CN105601559B - A kind of synthetic method of 2 pyridine carboxaldehyde - Google Patents

A kind of synthetic method of 2 pyridine carboxaldehyde Download PDF

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CN105601559B
CN105601559B CN201610126264.0A CN201610126264A CN105601559B CN 105601559 B CN105601559 B CN 105601559B CN 201610126264 A CN201610126264 A CN 201610126264A CN 105601559 B CN105601559 B CN 105601559B
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attapulgite
mno
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composite catalyst
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CN105601559A (en
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张宽宇
金文艺
丁亮
李静
张升
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ANHUI XINGYU CHEMICAL Co Ltd
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Abstract

The invention discloses a kind of synthetic method of 2 pyridine carboxaldehyde, belong to organic synthesis field.Potassium permanganate is supported on the modified attapulgite of acid by the present invention first, obtains MnO4 ‑Attapulgite, then again with coprecipitation by Fe3O4It is supported on MnO4 ‑A kind of MnO of high catalytic activity is obtained on attapulgite, after roasting2Composite catalyst, the present invention is successfully by the catalysis advantage of manganese dioxide and attapulgite Fe3O4The quick separating advantage of magnetic material combines so that catalyst manganese dioxide can reclaim and repeatable utilization.By MnO2Composite catalyst is used to prepare 2 pyridine carboxaldehydes, and reaction yield is high, mild condition, and reaction terminates rear catalyst and can separated and recycle from reaction solution by magnetic sedimentation.The present invention has the advantages such as environmental pollution is small, reaction cost is low, suitable for industrial applications.

Description

A kind of synthetic method of 2- pyridine carboxaldehydes
The present invention is divisional application, former Chinese Patent Application No.：201410720291.1 the applying date：December 2 in 2014 Day, patent name during application：A kind of preparation method of manganese dioxide composite catalyst and the synthetic method of 2- pyridine carboxaldehydes.
Technical field
The invention belongs to organic synthesis field, specifically, is related to a kind of preparation method of medicine intermediate, more specifically Say, be related to a kind of preparation method of manganese dioxide composite catalyst and the synthetic method of 2- pyridine carboxaldehydes.
Background technology
2- pyridine carboxaldehydes are caccagogue Bisacody (bisacody1) intermediates, are also widely used as Minute Organic Synthesis Raw material.The 2- pyridine carboxaldehyde synthetic routes of document report have many kinds, but are summed up mainly former with two kinds of different startings The route of material, first, using 2-Pyridinecarboxylic Acid as initiation material, through esterification, hydrazinolysis, reoxidize to obtain 2- pyridine carboxaldehydes (Huang Shengtang, Huang Improvement [J] chemical reagent of Wen Long, Zhang Huibin .2- pyridine carboxaldehyde synthesis techniques, 2005,27 (1):58)；Second, with 2- methyl Pyridine is raw material, aoxidize through N-, reset, hydrolyze after reoxidize and prepare 2- pyridine carboxaldehydes and (Dan Shiming, Yu Shuqin, Liao Hong, wait .2- Synthesis [J] Chinese Journal of Pharmaceuticals of pyridine carboxaldehyde, 1997,28 (8):377-378), but oxidant selenium dioxide used or Lead tetraacetate toxicity is big, easily causes environmental pollution, and yield is not high.It is a kind of very heavy in organic synthesis to synthesize aldehyde by alcohol The reaction wanted, aldehyde can be obtained by the oxidation of primary alconol, but because aldehyde is a kind of intermediate oxidation state material in alcohol and carboxylic acid, Hyperoxidation generation carboxylic acid is easy in course of reaction, therefore, it is necessary to suitable oxidant be selected, under appropriate reaction condition By oxidation of primary alcohols into aldehyde.
Through retrieval, the A of Chinese patent application publication number CN 101906068, the applying date is the patent Shen on June 4th, 2009 Please file disclose a kind of preparation method of 2- pyridine carboxaldehydes, its step is：(1) using 2- picolines as raw material, halogenated hydrocarbons is Solvent, benzamide are catalyst, three chlorine isocyanates are chlorinating agent, and temperature rising reflux reacts to obtain 2- PMCs；(2)2- PMC hydrolyzes in the basic conditions, and 2- pyridinemethanols are made in temperature reaction；(3) 2- pyridinemethanols are using halogenated hydrocarbons to be molten Agent, 2,2,6,6- tetramethyl piperidine nitrogen oxides and KBr are catalyst, are cooled to -10~0 DEG C, 10wt.% oxygen is added dropwise Agent is liquor natrii hypochloritis, and drop finishes and obtains 2- pyridine carboxaldehydes in 10~25 DEG C of insulations, the invention with oxidisability it is weaker 2,2, 6,6- tetramethyl piperidine nitrogen oxides and KBr are that 2- pyridinemethanols are oxidized to 2- pyridine carboxaldehydes by catalyst, after reaction terminates Catalyst can not recycle, and not only waste and also pollute environment so that reaction cost increase.Chinese patent application publication number CN 102241624 A, the applying date disclose a kind of preparation side of pyridine-2-formaldehyde for the patent application document on July 15th, 2011 Method, this method include：It is containing for auxiliary to prepare by carrier, molybdenum bismuth oxide, transition metal oxide of titanium dioxide There is the loaded catalyst of acidity regulator, using 2- picolines, oxygen gas and water as raw material, in fixed bed catalytic reactor Reaction, in 250-350 DEG C carry out gas phase oxidation generation pyridine-2-formaldehyde crude product, crude product after dichloromethane extracts, Extract, which is evaporated under reduced pressure, removes dichloromethane, and then rectifying obtains the sterling of content more than 98%, pyridine synthesis -2- first in the invention Need to be passed through oxygen during aldehyde, reaction has certain danger, and contains contents of many kinds of heavy metal ion in catalyst, these heavy metals Ion in the reaction can slow release into reaction solution so that content of beary metal is higher in reaction product, is not easy to remove, influences pyrrole The subsequent applications of pyridine -2- formaldehyde.
The content of the invention
1. to solve the problems, such as
The problems such as can not being recycled for catalyst in the prior art be present, polluting environment and easy peroxidating, this Invention provides a kind of preparation method of manganese dioxide composite catalyst and the synthetic method of 2- pyridine carboxaldehydes, to be fixed on concave convex rod MnO on soil2For catalyst, aoxidized to obtain 2- pyridine carboxaldehydes by 2- pyridinemethanols, reaction yield is high, and reaction terminates rear catalyst It can be recycled by magnetic sedimentation, it is free from environmental pollution and cost-effective, suitable for industrial applications.
2. technical scheme
In order to solve the above problems, the technical solution adopted in the present invention is as follows：
A kind of preparation method of manganese dioxide composite catalyst, its step are：
(1) by attapulgite miberal powder and deionized water in mass ratio 1:4 mixing, stir 40min, then stand 2h, discard Supernatant liquor and lower floor's sandy soil, obtain the suspension of attapulgite, and the attapulgite obtained after suspension is centrifuged is put Dried in baking oven under the conditions of 80 DEG C, it is standby；
(2) by the attapulgite obtained in above-mentioned steps and 2.5mol/L sulfuric acid solutions in mass ratio 1:3 mixing, at 80 DEG C Under the conditions of stir 1h, be subsequently cooled to room temperature, with deionized water rinsing to neutrality, dry grinding under the conditions of 80 DEG C in baking oven, 200 mesh sieves are crossed, obtain the modified attapulgite of acid；
(3) the modified attapulgite of the acid obtained in above-mentioned steps is added to 0.15-0.30mol/L liquor potassic permanganate In, 30min is stirred under the conditions of 40 DEG C, attapulgite is fully absorbed potassium permanganate, is then centrifuged for separating, with distillation water washing To neutrality, then washed 3-4 times with absolute ethyl alcohol, dried under the conditions of product then is placed in into 40-50 DEG C to constant weight and obtain MnO4 -- Attapulgite；
(4) MnO that will be obtained in above-mentioned steps4 -- attapulgite, which adds, contains Fe2+And Fe3+Saturation mixed solution in, 15-20min is stirred with 250-300rpm speed under the conditions of 40 DEG C, makes attapulgite saturation absorption iron Fe2+And Fe3+, then drip Add 0.5-0.6mol/L ammonia spirit, ammoniacal liquor to continue to be aged 20min after being added dropwise, obtain MnO4 -- attapulgite-Fe3O4 Composite, wherein, Fe2+With Fe3+Molar concentration rate be 1:(2-3)；
(5) after ageing terminates in above-mentioned steps, with magnetic separation method by MnO4 -- attapulgite-Fe3O4Composite is from suspension Separated in liquid, and be washed with distilled water to neutrality, then washed 3-4 times with absolute ethyl alcohol, product is then placed in 40-50 DEG C drying box in dry to constant weight；
(6) by the MnO in above-mentioned steps4 -- attapulgite-Fe3O4Composite is placed in reacting furnace, is protected in inert gas Then the lower temperature programming of shield naturally cools to room temperature, obtains MnO to 250-300 DEG C of roasting 3-4h2Composite catalyst；
(7) MnO that will be obtained in above-mentioned steps2Composite catalyst is ground, and is crossed 200 mesh sieves, is obtained MnO2Composite catalyst powder Body.
Preferably, the mass ratio of liquor potassic permanganate and attapulgite is (2-3) in the step (3):1.
Preferably, MnO in the step (4)4 -- attapulgite, ferric ion solutions, the mass ratio of ammoniacal liquor are (3-5):1: (2-3)。
Preferably, step (6) the Program programming rate is 4 DEG C/min.
A kind of synthetic method of 2- pyridine carboxaldehydes, its step are：
(a) 2- pyridinemethanols are dissolved in dichloromethane and stirred, wherein the concentration of 2- pyridinemethanols is 0.3-0.5g/ mL；
(b) by above-mentioned MnO2Composite catalyst powder is added in the solution in step (a) and is well mixed, at 38-45 DEG C Under the conditions of back flow reaction 3-4h；
(c) reaction solution is cooled to room temperature after back flow reaction terminates, then with magnetic separation method by MnO2Composite catalyst powder Body is separated from reaction solution, obtains dichloromethane reaction solution；
(d) the dichloromethane reaction solution obtained in step (c) is distilled to recover dichloromethane at ambient pressure, then in Gao Zhen Distilled under empty reduced pressure, collect 63~65 DEG C/1.73KPa cut, obtain 2- pyridine carboxaldehydes.
Preferably, MnO in described step (b)2The concentration of composite catalyst powder is 0.05-0.1g/mL.
Preferably, in described step (b) under the conditions of 40 DEG C back flow reaction 3.5h.
A kind of MnO2Composite catalyst, adopt and be prepared with the aforedescribed process.
MnO2Application of the composite catalyst in 2- pyridine carboxaldehydes are prepared.
3. beneficial effect
Compared to prior art, beneficial effects of the present invention are：
(1) significantly increase its specific surface area, then by potassium permanganate with the modified method activation attapulgite of acid in the present invention It is absorbed and fixed on attapulgite, obtains MnO4 -- attapulgite, by MnO4 -- attapulgite is calcined 3- under inert gas shielding The MnO that 4h is subsequently obtained2- attapulgite has catalytic activity, is easy to separate from reaction solution in order that obtaining catalyst, this With coprecipitation by Fe in invention3O4It is supported on MnO4 -- attapulgite, then it is calcined to obtain the MnO of high activity2It is compound to urge Agent powder；
(2) preparation method of a kind of manganese dioxide composite catalyst in the present invention, under appropriate conditions by catalyst Manganese dioxide load is in attapulgite-Fe3O4On magnetic material, successfully by the catalysis advantage of manganese dioxide and attapulgite- Fe3O4The quick separating advantage of magnetic material combines so that catalyst manganese dioxide can reclaim and repeatable utilization, load Manganese dioxide afterwards still keeps very high catalytic activity, compared with prior art, greatly reduces environmental pollution, and make product Later separation purifying is simpler, and the 2- pyridine carboxaldehydes of high-purity are can obtain through being evaporated under reduced pressure；
(3) synthetic method of 2- pyridine carboxaldehydes of the invention is using the activated manganese dioxide loaded as catalyst, suitable Under the conditions of back flow reaction obtain 2- pyridine carboxaldehydes, reaction yield is high, and catalyst can be recycled by magnetic sedimentation, dichloromethane It can recycle and reuse, the product purity for being evaporated under reduced pressure to obtain is high, does not have catalyst residual in reaction product, and reaction cost is low, Income is high；
(4) manganese dioxide load method and 2- pyridine carboxaldehyde preparation method techniques of the invention are simple, and mild condition is easily grasped Make, it is free from environmental pollution and cost-effective, suitable for industrial applications.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of preparation method of the present invention；
Fig. 2 is the structural representation of 2- pyridine carboxaldehydes in the present invention.
Embodiment
The present invention is further described below with reference to specific embodiment.
Embodiment 1
As depicted in figs. 1 and 2,
A kind of preparation method of manganese dioxide composite catalyst, its step are：
(1) by attapulgite miberal powder and deionized water in mass ratio 1:4 mixing, stir 40min, then stand 2h, discard Supernatant liquor and lower floor's sandy soil, obtain the suspension of attapulgite, and the attapulgite obtained after suspension is centrifuged is put Dried in baking oven under the conditions of 80 DEG C, it is standby；
(2) by the attapulgite obtained in above-mentioned steps and 2.5mol/L sulfuric acid solutions in mass ratio 1:3 mixing, at 80 DEG C Under the conditions of stir 1h, be subsequently cooled to room temperature, with deionized water rinsing to neutrality, dry grinding under the conditions of 80 DEG C in baking oven, 200 mesh sieves are crossed, obtain the modified attapulgite of acid；
(3) the modified attapulgite of the acid obtained in above-mentioned steps is added in 0.15mol/L liquor potassic permanganate, it is high The mass ratio of potassium manganate solution and attapulgite is 3:1,30min is stirred under the conditions of 40 DEG C, attapulgite is fully absorbed height Potassium manganate, it is then centrifuged for separating, is washed with distilled water to neutrality, is then washed 3 times with absolute ethyl alcohol, product is then placed in 40 Dried under the conditions of DEG C to constant weight and obtain MnO4 -- attapulgite；
(4) MnO that will be obtained in above-mentioned steps4 -- attapulgite, which adds, contains Fe2+And Fe3+Saturation mixed solution in, 20min is stirred with 250rpm speed under the conditions of 40 DEG C, makes attapulgite saturation absorption iron Fe2+And Fe3+, then it is added dropwise 0.5mol/L ammonia spirit, ammoniacal liquor continue to be aged 20min after being added dropwise, and obtain MnO4 -- attapulgite-Fe3O4Composite wood Material, wherein, Fe2+With Fe3+Molar concentration rate be 1:2, MnO4 -- attapulgite, ferric ion solutions, the mass ratio of ammoniacal liquor are 3: 1:2；
(5) after ageing terminates in above-mentioned steps, with magnetic separation method by MnO4 -- attapulgite-Fe3O4Composite is from suspension Separated in liquid, and be washed with distilled water to neutrality, then washed 3 times with absolute ethyl alcohol, product is then placed in 40 DEG C Dried in drying box to constant weight；
(6) by the MnO in above-mentioned steps4 -- attapulgite-Fe3O4Composite is placed in reacting furnace, is protected in inert gas 250 DEG C of roasting 4h are warming up to 4 DEG C/min speed programs under shield, room temperature is then naturally cooled to, obtains MnO2Composite catalyst；
(7) MnO that will be obtained in above-mentioned steps2Composite catalyst is ground, and is crossed 200 mesh sieves, is obtained MnO2Composite catalyst powder Body.
A kind of synthetic method of 2- pyridine carboxaldehydes, its step are：
(a) 2- pyridinemethanols are dissolved in dichloromethane and stirred, wherein the concentration of 2- pyridinemethanols is 0.3g/mL；
(b) by above-mentioned MnO2Composite catalyst powder is added in the solution in step (a) and is well mixed, in 38 DEG C of conditions Lower back flow reaction 4h, wherein MnO2The concentration of composite catalyst powder is 0.05g/mL；
(c) reaction solution is cooled to room temperature after back flow reaction terminates, then with magnetic separation method by MnO2Composite catalyst powder Body is separated from reaction solution, obtains dichloromethane reaction solution；
(d) the dichloromethane reaction solution obtained in step (c) is distilled to recover dichloromethane at ambient pressure, then in Gao Zhen Distilled under empty reduced pressure, collect 63~65 DEG C/1.73KPa cut, obtain 2- pyridine carboxaldehydes.
The yield that 2- pyridine carboxaldehydes are prepared in the present embodiment is 92%, analyzes its purity up to 99.5% through chromatography of gases, magnetic The MnO obtained after separation2Composite catalyst powder stable in catalytic performance, it can continue on for preparing 2- pyridine carboxaldehydes.
Embodiment 2
A kind of preparation method of manganese dioxide composite catalyst, its step are：
(1) by attapulgite miberal powder and deionized water in mass ratio 1:4 mixing, stir 40min, then stand 2h, discard Supernatant liquor and lower floor's sandy soil, obtain the suspension of attapulgite, and the attapulgite obtained after suspension is centrifuged is put Dried in baking oven under the conditions of 80 DEG C, it is standby；
(2) by the attapulgite obtained in above-mentioned steps and 2.5mol/L sulfuric acid solutions in mass ratio 1:3 mixing, at 80 DEG C Under the conditions of stir 1h, be subsequently cooled to room temperature, with deionized water rinsing to neutrality, dry grinding under the conditions of 80 DEG C in baking oven, 200 mesh sieves are crossed, obtain the modified attapulgite of acid；
(3) the modified attapulgite of the acid obtained in above-mentioned steps is added in 0.25mol/L liquor potassic permanganate, it is high The mass ratio of potassium manganate solution and attapulgite is 2.5:1,30min is stirred under the conditions of 40 DEG C, fully absorbs attapulgite Potassium permanganate, it is then centrifuged for separating, is washed with distilled water to neutrality, is then washed 4 times with absolute ethyl alcohol, be then placed in product Dried under the conditions of 45 DEG C to constant weight and obtain MnO4 -- attapulgite；
(4) MnO that will be obtained in above-mentioned steps4 -- attapulgite, which adds, contains Fe2+And Fe3+Saturation mixed solution in, 18min is stirred with 280rpm speed under the conditions of 40 DEG C, makes attapulgite saturation absorption iron Fe2+And Fe3+, then it is added dropwise 0.6mol/L ammonia spirit, ammoniacal liquor continue to be aged 20min after being added dropwise, and obtain MnO4 -- attapulgite-Fe3O4Composite wood Material, wherein, Fe2+With Fe3+Molar concentration rate be 1:2.5, MnO4 -- attapulgite, ferric ion solutions, the mass ratio of ammoniacal liquor are 4:1:2.5；
(5) after ageing terminates in above-mentioned steps, with magnetic separation method by MnO4 -- attapulgite-Fe3O4Composite is from suspension Separated in liquid, and be washed with distilled water to neutrality, then washed 4 times with absolute ethyl alcohol, product is then placed in 45 DEG C Dried in drying box to constant weight；
(6) by the MnO in above-mentioned steps4 -- attapulgite-Fe3O4Composite is placed in reacting furnace, is protected in inert gas 270 DEG C of roasting 3.5h are warming up to 4 DEG C/min speed programs under shield, room temperature is then naturally cooled to, obtains MnO2Composite catalyzing Agent；
(7) MnO that will be obtained in above-mentioned steps2Composite catalyst is ground, and is crossed 200 mesh sieves, is obtained MnO2Composite catalyst powder Body.
A kind of synthetic method of 2- pyridine carboxaldehydes, its step are：
(a) 2- pyridinemethanols are dissolved in dichloromethane and stirred, wherein the concentration of 2- pyridinemethanols is 0.4g/mL；
(b) by above-mentioned MnO2Composite catalyst powder is added in the solution in step (a) and is well mixed, in 40 DEG C of conditions Lower back flow reaction 3.5h, wherein, MnO2The concentration of composite catalyst powder is 0.08g/mL；
(c) reaction solution is cooled to room temperature after back flow reaction terminates, then with magnetic separation method by MnO2Composite catalyst powder Body is separated from reaction solution, obtains dichloromethane reaction solution；
(d) the dichloromethane reaction solution obtained in step (c) is distilled to recover dichloromethane at ambient pressure, then in Gao Zhen Distilled under empty reduced pressure, collect 63~65 DEG C/1.73KPa cut, obtain 2- pyridine carboxaldehydes.
The yield that 2- pyridine carboxaldehydes are prepared in the present embodiment is 94%, analyzes its purity up to 99.3% through chromatography of gases, magnetic The MnO obtained after separation2Composite catalyst powder stable in catalytic performance, it can continue on for preparing 2- pyridine carboxaldehydes.
Embodiment 3
A kind of preparation method of manganese dioxide composite catalyst, its step are：
(1) by attapulgite miberal powder and deionized water in mass ratio 1:4 mixing, stir 40min, then stand 2h, discard Supernatant liquor and lower floor's sandy soil, obtain the suspension of attapulgite, and the attapulgite obtained after suspension is centrifuged is put Dried in baking oven under the conditions of 80 DEG C, it is standby；
(2) by the attapulgite obtained in above-mentioned steps and 2.5mol/L sulfuric acid solutions in mass ratio 1:3 mixing, at 80 DEG C Under the conditions of stir 1h, be subsequently cooled to room temperature, with deionized water rinsing to neutrality, dry grinding under the conditions of 80 DEG C in baking oven, 200 mesh sieves are crossed, obtain the modified attapulgite of acid；
(3) the modified attapulgite of the acid obtained in above-mentioned steps is added in 0.30mol/L liquor potassic permanganate, it is high The mass ratio of potassium manganate solution and attapulgite is 2:1,30min is stirred under the conditions of 40 DEG C, attapulgite is fully absorbed height Potassium manganate, it is then centrifuged for separating, is washed with distilled water to neutrality, is then washed 4 times with absolute ethyl alcohol, product is then placed in 50 Dried under the conditions of DEG C to constant weight and obtain MnO4 -- attapulgite；
(4) MnO that will be obtained in above-mentioned steps4 -- attapulgite, which adds, contains Fe2+And Fe3+Saturation mixed solution in, 15min is stirred with 300rpm speed under the conditions of 40 DEG C, makes attapulgite saturation absorption iron Fe2+And Fe3+, then it is added dropwise 0.6mol/L ammonia spirit, ammoniacal liquor continue to be aged 20min after being added dropwise, and obtain MnO4 -- attapulgite-Fe3O4Composite wood Material, wherein, Fe2+With Fe3+Molar concentration rate be 1:3, MnO4 -- attapulgite, ferric ion solutions, the mass ratio of ammoniacal liquor are 5: 1:3；
(5) after ageing terminates in above-mentioned steps, with magnetic separation method by MnO4 -- attapulgite-Fe3O4Composite is from suspension Separated in liquid, and be washed with distilled water to neutrality, then washed 4 times with absolute ethyl alcohol, product is then placed in 50 DEG C Dried in drying box to constant weight；
(6) by the MnO in above-mentioned steps4 -- attapulgite-Fe3O4Composite is placed in reacting furnace, is protected in inert gas 300 DEG C of roasting 3h are warming up to 4 DEG C/min speed programs under shield, room temperature is then naturally cooled to, obtains MnO2Composite catalyst；
(7) MnO that will be obtained in above-mentioned steps2Composite catalyst is ground, and is crossed 200 mesh sieves, is obtained MnO2Composite catalyst powder Body.
A kind of synthetic method of 2- pyridine carboxaldehydes, its step are：
(a) 2- pyridinemethanols are dissolved in dichloromethane and stirred, wherein the concentration of 2- pyridinemethanols is 0.5g/mL；
(b) by above-mentioned MnO2Composite catalyst powder is added in the solution in step (a) and is well mixed, in 45 DEG C of conditions Lower back flow reaction 3h, wherein, MnO2The concentration of composite catalyst powder is 0.1g/mL；
(c) reaction solution is cooled to room temperature after back flow reaction terminates, then with magnetic separation method by MnO2Composite catalyst powder Body is separated from reaction solution, obtains dichloromethane reaction solution；
(d) the dichloromethane reaction solution obtained in step (c) is distilled to recover dichloromethane at ambient pressure, then in Gao Zhen Distilled under empty reduced pressure, collect 63~65 DEG C/1.73KPa cut, obtain 2- pyridine carboxaldehydes.
The yield that 2- pyridine carboxaldehydes are prepared in the present embodiment is 93%, analyzes its purity up to 99.6% through chromatography of gases, magnetic The MnO obtained after separation2Composite catalyst powder stable in catalytic performance, it can continue on for preparing 2- pyridine carboxaldehydes.

Claims (6)

1. a kind of synthetic method of 2- pyridine carboxaldehydes, its step are：
(a) 2- pyridinemethanols are dissolved in dichloromethane and stirred, wherein the concentration of 2- pyridinemethanols is 0.3-0.5g/mL；
(b) by MnO2Composite catalyst powder is added in the solution in step (a) and is well mixed, and is flowed back under the conditions of 38-45 DEG C anti- Answer 3-4h；
(c) reaction solution is cooled to room temperature after back flow reaction terminates, then with magnetic separation method by MnO2Composite catalyst powder is from anti- Answer in liquid and separate, obtain dichloromethane reaction solution；
(d) the dichloromethane reaction solution obtained in step (c) is distilled to recover dichloromethane at ambient pressure, then subtracted in high vacuum Distilled under the conditions of pressure, collect 63~65 DEG C/1.73KPa cut, obtain 2- pyridine carboxaldehydes；
MnO described in step (b)2Composite catalyst raw powder's production technology, its step are：
(1) by attapulgite miberal powder and deionized water in mass ratio 1:4 mixing, stir 40min, then stand 2h, discard upper strata Clear liquid and lower floor's sandy soil, obtain the suspension of attapulgite, and the attapulgite obtained after suspension is centrifuged is placed in baking Dried in case under the conditions of 80 DEG C, it is standby；
(2) by the attapulgite obtained in above-mentioned steps and 2.5mol/L sulfuric acid solutions in mass ratio 1:3 mixing, in 80 DEG C of conditions Lower stirring 1h, is subsequently cooled to room temperature, with deionized water rinsing to neutrality, dries grinding under the conditions of 80 DEG C in baking oven, crosses 200 Mesh sieve, obtain the modified attapulgite of acid；
(3) the modified attapulgite of the acid obtained in above-mentioned steps is added in 0.15-0.30mol/L liquor potassic permanganate, 30min is stirred under the conditions of 40 DEG C, attapulgite is fully absorbed potassium permanganate, is then centrifuged for separating, is washed with distilled water to Neutrality, then washed 3-4 times with absolute ethyl alcohol, dried under the conditions of product then is placed in into 40-50 DEG C to constant weight and obtain MnO4 -- recessed Convex rod soil；
(4) MnO that will be obtained in above-mentioned steps4 -- attapulgite, which adds, contains Fe2+And Fe3+Saturation mixed solution in, at 40 DEG C Under the conditions of 15-20min stirred with 250-300rpm speed, make attapulgite saturation absorption iron Fe2+And Fe3+, then it is added dropwise 0.5-0.6mol/L ammonia spirit, ammoniacal liquor continue to be aged 20min after being added dropwise, and obtain MnO4 -- attapulgite-Fe3O4It is multiple Condensation material, wherein, Fe2+With Fe3+Molar concentration rate be 1:(2-3)；
(5) after ageing terminates in above-mentioned steps, with magnetic separation method by MnO4 -- attapulgite-Fe3O4Composite is from suspension Separate, and be washed with distilled water to neutrality, then washed 3-4 times with absolute ethyl alcohol, product is then placed in 40-50 DEG C Dried in drying box to constant weight；
(6) by the MnO in above-mentioned steps4 -- attapulgite-Fe3O4Composite is placed in reacting furnace, under inert gas shielding Then temperature programming naturally cools to room temperature, obtains MnO to 250-300 DEG C of roasting 3-4h2Composite catalyst；
(7) MnO that will be obtained in above-mentioned steps2Composite catalyst is ground, and is crossed 200 mesh sieves, is obtained MnO2Composite catalyst powder.
A kind of 2. synthetic method of 2- pyridine carboxaldehydes according to claim 1, it is characterised in that：It is high in the step (3) The mass ratio of potassium manganate solution and attapulgite is (2-3):1.
A kind of 3. synthetic method of 2- pyridine carboxaldehydes according to claim 1, it is characterised in that：In the step (4) MnO4 -- attapulgite, ferric ion solutions, the mass ratio of ammoniacal liquor are (3-5):1:(2-3).
A kind of 4. synthetic method of 2- pyridine carboxaldehydes according to claim 1, it is characterised in that：Step (6) intermediate range Sequence programming rate is 4 DEG C/min.
A kind of 5. synthetic method of 2- pyridine carboxaldehydes according to claim 1, it is characterised in that：In described step (b) MnO2The concentration of composite catalyst powder is 0.05-0.1g/mL.
A kind of 6. synthetic method of 2- pyridine carboxaldehydes according to claim 1, it is characterised in that：In described step (b) The back flow reaction 3.5h under the conditions of 40 DEG C.
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