CN109369408A - A method of preparing 2- aminopropanol - Google Patents
A method of preparing 2- aminopropanol Download PDFInfo
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- CN109369408A CN109369408A CN201811463002.9A CN201811463002A CN109369408A CN 109369408 A CN109369408 A CN 109369408A CN 201811463002 A CN201811463002 A CN 201811463002A CN 109369408 A CN109369408 A CN 109369408A
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- reaction
- paraformaldehyde
- nitroethane
- aminopropanol
- aqueous solution
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods for preparing 2- aminopropanol, steps are as follows: (1) paraformaldehyde being dissolved in aqueous alkanolamine, form paraformaldehyde lysate, then the paraformaldehyde lysate is added dropwise in nitroethane and is reacted, stratification after reaction, and it is separated by distillation out unreacted nitroethane, the product after separating unreacted nitroethane forms intermediate product, has nitro-propanol in the intermediate product；(2) metallic catalyst is added in intermediate product, and is passed through H2 and is reacted, obtains reaction mixture after the reaction was completed；(3) reaction mixture obtained in step (2) is filtered, filtrate carries out rectification under vacuum and obtains 2- aminopropanol.This method has the characteristics that reaction efficiency is high, product purity is high, the three wastes are few, good economy performance, reduces the pollution to environment.
Description
Technical field
The present invention relates to a kind of organic preparation methods, and in particular to a kind of preparation method of 2- aminopropanol.
Background technique
2- aminopropanol is more representational substance in alkamine compound, is in pharmacy and agribusiness
Important source material, intermediate and chiral auxiliary especially synthesize the important source material of Ofloxacin.And Ofloxacin is in quinolones
One of outstanding extensive pedigree antibiotic is the biggish antibiotic of domestic sales volume, and demand is still constantly increasing.With 2- ammonia
The continuous decline of base propyl alcohol cost, the continuous expansion of application range, it is contemplated that every profession and trade is to the biggish increasing of the dosage of 2- aminopropanol
It is long.Therefore, just seem particularly significant to the Study of synthesis method of the compound.
The preparation method of 2- aminopropanol is mainly based on alanine reduction method at present.Such as patent CN1012004331A and
Patent CN1357534A makees reducing agent using boron hydride and obtains 2- aminopropanol through different approaches using alanine as raw material,
Middle boron hydride is expensive and consumption is big, and production cost is higher；Patent CN101648879A uses l-Alanine and H2For
Primary raw material, ruthenium charcoal are catalyst, carry out direct catalytic hydrogenation synthesis L-2- aminopropanol, but noble ruthenium Pd/carbon catalyst price
Valuableness is not suitable for large-scale production；Patent CN101660171A prepares 2- aminopropan using electrochemical reducing reduction alanine
Alcohol, this method electrolysis time is long, and yield is lower.
Patent CN101033193A and CN1887855A prepare 2- aminopropan then using propylene oxide as raw material, through different approaches
Alcohol.But there is low efficiency in two methods, be not suitable for industrialized production.
Patent CN101903331A is hydrolyzed reaction using 1- methoxyl group -2- propylamine as raw material in acid condition and 2- is made
Aminopropanol, this method postprocessing working procedures are complicated, and quantity of three wastes is big.
Summary of the invention
The purpose of the present invention is to provide a kind of 2- aminopropanol preparation method of green, this method has reaction efficiency
The characteristics of height, product purity are high, the three wastes are few, good economy performance, reduces the pollution to environment.
To achieve the above object the present invention adopts the following technical scheme: a kind of method for preparing 2- aminopropanol, including such as
Lower step:
(1) paraformaldehyde is dissolved in aqueous alkanolamine, forms paraformaldehyde lysate, it is then that the paraformaldehyde is molten
Solution drop, which is added in nitroethane, to be reacted, after reaction stratification, and is separated by distillation out unreacted nitre
Base ethane, the product after separating unreacted nitroethane form intermediate product, have nitro-propanol in the intermediate product；Except nitre
Outside base propyl alcohol, which further includes hydramine；
(2) metallic catalyst is added in intermediate product, and is passed through H2It is reacted, obtains reaction mixing after the reaction was completed
Object；
(3) reaction mixture obtained in step (2) is filtered, filtrate carries out rectification under vacuum and obtains 2- aminopropanol.
Preferably, in step (1), paraformaldehyde lysate be added drop-wise to the time in nitroethane be 30~60min, first
Reaction temperature is 10~60 DEG C.In step (2), the second reaction temperature is 50~100 DEG C, and pressure is controlled in 1~3MPa, reaction
Between be 2~4h.
Aqueous alkanolamine is both the basic catalyst of condensation reaction and the solvent of hydrogenation reaction in the present invention.So not
It reduced by only the depolymerization efficiency for improving paraformaldehyde, improve the yield of condensation reaction, and avoid organic molten using other
Agent reduces environmental pollution.
The present invention prepares 2- aminopropanol, reaction effect using nitroethane as primary raw material, through condensation, catalytic hydrogenating reduction
Rate is higher, and the purity of product can achieve 99% or more, and use the lower multimetal reforming catalyst of price, good economy performance.
In addition product and water are only generated in preparation process, and effectively reduce the use of organic solvent, three waste discharge is few, and it is environmentally friendly,
Realize green syt.
In order to avoid the waste of raw material, and keep the conversion ratio of raw material higher, nitroethane and paraformaldehyde in step (1)
Molar ratio be 1:0.5~1.1.Control of entire reaction time simultaneously in 1~2h, avoid intermediate product 2- nitro-propanol continue with
Formaldehyde reaction, improves raw material availability.The reaction time is is added drop-wise in nitroethane since paraformaldehyde lysate,
To ending at the end of reaction.
In step (1) aqueous alkanolamine be selected from monoethanolamine aqueous solution, diethanol amine aqueous solution, triethanolamine aqueous solution,
One of diisopropanol amine aqueous solution, triisopropanolamine aqueous solution, the mass ratio of paraformaldehyde and aqueous alkanolamine are 1:1
~3, aqueous alkanolamine can enable the complete depolymerization of paraformaldehyde, and reduce compared to inorganic base alkalinity is weaker and pH stable
The generation of disproportionated reaction.
Metallic catalyst is multimetal reforming catalyst in step (2), appointing preferably in Fe/Ni, Cu/Ni, Co/Ni, Al/Ni
One kind, the additive amount of metallic catalyst are the 0.5%~3% of nitro-propanol quality.
The resulting filter residue of filtering is metallic catalyst in step (3), continues to urge as metal in the filter residue return step (2)
Agent, to reduce production cost.
The rectification under vacuum mentioned in the method for the present invention step is carried out using the process conditions of this field routine.
Specific embodiment
The present invention will be further described combined with specific embodiments below.
In this application, the calculating of the molal quantity of paraformaldehyde is on the basis of the molal weight of formaldehyde, i.e., by paraformaldehyde
Molal weight be set as identical as the molal weight of formaldehyde.
Embodiment 1
60g paraformaldehyde is dissolved in the diisopropanol amine aqueous solution of 180g, it is under stirring condition that the lysate is slow
It is added dropwise in 150g nitroethane and is reacted, time for adding 30min reacts 1h at 60 DEG C again after being added dropwise.Instead
Stratification after answering, and it is separated by distillation out unreacted nitroethane.
Fe/Ni multimetal reforming catalyst is added in the reaction product, and is passed through H2It is reacted.Its temperature is controlled at 80 DEG C,
Pressure is controlled in 2MPa, reaction time 3h.It filters after reaction, hydrogenation catalyst can be continued to serve as after filter residue recycling, filtered
Liquid carries out rectification under vacuum and obtains 2- aminopropanol 120.7g, yield 80.5%, purity 99.2%.
Embodiment 2
60g paraformaldehyde is dissolved in 60g diethanol amine aqueous solution, under stirring condition by the lysate be slowly added dropwise into
It is reacted in 300g nitroethane, time for adding 60min reacts 1h at 10 DEG C again after being added dropwise.Reaction terminates
Stratification afterwards, and it is separated by distillation out unreacted nitroethane.
Cu/Ni multimetal reforming catalyst is added in the reaction product, and is passed through H2It is reacted.Its temperature is controlled at 100 DEG C,
Pressure is controlled in 1MPa, reaction time 2h.It filters after reaction, hydrogenation catalyst can be continued to serve as after filter residue recycling, filtered
Liquid carries out rectification under vacuum and obtains 2- aminopropanol 116.1g, yield 77.4%, purity 99.1%.
Embodiment 3
60g paraformaldehyde is dissolved in the monoethanolamine aqueous solution of 180g, is slowly dripped the lysate under stirring condition
It is added in 180.7g nitroethane and is reacted, time for adding 30min reacts 0.5h at 30 DEG C again after being added dropwise.
Stratification after reaction, and it is separated by distillation out unreacted nitroethane.
Co/Ni multimetal reforming catalyst is added in the reaction product, and is passed through H2It is reacted.Its temperature is controlled at 50 DEG C,
Pressure is controlled in 3MPa, reaction time 4h.It filters after reaction, filtrate carries out rectification under vacuum and obtains 2- aminopropanol
112.9g, yield 75.3%, purity 99.2%.
Embodiment 4
60g paraformaldehyde is dissolved in the triisopropanolamine aqueous solution of 120g, it is under stirring condition that the lysate is slow
It is added dropwise in 136.4g nitroethane and is reacted, time for adding 45min reacts 1h at 50 DEG C again after being added dropwise.
Stratification after reaction, and it is separated by distillation out unreacted nitroethane.
Al/Ni multimetal reforming catalyst is added in the reaction product, and is passed through H2It is reacted.Its temperature is controlled at 80 DEG C,
Pressure is controlled in 3MPa, reaction time 3h.It filters after reaction, filtrate carries out rectification under vacuum and obtains 2- aminopropanol
122.3g, yield 81.5%, purity 99.2%.
Embodiment 5
60g paraformaldehyde is dissolved in the triethanolamine aqueous solution of 120g, is slowly dripped the lysate under stirring condition
It is added in 136.4g nitroethane and is reacted, time for adding 45min reacts 1h at 50 DEG C again after being added dropwise.Instead
Stratification after answering, and it is separated by distillation out unreacted nitroethane.
Fe/Ni multimetal reforming catalyst is added in the reaction product, and is passed through H2It is reacted.Its temperature is controlled at 70 DEG C,
Pressure is controlled in 3MPa, reaction time 4h.It filters after reaction, filtrate carries out rectification under vacuum and obtains 2- aminopropanol
123.9g, yield 82.6%, purity 99.2%.
Comparative example 1
60g paraformaldehyde is dissolved in the NaOH aqueous solution of 120g 40%, is slowly dripped the lysate under stirring condition
It is added in 150g nitroethane and is reacted, time for adding 45min reacts 1h at 50 DEG C again after being added dropwise.Reaction
After stratification, and be separated by distillation out unreacted nitroethane.
Ruthenium Pd/carbon catalyst is added in the reaction product, and is passed through H2It is reacted.At 70 DEG C, pressure controls the control of its temperature
In 3MPa, reaction time 4h.It filters after reaction, filtrate carries out rectification under vacuum and obtains 2- aminopropanol 91.3g, yield
60.9%, purity 98.7%.
Claims (10)
1. a kind of method for preparing 2- aminopropanol, includes the following steps:
(1) paraformaldehyde is dissolved in aqueous alkanolamine, paraformaldehyde lysate is formed, then by the paraformaldehyde lysate
It is added dropwise in nitroethane and is reacted, after reaction stratification, and be separated by distillation out unreacted nitro second
Alkane, the product after separating unreacted nitroethane form intermediate product, have nitro-propanol in the intermediate product；
(2) metallic catalyst is added in intermediate product, and is passed through H2It is reacted, obtains reaction mixture after the reaction was completed；
(3) reaction mixture obtained in step (2) is filtered, filtrate carries out rectification under vacuum and obtains 2- aminopropanol.
2. the method according to claim 1, wherein
In step (1), the molar ratio of nitroethane and paraformaldehyde is 1:0.5~1.1.
3. the method according to claim 1, wherein the reaction time is 1~2h in step (1).
4. the method according to claim 1, wherein
In step (1), aqueous alkanolamine model is monoethanolamine aqueous solution, diethanol amine aqueous solution, triethanolamine aqueous solution, two different
Any one of propyl alcohol amine aqueous solution, triisopropanolamine aqueous solution；
The mass ratio of paraformaldehyde and aqueous alkanolamine is 1:1~3.
5. the method according to claim 1, wherein
Metallic catalyst is multimetal reforming catalyst in step (2).
6. according to the method described in claim 5, it is characterized in that,
Multimetal reforming catalyst is any one of Fe/Ni, Cu/Ni, Co/Ni, Al/Ni.
7. the method according to claim 1, wherein
The additive amount of metallic catalyst is the 0.5%~3% of nitro-propanol quality.
8. the method according to claim 1, wherein
The resulting filter residue of filtering is metallic catalyst in step (3), is continued in the filter residue return step (2) as metal catalytic
Agent.
9. the method according to claim 1, wherein
In step (1), paraformaldehyde lysate is added drop-wise to the time in nitroethane as 30~60min, and the first reaction temperature is
10~60 DEG C.
10. the method according to claim 1, wherein
In step (2), the second reaction temperature is 50~100 DEG C, and in 1~3MPa, the reaction time is 2~4h for pressure control.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201811463002.9A CN109369408A (en) | 2018-12-03 | 2018-12-03 | A method of preparing 2- aminopropanol |
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| CN201811463002.9A CN109369408A (en) | 2018-12-03 | 2018-12-03 | A method of preparing 2- aminopropanol |
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| CN109369408A true CN109369408A (en) | 2019-02-22 |
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| CN201811463002.9A Pending CN109369408A (en) | 2018-12-03 | 2018-12-03 | A method of preparing 2- aminopropanol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110172029A (en) * | 2019-06-28 | 2019-08-27 | 南京红宝丽醇胺化学有限公司 | A kind of method of continuous synthesis 2-amino-2-methyl-1-propanol |
-
2018
- 2018-12-03 CN CN201811463002.9A patent/CN109369408A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110172029A (en) * | 2019-06-28 | 2019-08-27 | 南京红宝丽醇胺化学有限公司 | A kind of method of continuous synthesis 2-amino-2-methyl-1-propanol |
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Application publication date: 20190222 |