CN1436877A - Paired 2,3,6-trimethyl phenol electrolyzing process of preparing 2,3,5-trimethyl hydroquinone - Google Patents
Paired 2,3,6-trimethyl phenol electrolyzing process of preparing 2,3,5-trimethyl hydroquinone Download PDFInfo
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- CN1436877A CN1436877A CN02103026.XA CN02103026A CN1436877A CN 1436877 A CN1436877 A CN 1436877A CN 02103026 A CN02103026 A CN 02103026A CN 1436877 A CN1436877 A CN 1436877A
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Abstract
The present invention is the paired 2,3,6-trimethyl phenyl electrolyzing process of pg 2,3,5-trimethyl hydroquinone. The main technological conditions includes plate-frame electrolyzer, graphite anode, nickel cathode, cationic exchange diaphragm, mixed solvent of water, alcohol and ether, electrolysis temperature 10-50 deg.c, current density smaller than 350 A.M(-2), anode solution containing TMP and small amount of catalyst, and cathode solution being the anode solution used in the previous time. The electrolyzed cathode solution as the coarse product will be treated in the subsequent conventional process. The present invention has product yield over 80%, purity of 98 % and current efficiency of 90%.
Description
The present invention is preparation vitamin-E (V
E) intermediate 2,3, the method for 5-Trimethylhydroquinone (TMHQ) belongs to the method that medicine intermediate prepares, especially paired electrolysis 2,3,6-pseudocuminol (TMP) preparation 2,3, the method of 5-Trimethylhydroquinone is applicable to the electrolytic process Synthetic 2,3, and the occasion of 5-Trimethylhydroquinone.
TMHQ English name 2,3,5-trimethylhydroquinone has another name called 2,3, and the 5-Trimethyl Hydroquinone is synthetic V
EMain intermediate, be called main ring.It and different vegetable alcohol (title side chain) condensation generate V
EV
EClaim tocopherol again, be widely used as medicament, nutrition agent and foodstuff additive.Recently, be used for fodder additives again in a large number, and the antioxidant of rubber, plastics.
Before the present invention makes, finish the prior art of reaction TMP → TMHQ and (see the Hunan chemical industry, 1999 (6): 14; Fine chemistry industry, 1998 (2): 13) three kinds of catalytic oxidation-reduction method, chemistry redox method and electrolytic process are arranged.Abroad with preceding two methods, domesticly to produce with the chemistry redox method, electrolytic process is not industrialization as yet.Catalytic oxidation-reduction and the technical process of chemistry redox method are long, side reaction is many, the three wastes are many, yield is not high.
Electrolysis legal system 2,3,5-trimethylbenzoquinone (TMBQ) had report 70 years last century, can be referring to (1) Org.syn, 1972,52:83; (2) CA74:64068P; (3) CA89:33323g.Wherein (1) generates the two sodium sulfate of oxyammonia by sulfurous gas, Sodium Nitrite and reaction of sodium bicarbonate, and electrolytic oxidation generates the two sodium sulfate of nitroso-group then.Again electrolytic solution is made oxygenant, in reacting oxidization-hydrogenation ratio 80% 4 hours with the TMP n-heptane solution below 12 ℃.(2) electrolytic preparation oxygenant and oxidizing reaction are incorporated in the electrolyzer carry out.Solution and (1) are similar, under 0 ℃, 7-8V, 3A electric current with steel electrode electrolysis 5 hours, TMBQ yield 94%.Last two indirect electrolytic oxidations owned by France, product is TMBQ.(3) be direct electrolysis method.With 5 gram TMP, 25 gram Na
2SO
4, 200ml methyl alcohol and 300ml water is made into acid electrolyte, uses the C anode, the Pb negative electrode, in the time of 30 ℃ with anode potential electrolysis in undivided cell of 1.8V.Get the mixture of TMBQ and TMHQ, total recovery only is 51.2%, current efficiency 72.6%.Do not see further report about electrolytic preparation TMHQ.
The objective of the invention is to overcome the shortcoming of prior art, provide a kind of technical process short, side reaction is few, the paired electrolysis 2,3 that the three wastes are few and yield is high, 6-pseudocuminol preparation 2,3, the method for 5-Trimethylhydroquinone.
Paired electrolysis 2,3, the method of 6-pseudocuminol is characterized in that selecting for use the plate and frame electrolyzer, and anode is with plumbous oxide or graphite, negative electrode nickel, copper, lead or its alloy, the barrier film cationic exchange membrane, anolyte is moisture, alcohol, the mixed solvent that ether constitutes, 2,3, the 6-pseudocuminol, sulfuric acid and catalyzer, water wherein, alcohol, ether three mass ratio is 9: 1～8: 1～8,2,3,6-pseudocuminol mass concentration 2-8%, h 2 so 4 concentration 1-10%, by the catalyst quality concentration 1-10 ‰ that vitriol and nonionic surface active agent constitute, catholyte is with the preceding once anolyte of electrolysis, electrolysis temperature 10-50 ℃, current density is less than 350Am
-2, anodic reaction is 2,3 in the electrolysis, the 6-pseudocuminol is oxidized to 2,3, the 5-trimethylbenzoquinone, cathodic reaction is 2,3, and the 5-trimethylbenzoquinone is reduced to 2,3, the 5-Trimethylhydroquinone, the electrolysis terminal point is determined by the 100%-130% of the theoretical electric weight of anodic reaction, catholyte is thick product, and the powder that takes a policy makes residual TMBQ further be reduced to TMHQ, decompression steams organic solvent then, and cooling, crystallization, filtration, drying get product.
The present invention is owing to adopt the paired electrolysis method, and oxidation and reduction reaction are carried out simultaneously,
(anodic oxidation)
(cathodic reduction) make total reaction TMP → TMHQ be able to one the step finish, technology is reasonable, side reaction seldom, the product purity height, the three wastes are few, total energy consumption is low, yield is more than 80%, current efficiency reaches 90%.
Now be exemplified below, embodiment 1-3 sees Table 1.
Table 1. embodiment 1-3 electrolytic condition and example 1 example 2 examples 3 solvents as a result, water: alcohol: ether (quality) 9: 8: 19: 5: 49: 2: 7TMP concentration/W% 643 acid concentrations/W% 645 catalyst concns/W ‰ 364 temperature/℃ 50 30 15 current densities/Am
-2450 350 310 current efficiency/% 75 90 89 product yields/W% 74 83 78 product purities/% 96 97 98
Embodiment 4. usefulness H type electrolyzers.Anode plumbic oxide, negative electrode are with plumbous, and barrier film adopts NF-1 type ion-exchange membrane, and electrode and diaphragm area are 0.47dm
2Get 8.0 gram TMP, successively add 70 gram alcohol, 20 gram ethers, 90 gram water, 8 gram sulfuric acid and 0.4 gram catalyzer, be made into anolyte.Catholyte is the anolyte of electrolysis last time.21 ℃ of electrolysis temperatures, bath voltage 5.2V, electric current 1.62A, electrolysis 4.8 hours.Take out catholyte, put in the flask, be heated to 50 ℃, add vat powder 2.5 grams, jam-pack.Stirring reaction 1.5-2.0 hour, make TMBQ residual in the catholyte further be reduced to TMHQ.Decompression steams organic solvent, adds 0.5 gram vat powder again, is cooled to 0 ℃, crystallization, filtration, drying.Get product 6.25 grams, purity 97%.Yield 78.1%, current efficiency 83.0%, direct current consumption 6.32kwh/kg.
Embodiment 5. electrolyzers are the same.Anode graphite, negative electrode nickel.Solvent is alcohol 60 grams, ether 30 grams, water 90 grams, sulfuric acid 4 grams, catalyzer 0.8 gram, TMP8.0 gram.29 ℃ of electrolysis temperatures.Bath voltage 4.8V, electric current 1.43A, electrolysis 5.0 hours.The electrolytic solution aftertreatment gets product 6.70 grams, purity 98%, yield 83.8%, current efficiency 90.0%, direct current consumption 5.05 kwh/kg with example 4.
Claims (1)
1, paired electrolysis 2,3,6-pseudocuminol preparation 2,3, the method of 5-Trimethylhydroquinone is characterized in that selecting for use the plate and frame electrolyzer, and anode is with plumbic oxide or graphite, negative electrode nickel, copper, lead or its alloy, the barrier film cationic exchange membrane, anolyte is moisture, alcohol, the mixed solvent that ether constitutes, 2,3, the 6-pseudocuminol, sulfuric acid and catalyzer, water wherein, alcohol, ether three mass ratio is 9: 1～8: 1～8,2,3,6-pseudocuminol mass concentration 2-8%, h 2 so 4 concentration 1-10%, by the catalyst quality concentration 1-10 ‰ that vitriol and nonionic surface active agent constitute, catholyte is with the preceding once anolyte of electrolysis, electrolysis temperature 10-50 ℃, current density is less than 350Am
-2, anodic reaction is 2,3 in the electrolysis, the 6-pseudocuminol is oxidized to 2,3, and the 5-trimethylbenzoquinone, cathodic reaction is 2,3, the 5-trimethylbenzoquinone is reduced to 2,3, the 5-Trimethylhydroquinone, the electrolysis terminal point is determined by the 100%-130% of the theoretical electric weight of anodic reaction.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN02103026.XA CN1436877A (en) | 2002-02-05 | 2002-02-05 | Paired 2,3,6-trimethyl phenol electrolyzing process of preparing 2,3,5-trimethyl hydroquinone |
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| CN02103026.XA CN1436877A (en) | 2002-02-05 | 2002-02-05 | Paired 2,3,6-trimethyl phenol electrolyzing process of preparing 2,3,5-trimethyl hydroquinone |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101078128B (en) * | 2007-06-30 | 2010-08-18 | 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 |
| CN103215613A (en) * | 2013-04-07 | 2013-07-24 | 重庆大学 | Method for producing hydroquinone through electrocatalytic reduction of p-benzoquinone |
| CN107805825A (en) * | 2017-11-28 | 2018-03-16 | 中国科学院新疆理化技术研究所 | The method of electrosynthesis glyoxal methyl phenyl ethers anisole |
-
2002
- 2002-02-05 CN CN02103026.XA patent/CN1436877A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101078128B (en) * | 2007-06-30 | 2010-08-18 | 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 |
| CN103215613A (en) * | 2013-04-07 | 2013-07-24 | 重庆大学 | Method for producing hydroquinone through electrocatalytic reduction of p-benzoquinone |
| CN107805825A (en) * | 2017-11-28 | 2018-03-16 | 中国科学院新疆理化技术研究所 | The method of electrosynthesis glyoxal methyl phenyl ethers anisole |
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