CN108218826A - A kind of method for preparing 1,3- propane sultones - Google Patents
A kind of method for preparing 1,3- propane sultones Download PDFInfo
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- CN108218826A CN108218826A CN201810062721.3A CN201810062721A CN108218826A CN 108218826 A CN108218826 A CN 108218826A CN 201810062721 A CN201810062721 A CN 201810062721A CN 108218826 A CN108218826 A CN 108218826A
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- propane
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- halogenated
- propane sulfonic
- sulfonic acids
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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
- C07D327/04—Five-membered rings
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Abstract
The invention discloses a kind of methods for preparing 1,3 propane sultones, and this method comprises the following steps：1. by 1, after 3 two halopropanes are mixed with sulfonating agent and solvent, sulfonating reaction is carried out at a certain temperature, obtains 1 halogenated 3 propane sulfonic acid sodium；2. 1 halogenated 3 propane sulfonic acid sodium of gained is added to the water, adds in strong acid for adjusting pH=1 3 and carry out acidification, concentration, filtering removal inorganic salts are further concentrated to dry 1 halogenated 3 propane sulfonic acid；3. 1 halogenated 3 propane sulfonic acid of gained is heated under vacuum, lactonization reaction is carried out to get 1,3 propane sultone.It has the following advantages that：1st, the method for the present invention raw materials used 1,3 two halopropane toxicity smallers, while safer, be more easy to get and it is recyclable continuously apply mechanically, be also convenient for storing, considerably reduce raw material and operating cost；2nd, the method for the present invention three wastes yield is few, reduces environmental pollution, and prepared product purity is high, up to more than 99%；Product water content is less than 0.1%.
Description
Technical field
The invention belongs to technical field of chemical synthesis, and in particular to a kind of method for preparing 1,3- propane sultones.
Background technology
1,3- propane sultone is a kind of important organic synthesis intermediate, is colourless or light yellow transparent liquid or nothing
Color clear crystals industrially have important application on different aspect, such as the synthesis of surfactant；Sulfonating agent, process hides,
Ink and sensitizing dye synthesis；The synthesis of electroplating intermediate, medicine, lithium secondary battery, ink etc..With the continuous expansion of its purposes
Greatly, market demand is also being continuously increased.At present, the common methods of synthesis 1,3- propane sultones are as follows：
Method one：Using propenyl and sodium hydrogensulfite as raw material, in the presence of initiator by sulfonation, acidification, dehydration,
Refined and etc. to obtain target product, specific reaction equation is as follows：
The raw material propylene alcohol toxicity that this method uses is larger.
Method two：Using methacrylaldehyde and sodium hydrogensulfite as raw material, by addition, restore, lactonize, refined and etc. obtain
Target product, specific reaction equation are as follows：
The raw material propylene aldehyde that this method uses is oxidized easily, and need hydrogenating reduction, requires consersion unit high, cost
It is relatively high.
Invention content
The object of the present invention is to provide a kind of methods for preparing 1,3- propane sultones, can effectively be overcome using the method
Many deficiencies of existing synthesis 1,3- propane sultone methods.
To achieve the above object, the technical solution adopted by the present invention is：This method comprises the following steps：
1. by 1, after bis- halopropanes of 3- are mixed with sulfonating agent and solvent, sulfonating reaction is carried out at a certain temperature, is obtained
To the halogenated -3- propane sulfonic acids sodium of 1-；
2. halogenated -3- propane sulfonic acids the sodium of gained 1- is added to the water, adds in strong acid and adjust pH=1-3 progress acidifications,
Concentration, filtering removal inorganic salts, are further concentrated to dry the halogenated -3- propane sulfonic acids of 1-；
3. halogenated -3- the propane sulfonic acids of gained 1- are heated under vacuum, lactonization reaction is carried out to get 1,3- propane
Sultones.
1. middle bis- halopropanes of 1,3- include 1,3- dibromopropanes, 1,3- dichloropropanes, the bromo- 3- chloropropanes of 1- to above-mentioned steps.
1. middle sulfonating agent includes sodium sulfite, sodium hydrogensulfite, sodium pyrosulfite to above-mentioned steps.
1. the molar ratio of middle bis- halopropanes of 1,3- and sulfonating agent is above-mentioned steps：1:1-6；Preferential 1:1-3.
1. middle solvent includes methanol, ethyl alcohol, isopropanol, the tert-butyl alcohol, N,N-dimethylformamide, 1,4- dioxies to above-mentioned steps
Six rings, tetrahydrofuran, acetonitrile, acetone；Preferential ethyl alcohol, methanol, isopropanol.
The dosage of above-mentioned steps 1. middle solvent is 2-15 times of bis- halopropane quality of 1,3-；It is 2-10 times preferential.
1. the middle sulfonating reaction time is 1-24 hours to above-mentioned steps；It is 5-10 hours preferential.
1. middle sulfonating reaction temperature is 50-120 DEG C to above-mentioned steps；Preferential 80 DEG C.
2. middle strong acid includes hydrochloric acid, sulfuric acid, nitric acid to above-mentioned steps；It is preferred that hydrochloric acid, sulfuric acid.
2. middle acidificatoin time is 1-24 hours to above-mentioned steps；It is 1-5 hours preferential.
2. middle souring temperature is 0-100 DEG C to above-mentioned steps；It is 10-35 DEG C preferential.
3. middle lactonization reaction temperature is 140-250 DEG C to above-mentioned steps；It is preferred that 150-200 DEG C.
Above-mentioned steps 3. in lactonize vacuum degree as -0.1Mpa.
The specific reaction equation that each step of the method for the present invention uses is as follows：
The method of the present invention is a kind of new method for preparing 1,3- propane sultones proposed using new thought, with showing
There are many synthetic methods to compare more safe efficient, environmentally friendly, have the following advantages that：
1st, raw materials used 1,3-, the bis- halopropane toxicity smallers of the method for the present invention while safer, are more easy to get and can
Recycling is continuously applied mechanically, and is also convenient for storing, is considerably reduced raw material and operating cost；
2nd, the method for the present invention three wastes yield is few, reduces environmental pollution, protects ecological environment.Meanwhile prepared production
Product purity is high, up to more than 99%；Product water content is less than 0.1%.
Specific embodiment
Embodiment 1：
1. 40g sodium sulfites (1.0eq) are added in into reaction bulb, the bromo- 3- chloropropanes 50g (1.0eq) of 1-, 250 milli of ethyl alcohol
It rises, 80 degree is warming up to after adding and is reacted 8 hours, be cooled to 10 degree, filtering obtains the chloro- 3- propane sulfonic acids sodium crude products of 1-.
2. the chloro- 3- propane sulfonic acids sodium crude products of 1- obtained by upper step are added in reaction bulb, 100 milliliters, less than 20 degree of water is added in
Add hydrochloric acid adjusting pH=1-3, be concentrated under reduced pressure and remove most of water, add in 80 milliliters of ethyl alcohol, be cooled to 10 degree, filter, filtrate is dense
It is reduced to dry the chloro- 3- propane sulfonic acids 48g of 1-.
3. the chloro- 3- propane sulfonic acids of 1- (- 0.1MPa) under 140-200 DEG C and condition of high vacuum degree obtained by upper step are lactonized
Reaction, while fraction is received, obtain 1.3- propane sultones 32g.Its total yield of products is 83%, purity >=99%.
Embodiment 2：
1. 10.4g sodium sulfites (1.0eq) are added in into reaction bulb, 1,3- dibromopropane 50g (3.0eq), 200 milli of ethyl alcohol
It rises, 80 degree is warming up to after adding and is reacted 10 hours, be cooled to 10 degree, filtering obtains the bromo- 3- propane sulfonic acids sodium crude products of 1-, (unreacted
1,3- dibromopropanes in filtrate, it is recyclable).
2. the bromo- 3- propane sulfonic acids sodium of 1- obtained by upper step is added in reaction bulb, 60 milliliters of water, less than 20 degree plus hydrochloric acid are added in
PH=1-3 is adjusted, is concentrated under reduced pressure and removes most of water, add in 35 milliliters of ethyl alcohol, is cooled to 10 degree, filtering, filtrate is concentrated to dryness
Obtain the bromo- 3- propane sulfonic acids 15g of 1-.
3. the bromo- 3- propane sulfonic acids of 1- (- 0.1MPa) under 140-200 DEG C and condition of high vacuum degree obtained by upper step are lactonized
Reaction, while fraction is received, obtain 1.3- propane sultones 8.1g.Its total yield of products is 80%, purity >=99%.
Embodiment 3：
1. 18.6g sodium sulfites (1.0eq), 1,3- dichloropropane 50g under room temperature, are added in into reactor
(3.0eq), 200 milliliters of ethyl alcohol are warming up to 80 degree and react 16 hours after adding, be cooled to 10 degree, and filtering obtains the chloro- 3- propane of 1-
Sodium sulfonate crude product (unreacted 1,3- dichloropropanes are recyclable in filtrate).
2. the chloro- 3- propane sulfonic acids sodium of 1- obtained by upper step is added in reaction bulb, 60 milliliters of water, less than 20 degree plus hydrochloric acid are added in
PH=1-3 is adjusted, is concentrated under reduced pressure and removes most of water, add in 35 milliliters of ethyl alcohol, is cooled to 10 degree, filtering, filtrate is concentrated to dryness
Obtain the chloro- 3- propane sulfonic acids 19g of 1-.
3. the chloro- 3- propane sulfonic acids of 1- (- 0.1MPa) under 140-200 DEG C and condition of high vacuum degree obtained by upper step are lactonized
Reaction, while fraction is received, obtain 1.3- propane sultones 12.4g.Its total yield of products is 75%, purity >=99%.
Claims (10)
1. a kind of method for preparing 1,3- propane sultones, method include the following steps：
1. by 1, after bis- halopropanes of 3- are mixed with sulfonating agent and solvent, sulfonating reaction is carried out at a certain temperature, obtains 1-
Halogenated -3- propane sulfonic acids sodium；
2. halogenated -3- propane sulfonic acids the sodium of gained 1- is added to the water, adds in strong acid for adjusting pH=1-3 and carry out acidification, concentrate,
Filtering removal inorganic salts, are further concentrated to dry the halogenated -3- propane sulfonic acids of 1-；
3. halogenated -3- the propane sulfonic acids of gained 1- are heated under vacuum, lactonization reaction is carried out to get 1,3- propane sulfonic acids
Lactone.
2. a kind of method for preparing 1,3- propane sultones according to claim 1, it is characterized in that：The step 1. in
Bis- halopropanes of 1,3- include 1,3- dibromopropanes, 1,3- dichloropropanes, the bromo- 3- chloropropanes of 1-.
3. a kind of method for preparing 1,3- propane sultones according to claim 1 or 2, it is characterized in that：The step
1. middle sulfonating agent includes sodium sulfite, sodium hydrogensulfite, sodium pyrosulfite.
4. a kind of method for preparing 1,3- propane sultones according to claim 1 or 2, it is characterized in that：The step
1. the molar ratio of middle bis- halopropanes of 1,3- and sulfonating agent is：1:1-6.
5. a kind of method for preparing 1,3- propane sultones according to claim 1 or 2, it is characterized in that：The step
1. middle solvent includes methanol, ethyl alcohol, isopropanol, the tert-butyl alcohol, N,N-dimethylformamide, 1,4- dioxane, tetrahydrofuran, second
Nitrile, acetone.
6. a kind of method for preparing 1,3- propane sultones according to claim 1 or 2, it is characterized in that：The step
1. the dosage of middle solvent is 2-15 times of bis- halopropane quality of 1,3-.
7. a kind of method for preparing 1,3- propane sultones according to claim 1 or 2, it is characterized in that：The step
1. the middle sulfonating reaction time is 1-24 hours；Sulfonating reaction temperature is 50-120 DEG C.
8. a kind of method for preparing 1,3- propane sultones according to claim 1 or 2, it is characterized in that：The step
2. middle strong acid includes hydrochloric acid, sulfuric acid, nitric acid.
9. a kind of method for preparing 1,3- propane sultones according to claim 1 or 2, it is characterized in that：The step
2. middle acidificatoin time is 1-24 hours；Souring temperature is 0-100 DEG C.
10. a kind of method for preparing 1,3- propane sultones according to claim 1 or 2, it is characterized in that：The step
3. middle lactonization reaction temperature is 140-250 DEG C；The vacuum degree that lactonizes is -0.1Mpa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483473A (en) * | 2019-09-08 | 2019-11-22 | 淮安瀚康新材料有限公司 | A kind of solvent-free method for preparing 1,3- propane sultone |
| CN114232041A (en) * | 2022-01-17 | 2022-03-25 | 中国计量大学 | High depth-diameter ratio blind hole copper filling electroplating solution and preparation method thereof |
| CN115448858A (en) * | 2022-08-01 | 2022-12-09 | 苏州亚科科技股份有限公司 | Efficient synthesis process of 2-chloroethyl sodium sulfonate |
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| CN103992251A (en) * | 2014-05-19 | 2014-08-20 | 景立秋 | Preparation method of chloroalkyl sulfonyl chloride |
| 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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2018
- 2018-01-23 CN CN201810062721.3A patent/CN108218826A/en active Pending
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| CN103992251A (en) * | 2014-05-19 | 2014-08-20 | 景立秋 | Preparation method of chloroalkyl sulfonyl chloride |
| 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 |
Non-Patent Citations (2)
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| J. WILLEMS: ""The aliphatic hydroxysulphonic acids and their internal esters : the sultones I. The aliphatic hydroxysulphonic acids"", 《BULL. SOC. CHIM. BELG.》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483473A (en) * | 2019-09-08 | 2019-11-22 | 淮安瀚康新材料有限公司 | A kind of solvent-free method for preparing 1,3- propane sultone |
| CN110483473B (en) * | 2019-09-08 | 2022-12-23 | 江苏瀚康新材料有限公司 | Method for preparing 1, 3-propane sultone |
| CN114232041A (en) * | 2022-01-17 | 2022-03-25 | 中国计量大学 | High depth-diameter ratio blind hole copper filling electroplating solution and preparation method thereof |
| CN114232041B (en) * | 2022-01-17 | 2023-11-21 | 中国计量大学 | High-depth-diameter-ratio blind hole copper filling electroplating solution and preparation method thereof |
| CN115448858A (en) * | 2022-08-01 | 2022-12-09 | 苏州亚科科技股份有限公司 | Efficient synthesis process of 2-chloroethyl sodium sulfonate |
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