CN104974088B - A kind of the efficient of pyridines nitrogen oxides, the preparation method of heterogeneous catalysiss - Google Patents
A kind of the efficient of pyridines nitrogen oxides, the preparation method of heterogeneous catalysiss Download PDFInfo
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- CN104974088B CN104974088B CN201510365861.4A CN201510365861A CN104974088B CN 104974088 B CN104974088 B CN 104974088B CN 201510365861 A CN201510365861 A CN 201510365861A CN 104974088 B CN104974088 B CN 104974088B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/89—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 with hetero atoms directly attached to the ring nitrogen atom
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/58—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems with hetero atoms directly attached to the ring nitrogen atom
- C07D215/60—N-oxides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
- C07D217/02—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines
- C07D217/08—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines with a hetero atom directly attached to the ring nitrogen atom
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Abstract
The invention discloses a kind of preparation method of the efficient heterogeneous catalysiss of pyridines nitrogen oxides.It is initial feed from monosubstituted or polysubstituted pyridine or pyridine derivate, the titanium dioxide of tungsten load（WO3/TiO2）For catalyst, hydrogen peroxide is oxidant, and final product is obtained in room temperature, aqueous solution.The present invention compared with prior art, with following superiority；1st, in the method for oxidation of the present invention, it is to avoid the use of acetic acid in common method, requirement to equipment are substantially reduced；2nd, the present invention efficiently prepares pyridines nitrogen oxides using the method for heterogeneous catalysiss, catalyst and system by it is simple filter or centrifugation be it is separable, it is easy to operate；3rd, this reaction is catalyst using the titanium dioxide of tungsten load, and in room temperature, aqueous solution, a step prepares pyridines nitrogen oxides, and the reaction condition for being adopted is gentle, environmental pollution is little.
Description
Technical field
The present invention relates to a kind of the efficient of pyridines nitrogen oxides, the preparation method of heterogeneous catalysiss.
Background technology
With growing interest of the people to environmental problem, Green Chemistry shows very wide as a new research field
Wealthy development prospect.How high energy consumption in organic synthesiss is solved with the method for environmental protection, and high pollution problem seems very heavy
Will.Pyridines nitrogen oxides are the important nitrogen-containing heterocycle compounds of a class, such as formula oneWith formula twoIt is shown,
Be widely used in being catalyzed, aoxidize, medicine, the field such as sterilization, therefore study the efficient preparation method of this kind of compound there is weight
The realistic meaning wanted.The method of pyridine synthesis class nitrogen oxides has at present（1）With pyridine compounds and their as raw material, in a large amount of acetic acid
Under conditions of presence, pyridines nitrogen oxides are prepared as oxidant with hydrogen peroxide.Acetic acid used by this technique will to equipment
Ask high, and need excessive acetic acid is distilled off after reacting completely, post processing also needs to repeatedly extraction, operates very numerous and diverse.（2）
With pyridine compounds and their as raw material, dichloromethane is solvent, obtains pyridines nitrogen oxides with metachloroperbenzoic acid oxidation.So
And, metachloroperbenzoic acid is expensive, and expression activitiy is high, there is cost and safety problem in a large amount of production.（3）With silicon
Titanium molecular sieve is catalyst, and hydrogen peroxide is that oxidant prepares pyridines nitrogen oxides, and although this method avoids a large amount of organic solvents
Use, but catalyst is relatively costly, and is not easily recycled utilization.There is obvious defect in three of the above preparation method,
The requirement of present price section industrialized production can not be met.Therefore in the urgent need to exploring the pyridines nitrogen oxides for being adapted to industrialized production
Preparation method.
The content of the invention
It is an object of the invention to provide a kind of simple to operate, economic and environment-friendly, yield is good, is adapted to one kind of industrialized production
The efficient of pyridines nitrogen oxides, the preparation method of heterogeneous catalysiss.
For achieving the above object, the present invention is employed the following technical solutions：
A kind of preparation method of pyridines nitrogen oxides, comprises the steps：
Pyridine or pyridine derivate and hydrogenperoxide steam generator are pressed by step one, the titanium dioxide with tungsten load as catalyst
According to 1:（1.5-3）Mixed in molar ratio it is uniform after, add the matter of a certain amount of catalyst, catalyst and pyridine or pyridine derivate
Measuring ratio is（0.02-0.3）:1；
Step 2, mixed liquor prepared by the step one stirring reaction 10-24 hour at 20-65 DEG C, by reacted liquid
Body naturally cools to room temperature, then in turn through filtering, washing, concentrate, obtains pyridine nitric oxide or pyridine after filtrate concentration
The finished product of the nitrogen oxides of derivant.
In the step one, pyridine derivate used is 2- picolines, 3- picolines, 4- picolines, 2,6- bis-
Picoline, 2,3 dimethyl pyridine, 2,4- lutidines, 3,5- lutidines, 2,4,6- trimethylpyridines, 2- chlorine pyrroles
One kind in pyridine, nicotinonitrile, quinoline and isoquinolin.
In the step one, the mol ratio of pyridine or pyridine derivate and hydrogenperoxide steam generator is 1:（2-2.5）.
In the step one, the mass ratio of catalyst and pyridine or pyridine derivate is（0.1-0.2）:1.
In the step one, in hydrogenperoxide steam generator, the mass fraction of solute is 30%.
The preparation method of the titanium dioxide of tungsten load, comprises the steps：
（a）1-2g wolframic acids are added in 500ml deionized waters, pH value of solution are adjusted with the ammonia of 1mol/L complete to wolframic acid
It is molten, 8-12g gas phase titanium dioxide is subsequently adding, after ultrasonic disperse 30-60 minutes, solvent is evaporated at a temperature of 55-65 DEG C；
（b）By step（a）Gained solid obtains the catalyst of white solid under oxygen atmosphere after roasting 2-3 hours, i.e.,
Tungsten load titanium dioxide, sintering temperature are 400-500 DEG C.
P25 of the titanium dioxide for business level, wolframic acid, ammonia are technical grade.
The present invention compared with prior art, with following superiority；1st, in the method for oxidation of the present invention, it is to avoid often
With the use of acetic acid in method, the requirement to equipment is substantially reduced；2nd, the present invention efficiently prepares pyrrole using the method for heterogeneous catalysiss
Pyridine class nitrogen oxides, catalyst and system by it is simple filter or centrifugation be it is separable, it is easy to operate；3rd, this reaction utilizes tungsten
The titanium dioxide of load is catalyst, and in room temperature, aqueous solution, a step prepares pyridines nitrogen oxides, the reaction condition for being adopted
Gently, environmental pollution is little；And the high income of product, purity is good.
Preparation technology of the present invention for an environmental protection, it is easy to operate, it is adapted to the methodology of organic synthesis of industrialized production.
Description of the drawings
Hydrogen nuclear magnetic resonance spectrograms of the Fig. 1 for the 3,5- dimethylpyridine-N-oxides obtained by embodiment 2.
Carbon-13 nmr spectra figures of the Fig. 2 for the 3,5- dimethylpyridine-N-oxides obtained by embodiment 2.
Hydrogen nuclear magnetic resonance spectrograms of the Fig. 3 for the 2- chloropyridine nitrogen oxides obtained by embodiment 3.
Carbon-13 nmr spectra figures of the Fig. 4 for the 2- chloropyridine nitrogen oxides obtained by embodiment 3.
Hydrogen nuclear magnetic resonance spectrograms of the Fig. 5 for the 2,4,6- trimethylpyridine-N- oxides obtained by embodiment 4.
Carbon-13 nmr spectra figures of the Fig. 6 for the 2,4,6- trimethylpyridine-N- oxides obtained by embodiment 4.
Hydrogen nuclear magnetic resonance spectrograms of the Fig. 7 for the 4- methyl pyridine nitrogen oxides obtained by embodiment 6.
Carbon-13 nmr spectra figures of the Fig. 8 for the 4- methyl pyridine nitrogen oxides obtained by embodiment 6.
Hydrogen nuclear magnetic resonance spectrograms of the Fig. 9 for the 2,3 dimethyl pyridine nitrogen oxides obtained by embodiment 7.
Carbon-13 nmr spectra figures of the Figure 10 for the 2,3 dimethyl pyridine nitrogen oxides obtained by embodiment 7.
Hydrogen nuclear magnetic resonance spectrograms of the Figure 11 for the 2,4- lutidines nitrogen oxides obtained by embodiment 10.
Carbon-13 nmr spectra figures of the Figure 12 for the 2,4- lutidines nitrogen oxides obtained by embodiment 10.
Hydrogen nuclear magnetic resonance spectrograms of the Figure 13 for the 3- methyl pyridine nitrogen oxides obtained by embodiment 12.
Carbon-13 nmr spectra figures of the Figure 14 for the 3- methyl pyridine nitrogen oxides obtained by embodiment 12.
Hydrogen nuclear magnetic resonance spectrograms of the Figure 15 for the 2- methyl pyridine nitrogen oxides obtained by embodiment 13.
Carbon-13 nmr spectra figures of the Figure 16 for the 2- methyl pyridine nitrogen oxides obtained by embodiment 13.
Hydrogen nuclear magnetic resonance spectrograms of the Figure 17 for the isoquinoline nitrogen oxide obtained by embodiment 14.
Carbon-13 nmr spectra figures of the Figure 18 for the isoquinoline nitrogen oxide obtained by embodiment 14.
Hydrogen nuclear magnetic resonance spectrograms of the Figure 19 for the 2,6- lutidines nitrogen oxides obtained by embodiment 15.
Carbon-13 nmr spectra figures of the Figure 20 for the 2,6- lutidines nitrogen oxides obtained by embodiment 15.
Hydrogen nuclear magnetic resonance spectrograms of the Figure 21 for the pyridine nitric oxide obtained by embodiment 16.
Carbon-13 nmr spectra figures of the Figure 22 for the pyridine nitric oxide obtained by embodiment 16.
Specific embodiment
Embodiment 1
A kind of preparation method of pyridines nitrogen oxides, comprises the steps：
Pyridine or pyridine derivate and hydrogenperoxide steam generator are pressed by step one, the titanium dioxide with tungsten load as catalyst
According to 1:（1.5-3）Mixed in molar ratio it is uniform after, add the matter of a certain amount of catalyst, catalyst and pyridine or pyridine derivate
Measuring ratio is（0.02-0.3）:1；
Step 2, mixed liquor prepared by the step one stirring reaction 10-24 hour at 20-65 DEG C, by reacted liquid
Body naturally cools to room temperature, then in turn through filtering, washing, concentrate, obtains pyridine nitric oxide or pyridine after filtrate concentration
The finished product of the nitrogen oxides of derivant.
In the step one, pyridine derivate used is 2- picolines, 3- picolines, 4- picolines, 2,6- bis-
Picoline, 2,3 dimethyl pyridine, 2,4- lutidines, 3,5- lutidines, 2,4,6- trimethylpyridines, 2- chlorine pyrroles
One kind in pyridine, nicotinonitrile, quinoline and isoquinolin.
In the step one, the mol ratio of pyridine or pyridine derivate and hydrogenperoxide steam generator is 1:（2-2.5）.
In the step one, the mass ratio of catalyst and pyridine or pyridine derivate is（0.1-0.2）:1.
In the step one, in hydrogenperoxide steam generator, the mass fraction of solute is 30%.
The preparation method of the titanium dioxide of tungsten load, comprises the steps：
（a）1-2g wolframic acids are added in 500ml deionized waters, pH value of solution are adjusted with the ammonia of 1mol/L complete to wolframic acid
It is molten, 8-12g gas phase titanium dioxide is subsequently adding, after ultrasonic disperse 30-60 minutes, solvent is evaporated at a temperature of 55-65 DEG C；
（b）By step（a）Gained solid obtains the catalyst of white solid under oxygen atmosphere after roasting 2-3 hours, i.e.,
Tungsten load titanium dioxide, sintering temperature are 400-500 DEG C.
P25 of the titanium dioxide for business level, wolframic acid, ammonia are technical grade.
The present invention is using the purity of pyridines nitrogen oxides obtained by high performance liquid chromatography detection.
Embodiment 2
The preparation of the titanium dioxide of tungsten load, comprises the steps：
（a）1.56g wolframic acids are added in 500ml deionized waters, pH value of solution are adjusted with the ammonia of 1mol/L complete to wolframic acid
It is molten, it is subsequently adding business-like titanium dioxide（P25）Solvent was steamed at a temperature of 60 DEG C after 30 minutes by 10g, ultrasonic disperse
It is dry；
（b）By step（a）In Muffle furnace, under oxygen atmosphere, roasting obtains the catalysis of white solid to gained solid after 2 hours
Agent, i.e. tungsten load titanium dioxide, sintering temperature are 450 DEG C, are designated as 5% WO3/TiO2。
The preparation of one kind 3,5- lutidines nitrogen oxides, comprises the steps：
Step one, the titanium dioxide with tungsten load as catalyst, by 20g 3,5- lutidines, the peroxide of 50mL30%
Change hydrogen solution, 1g steps（a）The catalyst of middle preparation is added in there-necked flask；
Step 2, mixed liquor prepared by step one stirring reaction 10 hours at 40 DEG C, by reacted liquid nature
Be cooled to room temperature, then in turn through filter, washing, concentration, filtrate concentration after obtain 3,5- lutidines nitrogen oxides into
Product 21.5g, yield:93.7%, high performance liquid chromatography detection purity is 95.8%.
Further to verify the effect of the present invention, by the present embodiment final obtained finished product, using Brooker (Bruker)
AV400 type nuclear magnetic resonance analyser is detected that testing result is as follows：As shown in the hydrogen nuclear magnetic resonance spectrogram of Fig. 1,1H-NMR
(CDCl3, 400MHz) δ: 8.00-7.88 (s, 2H), 7.00-6.91 (s, 1H), 2.40-2.21 (s, 6H)；Such as
Shown in the carbon-13 nmr spectra figure of Fig. 2,13C-NMR (CDCl3, 100MHz) δ: 136.4, 135.8 128.5, 18.0.
ESI-MS: M/Z calcd for C7H9NO+ : 123.0684, M+: found: 122.9165.。
Embodiment 3
The preparation of the titanium dioxide of tungsten load, comprises the steps：
（a）1.81g wolframic acids are added in 500ml deionized waters, pH value of solution are adjusted with the ammonia of 1mol/L complete to wolframic acid
It is molten, it is subsequently adding the business-like titanium dioxide of 12g（P25）, ultrasonic disperse is after 50 minutes, and solvent is steamed at a temperature of 55 DEG C
It is dry；
（b）By step（a）In Muffle furnace, under oxygen atmosphere, roasting obtains the catalysis of white solid to gained solid after 3 hours
Agent, i.e. tungsten load titanium dioxide, sintering temperature are 400 DEG C, are designated as 5% WO3/TiO2。
A kind of preparation of 2- chloropyridines nitrogen oxides, comprises the steps：
Step one, the titanium dioxide with tungsten load, will be the hydrogen peroxide of 20g 2- chloropyridines, 45mL30% molten as catalyst
Liquid, 3g steps（a）The catalyst of middle preparation is added in there-necked flask；
Step 2, mixed liquor prepared by step one stirring reaction 18 hours at 20 DEG C, by reacted liquid nature
Room temperature is cooled to, then in turn through filtering, washing, concentrate, after filtrate concentration, 2- chloropyridine nitrogen oxides finished products is obtained
22.8g, yield:94.8%, high performance liquid chromatography detection purity is 94.7%.By the present embodiment final obtained finished product, using cloth
Lu Ke (Bruker) AV400 type nuclear magnetic resonance analyser is detected that testing result is as follows：2-Chloropyridine-N-oxideAs shown in the hydrogen nuclear magnetic resonance spectrogram of Fig. 3,1H-NMR (CDCl3, 400MHz) δ: 8.28-8.24 (s, 1H),
8.15-8.10 (d, 1H), 7.28-7.26 (s, 1H), 7.26-7.20 (t, 1H);Such as the carbon-13 nmr spectra of Fig. 4
Shown in figure13C-NMR (CDCl3, 100MHz) δ: 138.7, 137.7, 133.3, 126.0, 125.8.。
Embodiment 4
The preparation of the titanium dioxide of tungsten load, comprises the steps：
（a）2g wolframic acids are added in 500ml deionized waters, the ammonia regulation pH value of solution with 1mol/L is entirely molten to wolframic acid,
It is subsequently adding the business-like titanium dioxide of 10.6g（P25）, solvent is evaporated at a temperature of 56 DEG C after 30 minutes by ultrasonic disperse；
（b）By step（a）In Muffle furnace, under oxygen atmosphere, roasting obtains the catalysis of white solid to gained solid after 3 hours
Agent, i.e. tungsten load titanium dioxide, sintering temperature are 430 DEG C, are designated as 5% WO3/TiO2。
A kind of preparation of 2,4,6- trimethylpyridines nitrogen oxides, comprises the steps：
Step one, the titanium dioxide with tungsten load as catalyst, by 20g 2，4，6-trimethylpyridine, the mistake of 45mL30%
Hydrogen peroxide solution, 1.1g steps（a）The catalyst of middle preparation is added in there-necked flask；
Step 2, mixed liquor prepared by step one stirring reaction 22 hours at 45 DEG C, by reacted liquid nature
Room temperature is cooled to, then in turn through filtering, washing, concentrate, after filtrate concentration, 2，4，6-trimethylpyridine nitrogen oxides is obtained
Finished product 20.8g, yield:92.0%, high performance liquid chromatography detection purity is 93.1%.
Further to verify the effect of the present invention, by the present embodiment final obtained finished product, using Brooker (Bruker)
AV400 type nuclear magnetic resonance analyser is detected that testing result is as follows：As shown in the hydrogen nuclear magnetic resonance spectrogram of Fig. 5,1H-NMR
(CDCl3, 400MHz) δ: 7.01-6.93 (s, 2H), 2.54-2.48 (s, 6H), 2.30-2.26 (s, 3H)；
As shown in the carbon-13 nmr spectra figure of Fig. 6,13C-NMR (CDCl3, 100MHz) δ: 148.0, 135.8, 124.8,
20.2, 18.0. ESI-MS: M/Z calcd for C7H9NO+ : 137.0840, M+: found: 136.8936.。
Embodiment 5
The preparation of the titanium dioxide of tungsten load, comprises the steps：
（a）1.6g wolframic acids are added in 500ml deionized waters, pH value of solution are adjusted with the ammonia of 1mol/L complete to wolframic acid
It is molten, it is subsequently adding the business-like titanium dioxide of 10.6g（P25）, ultrasonic disperse is after 30 minutes, and solvent is steamed at a temperature of 56 DEG C
It is dry；
（b）By step（a）In Muffle furnace, under oxygen atmosphere, roasting obtains the catalysis of white solid to gained solid after 3 hours
Agent, i.e. tungsten load titanium dioxide, sintering temperature are 430 DEG C, are designated as 5% WO3/TiO2。
A kind of preparation of Quinoline N-Oxide, comprises the steps：
Step one, the titanium dioxide with tungsten load as catalyst, by 50g quinoline, the hydrogenperoxide steam generator of 45mL30%,
11g steps（a）The catalyst of middle preparation is added in there-necked flask；
Step 2, mixed liquor prepared by step one stirring reaction 22 hours at 35 DEG C, by reacted liquid nature
Room temperature is cooled to, then in turn through filtering, washing, concentrate, after filtrate concentration, Quinoline N-Oxide product yield is obtained:
81.3%, high performance liquid chromatography detection purity is 89.8%.
Embodiment 6
The preparation of the titanium dioxide of tungsten load, comprises the steps：
（a）1.1g wolframic acids are added in 500ml deionized waters, pH value of solution are adjusted with the ammonia of 1mol/L complete to wolframic acid
It is molten, it is subsequently adding the business-like titanium dioxide of 11g（P25）, ultrasonic disperse is after 42 minutes, and solvent is steamed at a temperature of 61 DEG C
It is dry；
（b）By step（a）In Muffle furnace, under oxygen atmosphere, roasting obtains urging for white solid to gained solid after 2.1 hours
Agent, i.e. tungsten load titanium dioxide, sintering temperature are 400 DEG C, are designated as 5% WO3/TiO2。
A kind of preparation of 4- methyl pyridine nitrogen oxides, comprises the steps：
Step one, the titanium dioxide with tungsten load as catalyst, by 50g 4- picolines, the hydrogen peroxide of 70mL30%
Solution, 8g steps（a）The catalyst of middle preparation is added in there-necked flask；
Step 2, mixed liquor prepared by step one stirring reaction 16 hours at 50 DEG C, by reacted liquid nature
Room temperature is cooled to, then in turn through filtering, washing, concentrate, 4- methyl pyridine nitrogen oxides finished product receipts after filtrate concentration, is obtained
Rate:84.7%, high performance liquid chromatography detection purity is 94.3%.It is further to verify the effect of the present invention, the present embodiment is final
Using Brooker (Bruker) AV400 type nuclear magnetic resonance analyser, obtained finished product, is detected that testing result is as follows：4-
Picoline-N-oxideAs shown in the hydrogen nuclear magnetic resonance spectrogram of Fig. 7,1H-NMR (CDCl3, 400MHz) δ: 8.16-
8.08 (s, 2H), 7.16-7.11 (s, 2H), 2.40-2.32 (s, 3H);Such as the carbon-13 nmr spectra figure institute of Fig. 8
Show,13C-NMR (CDCl3, 100MHz) δ: 138.4, 137.5, 126.6, 20.1.。
Embodiment 7
The preparation of the titanium dioxide of tungsten load, comprises the steps：
（a）1g wolframic acids are added in 500ml deionized waters, the ammonia regulation pH value of solution with 1mol/L is entirely molten to wolframic acid,
It is subsequently adding the business-like titanium dioxide of 12g（P25）, solvent is evaporated at a temperature of 61 DEG C after 30 minutes by ultrasonic disperse；
（b）By step（a）In Muffle furnace, under oxygen atmosphere, roasting obtains the catalysis of white solid to gained solid after 2 hours
Agent, i.e. tungsten load titanium dioxide, sintering temperature are 485 DEG C, are designated as 5% WO3/TiO2。
A kind of preparation of 2,3 dimethyl pyridine nitrogen oxides, comprises the steps：
Step one, the titanium dioxide with tungsten load as catalyst, by 50g 2,3- lutidines, the peroxide of 60mL30%
Change hydrogen solution, 1g steps（a）The catalyst of middle preparation is added in there-necked flask；
Step 2, mixed liquor prepared by step one stirring reaction 20 hours at 30 DEG C, by reacted liquid nature
Be cooled to room temperature, then in turn through filter, washing, concentration, filtrate concentration after obtain 2,3- lutidines nitrogen oxides into
Product yield:92.1%, high performance liquid chromatography detection purity is 94.5%.Further to verify the effect of the present invention, by the present embodiment
Using Brooker (Bruker) AV400 type nuclear magnetic resonance analyser, final obtained finished product, is detected that testing result is as follows：2,
3-Lutidine-N-oxideAs shown in the hydrogen nuclear magnetic resonance spectrogram of Fig. 9,1H-NMR (CDCl3, 400MHz) δ:
8.20-8.14 (t, 1H), 7.09-6.99 (m, 2H), 2.54-2.48 (d, 3H), 2.37-2.32 (d, 3H);
As shown in the carbon-13 nmr spectra figure of Figure 10,13C-NMR (CDCl3, 100MHz) δ: 148.2, 137.0, 134.8,
127.1, 122.0, 19.5, 13.7.。
Embodiment 8
The preparation of the titanium dioxide of tungsten load, comprises the steps：
（a）1.6g wolframic acids are added in 500ml deionized waters, pH value of solution are adjusted with the ammonia of 1mol/L complete to wolframic acid
It is molten, it is subsequently adding the business-like titanium dioxide of 10.5g（P25）, ultrasonic disperse is after 48 minutes, and solvent is steamed at a temperature of 55 DEG C
It is dry；
（b）By step（a）In Muffle furnace, under oxygen atmosphere, roasting obtains urging for white solid to gained solid after 2.8 hours
Agent, i.e. tungsten load titanium dioxide, sintering temperature are 460 DEG C, are designated as 5% WO3/TiO2。
A kind of preparation of 3,5- lutidines nitrogen oxides, comprises the steps：
Step one, the titanium dioxide with tungsten load as catalyst, by 50g 3,5- lutidines, the peroxide of 55mL30%
Change hydrogen solution, 7g steps（a）The catalyst of middle preparation is added in there-necked flask；
Step 2, mixed liquor prepared by step one stirring reaction 10 hours at 20 DEG C, by reacted liquid nature
Be cooled to room temperature, then in turn through filter, washing, concentration, filtrate concentration after obtain 3,5- lutidines nitrogen oxides into
Product yield:95.8%, high performance liquid chromatography detection purity is 94.7%.
Embodiment 9
The preparation of the titanium dioxide of tungsten load, comprises the steps：
（a）1.4g wolframic acids are added in 500ml deionized waters, pH value of solution are adjusted with the ammonia of 1mol/L complete to wolframic acid
It is molten, it is subsequently adding the business-like titanium dioxide of 10g（P25）, ultrasonic disperse is after 30 minutes, and solvent is steamed at a temperature of 62 DEG C
It is dry；
（b）By step（a）In Muffle furnace, under oxygen atmosphere, roasting obtains urging for white solid to gained solid after 2.4 hours
Agent, i.e. tungsten load titanium dioxide, sintering temperature are 420 DEG C, are designated as 5% WO3/TiO2。
A kind of preparation of nicotinonitrile nitrogen oxides, comprises the steps：
Step one, the titanium dioxide with tungsten load as catalyst, by 50g nicotinonitriles, the hydrogen peroxide of 55mL30%
Solution, 2g steps（a）The catalyst of middle preparation is added in there-necked flask；
Step 2, mixed liquor prepared by step one stirring reaction 20 hours at 45 DEG C, by reacted liquid nature
Room temperature is cooled to, then in turn through filtering, washing, concentrate, nicotinonitrile nitrogen oxides finished product receipts after filtrate concentration, is obtained
Rate:84.6%, high performance liquid chromatography detection purity is 90.8%.
Embodiment 10
The preparation of the titanium dioxide of tungsten load, comprises the steps：
（a）2g wolframic acids are added in 500ml deionized waters, the ammonia regulation pH value of solution with 1mol/L is entirely molten to wolframic acid,
It is subsequently adding the business-like titanium dioxide of 9.5g（P25）, solvent is evaporated at a temperature of 59 DEG C after 54 minutes by ultrasonic disperse；
（b）By step（a）In Muffle furnace, under oxygen atmosphere, roasting obtains the catalysis of white solid to gained solid after 2 hours
Agent, i.e. tungsten load titanium dioxide, sintering temperature are 480 DEG C, are designated as 5% WO3/TiO2。
A kind of preparation of 2,4- lutidines nitrogen oxides, comprises the steps：
Step one, the titanium dioxide with tungsten load as catalyst, by 50g 2,4- lutidines, the peroxide of 50mL30%
Change hydrogen solution, 14g steps（a）The catalyst of middle preparation is added in there-necked flask；
Step 2, mixed liquor prepared by step one stirring reaction 23 hours at 60 DEG C, by reacted liquid nature
Be cooled to room temperature, then in turn through filter, washing, concentration, filtrate concentration after obtain 2,4- lutidines nitrogen oxides into
Product yield:90.4%, high performance liquid chromatography detection purity is 92.8%.Further to verify the effect of the present invention, by the present embodiment
Using Brooker (Bruker) AV400 type nuclear magnetic resonance analyser, final obtained finished product, is detected that testing result is as follows：2,
4-Lutidine-N-oxideAs shown in the hydrogen nuclear magnetic resonance spectrogram of Figure 11,1H-NMR (CDCl3, 400MHz) δ:
8.92-8.81 (t, 1H), 7.61-7.57 (s, 1H), 7.57-7.53 (d, 1H);Such as the carbon-13 nmr spectra of Figure 12
Shown in figure,13C-NMR (CDCl3, 100MHz) δ: 153.6, 150.9, 139.8, 129.3, 126.1, 21.5,
18.0.。
Embodiment 11
The preparation of the titanium dioxide of tungsten load, comprises the steps：
（a）1.7g wolframic acids are added in 500ml deionized waters, pH value of solution are adjusted with the ammonia of 1mol/L complete to wolframic acid
It is molten, it is subsequently adding the business-like titanium dioxide of 8g（P25）, solvent is evaporated at a temperature of 64 DEG C after 36 minutes by ultrasonic disperse；
（b）By step（a）In Muffle furnace, under oxygen atmosphere, roasting obtains urging for white solid to gained solid after 2.2 hours
Agent, i.e. tungsten load titanium dioxide, sintering temperature are 440 DEG C, are designated as 5% WO3/TiO2。
A kind of preparation of 2,4,6- trimethylpyridines nitrogen oxides, comprises the steps：
Step one, the titanium dioxide with tungsten load as catalyst, by 50g 2，4，6-trimethylpyridine, the mistake of 45mL30%
Hydrogen peroxide solution, 6g steps（a）The catalyst of middle preparation is added in there-necked flask；
Step 2, mixed liquor prepared by step one stirring reaction 15 hours at 65 DEG C, by reacted liquid nature
Room temperature is cooled to, then in turn through filtering, washing, concentrate, after filtrate concentration, 2，4，6-trimethylpyridine nitrogen oxides is obtained
Product yield:94.8%, high performance liquid chromatography detection purity is 94.0%.
Embodiment 12
The preparation of the titanium dioxide of tungsten load, comprises the steps：
（a）1.9g wolframic acids are added in 500ml deionized waters, pH value of solution are adjusted with the ammonia of 1mol/L complete to wolframic acid
It is molten, it is subsequently adding the business-like titanium dioxide of 9.6g（P25）, ultrasonic disperse is after 48 minutes, and solvent is steamed at a temperature of 55 DEG C
It is dry；
（b）By step（a）In Muffle furnace, under oxygen atmosphere, roasting obtains the catalysis of white solid to gained solid after 3 hours
Agent, i.e. tungsten load titanium dioxide, sintering temperature are 410 DEG C, are designated as 5% WO3/TiO2。
A kind of preparation of 3- methyl pyridine nitrogen oxides, comprises the steps：
Step one, the titanium dioxide with tungsten load as catalyst, by 50g 3- picolines, the hydrogen peroxide of 40mL30%
Solution, 10g steps（a）The catalyst of middle preparation is added in there-necked flask；
Step 2, mixed liquor prepared by step one stirring reaction 12 hours at 45 DEG C, by reacted liquid nature
Room temperature is cooled to, then in turn through filtering, washing, concentrate, 3- methyl pyridine nitrogen oxides finished product receipts after filtrate concentration, is obtained
Rate:84.8%, high performance liquid chromatography detection purity is 90.8%.It is further to verify the effect of the present invention, the present embodiment is final
Using Brooker (Bruker) AV400 type nuclear magnetic resonance analyser, obtained finished product, is detected that testing result is as follows：3-
Picoline-N-oxideAs shown in the hydrogen nuclear magnetic resonance spectrogram of Figure 13,1H-NMR (CDCl3, 400MHz) δ:
8.11-8.01 (t, 2H), 7.24-7.08 (m, 2H), 2.35-2.27 (d, 3H);Such as the carbon-13 nmr spectra of Figure 14
Shown in figure,13C-NMR (CDCl3, 100MHz) δ: 139.1, 136.8, 136.4, 127.1, 125.3, 18.2.。
Embodiment 13
The preparation of the titanium dioxide of tungsten load, comprises the steps：
（a）1.8g wolframic acids are added in 500ml deionized waters, pH value of solution are adjusted with the ammonia of 1mol/L complete to wolframic acid
It is molten, it is subsequently adding the business-like titanium dioxide of 11.2g（P25）, ultrasonic disperse is after 30 minutes, and solvent is steamed at a temperature of 56 DEG C
It is dry；
（b）By step（a）In Muffle furnace, under oxygen atmosphere, roasting obtains urging for white solid to gained solid after 2.7 hours
Agent, i.e. tungsten load titanium dioxide, sintering temperature are 500 DEG C, are designated as 5% WO3/TiO2。
A kind of preparation of 2- methyl pyridine nitrogen oxides, comprises the steps：
Step one, the titanium dioxide with tungsten load as catalyst, by 50g 2- picolines, the hydrogen peroxide of 55mL30%
Solution, 12g steps（a）The catalyst of middle preparation is added in there-necked flask；
Step 2, mixed liquor prepared by step one stirring reaction 19 hours at 25 DEG C, by reacted liquid nature
Room temperature is cooled to, then in turn through filtering, washing, concentrate, 2- methyl pyridine nitrogen oxides finished product receipts after filtrate concentration, is obtained
Rate:91.2%, high performance liquid chromatography detection purity is 92.6%.It is further to verify the effect of the present invention, the present embodiment is final
Using Brooker (Bruker) AV400 type nuclear magnetic resonance analyser, obtained finished product, is detected that testing result is as follows：2-
Picoline-N-oxideAs shown in the hydrogen nuclear magnetic resonance spectrogram of Figure 15,1H-NMR (CDCl3, 400MHz) δ:
8.28-8.20 (t, 1H), 7.27-7.21 (d, 1H), 7.20-7.09 (m, 2H), 2.54-2.46 (s, 3H);
As shown in the carbon-13 nmr spectra figure of Figure 16,13C-NMR (CDCl3, 100MHz) δ: 149.0, 139.3, 126.5,
125.5, 123.5, 17.7.。
Embodiment 14
The preparation of the titanium dioxide of tungsten load, comprises the steps：
（a）1.3g wolframic acids are added in 500ml deionized waters, pH value of solution are adjusted with the ammonia of 1mol/L complete to wolframic acid
It is molten, it is subsequently adding the business-like titanium dioxide of 11g（P25）, ultrasonic disperse is after 42 minutes, and solvent is steamed at a temperature of 57 DEG C
It is dry；
（b）By step（a）In Muffle furnace, under oxygen atmosphere, roasting obtains urging for white solid to gained solid after 2.9 hours
Agent, i.e. tungsten load titanium dioxide, sintering temperature are 490 DEG C, are designated as 5% WO3/TiO2。
A kind of preparation of isoquinoline nitrogen oxide, comprises the steps：
Step one, the titanium dioxide with tungsten load as catalyst, by 50g isoquinolin, the hydrogenperoxide steam generator of 40mL30%,
5g steps（a）The catalyst of middle preparation is added in there-necked flask；
Step 2, mixed liquor prepared by step one stirring reaction 24 hours at 40 DEG C, by reacted liquid nature
Room temperature is cooled to, then in turn through filtering, washing, concentrate, after filtrate concentration, isoquinoline nitrogen oxide product yield is obtained:
86.8%, high performance liquid chromatography detection purity is 94.8%.Further to verify the effect of the present invention, the present embodiment is finally obtained
Finished product, detected that testing result is as follows using Brooker (Bruker) AV400 type nuclear magnetic resonance analyser：
Isoquinoline-N-oxideAs shown in the hydrogen nuclear magnetic resonance spectrogram of Figure 17,1H-NMR (CDCl3, 400MHz)
δ: 8.80-8.74 (s, 1H), 8.18-8.11 (d, 1H), 7.83-7.76 (d, 1H), 7.65-7.55 (q,
4H);As shown in the carbon-13 nmr spectra figure of Figure 18,13C-NMR (CDCl3, 100MHz) δ: 138.6, 136.0, 129.4,
129.0, 128.7, 126.6.。
Embodiment 15
The preparation of the titanium dioxide of tungsten load, comprises the steps：
（a）1.5g wolframic acids are added in 500ml deionized waters, pH value of solution are adjusted with the ammonia of 1mol/L complete to wolframic acid
It is molten, it is subsequently adding the business-like titanium dioxide of 8.5g（P25）, ultrasonic disperse is after 60 minutes, and solvent is steamed at a temperature of 58 DEG C
It is dry；
（b）By step（a）In Muffle furnace, under oxygen atmosphere, roasting obtains urging for white solid to gained solid after 2.5 hours
Agent, i.e. tungsten load titanium dioxide, sintering temperature are 450 DEG C, are designated as 5% WO3/TiO2。
A kind of preparation of 2,6- lutidines nitrogen oxides, comprises the steps：
Step one, the titanium dioxide with tungsten load as catalyst, by 50g 2,6- lutidines, the peroxide of 60mL30%
Change hydrogen solution, 15g steps（a）The catalyst of middle preparation is added in there-necked flask；
Step 2, mixed liquor prepared by step one stirring reaction 19 hours at 55 DEG C, by reacted liquid nature
Be cooled to room temperature, then in turn through filter, washing, concentration, filtrate concentration after obtain 2,6- lutidines nitrogen oxides into
Product yield:84.5%, high performance liquid chromatography detection purity is 92.9%.Further to verify the effect of the present invention, by the present embodiment
Using Brooker (Bruker) AV400 type nuclear magnetic resonance analyser, final obtained finished product, is detected that testing result is as follows：2,
6-Lutidine-N-oxideAs shown in the hydrogen nuclear magnetic resonance spectrogram of Figure 19,1H-NMR (CDCl3, 400MHz) δ:
7.14-7.08 (d, 2H), 7.07-7.00 (m, 1H), 2.51-2.49 (s, 6H);Such as the carbon-13 nmr spectra of Figure 20
Shown in figure,13C-NMR (CDCl3, 100MHz) δ: 148.7, 124.4, 123.8, 18.0.。
Embodiment 16
The preparation of the titanium dioxide of tungsten load, comprises the steps：
（a）1.2g wolframic acids are added in 500ml deionized waters, pH value of solution are adjusted with the ammonia of 1mol/L complete to wolframic acid
It is molten, it is subsequently adding the business-like titanium dioxide of 10g（P25）, ultrasonic disperse is after 60 minutes, and solvent is steamed at a temperature of 60 DEG C
It is dry；
（b）By step（a）In Muffle furnace, under oxygen atmosphere, roasting obtains urging for white solid to gained solid after 2.5 hours
Agent, i.e. tungsten load titanium dioxide, sintering temperature are 450 DEG C, are designated as 5% WO3/TiO2。
A kind of preparation of pyridine nitric oxide, comprises the steps：
Step one, the titanium dioxide with tungsten load as catalyst, by 50g pyridines, the hydrogenperoxide steam generator of 70 mL30%,
10g steps（a）The catalyst of middle preparation is added in there-necked flask；
Step 2, mixed liquor prepared by step one stirring reaction 16 hours at 30 DEG C, by reacted liquid nature
Room temperature is cooled to, then in turn through filtering, washing, concentrate, after filtrate concentration, pyridine nitric oxide product yield is obtained:
86.6%, high performance liquid chromatography detection purity is 90.2%.Further to verify the effect of the present invention, the present embodiment is finally obtained
Finished product, detected that testing result is as follows using Brooker (Bruker) AV400 type nuclear magnetic resonance analyser：Pyridine-N-
oxideAs shown in the hydrogen nuclear magnetic resonance spectrogram of Figure 21,1H-NMR (CDCl3, 400MHz) δ: 8.31-8.13 (d,
2H), 7.38-7.18 (m, 3H);As shown in the carbon-13 nmr spectra figure of Figure 22,13C-NMR (CDCl3, 100MHz) δ:
139.2, 126.1 125.9.。
In sum, using above-mentioned technical proposal the present invention compared with prior art, with following superiority；1st, exist
In the method for oxidation of the present invention, it is to avoid the use of acetic acid in common method, requirement to equipment are substantially reduced；2nd, present invention profit
Pyridines nitrogen oxides are prepared efficiently with the method for heterogeneous catalysiss, catalyst and system pass through simple filtration or be centrifuged to divide
From easy to operate；3rd, this reaction is catalyst using the titanium dioxide of tungsten load, and in room temperature, aqueous solution, a step prepares pyridine
Class nitrogen oxides, the reaction condition for being adopted is gentle, environmental pollution is little；And the high income of product, purity is good.And this
Bright is the preparation technology of an environmental protection, easy to operate, is adapted to the methodology of organic synthesis of industrialized production.
Claims (5)
1. a kind of preparation method of pyridines nitrogen oxides, it is characterised in that comprise the steps：
Step one, first by pyridine or pyridine derivate and hydrogenperoxide steam generator according to 1:（1.5-3）Mixed in molar ratio after, so
The mass ratio for adding the titanium deoxide catalyst of a certain amount of tungsten load, catalyst and pyridine or pyridine derivate afterwards is（0.02-
0.3）:1；
Step 2, mixed liquor prepared by the step one stirring reaction 10-24 hour at 20-65 DEG C, by reacted liquid certainly
Room temperature is so cooled to, then in turn through filtering, washing, concentrate, after filtrate concentration, pyridine nitric oxide or pyridine derived is obtained
The finished product of the nitrogen oxides of thing；
In the step one, pyridine derivate used is 2- picolines, 3- picolines, 4- picolines, 2,6- dimethyl
Pyridine, 2,3 dimethyl pyridine, 2,4- lutidines, 3,5- lutidines, 2,4,6- trimethylpyridines, 2- chloropyridines,
One kind in nicotinonitrile, quinoline and isoquinolin；
In the preparation method of described pyridines nitrogen oxides, the preparation method of the titanium dioxide of tungsten load, comprises the steps：
（a）1-2g wolframic acids are added in 500ml deionized waters, the ammonia regulation pH value of solution with 1mol/L is entirely molten to wolframic acid, so
8-12g titanium dioxide is added afterwards, after ultrasonic disperse 30-60 minutes, solvent is evaporated at a temperature of 55-65 DEG C；
（b）By step（a）Gained solid obtains the catalyst of white solid, i.e. tungsten under oxygen atmosphere and bears after roasting 2-3 hours
The titanium dioxide of load, sintering temperature are 400-500 DEG C.
2. the preparation method of pyridines nitrogen oxides according to claim 1, it is characterised in that：Pyridine in the step one
Or the mol ratio of pyridine derivate and hydrogenperoxide steam generator is 1:（2-2.5）.
3. the preparation method of pyridines nitrogen oxides according to claim 1, it is characterised in that：It is catalyzed in the step one
The mass ratio of agent and pyridine or pyridine derivate is（0.1-0.2）:1.
4. the preparation method of pyridines nitrogen oxides according to claim 1, it is characterised in that：Peroxide in the step one
The mass fraction for changing solute in hydrogen solution is 30%.
5. the preparation method of pyridines nitrogen oxides according to claim 1, it is characterised in that：The dioxy of the tungsten load
The P25 of titanium dioxide used for business level in the preparation method of change titanium, wolframic acid, ammonia are technical grade.
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