CN104945313A - Preparation method of 2-methyl-3-bromopyridine - Google Patents
Preparation method of 2-methyl-3-bromopyridine Download PDFInfo
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- CN104945313A CN104945313A CN201510343444.XA CN201510343444A CN104945313A CN 104945313 A CN104945313 A CN 104945313A CN 201510343444 A CN201510343444 A CN 201510343444A CN 104945313 A CN104945313 A CN 104945313A
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- methyl
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- bromopyridine
- nitropyridine
- aminopyridine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
Abstract
The invention belongs to the field of organic synthesis and particularly relates to a preparation method of 2-methyl-3-bromopyridine. The preparation method includes the following steps that 1, diethyl malonate reacts with alkali metal to generate salt, then a methylbenzene solution of 2-chlorine-3-nitropyridine is added dropwise to be conducted a condensation reaction, and the 2-methyl-3-nitropyridine is obtained through decarboxylation under an acidic condition; 2, under the catalysis of Pd/C, methanol serves as a solvent, a hydrogenation reduction and suction filtration are conducted on the 2-methyl-3-nitropyridine, filtered liquid is condensed, and 2-methyl-3-aminopyridine is obtained; 3, the 2-methyl-3-aminopyridine reacts with acid to generate salt, the cooling is conducted to enable the temperature to be in -10 DEG C-0 DEG C, bromine is added dropwise, after the addition, then a sodium nitrite solution is added dropwise, after addition, pH of the solution is adjusted to be alkaline, then extracting, drying and concentration are conducted, and the 2-methyl-3-bromopyridine is obtained. The preparation method of the 2-methyl-3-bromopyridine has the advantages that the reaction condition is moderate, the operation is easy, the post-processing is simple, enlarged production is easy, and the preparation method is very suitable for industrial production; the catalysis effect is good, and the reaction yield ratio is high; the price of the raw material is low, and the production cost is low.
Description
Technical field
The invention belongs to organic synthesis field, be specifically related to a kind of preparation method of 2-methyl-3-bromopyridine.
Background technology
2-methyl-3-bromopyridine is a kind of important intermediate, is mainly used as medicine intermediate, organic synthesis intermediate, organic solvent, also for the production of dyestuff, spices and agricultural chemicals etc.
The principal synthetic routes of current 2-methyl-3-bromopyridine is for raw material with 2-picoline, with bromine reaction under the catalysis of Lewis acid, its product is the mixture of 3-bromine-2-methylpyridine and 5-bromine-2-methylpyridine, and 3-bromine-2-methylpyridine is separated with 5-bromine-2-methylpyridine is more difficult.The shortcoming of the method is: the consumption of aluminum chloride is large, and catalytic effect is poor; Bromine can carry out bromo in multiple position, and by product is many, and product yield is low; The boiling point of products therefrom 3-bromine-2-methylpyridine and the boiling point of 5-bromine-2-methylpyridine lower, segregation ratio is more difficult, needs special rectifier unit, suitability for industrialized production difficulty.
Summary of the invention
The object of the invention is to overcome the technical deficiency that in prior art, by product is many, productive rate is low, the preparation that a kind of productive rate is high, be applicable to the 2-methyl-3-bromopyridine of suitability for industrialized production is provided.
For solving the problems of the technologies described above, the technical scheme that the present invention takes is as follows:
A preparation method for 2-methyl-3-bromopyridine, comprises the steps:
(1) diethyl malonate and basic metal reaction generate salt, then the toluene solution dripping the chloro-3-nitropyridine of 2-carries out condensation reaction, and decarboxylation obtains 2-Methyl-3-nitropyridine in acid condition afterwards;
(2) 2-Methyl-3-nitropyridine is under Pd/C catalysis, methanol as solvent, hydrogenating reduction, suction filtration, and filtrate concentrates, and obtains 2-methyl-3-aminopyridine;
(3) 2-methyl-3-aminopyridine first generates salt with acid, is cooled to-10 DEG C-0 DEG C, drips bromine, drips off dropping sodium nitrite in aqueous solution, dropwises regulator solution pH for alkalescence, then carry out extracting, dry, concentrate, obtain 2-methyl-3-bromopyridine.
Further, the mol ratio of described diethyl malonate, basic metal, the chloro-3-nitropyridine of 2-is 5-6:1.1-1.3:1.
Further, described basic metal is selected from: the one in sodium Metal 99.5, potassium metal.
Further, in described step (2), hydrogenating reduction carries out in autoclave, and reduction temperature is 20-40 DEG C, reduction pressure position 0.5MPa.
Further, the suction filtration step in described step (2) adopts diatomite drainage, a small amount of washed with dichloromethane of filter cake.
Reaction equation of the present invention is:
Employing the invention has the beneficial effects as follows: reaction conditions is gentle, easy handling, and aftertreatment is simple, easily amplifies production, is very applicable to suitability for industrialized production; Excellent catalytic effect, yield is high; Cost of material is cheap, and production cost is low.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.These embodiments are illustrative completely, and they are only used for being specifically described the present invention, should not be construed as limitation of the present invention.
Embodiment 1
(1) preparation of 2-Methyl-3-nitropyridine: the mixture oil bath of diethyl malonate (80ml, 0.5mol) and sodium (2.53g, 0.11mol) is warming up to 90 DEG C, stirs 1h, after being warming up to 120 DEG C of stirring 45min, be cooled to room temperature.Drip the toluene solution of the chloro-3-nitropyridine (15.6g, 0.1mol) of 2-, dropwise, reaction solution is warming up to 110 DEG C of reaction 1.5h, is cooled to stirring at room temperature 15h.Remove solvent under reduced pressure, add 6N hydrochloric acid (100ml), after temperature rising reflux 3.5h, be cooled to room temperature.Regulate pH to be alkalescence with saturated sodium carbonate solution, be extracted with ethyl acetate, be associated with base phase, anhydrous sodium sulfate drying, suction filtration concentrates, and obtain 2-Methyl-3-nitropyridine, molar yield is 92%.
(2) preparation of 2-methyl-3-aminopyridine: be dissolved in methanol solution by 2-Methyl-3-nitropyridine (13.8g, 0.1mol), adds 10%Pd/C (0.1g), the reaction of this step is carried out in autoclave, logical hydrogen is 0.5MPa to pressure, is warming up to 20 DEG C, reaction 15h.Thin-layer chromatography monitoring is to reacting completely, and be cooled to room temperature, diatomite drainage, filter cake washed with dichloromethane, can prevent Pd/C from catching fire like this, filtrate concentrates the 2-methyl-3-aminopyridine of concentrating under reduced pressure, and molar yield is 94%.
(3) preparation of 2-methyl-3-bromopyridine: under cryosel bath cooling, by 2-methyl-3-aminopyridine (10.8g, 0.1mol) join 48%HBr(46ml, 0.4mol), add, be cooled to-5 DEG C, slow dropping bromine (15ml, 0.3mol), 30-35min adds, then below 0 DEG C, drip the sodium nitrite solution 42g of 40%, add in 1-1.1h, add and continue to stir 30min below 0 DEG C, then below 20 DEG C, slowly add the sodium hydroxide solution of 50%, reaction solution is extracted with ethyl acetate, there is basic unit's anhydrous sodium sulfate drying, suction filtration, concentrated, 2-methyl-3-the bromopyridine of evaporated under reduced pressure, molar yield is 95%.
Embodiment 2
(1) preparation of 2-Methyl-3-nitropyridine: the mixture oil bath of diethyl malonate (80ml, 0.5mol) and sodium (2.76g, 0.12mol) is warming up to 90 DEG C, stirs 1h, after being warming up to 120 DEG C of stirring 45min, be cooled to room temperature.Drip the toluene solution of the chloro-3-nitropyridine (15.6g, 0.1mol) of 2-, dropwise, reaction solution is warming up to 110 DEG C of reaction 1.5h, is cooled to stirring at room temperature 15h.Remove solvent under reduced pressure, add 6N hydrochloric acid (100ml), after temperature rising reflux 3.5h, be cooled to room temperature.Regulate pH to be alkalescence with saturated sodium carbonate solution, be extracted with ethyl acetate, be associated with base phase, anhydrous sodium sulfate drying, suction filtration concentrates, and obtain 2-Methyl-3-nitropyridine, molar yield is 95%.
(2) preparation of 2-methyl-3-aminopyridine: be dissolved in methanol solution by 2-Methyl-3-nitropyridine (13.8g, 0.1mol), adds 10%Pd/C (0.1g), the reaction of this step is carried out in autoclave, logical hydrogen is 0.5MPa to pressure, is warming up to 30 DEG C, reaction 15h.Thin-layer chromatography monitoring is to reacting completely, and be cooled to room temperature, diatomite drainage, filter cake washed with dichloromethane, can prevent Pd/C from catching fire like this, filtrate concentrates the 2-methyl-3-aminopyridine of concentrating under reduced pressure, and molar yield is 97%.
(3) preparation of 2-methyl-3-bromopyridine: step is with embodiment 1.
Embodiment 3
(1) preparation of 2-Methyl-3-nitropyridine: the mixture oil bath of diethyl malonate (80ml, 0.5mol) and sodium (2.99g, 0.13mol) is warming up to 90 DEG C, stirs 1h, after being warming up to 120 DEG C of stirring 45min, be cooled to room temperature.Drip the toluene solution of the chloro-3-nitropyridine (15.6g, 0.1mol) of 2-, dropwise, reaction solution is warming up to 110 DEG C of reaction 1.5h, is cooled to stirring at room temperature 15h.Remove solvent under reduced pressure, add 6N hydrochloric acid (100ml), after temperature rising reflux 3.5h, be cooled to room temperature.Regulate pH to be alkalescence with saturated sodium carbonate solution, be extracted with ethyl acetate, be associated with base phase, anhydrous sodium sulfate drying, suction filtration concentrates, and obtain 2-Methyl-3-nitropyridine, molar yield is 95%.
(2) preparation of 2-methyl-3-aminopyridine: be dissolved in methanol solution by 2-Methyl-3-nitropyridine (13.8g, 0.1mol), adds 10%Pd/C (0.1g), the reaction of this step is carried out in autoclave, logical hydrogen is 0.5MPa to pressure, is warming up to 40 DEG C, reaction 15h.Thin-layer chromatography monitoring is to reacting completely, and be cooled to room temperature, diatomite drainage, filter cake washed with dichloromethane, can prevent Pd/C from catching fire like this, filtrate concentrates the 2-methyl-3-aminopyridine of concentrating under reduced pressure, and molar yield is 95%.
(3) preparation of 2-methyl-3-bromopyridine: step is with embodiment 1.
Claims (5)
1. a preparation method for 2-methyl-3-bromopyridine, is characterized in that comprising the steps:
(1) diethyl malonate and basic metal reaction generate salt, then the toluene solution dripping the chloro-3-nitropyridine of 2-carries out condensation reaction, and decarboxylation obtains 2-Methyl-3-nitropyridine in acid condition afterwards;
(2) 2-Methyl-3-nitropyridine is under Pd/C catalysis, methanol as solvent, hydrogenating reduction, suction filtration, and filtrate concentrates, and obtains 2-methyl-3-aminopyridine;
(3) 2-methyl-3-aminopyridine first generates salt with acid, is cooled to-10 DEG C-0 DEG C, drips bromine, drips off dropping sodium nitrite in aqueous solution, dropwises regulator solution pH for alkalescence, then carry out extracting, dry, concentrate, obtain 2-methyl-3-bromopyridine.
2. the preparation method of a kind of 2-methyl-3-bromopyridine according to claim 1, is characterized in that the mol ratio of the chloro-3-nitropyridine of described diethyl malonate, basic metal, 2-is 5-6:1.1-1.3:1.
3. the preparation method of a kind of 2-methyl-3-bromopyridine according to claim 1, is characterized in that described basic metal is selected from: the one in sodium Metal 99.5, potassium metal.
4. the preparation method of a kind of 2-methyl-3-bromopyridine according to claim 1 and 2, it is characterized in that in described step (2), hydrogenating reduction carries out in autoclave, reduction temperature is 20-40 DEG C, reduction pressure position 0.5MPa.
5. the preparation method of a kind of 2-methyl-3-bromopyridine according to claim 3, is characterized in that the suction filtration step in described step (2) adopts diatomite drainage, a small amount of washed with dichloromethane of filter cake.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198802A (en) * | 2015-11-03 | 2015-12-30 | 江苏梦得电镀化学品有限公司 | Preparation method of 2-methyl-3-bromopyridine |
| CN106397310A (en) * | 2016-09-09 | 2017-02-15 | 安徽星宇化工有限公司 | 3-fluoropyridine preparation method high in yield and content |
| CN107056692A (en) * | 2017-06-25 | 2017-08-18 | 刘瑞海 | A kind of synthetic method of the bromopyridine of 2,6 dimethyl 3 |
| CN107082759A (en) * | 2017-06-25 | 2017-08-22 | 刘瑞海 | A kind of synthetic method of the bromopyridine of 2,3,4 trimethyl 6 |
| CN107089939A (en) * | 2017-06-25 | 2017-08-25 | 刘瑞海 | A kind of synthetic method of the bromopyridine of 2,5 dimethyl 3 |
| CN107162964A (en) * | 2017-06-25 | 2017-09-15 | 刘瑞海 | A kind of synthetic method of the bromopyridine of 2,6 dimethyl 4 |
| CN107162963A (en) * | 2017-06-25 | 2017-09-15 | 刘瑞海 | A kind of synthetic method of the picoline of 3 bromine 5 |
| CN107311920A (en) * | 2017-06-25 | 2017-11-03 | 刘瑞海 | A kind of synthetic method of the bromopyridine of 2,3,5 trimethyl 6 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198802A (en) * | 2015-11-03 | 2015-12-30 | 江苏梦得电镀化学品有限公司 | Preparation method of 2-methyl-3-bromopyridine |
| CN106397310A (en) * | 2016-09-09 | 2017-02-15 | 安徽星宇化工有限公司 | 3-fluoropyridine preparation method high in yield and content |
| CN106397310B (en) * | 2016-09-09 | 2019-04-12 | 安徽星宇化工有限公司 | A kind of preparation method of 3- fluorine pyridine |
| CN107056692A (en) * | 2017-06-25 | 2017-08-18 | 刘瑞海 | A kind of synthetic method of the bromopyridine of 2,6 dimethyl 3 |
| CN107082759A (en) * | 2017-06-25 | 2017-08-22 | 刘瑞海 | A kind of synthetic method of the bromopyridine of 2,3,4 trimethyl 6 |
| CN107089939A (en) * | 2017-06-25 | 2017-08-25 | 刘瑞海 | A kind of synthetic method of the bromopyridine of 2,5 dimethyl 3 |
| CN107162964A (en) * | 2017-06-25 | 2017-09-15 | 刘瑞海 | A kind of synthetic method of the bromopyridine of 2,6 dimethyl 4 |
| CN107162963A (en) * | 2017-06-25 | 2017-09-15 | 刘瑞海 | A kind of synthetic method of the picoline of 3 bromine 5 |
| CN107311920A (en) * | 2017-06-25 | 2017-11-03 | 刘瑞海 | A kind of synthetic method of the bromopyridine of 2,3,5 trimethyl 6 |
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Application publication date: 20150930 |