CN107382830B - A kind of separation method drawing pyridine derivate in azoles production - Google Patents
A kind of separation method drawing pyridine derivate in azoles production Download PDFInfo
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- CN107382830B CN107382830B CN201710705196.8A CN201710705196A CN107382830B CN 107382830 B CN107382830 B CN 107382830B CN 201710705196 A CN201710705196 A CN 201710705196A CN 107382830 B CN107382830 B CN 107382830B
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- pyridine derivate
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- 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
Abstract
The present invention relates to a kind of separation methods of pyridine derivate in drawing azoles production, belong to chemical separation technology field.The specific steps of the separation method of pyridine derivate include: the separation of 1) pyridine derivate crude product in a kind of drawing azoles production: after drawing the nitrogen oxidation or nitrification or chlorination or the reaction of etherificate in azoles production stage, proper proportion pure water is added, and the pH of water layer or organic layer in adjustment and control system, organic solvent extraction is added, isolates unreacted pyridine derivate crude product by normal pressure；2) gained pyridine derivate crude product carries out rectification under vacuum, continues moisturizing in distillation process, rectifying obtains the mixed liquor of pyridine derivate and water, the pyridine derivate of layered isolated high-purity.Pyridine derivate is separated and recovered using the technique, easy to operate, technique is easily controllable, and 97% or more the pyridine derivate rate of recovery, product purity is up to 99.5%.
Description
Technical field
The invention belongs to chemical separation technology fields, specifically, being related to pyridine derivate in a kind of production of drawing azoles
Separation method.
Background technique
Drawing azole drug is the proton pump inhibitor for treating digestive tract ulcer.Because of magical effect, Omeprazole
The continuous expansion of medicine series demand, to more and more important not by the recycling of the pyridine derivate of reaction conversion.
It is general draw azole drug be all have chloride containing pyridine ring and the derivative of corresponding benzimidazole object this two
A important intermediate condensation is made.Draw the synthesis process of chloride of the azole drug important intermediate containing pyridine ring all by pyridine
Derivative is made by nitrogen oxidation, nitrification (or chloro), etherificate, rearrangement, this several process of chlorination.First with hydrogen peroxide by pyridine
Derivative is oxidized to the nitrogen oxides of pyridine derivate, and the conversion ratio of pyridine derivate is only 90% left side in this reaction process
The right side still has more raw material to fail to react, fail reaction raw material take subsequent process to, not only influence target product purification,
Product yield is directly affected, the load of environmental treatment is also increased.
The method of common rectifying recycles pyridine derivate from waste liquid at present, but due to the boiling point of pyridine derivate compared with
Height, when rectifying, with traditional rectifying mode rectifying, Nei Wengao, system complicated component, risk is big, and band when conventional distillation
Impurity out, rectifying still bottom residual is more, can only obtain the mixed liquor containing pyridine derivate 50% or so, also needs further progress smart
System purification, complex process, product yield are low.
Summary of the invention
For content mentioned in the present application in addition to specified otherwise, remaining is mass percentage.
In order to solve the problems, such as background technique, the present invention provides a kind of points of pyridine derivate in drawing azoles production
From method, specific technical solution is as follows:
The specific steps of the separation method of pyridine derivate include: in a kind of drawing azoles production
1) separation of pyridine derivate crude product: the anti-of nitrogen oxidation in azoles production stage or nitrification or chlorination or etherificate is being drawn
Ying Hou is added proper proportion pure water, and the pH of water layer or organic layer in adjustment and control system, adds organic solvent, extract unreacted
Pyridine derivate, frequent pressure fractionating obtains pyridine derivate crude product；
2) purification of pyridine derivate: tower bottom of rectifying tower is added in resulting pyridine derivate crude product, carries out rectification under vacuum, essence
Continue moisturizing during evaporating, keeps water content 10-20%, obtain the mixed liquor of pyridine derivate and water, stratification obtains height
Purity pyridine derivate.
Further, unreacted pyridine is isolated in step 1) from target material after nitrogen oxidation or nitrification or chlorination to spread out
The step of biological crude product includes:
1) after nitrogen oxidation or nitrification or chlorination, the pure water of 3-3.2 times of volume is added in system, adjusts pH 2-
5, the organic solvent one of 2-10 times of volume is added, is extracted, extraction terminates separation organic layer and water layer, and organic layer continues next
Step draws azoles production reaction, and water layer is stand-by；
2) water layer pH 9-14 is adjusted, the organic solvent two of 2-10 times of volume is added, is extracted, gained organic layer passes through
Normal pressure fractionation recycling organic solvent, obtains pyridine derivate crude product.
Further, the step of isolating unreacted pyridine derivate from target material after etherificate in step 1) packet
It includes:
1) after etherification reaction, the pure water of 3-3.2 times of volume is added in system, regulation system pH 9-14 is added
The organic solvent two of 2-10 times of volume, is extracted, and organic layer and water layer are separated；
2) the pH 2-5 of organic layer, stratification after stirring are adjusted, pyridine derivate enters water layer；
3) the pH 9-14 for adjusting water layer, is added the organic solvent two of 2-10 times of volume, is extracted, and gained organic layer is logical
Normal pressure fractionation recycling organic solvent is crossed, pyridine derivate crude product is obtained.
Further, rectifying condition described in step 2) are as follows: vacuum degree -0.094MPa arrives 0.096Mpa, kettle temperature 120-130
DEG C, 92-95 DEG C of top temperature, overhead reflux ratio 1:4-6.
Further, the organic solvent one is methylene chloride, chloroform, dichloroethanes, ethyl acetate, butyl acetate
One of.
Further, the organic solvent two is methylene chloride, chloroform, dichloroethanes, ethyl acetate, one in benzene
Kind.
Beneficial effects of the present invention:
The present application will be drawn by the pH of water layer or organic layer in regulation mixture system, addition organic solvent extraction
Unconverted pyridine derivate Coarse liquid separation comes out in azoles production technology, and the pyridine derivate crude liquid and water isolated carry out together
Rectification under vacuum obtains pyridine derivate aqueous solution, obtains the pyridine derivate of 99.5% or more purity using layering, pyridine spreads out
97% or more biological recovery rate.
The production technology is done using organic solvent used in corresponding drawing azoles production stage and is extracted by adjustment and control system pH
Agent is taken, it is simple and convenient to isolate unreacted pyridine derivate crude product from a certain step for drawing azoles to produce, it avoids drawing azoles
The pyridine derivate raw material for failing reaction in synthesis takes subsequent process to, influences purification and the product yield of target product, subtracts
The load of few environmental treatment, while using drawing flux used in azoles synthesis step to make extractant, it avoids drawing other in azoles synthesis
The introducing of impurity causes to draw azoles production later product purification & isolation difficult.
Obtained pyridine derivate crude liquid and water are subjected to rectifying together, the presence of proper proportion moisture improves rectifying
The boiling characteristics of material in system reduce the operation temperature of rectifying, and rectification process mild condition, easily controllable, rectifying obtains pyrrole
The aqueous solution of piperidine derivatives obtains the pyridine derivate of 99.5% or more purity by layering；The pyridine handled by preceding process
Derivative crude product only need to be added water as rectifying adjuvant, cooperate corresponding rectification process parameter, can improve rectification system object
Property, energy conservation and environmental protection, low-cost and pollution-less, separative efficiency height.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
Embodiment 1
Specific step is as follows for separation and recovery pyridine derivate after drawing the nitrogen oxidation reaction in azoles production stage:
1) after drawing the nitrogen oxidation reaction in azoles production stage, the pure water of 3 times of volumes is added in system, adjusting pH is 2,
The chlorinated hydrocarbon organic solvent of 2 times of volumes is added, selects methylene chloride herein, is extracted, extraction terminate separation organic layer and
Water layer, organic layer continue to draw azoles production reaction in next step, and water layer is stand-by；
2) adjusting water layer pH is 9, and the arene organic solvent of 2 times of volumes is added, selects benzene herein, is extracted, institute
Organic layer normal pressure fractionation recycling organic solvent at 80-82 DEG C is obtained, pyridine derivate crude product is obtained；
3) purification of pyridine derivate: tower bottom of rectifying tower is added in resulting pyridine derivate crude product, carries out rectification under vacuum, very
Reciprocal of duty cycle -0.094MPa, 120 DEG C of kettle temperature, top is 92 DEG C, overhead reflux ratio 1:4 warm, continues moisturizing in distillation process, keeps water content
10%, rectifying obtains the mixed liquor of pyridine derivate and water, and stratification obtains high-purity pyridine derivate.
Experimental result:
The separating-purifying effect of pyridine derivate after the reaction of 1 nitrogen oxidation of table
Above data shows to draw in azoles production technology, unreacted pyridine derivate quilt by regulation pH and solvent extraction
It separates, while being separated by rectification and purification well, obtain the pyridine derivate of purity 99.5-99.75%, it is pyridine derived
The object rate of recovery is up to 98% or more.
Embodiment 2
Specific step is as follows for separation and recovery pyridine derivate after drawing the nitration reaction in azoles production stage:
1) after drawing the nitration reaction in azoles production stage, the pure water of 3.1 times of volumes is added in system, adjusting pH is 3,
The chlorinated hydrocarbon organic solvent of 5 times of volumes is added, selects dichloroethanes herein, is extracted, extraction terminate separation organic layer and
Water layer, organic layer continue to draw azoles production reaction in next step, and water layer is stand-by；
2) adjusting water layer pH is 12, and the chlorinated hydrocarbon organic solvent of 5 times of volumes is added, and selects chloroform to do herein organic
Solvent is extracted, and gained organic layer normal pressure fractionation recycling organic solvent at 61-63 DEG C obtains pyridine derivate crude product；
3) purification of pyridine derivate: tower bottom of rectifying tower is added in resulting pyridine derivate crude product, carries out rectification under vacuum, very
Reciprocal of duty cycle -0.095MPa, 125 DEG C of kettle temperature, top is 93 DEG C, overhead reflux ratio 1:5 warm, continues moisturizing in distillation process, keeps water content
15%, rectifying obtains the mixed liquor of pyridine derivate and water, and stratification obtains high-purity pyridine derivate.
Experimental result
The separating-purifying effect of pyridine derivate after 2 nitration reaction of table
Above data shows to draw in azoles production technology, unreacted pyridine derivate quilt by regulation pH and solvent extraction
It separates, while being separated by rectification and purification well, obtain the pyridine derivate that purity is 99.5%-99.7%, pyridine
The derivative rate of recovery is up to 97.5% or more.
Embodiment 3
Specific step is as follows for separation and recovery pyridine derivate after drawing the chlorination reaction in azoles production stage:
1) after drawing the chlorination reaction in azoles production stage, the pure water of 3.2 times of volumes is added in system, adjusting pH is 5,
The based organic solvent of 10 times of volumes is added, selects ethyl acetate herein, is extracted, extraction terminates separation organic layer and water
Layer, organic layer continue to draw azoles production reaction in next step, and water layer is stand-by；
2) adjusting water layer pH is 14, and the based organic solvent of 10 times of volumes is added, selects ethyl acetate herein, is extracted
It takes, gained organic layer normal pressure fractionation recycling organic solvent at 77-79 DEG C obtains pyridine derivate crude product；
3) purification of pyridine derivate: tower bottom of rectifying tower is added in resulting pyridine derivate crude product, carries out rectification under vacuum, very
Reciprocal of duty cycle -0.096MPa, 130 DEG C of kettle temperature, top is 95 DEG C, overhead reflux ratio 1:6 warm, continues moisturizing in distillation process, keeps water content
20%, rectifying obtains the mixed liquor of pyridine derivate and water, and stratification obtains high-purity pyridine derivate.
Experimental result:
The separating-purifying effect of pyridine derivate after 3 chlorination reaction of table
Above data shows to draw in azoles production technology, unreacted pyridine derivate quilt by regulation pH and solvent extraction
It separates, while being separated by rectification and purification well, obtain the pyridine derivate that purity is 99.5%-99.7%, pyridine
The derivative rate of recovery is up to 97.2% or more.
Embodiment 4
Specific step is as follows for separation and recovery pyridine derivate after drawing the etherification reaction in azoles production stage:
1) after drawing the etherification reaction in azoles production stage, the pure water of 3.1 times of volumes, regulation system pH are added in system
12, the chlorinated hydrocarbon organic solvent of 7 times of volumes is added, selects methylene chloride to do organic solvent herein, is extracted, separates organic
Layer and water layer；
2) pH 4 of organic layer, stratification after stirring are adjusted, pyridine derivate enters water layer；
3) pH 11 for adjusting water layer, is added the arene organic solvent of 7 times of volumes, selects benzene herein, extracted,
Gained organic layer carries out normal pressure fractionation recycling organic solvent at 79-81 DEG C, obtains pyridine derivate crude product.
4) purification of pyridine derivate: tower bottom of rectifying tower is added in resulting pyridine derivate crude product, carries out rectification under vacuum, very
Reciprocal of duty cycle -0.095MPa, 127 DEG C of kettle temperature, top is 93 DEG C, overhead reflux ratio 1:5 warm, continues moisturizing in distillation process, keeps water content
16%, rectifying obtains the mixed liquor of pyridine derivate and water, and stratification obtains high-purity pyridine derivate.
Experimental result
The separating-purifying effect of pyridine derivate after 4 etherification reaction of table
Above data shows to draw in azoles production technology, unreacted pyridine derivate quilt by regulation pH and solvent extraction
It separates, while being separated by rectification and purification well, obtain the pyridine derivate that purity is 99.5%-99.7%, pyridine
The derivative rate of recovery is up to 97% or more.
Analyze experimental design:
1. 3,5- trimethylpyridines are that raw material produces in the production stage of Omeprazole in nitrogen oxidation or nitrification or chlorine with 2
2,3,5- trimethylpyridine of pyridine derivate is recycled after changing reaction:
1) after nitrogen oxidation or nitrification or chlorination, the pure water of 3 times of volumes is added in system, adjusts pH3, is added 8
The organic solvent one of times volume, selects chloroform herein, is extracted, and extraction terminates separation organic layer and water layer, organic layer
Continue the production reaction of next step Omeprazole, water layer is stand-by；
2) water layer pH 11 is adjusted, the organic solvent two of 8 times of volumes is added, selects chloroform herein, is extracted, institute
It obtains organic layer normal pressure at 60-62 DEG C to be fractionated, recycles organic solvent dichloromethane, obtain pyridine derivate crude product；
3) purification of pyridine derivate: tower bottom of rectifying tower is added in resulting pyridine derivate crude product, carries out rectification under vacuum, very
Reciprocal of duty cycle -0.094MPa, 125 DEG C of kettle temperature, top is 93 DEG C, overhead reflux ratio 1:3 warm, continues moisturizing in distillation process, keeps water content
15%, the mixed liquor of pyridine derivate and water is obtained, stratification obtains high-purity pyridine derivate.
2. 3,5- trimethylpyridines recycle pyrrole in the production stage for raw material production Omeprazole after etherification reaction with 2
Piperidine derivatives:
1) after etherification reaction, the pure water of 3 times of volumes is added in system, 8 times of bodies are added in regulation system pH 11
Long-pending organic solvent two, selects chloroform herein, is extracted, and separates organic layer and water layer；
2) pH 3 of organic layer, stratification after stirring are adjusted, pyridine derivate enters water layer；
3) pH 11 for adjusting water layer, is added the organic solvent two of 8 times of volumes, selects chloroform herein, extracted,
Gained organic layer is fractionated recycling organic solvent by normal pressure, obtains pyridine derivate crude product；
4) purification of pyridine derivate: tower bottom of rectifying tower is added in resulting pyridine derivate crude product, carries out rectification under vacuum, very
Reciprocal of duty cycle -0.094MPa, 125 DEG C of kettle temperature, top is 93 DEG C, overhead reflux ratio 1:3 warm, continues moisturizing in distillation process, keeps water content
15%, the mixed liquor of pyridine derivate and water is obtained, stratification obtains high-purity pyridine derivate.
3. existing recovery scheme: being In after raw material produces Omeprazole W-response with 2,3,5- trimethylpyridines
Contain and sequentially add acetone in the production waste liquid of 2,3,5- trimethylpyridines, normal heptane, binary acid, toluene, pass sequentially through into salt,
Crystallization, washing, parsing, extraction and precipitation obtain pyridine derivate fine work.
Experimental result:
Illustrate:
" yield based on the step " is on the basis of the pyridine derivate contained in system after the reaction step in table
Calculated yield.
Above data, it can be seen that using the recycling method of purification of the present application, final products purity reaches 99.5%
More than, the rate of recovery based on the step reaches 97% or more, and no matter compared with the prior art product purity or product yield all have
Have greatly improved, and compared to the prior art, the present application separate process steps are simple, and it is convenient to operate.
Finally, it is stated that preferred embodiment above is only used to illustrate the technical scheme of the present invention and not to limit it, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (3)
1. a kind of separation method for drawing pyridine derivate in azoles production, which is characterized in that pyridine in a kind of drawing azoles production
The specific steps of the separation method of derivative include:
1) separation of pyridine derivate crude product: nitrogen oxidation or nitrification or chlorination or the reaction of etherificate in drawing azoles production stage
Afterwards, unreacted pyridine derivate crude product is isolated from target material；
2) purification of pyridine derivate: tower bottom of rectifying tower is added in resulting pyridine derivate crude product, carries out rectification under vacuum, rectifying
Continue moisturizing in journey, keep water content 10-20%, tower top rectifying obtains the mixed liquor of pyridine derivate and water, and stratification obtains
To high-purity pyridine derivate；
Isolate unreacted pyridine derivate crude product in step 1) from target material after nitrogen oxidation or nitrification or chlorination
Step includes:
(1) after nitrogen oxidation or nitrification or chlorination, the pure water of 3-3.2 times of volume is added in system, adjusts pH 2-5, adds
The organic solvent one for entering 2-10 times of volume, is extracted, and extraction terminates separation organic layer and water layer, and organic layer continues to draw in next step
Azoles production reaction, water layer are stand-by；
(2) water layer pH 9-14 is adjusted, the organic solvent two of 2-10 times of volume is added, is extracted, gained organic layer passes through normal pressure
Fractionation recycling organic solvent, while obtaining pyridine derivate crude product；
The step of isolating unreacted pyridine derivate from target material after etherificate in step 1) include:
(1) after etherification reaction, the pure water of 3-3.2 times of volume is added in system, 2-10 is added in regulation system pH9-14
The organic solvent two of times volume, is extracted, and organic layer and water layer are separated；
(2) the pH 2-5 of organic layer, stratification after stirring are adjusted, pyridine derivate enters water layer；
(3) the pH 9-14 for adjusting water layer, is added the organic solvent two of 2-10 times of volume, is extracted, and gained organic layer passes through normal
Pressure fractionating recycles organic solvent, obtains pyridine derivate crude product；
The drawing azoles production stage is the production stage for producing Omeprazole for raw material with 2,3,5- trimethylpyridines；Described
Pyridine derivate is 2,3,5- trimethylpyridines；
Rectifying condition described in step 2) are as follows: vacuum degree -0.094MPa arrives -0.096Mpa, 120-130 DEG C of kettle temperature, pushes up temperature 92-
95 DEG C, overhead reflux ratio 1:3.
2. a kind of separation method for drawing pyridine derivate in azoles production according to claim 1, it is characterised in that: described
Organic solvent one is one of methylene chloride, chloroform, dichloroethanes, ethyl acetate, butyl acetate.
3. a kind of separation method for drawing pyridine derivate in azoles production according to claim 1, it is characterised in that: described
Organic solvent two is one of methylene chloride, chloroform, dichloroethanes, ethyl acetate, benzene.
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