CN102241624A - Preparation method of pyridine-2-formaldehyde - Google Patents
Preparation method of pyridine-2-formaldehyde Download PDFInfo
- Publication number
- CN102241624A CN102241624A CN2011101985149A CN201110198514A CN102241624A CN 102241624 A CN102241624 A CN 102241624A CN 2011101985149 A CN2011101985149 A CN 2011101985149A CN 201110198514 A CN201110198514 A CN 201110198514A CN 102241624 A CN102241624 A CN 102241624A
- Authority
- CN
- China
- Prior art keywords
- formaldehyde
- pyridine
- preparation
- aqueous solution
- ammonium molybdate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to a preparation method of pyridine-2-formaldehyde. The preparation method comprises the following two steps: preparing an acidity-regulator-containing supported catalyst with titanium dioxide used as a carrier, molybdenum bismuth oxide used as a main body and transition metal oxide used as an auxiliary, carrying out gas-phase oxidation reaction on 2-methyl pyridine, oxygen and water used as raw materials in a fixed bed catalytic reactor at 250-350 DEG C to obtain a crude pyridine-2-formaldehyde product, extracting the crude product with dichloromethane, carrying out pressure-reduced distillation on the extract to remove dichloromethane, and then rectifying to obtain a pure product with a pyridine-2-formaldehyde content more than 98%. The preparation method provided by the invention has the advantages of simple preparation process, high efficiency, low cost, high catalytic reaction activity and selectivity, easy separation of main products and by-products and high purity.
Description
Technical field
The present invention relates to the preparation method of pyridine-2-formaldehyde.
Background technology
Pyridine-2-formaldehyde is a kind of important medicine intermediate and fine chemical material, and it is mainly used in synthetic caccagogue bisacodyl.In addition, also be used for synthesizing new nicotinic insecticide and some and have the molecule of specific function such as fluorescent chelating agent etc.Recently, aspect synthetic novel material and the chiral catalyst related application is being arranged also.The preparation method that the preparation method of existing pyridine-2-formaldehyde mainly contains existing pyridine-2-formaldehyde mainly contains following several: method one, under catalyst action, use O
2, chemical oxidizing agent oxidation 2-piconol such as hydrogen peroxide, tertbutanol peroxide prepares pyridine-2-formaldehyde, (Tetrahedron Letters, 2006,47 (6): 923 – 926; Advanced Synthesis ﹠amp; Catalysis, 2009,351 (1+2): 89-92) this method has the advantage of productive rate height, environmental protection, but the preparation method of used raw material 2-piconol is more loaded down with trivial details; Method two, He Yimin etc. are raw material with three chlorine isocyanates and 2-picoline, benzamide is a catalyzer, makes pyridine-2-formaldehyde, (CN101906068,2010), and this operational path is long, and process is loaded down with trivial details, and total recovery is lower; Method three, catalytic reduction method are promptly used H
2With 2-cyanopyridine catalytic reduction is the 2-pyridylaldehyde, (Chinese Journal of Pharmaceuticals, 2007, (7): 480-480), but the costing an arm and a leg of raw material 2-cyanopyridine; Method four, the oxygen vapour phase oxidation process, this method is because reaction has only a step, and product separation is simple, and catalyzer is reusable, so than additive method bigger advantage is arranged.2-picoline gasification back is mixed with oxygen and water vapour; by the fixed-bed reactor of catalyzer are housed; direct oxidation is a pyridine-2-formaldehyde; (colleges and universities' chemical engineering journal. 2002,16 (4): 436-440), catalyst system therefor is a carrier with alkaline bentonite or silica gel; vanadium, molybdenum are active constituent; the selectivity of this method reaction is 80% ~ 90%, and the transformation efficiency of 2-picoline has only 50% ~ 58%, has caused ultimate yield on the low side.
Summary of the invention
The objective of the invention is to develop a kind of efficient, lower-cost and have a preparation method of the pyridine-2-formaldehyde of industrial applications prospect.
The preparation method of pyridine-2-formaldehyde of the present invention may further comprise the steps:
The first step is with ammonium molybdate, Bismuth trinitrate, transition metal mixtures, acidity regulator and organic complexing agent are made into the aqueous solution, be heated to 60～80 ℃, add titanium dioxide then, mix, behind the evaporated under reduced pressure moisture, the gained solid is ground, add again after suitable quantity of water is extruded into strip, smoked 2 ~ 4 hours in 80-120 ℃, then in 400 ~ 600 ℃ of calcinings 8 ~ 10 hours, obtain strip catalyst, the weight ratio of used titanium dioxide and ammonium molybdate is 9 ~ 12:1, and the weight ratio of used Bismuth trinitrate and ammonium molybdate is 0.3 ~ 1.8:1, and the weight ratio of transition metal mixtures and ammonium molybdate is 0.2 ~ 0.5:1, the mass ratio of acidity regulator and ammonium molybdate is 0.1 ~ 0.5:1, and the weight ratio of organic complexing agent and ammonium molybdate is 1 ~ 2:1;
Second step will be gone up the catalyzer that makes of step and be put into fixed-bed reactor, the fixed bed reaction actuator temperature is remained on 250 ~ 350 ℃, to fixed-bed reactor aerating oxygen and water after 1 hour, in fixed-bed reactor, continue aerating oxygen and mass concentration again and be 5 ~ 20% the 2-picoline aqueous solution, under 250 ~ 350 ℃, carry out gas phase oxidation, generate the thick product aqueous solution of pyridine-2-formaldehyde, the thick product aqueous solution is through dichloromethane extraction, methylene dichloride is removed in the extraction liquid underpressure distillation, rectifying obtains pure product then, the speed of above-mentioned aerating oxygen is 100 ~ 250mL/min, the input speed of water and oxygen than and the input speed ratio of the 2-picoline aqueous solution and oxygen be 1:1000 ~ 1250.
Among the present invention, used transition metal salt is iron nitrate, Xiao Suangu, nickelous nitrate, manganous nitrate or chromium nitrate, acidity regulator is saltpetre, potassium hydroxide, salt of wormwood, SODIUMNITRATE, sodium hydroxide or yellow soda ash, and organic complexing agent is oxalic acid, citric acid or tartrate.
Preparation technology of the present invention is simple, and raw materials cost is low, and reaction conversion ratio and selectivity height, product are easy to separate, and the finished product purity height has stronger industrial applications and is worth.
Embodiment
Further specify the present invention below in conjunction with embodiment.
Embodiment 1
8.0g ammonium molybdate, 14.4g Bismuth trinitrate, 1.6g iron nitrate, 4g SODIUMNITRATE and 16.0g oxalic acid are dissolved in 450ml water, be heated to 70 ℃, add titanium dioxide 96g, mix, behind the evaporated under reduced pressure moisture, the gained solid is ground, add again after suitable quantity of water is extruded into strip, smoked 2 hours in 120 ℃, then in 600 ℃ of calcinings 8 hours, obtain the black strip catalyst, it is standby to be converted into 3-4mm.
The black strip catalyst that the last step makes is put into fixed-bed reactor, the fixed bed reaction actuator temperature is remained on 350 ℃, to fixed-bed reactor aerating oxygen and water, the speed of oxygen is 250mL/min, the speed of water is 0.2mL/min, after 1 hour, in fixed-bed reactor, continue aerating oxygen and mass concentration and be the aqueous solution of 20% 2-picoline, the aqueous solution speed of 2-picoline is 0.2mL/min, under 350 ℃, carry out gas phase oxidation, generate the pyridine-2-formaldehyde crude product aqueous solution, the crude product aqueous solution is through dichloromethane extraction, and methylene dichloride is removed in the extraction liquid underpressure distillation, and rectifying obtains content pure product more than 98% then, transformation efficiency 96.8 % of 2-picoline, selectivity 92.2 % of pyridine-2-formaldehyde.
Embodiment 2
8.0g ammonium molybdate, 8.8g Bismuth trinitrate, 2.0g Xiao Suangu, 2.4g sodium hydroxide and 12.0g citric acid are dissolved in 450ml water, be heated to 60 ℃, add titanium dioxide 84g, mix, behind the evaporated under reduced pressure moisture, the gained solid is ground, add again after suitable quantity of water is extruded into strip, smoked 3 hours in 100 ℃, then in 500 ℃ of calcinings 9 hours, obtain the black strip catalyst, it is standby to be converted into 3-4mm.
The black strip catalyst that the last step makes is put into fixed-bed reactor, the fixed bed reaction actuator temperature is remained on 320 ℃, to fixed-bed reactor aerating oxygen and water, the speed of oxygen is 200mL/min, the speed of water is 0.18mL/min, after 1 hour, in fixed-bed reactor, continue aerating oxygen and mass concentration and be the aqueous solution of 10% 2-picoline, the aqueous solution speed of 2-picoline is 0.18mL/min, under 320 ℃, carry out gas phase oxidation, generate the pyridine-2-formaldehyde crude product aqueous solution, the crude product aqueous solution is through dichloromethane extraction, and methylene dichloride is removed in the extraction liquid underpressure distillation, and rectifying obtains content pure product more than 98% then, transformation efficiency 96.1 % of 2-picoline, selectivity 90.2 % of pyridine-2-formaldehyde.
Embodiment 3
8.0g ammonium molybdate, 2.4g Bismuth trinitrate, 4.0g chromium nitrate, 0.8g saltpetre and 8.0g tartrate are dissolved in 450ml water, be heated to 80 ℃, add titanium dioxide 72g, mix, behind the evaporated under reduced pressure moisture, the gained solid is ground, add again after suitable quantity of water is extruded into strip, smoked 4 hours in 80 ℃, then in 400 ℃ of calcinings 10 hours, obtain the black strip catalyst, it is standby to be converted into 3-4mm.
The black strip catalyst that the last step makes is put into fixed-bed reactor, the fixed bed reaction actuator temperature is remained on 250 ℃, to fixed-bed reactor aerating oxygen and water, the speed of oxygen is 100mL/min, the speed of water is 0.10mL/min, after 1 hour, in fixed-bed reactor, continue aerating oxygen and mass concentration and be the aqueous solution of 5% 2-picoline, the aqueous solution speed of 2-picoline is 0.10mL/min, under 250 ℃, carry out gas phase oxidation, generate the pyridine-2-formaldehyde crude product aqueous solution, the crude product aqueous solution is through dichloromethane extraction, and methylene dichloride is removed in the extraction liquid underpressure distillation, and rectifying obtains content pure product more than 98% then, transformation efficiency 95.3 % of 2-picoline, the selectivity 88.8% of pyridine-2-formaldehyde.
Claims (4)
1. the preparation method of a pyridine-2-formaldehyde in turn includes the following steps:
The first step is with ammonium molybdate, Bismuth trinitrate, transition metal mixtures, acidity regulator and organic complexing agent are made into the aqueous solution, be heated to 60～80 ℃, add titanium dioxide then, mix, behind the evaporated under reduced pressure moisture, the gained solid is ground, add again after suitable quantity of water is extruded into strip, smoked 2 ~ 4 hours in 80-120 ℃, then in 400 ~ 600 ℃ of calcinings 8 ~ 10 hours, obtain strip catalyst, the weight ratio of used titanium dioxide and ammonium molybdate is 9 ~ 12:1, and the weight ratio of used Bismuth trinitrate and ammonium molybdate is 0.3 ~ 1.8:1, and the weight ratio of transition metal mixtures and ammonium molybdate is 0.2 ~ 0.5:1, the mass ratio of acidity regulator and ammonium molybdate is 0.1 ~ 0.5:1, and the weight ratio of organic complexing agent and ammonium molybdate is 1 ~ 2:1;
Second step will be gone up the catalyzer that makes of step and be put into fixed-bed reactor, the fixed bed reaction actuator temperature is remained on 250 ~ 350 ℃, to fixed-bed reactor aerating oxygen and water after 1 hour, in fixed-bed reactor, continue aerating oxygen and mass concentration again and be 5 ~ 20% the 2-picoline aqueous solution, under 250 ~ 350 ℃, carry out gas phase oxidation, generate the thick product aqueous solution of pyridine-2-formaldehyde, the thick product aqueous solution is through dichloromethane extraction, methylene dichloride is removed in the extraction liquid underpressure distillation, rectifying obtains pure product then, the speed of above-mentioned aerating oxygen is 100 ~ 250mL/min, the input speed of water and oxygen than and the input speed ratio of the 2-picoline aqueous solution and oxygen be 1:1000 ~ 1250.
2. by the preparation method of the described pyridine-2-formaldehyde of claim 1, it is characterized in that used transition metal mixtures is iron nitrate, Xiao Suangu, nickelous nitrate, manganous nitrate or chromium nitrate in the first step.
3. by the preparation method of the described pyridine-2-formaldehyde of claim 1, it is characterized in that used acidity regulator is saltpetre, potassium hydroxide, salt of wormwood, SODIUMNITRATE, sodium hydroxide or yellow soda ash in the first step.
4. by the preparation method of the described pyridine 2-of claim 1 formaldehyde, it is characterized in that used organic complexing agent is oxalic acid, citric acid or tartrate in the first step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110198514 CN102241624B (en) | 2011-07-15 | 2011-07-15 | Preparation method of pyridine-2-formaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110198514 CN102241624B (en) | 2011-07-15 | 2011-07-15 | Preparation method of pyridine-2-formaldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102241624A true CN102241624A (en) | 2011-11-16 |
| CN102241624B CN102241624B (en) | 2012-12-12 |
Family
ID=44959904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110198514 Expired - Fee Related CN102241624B (en) | 2011-07-15 | 2011-07-15 | Preparation method of pyridine-2-formaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102241624B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617453A (en) * | 2012-03-21 | 2012-08-01 | 浙江大学 | Method for preparing pyridine-4-formaldehyde |
| CN102627599A (en) * | 2012-03-22 | 2012-08-08 | 浙江大学 | Preparation method of pyridine-3-formaldehyde |
| CN105601559A (en) * | 2014-12-02 | 2016-05-25 | 安徽星宇化工有限公司 | Synthetic method for 2-pyridylaldehyde |
| CN110963897A (en) * | 2018-09-28 | 2020-04-07 | 中国石油化工股份有限公司 | Method for improving selectivity of effective product by adding water vapor in oxidizing atmosphere |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1135561A (en) * | 1997-05-20 | 1999-02-09 | Koei Chem Co Ltd | Production of hetero-aromatic aldehyde |
| CN1290252A (en) * | 1998-12-18 | 2001-04-04 | 广荣化学工业株式会社 | Method for producing heteroaromatic aldehydes |
| CN101817780A (en) * | 2010-04-13 | 2010-09-01 | 浙江大学 | Preparation method of pyridine-2-formaldehyde |
-
2011
- 2011-07-15 CN CN 201110198514 patent/CN102241624B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1135561A (en) * | 1997-05-20 | 1999-02-09 | Koei Chem Co Ltd | Production of hetero-aromatic aldehyde |
| CN1290252A (en) * | 1998-12-18 | 2001-04-04 | 广荣化学工业株式会社 | Method for producing heteroaromatic aldehydes |
| CN101817780A (en) * | 2010-04-13 | 2010-09-01 | 浙江大学 | Preparation method of pyridine-2-formaldehyde |
Non-Patent Citations (3)
| Title |
|---|
| 李静等: "钼钒酸铋体系催化剂上丙烷的选择氧化反应", 《应用化学》, vol. 13, no. 2, 30 April 1996 (1996-04-30), pages 88 - 90 * |
| 杜曦 等: "烷基苯及其衍生物氧化合成芳香醛酮的技术研究进展", 《应用化工》, vol. 37, no. 4, 30 April 2008 (2008-04-30), pages 442 - 445 * |
| 陈英奇 等: "2-甲基吡啶气相催化氧化合成2-吡啶甲醛的研究", 《高校化学工程学报》, vol. 16, no. 4, 31 August 2002 (2002-08-31), pages 436 - 440 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617453A (en) * | 2012-03-21 | 2012-08-01 | 浙江大学 | Method for preparing pyridine-4-formaldehyde |
| CN102627599A (en) * | 2012-03-22 | 2012-08-08 | 浙江大学 | Preparation method of pyridine-3-formaldehyde |
| CN105601559A (en) * | 2014-12-02 | 2016-05-25 | 安徽星宇化工有限公司 | Synthetic method for 2-pyridylaldehyde |
| CN105601559B (en) * | 2014-12-02 | 2018-01-09 | 安徽星宇化工有限公司 | A kind of synthetic method of 2 pyridine carboxaldehyde |
| CN110963897A (en) * | 2018-09-28 | 2020-04-07 | 中国石油化工股份有限公司 | Method for improving selectivity of effective product by adding water vapor in oxidizing atmosphere |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102241624B (en) | 2012-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ordomsky et al. | Biphasic single-reactor process for dehydration of xylose and hydrogenation of produced furfural | |
| CN100560581C (en) | A kind of method for preparing caprolactone by cyclohexanone by catalytic oxidation | |
| Lin et al. | Zirconia-supported rhenium oxide as an efficient catalyst for the synthesis of biomass-based adipic acid ester | |
| CN101306986B (en) | Process for preparing benzaldehyde by catalytic oxidation of phenylethene | |
| CN102206147B (en) | Method for oxidizing cyclohexane | |
| CN102241624B (en) | Preparation method of pyridine-2-formaldehyde | |
| EP2130583A1 (en) | Method for producing carbonyl compound | |
| CN103467434B (en) | Method for preparing eta-caprolactone by composite catalysis | |
| CN102206149B (en) | Method for preparing corresponding diacid by catalytic oxidization of naphthene | |
| CN102452894B (en) | Method for catalytic oxidation of cyclic ketone by nanometer Beta molecule sieve | |
| CN101817780B (en) | Preparation method of pyridine-2-formaldehyde | |
| CN102989459A (en) | Catalyst for preparing epsilon-caprolactone by oxidizing cyclohexanone/oxygen under aldehyde-assisted oxidizing action | |
| CN102617453A (en) | Method for preparing pyridine-4-formaldehyde | |
| EP1175382B1 (en) | Method for the dihydroxylation of olefins using transition-metal catalysts | |
| CN104341274A (en) | Method for simultaneously producing dihydroxybenzene and benzoquinone | |
| KR20120106961A (en) | Method for producing diols by hydrogenation of a carboxylic acid-containing mixture using cobalt-containing catalysts | |
| CN102850205B (en) | Method for producing 1,2-cyclohexanediol and adipic acid | |
| EP3130586B1 (en) | Process for treating homoserine-based compound | |
| CN108026048A (en) | The manufacture method of epsilon-caprolactams | |
| CN112791744A (en) | Modified titanium-silicon molecular sieve, and preparation method and application thereof | |
| CN101121650A (en) | Method for synthesizing methoxyacetone by 1-methoxy-2-propanol gas phase oxidation dehydrogenation | |
| CN102766037B (en) | Method for preparing adipic acid from cyclohexene | |
| CN102627599A (en) | Preparation method of pyridine-3-formaldehyde | |
| CN113908828B (en) | Bismuth molybdate catalyst for preparing cyclohexene oxide by cyclohexene epoxidation, and preparation method and application thereof | |
| CN111517984B (en) | Method for synthesizing cyclohexanone oxime by catalyzing cyclohexanone with titanium ammonium phosphotungstate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121212 Termination date: 20130715 |