CN104328453A - Method for paired electrosynthesis of benzaldehyde and tetramethyl piperidinol - Google Patents
Method for paired electrosynthesis of benzaldehyde and tetramethyl piperidinol Download PDFInfo
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- CN104328453A CN104328453A CN201410612405.0A CN201410612405A CN104328453A CN 104328453 A CN104328453 A CN 104328453A CN 201410612405 A CN201410612405 A CN 201410612405A CN 104328453 A CN104328453 A CN 104328453A
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- tetramethylpiperidinol
- pure water
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Abstract
The invention relates to a method for preparing benzaldehyde and tetramethyl piperidinol and particularly relates to a method for paired electrosynthesis of benzaldehyde and tetramethyl piperidinol. The method comprises the following steps: installing a Nafion117 positive ion membrane on an H type diaphragm electrolytic cell; adding pure water, HaOH and benzyl alcohol into an anode pond and stirring till the components are fully dissolved and uniformly mixed; adding an ethanol solution, NaOH and tetramethyl piperidone into the cathode pond and stirring till the components are fully dissolved and uniformly mixed, maintaining the temperature of the anode and cathode ponds at 25 DEG C by virtue of a thermostatic waterbath for electrolysis, and then obtaining benzaldehyde and tetramethyl piperidinol by filtering, distilling and separating steps and the like.
Description
Technical field
The present invention relates to a kind of method preparing phenyl aldehyde and tetramethylpiperidinol, especially a kind of paired electrosynthesis method adopting electrolysis tech simultaneously to prepare phenyl aldehyde and tetramethylpiperidinol.
Technical background
Phenyl aldehyde and tetramethylpiperidinol are all important fine-chemical intermediate and raw material, phenyl aldehyde is widely used in the fields such as medicine, food, agricultural chemicals dyestuff, and tetramethylpiperidinol is then a kind of important matrix of biosynthesis block amine photostabilizer (being called for short HALS).
Electrochemical method for synthesizing is because of its mild condition, simple to operate, environmentally safe, be called green synthesis techniques, especially paired electrosynthesis technology, it not only has outside the general advantage of electrosynthesis, but also has current efficiency and spatiotemporal efficiency is high, production cost is low, save the concern of the advantage such as electric energy and extremely people.
The electrosynthesis method of current phenyl aldehyde mainly with Mn (III)/Mn (II), Ce (IV)/Ce (III) plasma to for medium, metallic lead is the indirect electrooxidation toluene method of anode, as " modern chemical industry ", 1996, (6): P
33-35" the Indirect Electrooxidation synthesizing benzaldehyde " of upper report, also has and adopts metallic nickel to be anode, and in basic solution, phenyl aldehyde prepared by selective oxidation phenylcarbinol, as " chemical journal ", and 2010,68(16): P
1649-1652" in basic solution, the selectivity catalytic oxidation of phenylcarbinol is studied " of upper report; And about the synthetic method of tetramethylpiperidinol be mainly raw material with tetramethylpiperidone, be prepared by catalytic hydrogenation, chemical reduction or electrochemical reduction method, wherein catalytic hydrogenation is the industrial method preparing tetramethylpiperidinol at present, although its reaction yield is up to 96.5%, but need shortening under high temperature, high pressure, high to equipment requirements, and there is certain danger in reaction process; And its electrosynthesis method bibliographical information mainly obtains with electro-reduction tetramethylpiperidone, as " fine chemistry industry ", 2003,20(8): P
: 483-495" electrochemical process synthesis 2,2,6, the 6-tetramethyl--4-piperidine alcohols " of upper publication etc.
From existing documents and materials report, the electrosynthesis method of phenyl aldehyde and tetramethylpiperidinol is mainly based on one pole electrosynthesis, and this method is compared with paired electrosynthesis technology, not only current efficiency and spatiotemporal efficiency lower, and production cost and energy consumption also all higher.Therefore, the method adopting paired electrosynthesis technology to research and develop synthesizing benzaldehyde and tetramethylpiperidinol further has certain realistic meaning.
Summary of the invention
Technical problem to be solved by this invention is: how to adopt phenylcarbinol and tetramethylpiperidone synthesizing benzaldehyde and tetramethylpiperidinol simultaneously, and then provides a kind of method of paired electrolysis synthesizing benzaldehyde and tetramethylpiperidinol simultaneously.
The technical solution adopted in the present invention is: a kind of method of paired electrosynthesis phenyl aldehyde and tetramethylpiperidinol, follows these steps to carry out:
Step one, H type diaphragm sell is loaded onto Nafion117 cationic membrane, in anode pool, add the pure water of 40 unit milliliters, the NaOH of 1.0 unit of gram, the phenylcarbinol of 5.2 unit milliliters, stir and make it dissolve completely and mix; Add the ethanolic soln of 40 unit milliliters 30%, the NaOH of 0.8 unit of gram, the tetramethylpiperidone of 3.1 unit of gram in cathode pool, stirring and make it dissolve completely and mix, is 25 DEG C by water bath with thermostatic control holding anode pond and cathode pool temperature;
Step 2, be anode with NiOOH, zinc metal sheet is negative electrode, and Faradaic current is set as 0.3A, constant-current electrolysis 6432 seconds, and electrolysis is complete;
Step 3, in anolyte, acid neutralization is 2-3 to pH, extracts, separatory, wash the NaOH in organic phase with water, then use anhydrous Na by ethyl acetate
2sO
4carry out drying, through being separated, distilling, obtained products benzene formaldehyde;
Step 4, catholyte proceed in beaker, are neutralized to neutrality with dilute hydrochloric acid, distill, until all steamed by ethanol, then add cold water under agitation to crystallization to remaining liquid, filter and obtain tetramethylpiperidinol.
As a kind of optimal way: step one Nafion117 cationic membrane used uses advance row relax, treating processes be Nafion117 cationic membrane is put into 5% H
2o
2boil 30 minutes in the aqueous solution, cleaned with pure water after cooling, then put into the H of 0.5 mol/L
2sO
4boil one hour in solution, then clean with pure water, finally soak 24 hours in pure water, change water therebetween three times.
As a kind of optimal way: the NiOOH electrode in step 2 and zinc metal sheet electrode production process are, nickel foam is cut into pole plate, successively with alcohol, dilute hydrochloric acid cleaning, clean with pure water, be then working electrode with nickel foam, saturated calomel electrode is reference electrode again, nickel plate is supporting electrode, adopt Faradaic current to be that 0.3 A carries out constant-current electrolysis until electrode surface generates the NiOOH of black, be NiOOH electrode, NiSO in electrolytic solution used
4concentration is 0.1 mol/L, CH
3cOONa concentration is 0.1 mol/L, NaOH concentration is 0.5 mol/L; Be the zinc metal sheet electrode sand papering light of 99% by purity, with alcohol washes, then use rare Na
2cO
3cleaning, finally washes with water clean, is zinc metal sheet electrode.
As a kind of optimal way: extract by ethyl acetate in step 3, separatory obtains organic phase, and then by ethyl acetate to aqueous phase extracting twice, merge the organic phase obtained for three times.
As a kind of optimal way: the tetramethylpiperidinol obtained step 4, carry out secondary recrystallization with after dissolve with ethanol, the tetramethylpiperidinol that obtained purity is higher.
The invention has the beneficial effects as follows: obtain phenyl aldehyde and tetramethylpiperidinol two kinds of high value-added products in yin, yang the two poles of the earth simultaneously, and anodic current efficiency is between 78.8% ~ 86.5%, cathode efficiency is between 58.4% ~ 69.5%, and the total current of electrolytic reaction is most effective reaches more than 155%; Compared with one pole electrosynthesis method, the method not only can obtain a kind of product more, and total current efficiency and spatiotemporal efficiency are improved all largely, and production cost and energy consumption also reduce greatly, its remarkable in economical benefits.
Embodiment
embodiment 1
The pre-treatment of cationic membrane:
Nafion117 cationic membrane is put into the H of 5%
2o
2boil 30 minutes in the aqueous solution, cleaned with pure water after cooling.Then the H of 0.5 mol/L is put into
2sO
4boil one hour in solution, then clean with pure water, finally soak 24 hours in pure water, change water therebetween three times, stand-by.
The preparation of electrode and pre-treatment
Anode: nickel foam is cut into 2 × 2.5 rectangles, successively with alcohol, dilute hydrochloric acid cleaning, then cleans with pure water, stand-by; Take nickel foam as working electrode, saturated calomel electrode is reference electrode, and nickel plate is supporting electrode, and adopt Faradaic current to be 0.3 A, electrolytic solution consists of 0.1 mol/L NiSO
4+ 0.1 mol/L CH
3cOONa+0.5 mol/L NaOH, carries out constant-current electrolysis until electrode surface generates the NiOOH of black, is NiOOH electrode, stand-by.
Negative electrode: by purity be 99% zinc metal sheet be cut into 2.5 × 2 rectangles, with sand papering light, with alcohol washes, then use rare Na
2cO
3cleaning, finally washes with water clean, stand-by.
The cationic exchange membrane handled well is placed in the diaphragm sell of H type, Zn sheet is adopted to be negative electrode, NiOOH is anode, 40mL pure water and solid NaOH 1.0g is added in anode pool, ethanolic soln and the solid NaOH 0.8g of 40mL 30% is added in cathode pool, starting induction stirring instrument makes it dissolve completely, then in anode pool, phenylcarbinol 5.2mL is added, tetramethylpiperidone 3.10g is added in cathode pool, stir after 5 minutes, by water bath with thermostatic control, reacting liquid temperature is adjusted to 25 DEG C, Faradaic current is set as 0.3A, constant-current electrolysis 6432s; Electrolysis is complete, and anolyte is added H
2sO
4solution is neutralized to pH and proceeds in 100mL separating funnel after 2-3, with ethyl acetate carry out extracting, separatory, again to aqueous phase back extraction twice, combined ethyl acetate, washes three times (each 10mL), by anhydrous sodium sulphate, drying and dehydrating is carried out to it, then after being separated, distilling, obtain products benzene formaldehyde, adopt reversed-phased high performace liquid chromatographic to analyze product, its purity can reach more than 99.0%, and the yield of phenyl aldehyde is that 86.5%(adopts rp-hplc determination product yield.Liquid phase chromatogram condition is Shim-pack VP-ODS C
18chromatographic column (150 × 4.6um), moving phase is acetonitrile: water=55:45, flow velocity 0.8mL/min, column temperature 40 DEG C, and determined wavelength is 250nm, and sample size is 20.00 μ L.); Catholyte then proceeds in beaker, neutrality is neutralized to dilute hydrochloric acid, then carry out distilling, concentrating, when cut temperature becomes 100 DEG C, namely ethanol all steam, add cold water under agitation, product tetramethylpiperidinol crystallization, get appropriate supernatant liquor, adopt the amount of remaining tetramethylpiperidone in this solution of high effective liquid chromatography for measuring, calculating its transformation efficiency is the amount that 69.5%(adopts remaining raw material tetramethylpiperidone in high effective liquid chromatography for measuring filtrate, by the transformation efficiency obtaining product tetramethylpiperidinol that converts.Liquid phase chromatogram condition is Hypersil BDS C
18chromatographic column (250 × 4.6um, 5um), moving phase is methyl alcohol, flow velocity 0.8mL/min, column temperature 30 DEG C, and determined wavelength is 221nm, and sample size is 20.00 μ L.), and the total current efficiency of whole electrolytic reaction reaches 156.0%.
embodiment 2
Experimentation only changes the add-on of ethanol in cathode pool, and its concentration brings up to 40% by 30%, and all the other are with embodiment 1.Experimental result shows, the yield of phenyl aldehyde is 83.2%, and the transformation efficiency of tetramethylpiperidone is 65.3%, the total current efficiency of whole electrolytic reaction be 148.5%. it can thus be appreciated that, the reduction reaction of tetramethylpiperidone is accelerated by the volume fraction increasing ethanol in catholyte, improve the transformation efficiency of product, its effect is also not obvious.Illustrate in cathode pool and add the reduction reaction that 30% ethanolic soln can meet tetramethylpiperidone, meanwhile, because the liberation of hydrogen side reaction of negative electrode also can generate OH
-, and be conducive to the reduction of tetramethylpiperidone.
embodiment 3
Experimentation only changes the add-on of tetramethylpiperidone in cathode pool, reduces to 2.33g by 3.10g, and all the other are with embodiment 1.Experimental result shows, the yield of phenyl aldehyde is 78.8%, the transformation efficiency of tetramethylpiperidone is then 58.4%, the total current efficiency of its electrolytic reaction is that 137.2%. is compared with embodiment 1, the total current efficiency of electrolytic reaction reduces about 15%, illustrates when in catholyte, the concentration of tetramethylpiperidone is lower, and the consumption of electric energy is not only for the reduction of tetramethylpiperidone, also may be used for the precipitation of electrode side reaction hydrogen, thus cause the current efficiency of negative electrode to decrease.
Claims (5)
1. a method for paired electrosynthesis phenyl aldehyde and tetramethylpiperidinol, is characterized in that following these steps to carry out:
Step one, H type diaphragm sell is loaded onto Nafion117 cationic membrane, in anode pool, add the pure water of 40 unit milliliters, the NaOH of 1.0 unit of gram, the phenylcarbinol of 5.2 unit milliliters, stir and make it dissolve completely and mix; Add the ethanolic soln of 40 unit milliliters 30%, the NaOH of 0.8 unit of gram, the tetramethylpiperidone of 3.1 unit of gram in cathode pool, stirring and make it dissolve completely and mix, is 25 DEG C by water bath with thermostatic control holding anode pond and cathode pool temperature;
Step 2, be anode with NiOOH, zinc metal sheet is negative electrode, and Faradaic current is set as 0.3A, constant-current electrolysis 6432 seconds, and electrolysis is complete;
Step 3, in anolyte, acid neutralization is 2-3 to pH, extracts, separatory, wash the NaOH in organic phase with water, then use anhydrous Na by ethyl acetate
2sO
4carry out drying, through being separated, distilling, obtained products benzene formaldehyde;
Step 4, catholyte proceed in beaker, are neutralized to neutrality with dilute hydrochloric acid, distill, until all steamed by ethanol, then add cold water under agitation to crystallization to remaining liquid, filter and obtain tetramethylpiperidinol.
2. the method for a kind of paired electrosynthesis phenyl aldehyde according to claim 1 and tetramethylpiperidinol, is characterized in that: step one Nafion117 cationic membrane used uses advance row relax, treating processes be Nafion117 cationic membrane is put into 5% H
2o
2boil 30 minutes in the aqueous solution, cleaned with pure water after cooling, then put into the H of 0.5 mol/L
2sO
4boil one hour in solution, then clean with pure water, finally soak 24 hours in pure water, change water therebetween three times.
3. the method for a kind of paired electrosynthesis phenyl aldehyde according to claim 1 and tetramethylpiperidinol, it is characterized in that: the NiOOH electrode in step 2 and zinc metal sheet electrode production process are, nickel foam is cut into pole plate, successively with alcohol, dilute hydrochloric acid cleaning, clean with pure water again, then be working electrode with nickel foam, saturated calomel electrode is reference electrode, nickel plate is supporting electrode, Faradaic current is adopted to be that 0.3 A carries out constant-current electrolysis until electrode surface generates the NiOOH of black, be NiOOH electrode, NiSO in electrolytic solution used
4concentration is 0.1 mol/L, CH
3cOONa concentration is 0.1 mol/L, NaOH concentration is 0.5 mol/L; Be the zinc metal sheet electrode sand papering light of 99% by purity, with alcohol washes, then clean with rare Na2CO3, finally wash with water clean, be zinc metal sheet electrode.
4. the method for a kind of paired electrosynthesis phenyl aldehyde according to claim 1 and tetramethylpiperidinol, it is characterized in that: extract by ethyl acetate in step 3, separatory obtains organic phase, and then by ethyl acetate to aqueous phase extracting twice, merges the organic phase obtained for three times.
5. the method for a kind of paired electrosynthesis phenyl aldehyde according to claim 1 and tetramethylpiperidinol, is characterized in that: the tetramethylpiperidinol obtained step 4, carries out secondary recrystallization with after dissolve with ethanol, the tetramethylpiperidinol that obtained purity is higher.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1322859A (en) * | 2001-04-17 | 2001-11-21 | 华东理工大学 | Paired electrolysis procss of preparing glyoxalic acid |
| CN101078128A (en) * | 2007-06-30 | 2007-11-28 | 广西壮族自治区化工研究院 | Method and device for preparing mannitol and potassium iodate by electrolysis in pairs |
| CN103628086A (en) * | 2013-12-04 | 2014-03-12 | 太原理工大学 | Method for paired electrolysis during synthesis of benzaldehyde, sorbitol and mannitol |
-
2014
- 2014-11-05 CN CN201410612405.0A patent/CN104328453A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1322859A (en) * | 2001-04-17 | 2001-11-21 | 华东理工大学 | Paired electrolysis procss of preparing glyoxalic acid |
| CN101078128A (en) * | 2007-06-30 | 2007-11-28 | 广西壮族自治区化工研究院 | Method and device for preparing mannitol and potassium iodate by electrolysis in pairs |
| CN103628086A (en) * | 2013-12-04 | 2014-03-12 | 太原理工大学 | Method for paired electrolysis during synthesis of benzaldehyde, sorbitol and mannitol |
Non-Patent Citations (1)
| Title |
|---|
| 刘欣等: "电化学法合成2 ,2 ,6 ,6-四甲基-4-哌啶醇", 《精细化工》, vol. 20, no. 8, 15 August 2003 (2003-08-15) * |
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Application publication date: 20150204 |