CN106117163A - A kind of 3 (N morpholine) 2 hydroxy-propanesulfonic acid synthesis technique - Google Patents
A kind of 3 (N morpholine) 2 hydroxy-propanesulfonic acid synthesis technique Download PDFInfo
- Publication number
- CN106117163A CN106117163A CN201610442325.4A CN201610442325A CN106117163A CN 106117163 A CN106117163 A CN 106117163A CN 201610442325 A CN201610442325 A CN 201610442325A CN 106117163 A CN106117163 A CN 106117163A
- Authority
- CN
- China
- Prior art keywords
- morpholine
- hydroxy
- temperature
- propanesulfonic acid
- synthesis technique
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The present invention relates to a kind of 3 (N morpholine) 2 hydroxy-propanesulfonic acid synthesis technique, disclose the preparation method of a kind of N substituted morpholines organic compounds, comprise the following steps: that cyclodehydration obtains morpholine, again through neutralizing, filter, rectification, synthesis obtains 3 (N morpholine) 2 hydroxy-propanesulfonic acids, eventually pass chromatography and purification obtains final products, the method reaction condition that the present invention provides is gentle, easy and simple to handle, safety is high, it is prone to industrialization, stable yield is more than 95%, and reagent is cheap and simple and easy to get, there is obvious cost and technical advantage.
Description
Technical field
The invention belongs to chemical field, it is more particularly related to a kind of 3-(N-morpholine)-2-hydroxy-propanesulfonic acid closes
Become technique.
Background technology
Containing active stronger hydroxyl in 3-(N-morpholine)-2-hydroxy-propanesulfonic acid molecular structure, contain again hydrophilic sulfonic acid
Salt groups, wherein halogen atom is susceptible to replacement, elimination reaction, is function monomer important in synthetic high polymer industry, also
Can be used as organic chemical industry's intermediate, be important multi-functional material.Existing 3-(N-morpholine)-2-hydroxy-propanesulfonic acid is big
How being reacted under the effect of base catalyst formed by water and epoxychloropropane, its response time is long, and product yield is relatively
Low and purity is the highest, and the purity of product often affects preparation and the performance of downstream product.Also can produce during simultaneous reactions
Raw substantial amounts of waste reaction solution, waste resource, pollution environment.
Summary of the invention
Problem to be solved by this invention is to provide a kind of 3-(N-morpholine)-2-hydroxy-propanesulfonic acid synthesis technique.
To achieve these goals, the technical scheme that the present invention takes is:
A kind of 3-(N-morpholine)-2-hydroxy-propanesulfonic acid synthesis technique, comprises the steps:
(1) cyclodehydration
Diethanolamine is joined in reactor, then rise high-temperature, and add sulphuric acid, stirring reaction 70-80min；
(2) neutralize
Reaction is cooled to 60 DEG C after terminating, and adds the NaOH of 1mol/L in a kettle., and keep in the case of continuously stirred
Temperature is below 60 DEG C, and control pH value is 6.9-7.1, neutralizes complete, is stirred for 20-30min；
(3) filtration, rectification
Reactant liquor after neutralization filters after being cooled to room temperature, removes sodium sulfate, and 45% sodium hydroxide adding 1.5 times is molten
Liquid mixes with filtrate, and carries out rectification, collects fraction；
(4) synthesis
Adding 2-hydroxypropionate sodium in fraction liquid, making morpholine is 1:1.2 with the ratio of 2-hydroxypropionate sodium, and stirring adds
Hot reflux 3-4h；
(5) chromatography
Question response liquid is cooled to room temperature, carries out sodium ion exchange resin with 100g strongly acidic styrene type cation exchange resin
Chromatography；
(6) purification
With 5% ammonia eluting, it is concentrated in vacuo, is adjusted to pH=5.0 with glacial acetic acid, with the ethanol dilution of 10 times of volumes, white solid
Separate out, filter, washing with alcohol, vacuum drying.
Preferably, diethanolamine temperature is first risen to 55 DEG C by described step (1), adds concentrated sulphuric acid.
Preferably, described step (1) temperature of reactor when dripping concentrated sulphuric acid to control at 55～60 DEG C, completion of dropwise addition
After temperature is risen to 200～240 DEG C.
Preferably, adding catalyst in described step (1) reactor, described catalyst is Ni, Cu and MoO3Mixture.
Preferably, in described step (1), catalyst is Ni, Cu and MoO3Mass values be 1:3:4.
Preferably, described step (3) is evaporating the temperature of Time-sharing control tower top respectively at 130-134 DEG C and 160-164 DEG C.
Beneficial effect: the present invention relates to a kind of 3-(N-morpholine)-2-hydroxy-propanesulfonic acid synthesis technique, discloses a kind of N
The preparation method of substituted morpholines organic compounds, comprise the following steps: cyclodehydration obtain morpholine, again through neutralization, filter,
Rectification, synthesis obtain 3-(N-morpholine)-2-hydroxy-propanesulfonic acid, eventually pass chromatography and purification obtain final products, the present invention carries
The method reaction condition of confession is gentle, easy and simple to handle, and safety is high, it is easy to industrialization, stable yield is more than 95%, and reagent valency
Lattice are cheap and simple and easy to get, have obvious cost and technical advantage.
Detailed description of the invention
Embodiment 1:
A kind of 3-(N-morpholine)-2-hydroxy-propanesulfonic acid synthesis technique, comprises the steps:
(1) cyclodehydration
Diethanolamine is joined in reactor, first diethanolamine temperature is risen to 55 DEG C, add concentrated sulphuric acid, drip concentrated sulphuric acid
Time reactor temperature to control, at 55 DEG C, after completion of dropwise addition, temperature to rise to 200 DEG C, and add sulphuric acid and catalyst: Ni, Cu
And MoO3Mixture, described Ni, Cu and MoO3Mass values be 1:3:4 stirring reaction 70min；
(2) neutralize
Reaction is cooled to 60 DEG C after terminating, and adds the NaOH of 1mol/L in a kettle., and keep in the case of continuously stirred
Temperature is below 60 DEG C, and controlling pH value is 6.9, neutralizes complete, is stirred for 20min；
(3) filtration, rectification
Reactant liquor after neutralization filters after being cooled to room temperature, removes sodium sulfate, and 45% sodium hydroxide adding 1.5 times is molten
Liquid mixes with filtrate, and carries out rectification, collect fraction, described in evaporate the temperature of Time-sharing control tower top respectively at 130 DEG C and 160 DEG C；
(4) synthesis
Adding 2-hydroxypropionate sodium in fraction liquid, making morpholine is 1:1.2 with the ratio of 2-hydroxypropionate sodium, and stirring adds
Hot reflux 3h；
(5) chromatography
Question response liquid is cooled to room temperature, carries out sodium ion exchange resin with 100g strongly acidic styrene type cation exchange resin
Chromatography；
(6) purification
With 5% ammonia eluting, it is concentrated in vacuo, is adjusted to pH=5.0 with glacial acetic acid, with the ethanol dilution of 10 times of volumes, white solid
Separate out, filter, washing with alcohol, vacuum drying.
Embodiment 2:
A kind of 3-(N-morpholine)-2-hydroxy-propanesulfonic acid synthesis technique, comprises the steps:
(1) cyclodehydration
Diethanolamine is joined in reactor, first diethanolamine temperature is risen to 55 DEG C, add concentrated sulphuric acid, drip concentrated sulphuric acid
Time reactor temperature to control, at 57.5 DEG C, after completion of dropwise addition, temperature to rise to 200～240 DEG C, and add sulphuric acid and catalysis
Agent: Ni, Cu and MoO3Mixture, described Ni, Cu and MoO3Mass values be 1:3:4 stirring reaction 750min；
(2) neutralize
Reaction is cooled to 60 DEG C after terminating, and adds the NaOH of 1mol/L in a kettle., and keep in the case of continuously stirred
Temperature is below 60 DEG C, and controlling pH value is 7, neutralizes complete, is stirred for 25min；
(3) filtration, rectification
Reactant liquor after neutralization filters after being cooled to room temperature, removes sodium sulfate, and 45% sodium hydroxide adding 1.5 times is molten
Liquid mixes with filtrate, and carries out rectification, collect fraction, described in evaporate the temperature of Time-sharing control tower top respectively at 132 DEG C and 162 DEG C；
(4) synthesis
Adding 2-hydroxypropionate sodium in fraction liquid, making morpholine is 1:1.2 with the ratio of 2-hydroxypropionate sodium, and stirring adds
Hot reflux 3.5h；
(5) chromatography
Question response liquid is cooled to room temperature, carries out sodium ion exchange resin with 100g strongly acidic styrene type cation exchange resin
Chromatography；
(6) purification
With 5% ammonia eluting, it is concentrated in vacuo, is adjusted to pH=5.0 with glacial acetic acid, with the ethanol dilution of 10 times of volumes, white solid
Separate out, filter, washing with alcohol, vacuum drying.
Embodiment 3:
A kind of 3-(N-morpholine)-2-hydroxy-propanesulfonic acid synthesis technique, comprises the steps:
(1) cyclodehydration
Diethanolamine is joined in reactor, first diethanolamine temperature is risen to 55 DEG C, add concentrated sulphuric acid, drip concentrated sulphuric acid
Time reactor temperature to control, at 57 DEG C, after completion of dropwise addition, temperature to rise to 225 DEG C, and add sulphuric acid and catalyst: Ni, Cu
And MoO3Mixture, described Ni, Cu and MoO3Mass values be 1:3:4 stirring reaction 80min；
(2) neutralize
Reaction is cooled to 60 DEG C after terminating, and adds the NaOH of 1mol/L in a kettle., and keep in the case of continuously stirred
Temperature is below 60 DEG C, and controlling pH value is 7.1, neutralizes complete, is stirred for 30min；
(3) filtration, rectification
Reactant liquor after neutralization filters after being cooled to room temperature, removes sodium sulfate, and 45% sodium hydroxide adding 1.5 times is molten
Liquid mixes with filtrate, and carries out rectification, collect fraction, described in evaporate the temperature of Time-sharing control tower top respectively at 134 DEG C and 164 DEG C；
(4) synthesis
Adding 2-hydroxypropionate sodium in fraction liquid, making morpholine is 1:1.2 with the ratio of 2-hydroxypropionate sodium, and stirring adds
Hot reflux 4h；
(5) chromatography
Question response liquid is cooled to room temperature, carries out sodium ion exchange resin with 100g strongly acidic styrene type cation exchange resin
Chromatography；
(6) purification
With 5% ammonia eluting, it is concentrated in vacuo, is adjusted to pH=5.0 with glacial acetic acid, with the ethanol dilution of 10 times of volumes, white solid
Separate out, filter, washing with alcohol, vacuum drying.
After process above processes, taking out sample respectively, measurement result is as follows:
| Detection project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Prior art index |
| Yield (%) | 95 | 96 | 94 | 85 |
| Stability | Good | Good | Typically | Typically |
| Toxicity | Low | Low | Low | Medium |
Can draw according to above table data, the Fructus Jujubae vinegar produced when embodiment 2 parameter produces than prior art
The advantage that acidity is high, bacterial population is few, amino acid content is high of Fructus Jujubae vinegar.
The present invention relates to a kind of 3-(N-morpholine)-2-hydroxy-propanesulfonic acid synthesis technique, disclosed a kind of N and replace morpholine class
The preparation method of organic compound, comprises the following steps: that cyclodehydration obtains morpholine, again through neutralization, filtration, rectification, synthesis
Obtaining 3-(N-morpholine)-2-hydroxy-propanesulfonic acid, eventually pass chromatography and purification obtains final products, the method that the present invention provides is anti-
Answering mild condition, easy and simple to handle, safety is high, it is easy to industrialization, stable yield is more than 95%, and reagent is cheap and simple
Singly it is easy to get, there is obvious cost and technical advantage.
The foregoing is only embodiments of the invention, not thereby limit the scope of the claims of the present invention, every utilize this
Equivalent structure or equivalence flow process that bright description is made convert, or are directly or indirectly used in other relevant technology necks
Territory, is the most in like manner included in the scope of patent protection of the present invention.
Claims (6)
1. 3-(N-morpholine)-2-hydroxy-propanesulfonic acid synthesis technique, it is characterised in that comprise the steps:
(1) cyclodehydration
Diethanolamine is joined in reactor, then rise high-temperature, and add sulphuric acid, stirring reaction 70-80min；
(2) neutralize
Reaction is cooled to 60 DEG C after terminating, and adds the NaOH of 1mol/L in a kettle., and keep in the case of continuously stirred
Temperature is below 60 DEG C, and control pH value is 6.9-7.1, neutralizes complete, is stirred for 20-30min；
(3) filtration, rectification
Reactant liquor after neutralization filters after being cooled to room temperature, removes sodium sulfate, and 45% sodium hydroxide adding 1.5 times is molten
Liquid mixes with filtrate, and carries out rectification, collects fraction；
(4) synthesis
Adding 2-hydroxypropionate sodium in fraction liquid, making morpholine is 1:1.2 with the ratio of 2-hydroxypropionate sodium, and stirring adds
Hot reflux 3-4h；
(5) chromatography
Question response liquid is cooled to room temperature, carries out sodium ion exchange resin with 100g strongly acidic styrene type cation exchange resin
Chromatography；
(6) purification
With 5% ammonia eluting, it is concentrated in vacuo, is adjusted to pH=5.0 with glacial acetic acid, with the ethanol dilution of 10 times of volumes, white solid
Separate out, filter, washing with alcohol, vacuum drying.
2. according to a kind of 3-(N-the morpholine)-2-hydroxy-propanesulfonic acid synthesis technique described in claim 1, it is characterised in that: described
Diethanolamine temperature is first risen to 55 DEG C by step (1), adds concentrated sulphuric acid.
3. according to a kind of 3-(N-the morpholine)-2-hydroxy-propanesulfonic acid synthesis technique described in claim 1, it is characterised in that: described
Step (1) drip concentrated sulphuric acid time reactor temperature to control at 55～60 DEG C, after completion of dropwise addition, temperature is risen to 200～
240℃。
4. according to a kind of 3-(N-the morpholine)-2-hydroxy-propanesulfonic acid synthesis technique described in claim 1, it is characterised in that: described
Adding catalyst in step (1) reactor, described catalyst is Ni, Cu and MoO3Mixture.
5. according to a kind of 3-(N-the morpholine)-2-hydroxy-propanesulfonic acid synthesis technique described in claim 1, it is characterised in that: described
In step (1) catalyst be the mass values of Ni, Cu and MoO3 be 1:3:4.
6. according to a kind of 3-(N-the morpholine)-2-hydroxy-propanesulfonic acid synthesis technique described in claim 1, it is characterised in that: described
Step (3) is evaporating the temperature of Time-sharing control tower top respectively at 130-134 DEG C and 160-164 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610442325.4A CN106117163A (en) | 2016-06-21 | 2016-06-21 | A kind of 3 (N morpholine) 2 hydroxy-propanesulfonic acid synthesis technique |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610442325.4A CN106117163A (en) | 2016-06-21 | 2016-06-21 | A kind of 3 (N morpholine) 2 hydroxy-propanesulfonic acid synthesis technique |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106117163A true CN106117163A (en) | 2016-11-16 |
Family
ID=57470243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610442325.4A Pending CN106117163A (en) | 2016-06-21 | 2016-06-21 | A kind of 3 (N morpholine) 2 hydroxy-propanesulfonic acid synthesis technique |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106117163A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134403A (en) * | 2018-09-27 | 2019-01-04 | 湖南恒泰化工有限公司 | A kind of preparation method of 2-morpholine ethane sulfonic acid |
-
2016
- 2016-06-21 CN CN201610442325.4A patent/CN106117163A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 田铁生: "N-烷基化", 《有机合成单元过程》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134403A (en) * | 2018-09-27 | 2019-01-04 | 湖南恒泰化工有限公司 | A kind of preparation method of 2-morpholine ethane sulfonic acid |
| CN109134403B (en) * | 2018-09-27 | 2022-08-16 | 湖南恒泰化工有限公司 | Preparation method of 2-morpholine ethanesulfonic acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105001087A (en) | Method and apparatus for producing formic esters by comprehensively utilizing metronidazole hydroxylation synthesis wastewater | |
| CN107899371A (en) | A kind of ionic eutectic solvent of new and effective reversible absorption ammonia | |
| CN101773840B (en) | Method for hydrothermal synthesis of carbon-silicon composite solid acid catalyst | |
| CN102675172A (en) | Preparation method of tiamulin base | |
| CN110776418A (en) | Method for preparing maleic acid ester by catalyzing maleic anhydride with ionic liquid | |
| CN106117163A (en) | A kind of 3 (N morpholine) 2 hydroxy-propanesulfonic acid synthesis technique | |
| CN105268466A (en) | Method for preparing Cu-Ni diatom doped mesoporous molecular sieve catalyst | |
| CN104492494A (en) | Magnetic iron oxide-immobilized ionic liquid solid acid material catalyst and preparation method thereof | |
| CN104785294A (en) | Ionic liquid-based catalyst and preparation method and application thereof | |
| CN103373980B (en) | Method for synthesizing trioxymethylene | |
| CN102976897A (en) | Method for purifying tetrafluoro propanol | |
| CN106608832B (en) | The process of liquid ammonia process for caustic soda purification and Ammonia Process co-producing ethanol amine | |
| CN102626656B (en) | Preparation method of acidic ionic liquid hydrothermal carbonization material | |
| CN116328790A (en) | Preparation method of solid acid catalyst and application of solid acid catalyst in diethylene glycol dibenzoate synthesis | |
| CN109988080A (en) | A method of using macropore strong acid cation exchanger resin as catalyst preparation imines | |
| CN115028584A (en) | Ionic liquid for producing glutaraldehyde | |
| CN109607915A (en) | A kind of processing method of Benzotriazole Ultraviolet Stabilizer production waste water | |
| CN110759808A (en) | Production process and production system of 1, 3-butanediol | |
| CN109180458A (en) | A kind of method of sodium lactate acidolysis production lactic acid | |
| CN108554451A (en) | A kind of transition metal natural polymer hybrid catalyst and the preparation method and application thereof | |
| CN107159141A (en) | A kind of method that utilization oil-tea camellia husks grafting TGA prepares metal ion adsorbent | |
| CN102962098B (en) | Catalyst for synthesizing sec-Butyl Acetate and preparation method thereof | |
| CN106554263B (en) | A kind of preparation method of cyclopropyl methyl ketone | |
| CN106995390B (en) | A method of it reducing waste water in promotor diphenylguanidine production process and generates | |
| CN109053522A (en) | Trimethylolpropane-three-(3- aziridine base)-propionic ester and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161116 |