CN104557702B - A kind of method of purification of high-sulfur isoquinolin - Google Patents
A kind of method of purification of high-sulfur isoquinolin Download PDFInfo
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- CN104557702B CN104557702B CN201510012200.3A CN201510012200A CN104557702B CN 104557702 B CN104557702 B CN 104557702B CN 201510012200 A CN201510012200 A CN 201510012200A CN 104557702 B CN104557702 B CN 104557702B
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- isoquinolin
- sulfur
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- toluene
- raffinate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
- C07D217/02—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines
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Abstract
The invention discloses a kind of methods of purification of high-sulfur isoquinolin, include the following steps：Organic solvent and chlorination hydrogen source are added in isoquinolin raffinate, isoquinolin and hydrogen chloride is made to generate thermal dehydration after isoquinoline hydrochloride, after treating moisture evaporation, isoquinoline hydrochloride is collected, the isoquinoline hydrochloride with lye is decomposed, obtains isoquinolin；In the isoquinolin raffinate, the mass percentage of isoquinolin is 50%~100%；The ratio between molal quantity of isoquinolin is (0.1~1.0) in the molal quantity of the hydrogen chloride and isoquinolin raffinate：1；The organic solvent is toluene, benzene or naphtha；The chlorination hydrogen source is hydrochloric acid or hydrogen chloride gas.The method of purification of high-sulfur isoquinolin provided by the invention can be such that isoquinolin raffinate mass percentage improves to more than 95%, be repeated once this process, its mass percentage can be made to improve to more than 99%.
Description
Technical field
The present invention relates to chemical products to purify field, more particularly, to a kind of isoquinolin from the sulfide impurities containing high-content
The method that high-purity isoquinoline is extracted in raw material.
Background technology
Isoquinolin is a kind of important chemical intermediate, is the starting material of many high value chemical products, such as treats blood
The praziquantel of fluke disease is also widely used in the polyimides engineering material in the fields such as nanometer, liquid crystal, seperation film, laser etc..
Its dosage is very big, and after 2005, present increases trend always year by year.Isoquinolin although there are many kinds of synthetic method,
It is that so far, none of these methods is economical, so the separation of coal tar wash oil is mainly derived from present, however it is being washed
Content in oil is very little again, it may be said that resource is very in short supply, and the separating-purifying isoquinolin from washing oil, due to impurity kind
Class is more and high, so separating difficulty is also very large.In view of Yi Shang isoquinolin demand and the contradiction in source, improve its recycling
Rate and purity are very important.Chinese patent literature CN101747269 discloses a kind of method of purification of high-sulfur isoquinolin, this
Method extracts high-purity isoquinoline, and effect is very good, and purity is high, and impurity is low.However the method purification high-purity isoquinoline, recycling
Rate is about 50%, and the impurity content obtained in raffinate is very high, especially some sulfur-containing compounds (two membered heterocyclic compound of nitrogen sulphur,
The predominantly various isomers of pyridine bithiophene, their boiling point are very close with isoquinolin all at 240~250 DEG C or so),
About 10~20%, isoquinolin content is 50~80%, such a high-sulfur isoquinolin, then removes raising isoquinolin with rectification method
Content, especially sulfur-containing impurities to reduction, poor effect.
The content of the invention
It is an object of the invention to provide a kind of method of purification of high-sulfur isoquinolin, in the presence of solving the prior art
The above problem.
A kind of method of purification of high-sulfur isoquinolin, includes the following steps：
Organic solvent and chlorination hydrogen source are added in isoquinolin raffinate, isoquinolin and hydrogen chloride is made to generate isoquinoline hydrochloride
After be heated to reflux, after treating moisture evaporation, collect isoquinoline hydrochloride, the isoquinoline hydrochloride with lye is decomposed, is obtained
To isoquinolin.
Preferably, in the isoquinolin raffinate, the mass percentage of isoquinolin is 50%~100%.
Preferably, the ratio between molal quantity of isoquinolin is (0.1 in the molal quantity of the hydrogen chloride and isoquinolin raffinate
~1.0)：1.
Preferably, the organic solvent is toluene, benzene or naphtha.
Preferably, the chlorination hydrogen source is hydrochloric acid or hydrogen chloride gas.
Preferably, further include and the isoquinoline hydrochloride is reduced into isoquinolin with lye, then add salt
Acid and toluene, second of thermal dehydration is into salt.
Preferably, further include and direct plunge into the isoquinoline hydrochloride in reaction kettle, add in solid hydroxide
Sodium, the ratio between the molal quantity of the sodium hydroxide and the molal quantity of isoquinoline hydrochloride are (0.01~0.2)：1, add Shui Hejia
Benzene, then second of thermal dehydration is into salt.
Preferably, mixing component is equipped in the reaction kettle, a kettle mouth of the reaction kettle is equipped with one
Steam pipeline, the steam pipeline are connected by two 90 degree of adapters with heat exchanger, and mouth is equipped with glass oil under the heat exchanger
Separator, the return duct of the oil water separator access another kettle of the reaction kettle by one with U-shaped curved pipeline
Mouthful.
The advantage of the invention is that：Using the method for the present invention, isoquinolin raffinate content can be made to improve to more than 95%, it is heavy
A multiple deuterzooid process, can be such that its content improves to more than 99%.
Specific embodiment
With reference to embodiment, the invention will be further described, but protection scope of the present invention is not only limited to implement
Example.
The method of purification of high-sulfur isoquinolin provided by the invention, it is preferred to use the reactor of high dehydration efficiency, disengagement area
Greatly, gas phase pipe caliber is big, and heat exchanger (condenser) area is big and mixing effect is good.
The principle of the present invention is：Isoquinolin raffinate is all alkaline matter, all with hydrogen chloride hydrochloric acid salt, for the ease of rear
Sequence is explained, the ingredient in this isoquinolin raffinate is collectively referred to as azacyclo-.By hydrochloric acid add in isoquinolin raffinate mixture in, no matter salt
Acid be it is a small amount of or excessive, various azacyclo- ingredients in mixture therewith into salt be not selectively, become one it is homogeneous
Azacyclo- hydrochloric acid saline solution.But when the water in hydrochloric acid is clean with toluene azeotropic distillation removal, hydrochloride will be from
It is separated out in toluene, the purity of the hydrochloride separated out is either with or without changing, this will be divided into two kinds of situations, if the amount of hydrochloric acid is
It is excessive, then to be not selectively, if hydrochloric acid is a small amount of, then the hydrochloride separated out be it is selective, i.e.,
Based on a certain azacyclo-.Reason is very simple, and hydrochloride is with chlorion and the presence of heterocyclic nitrogen ion mode in water
, and heterocyclic nitrogen is also reversible with hydrionic combination generation heterocyclic nitrogen cation, several azacyclo-s are given birth to hydrogen ion reaction
Ability into heterocyclic nitrogen cation is the same, without selective, thus in aqueous solution, no matter hydrochloric acid is a small amount of or mistake
Amount, hydrochloride be also not selectively, certainly also without refining effect, but when water is removed, azacyclo- cation with
Chlorion will combine generation solid hydrochloride, and as moisture is fewer and fewer, hydrochloride will slowly be precipitated because of supersaturation,
This process is the process of a recrystallization again, once a certain azacyclo- hydrochloric acid salt crystal generation, will become crystal seed, and is induced
What is be precipitated in solution is all a kind of this azacyclo- hydrochloride, when the hydrogen chloride in solution is fewer than the molal quantity of all azacyclo-s,
Finally some azacyclo- cannot be stayed in a solvent, into salting out so as to reach separated purpose.It is which kind of azepine on earth
Ring can be precipitated, that just sees in raw material which kind of substance accounts for main component, and in the present invention, isoquinolin accounts for mainly, so as into salt
What is be precipitated is exactly isoquinolin.
Therefore, using above-mentioned principle, in benzene, first benzene kind solvent, by isoquinolin raffinate and appropriate hydrochloric acid into salt (it is required that：
Hydrogen chloride molal quantity in hydrochloric acid is less than molal quantity total in isoquinolin raffinate), the moisture in hydrochloric acid is then sloughed again, makes salt
Hydrochlorate crystallizes out, and the hydrochloride so obtained is after centrifugation, and filter cake caustic digestion, dissociate isoquinolin, isoquinoline at this time
Quinoline quality percent purity reaches more than 95%.
During again by the mass percentage of isoquinolin from 95% raising to 99%, it can be selected there are two types of mode using the method
It selects, the first, then the isoquinoline hydrochloride of quality percent purity 95% is added its decomposition-reduction into isoquinolin with alkali again
Enter hydrochloric acid, toluene, thermal dehydration repeats preceding step into salt.Second, after obtaining the isoquinoline hydrochloride of 95% purity, no
It by its decomposition-reduction into isoquinolin, and is direct plungeed into kettle, adds in a small amount of solid sodium hydroxide, the amount of sodium hydroxide is different
The 1~20% of the molal quantity of quinoline hydrochloride adds suitable water and toluene, is then dehydrated into salt, finally can also obtain
99% with the isoquinoline hydrochloride for percent purity of improving quality.
Embodiment 1：
The first step：In the 2L reaction bulbs with oil water separator, 70% isoquinolin raw material of mass percentage is added in
(100g, 0.774M) (contain 15% sulfide impurities), add in 300mL toluene, the hydrochloric acid of mass percentage 30% (65.8g,
0.542M) g is finished, and temperature rises to 70 DEG C or so, is immediately heated to reflux, and the steam of toluene and water is condensed into water knockout drum,
Be layered at once, upper toluene is back in bottle, and lower water is released mutually by valve, about 1 it is small when after, moisture is most, is cooled to room
Temperature, filtering, filter cake are washed with toluene, drained, and mother liquor isoquinolin mass percentage is 25%, and sulfur-containing impurities quality percentage always contains
It measures as 50%.Filter cake is decomposed with 30% liquid caustic soda of mass percentage, purity 95.5%, and biodiversity percentage composition is 7.5%,
Common 70g, yield 92%.
Second step：The isoquinolin (isoquinolin net content 0.480M) of above-mentioned 95.5% content is added in bottle again, is added in
Toluene (300mL), 30% hydrochloric acid (56.6g, 0.465M), finishes, and temperature rises to 70 DEG C or so, is immediately heated to reflux, first
The steam of benzene and water is condensed into water knockout drum, is layered at once, and upper toluene is back in bottle, and lower water mutually by valve, is released,
About 1 it is small when after, moisture is most, is cooled to room temperature, and filtering, filter cake washs with toluene, drained.Filter cake 30% liquid of mass percentage
Caustic digestion, purity 99.4%, biodiversity percentage composition are 7.8%, common 64g, yield 95%.
Two step total recoverys reach 87.4%.
Embodiment 2：
The first step in repeating embodiment 1 obtains the hydrochloride that 90g purity is 95.5%, is directly added into bottle,
Addition solid sodium hydroxide (1.9g, 0.048M), water (30g), toluene (300mL), stirring and dissolving are heated to reflux, first
The steam of benzene and water is condensed into water knockout drum, is layered at once, and upper toluene is back in bottle, and lower water mutually by valve, is released,
About 1 it is small when after, moisture is most, is cooled to room temperature, and filtering, filter cake washs with toluene, drained.Filter cake 30% liquid of mass percentage
Caustic digestion, purity 99.4%, biodiversity percentage composition are 7.8%, common 65g, yield 96%.
Embodiment 3：
Equipment designs and installation：The design of dehydrating kettle.In a kettle mouth of the 5000L reaction kettles with stirring, installation one
Root 150-200mm's walks to evaporate the iron pipe of uprising gas, carries out Insulation, passes through two 90 degree of adapters, access one
The heat exchanger of vertical 15-25 squares of root, mouth accesses the glass oil water separator of a 50-100L, oil water separator under heat exchanger
Reflux official pass through a kettle mouth that reaction kettle is accessed with U-shaped curved pipeline.Here it is the very strong oil of a water separation capability
Water separates reaction kettle.
It feeds intake：In above-mentioned 5000L reaction kettles, add in 76% isoquinolin raw material of mass percentage and (contain 13% sulphur
Compound impurity) (2 tons, 15.48kmol), toluene (600 kilograms) is added in, 30% hydrochloric acid (1.4 tons, 11.77kmol), temperature is certainly
70 degree so are raised to, is heated to flowing back, the steam of toluene and water is condensed into water knockout drum, is layered at once, and upper toluene is back to bottle
In, lower water is released mutually by valve, about 1 it is small when after, moisture is most, is cooled to room temperature, and centrifugation, filter cake is washed with toluene.It obtains
2.4 tons of hydrochlorides.
1.2 tons of hydrochlorides are taken, are decomposed with 30% liquid caustic soda of mass percentage, purity 96.1%, biodiversity percentage contains
It measures as 7.1%, totally 0.7 ton, yield 93%.Again put into dehydrating kettle, addition toluene (1 ton), 30% hydrochloric acid (625 kilograms,
5.15kmol), temperature is raised to 70 degree naturally, is heated to flowing back, and the steam of toluene and water is condensed into water knockout drum, is layered at once,
Upper toluene is back in bottle, and lower water is released mutually by valve, about 1 it is small when after, moisture is most, is cooled to room temperature, and centrifuges, filter
Cake is washed with toluene.Obtain 900 tons of hydrochlorides.After decomposition, 680 kilograms of purity are obtained as 99.3% isoquinolin, aqueous 7%,
Yield 95%.
Other 1.2 tons of hydrochlorides are taken, are directly rejoined in dehydrating kettle, add in toluene (1 ton), piece alkali (29 kilograms), water
(500 kilograms), are heated to flowing back, and the steam of toluene and water is condensed into water knockout drum, is layered at once, and upper toluene is back to bottle
In, lower water is released mutually by valve, about 1 it is small when after, moisture is most, is cooled to room temperature, and centrifugation, filter cake is washed with toluene.It obtains
Filter cake with 30% liquid caustic soda of mass percentage decompose after, obtain 700 kilograms of purity be 99.2% isoquinolin, aqueous 7%.It receives
Rate：96%.
Embodiment 4：
In the 2L reaction bulbs with reflux condensing tube, 70% isoquinolin raw material of mass percentage is added in (containing 15%
Sulfide impurities) (100g), toluene (300mL) is added in, in the case of stirring, is slowly passed through dry hydrogen chloride (21g), is led to
Finish, be cooled to room temperature, filter, filter cake is washed with toluene, drained, and mother liquor isoquinolin content is 30%, sulfur-containing impurities quality percentage
Total content is 45%.Filter cake is decomposed with 30% liquid caustic soda of mass percentage, purity 93.5%, and biodiversity percentage composition is
7.5%, common 70g, yield 90%.
The isoquinolin of above-mentioned mass percentage 90% is added in bottle again, adds in toluene (300mL), the situation of stirring
Under, dry hydrogen chloride (17) g is passed through, leads to and finishes, be cooled to room temperature, is filtered, filter cake is washed with toluene, and filter cake is decomposed with liquid caustic soda,
Obtain 70g, aqueous 7.1%, purity is 98.5% isoquinolin, yield 95%.
Embodiment 5：
The above-mentioned isoquinolin finally obtained, also containing a small amount of toluene and moisture, then the rectifying by 10 pieces of numbers of plates or so
Tower rectifying removes, and finally steams qualified finished product isoquinolin.
Finally it should be noted that：Above example is only to illustrate the present invention and not limits technology described in the invention
Scheme；Therefore, although this specification with reference to above-mentioned each embodiment to present invention has been detailed description, this
Field it is to be appreciated by one skilled in the art that still can modify to the present invention or equivalent substitution；And all do not depart from this
The technical solution of the spirit and scope of invention and its improvement should all be covered in scope of the presently claimed invention.
Claims (6)
1. a kind of method of purification of high-sulfur isoquinolin, which is characterized in that include the following steps：
Organic solvent and chlorination hydrogen source are added in isoquinolin raffinate, is added after making isoquinolin and hydrogen chloride generation isoquinoline hydrochloride
Heat dehydration after treating moisture evaporation, collects isoquinoline hydrochloride, the isoquinoline hydrochloride with lye is decomposed, is obtained different
Quinoline；In the isoquinolin raffinate, the mass percentage of isoquinolin is 50%~100%；The molal quantity of the hydrogen chloride with
The ratio between molal quantity of isoquinolin is (0.1~1.0) in isoquinolin raffinate：1.
2. the method for purification of high-sulfur isoquinolin as described in claim 1, which is characterized in that the organic solvent is toluene, benzene
Or naphtha.
3. the method for purification of high-sulfur isoquinolin as described in claim 1, which is characterized in that the chlorination hydrogen source is hydrochloric acid or chlorine
Change hydrogen.
4. the method for purification of high-sulfur isoquinolin as described in claim 1, which is characterized in that further include the isoquinolin hydrochloric acid
Salt is reduced into isoquinolin with lye, then adds hydrochloric acid and toluene, and second of thermal dehydration is into salt.
5. the method for purification of high-sulfur isoquinolin as described in claim 1, which is characterized in that further include the isoquinolin hydrochloric acid
Salt is direct plungeed into reaction kettle, adds in solid sodium hydroxide, the molal quantity of the sodium hydroxide and mole of isoquinoline hydrochloride
The ratio between number is (0.01~0.2)：1, water and toluene are added, then second of thermal dehydration is into salt.
6. the method for purification of high-sulfur isoquinolin as claimed in claim 5, which is characterized in that mixing part is equipped in the reaction kettle
Part, a kettle mouth of the reaction kettle are equipped with a steam pipeline, and the steam pipeline is by two 90 degree of adapters and changes
Hot device is connected, and mouth is equipped with glass oil water separator under the heat exchanger, and the return duct of the oil water separator is by one with U-shaped
Curved pipeline accesses another kettle mouth of the reaction kettle.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2510877A (en) * | 1950-06-06 | Resolution of nitrogen base | ||
| EP0185792A1 (en) * | 1984-12-24 | 1986-07-02 | Nippon Steel Chemical Co., Ltd. | Process for production of decahydroisoquinoline |
| CN101747269A (en) * | 2009-12-23 | 2010-06-23 | 上海新明高新科技发展有限公司 | Purification method of isoquinoline |
| CN103641780A (en) * | 2013-12-05 | 2014-03-19 | 南京理工大学 | Method for purifying isoquinoline from crude product of coal tar |
-
2015
- 2015-01-09 CN CN201510012200.3A patent/CN104557702B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2510877A (en) * | 1950-06-06 | Resolution of nitrogen base | ||
| EP0185792A1 (en) * | 1984-12-24 | 1986-07-02 | Nippon Steel Chemical Co., Ltd. | Process for production of decahydroisoquinoline |
| CN101747269A (en) * | 2009-12-23 | 2010-06-23 | 上海新明高新科技发展有限公司 | Purification method of isoquinoline |
| CN103641780A (en) * | 2013-12-05 | 2014-03-19 | 南京理工大学 | Method for purifying isoquinoline from crude product of coal tar |
Non-Patent Citations (1)
| Title |
|---|
| 从喹啉残液中提取工业异喹啉;魏庆开;《染料与化工》;20011130;全文 * |
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