CN102643185B - Green and simple preparation method for 2,3,5-trimethylbenzoquinone (TMBQ) - Google Patents
Green and simple preparation method for 2,3,5-trimethylbenzoquinone (TMBQ) Download PDFInfo
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Abstract
The invention discloses a preparation method for 2,3,5-trimethylbenzoquinone, which comprises the following steps of: dropwise adding a mixed solution of 50 percent of sulfuric acid and oxidant-glacial acetic acid at the temperature of 30 DEG C by taking 2,3,6-trimethylphenol as a raw material and petroleum ether as a solvent; standing after reaction is ended to separate out upper layer organic phases; extracting an aqueous phase by using the petroleum ether; merging the organic phases and then washing to be nearly neutral; evaporating to remove the organic phases; cooling; and performing vacuum drying to obtain the 2,3,5-trimethylbenzoquinone. The yield is higher than 86 percent, and the purity is higher than 98.5 percent. The preparation method for the 2,3,5-trimethylbenzoquinone has the advantages that the used raw materials are wide in source, the cost is low, the reaction time is short, the energy consumption is low, the post-processing operation is simple, and the product yield and the purity are higher. Meanwhile, reagents capable of polluting the environment, such as heavy metal and concentrated acid, used by a traditional method are omitted by the preparation method for the 2,3,5-trimethylbenzoquinone; the used solvent can also be repeatedly and mechanically used, therefore, the production cost is reduced, and meanwhile, the environmental pollution is avoided, and the requirement of the green and environmental protection of the modern industrial production is met. In a word, the preparation method has the advantages that the environment cannot be polluted, the requirement on reaction equipment is low and the production cost is low, and is extremely suitable for industrial large-scale production.
Description
Technical field
The invention belongs to chemosynthesis technical field, be specifically related to the green simple method for preparing of a kind of 2,3,5-trimethylbenzoquinoe (TMBQ).
Background technology
2,3,5-trimethylbenzoquinoe (2,3,5-trimethylbenzoquinone is called for short TMBQ) is the precursor compound of the important intermediate-TMHQ (2,3,5-trimethylhydroquinone is called for short TMHQ) of synthesising complex E.Because vitamin-E is a kind of important fat-soluble biological antioxidant, be widely used in the fields such as medicine, healthcare products, food, makeup, livestock industry, domestic and international market sharply increases the demand of vitamin-E.But the main dependence on import of China's vitamin-E, and 2,3,5-trimethylbenzoquinoe is the key factor of restriction vitamin-E output.Therefore, its important intermediate synthetic has larger using value and higher economic benefit.
The synthetic method of 2,3,5-trimethylbenzoquinoe is mainly divided into trimethylammonium phenol oxidation style and unsym-trimethyl benzene (1,2,4-trimethylbenzene is called for short TMB) oxidation style by the raw material of its use.Domestic production TMBQ, mainly by 2,3,6-TMP (2,3,6-trimethylphenol is called for short TMP) oxidation style, first uses 40% sulfuric acid sulfonation at present, then passes through MnO
2oxidation.Although this law flow process is short, equipment is simple, and yield is also relatively high, and the method is owing to having used MnO
2make oxygenant, a large amount of manganese ore mud residues that produce have inevitably produced heavy metal contamination to environment, do not meet the regulation of Law on Environmental Protection.[money east, Wang Kaiyi, Pang Minghong. direct oxidation method intermediate of synthetic vitamin E TMHQ. fine chemistry industry .1998,2,13-15]
Domestic Zhejiang Medicine Co adopts continuous catalysis oxidation style, usings cupric chloride, magnesium chloride as catalyzer, and primary isoamyl alcohol is solvent, and 2,3,6-TMP can oxidizedly obtain 2,3,5-trimethylbenzoquinoe.The product yield obtaining by this technique and purity are all higher, but this law is higher to equipment requirements, and the solvent primary isoamyl alcohol price that this law adopts is also relatively expensive, so present method cost when scale operation is relatively high.[resonant China, Zang Hengchang. the feasibility study of continuous catalysis oxidation legal system 2,3,5-trimethylbenzoquinoe. Chemical Industry in Guangzhou .2011,39 (9), 104-105]
By unsym-trimethyl benzene, being oxidized the method for preparing 2,3,5-trimethylbenzoquinoe also has report, and this method can obtain target product through steps such as oversulfonate, nitrated, reduction, hydrolysis, oxidations.But this law Technology is complicated, step is many, the three wastes are many, is substantially eliminated at present.[Sun Jianmei, Lu Hongfang, the lotus .2 of south man, the synthetic method brief introduction of 3,5-trimethylammonium para benzoquinone. Tianjin chemical industry .2002,5,26-27; Long Zhicheng. synthesizing of Trimethylhydroquinone. Sichuan chemical industry .2005,8 (6), 1-3.]
Unsym-trimethyl benzene can also be prepared 2,3,5-trimethylbenzoquinoe by oxygenant-Peracetic Acid direct oxidation method, but this method yield only has 35%, and oxygenant price is relatively costly and consumption is large, cost is higher and plant factor is low, is not suitable for equally industrialized production.[Sun Jianmei, Lu Hongfang, the lotus .2 of south man, the synthetic method brief introduction of 3,5-trimethylammonium to benzene quinhydrones. Tianjin chemical industry .2002,5,26-27].
Also there are at present a lot of researchists to utilize various new catalysts that unsym-trimethyl benzene is oxidized to prepare 2,3,5-trimethylbenzoquinoe.Reported method has γ-Al
2o
3for catalyzer, acetic acid is solvent, and hydrogen peroxide is oxygenant, under mechanical stirring and heating condition, prepares 2,3,5-trimethylbenzoquinoe.Although this method transformation efficiency is higher, the raw material of use is also cleaner, and the preparation of catalyzer is relatively loaded down with trivial details.[Masaru?Higuchi,Itokazu?Teruo.JP51043730,14-Apr-1976.]
Also have by the mode of cyclic voltammetric and electrolysis and by unsym-trimethyl benzene catalytic oxidation, prepared the report of 2,3,5-trimethylbenzoquinoe, with Ti/nanoTiO
2-Pt does electrode, and in ion diaphragm electrolyzer, reaction generates TMBQ.The electrode that this method is used is precious metal, and energy loss is very big, can not be as the method for suitability for industrialized production.[Yu Chenxiu, Chu Daobao, azurite. the electrosynthesis research of trimethylbenzoquinone. Chaohu College institute reports .2008, and 10 (3), 82-85.]
The people such as Qian Dong also once used MnO
2-H
2sO
4-H
2o as oxidizer system [money east, He Houqun, Wang Kaiyi. direct oxidation method synthesizes TMHQ. chemical reagent .2002,24 (4), 231-232.].First reaction needs 2,3,6-TMP to be oxidized to phenol sulfonic acid with 40% dilute sulphuric acid.Because phenol sulfonic acid is easy to caking, can add MnO needed first to add water to be dissolved before carrying out oxidizing reaction after
2proceed reaction, cause oxidation products purity lower; Secondly because reaction is for inhomogeneous reaction, exist the manganese slag of long reaction time, generation to defects such as environments, institute in this way cannot realize industrialization.
The people such as Qian Dong also once reported use H
2o
2-AcOH-HCl system as the reaction of oxygenant [money east, Wang Kaiyi, Pang Minghong. direct oxidation method intermediate of synthetic vitamin E TMHQ. fine chemistry industry .1998,15 (2), 13-15.].We also once attempted using this method to prepare TMBQ, found that after having reacted and can not get orange-yellow needle crystal, product after steaming desolventizes is always oily matter, high performance thin layer chromatography (thin-layer chromatography, abbreviation TLC) under monitoring reaction and display principal spot, there is a blackening by-product object point, be difficult to remove this by product by conventional chemical method, therefore cause product cannot form crystallization sterling.
Summary of the invention
The object of the invention is for overcoming above-mentioned the deficiencies in the prior art, simply effective, environment amenable environment-friendly preparation method thereof of a kind of 2,3,5-trimethylbenzoquinoe (TMBQ) is provided.
For achieving the above object, the present invention adopts following technical proposals:
A kind of 2, the preparation method of 3,5-trimethylbenzoquinone (TMBQ), with 2,3,6-pseudocuminol (TMP) is raw material, first by sulfuric acid, its sulfonation is generated to corresponding 4-sulfonic group-2,3,6-pseudocuminol, miscible fluid by Glacial acetic acid-superoxide is oxidized generation 2,3,5-trimethylbenzoquinoe again.
Further, it comprises the steps: 2, 3, 6-pseudocuminol is dissolved in organic solvent, at 30～80 ℃, drip mass concentration and be 30%～98% sulphuric acid soln, dropwise insulation reaction 10～40 minutes, toward reaction system, drip subsequently the mixing solutions of Glacial acetic acid-superoxide, wherein 2, 3, 6-pseudocuminol and Glacial acetic acid, the mol ratio of superoxide is in 1:(4～7): (4～7), after reaction finishes, stratification, water organic solvent extraction, merge organic phase, be washed till pH and be about 6～7, remove organic solvent, cooling, after vacuum-drying, obtain orange-yellow 2, 3, 5-trimethylbenzoquinone needle crystal.
Reaction equation involved in the present invention:
Described organic solvent is sherwood oil, tetrahydrofuran (THF), normal hexane or hexanaphthene.
Described superoxide is hydrogen peroxide, Peracetic Acid, peroxy tert-butyl alcohol or benzoyl hydroperoxide.
The mol ratio of described 2,3,6-TMP and sulphuric acid soln is 1:5～1:1.
Preferably, the mol ratio of described 2,3,6-TMP and sulphuric acid soln is 1:4.
Described h 2 so 4 concentration is 30%～98%.
Preferably, described h 2 so 4 concentration is 50%.
The mol ratio of described 2,3,6-TMP and Glacial acetic acid, superoxide is preferably 1:(5～7): (5～7), further preferred 1:6:6.
Adopting the time of sulfuric acid sulfonation reaction is 30 minutes; Temperature is 30 ℃.
Adopt dilute sodium bicarbonate solution, saturated nacl aqueous solution, distilled water wash respectively 1 time, being washed till pH is 6～7.
Most preferred scheme is:
2,3,6-TMP petroleum ether dissolution, stirs at 30 ℃ and dropwise drips 50% sulfuric acid, dropwises rear insulation reaction 20 minutes, dropwise drips the mixing solutions of acetic acid-hydrogen peroxide, drips to finish at 30 ℃, to continue reaction 20-30 minute.Standing after completion of the reaction, minute water-yielding stratum with petroleum ether extraction 3 times, merges organic phase, and uses respectively dilute sodium bicarbonate solution, saturated nacl aqueous solution, distilled water wash each 1 time, is about 7 to pH.The sherwood oil that steaming removes carries out recovery, cooling, and vacuum-drying can obtain orange-yellow needle crystal TMBQ.Yield is greater than 86%, and purity is greater than 98.5%.
The present invention relates to a kind of vitamin-E intermediate-2, the preparation method of 3,5-trimethylbenzoquinone, first by certain density sulfuric acid by after its sulfonation, miscible fluid by hydrogen peroxide-Glacial acetic acid is oxidized again, and the effect of Glacial acetic acid in this preparation method is the transformation efficiency that can improve product.The embodiment result of being undertaken by the present invention proves, if only carry out oxidizing reaction by hydrogen peroxide system, selectivity is low, and in product, occurs a large amount of earth sample by products.
The invention has the beneficial effects as follows:
(1) the present invention uses peroxide oxidant, and the phenol sulfonic acid generating can dissolve voluntarily, has solved MnO
2the problem of method caking.Because oxidizing reaction is to carry out in homogeneous phase, so the reaction times is short, product purity is compared with MnO simultaneously
2method height a lot.
(2) selected raw material 2,3,6-TMP, sulfuric acid sulfonation agent and the equal wide material sources of 30% hydrogen peroxide oxidant are easy to get, and clean environment firendly and price are more cheap, greatly reduce production cost.Reaction times is short, and operational path is short, and reaction conditions is simple and easy to implement, and products obtained therefrom purity and yield are all higher.Simultaneously, the present invention has avoided heavy metal that traditional method used and concentrated acid etc. environment to be had to the reagent of pollution, and the three wastes that reaction produces are few, and reaction solvent used can also be applied mechanically repeatedly, when having reduced production cost, avoid environmental pollution, met the requirement of modernization industry production environmental protection.
(3) selected Glacial acetic acid has played the effect of the donor of proton, its acidity is not strong, be unlikely to make raw material excessively oxidated generation coupling by product in hydrogen peroxide system, acetic acid can also form the oxidation system with certain shock absorption with hydrogen peroxide simultaneously, played the effect with hydrogen peroxide synergistic oxidation, thereby made raw material be easy to be oxidized to target product.
In a word, this preparation method environmentally safe, conversion unit requires low, and production cost is low, is very suitable for industrialized production.
Accompanying drawing explanation
Fig. 1 and Fig. 2 be respectively the high-efficient liquid phase chromatogram of the embodiment of the present invention 2 prepared products gentle-mass spectrum.The purity of product TMBQ is about 98.5% as shown in Figure 1; The molecular ion peak of product is 150.1 as shown in Figure 2, and confirmation is desired product TMBQ.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1:
Take the 2,3,6-TMP of 0.03mol in the three-necked flask of 250mL, add the sherwood oil of 35mL to be placed on constant temperature oil bath, 30 ℃ of temperature controls.Treat material dissolution and homo(io)thermism, drip 50% aqueous sulfuric acid of 4 times of equivalents, rate of addition is unsuitable too fast, can control rate of addition by constant pressure funnel, dropwises rear insulation reaction 30 minutes.Then measure the hydrogen peroxide of 6 times of equivalents 30%, in above-mentioned reaction system, dropwise drip, dropwise at 30 ℃ and react half an hour.Reaction produces a large amount of earth shape things, finishes rear stratification, filters elimination solid, isolate water and sherwood oil phase, water is used petroleum ether extraction 3 times again, merges organic phase, and with dilute sodium bicarbonate solution, saturated sodium-chloride and distilled water, being washed till pH is successively neutral left and right.Steam except sherwood oil, cooling orange-yellow oily thing, low the obtaining by wet distillation purifying of product purity can orange-yellow needle crystal, but yield is only 10%, purity 98.5%.
Embodiment 2:
Take the 2,3,6-TMP of 0.03mol in the three-necked flask of 250mL, add the sherwood oil of 35mL to be placed on constant temperature oil bath, 30 ℃ of temperature controls.Treat material dissolution and homo(io)thermism, drip 50% aqueous sulfuric acid of 4 times of equivalents, rate of addition is unsuitable too fast, can control rate of addition by constant pressure funnel, dropwises rear insulation reaction 30 minutes.Measure respectively the acetic acid of 6 times of equivalents and 30% hydrogen peroxide (acetic acid and hydrogen peroxide are phase equivalent), be mixed in the constant pressure funnel of 50mL, in above-mentioned reaction system, dropwise drip, dropwise at 30 ℃ and react half an hour.Reaction finishes rear stratification, isolates water and sherwood oil phase, and water is used petroleum ether extraction 3 times again, merges organic phase, and with dilute sodium bicarbonate solution, saturated sodium-chloride and distilled water, being washed till pH is successively neutral left and right.Steam except sherwood oil, cooling orange-yellow needle crystal, 29～29.5 ℃ of fusing points, yield is greater than 86%, purity 98.5%, gas chromatography-mass spectrum result: m/z=152.2 (as shown in Figure 2).Provable by figure: the product by embodiment gained is TMBQ.
Embodiment 3:
Take the 2,3,6-TMP of 0.03mol in the three-necked flask of 250mL, add the sherwood oil of 35mL to be placed on constant temperature oil bath, 30 ℃ of temperature controls.Treat material dissolution and homo(io)thermism, drip 50% aqueous sulfuric acid of 2 times of equivalents, rate of addition is unsuitable too fast, can control rate of addition by constant pressure funnel, dropwises rear insulation reaction 30 minutes.Measure respectively the acetic acid of 6 times of equivalents and 30% hydrogen peroxide (acetic acid and hydrogen peroxide are phase equivalent), be mixed in the constant pressure funnel of 50mL, in above-mentioned reaction system, dropwise drip, dropwise at 30 ℃ and react half an hour.Reaction finishes rear stratification, isolates water and sherwood oil phase, and water is used petroleum ether extraction 3 times again, merges organic phase, and with dilute sodium bicarbonate solution, saturated sodium-chloride and distilled water, being washed till pH is successively neutral left and right.Steam except sherwood oil, cooling orange-yellow oily thing, yield calculates 72% with oily matter, and purity is 81%.
Embodiment 4:
Take the 2,3,6-TMP of 0.03mol in the three-necked flask of 250mL, add the sherwood oil of 35mL to be placed on constant temperature oil bath, 30 ℃ of temperature controls.Treat material dissolution and homo(io)thermism, drip 50% aqueous sulfuric acid of 3 times of equivalents, rate of addition is unsuitable too fast, can control rate of addition by constant pressure funnel, dropwises rear insulation reaction 30 minutes.Measure respectively the acetic acid of 6 times of equivalents and 30% hydrogen peroxide (acetic acid and hydrogen peroxide are phase equivalent), be mixed in the constant pressure funnel of 50mL, in above-mentioned reaction system, dropwise drip, dropwise at 30 ℃ and react half an hour.Reaction finishes rear stratification, isolates water and sherwood oil phase, and water is used petroleum ether extraction 3 times again, merges organic phase, and with dilute sodium bicarbonate solution, saturated sodium-chloride and distilled water, being washed till pH is successively neutral left and right.Steam except sherwood oil, cooling orange-yellow needle crystal, 29～30 ℃ of fusing points, productive rate is 60%, purity 98%, the equivalent that can infer thus 50% sulfuric acid is preferably 4 times of raw material TMP.
Embodiment 5:
Take the 2,3,6-TMP of 0.03mol in the three-necked flask of 250mL, add the sherwood oil of 35mL to be placed on constant temperature oil bath, 30 ℃ of temperature controls.Treat material dissolution and homo(io)thermism, drip 50% aqueous sulfuric acid of 4 times of equivalents, rate of addition is unsuitable too fast, can control rate of addition by constant pressure funnel, dropwises rear insulation reaction 30 minutes.Measure respectively the acetic acid of 4 times of equivalents and 30% hydrogen peroxide (acetic acid and hydrogen peroxide are phase equivalent), be mixed in the constant pressure funnel of 50mL, in above-mentioned reaction system, dropwise drip, dropwise at 30 ℃ and react half an hour.Reaction finishes rear stratification, isolates water and sherwood oil phase, and water is used petroleum ether extraction 3 times again, merges organic phase, and with dilute sodium bicarbonate solution, saturated sodium-chloride and distilled water, being washed till pH is successively neutral left and right.Steam except sherwood oil cooling orange-yellow pulverulent solids, 40～41 ℃ of fusing points, yield 81%, the purity 69% of obtaining.
Embodiment 6:
Take the 2,3,6-TMP of 0.03mol in the three-necked flask of 250mL, add the sherwood oil of 35mL to be placed on constant temperature oil bath, 30 ℃ of temperature controls.Treat material dissolution and homo(io)thermism, drip 50% aqueous sulfuric acid of 4 times of equivalents, rate of addition is unsuitable too fast, can control rate of addition by constant pressure funnel, dropwises rear insulation reaction 30 minutes.Measure respectively the acetic acid of 5 times of equivalents and 30% hydrogen peroxide, be mixed in the constant pressure funnel of 50mL, in above-mentioned reaction system, dropwise drip, dropwise at 30 ℃ and react half an hour.Reaction finishes rear stratification, isolates water and sherwood oil phase, and water is used petroleum ether extraction 3 times again, merges organic phase, and with dilute sodium bicarbonate solution, saturated sodium-chloride and distilled water, being washed till pH is successively neutral left and right.Steam except sherwood oil, cooling orange-yellow oily thing, yield is calculated as 83% with oily matter, purity 78%.
Embodiment 7:
Take the 2,3,6-TMP of 0.03mol in the three-necked flask of 250mL, add the sherwood oil of 35mL to be placed on constant temperature oil bath, 30 ℃ of temperature controls.Treat material dissolution and homo(io)thermism, drip 50% aqueous sulfuric acid of 3 times of equivalents, rate of addition is unsuitable too fast, can control rate of addition by constant pressure funnel, dropwises rear insulation reaction 30 minutes.Measure respectively the acetic acid of 7 times of equivalents and 30% hydrogen peroxide (acetic acid and hydrogen peroxide are phase equivalent), be mixed in the constant pressure funnel of 50mL, in above-mentioned reaction system, dropwise drip, dropwise at 30 ℃ and react half an hour.Reaction finishes rear stratification, isolates water and sherwood oil phase, and water is used petroleum ether extraction 3 times again, merges organic phase, and with dilute sodium bicarbonate solution, saturated sodium-chloride and distilled water, being washed till pH is successively neutral left and right.Steam except sherwood oil, cooling orange-yellow oily thing, yield is calculated as 77% with oily matter, purity 62%.The equivalent that can infer thus Glacial acetic acid and hydrogen peroxide is preferably 6 times of raw material TMP.
Embodiment 8:
Take the 2,3,6-TMP of 0.03mol in the three-necked flask of 250mL, add the sherwood oil of 35mL to be placed on constant temperature oil bath, 30 ℃ of temperature controls.Treat material dissolution and homo(io)thermism, drip 30% aqueous sulfuric acid of 4 times of equivalents, rate of addition is unsuitable too fast, can control rate of addition by constant pressure funnel, dropwises rear insulation reaction 30 minutes, in reaction process, generates all the time without phenol sulfonic acid solid.Measure respectively the acetic acid of 6 times of equivalents and 30% hydrogen peroxide (acetic acid and hydrogen peroxide are phase equivalent), be mixed in the constant pressure funnel of 50mL, in above-mentioned reaction system, dropwise drip, dropwise at 30 ℃ and react half an hour.Reaction finishes rear stratification, isolates water and sherwood oil phase, and water is used petroleum ether extraction 3 times again, merges organic phase, and with dilute sodium bicarbonate solution, saturated sodium-chloride and distilled water, being washed till pH is successively neutral left and right.Steam except petroleum ether solvent, find to produce a large amount of yellow powder powder solids, 42 ℃ of fusing points, yield 83%, purity 57%.
Embodiment 9:
Take the 2,3,6-TMP of 0.03mol in the three-necked flask of 250mL, add the sherwood oil of 35mL to be placed on constant temperature oil bath, 60 ℃ of temperature controls (reflux temperature).Treat material dissolution and homo(io)thermism, drip 50% aqueous sulfuric acid of 4 times of equivalents, rate of addition is unsuitable too fast, can control rate of addition by constant pressure funnel, dropwises rear insulation reaction 30 minutes.Measure respectively the acetic acid of 6 times of equivalents and 30% hydrogen peroxide, be mixed in the constant pressure funnel of 50mL, in above-mentioned reaction system, dropwise drip, dropwise at 60 ℃ and react half an hour.Reaction finishes rear stratification, isolates water and sherwood oil phase, and water is used petroleum ether extraction 3 times again, merges organic phase, and with dilute sodium bicarbonate solution, saturated sodium-chloride and distilled water, being washed till pH is successively neutral left and right.Steam except sherwood oil, cooling orange-yellow oily thing, yield calculates 79% with oily matter, and purity is 70%, and efficient thin layer shows a lot of assorted points under principal spot, tentatively can judge that under hydrogen peroxide oxidation condition high temperature can cause the generation of side reaction.
Embodiment 10:
Take the 2,3,6-TMP of 0.03mol in the three-necked flask of 250mL, add the sherwood oil of 35mL to be placed on constant temperature oil bath, 30 ℃ of temperature controls.Treat material dissolution and homo(io)thermism, drip 98% aqueous sulfuric acid of 4 times of equivalents, rate of addition is unsuitable too fast, can control rate of addition by constant pressure funnel, dropwises rear insulation reaction 30 minutes.Measure respectively the acetic acid of 6 times of equivalents and 30% hydrogen peroxide, be mixed in the constant pressure funnel of 50mL, in above-mentioned reaction system, dropwise drip, dropwise at 30 ℃ and react half an hour.Reaction finishes rear stratification, isolates water and sherwood oil phase, and water is used petroleum ether extraction 3 times again, merges organic phase, and with dilute sodium bicarbonate solution, saturated sodium-chloride and distilled water, being washed till pH is successively neutral left and right.Steam except sherwood oil, cooling orange-yellow needle crystal, 29～29.5 ℃ of fusing points, yield is 40%, purity is greater than 98.5%.Although this method can obtain the 2,3,5-trimethylbenzoquinoe that purity is higher but this method is passed through concentrated acid sulfonation, corrodibility requires greatly high to conversion unit, and reaction products therefrom yield is also low.
Embodiment 11:
Take the 2,3,6-TMP of 0.03mol in the three-necked flask of 250mL, add the sherwood oil of 35mL to be placed on constant temperature oil bath, 30 ℃ of temperature controls.Treat material dissolution and homo(io)thermism, drip 50% aqueous sulfuric acid of 4 times of equivalents, rate of addition is unsuitable too fast, can control rate of addition by constant pressure funnel, dropwises rear insulation reaction 30 minutes.The Peracetic Acid (acetic acid and Peracetic Acid are phase equivalent) that measures respectively acetic acid and the 50-60% of 6 times of equivalents, is mixed in the constant pressure funnel of 50mL, in above-mentioned reaction system, dropwise drips, and dropwises at 30 ℃ and reacts half an hour.Reaction finishes rear stratification, isolates water and sherwood oil phase, and water is used petroleum ether extraction 3 times again, merges organic phase, and with dilute sodium bicarbonate solution, saturated sodium-chloride and distilled water, being washed till pH is successively neutral left and right.Steam except sherwood oil, cooling orange-yellow needle crystal, 29～29.5 ℃ of fusing points, yield is 45%, purity is 98.5%.Although this method can obtain the 2,3,5-trimethylbenzoquinoe that purity is higher but the Peracetic Acid price that this method is used is relatively costly, and reaction products therefrom yield is also low.
Embodiment 12:
Take the 2,3,6-TMP of 0.03mol in the three-necked flask of 250mL, add the sherwood oil of 35mL to be placed on constant temperature oil bath, 30 ℃ of temperature controls.Treat material dissolution and homo(io)thermism, drip 50% aqueous sulfuric acid of 4 times of equivalents, rate of addition is unsuitable too fast, can control rate of addition by constant pressure funnel, dropwises rear insulation reaction 30 minutes.The acetic acid and the benzoyl hydroperoxide (acetic acid and benzoyl hydroperoxide are phase equivalent) that measure respectively 6 times of equivalents, be mixed in the constant pressure funnel of 50mL, in above-mentioned reaction system, dropwise drips, and dropwises at 30 ℃ and react half an hour.Reaction finishes rear stratification, isolates water and sherwood oil phase, and water is used petroleum ether extraction 3 times again, merges organic phase, and with dilute sodium bicarbonate solution, saturated sodium-chloride and distilled water, being washed till pH is successively neutral left and right.Steam except sherwood oil, cooling orange-yellow needle crystal, 29～29.5 ℃ of fusing points, yield is 70%, purity is greater than 98.5%.Although this method can obtain all higher 2,3,5-trimethylbenzoquinoe products of purity and yield, the price of the benzoyl hydroperoxide that this method is used is relatively costly, is not suitable for industrialization and uses in a large number.
Embodiment 13:
Take the 2,3,6-TMP of 0.03mol in the three-necked flask of 250mL, add the sherwood oil of 35mL to be placed on constant temperature oil bath, 30 ℃ of temperature controls.Treat material dissolution and homo(io)thermism, drip 50% aqueous sulfuric acid of 4 times of equivalents, rate of addition is unsuitable too fast, can control rate of addition by constant pressure funnel, dropwises rear insulation reaction 30 minutes.The acetic acid and the peroxy tert-butyl alcohol (acetic acid and peroxy tert-butyl alcohol are phase equivalent) that measure respectively 6 times of equivalents, be mixed in the constant pressure funnel of 50mL, in above-mentioned reaction system, dropwise drips, and dropwises at 30 ℃ and react half an hour.Reaction finishes rear stratification, isolates water and sherwood oil phase, and water is used petroleum ether extraction 3 times again, merges organic phase, and with dilute sodium bicarbonate solution, saturated sodium-chloride and distilled water, being washed till pH is successively neutral left and right.Steam except sherwood oil, cooling orange-yellow needle crystal, 29～29.5 ℃ of fusing points, yield is 87%, purity is greater than 98.5%.Although this method can obtain purity and the higher 2,3,5-trimethylbenzoquinoe product of yield, the peroxy tert-butyl alcohol price that this method is used is also very expensive, so consider preferred hydrogen peroxide from production cost.
Embodiment 14:
Take the 2,3,6-TMP of 0.03mol in the three-necked flask of 250mL, add the normal hexane of 35mL, be placed on constant temperature oil bath, 70 ℃ of temperature controls.Treat material dissolution and homo(io)thermism, drip 50% aqueous sulfuric acid of 4 times of equivalents, rate of addition is unsuitable too fast, can control rate of addition by constant pressure funnel, dropwises rear insulation reaction 30 minutes.Measure respectively the acetic acid of 6 times of equivalents and 30% hydrogen peroxide, be mixed in the constant pressure funnel of 50mL, in above-mentioned reaction system, dropwise drip, dropwise at 30 ℃ and react half an hour.Reaction finishes rear stratification, isolates water and sherwood oil phase, and water is used petroleum ether extraction 3 times again, merges organic phase, and with dilute sodium bicarbonate solution, saturated sodium-chloride and distilled water, being washed till pH is successively neutral left and right.Steam except sherwood oil cooling orange-yellow needle crystal, yield 84%, purity 98%, 29～30 ℃ of the fusing points of obtaining.
Embodiment 15:
Take 2 of 0.03mol, 3,6-pseudocuminol is in the three-necked flask of 250mL, add the hexanaphthene of 35mL to be placed on constant temperature oil bath, 80 ℃ of temperature controls are treated material dissolution and homo(io)thermism, drip 50% aqueous sulfuric acid of 3 times of equivalents, and rate of addition is unsuitable too fast, can control rate of addition by constant pressure funnel, dropwise rear insulation reaction 30 minutes.Measure respectively the acetic acid of 6 times of equivalents and 30% hydrogen peroxide, be mixed in the constant pressure funnel of 50mL, in above-mentioned reaction system, dropwise drip, dropwise at 30 ℃ and react half an hour.Reaction finishes rear stratification, isolates water and sherwood oil phase, and water is used petroleum ether extraction 3 times again, merges organic phase, and with dilute sodium bicarbonate solution, saturated sodium-chloride and distilled water, being washed till pH is successively neutral left and right.Steam except sherwood oil cooling orange-yellow needle crystal, yield 85%, purity 98%, 28～29.5 ℃ of the fusing points of obtaining.
Embodiment 16:
Take the 2,3,6-TMP of 0.03mol in the three-necked flask of 250mL, add the tetrahydrofuran (THF) of 35mL to be placed on constant temperature oil bath, 30 ℃ of temperature controls.Treat material dissolution and homo(io)thermism, drip 50% aqueous sulfuric acid of 2 times of equivalents, rate of addition is unsuitable too fast, can control rate of addition by constant pressure funnel, dropwises rear insulation reaction 30 minutes.Measure respectively the acetic acid of 6 times of equivalents and 30% hydrogen peroxide, be mixed in the constant pressure funnel of 50mL, in above-mentioned reaction system, dropwise drip, dropwise at 30 ℃ and react half an hour.Steam petroleum ether extraction 3 times for tetrahydrofuran (THF) water, sherwood oil is used respectively distilled water mutually, saturated aqueous common salt, dilute aqueous solution of sodium bicarbonate wash to PH be 7.The orange-yellow needle crystal of evaporate to dryness possibility, yield is 83%, 29～31 ℃ of fusing points, purity is 98%.
By above embodiment, can be inferred: selected solvent is on the productive rate of product TMBQ and almost not impact of purity, but because sherwood oil is cheap, and boiling point is lower, therefore need the required temperature of back flow reaction also low than other solvents, meet the requirement of suitability for industrialized production, so preferred sherwood oil.
Annex---table 1: the contrast of embodiment 1-16 technological condition and yield, purity
Note: in table, equivalence ratio refers to sulfuric acid, the acetic acid of raw material TMP and 50%, the mol ratio of superoxide.
The present invention is not limited to the technology described in embodiment, and this description is illustrative and nonrestrictive, and authority of the present invention is limited by claim, and cited embodiment is used for wherein a kind of preparation method is described, but does not limit the present invention.The reaction conditions that can expect according to the present invention based on those skilled in the art, as changed the technology related to the present invention such as experiment reagent, reactant ratio and temperature of reaction, all within protection scope of the present invention.
Claims (1)
1. a preparation method for 2,3,5-trimethylbenzoquinoe, is characterized in that,
Take 2 of 0.03mol, 3, 6-pseudocuminol is in the three-necked flask of 250mL, add the sherwood oil of 35mL to be placed on constant temperature oil bath, 30 ℃ of temperature controls, treat material dissolution and homo(io)thermism, drip 50% aqueous sulfuric acid of 4 times of equivalents, rate of addition is unsuitable too fast, can control rate of addition by constant pressure funnel, dropwise rear insulation reaction 30 minutes, measure respectively the acetic acid of 6 times of equivalents and 30% hydrogen peroxide, acetic acid and hydrogen peroxide are phase equivalent, be mixed in the constant pressure funnel of 50mL, in above-mentioned reaction system, dropwise drip, dropwise at 30 ℃ and react half an hour, reaction finishes rear stratification, isolate water and sherwood oil phase, water is used petroleum ether extraction 3 times again, merge organic phase, use successively dilute sodium bicarbonate solution, saturated sodium-chloride and distilled water are washed till pH for neutral left and right, steam except sherwood oil, cooling orange-yellow needle crystal, 29～29.5 ℃ of fusing points, yield is greater than 86%, purity 98.5%, gas chromatography-mass spectrum result: m/z=152.2,
Or take 2 of 0.03mol, 3, 6-pseudocuminol is in the three-necked flask of 250mL, add the sherwood oil of 35mL to be placed on constant temperature oil bath, 30 ℃ of temperature controls, treat material dissolution and homo(io)thermism, drip 50% aqueous sulfuric acid of 4 times of equivalents, rate of addition is unsuitable too fast, can control rate of addition by constant pressure funnel, dropwise rear insulation reaction 30 minutes, measure respectively acetic acid and the peroxy tert-butyl alcohol of 6 times of equivalents, acetic acid and peroxy tert-butyl alcohol are phase equivalent, be mixed in the constant pressure funnel of 50mL, in above-mentioned reaction system, dropwise drip, dropwise at 30 ℃ and react half an hour, reaction finishes rear stratification, isolate water and sherwood oil phase, water is used petroleum ether extraction 3 times again, merge organic phase, use successively dilute sodium bicarbonate solution, saturated sodium-chloride and distilled water are washed till pH for neutral left and right, steam except sherwood oil, cooling orange-yellow needle crystal, 29～29.5 ℃ of fusing points, yield is 87%, purity is greater than 98.5%,
Or take 2 of 0.03mol, 3, 6-pseudocuminol is in the three-necked flask of 250mL, the normal hexane that adds 35mL, be placed on constant temperature oil bath, 70 ℃ of temperature controls, treat material dissolution and homo(io)thermism, drip 50% aqueous sulfuric acid of 4 times of equivalents, rate of addition is unsuitable too fast, can control rate of addition by constant pressure funnel, dropwise rear insulation reaction 30 minutes, measure respectively the acetic acid of 6 times of equivalents and 30% hydrogen peroxide, be mixed in the constant pressure funnel of 50mL, in above-mentioned reaction system, dropwise drip, dropwise at 30 ℃ and react half an hour, reaction finishes rear stratification, isolate water and sherwood oil phase, water is used petroleum ether extraction 3 times again, merge organic phase, use successively dilute sodium bicarbonate solution, saturated sodium-chloride and distilled water are washed till pH for neutral left and right, steam except sherwood oil, cooling orange-yellow needle crystal, yield 84%, purity 98%, 29～30 ℃ of fusing points,
Or take 2 of 0.03mol, 3, 6-pseudocuminol is in the three-necked flask of 250mL, add the hexanaphthene of 35mL to be placed on constant temperature oil bath, 80 ℃ of temperature controls are treated material dissolution and homo(io)thermism, drip 50% aqueous sulfuric acid of 3 times of equivalents, rate of addition is unsuitable too fast, can control rate of addition by constant pressure funnel, dropwise rear insulation reaction 30 minutes, measure respectively the acetic acid of 6 times of equivalents and 30% hydrogen peroxide, be mixed in the constant pressure funnel of 50mL, in above-mentioned reaction system, dropwise drip, dropwise at 30 ℃ and react half an hour, reaction finishes rear stratification, isolate water and sherwood oil phase, water is used petroleum ether extraction 3 times again, merge organic phase, use successively dilute sodium bicarbonate solution, saturated sodium-chloride and distilled water are washed till pH for neutral left and right, steam except sherwood oil, cooling orange-yellow needle crystal, yield 85%, purity 98%, 28～29.5 ℃ of fusing points,
Or take 2 of 0.03mol, 3, 6-pseudocuminol is in the three-necked flask of 250mL, add the tetrahydrofuran (THF) of 35mL to be placed on constant temperature oil bath, 30 ℃ of temperature controls, treat material dissolution and homo(io)thermism, drip 50% aqueous sulfuric acid of 2 times of equivalents, rate of addition is unsuitable too fast, can control rate of addition by constant pressure funnel, dropwise rear insulation reaction 30 minutes, measure respectively the acetic acid of 6 times of equivalents and 30% hydrogen peroxide, be mixed in the constant pressure funnel of 50mL, in above-mentioned reaction system, dropwise drip, dropwise at 30 ℃ and react half an hour, steam petroleum ether extraction 3 times of tetrahydrofuran (THF) water, sherwood oil is used respectively distilled water mutually, saturated aqueous common salt, dilute aqueous solution of sodium bicarbonate wash to pH be 7, the orange-yellow needle crystal of evaporate to dryness possibility, yield is 83%, 29～31 ℃ of fusing points, purity is 98%.
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