique physiology and biological activity, has a wide range of applications in agricultural chemicals, medicine and other fields.Benzothiazole compound is the important source material of making white dyes, fluorescence dye, also has consequence in highly sensitive developer synthetic.
At present, bibliographical information 6-methoxyl group benzo thiazole synthetic mainly contains two kinds of methods: the one, with the reduction and getting after diazotization in sulphuric acid soln or phosphoric acid solution of 2-amino-6-methoxyl group benzo thiazole; The 2nd, in organic solvent, carry out the diazotization post-heating with 2-amino-6-methoxyl group benzo thiazole and decompose and get with nitrous acid ester.The main problem of these methods is condition harshness, reagent costliness, low, the complex process of yield, is difficult to scale operation.Therefore seek that a kind of technology is simple, the preparation method of the 6-methoxyl group benzo thiazole that can amplify production is significant.
Summary of the invention
The objective of the invention is to remedy above-mentioned the deficiencies in the prior art, a kind of preparation method of 6-methoxyl group benzo thiazole is provided, this method reaction conditions gentleness, more easy to control, technology is simple, helps scale operation.
The technical scheme that realizes the object of the invention is: a kind of preparation method of 6-methoxyl group benzo thiazole, this method is: with 2-amino-6-methoxyl group benzo thiazole, the Hypophosporous Acid, 50 solution of 20～50wt% and the Red copper oxide mixing of catalytic amount, under-10～15 ℃, agitation condition, in this mixture, slowly drip 25～35wt% sodium nitrite solution then, in-10～15 ℃ of reactions 2～6 hours, wherein, the mol ratio of 2-amino-6-methoxyl group benzo thiazole, Hypophosporous Acid, 50 and Sodium Nitrite is 1: 6～26: 1～1.1; With gained reaction solution dilution, with in the saturated sodium carbonate solution and after, extraction, merge organic phase, washing, drying, condensing crystal promptly obtains 6-methoxyl group benzo thiazole.
Be with 1～2 times of gained reaction solution dilution among the above-mentioned preparation method.
Be to adopt ethyl acetate, ether, methylene dichloride or toluene to extract among the above-mentioned preparation method.
Adopt the saturated common salt water washing after merging organic phase among the above-mentioned preparation method.
Be to adopt sal epsom or sodium sulfate that the organic phase after washing is carried out drying among the above-mentioned preparation method.
The inventive method adopts the single stage method reaction, 2-amino-6-methoxyl group benzo thiazole and Hypophosporous Acid, 50 salify and excessive Hypophosporous Acid, 50 as the reductive agent of diazonium salt, add catalyzer simultaneously, drip sodium nitrite solution again, the limit is carried out the diazotization reaction limit and is carried out the hydrogen replacement(metathesis)reaction, and step simplifies the operation; Use catalyst oxidation cuprous simultaneously, the hydrogen replacement(metathesis)reaction is carried out simultaneously with diazotization reaction at a lower temperature, can reduce the hydrolysis reaction in the temperature-rise period, improved selectivity; Entire reaction processing condition gentleness, simple to operate, yield is higher, for industrial production provides further technical support.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment, but protection scope of the present invention is not limited to following examples.
Embodiment 1
In the 500mL there-necked flask, add 2-amino-6-methoxyl group benzo thiazole 10g (55.5mmol), 30wt% Hypophosporous Acid, 50 solution 160mL (containing Hypophosporous Acid, 50 873mmol), Red copper oxide 0.5g (3.5mmol), drip the 10mL sodium nitrite in aqueous solution after stirring is cooled to 5 ℃ and (contain Sodium Nitrite 4g, 58mmol), in 5 ℃ of reactions 2 hours, then with 2 times of gained reaction solution dilutions, neutralize with saturated sodium carbonate solution, ethyl acetate extraction, use the saturated common salt water washing after merging organic phase, dried over mgso, condensing crystal get the off-white color crystal.Adopt MS, HNMR that product is characterized, confirm that gained off-white color crystal is a 6-methoxyl group benzo thiazole.Productive rate is 79%, and purity is 98.5%.
MS?m/z(％)：165(M
+，100)，150(53)，122(32)。
1H-NMRδ：3.90(3H，s，OCH
3)，7.12(1H，d，C
5-H)，7.41(1H，d，C
7-H)，8.00(1H，d，C
4-H)，8.82(1H，s，C
2-H)。
Embodiment 2
In the 500mL there-necked flask, add 2-amino-6-methoxyl group benzo thiazole 10g (55.5mmol), 30wt% Hypophosporous Acid, 50 solution 80mL (containing Hypophosporous Acid, 50 437mmol), Red copper oxide (adopts the Red copper oxide of catalytic amount to get final product, consumption is 0.5g in the present embodiment, 3.5mmol), drip the 10mL sodium nitrite in aqueous solution after stirring is cooled to 0 ℃ and (contain Sodium Nitrite 4g, 58mmol), in 0 ℃ of reaction 3 hours, then with 1 times of gained reaction solution dilution, with saturated sodium carbonate solution neutralization, extracted with diethyl ether, use the saturated common salt water washing after the merging organic phase, dried over mgso, condensing crystal get the off-white color crystal.By the method identical product is characterized, confirm that such white crystal is a 6-methoxyl group benzo thiazole with embodiment 1.Productive rate is 51%, and purity is 98.5%.
Embodiment 3
In the 500mL there-necked flask, add 2-amino-6-methoxyl group benzo thiazole 10g (55.5mmol), 20wt% Hypophosporous Acid, 50 solution 160mL (containing Hypophosporous Acid, 50 558mmol), Red copper oxide 0.5g (3.5mmol), drip the 8mL sodium nitrite in aqueous solution after stirring is cooled to 15 ℃ and (contain Sodium Nitrite 4g, 58mmol), in 15 ℃ of reactions 2 hours, then with 1.5 times of gained reaction solution dilutions, neutralize with saturated sodium carbonate solution, dichloromethane extraction, use the saturated common salt water washing after merging organic phase, dried over sodium sulfate, condensing crystal get the off-white color crystal.By the method identical product is characterized, confirm that such white crystal is a 6-methoxyl group benzo thiazole with embodiment 1.Productive rate is 58%, and purity is 98.5%.
Embodiment 4
In the 500mL there-necked flask, add 2-amino-6-methoxyl group benzo thiazole 10g (55.5mmol), 50wt% Hypophosporous Acid, 50 solution 150mL (containing Hypophosporous Acid, 50 1.44mol), Red copper oxide 0.5g (3.5mmol), drip the 10mL sodium nitrite in aqueous solution after stirring is cooled to-8 ℃ and (contain Sodium Nitrite 4g, 58mmol), in-8 ℃ of reactions 5 hours, then with 2 times of gained reaction solution dilutions, neutralize with saturated sodium carbonate solution, the toluene extraction, use the saturated common salt water washing after merging organic phase, dried over mgso, condensing crystal get the off-white color crystal and are 6-methoxyl group benzo thiazole.Productive rate is 65%, and purity is 98.5%.
Claims (5)
1. the preparation method of a 6-methoxyl group benzo thiazole, it is characterized in that: with 2-amino-6-methoxyl group benzo thiazole, the Hypophosporous Acid, 50 solution of 20～50wt% and the Red copper oxide mixing of catalytic amount, under-10～15 ℃, agitation condition, in this mixture, slowly drip 25～35wt% sodium nitrite solution then, in-10～15 ℃ of reactions 2～6 hours, wherein, the mol ratio of 2-amino-6-methoxyl group benzo thiazole, Hypophosporous Acid, 50 and Sodium Nitrite is 1: 6～26: 1～1.1; With gained reaction solution dilution, with in the saturated sodium carbonate solution and after, extraction, merge organic phase, washing, drying, condensing crystal promptly obtains 6-methoxyl group benzo thiazole.
2. the preparation method of 6-methoxyl group benzo thiazole according to claim 1 is characterized in that: with 1～2 times of gained reaction solution dilution.
3. the preparation method of 6-methoxyl group benzo thiazole according to claim 1 is characterized in that: adopt ethyl acetate, ether, methylene dichloride or toluene to extract.
4. the preparation method of 6-methoxyl group benzo thiazole according to claim 1 is characterized in that: adopt the saturated common salt water washing after merging organic phase.
5. the preparation method of 6-methoxyl group benzo thiazole according to claim 1 is characterized in that: the organic phase after adopting sal epsom or sodium sulfate to washing is carried out drying.
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| CN201010100973A CN101774981A (en) | 2010-01-22 | 2010-01-22 | Method for preparation of 6-methoxybenzothiazole |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485620A (en) * | 2018-12-26 | 2019-03-19 | 安徽工大化工科技有限公司 | A kind of preparation method of 2- methoxyl group -6- methoxybenzothiazole |
-
2010
- 2010-01-22 CN CN201010100973A patent/CN101774981A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485620A (en) * | 2018-12-26 | 2019-03-19 | 安徽工大化工科技有限公司 | A kind of preparation method of 2- methoxyl group -6- methoxybenzothiazole |
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Open date: 20100714 |