CN107915674A - A kind of 2 picoline catalysis oxidation prepares the preparation method of 2 pyridine carboxaldehydes - Google Patents
A kind of 2 picoline catalysis oxidation prepares the preparation method of 2 pyridine carboxaldehydes Download PDFInfo
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Abstract
The invention discloses the preparation method that a kind of 2 picoline catalysis oxidation prepares 2 pyridine carboxaldehydes, comprise the following steps：First using ammonium molybdate, sodium citrate, manganese acetate, sodium hydroxide as raw material, composite catalyst is prepared；Then with 2 picolines and glacial acetic acid, and after adding hydrogen peroxide catalytic oxidation, acetic acid anhydride reactant is added dropwise, 2 picolyl of acetic acid is made；Then sodium hydroxide solution is added dropwise into 2 picolyl of acetic acid 2 pyridinemethanols of preparation is hydrolyzed；Finally 2 pyridinemethanols and dichloromethane are mixed evenly, it is transferred in three-necked flask, then composite catalyst and hydrogen peroxide obtained above are added, 1 3h is reacted in stirring at 30 40 DEG C after addition, is cooled to room temperature after reaction, filtering, filtrate is collected, and air-distillation removes dichloromethane, and then residue vacuum decompression is distilled, the cut of 63 65 DEG C/1.73kPa is collected, 2 pyridine carboxaldehydes are made.Method provided by the invention is simple, environmental protection, and target product yield is high.
Description
Technical field：
The present invention relates to the preparation field of 2- pyridine carboxaldehydes, is specifically related to a kind of 2- picolines catalysis oxidation and prepares 2-
The preparation method of pyridine carboxaldehyde.
Background technology：
2- pyridine carboxaldehydes are the intermediates of caccagogue Bisacody, and the raw material of synthesis organophosphorus compounds antidote.
Currently used method is using 2- picolines as raw material, aoxidize through N-, be acylated, hydrolyze after reoxidize obtained 2- pyridine carboxaldehydes,
But oxidant selenium dioxide used or lead tetraacetate toxicity are big, easily cause environmental pollution；Also 2- picolines can be used oxidized, again
Row is esterified, reoxidizes, resetting, hydrolyzing and obtain, but this method step is long, cumbersome, and yield is relatively low.Also useful 2- methyl pyrrole
Pyridine is mixed with iodine, and obtained compound heats in DMSO and obtains 2- pyridine carboxaldehydes, but total recovery is low, and cost is higher, is not easy
It is prepared by amplification.
Patent 200910143970.6 discloses the preparation method of 2- pyridine carboxaldehydes, comprises the following steps：(1) with 2- methyl
Pyridine is raw material, and halogenated hydrocarbons is solvent, benzamide is catalyst, three chlorine isocyanates are chlorinating agent, and temperature rising reflux reacts
To 2- chloromethylpyridine；(2) 2- chloromethylpyridine hydrolyzes in alkaline conditions, and 2- pyridinemethanols are made in temperature reaction；(3) 2- pyrroles
For pyridine methanol using halogenated hydrocarbons as solvent, 2,2,6,6- tetramethyl piperidine nitrogen oxides and potassium bromide are catalyst, are cooled to -10~0
DEG C, the oxidant that 10wt.% is added dropwise is liquor natrii hypochloritis, and drop finishes obtains 2- pyridine carboxaldehydes in 10~25 DEG C of insulations.The present invention
The preparation method high income of offer, but the catalyst used in this method has certain toxicity, there is certain harm to environment.
The content of the invention：
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of 2- picolines catalysis oxidation to prepare 2- pyridines
The preparation method of formaldehyde.This method mild condition, easy to operate, target product yield is high.
To achieve the above object, the present invention uses following technical scheme：
A kind of 2- picolines catalysis oxidation prepares the preparation method of 2- pyridine carboxaldehydes, comprises the following steps：
(1) using deionized water as solvent, ammonium molybdate solution is prepared, sodium citrate solution, acetic acid manganese solution, sodium hydroxide is molten
Liquid；
(2) absolute ethyl alcohol and hexamethylene are mixed, and adds glacial acetic acid, triethylamine and butyl titanate, be stirred
After even, it be transferred in reaction kettle and 20h is reacted at 150 DEG C, after reaction, is cooled to room temperature, obtains reaction solution；
(3) by after ammonium molybdate solution, sodium citrate solution and acetic acid manganese solution are mixed evenly made from step (1),
It is added at the same time in reactor with sodium hydroxide solution, stirring reaction 0.5-1.5h at 40-50 DEG C, the reaction solution after reaction adds
Into reaction solution made from step (2), stirring 30min is placed in high temperature oven, the reaction was continued at 120-180 DEG C 3h, reaction
After be cooled to room temperature, by reacting liquid filtering, obtained solid is washed with deionized water, absolute ethyl alcohol successively, dry, is made
Composite catalyst；
(4) 2- picolines, glacial acetic acid are added in three-necked flask, it is 25% hydrogen peroxide that concentration, which is then added dropwise, stirring
After mixing, 80-90 DEG C is to slowly warm up to, reaction solution, is evaporated under reduced pressure, removes 126-127 by stirring reaction 2-4h after reaction
DEG C/2.00kPa front-end volatiles, acetic anhydride is added dropwise into residue, and 135 DEG C are to slowly warm up to, continue stirring reaction 30min, instead
Reaction solution is evaporated under reduced pressure after answering, collects the component of 117-119 DEG C/2.93kPa, acetic acid 2- picolyls are made；
(5) sodium hydroxide solution is added dropwise into acetic acid 2- picolyls, then hydrolysis 5h, reaction terminate at 90 DEG C
Postcooling is evaporated under reduced pressure reaction solution, collects 92-93 DEG C/1.06kPa cuts, 2- pyridinemethanols are made to room temperature；
(6) 2- pyridinemethanols and dichloromethane are mixed evenly, are transferred in three-necked flask, then add above-mentioned system
The composite catalyst and hydrogen peroxide obtained, 1-3h is reacted in stirring at 30-40 DEG C after addition, is cooled to room after reaction
Temperature, filtering, collects filtrate, and air-distillation removes dichloromethane, and then residue vacuum decompression is distilled, and 63-65 DEG C of collection/
The cut of 1.73kPa, is made 2- pyridine carboxaldehydes.
As the preferred of above-mentioned technical proposal, in step (1), the mass concentration of the sodium hydroxide solution is 15%.
As the preferred of above-mentioned technical proposal, in step (1), the ammonium molybdate solution, sodium citrate solution, manganese acetate is molten
The molar concentration of liquid is respectively 0.5-0.8moL/L, 0.1moL/L, 0.5-0.8moL/L.
As the preferred of above-mentioned technical proposal, in step (3), ammonium molybdate solution, the mass ratio of sodium citrate solution are 5：
(0.1-0.5)。
As the preferred of above-mentioned technical proposal, in step (2), absolute ethyl alcohol, hexamethylene, glacial acetic acid, triethylamine, metatitanic acid four
The volume ratio of butyl ester is 5:50:5:1:1.
As the preferred of above-mentioned technical proposal, in step (4), the 2- picolines, glacial acetic acid, the volume ratio of hydrogen peroxide
For 1:3:5.
As the preferred of above-mentioned technical proposal, in step (6), 2- pyridinemethanols, composite catalyst, the mass ratio of hydrogen peroxide
For (6-11)：(1-2)：4.
As the preferred of above-mentioned technical proposal, in step (3), the composite catalyst in parts by weight, by 30-55 parts
Molybdenum, 15-35 part manganese and 1-3 parts of nano-titanium dioxide compositions.
The invention has the advantages that：
The present invention prepares catalyst as raw material using ammonium molybdate, manganese acetate using the method for co-precipitation, and before co-precipitation
Sodium citrate solution is added, effectively controls the speed of salt precipitation；On the other hand, the present invention prepares nanometer using sol-gal process
Titanium dioxide, and the glue after precipitation is added dropwise into nano titanic oxide sol, and react at a certain temperature, it is obtained compound
Catalyst is made of molybdenum, manganese and nano-titanium dioxide, its catalytic activity is high, asepsis environment-protecting；
The present invention is by rationally adjusting the conditions of each reactions steps so that the yield of intermediate product and target product and
Purity is all very high, and the raw material used is all nontoxic, is conducive to environmental protection, cost is low.
Embodiment：
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving
The present invention is released, any restriction will not be formed to the present invention.
Embodiment 1
A kind of 2- picolines catalysis oxidation prepares the preparation method of 2- pyridine carboxaldehydes, comprises the following steps：
(1) using deionized water as solvent, ammonium molybdate solution is prepared, sodium citrate solution, acetic acid manganese solution, sodium hydroxide is molten
Liquid；
(2) absolute ethyl alcohol and hexamethylene are mixed, and adds glacial acetic acid, triethylamine and butyl titanate, be stirred
After even, it be transferred in reaction kettle and 20h is reacted at 150 DEG C, after reaction, is cooled to room temperature, obtains reaction solution；
(3) by after ammonium molybdate solution, sodium citrate solution and acetic acid manganese solution are mixed evenly made from step (1),
It is added at the same time in reactor with sodium hydroxide solution, stirring reaction 0.5h, the reaction solution after reaction are added to step at 40-50 DEG C
Suddenly in reaction solution made from (2), stirring 30min is placed in high temperature oven, and the reaction was continued at 120 DEG C 3h is cold after reaction
But to room temperature, by reacting liquid filtering, obtained solid is washed with deionized water, absolute ethyl alcohol successively, dry, and composite catalyzing is made
Agent；Wherein, ammonium molybdate solution, the mass ratio of sodium citrate solution are 5：0.1；The composite catalyst in parts by weight, by 30
Part molybdenum, 15 parts of manganese and 1 part of nano-titanium dioxide composition；
(4) 2- picolines, glacial acetic acid are added in three-necked flask, it is 25% hydrogen peroxide that concentration, which is then added dropwise, stirring
After mixing, 80-90 DEG C is to slowly warm up to, reaction solution, is evaporated under reduced pressure by stirring reaction 2h after reaction, 126-127 DEG C of removing/
2.00kPa front-end volatiles, acetic anhydride is added dropwise into residue, and is to slowly warm up to 135 DEG C, continues stirring reaction 30min, reaction knot
Reaction solution is evaporated under reduced pressure after beam, collects the component of 117-119 DEG C/2.93kPa, acetic acid 2- picolyls are made；Yield
For 80.9%；
(5) sodium hydroxide solution is added dropwise into acetic acid 2- picolyls, then hydrolysis 5h, reaction terminate at 90 DEG C
Postcooling is evaporated under reduced pressure reaction solution, collects 92-93 DEG C/1.06kPa cuts, 2- pyridinemethanols are made to room temperature；Yield
91.3%；
(6) 2- pyridinemethanols and dichloromethane are mixed evenly, are transferred in three-necked flask, then add above-mentioned system
The composite catalyst and hydrogen peroxide obtained, 1h is reacted in stirring at 30-40 DEG C after addition, is cooled to room temperature after reaction,
Filtering, collects filtrate, and air-distillation removes dichloromethane, and then residue vacuum decompression is distilled, and 63-65 DEG C of collection/
The cut of 1.73kPa, is made 2- pyridine carboxaldehydes, yield 97.6%；Wherein, 2- pyridinemethanols, composite catalyst, hydrogen peroxide
Mass ratio is 6：1：4.
Embodiment 2
A kind of 2- picolines catalysis oxidation prepares the preparation method of 2- pyridine carboxaldehydes, comprises the following steps：
(1) using deionized water as solvent, ammonium molybdate solution is prepared, sodium citrate solution, acetic acid manganese solution, sodium hydroxide is molten
Liquid；
(2) absolute ethyl alcohol and hexamethylene are mixed, and adds glacial acetic acid, triethylamine and butyl titanate, be stirred
After even, it be transferred in reaction kettle and 20h is reacted at 150 DEG C, after reaction, is cooled to room temperature, obtains reaction solution；
(3) by after ammonium molybdate solution, sodium citrate solution and acetic acid manganese solution are mixed evenly made from step (1),
It is added at the same time in reactor with sodium hydroxide solution, stirring reaction 1.5h, the reaction solution after reaction are added to step at 40-50 DEG C
Suddenly in reaction solution made from (2), stirring 30min is placed in high temperature oven, and the reaction was continued at 180 DEG C 3h is cold after reaction
But to room temperature, by reacting liquid filtering, obtained solid is washed with deionized water, absolute ethyl alcohol successively, dry, and composite catalyzing is made
Agent；Wherein, ammonium molybdate solution, the mass ratio of sodium citrate solution are 5：0.5；The composite catalyst in parts by weight, by 55
Part molybdenum, 35 parts of manganese and 3 parts of nano-titanium dioxides compositions；
(4) 2- picolines, glacial acetic acid are added in three-necked flask, it is 25% hydrogen peroxide that concentration, which is then added dropwise, stirring
After mixing, 80-90 DEG C is to slowly warm up to, reaction solution, is evaporated under reduced pressure by stirring reaction 4h after reaction, 126-127 DEG C of removing/
2.00kPa front-end volatiles, acetic anhydride is added dropwise into residue, and is to slowly warm up to 135 DEG C, continues stirring reaction 30min, reaction knot
Reaction solution is evaporated under reduced pressure after beam, collects the component of 117-119 DEG C/2.93kPa, acetic acid 2- picolyls are made；Yield
For 85.3%；
(5) sodium hydroxide solution is added dropwise into acetic acid 2- picolyls, then hydrolysis 5h, reaction terminate at 90 DEG C
Postcooling is evaporated under reduced pressure reaction solution, collects 92-93 DEG C/1.06kPa cuts, 2- pyridinemethanols are made to room temperature；Yield
92.5%；
(6) 2- pyridinemethanols and dichloromethane are mixed evenly, are transferred in three-necked flask, then add above-mentioned system
The composite catalyst and hydrogen peroxide obtained, 3h is reacted in stirring at 30-40 DEG C after addition, is cooled to room temperature after reaction,
Filtering, collects filtrate, and air-distillation removes dichloromethane, and then residue vacuum decompression is distilled, and 63-65 DEG C of collection/
The cut of 1.73kPa, is made 2- pyridine carboxaldehydes, yield 98.0%；Wherein, 2- pyridinemethanols, composite catalyst, hydrogen peroxide
Mass ratio is 11：2：4.
Embodiment 3
A kind of 2- picolines catalysis oxidation prepares the preparation method of 2- pyridine carboxaldehydes, comprises the following steps：
(1) using deionized water as solvent, ammonium molybdate solution is prepared, sodium citrate solution, acetic acid manganese solution, sodium hydroxide is molten
Liquid；
(2) absolute ethyl alcohol and hexamethylene are mixed, and adds glacial acetic acid, triethylamine and butyl titanate, be stirred
After even, it be transferred in reaction kettle and 20h is reacted at 150 DEG C, after reaction, is cooled to room temperature, obtains reaction solution；
(3) by after ammonium molybdate solution, sodium citrate solution and acetic acid manganese solution are mixed evenly made from step (1),
It is added at the same time in reactor with sodium hydroxide solution, stirring reaction 0.7h, the reaction solution after reaction are added to step at 40-50 DEG C
Suddenly in reaction solution made from (2), stirring 30min is placed in high temperature oven, and the reaction was continued at 130 DEG C 3h is cold after reaction
But to room temperature, by reacting liquid filtering, obtained solid is washed with deionized water, absolute ethyl alcohol successively, dry, and composite catalyzing is made
Agent；Wherein, ammonium molybdate solution, the mass ratio of sodium citrate solution are 5：0.2；The composite catalyst in parts by weight, by 35
Part molybdenum, 20 parts of manganese and 1.5 parts of nano-titanium dioxides compositions；
(4) 2- picolines, glacial acetic acid are added in three-necked flask, it is 25% hydrogen peroxide that concentration, which is then added dropwise, stirring
After mixing, 80-90 DEG C is to slowly warm up to, reaction solution, is evaporated under reduced pressure, removes 126-127 by stirring reaction 2.5h after reaction
DEG C/2.00kPa front-end volatiles, acetic anhydride is added dropwise into residue, and 135 DEG C are to slowly warm up to, continue stirring reaction 30min, instead
Reaction solution is evaporated under reduced pressure after answering, collects the component of 117-119 DEG C/2.93kPa, acetic acid 2- picolyls are made；
Yield is 82.8%；
(5) sodium hydroxide solution is added dropwise into acetic acid 2- picolyls, then hydrolysis 5h, reaction terminate at 90 DEG C
Postcooling is evaporated under reduced pressure reaction solution, collects 92-93 DEG C/1.06kPa cuts, 2- pyridinemethanols are made to room temperature；Yield
91.9%；
(6) 2- pyridinemethanols and dichloromethane are mixed evenly, are transferred in three-necked flask, then add above-mentioned system
The composite catalyst and hydrogen peroxide obtained, 1.5h is reacted in stirring at 30-40 DEG C after addition, is cooled to room after reaction
Temperature, filtering, collects filtrate, and air-distillation removes dichloromethane, and then residue vacuum decompression is distilled, and 63-65 DEG C of collection/
The cut of 1.73kPa, is made 2- pyridine carboxaldehydes, yield 97.9%；Wherein, 2- pyridinemethanols, composite catalyst, hydrogen peroxide
Mass ratio is 8：1：4.
Embodiment 4
A kind of 2- picolines catalysis oxidation prepares the preparation method of 2- pyridine carboxaldehydes, comprises the following steps：
(1) using deionized water as solvent, ammonium molybdate solution is prepared, sodium citrate solution, acetic acid manganese solution, sodium hydroxide is molten
Liquid；
(2) absolute ethyl alcohol and hexamethylene are mixed, and adds glacial acetic acid, triethylamine and butyl titanate, be stirred
After even, it be transferred in reaction kettle and 20h is reacted at 150 DEG C, after reaction, is cooled to room temperature, obtains reaction solution；
(3) by after ammonium molybdate solution, sodium citrate solution and acetic acid manganese solution are mixed evenly made from step (1),
It is added at the same time in reactor with sodium hydroxide solution, stirring reaction 0.9h, the reaction solution after reaction are added to step at 40-50 DEG C
Suddenly in reaction solution made from (2), stirring 30min is placed in high temperature oven, and the reaction was continued at 140 DEG C 3h is cold after reaction
But to room temperature, by reacting liquid filtering, obtained solid is washed with deionized water, absolute ethyl alcohol successively, dry, and composite catalyzing is made
Agent；Wherein, ammonium molybdate solution, the mass ratio of sodium citrate solution are 5：0.3；The composite catalyst in parts by weight, by 40
Part molybdenum, 25 parts of manganese and 2 parts of nano-titanium dioxides compositions；
(4) 2- picolines, glacial acetic acid are added in three-necked flask, it is 25% hydrogen peroxide that concentration, which is then added dropwise, stirring
After mixing, 80-90 DEG C is to slowly warm up to, reaction solution, is evaporated under reduced pressure by stirring reaction 3h after reaction, 126-127 DEG C of removing/
2.00kPa front-end volatiles, acetic anhydride is added dropwise into residue, and is to slowly warm up to 135 DEG C, continues stirring reaction 30min, reaction knot
Reaction solution is evaporated under reduced pressure after beam, collects the component of 117-119 DEG C/2.93kPa, acetic acid 2- picolyls are made；Yield
For 88.3%；
(5) sodium hydroxide solution is added dropwise into acetic acid 2- picolyls, then hydrolysis 5h, reaction terminate at 90 DEG C
Postcooling is evaporated under reduced pressure reaction solution, collects 92-93 DEG C/1.06kPa cuts, 2- pyridinemethanols are made to room temperature；Yield
90.5%；
(6) 2- pyridinemethanols and dichloromethane are mixed evenly, are transferred in three-necked flask, then add above-mentioned system
The composite catalyst and hydrogen peroxide obtained, 2h is reacted in stirring at 30-40 DEG C after addition, is cooled to room temperature after reaction,
Filtering, collects filtrate, and air-distillation removes dichloromethane, and then residue vacuum decompression is distilled, and 63-65 DEG C of collection/
The cut of 1.73kPa, is made 2- pyridine carboxaldehydes, yield 97.6%；Wherein, 2- pyridinemethanols, composite catalyst, hydrogen peroxide
Mass ratio is 9：2：4.
Embodiment 5
A kind of 2- picolines catalysis oxidation prepares the preparation method of 2- pyridine carboxaldehydes, comprises the following steps：
(1) using deionized water as solvent, ammonium molybdate solution is prepared, sodium citrate solution, acetic acid manganese solution, sodium hydroxide is molten
Liquid；
(2) absolute ethyl alcohol and hexamethylene are mixed, and adds glacial acetic acid, triethylamine and butyl titanate, be stirred
After even, it be transferred in reaction kettle and 20h is reacted at 150 DEG C, after reaction, is cooled to room temperature, obtains reaction solution；
(3) by after ammonium molybdate solution, sodium citrate solution and acetic acid manganese solution are mixed evenly made from step (1),
It is added at the same time in reactor with sodium hydroxide solution, stirring reaction 1.1h, the reaction solution after reaction are added to step at 40-50 DEG C
Suddenly in reaction solution made from (2), stirring 30min is placed in high temperature oven, and the reaction was continued at 160 DEG C 3h is cold after reaction
But to room temperature, by reacting liquid filtering, obtained solid is washed with deionized water, absolute ethyl alcohol successively, dry, and composite catalyzing is made
Agent；Wherein, ammonium molybdate solution, the mass ratio of sodium citrate solution are 5：0.4；The composite catalyst in parts by weight, by 50
Part molybdenum, 30 parts of manganese and 3 parts of nano-titanium dioxides compositions；
(4) 2- picolines, glacial acetic acid are added in three-necked flask, it is 25% hydrogen peroxide that concentration, which is then added dropwise, stirring
After mixing, 80-90 DEG C is to slowly warm up to, reaction solution, is evaporated under reduced pressure, removes 126-127 by stirring reaction 3.5h after reaction
DEG C/2.00kPa front-end volatiles, acetic anhydride is added dropwise into residue, and 135 DEG C are to slowly warm up to, continue stirring reaction 30min, instead
Reaction solution is evaporated under reduced pressure after answering, collects the component of 117-119 DEG C/2.93kPa, acetic acid 2- picolyls are made；
Yield is 85.5%；
(5) sodium hydroxide solution is added dropwise into acetic acid 2- picolyls, then hydrolysis 5h, reaction terminate at 90 DEG C
Postcooling is evaporated under reduced pressure reaction solution, collects 92-93 DEG C/1.06kPa cuts, 2- pyridinemethanols are made to room temperature；Yield
91.3%；
(6) 2- pyridinemethanols and dichloromethane are mixed evenly, are transferred in three-necked flask, then add above-mentioned system
The composite catalyst and hydrogen peroxide obtained, 3h is reacted in stirring at 30-40 DEG C after addition, is cooled to room temperature after reaction,
Filtering, collects filtrate, and air-distillation removes dichloromethane, and then residue vacuum decompression is distilled, and 63-65 DEG C of collection/
The cut of 1.73kPa, is made 2- pyridine carboxaldehydes, yield 98.0%；Wherein, 2- pyridinemethanols, composite catalyst, hydrogen peroxide
Mass ratio is 10：1：4.
Claims (8)
1. a kind of 2- picolines catalysis oxidation prepares the preparation method of 2- pyridine carboxaldehydes, it is characterised in that comprises the following steps：
(1) using deionized water as solvent, ammonium molybdate solution, sodium citrate solution, acetic acid manganese solution, sodium hydroxide solution are prepared；
(2) absolute ethyl alcohol and hexamethylene are mixed, and adds glacial acetic acid, triethylamine and butyl titanate, after being uniformly mixed,
It is transferred in reaction kettle and 20h is reacted at 150 DEG C, after reaction, is cooled to room temperature, obtains reaction solution；
(3) by after ammonium molybdate solution, sodium citrate solution and acetic acid manganese solution are mixed evenly made from step (1), and hydrogen
Sodium hydroxide solution is added in reactor at the same time, and stirring reaction 0.5-1.5h, the reaction solution after reaction are added to step at 40-50 DEG C
Suddenly in reaction solution made from (2), stirring 30min is placed in high temperature oven, and the reaction was continued at 120-180 DEG C 3h, reaction terminates
To room temperature, by reacting liquid filtering, obtained solid is washed postcooling with deionized water, absolute ethyl alcohol successively, dry, is made compound
Catalyst；
(4) 2- picolines, glacial acetic acid are added in three-necked flask, it is 25% hydrogen peroxide that concentration, which is then added dropwise, is stirred
Afterwards, 80-90 DEG C is to slowly warm up to, reaction solution, is evaporated under reduced pressure by stirring reaction 2-4h after reaction, 126-127 DEG C of removing/
2.00kPa front-end volatiles, acetic anhydride is added dropwise into residue, and is to slowly warm up to 135 DEG C, continues stirring reaction 30min, reaction knot
Reaction solution is evaporated under reduced pressure after beam, collects the component of 117-119 DEG C/2.93kPa, acetic acid 2- picolyls are made；
(5) sodium hydroxide solution is added dropwise into acetic acid 2- picolyls, then the hydrolysis 5h at 90 DEG C, cold after reaction
But to room temperature, reaction solution is evaporated under reduced pressure, collects 92-93 DEG C/1.06kPa cuts, 2- pyridinemethanols are made；
(6) 2- pyridinemethanols and dichloromethane are mixed evenly, are transferred in three-necked flask, then added obtained above
Composite catalyst and hydrogen peroxide, 1-3h is reacted in stirring at 30-40 DEG C after addition, is cooled to room temperature after reaction, mistake
Filter, collects filtrate, and air-distillation removes dichloromethane, and then residue vacuum decompression is distilled, and 63-65 DEG C of collection/
The cut of 1.73kPa, is made 2- pyridine carboxaldehydes.
2. a kind of 2- picolines catalysis oxidation as claimed in claim 1 prepares the preparation method of 2- pyridine carboxaldehydes, its feature
It is：In step (1), the mass concentration of the sodium hydroxide solution is 15%.
3. a kind of 2- picolines catalysis oxidation as claimed in claim 1 prepares the preparation method of 2- pyridine carboxaldehydes, its feature
It is：In step (1), the ammonium molybdate solution, sodium citrate solution, the molar concentration of acetic acid manganese solution is respectively 0.5-
0.8moL/L、0.1moL/L、0.5-0.8moL/L。
4. a kind of 2- picolines catalysis oxidation as claimed in claim 1 prepares the preparation method of 2- pyridine carboxaldehydes, its feature
It is：In step (3), ammonium molybdate solution, the mass ratio of sodium citrate solution are 5：(0.1-0.5).
5. a kind of 2- picolines catalysis oxidation as claimed in claim 1 prepares the preparation method of 2- pyridine carboxaldehydes, its feature
It is：In step (2), absolute ethyl alcohol, hexamethylene, glacial acetic acid, triethylamine, the volume ratio of butyl titanate are 5:50:5:1:1.
6. a kind of 2- picolines catalysis oxidation as claimed in claim 1 prepares the preparation method of 2- pyridine carboxaldehydes, its feature
It is：In step (4), the 2- picolines, glacial acetic acid, the volume ratio of hydrogen peroxide are 1:3:5.
7. a kind of 2- picolines catalysis oxidation as claimed in claim 1 prepares the preparation method of 2- pyridine carboxaldehydes, its feature
It is：In step (6), 2- pyridinemethanols, composite catalyst, the mass ratio of hydrogen peroxide are (6-11)：(1-2)：4.
8. a kind of 2- picolines catalysis oxidation as claimed in claim 1 prepares the preparation method of 2- pyridine carboxaldehydes, its feature
It is：In step (3), the composite catalyst in parts by weight, by 30-55 parts of molybdenums, 15-35 parts of manganese and 1-3 parts of nano-silicas
Change titanium composition.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104399486A (en) * | 2014-12-02 | 2015-03-11 | 安徽星宇化工有限公司 | Preparation method for manganese dioxide composite catalyst and synthetic method for 2-pyridylaldehyde |
| CN107043348A (en) * | 2017-06-26 | 2017-08-15 | 刘瑞海 | A kind of synthetic method of 4 pyridinemethanol |
| CN107286086A (en) * | 2017-05-23 | 2017-10-24 | 河北科技大学 | N cyanogen methyl is double（Trifluoromethyl）The preparation method and N cyanogen methyl of niacinamide are double（Trifluoromethyl）The application of niacinamide |
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| CN104399486A (en) * | 2014-12-02 | 2015-03-11 | 安徽星宇化工有限公司 | Preparation method for manganese dioxide composite catalyst and synthetic method for 2-pyridylaldehyde |
| CN107286086A (en) * | 2017-05-23 | 2017-10-24 | 河北科技大学 | N cyanogen methyl is double（Trifluoromethyl）The preparation method and N cyanogen methyl of niacinamide are double（Trifluoromethyl）The application of niacinamide |
| CN107043348A (en) * | 2017-06-26 | 2017-08-15 | 刘瑞海 | A kind of synthetic method of 4 pyridinemethanol |
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| 于艳辉等: "溶胶-凝胶法制备含铁的纳米TiO2 光催化剂及其表征", 《应用化学》 * |
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