CN106349153B - 2-methyl-5-vinylpyrine synthetic method - Google Patents
2-methyl-5-vinylpyrine synthetic method Download PDFInfo
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- CN106349153B CN106349153B CN201610729936.7A CN201610729936A CN106349153B CN 106349153 B CN106349153 B CN 106349153B CN 201610729936 A CN201610729936 A CN 201610729936A CN 106349153 B CN106349153 B CN 106349153B
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- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/127—Preparation from compounds containing pyridine rings
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- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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- 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
- C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/46—Oxygen atoms
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Abstract
The invention discloses a kind of 2-methyl-5-vinylpyrine synthetic methods; purpose is; reduce synthesis step; simplify treatment process; improve yield and save the cost; the usage amount for reducing industrial chemicals, is effectively protected environment, used technical solution are as follows: (1) raw material 6- methyinicotinate is reduced into 2- methyl -5- pyridyl carboxylaldehyde；(2) phosphorus ylide reagent is prepared；(3) 2- methyl -5- pyridyl carboxylaldehyde and phosphorus ylide reagent are reacted and 2-methyl-5-vinylpyrine is made, product is made in concentration rectifying.
Description
Technical field
The invention belongs to medicine intermediate and new material technical field of organic synthesis, and in particular to a kind of 2- methyl-
5- vinylpyridine synthetic method.
Background technique
2-methyl-5-vinylpyrine has a wide range of applications value in organic new material and new drug development, is a kind of
Important monomer.Such as the butylbenzene pyrrole latex for dipped cord can be made with butadiene and styrene emulsion copolymerization；It is added
Polyacrylonitrile can improve its dyeing capacity.And excellent cation exchange resin can be aggregated into.Current 2- methyl -5- vinylpyridine
It is more complex that there are synthesis technologies in pyridine synthetic method, and higher cost, yield is low, and industrial chemicals dosage is more, unfriendly to environment
Defect.
Summary of the invention
In order to solve the problems in the prior art, the present invention proposes that one kind reduces synthesis step, simplifies treatment process,
It effectively improves yield and has saved cost, reduce the usage amount of industrial chemicals, effectively protect the 2- methyl -5- of environment
Vinylpyridine synthetic method.
In order to achieve the goal above, the technical scheme adopted by the invention is as follows: the following steps are included:
1) at a temperature of -10 to 15 DEG C, 6- methyinicotinate is dissolved in ether organic solvent, solution A is obtained, it will
Solution A is slowly dropped in metal organic reducing reagent, obtains solution B；
2) bromomethane triphenyl microcosmic salt is taken, and ether organic solvent is added, obtains solution C, to solution below 5 DEG C of temperature
Potassium tert-butoxide is added in C to be reacted, stirs to get solution D after reaction；
3) solution B for obtaining step 1) is slowly dropped in the solution D that step 2) obtains, and rate of addition guarantees reaction temperature
Degree is no more than 10 DEG C, continues sufficiently reaction after being added dropwise, obtains reaction solution, is filtered to reaction solution and removes reaction product three
Phenylphosphine obtains filtrate, and after filtrate is concentrated under reduced pressure, rectifying collects the fraction of 110~130 DEG C of boiling ranges to get 2- first is arrived
Base -5- vinylpyridine.
In the step 1) ratio of the cubical content of the quality and ether organic solvent of 6- methyinicotinate be (1:3)~
(1:6), mass unit g, cubical content unit are ml.
The ratio of the cubical content of the quality and metal organic reducing reagent of the 6- methyinicotinate be (1:1)~(1:
1.8), mass unit g, cubical content unit are ml.
Metal organic reducing reagent in the step 1) is organic metal lithium, organic metal copper, organic metal zinc, organic
One or both of metallic tin and organometallic aluminium.
When solution A being added drop-wise to the time in metal organic reducing reagent not less than 2h in the step 1), and being added dropwise
Reaction environment uses nitrogen atmosphere.
The quality of bromomethane triphenyl microcosmic salt is 2.8 of the quality of 6- methyinicotinate in step 1) in the step 2)
~4.2 times.
The ratio of the cubical content of the quality and ether organic solvent of bromomethane triphenyl microcosmic salt is (1:4) in the step 2)
~(1:8), mass unit g, cubical content unit are ml.
The quality of the bromomethane triphenyl microcosmic salt is 1.5~3 times of the quality of potassium tert-butoxide.
The ether organic solvent is ether, methyl tertiary butyl ether(MTBE), 1,4- dioxane or THF.
It is used when rectifying in the step 3) and faces methyl hydroquinone as polymerization inhibitor.
Compared with prior art, the present invention is by metal organic reducing reagent to the 6- first being dissolved in ether organic solvent
Base methyl nicotinate carries out reduction reaction, and 2- methyl -5- pyridyl carboxylaldehyde is made, utilizes the bromine first being dissolved in ether organic solvent
Alkane triphenyl microcosmic salt and potassium tert-butoxide are prepared into phosphorus ylide reagent, then try 2- methyl -5- pyridyl carboxylaldehyde and phosphorus ylide
Agent carries out reacting obtained 2-methyl-5-vinylpyrine, and the 2- methyl -5- pyridyl carboxylaldehyde that the present invention obtains is direct without processing
Investment next step is reacted, and -5 vinylpyridine of 2- methyl is directly prepared into, and is finally to obtain purity as 98% by concentration rectifying
Product, 2-methyl-5-vinylpyrine have a wide range of applications value in organic new material and new drug development, the present invention and existing
There is the technique for preparing 2-methyl-5-vinylpyrine compared to experimental procedure is reduced, simplifies treatment process, effectively improve
Yield, and cost has been saved, the usage amount of industrial chemicals is reduced, environment is effectively protected, is established for industrialized production
Basis.
Further, because the reaction yield of metal organic reducing agent is very high, 6- methyinicotinate, ether organic solvent and
The proportion of metal organic reducing reagent is optimum proportioning, and 6- methyinicotinate is made almost can be all converted to target product.
Further, 6- methyinicotinate is dissolved in ether organic solvent, and is slowly dropped to metal organic reducing
In reagent, strict control time for adding is conducive to control reaction temperature, and 6- methyinicotinate is made more fully to carry out restoring instead
It answers, 2- methyl -5- pyridyl carboxylaldehyde is made, while using nitrogen displaced air, makes reaction environment nitrogen atmosphere, nitrogen protection
Organic metal reducing agent can be prevented by oxygen, moisture, the carbon dioxide damage in air, prevent metallo-organic compound certainly
Combustion, plays the role of safeguard protection.
Further, phosphorus leaf is prepared into using the bromomethane triphenyl microcosmic salt and potassium tert-butoxide that are dissolved in ether organic solvent
Vertical moral reagent, bromomethane triphenyl microcosmic salt are handled through highly basic potassium tert-butoxide, are lost hydrogen bromide and are generated phosphorus ylide reagent, and make uncle
Butanol potassium excessively allows bromomethane triphenyl microcosmic salt sufficiently to react.
Further, using methyl hydroquinone is faced as polymerization inhibitor when rectifying, adjacent methyl hydroquinone can bury in oblivion freedom
Base, prevent -5 vinylpyridine of 2- methyl from polymerization reaction occurs, can achieve higher pure by accurate rectification process
Degree can further increase the purity for obtaining 2-methyl-5-vinylpyrine product.
Detailed description of the invention
Fig. 1 is the gas chromatogram of embodiment one；
Fig. 2 is that the gas chromatograph results of embodiment one are analyzed.
Specific embodiment
Below with reference to specific embodiment and Figure of description the present invention will be further explained explanation.
The present invention the following steps are included:
1) at a temperature of -10 to 15 DEG C, 6- methyinicotinate is dissolved in ether organic solvent, solution A is obtained, it will
Solution A is slowly dropped in metal organic reducing reagent, and the time that solution A is added drop-wise in metal organic reducing reagent is not less than
2h, and reaction environment when dropwise addition uses nitrogen atmosphere, obtains solution B；Ether organic solvent be ether, methyl tertiary butyl ether(MTBE),
Isosorbide-5-Nitrae-dioxane or THF, metal organic reducing reagent are organic metal lithium, organic metal copper, organic metal zinc, organic metal
One or both of tin and organometallic aluminium, the ratio of the cubical content of the quality and ether organic solvent of 6- methyinicotinate
For (1:3)~(1:6), the ratio of the cubical content of the quality and metal organic reducing reagent of 6- methyinicotinate be (1:1)~
(1:1.8)；
2) bromomethane triphenyl microcosmic salt is taken, and ether organic solvent is added, obtains solution C, to solution below 5 DEG C of temperature
Potassium tert-butoxide is added in C to be reacted, stirs to get solution D after reaction；Ether organic solvent is ether, methyl tertbutyl
Ether, Isosorbide-5-Nitrae-dioxane or THF, the quality of bromomethane triphenyl microcosmic salt are the quality of 6- methyinicotinate in step 1)
2.8~4.2 times, the ratio of the cubical content of the quality and ether organic solvent of bromomethane triphenyl microcosmic salt is (1:4)~(1:8),
The quality of bromomethane triphenyl microcosmic salt is 1.5~3 times of the quality of potassium tert-butoxide；
3) solution B for obtaining step 1) is slowly dropped in the solution D that step 2) obtains, and rate of addition guarantees reaction temperature
Degree is no more than 10 DEG C, continues sufficiently reaction after being added dropwise, obtains reaction solution, is filtered to reaction solution and removes reaction product three
Phenylphosphine obtains filtrate, and after filtrate is concentrated under reduced pressure, rectifying collects the fraction of 110~130 DEG C of boiling ranges to get 2- first is arrived
Base -5- vinylpyridine, using methyl hydroquinone is faced as polymerization inhibitor when rectifying, mass unit is g, cubical content list in method
Position is ml.
The present invention specifically includes the following steps:
(1) reduction of 6- methyinicotinate: 300 are taken to arrive 400ml metal organic reducing reagent (metal organic reducing reagent
It is one or both of organic metal lithium, organic metal copper, organic metal zinc, organic metal tin and organometallic aluminium) it places
It in 1000ml four-hole bottle, is cooled at -10 to 15 DEG C, 50 to 100 grams of 6- methyinicotinates is arrived into 250ml ethers with 150
After organic solvent dissolution (it is ether, methyl tertiary butyl ether(MTBE), Isosorbide-5-Nitrae-dioxane or THF that ethers, which has organic solvent), it is slowly added dropwise
Into four-hole bottle, time for adding cannot be below 2h, whole system nitrogen displaced air before being added dropwise；The reaction equation of step (1)
Are as follows:
(2) prepared by phosphorus ylide reagent: taking 150g to 240g bromomethane triphenyl microcosmic salt to be put in 2L four-hole bottle, is added
400 to 500ml ether organic solvent (ether organic solvent is ether, methyl tertiary butyl ether(MTBE), Isosorbide-5-Nitrae-dioxane or THF), when
Bottle internal solvent temperature is reduced to after 5 DEG C or less is added potassium tert-butoxide 50 to 70g in batches, stirs 1h to continue after reaction,
It is spare；
(3) reaction solution obtained in step (1) is slowly dropped in step (2), controls rate of addition, in reaction
Reacting liquid temperature can rise, and temperature is no more than 10 DEG C, the reaction was continued after being added dropwise 30min, and react fully progress, fills
Point post-reaction treatment reaction solution, is filtered to remove reaction product triphenylphosphine, 80 DEG C of filtrate be concentrated under reduced pressure after rectifying collect 110 to
The fraction of 130 DEG C of boiling ranges is up to 2-methyl-5-vinylpyrine product, negative pressure≤0.08MPa of reduced pressure, and when rectifying is added
Face methyl hydroquinone as polymerization inhibitor, the reaction equation of step (3) are as follows:
Embodiment one:
1) it takes 350ml metal organic reducing reagent to be placed in 1000ml four-hole bottle, is cooled at -10 DEG C, by 65 grams of 6-
Methyinicotinate is slowly dropped in four-hole bottle after being dissolved with 200ml ether organic solvent, and time for adding cannot be below 2h, drop
Whole system nitrogen displaced air before adding；
2) it takes 173g bromomethane triphenyl microcosmic salt to be put in 2L four-hole bottle, 400ml ether organic solvent is added, when molten in bottle
Agent temperature is reduced to after 5 DEG C or less is added potassium tert-butoxide 57g in batches, spare to continue stirring 1h after reaction；
3) 1) reaction solution obtained in is slowly dropped in 2), controls rate of addition, reacting liquid temperature in reaction
It can rise, temperature is no more than 10 DEG C, the reaction was continued after being added dropwise 30min, and react fully progresss, after sufficiently reacting
Reaction solution is managed, is filtered to remove reaction product triphenylphosphine, 110 to 130 DEG C of boiling ranges are collected in rectifying after 80 DEG C of filtrate reduced pressures
Fraction is up to product, negative pressure≤0.08MPa of reduced pressure, and when rectifying, which is added, faces methyl hydroquinone 1g as polymerization inhibitor, is total to
Obtain product 38.2g, total recovery 74.9%.Gas chromatographic analysis, chromatograph model are carried out to the product of embodiment one
N2000, chromatographic integration method is area normalization method, referring to the gas chromatogram of Fig. 1 embodiment one and the chromatography result of Fig. 2
It obtains: finding out that the product G C purity degree obtained using the method for the present invention reaches 99% or more from testing result, the present invention is effective
The generation of by-product is reduced, reaction yield is very high to offer convenience to subsequent processing, so that product purity reaches ideal standard.
Embodiment two:
The method of the present invention includes:
1) at a temperature of -10 to 15 DEG C, 6- methyinicotinate is dissolved in ether organic solvent, solution A is obtained, it will
Solution A is slowly dropped in metal organic reducing reagent, and the time that solution A is added drop-wise in metal organic reducing reagent is not less than
2h, and reaction environment when dropwise addition uses nitrogen atmosphere, obtains solution B；Ether organic solvent is ether, the examination of metal organic reducing
Agent is organic metal lithium, and the ratio of the cubical content of the quality and ether organic solvent of 6- methyinicotinate is 1:3,6- methyl cigarette
The ratio of the cubical content of the quality and metal organic reducing reagent of sour methyl esters is 1:1；
2) bromomethane triphenyl microcosmic salt is taken, and ether organic solvent is added, obtains solution C, to solution below 5 DEG C of temperature
Potassium tert-butoxide is added in C to be reacted, stirs to get solution D after reaction；Ether organic solvent is ether, bromomethane triphen
The quality of base microcosmic salt is 2.8 times of the quality of 6- methyinicotinate in step 1), the quality and ether of bromomethane triphenyl microcosmic salt
The ratio of the cubical content of class organic solvent is 1:4, and the quality of bromomethane triphenyl microcosmic salt is 1.5 times of the quality of potassium tert-butoxide；
3) solution B for obtaining step 1) is slowly dropped in the solution D that step 2) obtains, and rate of addition guarantees reaction temperature
Degree is no more than 10 DEG C, continues sufficiently reaction after being added dropwise, obtains reaction solution, is filtered to reaction solution and removes reaction product three
Phenylphosphine obtains filtrate, and after filtrate is concentrated under reduced pressure, rectifying collects the fraction of 110~130 DEG C of boiling ranges to get 2- first is arrived
Base -5- vinylpyridine, using methyl hydroquinone is faced as polymerization inhibitor when rectifying, mass unit is g, cubical content list in method
Position is ml.
Embodiment three:
The method of the present invention includes:
1) at a temperature of -10 to 15 DEG C, 6- methyinicotinate is dissolved in ether organic solvent, solution A is obtained, it will
Solution A is slowly dropped in metal organic reducing reagent, and the time that solution A is added drop-wise in metal organic reducing reagent is not less than
2h, and reaction environment when dropwise addition uses nitrogen atmosphere, obtains solution B；Ether organic solvent is methyl tertiary butyl ether(MTBE), and metal has
Machine go back original reagent is organic metal lithium and organic metal copper, the quality of 6- methyinicotinate and the cubical content of ether organic solvent
Ratio be 1:4, the ratio of the cubical content of the quality and metal organic reducing reagent of 6- methyinicotinate is 1:1.2；
2) bromomethane triphenyl microcosmic salt is taken, and ether organic solvent is added, obtains solution C, to solution below 5 DEG C of temperature
Potassium tert-butoxide is added in C to be reacted, stirs to get solution D after reaction；Ether organic solvent is methyl tertiary butyl ether(MTBE), bromine
The quality of methane triphenyl microcosmic salt is 3 times of the quality of 6- methyinicotinate in step 1), the matter of bromomethane triphenyl microcosmic salt
The ratio of the cubical content of amount and ether organic solvent is 1:5, and the quality of bromomethane triphenyl microcosmic salt is the quality of potassium tert-butoxide
1.7 again；
3) solution B for obtaining step 1) is slowly dropped in the solution D that step 2) obtains, and rate of addition guarantees reaction temperature
Degree is no more than 10 DEG C, continues sufficiently reaction after being added dropwise, obtains reaction solution, is filtered to reaction solution and removes reaction product three
Phenylphosphine obtains filtrate, and after filtrate is concentrated under reduced pressure, rectifying collects the fraction of 110~130 DEG C of boiling ranges to get 2- first is arrived
Base -5- vinylpyridine, using methyl hydroquinone is faced as polymerization inhibitor when rectifying, mass unit is g, cubical content list in method
Position is ml.
Example IV:
The method of the present invention includes:
1) at a temperature of -10 to 15 DEG C, 6- methyinicotinate is dissolved in ether organic solvent, solution A is obtained, it will
Solution A is slowly dropped in metal organic reducing reagent, and the time that solution A is added drop-wise in metal organic reducing reagent is not less than
2h, and reaction environment when dropwise addition uses nitrogen atmosphere, obtains solution B；Ether organic solvent is Isosorbide-5-Nitrae-dioxane, and metal has
Machine go back original reagent is organic metal zinc and organometallic aluminium, the quality of 6- methyinicotinate and the cubical content of ether organic solvent
Ratio be 1:5, the ratio of the cubical content of the quality and metal organic reducing reagent of 6- methyinicotinate is 1:1.6；
2) bromomethane triphenyl microcosmic salt is taken, and ether organic solvent is added, obtains solution C, to solution below 5 DEG C of temperature
Potassium tert-butoxide is added in C to be reacted, stirs to get solution D after reaction；Ether organic solvent is Isosorbide-5-Nitrae-dioxane, bromine
The quality of methane triphenyl microcosmic salt is 3.5 times of the quality of 6- methyinicotinate in step 1), bromomethane triphenyl microcosmic salt
The ratio of the cubical content of quality and ether organic solvent is 1:6, and the quality of bromomethane triphenyl microcosmic salt is the quality of potassium tert-butoxide
2 times；
3) solution B for obtaining step 1) is slowly dropped in the solution D that step 2) obtains, and rate of addition guarantees reaction temperature
Degree is no more than 10 DEG C, continues sufficiently reaction after being added dropwise, obtains reaction solution, is filtered to reaction solution and removes reaction product three
Phenylphosphine obtains filtrate, and after filtrate is concentrated under reduced pressure, rectifying collects the fraction of 110~130 DEG C of boiling ranges to get 2- first is arrived
Base -5- vinylpyridine, using methyl hydroquinone is faced as polymerization inhibitor when rectifying, mass unit is g, cubical content list in method
Position is ml.
Embodiment five:
The method of the present invention includes:
1) at a temperature of -10 to 15 DEG C, 6- methyinicotinate is dissolved in ether organic solvent, solution A is obtained, it will
Solution A is slowly dropped in metal organic reducing reagent, and the time that solution A is added drop-wise in metal organic reducing reagent is not less than
2h, and reaction environment when dropwise addition uses nitrogen atmosphere, obtains solution B；Ether organic solvent is THF, the examination of metal organic reducing
Agent is organic metal zinc and organic metal tin, and the ratio of the cubical content of the quality and ether organic solvent of 6- methyinicotinate is
The ratio of the cubical content of the quality and metal organic reducing reagent of 1:6,6- methyinicotinate is 1:1.8；
2) bromomethane triphenyl microcosmic salt is taken, and ether organic solvent is added, obtains solution C, to solution below 5 DEG C of temperature
Potassium tert-butoxide is added in C to be reacted, stirs to get solution D after reaction；Ether organic solvent is THF, bromomethane triphen
The quality of base microcosmic salt is 4.2 times of the quality of 6- methyinicotinate in step 1), the quality and ether of bromomethane triphenyl microcosmic salt
The ratio of the cubical content of class organic solvent is 1:8, and the quality of bromomethane triphenyl microcosmic salt is 3 times of the quality of potassium tert-butoxide；
3) solution B for obtaining step 1) is slowly dropped in the solution D that step 2) obtains, and rate of addition guarantees reaction temperature
Degree is no more than 10 DEG C, continues sufficiently reaction after being added dropwise, obtains reaction solution, is filtered to reaction solution and removes reaction product three
Phenylphosphine obtains filtrate, and after filtrate is concentrated under reduced pressure, rectifying collects the fraction of 110~130 DEG C of boiling ranges to get 2- first is arrived
Base -5- vinylpyridine, using methyl hydroquinone is faced as polymerization inhibitor when rectifying, mass unit is g, cubical content list in method
Position is ml.
Embodiment six:
The method of the present invention includes:
1) at a temperature of -10 to 15 DEG C, 6- methyinicotinate is dissolved in ether organic solvent, solution A is obtained, it will
Solution A is slowly dropped in metal organic reducing reagent, and the time that solution A is added drop-wise in metal organic reducing reagent is not less than
2h, and reaction environment when dropwise addition uses nitrogen atmosphere, obtains solution B；Ether organic solvent is methyl tertiary butyl ether(MTBE), and metal has
Machine go back original reagent is organic metal tin, and the ratio of the cubical content of the quality and ether organic solvent of 6- methyinicotinate is 1:
The ratio of the cubical content of the quality and metal organic reducing reagent of 4.5,6- methyinicotinates is 1:1.7；
2) bromomethane triphenyl microcosmic salt is taken, and ether organic solvent is added, obtains solution C, to solution below 5 DEG C of temperature
Potassium tert-butoxide is added in C to be reacted, stirs to get solution D after reaction；Ether organic solvent is methyl tertiary butyl ether(MTBE), bromine
The quality of methane triphenyl microcosmic salt is 4 times of the quality of 6- methyinicotinate in step 1), the matter of bromomethane triphenyl microcosmic salt
The ratio of the cubical content of amount and ether organic solvent is 1:7, and the quality of bromomethane triphenyl microcosmic salt is the quality of potassium tert-butoxide
2.5 again；
3) solution B for obtaining step 1) is slowly dropped in the solution D that step 2) obtains, and rate of addition guarantees reaction temperature
Degree is no more than 10 DEG C, continues sufficiently reaction after being added dropwise, obtains reaction solution, is filtered to reaction solution and removes reaction product three
Phenylphosphine obtains filtrate, and after filtrate is concentrated under reduced pressure, rectifying collects the fraction of 110~130 DEG C of boiling ranges to get 2- first is arrived
Base -5- vinylpyridine, using methyl hydroquinone is faced as polymerization inhibitor when rectifying, mass unit is g, cubical content list in method
Position is ml.
The present invention prepares the technique of 2-methyl-5-vinylpyrine, simplifies treatment process, effectively improves yield,
And cost has been saved, the usage amount of industrial chemicals is reduced, environment is effectively protected, is laid a good foundation for industrialized production.
Claims (9)
1. a kind of 2-methyl-5-vinylpyrine synthetic method, which comprises the following steps:
1) at a temperature of -10 to 15 DEG C, 6- methyinicotinate is dissolved in ether organic solvent, solution A is obtained, by solution
A is slowly dropped in metal organic reducing reagent, obtains solution B；
2) bromomethane triphenyl microcosmic salt is taken, and ether organic solvent is added, obtains solution C, below 5 DEG C of temperature into solution C
Potassium tert-butoxide is added to be reacted, stirs to get solution D after reaction；
3) solution B for obtaining step 1) is slowly dropped in the solution D that step 2) obtains, and rate of addition guarantees reaction temperature not
Continue sufficiently reaction more than 10 DEG C, after being added dropwise, obtain reaction solution, reaction solution is filtered and removes reaction product triphenyl
Phosphine obtains filtrate, and after filtrate is concentrated under reduced pressure, rectifying collects the fraction of 110~130 DEG C of boiling ranges to get 2- methyl -5- is arrived
Vinylpyridine；
Metal organic reducing reagent in the step 1) is organic metal lithium, organic metal copper, organic metal zinc, organic metal
One or both of tin and organometallic aluminium.
2. a kind of 2-methyl-5-vinylpyrine synthetic method according to claim 1, which is characterized in that the step
1) ratio of the cubical content of the quality and ether organic solvent of 6- methyinicotinate is (1:3)~(1:6) in, and mass unit is
G, cubical content unit are ml.
3. a kind of 2-methyl-5-vinylpyrine synthetic method according to claim 2, which is characterized in that the 6- first
The ratio of the cubical content of the quality and metal organic reducing reagent of base methyl nicotinate be (1:1)~(1:1.8), mass unit g,
Cubical content unit is ml.
4. a kind of 2-methyl-5-vinylpyrine synthetic method according to claim 1, which is characterized in that the step
1) reaction environment when solution A being added drop-wise to the time in metal organic reducing reagent not less than 2h in, and being added dropwise uses nitrogen
Atmosphere.
5. a kind of 2-methyl-5-vinylpyrine synthetic method according to claim 1, which is characterized in that the step
2) quality of bromomethane triphenyl microcosmic salt is 2.8~4.2 times of the quality of 6- methyinicotinate in step 1) in.
6. a kind of 2-methyl-5-vinylpyrine synthetic method according to claim 5, which is characterized in that the step
2) ratio of the cubical content of the quality and ether organic solvent of bromomethane triphenyl microcosmic salt is (1:4)~(1:8), mass unit in
For g, cubical content unit is ml.
7. a kind of 2-methyl-5-vinylpyrine synthetic method according to claim 6, which is characterized in that the bromine first
The quality of alkane triphenyl microcosmic salt is 1.5 to 3 times of potassium tert-butoxide quality.
8. a kind of 2-methyl-5-vinylpyrine synthetic method according to claim 7, which is characterized in that the ethers
Organic solvent is ether, methyl tertiary butyl ether(MTBE), 1,4- dioxane or THF.
9. a kind of 2-methyl-5-vinylpyrine synthetic method according to claim 1, which is characterized in that the step
3) use adjacent methyl hydroquinone as polymerization inhibitor when rectifying in.
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