CN102382122A - Preparation technology of 2,5-dioctyl phthalate-3,4-ethylenedioxy thiophene - Google Patents
Preparation technology of 2,5-dioctyl phthalate-3,4-ethylenedioxy thiophene Download PDFInfo
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- CN102382122A CN102382122A CN2011102766986A CN201110276698A CN102382122A CN 102382122 A CN102382122 A CN 102382122A CN 2011102766986 A CN2011102766986 A CN 2011102766986A CN 201110276698 A CN201110276698 A CN 201110276698A CN 102382122 A CN102382122 A CN 102382122A
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Abstract
The invention relates to a preparation technology of 2,5-dioctyl phthalate-3,4-ethylenedioxy thiophene, comprising the following steps of: Step 1, carrying out esterification reaction to obtain dimethyl thioglycolate; Step 2, carrying out condensation reaction, etherification reaction and hydrolysis reaction to obtain 2,5-dioctyl phthalate-3,4-ethylenedioxy thiophene. The preparation technology provided by the invention specifically comprises the following steps of: adding dimethyl thioglycolate in a reaction kettle into an ethanol solution of sodium ethoxide, carrying out condensation reaction with diethyl oxalate under the refluxing condition for 3-4 hours, adjusting acid and distilling a solvent after the reaction; adding dichloroethane, a toluene solvent and a triethylamine catalyst, carrying out etherification reaction at the temperature of 80-90 DEG C for 6-12 hours, distilling the toluene solvent and dichloroethane, and washing; adding an alkaline solution and carrying out hydrolysis reaction under the refluxing condition, followed by acidification, air pump filtration, washing and drying to obtain the product. As the reactions are carried out by a one-pot method and the synthetic technology is optimized and improved, the total yield of the product reaches over 80%.
Description
Technical field
The invention belongs to fine chemistry industry organic synthesis field, relate to a kind of 2,5-dioctyl phthalate-3, the preparation technology of 4-enedioxy thiophene.
Background technology
2,5-dioctyl phthalate-3,4-enedioxy thiophene, outward appearance is a light yellow solid, it is used for preparing 3 as a kind of electron chemistry organic intermediate, 4-enedioxy thiophene EDOT.
In recent years; With polyaniline, polypyrrole, Polythiophene etc. is that some conductive polymerss of representative rely on its excellent characteristic to move towards market gradually; Wherein gather (3,4-enedioxy thiophene) with its specific conductivity height, environment Heat stability is good, be difficult for characteristic such as oxidized and more become nova bright in the organic conductive polymkeric substance.Along with the solution of PEDOT processing problems, PEDOT has obtained the extensive concern and the application of every profession and trade each side especially.In traditional three big conductive polymers-polyanilines, polypyrrole and the Polythiophene, because the carinogenicity of polyaniline, its application is greatly limited, the market of fading out basically; Polythiophene is because of its performance more superior than polypyrrole, good processing properties more, low production cost day by day, the existing a few days ago trend that replaces polypyrrole.The PEDOT application development of Japan is very swift and violent over nearly 3 years, and the influence that Taiwan receives the Japanese fast development impetus also begins develop rapidly, and domestic existing part enterprise takes up to study the application of PEDOT.
At present, 2,5-dioctyl phthalate-3,4-enedioxy thiophene synthetic all is to be that starting raw material synthesizes with sulfo-two sweet acid mostly, but relevant report technology for a long time is comparatively complicated, and it is long that each goes on foot reaction time, and yield is lower, thus it is very difficult to be converted into industriallization.Publication number is a Synthetic 2 in the patent of invention of CN101062927A, 5-dioctyl phthalate-3, and the total yield of 4-enedioxy thiophene is merely 52.8%.
Summary of the invention
Technical problem to be solved by this invention is the deficiency to prior art: existing preparation 2, and 5-dioctyl phthalate-3, the method raw materials cost of 4-enedioxy thiophene is high, low, the complex process of product yield; And provide that a kind of technology is easy, yield is high 2,5-dioctyl phthalate-3, the preparation technology of 4-enedioxy thiophene; It adopts " one kettle way " to react; And synthesis technique is optimized and improves, can avoid the loss of product in the last handling process, the total recovery of product is reached more than 80%.
It is to be starting raw material with the ethyl chloroacetate, makes through esterification, condensation, etherificate, hydrolysis reaction, and reaction formula is:
The present invention is that starting raw material is realized through following technical scheme with the ethyl chloroacetate, specifically comprises the steps:
The first step: esterification:
Add earlier ethyl chloroacetate, salt phase-transfer catalyst and inert solvent in reaction kettle, then under agitation condition with Na
2Splash into after S is dissolved in water in advance in the above-mentioned solution, 110 ~ 130 ℃ of reaction 3 ~ 6h, reaction finish after filters, underpressure distillation, the fraction of collection under 160 ~ 170 ℃/0.0lMPa obtains sulfo-two sweet diethyl phthalates;
Second step: condensation, etherificate, hydrolysis reaction:
(1) in reaction kettle, the sweet diethyl phthalates of sulfo-two are added in the ethanolic soln of sodium ethylates, with diethyl oxalate condensation reaction 3-4h under refluxad, reaction finish back acid adjustment, distilling off solvent;
(2) then in aforesaid reaction vessel, add ethylene dichloride, toluene solvant, triethylamine catalyzer, 80-90 ℃ of etherification reaction 6-12h distills out toluene solvant and ethylene dichloride, and washing obtains 2,5-diethyl dicarboxylate-3,4-enedioxy thiophene;
(3) in aforesaid reaction vessel, add the basic soln reaction that under refluxad is hydrolyzed again, react and finish after obtain hydrolysate 2,5-dioctyl phthalate-3,4-enedioxy thiophene after the acidifying, suction filtration, washing, drying.
In the such scheme, as improvement, in the first step esterification, said ethyl chloroacetate and Na
2The mass ratio of S is 0.36: 0.13-0.2, described salt phase-transfer catalyst are one or both the mixing in trityl chlorination sulfosalt catalyzer and the normal-butyl pyridinium salt, and consumption is ethyl chloroacetate and Na
2The S gross weight and 0.1%-0.5wt%.Said step also is included in filters the back with sherwood oil or ethyl acetate extraction filter cake, carries out underpressure distillation after extraction liquid after the extraction and filtrating are merged.
Said Na
2The S employing adds water to the mode that splashes into again after the dissolving in advance can make the full and uniform contact of reactant; Reaction can fully be carried out; Add the salt phase-transfer catalyst simultaneously and use toluene double as inert solvent and the impermeable agent of handling through molecular sieve drying; Can play impermeable role completely through the mode of phase transition, make ethyl chloroacetate at Na
2The problem that hydrolysis takes place in the strong basicity system of S is resolved.Through this process is optimized and improves, the ethyl chloroacetate reaction yield is reached more than 90%.
In the such scheme, as improvement, second step was that the step in condensation, etherificate, the hydrolysis reaction is:
In reaction kettle, under agitation condition, be that the ethanolic soln of the sodium ethylate of 15wt%-18wt% mixes with sulfo-two sweet diethyl phthalates and concentration; Be cooled to 0-10 ℃ then, after wherein dripping diethyl oxalate, dropwising, progressively accelerate stirring velocity again to 400-600r/min; Be warming up to backflow simultaneously; Stirring reaction 3-4h under refluxad, the acid adjustment neutralization steams ethanol; By weight, said sulfo-two sweet diethyl phthalates: sodium ethylate: diethyl oxalate is 0.28: 0.21-0.23: 0.22-0.24;
Then in aforesaid reaction vessel under agitation condition adds the mixture of triethylamine catalyzer and ethylene dichloride, add toluene solvant then, progressively accelerate stirring velocity to 400-600 r/min; 80-90 ℃ of stirring reaction 6-12h; After reaction finishes, steam and remove toluene solvant and ethylene dichloride, washing; By weight, said sulfo-two sweet diethyl phthalates: ethylene dichloride: triethylamine is 0.28: 0.25-0.27:0.01-0.02;
Then in aforesaid reaction vessel, add the NaOH aqueous solution of 10wt%-14wt%, under refluxad react 1.5-2h, after the hydrolysis fully, acidifying, suction filtration, washing, drying obtain hydrolysate 2,5-dioctyl phthalate-3,4-enedioxy thiophene.
Second step of this patent is carried out " one kettle way " processing to condensation, etherificate, three step of hydrolysis building-up reactions, makes these three steps under the condition of not transformation reaction still, carry out successive reaction, has avoided the loss in per step independent process; And reaction proceeds to etherificate during the stage, directly adds ethylene dichloride and sulfo-two sweet diethyl phthalates react, and can avoid product that aforementioned condensation reaction generates in the loss of passing through under the situation such as blanking, aftertreatment; When proceeding to hydrolysis reaction, effective constituent directly is hydrolyzed under reasonable process conditions, so, this step total recovery is reached more than the 85-90%.The present invention passes through control material consumption in the reaction of second step " one kettle way "; Technologies such as temperature of reaction, reaction times, stirring velocity, tear drop mode; Reduced aftertreatment middle-chain simultaneously; Avoided loss of active ingredients, made entire reaction more thorough more fully, yield can be increased to 85-90%.
According to the invention 2,5-dioctyl phthalate-3, the preparation method of 4-enedioxy thiophene has following characteristics:
(1) yield is higher, and total recovery can reach more than 80%.
(2) solvent can be recycled in the reaction, does not contain other impurity component.
(3) starting material are easy to get, and the catalyst system therefor consumption is few, price is low, are fit to production.
(4) adopt " one kettle way " to react continuously, synthesis technique is simple, has reduced by two steps than traditional method, has practiced thrift the PT, reduces each the step loss in the technical process, has improved yield, has reduced cost.
Description of drawings
Fig. 1 is the infrared spectrogram of embodiment 1 synthetic sulfo-two sweet diethyl phthalates, wherein X-coordinate wavenumber (cm
-1) be wave number, ordinate zou Transmission (%) is transmitance (%).
Fig. 2 is embodiment 1 synthetic 2,5-dioctyl phthalate-3, the infrared spectrogram of 4-enedioxy thiophene, wherein X-coordinate wavenumber (cm
-1) be wave number, ordinate zou Transmission (%) is transmitance (%).
Embodiment
Embodiment 1
(1) sulfo-two sweet diethyl phthalates is synthetic
In the 500ml four-hole boiling flask of stirring, prolong, TM is housed; Add ethyl chloroacetate 122.5g (1mol) earlier; Add 0.4g trityl chlorination sulfosalt catalyzer then; Add the toluene solvant 200ml that handled through molecular sieve drying again, mix, again under agitation condition with Na
2S 78g (Na
2S calculates by purity 60%) be dissolved in the 100g water,, temperature in 1h, slowly is added drop-wise in the four-hole boiling flask postheating to 120 ℃ reaction 3h when being 15-20 ℃ with tap funnel; After reaction finished, cooling, filtration were used petroleum ether extraction with filter cake; And extraction liquid mixed the back underpressure distillation with filtrating, the fraction of collection under the 160-170 ℃/0.0lMPa obtains sulfo-two sweet diethyl phthalate 94.2g; It is carried out GC analyze product purity 99%, sulfo-two sweet diethyl phthalate yields 91.4%.
Carry out IR spectroscopy (adopting the FTIR920 type Fourier transformation infrared spectrometer of Tianjin Tuopu Equipment Co., Ltd.) figure and see Fig. 1.
Product results of IR: 2980 ㎝
-1Be CH
2And CH
3The stretching vibration absorption peak; 1732 ㎝
-1Stretching vibration absorption peak for C=O; 1440-1410 ㎝
-1Be S-CH
2Absorption peak; 900-1250 ㎝
-1Absorption peak for C-O-C; The constitutional features that meets sulfo-two sweet diethyl phthalates.
(2) 2,5-dioctyl phthalate-3,4-enedioxy thiophene synthetic
In the 500ml four-hole boiling flask of stirring, prolong, TM is housed, under agitation condition, add above-mentioned carboxylate sulfo-two sweet diethyl phthalate 41.2g (0.2mol) respectively, contain the ethanolic soln 200ml of sodium ethylate 30.8g (0.45mol); Mix, be cooled to 5 ℃ then, in 0.5h, drip diethyl oxalate 32.2g (0.22mol); Progressively accelerate stirring velocity after dropwising to 400-600r/min, be warming up to backflow simultaneously, under refluxad keep 3h; Carry out condensation reaction; After reaction finishes, first acid adjustment neutralization, redistillation goes out ethanol;
Then directly in above-mentioned reaction solution, slowly drip the mixture of triethylamine catalyzer 1.5g and ethylene dichloride 39.5g (0.21mol), add the toluene solvant of crossing through dry, progressively accelerate stirring velocity to 400-600r/min; And simultaneously temperature is remained on 80-90 ℃ of reaction 6h; Obtain 2,5-diethyl dicarboxylate-3,4-enedioxy thiophene; Distill out ethylene dichloride and toluene, washing;
In above-mentioned reaction solution, directly add the NaOH aqueous solution 350ml of 10wt% again, under agitation condition, be heated to back flow reaction 1.5h, reaction finishes the back with dense HCl neutralization; After suction filtration, washing, drying, obtain hydrolysate 2,5-dioctyl phthalate-3,4-enedioxy thiophene 41.6g; It is carried out liquid-phase chromatographic analysis, and product purity is 99%, 2; 5-dioctyl phthalate-3, the yield of 4-enedioxy thiophene is 88.3%.
Carry out IR spectroscopy (adopting the FTIR920 type Fourier transformation infrared spectrometer of Tianjin Tuopu Equipment Co., Ltd.) figure and see Fig. 2.
Product results of IR: 2930 ㎝
-1Be C-H stretching vibration absorption peak; 1700 ㎝
-1Stretching vibration absorption peak for C=O; 1436 ㎝
-1Be S-CH
2Absorption peak; 1268 ㎝
-1Absorption peak for the C-O-C medium tenacity; 1400-1500 ㎝
-1Absorption band for aromatic nucleus C skeleton; 3560 ㎝
-1Be-OH absorption peak, meet 2,5-dioctyl phthalate-3,4-vinyl dioxy thiophene-constitutional features.
To sum up, 2,5-dioctyl phthalate-3, the total recovery of 4-enedioxy thiophene is 80.7%.
Embodiment 2
(1) sulfo-two sweet diethyl phthalates is synthetic
In the 500ml four-hole boiling flask of stirring, prolong, TM is housed; Add earlier ethyl chloroacetate 122.5g (1mol), add normal-butyl pyridinium salt catalyzer 0.4g then, and the toluene solvant 200ml that handled through molecular sieve drying; Mix, again under agitation condition with Na
2S 78g (Na
2S calculates by purity 60%) be dissolved in the 100g water,, temperature in 1h, slowly is added drop-wise in the four-hole boiling flask postheating to 120 ℃ reaction 3h when being 15-20 ℃ with tap funnel; After reaction finished, cooling, filtration were used petroleum ether extraction with filter cake; And extraction liquid mixed the back underpressure distillation with filtrating, the fraction of collection under the 160-170 ℃/0.0lMPa obtains sulfo-two sweet diethyl phthalate 91.8g; It is carried out GC analyze product purity 99%, sulfo-two sweet diethyl phthalate yields 89.1%.
(2) 2,5-dioctyl phthalate-3,4-enedioxy thiophene synthetic
2,5-dioctyl phthalate-3,4-enedioxy thiophene synthetic referring to the foregoing description 1.
Embodiment 3
(1) sulfo-two sweet diethyl phthalates is synthetic
In the 500ml four-hole boiling flask of stirring, prolong, TM is housed, add ethyl chloroacetate 122.5g (1mol) earlier, add normal-butyl pyridinium salt 0.8g then; And through the toluene solvant 200ml that molecular sieve drying was handled, mix, under agitation condition, Na2S 78g (Na2S calculates by purity 60%) is dissolved in the 100g water again; When temperature is 15-20 ℃, in 1h, slowly be added drop-wise in the four-hole boiling flask with tap funnel, postheating to 120 ℃ reaction 3h is after reaction finishes; Cooling, filtration are used petroleum ether extraction with filter cake, and extraction liquid is mixed the back underpressure distillation with filtrating; Collect the fraction under the 160-170 ℃/0.0lMPa, obtain sulfo-two sweet diethyl phthalate 92.4g, it is carried out GC analyze; Product purity 99%, sulfo-two sweet diethyl phthalate yields 89.7%.
(2) 2,5-dioctyl phthalate-3,4-enedioxy thiophene synthetic
2,5-dioctyl phthalate-3,4-enedioxy thiophene synthetic referring to the foregoing description 1.
Claims (4)
1. one kind 2,5-dioctyl phthalate-3, the preparation technology of 4-enedioxy thiophene, it is characterized in that: it may further comprise the steps:
The first step: esterification:
Add earlier ethyl chloroacetate, salt phase-transfer catalyst and inert solvent in reaction kettle, then under agitation condition with Na
2Splash into after S is dissolved in water in advance in the above-mentioned solution, 110 ~ 130 ℃ of reaction 3 ~ 6h, reaction finish after filters, underpressure distillation, the fraction of collection under 160 ~ 170 ℃/0.0lMPa obtains sulfo-two sweet diethyl phthalates;
Second step: condensation, etherificate, hydrolysis reaction:
(1) in reaction kettle, the sweet diethyl phthalates of sulfo-two are added in the ethanolic soln of sodium ethylates, with diethyl oxalate condensation reaction 3-4h under refluxad, reaction finish back acid adjustment, distilling off solvent;
(2) then in aforesaid reaction vessel, add ethylene dichloride, toluene solvant, triethylamine catalyzer, 80-90 ℃ of etherification reaction 6-12h distills out toluene solvant and ethylene dichloride, and washing obtains 2,5-diethyl dicarboxylate-3,4-enedioxy thiophene;
(3) in aforesaid reaction vessel, add the basic soln reaction that under refluxad is hydrolyzed again, react and finish after obtain hydrolysate 2,5-dioctyl phthalate-3,4-enedioxy thiophene after the acidifying, suction filtration, washing, drying.
2. according to claim 12,5-dioctyl phthalate-3, the preparation technology of 4-enedioxy thiophene is characterized in that: said ethyl chloroacetate and Na
2The mass ratio of S is 0.36: 0.13-0.2, described salt phase-transfer catalyst are one or both the mixing in trityl chlorination sulfosalt catalyzer and the normal-butyl pyridinium salt, and consumption is ethyl chloroacetate and Na
2The S gross weight and 0.1%-0.5wt%.
3. according to claim 12; 5-dioctyl phthalate-3; The preparation technology of 4-enedioxy thiophene is characterized in that: also be included in the said the first step esterification and filter the back with sherwood oil or ethyl acetate extraction filter cake, carry out underpressure distillation after extraction liquid after the extraction and filtrating are merged.
4. according to claim 12,5-dioctyl phthalate-3, the preparation technology of 4-enedioxy thiophene is characterized in that: the concrete steps in said second step are:
In reaction kettle, under agitation condition, be that the ethanolic soln of the sodium ethylate of 15wt%-18wt% mixes with sulfo-two sweet diethyl phthalates and concentration; Be cooled to 0-10 ℃ then, after wherein dripping diethyl oxalate, dropwising, progressively accelerate stirring velocity again to 400-600r/min; Be warming up to backflow simultaneously; Stirring reaction 3-4h under refluxad, the acid adjustment neutralization steams ethanol; By weight, said sulfo-two sweet diethyl phthalates: sodium ethylate: diethyl oxalate is 0.28: 0.21-0.23: 0.22-0.24;
Then in aforesaid reaction vessel under agitation condition adds the mixture of triethylamine catalyzer and ethylene dichloride, add toluene solvant then, progressively accelerate stirring velocity to 400-600 r/min; 80-90 ℃ of stirring reaction 6-12h; After reaction finishes, steam and remove toluene solvant and ethylene dichloride, washing; By weight, said sulfo-two sweet diethyl phthalates: ethylene dichloride: triethylamine is 0.28: 0.25-0.27:0.01-0.02;
Then in aforesaid reaction vessel, add the NaOH aqueous solution of 10wt%-14wt%, under refluxad react 1.5-2h, after the hydrolysis fully, acidifying, suction filtration, washing, drying obtain hydrolysate 2,5-dioctyl phthalate-3,4-enedioxy thiophene.
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| CN104370943A (en) * | 2014-11-03 | 2015-02-25 | 南开大学 | Preparation method and application of [Cu2(HL)2(Mu2-OH)2(H2O)5] |
| CN104370943B (en) * | 2014-11-03 | 2016-08-24 | 南开大学 | A kind of [Cu2(HL)2(μ2-OH)2(H2o)5] preparation method and application |
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Application publication date: 20120321 |