CN107311920A - A kind of synthetic method of the bromopyridine of 2,3,5 trimethyl 6 - Google Patents
A kind of synthetic method of the bromopyridine of 2,3,5 trimethyl 6 Download PDFInfo
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- CN107311920A CN107311920A CN201710497613.4A CN201710497613A CN107311920A CN 107311920 A CN107311920 A CN 107311920A CN 201710497613 A CN201710497613 A CN 201710497613A CN 107311920 A CN107311920 A CN 107311920A
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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 present invention relates to organic chemistry filed, particularly a kind of synthetic method of the bromopyridine of 2,3,5 trimethyl 6 comprises the following steps：Diethyl malonate and alkali metal reaction generation salt, then the toluene solution progress condensation reaction of the chloropyridine of 2,3 dimethyl, 6 nitro 5 is added dropwise, decarboxylation obtains the nitropyridine of 2,3,5 trimethyl 6 in acid condition afterwards；The nitropyridine of 2,3,5 trimethyl 6 is under Pd/C catalysis, methanol as solvent, hydrogenating reduction, suction filtration, filtrate concentration, obtains the aminopyridine of 2,3,5 trimethyl 6；The aminopyridine of 2,3,5 trimethyl 6 first generates salt with acid, is cooled to 9 DEG C 4 DEG C, and bromine is added dropwise, and drips off dropwise addition sodium nitrite in aqueous solution, completion of dropping regulation pH value of solution is alkalescence, then is extracted, dried, concentrated, and obtains the bromopyridine of 2,3,5 trimethyl 6.The beneficial effect of the inventive method is：Reaction condition is gentle, high income, and raw material is easy to get, and cost is relatively low, and process route is short, with industrial prospect.
Description
Technical field
The present invention relates to organic chemistry filed, particularly a kind of synthetic method of 2,3,5- trimethyl -6- bromopyridines.
Background technology
Pyridine and its derivatives are widely distributed in nature.All contain in the structure of many plant components such as alkaloid
Pyridine cycle compound, they are the bases for producing many important compounds, are medicine, agricultural chemicals, dyestuff, surfactant, rubber
Indispensable raw material in the production such as auxiliary agent, feed addictive, food additives, adhesive.2,3,5- trimethyl -6- bromopyridines
It is the important intermediate of organic synthesis, is mainly used in medicine intermediate, organic synthesis, organic solvent can also be applied to dyestuff life
In terms of production, pesticide producing and spices.At present, there is yield in 2 reported, the synthetic method of 3,5- trimethyl -6- bromopyridines
It is low, the shortcomings of process route is long.
The content of the invention
The present invention needs to be to provide the problem of solution a kind of high income, process route rationally, suitable for the 2 of industrialized production,
The synthetic method of 3,5- trimethyl -6- bromopyridines.
To solve above-mentioned technical problem, the synthetic method of trimethyl -6- bromopyridines of one kind 2,3,5- of the invention, including
Following steps：
Diethyl malonate and alkali metal reaction generation salt, then be added dropwise the chloropyridine of 2,3 dimethyl -6- nitros -5 toluene it is molten
Liquid carries out condensation reaction, and decarboxylation obtains 2,3,5- trimethyl -6- nitropyridines in acid condition afterwards；
2,3,5- trimethyl -6- nitropyridines are under Pd/C catalysis, and methanol as solvent, hydrogenating reduction, suction filtration, filtrate is dense
Contracting, obtains 2,3,5- trimethyl -6- aminopyridines；
2,3,5- trimethyl -6- aminopyridines first generate salt with acid, are cooled to -9 DEG C -4 DEG C, and bromine is added dropwise, dropwise addition is dripped off
Sodium nitrite in aqueous solution, completion of dropping regulation pH value of solution is alkalescence, then is extracted, dried, concentrated, obtain 2,3,5- trimethyls-
6- bromopyridines.
Further, the diethyl malonate, alkali metal, 2, the mol ratio of the chloropyridine of 3 dimethyl -6- nitros -5 is
4.2-5.3:1.4-1.7：1.2.
Further, the alkali metal is selected from one kind between metallic sodium, metallic potassium.
The beneficial effect of the inventive method is：Reaction condition is gentle, high income, and raw material is easy to get, and cost is relatively low, technique road
Line is short, with industrial prospect.
Embodiment
Embodiment one：
Diethyl malonate and metallic sodium reaction generation salt, then be added dropwise the chloropyridine of 2,3 dimethyl -6- nitros -5 toluene it is molten
Liquid carries out condensation reaction, and decarboxylation obtains 2,3,5- trimethyl -6- nitropyridines in acid condition afterwards；Wherein malonic acid diethyl
Ester, metallic sodium, 2, the mol ratio of the chloropyridine of 3 dimethyl -6- nitros -5 is 4.2:1.4： 1.2.
2,3,5- trimethyl -6- nitropyridines are under Pd/C catalysis, and methanol as solvent, hydrogenating reduction, suction filtration, filtrate is dense
Contracting, obtains 2,3,5- trimethyl -6- aminopyridines；
2,3,5- trimethyl -6- aminopyridines first generate salt with acid, are cooled to -9 DEG C, and bromine is added dropwise, dropwise addition nitrous is dripped off
Acid sodium aqueous solution, completion of dropping regulation pH value of solution is alkalescence, then is extracted, dried, concentrated, and obtains 2,3,5- trimethyl -6- bromines
Pyridine.
Embodiment two：
Diethyl malonate and metal nak response generation salt, then be added dropwise the chloropyridine of 2,3 dimethyl -6- nitros -5 toluene it is molten
Liquid carries out condensation reaction, and decarboxylation obtains 2,3,5- trimethyl -6- nitropyridines in acid condition afterwards；Wherein malonic acid diethyl
Ester, metallic potassium, 2, the mol ratio of the chloropyridine of 3 dimethyl -6- nitros -5 is 5.3:1.7：1.2.
2,3,5- trimethyl -6- nitropyridines are under Pd/C catalysis, and methanol as solvent, hydrogenating reduction, suction filtration, filtrate is dense
Contracting, obtains 2,3,5- trimethyl -6- aminopyridines；
2,3,5- trimethyl -6- aminopyridines first generate salt with acid, are cooled to 4 DEG C, and bromine is added dropwise, dropwise addition nitrous acid is dripped off
Sodium water solution, completion of dropping regulation pH value of solution is alkalescence, then is extracted, dried, concentrated, and obtains 2,3,5- trimethyl -6- bromine pyrroles
Pyridine.
Embodiment three：
Diethyl malonate and metallic sodium reaction generation salt, then be added dropwise the chloropyridine of 2,3 dimethyl -6- nitros -5 toluene it is molten
Liquid carries out condensation reaction, and decarboxylation obtains 2,3,5- trimethyl -6- nitropyridines in acid condition afterwards；Wherein malonic acid diethyl
Ester, metallic sodium, 2, the mol ratio of the chloropyridine of 3 dimethyl -6- nitros -5 is 4.8:1.5： 1.2.
2,3,5- trimethyl -6- nitropyridines are under Pd/C catalysis, and methanol as solvent, hydrogenating reduction, suction filtration, filtrate is dense
Contracting, obtains 2,3,5- trimethyl -6- aminopyridines；
2,3,5- trimethyl -6- aminopyridines first generate salt with acid, are cooled to -2 DEG C, and bromine is added dropwise, dropwise addition nitrous is dripped off
Acid sodium aqueous solution, completion of dropping regulation pH value of solution is alkalescence, then is extracted, dried, concentrated, and obtains 2,3,5- trimethyl -6- bromines
Pyridine.
Claims (3)
1. one kind 2,3, the synthetic method of 5- trimethyl -6- bromopyridines, it is characterised in that comprise the following steps：
Diethyl malonate and alkali metal reaction generation salt, then the toluene solution of the chloropyridine of 2,3 dimethyl -6- nitros -5 is added dropwise enters
Row condensation reaction, decarboxylation obtains 2,3,5- trimethyl -6- nitropyridines in acid condition afterwards；
2,3,5- trimethyl -6- nitropyridines are under Pd/C catalysis, methanol as solvent, hydrogenating reduction, suction filtration, filtrate concentration, obtain
2,3,5- trimethyl -6- aminopyridines；
2,3,5- trimethyl -6- aminopyridines first generate salt with acid, are cooled to -9 DEG C -4 DEG C, and bromine is added dropwise, dropwise addition nitrous is dripped off
Acid sodium aqueous solution, completion of dropping regulation pH value of solution is alkalescence, then is extracted, dried, concentrated, and obtains 2,3,5- trimethyl -6- bromines
Pyridine.
2. according to the synthetic method of the trimethyl -6- bromopyridines of one kind 2,3,5- described in claim 1, it is characterised in that：It is described
Diethyl malonate, alkali metal, 2, the mol ratio of the chloropyridine of 3 dimethyl -6- nitros -5 is 4.2-5.3:1.4-1.7：1.2.
3. according to the synthetic method of the trimethyl -6- bromopyridines of one kind 2,3,5- described in claim 2, it is characterised in that：It is described
Alkali metal is selected from one kind between metallic sodium, metallic potassium.
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| CN201710497613.4A CN107311920A (en) | 2017-06-25 | 2017-06-25 | A kind of synthetic method of the bromopyridine of 2,3,5 trimethyl 6 |
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| CN201710497613.4A CN107311920A (en) | 2017-06-25 | 2017-06-25 | A kind of synthetic method of the bromopyridine of 2,3,5 trimethyl 6 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109748858A (en) * | 2017-11-08 | 2019-05-14 | 丹阳市易通安全技术服务有限公司 | A kind of synthetic method of 2,5- dimethyl -3- bromopyridine |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560183A (en) * | 2009-04-07 | 2009-10-21 | 浙江医药股份有限公司新昌制药厂 | Method for preparing 5-bromo-2-methylpyridine |
| CN104945313A (en) * | 2015-06-19 | 2015-09-30 | 洪帅金 | Preparation method of 2-methyl-3-bromopyridine |
| CN104974082A (en) * | 2015-07-26 | 2015-10-14 | 陈吉美 | Preparation method of 2-methyl-4-bromopyridine |
| 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 |
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2017
- 2017-06-25 CN CN201710497613.4A patent/CN107311920A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560183A (en) * | 2009-04-07 | 2009-10-21 | 浙江医药股份有限公司新昌制药厂 | Method for preparing 5-bromo-2-methylpyridine |
| CN104945313A (en) * | 2015-06-19 | 2015-09-30 | 洪帅金 | Preparation method of 2-methyl-3-bromopyridine |
| CN104974082A (en) * | 2015-07-26 | 2015-10-14 | 陈吉美 | Preparation method of 2-methyl-4-bromopyridine |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109748858A (en) * | 2017-11-08 | 2019-05-14 | 丹阳市易通安全技术服务有限公司 | A kind of synthetic method of 2,5- dimethyl -3- bromopyridine |
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