CN107556286A - A kind of synthetic method of 1,3 propene sultone - Google Patents
A kind of synthetic method of 1,3 propene sultone Download PDFInfo
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- CN107556286A CN107556286A CN201710892941.4A CN201710892941A CN107556286A CN 107556286 A CN107556286 A CN 107556286A CN 201710892941 A CN201710892941 A CN 201710892941A CN 107556286 A CN107556286 A CN 107556286A
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Abstract
The invention discloses a kind of synthetic method of 1,3 propene sultones, comprise the following steps：1st, the synthesis of 1 chloropropene alcohol；2nd, the synthesis of propilolic alcohol；3rd, the synthesis of 3 hydroxy sulfonic acid；4th, the synthesis of 1,3 propene sultones.This method synthetic route is simple, and raw material is cheap and easily-available, and synthesis cost is low, and high income.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to the synthetic method of one kind 1,3- propene sultones.
Background technology
Because use is little before 1,3- propene sultone, rarely has the report of its synthetic method.In recent years, due to it
Available for lithium battery additive, therefore it is taken seriously, the patent of invention around its synthetic method increases rapidly, is summed up, main
There are following several routes：
1st, using propylene as Material synthesis 1,3- propene sultones, see：CN105622833；
2nd, using enoyl- chlorine or bromine as Material synthesis 1,3- propene sultones, see：JP2009108934、
WO2006085149, JP2009076617 and WO206088149；
3rd, with 1,3-PS for Material synthesis 1,3- propene sultones, see Kr2007101716, CN106279097,
JP2009076617, Kr2009076617 and WO2006085149；
4th, using chlorination glycerine as Material synthesis 1,3- propene sultones, WO2011016440 is seen；
5th, using propenyl as Material synthesis 1,3- propene sultones, WO2006085149 is seen；
6th, using propilolic alcohol as Material synthesis 1,3- propene sultones, CN101456856 is seen.
In summary, 6 routes of the above have his own strong points, but are all not easy, comparatively, using propilolic alcohol as Material synthesis 1,
The process route of 3- propene sultones is relatively easy, and raw material is also relatively easy to get, and yield is also good, and this route has industrialization latent
Power, but its shortcoming is that propilolic alcohol is not cheap, and price is relatively expensive.
The content of the invention
In order to solve the above-mentioned problems of the prior art, the invention provides the synthesis of one kind 1,3- propene sultones
Method, this method synthetic route is simple, and raw material is cheap and easily-available, and synthesis cost is low, and high income.
Technical scheme is used by realizing above-mentioned purpose of the present invention：
The synthetic method of one kind 1,3- propene sultones, comprises the following steps：
1st, the synthesis of 1- chloropropenes alcohol：
In saturated sodium carbonate solution, add along 1,3- dichloropropylenes, along the mol ratio of 1,3- dichloropropylenes and sodium carbonate
For 1:1~1.5, it is heated to flowing back under stirring, continues to be stirred at reflux 7~9 hours, after backflow terminates, cooling layering, obtains 1- chlorine
Propenyl crude product；
2nd, the synthesis of propilolic alcohol：
To 1- chloropropene alcohol crude product addition solvent tertiary butanol, 70~80 DEG C are heated under stirring, insulation, is slowly added under stirring
Enter piece alkali, the mol ratio of piece alkali and 1- chloropropene alcohol is 1.1~1:1, continue to stir after adding, 1.5~2.5 hours, be cooled to
Room temperature, add hydrochloric acid solution and adjust pH value to 7~8, precipitated sodium chloride crystal, filtering, take filtrate, obtain the tert-butyl alcohol of propilolic alcohol
Solution；
3rd, the synthesis of 3- hydroxies sulfonic acid：
3.1st, in reaction bulb, the t-butanol solution of propilolic alcohol, solution of sodium bisulfite, sodium sulfite solution is added and is drawn
Agent TBHP is sent out, propilolic alcohol, sodium hydrogensulfite, the mol ratio of TBHP are 1:1~1.2：0.01~
0.1：0.2~0.3, while 40-50 DEG C is heated to, the pH value of control system is 7.5~8, after the completion of charging, is incubated and keeps pH
It is worth for 7.5~8, continues reaction 4 hours, obtain mixed liquor；
3.2nd, mixed liquor is subjected to air-distillation, steams the azeotropic mixture of tert-butyl group alcohol and water, be subsequently added into hydrochloric acid solution acid
It is 2 to change to pH, and after acidifying terminates, it is sticky to be concentrated under reduced pressure into material, then adds methanol, is stirred at reflux dissolving 3- hydroxy sulphurs
Acid, after backflow terminates, cooling, precipitation is separated out, filtering, by filtrate normal pressure concentration and recovery methanol, then is concentrated filtrate to not
Untill water outlet, 3- hydroxy sulfonic acid is obtained；
4th, the synthesis of 1,3- propene sultones：
The 3- hydroxy sulfonic acid for accounting for 3- hydroxy sulfonic acid gross mass 15~25%, oil bath heating are added into flash distillation bottle
To 135~155 DEG C, while 1-4mmHg is evacuated down to, it is 135~155 DEG C to control the temperature in flash distillation bottle, by remaining 3- hydroxyls
Base propene sulfonic acid is continuously slowly pumped into flash distillation bottle and is dehydrated, and 70 DEG C of water condensations, obtains 1,3- propene sultones.
Further, in step 2.2, diethyl hydroxylamine is added while adding the tert-butyl alcohol as polymerization inhibitor, diethyl hydroxylamine
The quality of addition is the 0.001~0.01 of 1- chloropropene alcohol quality.
Further, in step 2.2, piece alkali will be slowly added to, and the feed time of piece alkali is 0.5~1.5h.
Further, the t-butanol solution of propilolic alcohol, sulphite and TBHP feed as follows：
1st, the tert-butyl group mistake for accounting for TBHP gross mass 20~30% is added into the t-butanol solution of propilolic alcohol
Hydrogen oxide, stir, dropping liquid A is made；
2nd, Jiang Shui, sodium hydrogensulfite and account for sodium sulfite gross mass 0.75-0.85% it is well mixed, be configured to be added dropwise
Liquid B；
3rd, in reaction bulb, water and remaining sodium sulfite, stirring and dissolving are added, continuously adds remaining t-butyl peroxy
Change hydrogen, after stirring and dissolving, dropping liquid A and dropping liquid B is added dropwise simultaneously into reaction bulb, time for adding 4~5 hours, process is added dropwise
The pH of beginning control system is 7.5~8.
Further, in step 2.4, added into flash distillation bottle to mequinol as polymerization inhibitor, mequinol is added
Quality is the 0.01~0.1 of 3- hydroxy sulfonic acid quality.
Further, in step 2.3.2, be concentrated under reduced pressure into material it is sticky before, be first evacuated to 0.09MPa, and depressurize dense
All the time 90~100 DEG C of kettle degree is controlled in compression process.
Further, in step 2.3.2, by filtrate air-distillation to kettle temperature up to 90~100 DEG C, then it is evacuated to 0.01~
0.1MPa, kettle temperature is concentrated under reduced pressure into up to 125~135 DEG C, untill being concentrated into not water outlet.
Further, it is by the method that 1,3- propene sultones further purify：The 1,3- propylene sulphurs that step 2.4 is obtained
Acid lactone dichloromethane or ethyl acetate dissolving, filtering, filtering are recrystallized with n-hexane, filtered, dried, obtain more high-purity
The 1,3- propene sultones of degree.
Compared with prior art, the advantages of the present invention are：
1st, purification of the raw material of this method along 1,3- dichloropropylenes for accessory substance DD mixtures, cheap, source is sufficient,
The synthesis cost of 1,3- propene sultones is greatly lowered.
2nd, this method synthetic route is relatively easy, and purifying technique is relatively easy, using normal pressure or decompression operation, and temperature
Degree is not high, safely controllable, and product purity is high, high income.
Embodiment
With reference to embodiment, the present invention is described in detail.
Embodiment 1
1st, the synthesis of 1- chloropropenes alcohol：
In 2000ml reaction bulbs, 1100ml water and 349g sodium carbonate are added, is well mixed, is added under stirring into reaction bulb
Enter 333g (3mole, content 97wt%) along 1,3- dichloropropylenes, be heated to flowing back, continue to be stirred vigorously backflow 8 hours, now
Almost without along the backflow of 1,3- dichloropropylenes, 102~105 DEG C of reaction bulb Nei Wenda, backflow terminates, and is cooled to 80 DEG C, layering, pours out
Upper strata colored liquid layering, removes lower floor, obtains 260g 1- chloropropenes alcohol (aqueous 5wt%), tear pure 247g open into separatory funnel,
Yield 91.0%.
2nd, the synthesis of propilolic alcohol：
In reaction bulb, 1- chloropropenes alcohol (2.64mol), the 741g tert-butyl alcohols and 1g polymerization inhibitors two that step 1 synthesizes are added
Ethylhydroxyl amine, 70 DEG C are warming up under stirring, insulation, stirring subsequent point point adds 109g pieces alkali (2.725), the feed time of piece alkali
About 1 hour, continue stirring reaction 2h after adding, now take 1- chloropropene alcohol to be analyzed, more than 95wt% 1- chloropropene alcohol
All convert, cooled to 30 DEG C, 37wt% hydrochloric acid solution regulation is added dropwisePH values precipitated sodium chloride crystal, filter, 100g to 7
The tert-butyl group washs filter cake, takes filtrate, obtains the t-butanol solution of 1023g propilolic alcohols, the mass fraction of propilolic alcohol is
13.45wt%, tear pure 137.6g, yield 93% open.
3rd, the synthesis of 3- hydroxies sulfonic acid：
3.1st, in reaction bulb, the t-butanol solution (propilolic alcohol 1.5mol, 84g) of the propilolic alcohol of 625g steps 2 is added, is added
Enter 4.2g TBHPs, be pumped into after stirring in dropping tank, as dropping liquid A；In reaction bulb, 675g is added
Water, lower addition 161g sodium hydrogensulfites and 37.8g sodium sulfites are stirred, stirring is complete to dissolving at 35 DEG C, and suction dropping tank is
Dropping liquid B.
3.2nd, in reaction bulb, 350g water and 9.5g sodium sulfites, stirring and dissolving is added, continuously adds 1.5g tert-butyl group mistakes
Hydrogen oxide makees bed material, and 40 DEG C are warming up under stirring and is incubated, while dropping liquid A and dropping liquid B is added dropwise into reaction bulb, during dropwise addition
Between be 4~5h, 50 DEG C of the temperature ＜ of control system during dropwise addition,PH values are 7.5~8, after being added dropwise to complete, at 40~50 DEG C andPContinue reaction 4 hours under H values 7.5~8；
3.3rd, after reaction terminates, atmospheric distillation plant is changed, air-distillation goes out the azeotropic mixture of the tert-butyl alcohol and water, reclaims uncle 600g
Butanol, 40 DEG C being cooled to, 264g 37wt% hydrochloric acid solutions are added dropwise and are acidified, caused sulfur dioxide is absorbed with liquid caustic soda solution,
After acidifying terminates, 2g is added to mequinol, 0.09MPa is evacuated to, is concentrated under reduced pressure, control the temperature in reaction bulb
100 DEG C, it is sticky to be concentrated into material, changes reflux, and 500ml methanol is added dropwise into reaction bulb, is heated to flowing back, is stirred at reflux
2h, 40 DEG C are cooled to, separate out precipitation, filtering, wash filter cake 2 times with 100ml methanol, take filtrate, filtrate is added in reaction bulb,
Air-distillation reclaims methanol, is then evacuated to 0.095MPa, is concentrated under reduced pressure into reaction bulb to 100 DEG C of reaction bulb Nei Wenduda
130 DEG C of Nei Wenda, untill being concentrated into not water outlet, 157g3- hydroxies sulfonic acid (M138) (aqueous 5wt%) is obtained, is torn open pure
149g, yield 72% (in terms of propilolic alcohol sterling).
4th, the synthesis of 1,3- propene sultones：
In 250ml flashes bottle, 30g3- hydroxies sulfonic acid and 3g are added to mequinol, is stirred vigorously lower oil bath liter
Temperature while is evacuated to 2mmHg to 135 DEG C, and with 70 DEG C of water condensations, remaining 3- hydroxies sulfonic acid was connected in 1 hour
Continuous be pumped into flash distillation bottle is dehydrated, and it is 135~155 DEG C to control the temperature in flash distillation bottle in dehydration all the time, collects condensation
Liquid, obtain 102g1,3- propene sultones (M120), gray crystals, yield 79% (in terms of 3- hydroxy sulfonic acid), purity
99.2%, 79~83 DEG C of fusing point, in terms of propilolic alcohol, yield 56.7%, with along 1,3- dichloropropylene meters, yield 51%.
1,3- propene sultones dichloromethane or ethyl acetate are dissolved, decolorization filtering, by filtrate with n-hexane weight
Crystallization, filter, dry, obtain white crystalline powder, purity 99.9%, yield 70% (in terms of 3- hydroxy sulfonic acid).
Claims (8)
1. one kind 1, the synthetic method of 3- propene sultones, it is characterised in that comprise the following steps：
1.1st, the synthesis of 1- chloropropenes alcohol：
In saturated sodium carbonate solution, add along 1,3- dichloropropylenes, be 1 along the mol ratio of 1,3- dichloropropylenes and sodium carbonate:1
~1.5, it is heated to flowing back under stirring, continues to be stirred at reflux 7~9 hours, after backflow terminates, cooling layering, obtains 1- chloropropenes
Alcohol crude product；
1.2nd, the synthesis of propilolic alcohol：
Solvent tertiary butanol is added to 1- chloropropene alcohol crude product, 70~80 DEG C are heated under stirring, insulation, piece is slowly added under stirring
The mol ratio of alkali, piece alkali and 1- chloropropene alcohol is 1.1~1:1, continue to stir after adding, 1.5~2.5 hours, be cooled to room temperature,
Add hydrochloric acid solution and adjust pH value to 7~8, precipitated sodium chloride crystal, filtering, take filtrate, obtain the t-butanol solution of propilolic alcohol；
1.3rd, the synthesis of 3- hydroxies sulfonic acid：
2.3.1, in reaction bulb, t-butanol solution, solution of sodium bisulfite, sodium sulfite solution and the initiation of propilolic alcohol are added
Agent TBHP, propilolic alcohol, sodium hydrogensulfite, the mol ratio of TBHP are 1:1~1.2：0.01~
0.1：0.2~0.3, while 40-50 DEG C is heated to, the pH value of control system is 7.5~8, after the completion of charging, is incubated and keeps pH
It is worth for 7.5~8, continues reaction 4 hours, obtain mixed liquor；
1.3.2 mixed liquor, is subjected to air-distillation, steams the azeotropic mixture of tert-butyl group alcohol and water, is subsequently added into hydrochloric acid solution acidifying
It is 2 to pH, after acidifying terminates, it is sticky to be concentrated under reduced pressure into material, then adds methanol, is stirred at reflux dissolving 3- hydroxy sulphurs
Acid, after backflow terminates, cooling, precipitation is separated out, filtering, by filtrate normal pressure concentration and recovery methanol, then is concentrated filtrate to not
Untill water outlet, 3- hydroxy sulfonic acid is obtained；
1.4th, the synthesis of 1,3- propene sultones：
The 3- hydroxy sulfonic acid for accounting for 3- hydroxy sulfonic acid gross mass 15~25% is added into flash distillation bottle, oil bath is warming up to
135~155 DEG C, while 1-4mmHg is evacuated down to, it is 135~155 DEG C to control the temperature in flash distillation bottle, by remaining 3- hydroxyls
Propene sulfonic acid is continuously slowly pumped into flash distillation bottle and is dehydrated, and 70 DEG C of water condensations, obtains 1,3- propene sultones.
2. the synthetic method of 1,3- propene sultones according to claim 1, it is characterised in that：In step 2.2, add
Diethyl hydroxylamine is added while the tert-butyl alcohol as polymerization inhibitor, the quality that diethyl hydroxylamine adds is 1- chloropropene alcohol quality
0.001~0.01.
3. the synthetic method of 1,3- propene sultones according to claim 1, it is characterised in that：In step 2.2, piece alkali
It is slowly added to, the feed time of piece alkali is 0.5~1.5h.
4. the synthetic method of 1,3- propene sultones according to claim 1, it is characterised in that the tert-butyl alcohol of propilolic alcohol
Solution, sulphite and TBHP feed as follows：
4.1st, the t-butyl peroxy for accounting for TBHP gross mass 20~30% is added into the t-butanol solution of propilolic alcohol
Change hydrogen, stir, dropping liquid A is made；
4.2nd, Jiang Shui, sodium hydrogensulfite and account for sodium sulfite gross mass 0.75-0.85% it is well mixed, be configured to dropping liquid
B；
4.3rd, in reaction bulb, water and remaining sodium sulfite, stirring and dissolving are added, continuously adds remaining tert-butyl hydroperoxide
Hydrogen, after stirring and dissolving, dropping liquid A and dropping liquid B is added dropwise simultaneously into reaction bulb, time for adding 4~5 hours, process is added dropwise and begins
The pH of control system is 7.5~8.
5. the synthetic method of 1,3- propene sultones according to claim 1, it is characterised in that：In step 2.4, to sudden strain of a muscle
Steam and added in bottle to mequinol as polymerization inhibitor, be the 0.01 of 3- hydroxy sulfonic acid quality to the quality that mequinol adds
~0.1.
6. the synthetic method of 1,3- propene sultones according to claim 1, it is characterised in that：In step 2.3.2, subtract
Pressure be concentrated into material it is sticky before, be first evacuated to 0.09MPa, and control 90~100 DEG C of kettle degree during being concentrated under reduced pressure all the time.
7. the synthetic method of 1,3- propene sultones according to claim 1, it is characterised in that：, will in step 2.3.2
Filtrate air-distillation is then evacuated to 0.01~0.1MPa to kettle temperature up to 90~100 DEG C, be concentrated under reduced pressure into kettle temperature up to 125~
135 DEG C, untill being concentrated into not water outlet.
8. the synthetic method of 1,3- propene sultones according to claim 1, it is characterised in that by 1,3- propene sulfonic acids
The method that lactone further purifies is：The 1,3- propene sultones dichloromethane or ethyl acetate that step 2.4 is obtained are molten
Solution, filtering, filtering is recrystallized with n-hexane, is filtered, and is dried, is obtained 1, the 3- propene sultones of higher purity.
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Cited By (5)
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| CN109180432A (en) * | 2018-11-02 | 2019-01-11 | 浙江工业大学 | A kind of preparation of chlorallylene alcohol and separation method |
| CN110105326A (en) * | 2019-02-26 | 2019-08-09 | 武汉松石科技股份有限公司 | A kind of preparation method of 1,3- propane sultone |
| CN112358416A (en) * | 2020-11-03 | 2021-02-12 | 北京科技大学 | Preparation method of trans-3-chloro-2-propenyl hydroxylamine |
| CN114149404A (en) * | 2020-09-07 | 2022-03-08 | 石家庄圣泰化工有限公司 | Purification method of 1-propylene-1, 3-sultone |
| CN116283488A (en) * | 2023-03-17 | 2023-06-23 | 唐山偶联硅业有限公司 | Preparation method of propargyl alcohol |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180432A (en) * | 2018-11-02 | 2019-01-11 | 浙江工业大学 | A kind of preparation of chlorallylene alcohol and separation method |
| CN110105326A (en) * | 2019-02-26 | 2019-08-09 | 武汉松石科技股份有限公司 | A kind of preparation method of 1,3- propane sultone |
| CN114149404A (en) * | 2020-09-07 | 2022-03-08 | 石家庄圣泰化工有限公司 | Purification method of 1-propylene-1, 3-sultone |
| CN112358416A (en) * | 2020-11-03 | 2021-02-12 | 北京科技大学 | Preparation method of trans-3-chloro-2-propenyl hydroxylamine |
| CN116283488A (en) * | 2023-03-17 | 2023-06-23 | 唐山偶联硅业有限公司 | Preparation method of propargyl alcohol |
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Application publication date: 20180109 |