CN1903841A - Preparation method of 3-methyl piperidine - Google Patents
Preparation method of 3-methyl piperidine Download PDFInfo
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- CN1903841A CN1903841A CN 200510060201 CN200510060201A CN1903841A CN 1903841 A CN1903841 A CN 1903841A CN 200510060201 CN200510060201 CN 200510060201 CN 200510060201 A CN200510060201 A CN 200510060201A CN 1903841 A CN1903841 A CN 1903841A
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- methyl piperidine
- methyl
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Abstract
The present invention provides a preparation method of 3-methyl piperidine. Said method is characterized by that it uses 2-methyl-1,5-pentamethylene diamine as raw material, uses gas diluting agent as carrier, in the presence of alumino silica gel catalyst makes them implement gas-phase ring-closing reaction, its reaction temperature is above 193deg.C, then collects the reaction product from reaction mixed gas.
Description
That technical field the present invention relates to is a kind of preparation method of 3-methyl piperidine.
Background technology can make the 3-picoline by the 3-methyl piperidine, and the latter is preparation agricultural chemical insecticide and vitamins B
3---the main raw material of nicotinic acid, niacinamide.In the past, the 3-methyl piperidine did not have industrialized producing technology, and obtain the 3-methyl piperidine then needs the 3-picoline is carried out restoring operation, and the 3-picoline also only obtains from the byproduct of producing pyridine.
Summary of the invention is at above-mentioned deficiency, and the present invention will solve the technical problem that the 3-methyl piperidine does not have industrialized producing technology, so that a kind of preparation method applicable to mass-produced 3-methyl piperidine to be provided.
The preparation method of 3-methyl piperidine provided by the invention, earlier with the 2-methyl isophthalic acid, the 5-pentamethylene diamine is a raw material, with the diluent for gases is carrier, in the presence of the alumino silica gel catalyzer, carry out the gas phase ring-closure reaction, temperature of reaction is more than 193 ℃, collecting reaction product from reaction mixture gas then, and the chemical reaction equation of described reaction is:
The preparation method of 3-methyl piperidine provided by the invention, the temperature of reaction when carrying out the gas phase ring-closure reaction are 230～350 ℃, preferred 250～300 ℃.When being lower than 200 ℃, conversion of raw material is very low; And when being higher than 350 ℃, then can cause side reaction to increase, and 3-methyl piperidine yield is reduced, catalyst life shortens.Carry out the gas phase ring-closure reaction and generally under normal pressure, carry out, also can a little more than or a little less than non-pressurized condition under carry out.
The preparation method of 3-methyl piperidine provided by the invention carries out the gas phase ring-closure reaction and can carry out in fixed-bed reactor, also can carry out in fluidized-bed reactor.If carry out in fixed-bed reactor, reactor is that internal diameter is 21mm, and length is the stainless steel tube of 3.6m, and reactor is outside with the heating of melting salt salt bath.Generally speaking at reactor built-in thermoelectric idol temperature-measuring casing to measure bed temperature.
The preparation method of 3-methyl piperidine provided by the invention, employed diluent for gases comprises N when carrying out the gas phase ring-closure reaction
2, water vapor, H
2In a kind of, or two or three mixed gas wherein, preferred N
2
The preparation method of 3-methyl piperidine provided by the invention, when carrying out the gas phase ring-closure reaction in material mixed gas the 2-methyl isophthalic acid, the volumetric concentration of 5-pentamethylene diamine does not have special stipulation, generally selects 5～30%.Excessive concentration, transformation efficiency reduces, and side reactions such as polymerization increase; Concentration is low excessively, is unfavorable for suitability for industrialized production.
The preparation method of 3-methyl piperidine provided by the invention, collecting reaction product can adopt well-known method from reaction mixture gas, as reaction mixture gas is carried out direct condensation; Equally, purified product also can adopt well-known method, as crude product is distilled.
The preparation method of 3-methyl piperidine provided by the invention, the main component of employed alumino silica gel catalyzer are the oxide compounds of Al and Si, preferred Al
2O
3And SiO
2, Al wherein
2O
3Weight content in the alumino silica gel catalyzer is 1～20%, preferred 2～15%.
The preparation method of 3-methyl piperidine provided by the invention, employed alumino silica gel specific surface area of catalyst is 100～800m
2/ g, preferred 200～600m
2/ g.Employed alumino silica gel catalyst particles granularity does not have particular determination, can adopt to be easy to all size processing, load.
The preparation method of 3-methyl piperidine provided by the invention, to produce the byproduct 2-methyl isophthalic acid of adiponitrile in the terylene industrial that is on a grand scale, the 5-pentamethylene diamine is a raw material, economy is easy to get, and has guaranteed the low-cost raw material supply of preparation 3-methyl piperidine.Be applied in the gas phase ring-closure reaction of alumino silica gel catalyzer under existing simultaneously, make the selectivity of product of reaction and yield all than higher.As seen, the invention provides the preparation method of the 3-methyl piperidine that a kind of production cost is low, product purity is high.
Embodiment
Embodiment 1, earlier with the 2-methyl isophthalic acid after water vapor and the vaporization, the 5-pentamethylene diamine mixes, and carries out the gas phase ring-closure reaction then in the presence of the alumino silica gel catalyzer, 195 ℃ of temperature of reaction, collecting reaction product from reaction mixture gas again, purification at last promptly gets the 3-methyl piperidine.
Embodiment 2, be 21mm at internal diameter, longly be 3.6m, built-in thermoelectric idol temperature tube is packed in the outside stainless steel tubulation formula reactor that heats with the melting salt salt bath and is contained 8%Al
2O
3, specific surface area is the alumino silica gel catalyzer 500g of 325m2/g, volume is about 720ml.With the 2-methyl isophthalic acid, the 5-pentamethylene diamine is vaporized under 250 ℃ of temperature through vaporizer, then with N earlier
2Mix, form and contain the 2-methyl isophthalic acid, the gas mixture of 5-pentamethylene diamine 21.4% enters in the tubular reactor that is filled with catalyzer, and 2-methyl isophthalic acid, the flow of 5-pentamethylene diamine are 300g/hr.300 ℃ of the outside melting salt salt temperatures of reactor.Again reaction mixture gas is carried out the condensation collecting reaction product, this product contains through gc analysis: 3-methyl piperidine 97.4%, 3-picoline 1.3%, 2-methyl isophthalic acid, 5-pentamethylene diamine 0.6% and 0.7% not clear organism.At last, reaction product is distilled purification, content is 99.5% 3-methyl piperidine.
Embodiment 3, press the described methods operation of embodiment 2, just reactor is heated the fused salt salt temperature brings up to 350 ℃, the product of collecting behind the analytical reaction gaseous mixture condensation: 3-methyl piperidine 86.8%, 3-picoline 5.9% and 7.3% is failed to understand organism.
Embodiment 4, press the described methods operation of embodiment 2, but do not have N
2As diluent gas, be 315 ℃, 2-methyl isophthalic acid in temperature, 5-pentamethylene diamine inlet amount is under 300g/ hour the condition, recording product, to contain the 3-methyl piperidine only be 53.4%, also has 21.7%3-picoline and 24.9% other organism.Though this also can carry out this example explanation when being reflected at no diluent for gases, product purity is low excessively.
Following table has been enumerated and obtained the embodiment that different products are formed under the step identical with embodiment 2, different reaction process condition:
| Embodiment | Diluent for gases | In the silica-alumina catalyst | Temperature of reaction (℃) | Product is formed | ||||
| 2 methyl pentamethylenediamine (%) | 3-methyl piperidine (%) | 3-picoline (%) | Not clear organism (%) | |||||
| Al 2O 3Content (%) | Specific surface area (mu/g) | |||||||
| 5 | N 2 | 3 | 750 | 240 | 8.7 | 89.9 | 1.1 | 0.3 |
| 6 | N 2 | 3 | 615 | 350 | 2.4 | 94.1 | 2.0 | 1.5 |
| 7 | N 2 | 12 | 250 | 350 | 0.4 | 94.6 | 1.9 | 3.1 |
| 8 | H 2 | 8 | 600 | 250 | 8.3 | 90.7 | 0.7 | 0.3 |
| 9 | H 2 | 8 | 125 | 300 | 2.1 | 96.7 | 0.6 | 0.6 |
Claims (10)
1, a kind of preparation method of 3-methyl piperidine, it is characterized in that earlier with the 2-methyl isophthalic acid, the 5-pentamethylene diamine is a raw material, with the diluent for gases is carrier, in the presence of the alumino silica gel catalyzer, carry out the gas phase ring-closure reaction, temperature of reaction is more than 193 ℃, collecting reaction product from reaction mixture gas then, and the chemical reaction equation of described reaction is:
2, the preparation method of 3-methyl piperidine as claimed in claim 1, the temperature of reaction when it is characterized in that carrying out the gas phase ring-closure reaction are 230～350 ℃.
3, the preparation method of 3-methyl piperidine as claimed in claim 1 or 2, the temperature of reaction when it is characterized in that carrying out the gas phase ring-closure reaction are 250～300 ℃.
4, the preparation method of 3-methyl piperidine as claimed in claim 1, employed diluent for gases is N when it is characterized in that carrying out the gas phase ring-closure reaction
2, water vapor, H
2At least a among the three.
5, as the preparation method of claim 1 or 4 described 3-methyl piperidines, employed diluent for gases is N when it is characterized in that carrying out the gas phase ring-closure reaction
2
6, the preparation method of 3-methyl piperidine as claimed in claim 1, when it is characterized in that carrying out the gas phase ring-closure reaction in material mixed gas the 2-methyl isophthalic acid, the volumetric concentration of 5-pentamethylene diamine is 2～50%.
7, as the preparation method of claim 1 or 6 described 3-methyl piperidines, when it is characterized in that carrying out the gas phase ring-closure reaction in material mixed gas the 2-methyl isophthalic acid, the volumetric concentration of 5-pentamethylene diamine is 5～30%.
8, the preparation method of 3-methyl piperidine as claimed in claim 1, the main component that it is characterized in that employed alumino silica gel catalyzer is Al
2O
3And SiO
2
9, the preparation method of 3-methyl piperidine as claimed in claim 8 is characterized in that Al in the employed alumino silica gel catalyzer
2O
3Weight content be 1～20%; The specific surface area of alumino silica gel catalyzer is 100～800m
2/ g.
10, the preparation method of 3-methyl piperidine as claimed in claim 8 or 9 is characterized in that Al in the employed alumino silica gel catalyzer
2O
3Weight content be 2～15%; The specific surface area of alumino silica gel catalyzer is 200～600m
2/ g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510060201 CN1903841A (en) | 2005-07-29 | 2005-07-29 | Preparation method of 3-methyl piperidine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510060201 CN1903841A (en) | 2005-07-29 | 2005-07-29 | Preparation method of 3-methyl piperidine |
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| Publication Number | Publication Date |
|---|---|
| CN1903841A true CN1903841A (en) | 2007-01-31 |
Family
ID=37673223
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|---|---|---|---|
| CN 200510060201 Pending CN1903841A (en) | 2005-07-29 | 2005-07-29 | Preparation method of 3-methyl piperidine |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104844539A (en) * | 2014-02-17 | 2015-08-19 | 上海凯赛生物技术研发中心有限公司 | Piperidine preparation method |
| CN112010802A (en) * | 2020-08-13 | 2020-12-01 | 浙江新和成股份有限公司 | Continuous preparation method of 3-methylpyridine |
| CN112759547A (en) * | 2021-02-01 | 2021-05-07 | 铂尊投资集团有限公司 | 3-methylpyridine continuous production system and preparation method |
-
2005
- 2005-07-29 CN CN 200510060201 patent/CN1903841A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104844539A (en) * | 2014-02-17 | 2015-08-19 | 上海凯赛生物技术研发中心有限公司 | Piperidine preparation method |
| CN104844539B (en) * | 2014-02-17 | 2018-08-24 | 上海凯赛生物技术研发中心有限公司 | A kind of preparation method of piperidines |
| CN112010802A (en) * | 2020-08-13 | 2020-12-01 | 浙江新和成股份有限公司 | Continuous preparation method of 3-methylpyridine |
| CN112759547A (en) * | 2021-02-01 | 2021-05-07 | 铂尊投资集团有限公司 | 3-methylpyridine continuous production system and preparation method |
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