CN106946844A - A kind of synthetic method of 1,4 butane sultones - Google Patents
A kind of synthetic method of 1,4 butane sultones Download PDFInfo
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- CN106946844A CN106946844A CN201710182914.8A CN201710182914A CN106946844A CN 106946844 A CN106946844 A CN 106946844A CN 201710182914 A CN201710182914 A CN 201710182914A CN 106946844 A CN106946844 A CN 106946844A
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- isosorbide
- nitrae
- synthetic method
- butenol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
- C07D327/06—Six-membered rings
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
A kind of synthetic method of Isosorbide-5-Nitrae butane sultones, belongs to medicine intermediate synthesis technical field.It is characterised in that it includes following steps：Bisulfites is added to the water stirring and dissolving for solution in advance, the PH for being subsequently added sodium sulfite adjustment system is 7.5 ~ 9；It is warming up to after 45 DEG C ~ 55 DEG C and butenol was at the uniform velocity added dropwise in 10 ~ 20 minutes, control the temperature of addition reaction at 60 DEG C ~ 70 DEG C, after completion of dropwise addition, continues to stop reacting and being cooled to room temperature after reacting 20 ~ 30 minutes；Described butenol and the mol ratio of bisulfites are 1：1.05~1.3；Acid is added dropwise in the backward system that cools acid to presenting, stirs 50 ~ 70 minutes, add alcohol crystallization, filter to obtain settled solution；Settled solution rectifying is obtained into Isosorbide-5-Nitrae butane sultone.Reactions steps of the present invention are few, high income, pair are turned one's coat point recoverable and environmental pressure are small.
Description
Technical field
A kind of synthetic method of Isosorbide-5-Nitrae-butane sultones, belongs to medicine intermediate synthesis technical field.
Background technology
Isosorbide-5-Nitrae-butane sultones is a kind of important chemical and medicine industry intermediate, is lived available for synthesis photosensitive material, surface
Property agent, sulfonating agent and dye sensitiser etc..In addition the electrokinetic cell additive done with Isosorbide-5-Nitrae-butane sultones, can reduce electricity
Insertion of the pond solvent to electrode, extends electrode life, improves electricity cycle efficieny, adds circulating battery number of times, improves battery
Use time.
1,4- butane sultones is mainly synthesized by following methods in the prior art.
1）Be made Isosorbide-5-Nitrae-butane sultones through four-step reaction using tetrahydrofuran and excess acetyl chloride, the synthesis step compared with
Many, total recovery 45%, side reaction and by-product are more, and industrial value is little；
C4H8O + CH3COCl → CH3COOCH2CH2CH2CH2Cl
CH3COO(CH2)3CH2Cl+ Na2SO3 +H2O →HO(CH2)4SO3Na+CH3COONa NaCl+SO2
HO(CH2)4SO3Na + H2SO4 →HO(CH2)4SO3H + Na2SO4 .
HO(CH2)4SO3H →C4H8O3S + H2O
2）Chlorobutane and thionyl chloride is used to prepare product through three-step reaction for raw material, but a large amount of generations are currently without the first of value
Sulphonic acid ester in base, separating-purifying is more difficult, and yield is 30% or so；
3）Isosorbide-5-Nitrae-butane sultones is prepared in ether and dichloromethane system with 1-n- butylene, the reaction can produce a large amount of pairs
Production, rectifying separation is difficult, and uses dangerous solvents ether, and final products yield is relatively low；
4）Product is prepared through 4 step reactions using dioxane and sulfur trioxide as raw material, the reaction not only produces solid waste barium sulfate, and
Also need to carry out hydrogenation addition reaction in autoclave, reaction time is long, equipment requirement is high.
In above method reaction time length, equipment requirement is high, by-product is more, environmental pressure is big, industrialization is difficult.
The content of the invention
The technical problem to be solved in the present invention is：Overcoming the deficiencies in the prior art, there is provided a kind of reaction time is short, raw material is easy
Obtain, reaction is gentle, the synthetic method of the 1,4- butane sultones of high income.
The technical solution adopted for the present invention to solve the technical problems is：The synthetic method of the Isosorbide-5-Nitrae-butane sultones,
It is characterised in that it includes following steps：
1）Bisulfites is added to the water stirring and dissolving for solution in advance, the PH for being subsequently added sodium sulfite adjustment system is
7.5~9；
2）Be warming up to after 45 DEG C ~ 55 DEG C and butenol be at the uniform velocity added dropwise in 10 ~ 20 minutes, control addition reaction temperature 60 DEG C ~
70 DEG C, after completion of dropwise addition, continue to stop reacting and being cooled to room temperature after reacting 20 ~ 30 minutes；Described butenol and sulfurous acid
The mol ratio of hydrogen salt is 1：1.05~1.3；
3）Acid is added dropwise in the backward system that cools acid to presenting, stirs 50 ~ 70 minutes, add alcohol crystallization, filter to obtain settled solution；
4）Settled solution rectifying is obtained into Isosorbide-5-Nitrae-butane sultone.
The invention discloses a kind of synthetic method of Isosorbide-5-Nitrae-butane sultones, the inventors found that in specific alkali
Property environment under can accelerate butenol and bisulfites addition reaction and reaction it is gentle, the sodium sulfite added can be seen
As base catalyst, the alkaline environment of formation can greatly promote production efficiency and conversion ratio, preferably ensure product
Purity.Because bisulfites is acid material in traditional cognitive, it is considered that can not exist and be added in alkaline environment
Into reaction, so it is acidity to generally require special regulation system, to ensure the stabilization of sulphite.And the present inventor beats
It is broken conventional, solution is adjusted to weak base row environment using sodium sulfite, it is gentleer due to reacting, it is possible in higher temperature
Degree is lower to carry out addition reaction, so as to obtain bigger conversion ratio under higher production efficiency.This method avoids previous methods
Middle length reaction time and raw material obtain difficult shortcoming, and react gentle, high income, with good industrial value and benefit.
It is preferred that, step 2）The butenol and step 3 of dropwise addition）The molar ratio of the alcohol of middle addition is 1：1.0~5.0.Add
Alcohol separates out the sodium salt to be formed.
It is preferred that, described alcohol is methanol, ethanol, ethylene glycol, propyl alcohol or triglyceride.Present invention reaction is gentle, gained
Product is disposable, and selected alcohol is easy to get.
It is preferred that, the PH for adding system after sodium sulfite adjustment is 8.5.When the PH of system is adjusted into 8.5, reaction
System is most stable, and reaction efficiency highest, yield are maximum.
It is preferred that, described butenol and the mol ratio of bisulfites are 1：1.1~1.2.Under present invention process, butylene
The conversion ratio of alcohol is larger, and conversion ratio is improved without more excessive addition bisulfites.In conversion ratio originally higher feelings
The effect of more excessive addition sulphite is little under condition.
It is preferred that, described bisulfites is sodium hydrogensulfite or potassium bisulfite.
It is preferred that, step 3）The acid being added dropwise after cooling is hydrochloric acid or sulfuric acid.
It is preferred that, step 2）The temperature of system is 50 DEG C when butenol is at the uniform velocity added dropwise in middle beginning.Start that butenol is added dropwise
Temperature can be such that addition reaction starts with a more suitably reaction rate, and be capable of minimum reduces shadow of the alkaline environment to ionization
Ring, it is ensured that addition reaction is carried out.
Compared with prior art, a kind of synthetic method of Isosorbide-5-Nitrae-butane sultones of the invention is had the advantage that
It is：Butenol and bisulfites of the present invention carry out an addition under alkaline environment and prepare intermediate, and can be original anti-
Answer and be acidified in kettle, reduce number of devices, reduce production cost；And moisture obtained by cyclodehydration and it can be used for matching somebody with somebody alkaline
Property solution, reduce waste water generation, reduce environmental pressure；Alcohols used by salinity is separated out to use through distilling Posterior circle；The reaction simultaneously
Raw material is easily obtained, high income, reaction are gentle, with good industrial value.
Embodiment
The present invention is described in more detail below by specific embodiment.
Embodiment 1
1）Sodium hydrogensulfite and water are added in four-hole bottle in advance, stirring and dissolving, are subsequently added sodium sulfite adjustment system PH=
8.5；2）50 DEG C are warming up to, butenol is gradually added dropwise into four-hole bottle by constant pressure funnel in 10 minutes, 65 DEG C of temperature control,
The mol ratio of butenol and bisulfites is 1：1.15；After completion of dropwise addition, continue to stop reacting and cooling after reacting 25 minutes
To room temperature；3）Sulfuric acid to system is added dropwise into four-hole bottle and is presented acid, stirs 60 minutes, methanol is added, the butenol of dropwise addition and
The molar ratio of the methanol of addition is 1：1.0, now there are a large amount of white solids to separate out, filter to obtain settled solution；4）Institute will be reacted
Obtain filtrate rectifying under 120 DEG C and -0.095Mpa to remove water, until anhydrous outflow, then raise temperature to 160 DEG C of continuation rectifying, obtain
Isosorbide-5-Nitrae-butane sultone, purity 99.5%, yield 87.3%.
Embodiment 2
1）Sodium hydrogensulfite and water are added in four-hole bottle in advance, stirring and dissolving, are subsequently added sodium sulfite adjustment system PH=
8.5；2）52 DEG C are warming up to, butenol is gradually added dropwise into four-hole bottle by constant pressure funnel in 12 minutes, 62 DEG C of temperature control,
The mol ratio of butenol and bisulfites is 1：1.2；After completion of dropwise addition, continue to stop reacting and being cooled to after reacting 23 minutes
Room temperature；3）Sulfuric acid to system is added dropwise into four-hole bottle and is presented acid, stirs 55 minutes, ethanol is added, the butenol of dropwise addition and plus
The molar ratio of the ethanol entered is 1：2.0, now there are a large amount of white solids to separate out, filter to obtain settled solution；4）Will reaction gained
Filtrate rectifying under 120 DEG C and -0.095Mpa is removed water, until anhydrous outflow, is then raised temperature to 160 DEG C of continuation rectifying, is obtained 1,
4- butane sultones, purity 99.3%, yield 83.5%.
Embodiment 3
1）Potassium bisulfite and water are added in four-hole bottle in advance, stirring and dissolving, are subsequently added sodium sulfite adjustment system PH=8；
2）48 DEG C are warming up to, butenol, 68 DEG C of temperature control, butylene are gradually added dropwise into four-hole bottle by constant pressure funnel in 13 minutes
The mol ratio of alcohol and bisulfites is 1：1.1；After completion of dropwise addition, continue to stop reacting and being cooled to room after reacting 28 minutes
Temperature；3）Hydrochloric acid to system is added dropwise into four-hole bottle and is presented acid, stirs 65 minutes, ethylene glycol is added, the butenol of dropwise addition and plus
The molar ratio of the ethylene glycol entered is 1：3.0, now there are a large amount of white solids to separate out, filter to obtain settled solution；4）Institute will be reacted
Obtain filtrate rectifying under 120 DEG C and -0.095Mpa to remove water, until anhydrous outflow, then raise temperature to 160 DEG C of continuation rectifying, obtain
Isosorbide-5-Nitrae-butane sultone, purity 99.2%, yield 82.8%.
Embodiment 4
1）Sodium hydrogensulfite and water are added in four-hole bottle in advance, stirring and dissolving, are subsequently added sodium sulfite adjustment system PH=
7.5；2）55 DEG C are warming up to, butenol is gradually added dropwise into four-hole bottle by constant pressure funnel in 18 minutes, 60 DEG C of temperature control,
The mol ratio of butenol and bisulfites is 1：1.3；After completion of dropwise addition, continue to stop reacting and being cooled to after reacting 30 minutes
Room temperature；3）Hydrochloric acid to system is added dropwise into four-hole bottle and is presented acid, stirs 50 minutes, propyl alcohol is added, the butenol of dropwise addition and plus
The molar ratio of the propyl alcohol entered is 1：4.0, now there are a large amount of white solids to separate out, filter to obtain settled solution；4）Will reaction gained
Filtrate rectifying under 120 DEG C and -0.095Mpa is removed water, until anhydrous outflow, is then raised temperature to 160 DEG C of continuation rectifying, is obtained 1,
4- butane sultones, purity 98.9%, yield 81.3%.
Embodiment 5
1）Potassium bisulfite and water are added in four-hole bottle in advance, stirring and dissolving, are subsequently added sodium sulfite adjustment system PH=9；
2）45 DEG C are warming up to, butenol, 70 DEG C of temperature control, butylene are gradually added dropwise into four-hole bottle by constant pressure funnel in 20 minutes
The mol ratio of alcohol and bisulfites is 1：1.05；After completion of dropwise addition, continue to stop reacting and being cooled to room after reacting 20 minutes
Temperature；3）Sulfuric acid to system is added dropwise into four-hole bottle and is presented acid, stirs 70 minutes, triglyceride is added, the butenol of dropwise addition and
The molar ratio of the triglyceride of addition is 1：5.0, now there are a large amount of white solids to separate out, filter to obtain settled solution；4）Will be anti-
Answer the rectifying under 120 DEG C and -0.095Mpa of gained filtrate to remove water, until anhydrous outflow, then raise temperature to 160 DEG C of continuation rectifying,
Obtain Isosorbide-5-Nitrae-butane sultone, purity 98.8%, yield 82.0%.
Comparative example 1
1）Sodium hydrogensulfite water is added in four-hole bottle in advance, stirring and dissolving, be subsequently added NaOH adjustment system PH=8.5；
2）50 DEG C are warming up to, butenol, 65 DEG C of temperature control are gradually added dropwise into four-hole bottle by constant pressure funnel in 10 minutes.Instead
Reflecting to proceed, and the actual effect for adding NaOH regulation is to convert sodium hydrogensulfite for sodium sulphate.Can not be complete
Into addition reaction.
Comparative example 2
Basic process and process conditions be the same as Example 1, the difference is that adjusting pH to alkalescence without addition sodium sulfite, but are adjusted
PH is acidity.Because reaction is violent, can only the control of reaction temperature highest no more than 50 DEG C, reaction rate is slower, the reaction time
It is longer.Obtain Isosorbide-5-Nitrae-butane sultone, purity 97.3%, yield 72.1%.
The present invention is a kind of few reactions steps, high income, secondary turn one's coat point recoverable and the small Isosorbide-5-Nitrae-fourth of environmental pressure
Alkane sultone synthetic method.
The above, is only presently preferred embodiments of the present invention, is not the limitation for making other forms to the present invention, appoints
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But it is every without departing from technical solution of the present invention content, the technical spirit according to the present invention is to above example institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection domain of technical solution of the present invention.
Claims (8)
1. the synthetic method of a kind of Isosorbide-5-Nitrae-butane sultones, it is characterised in that comprise the following steps：
1）Bisulfites is added to the water stirring and dissolving for solution in advance, the PH for being subsequently added sodium sulfite adjustment system is
7.5~9；
2）Be warming up to after 45 DEG C ~ 55 DEG C and butenol be at the uniform velocity added dropwise in 10 ~ 20 minutes, control addition reaction temperature 60 DEG C ~
70 DEG C, after completion of dropwise addition, continue to stop reacting and being cooled to room temperature after reacting 20 ~ 30 minutes；Described butenol and sulfurous acid
The mol ratio of hydrogen salt is 1：1.05~1.3；
3）Acid is added dropwise in the backward system that cools acid to presenting, stirs 50 ~ 70 minutes, add alcohol crystallization, filter to obtain settled solution；
4）Settled solution rectifying is obtained into Isosorbide-5-Nitrae-butane sultone.
2. a kind of synthetic method of Isosorbide-5-Nitrae-butane sultones according to claim 1, it is characterised in that：Step 2）It is added dropwise
Butenol and step 3）The molar ratio of the alcohol of middle addition is 1：1.0~5.0.
3. a kind of synthetic method of Isosorbide-5-Nitrae-butane sultones according to claim 2, it is characterised in that：Described alcohol is
Methanol, ethanol, ethylene glycol, propyl alcohol or triglyceride.
4. a kind of synthetic method of Isosorbide-5-Nitrae-butane sultones according to claim 1, it is characterised in that：It is described to add Asia
The PH of system is 8.5 after sodium sulphate adjustment.
5. a kind of synthetic method of Isosorbide-5-Nitrae-butane sultones according to claim 1, it is characterised in that：Described butylene
The mol ratio of alcohol and bisulfites is 1：1.1~1.2.
6. a kind of synthetic method of Isosorbide-5-Nitrae-butane sultones according to claim 1, it is characterised in that：Described sulfurous
Sour hydrogen salt is sodium hydrogensulfite or potassium bisulfite.
7. a kind of synthetic method of Isosorbide-5-Nitrae-butane sultones according to claim 1, it is characterised in that：Step 3）Cooling
The acid being added dropwise afterwards is hydrochloric acid or sulfuric acid.
8. a kind of synthetic method of Isosorbide-5-Nitrae-butane sultones according to claim 1, it is characterised in that：Step 2）In open
The temperature of system is 50 DEG C when beginning that butenol is at the uniform velocity added dropwise.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108558821A (en) * | 2018-04-10 | 2018-09-21 | 武汉松石科技股份有限公司 | A kind of preparation method of 1,4- butane sultones |
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| CN101012218A (en) * | 2007-01-23 | 2007-08-08 | 王四新 | Method of synthesizing 1,3-propane sultone |
| CN102807552A (en) * | 2012-07-31 | 2012-12-05 | 福建创鑫科技开发有限公司 | Method for synthetizing 2, 4-butane sulfonic acid lactone |
| CN106146453A (en) * | 2016-07-26 | 2016-11-23 | 张家港瀚康化工有限公司 | The preparation method of 1,3 propane sultone |
| CN106397392A (en) * | 2016-08-31 | 2017-02-15 | 湖北吉和昌化工科技有限公司 | 1,4-butane sultone and synthesis process thereof |
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2017
- 2017-03-24 CN CN201710182914.8A patent/CN106946844A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101012218A (en) * | 2007-01-23 | 2007-08-08 | 王四新 | Method of synthesizing 1,3-propane sultone |
| CN102807552A (en) * | 2012-07-31 | 2012-12-05 | 福建创鑫科技开发有限公司 | Method for synthetizing 2, 4-butane sulfonic acid lactone |
| CN106146453A (en) * | 2016-07-26 | 2016-11-23 | 张家港瀚康化工有限公司 | The preparation method of 1,3 propane sultone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108558821A (en) * | 2018-04-10 | 2018-09-21 | 武汉松石科技股份有限公司 | A kind of preparation method of 1,4- butane sultones |
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Application publication date: 20170714 |