CN104003847B - A kind of directional synthesis method of 2,5 di tert butyl hydroquinone - Google Patents
A kind of directional synthesis method of 2,5 di tert butyl hydroquinone Download PDFInfo
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- CN104003847B CN104003847B CN201410209860.6A CN201410209860A CN104003847B CN 104003847 B CN104003847 B CN 104003847B CN 201410209860 A CN201410209860 A CN 201410209860A CN 104003847 B CN104003847 B CN 104003847B
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- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
Abstract
The invention belongs to fine chemicals and chemical industry synthesis field, disclose a kind of directed one-step synthesis method method generating 2,5-di-tert-butyl hydroquinones.This method is with the tert-butyl alcohol and hydroquinone for raw material, with water for solvent, under catalyst action, directed generates 2,5-di-tert-butyl hydroquinones.Synthetic method of the present invention adopts one-step method controlled syntheses 2,5-di-tert-butyl hydroquinone, simple to operation, low for equipment requirements；2,5-di-tert-butyl hydroquinone's yields reach 90%, and purity reaches more than 99%, and raw material is close to and is completely converted into target product, and selectivity and Atom economy are high；The catalyst attrition of synthetic method of the present invention is minimum, and avoids the use of the organic solvent such as aromatic hydrocarbon and ketone, and reaction mother liquor can repeatedly use, and decreases the pollution to environment to greatest extent.
Description
Technical field
The invention belongs to fine chemicals and chemical industry synthesis field, be specifically related to the directional synthesis method of a kind of 2,5-di-tert-butyl hydroquinones.
Background technology
2,5-di-tert-butyl hydroquinone (DTBHQ) is a kind of antioxidant being widely used in the chemical industries such as resin, plastics, rubber, suitable in production and applications such as natural rubber, latex, rubber polymer, oils and rubber, be also a kind of nontoxic, without bad smell, free of contamination plastic anti-aging agent.
Relative to other chemical products, the synthesising process research of DTBHQ is few in number, and preparation method mostly is: with hydroquinone and the tert-butyl alcohol for raw material, and dehydration generates DTBHQ in organic solvent.Obtained DTBHQ has that yield is low, purity is low and the shortcoming and defect such as physical appearance difference, and need to through complex aftertreatment technology, as through Zn powder+hydrochloric acid decolouring, reproducibility salt decolouring etc..If Cai Keying etc. is with methyl tertiary butyl ether(MTBE) (MTEB), hydroquinone for raw material, with acid cation exchange resin for catalyst, chlorobenzene is the experiment of solvent synthesis DTBHQ, and reaction temperature is 80 DEG C, when the response time is 7h, but DTBHQ purity is only 91.9% (Cai Keying, Aihua YANG, Zhai enriches people, Wei Xianyong. synthesize 2 with methyl tertiary butyl ether(MTBE), 5-di-tert-butyl hydroquinone. Speciality Petrochemicals .2001,3:22-24.).Cheng Lihua etc. are with MTEB, hydroquinone for raw material, with sulphuric acid as catalyst, chlorobenzene or toluene are that solvent has synthesized DTBHQ, the highest yield 60% (Cheng Lihua, Teng Junjiang, Wang Shuqing, Zhang Jianheng .MTBE synthesis 2, the research of 5-di-tert-butyl hydroquinone. petrochemical industry Journal of Chinese Universities .2009,22 (1): 45-48.).Zhang Ruxiang reports use hydroquinone and the tert-butyl alcohol is raw material, oxalic acid is catalyst, chlorobenzene has synthesized DTBHQ as solvent, response time is 6h, reaction temperature is 90 DEG C, the highest yield obtaining DTBHQ be only 25.2% (Zhang Ruxiang. Catalyzed by Oxalic Acid DTBHQ study on the synthesis. Hunan University of Arts and Science journal .2006,18 (1): 36-37,46.).United States Patent (USP) (USpatent:US06255538.) is reported with the tert-butyl alcohol, hydroquinone for raw material, and first alcohol and water is as solvent, and p-methyl benzenesulfonic acid (PTSA) is as catalyst, at N2Protection under synthesized DTBHQ, reaction temperature 58～60 DEG C, the response time is 14h; the yield of DTBHQ is 70%, and purity reaches 98%, in the liquid acid catalytic reaction report of existing synthesis DTBHQ; this patent DTBHQ yield and purity are all the highest, and avoid benzene series organic solvent.But this patented method needs to use N2Protection, and use expensive PTSA as catalyst, improve equipment requirements and production cost.Bibliographical information is separately had to use solid catalyst (modified silica-gel) to substitute liquid acid (BogdanC.Gagea, AndreiN.Parvulescu, GeorgesPoncelet, andVasileI.Parvulescu.Alkylationofhydroquinonewithtert-b utanoloversilica-immobilizedtriflatederivatives.Catalysi sLetters.105,34 (2005)), obtain higher conversion ratio, but used catalyst is costly, and high-temperature high-voltage reaction condition is high to equipment requirements, it is unfavorable for large-scale industrial production.
To sum up, the defect that the synthesis technique of tradition DTBHQ exists has:
(1) using larger amount of organic solvent, environmental pollution is comparatively serious.The post processing of dissolvent residual can increase the complexity of technique.
(2) use catalyst costly, such as p-methyl benzenesulfonic acid, ionic liquid, modified solid catalyst etc., cause production cost too high.
(3) product yield is low, and purity is low, causes that post processing purifying process is complicated, and wastage of material is serious.Complicated technique not only reduces the yield of product, also can expend the substantial amounts of energy.
Summary of the invention
In order to overcome shortcoming and the deficiency of prior art, the primary and foremost purpose of the present invention is in that the synthetic method providing a kind of simple and easy single step reaction orientation to generate 2,5-di-tert-butyl hydroquinones.Described synthetic method completely avoid must additionally add organic solvent in traditional handicraft, and reaction condition is gentle, simple to operation, low for equipment requirements, while significantly reducing production cost, can maximize the yield and purity that ensure product.
The purpose of the present invention is achieved through the following technical solutions:
The directional synthesis method of a kind of 2,5-di-tert-butyl hydroquinones, comprises the steps: with the tert-butyl alcohol and hydroquinone for raw material, with water for solvent, add catalyst, after carrying out insulation reaction, cooling, precipitate out solid crystal, filter, after filtering residue washing, dry and obtain 2,5-di-tert-butyl hydroquinones.
The directional synthesis method of above-mentioned 2,5-di-tert-butyl hydroquinones, concrete synthesis step is as follows:
(1) in a kettle. by hydroquinone, water and the tert-butyl alcohol mixing accounting for the total consumption 1/5～1/2 of the tert-butyl alcohol, heating for dissolving；
In step (1), the consumption of the tert-butyl alcohol should meet the requirement fully dissolving hydroquinone；
(2) by the remaining tert-butyl alcohol and catalyst mix, then being slowly dropped in aforesaid reaction vessel, keeping temperature of reaction kettle after being added dropwise to complete is 60～99 DEG C, isothermal reaction 0.1～18.0h；
Preferably, described hydroquinone is 1:2～1:10 with the mol ratio of the total consumption of the tert-butyl alcohol；It is furthermore preferred that the mol ratio of described hydroquinone and the total consumption of the tert-butyl alcohol is 1:3～1:7；
Preferably, the total consumption of the described tert-butyl alcohol is 100:0～30:70 with the mass ratio of water；It is furthermore preferred that the mass ratio of the total consumption of the described tert-butyl alcohol and water is 100:0～70:30；
Preferably, described hydroquinone is 10:1～1:3 with the mol ratio of catalyst；It is furthermore preferred that the mol ratio of described hydroquinone and catalyst is 2:1～1:2；
Preferably, described catalyst is sulphuric acid or vitriolated mixed acid；It is furthermore preferred that the molar content of sulphuric acid is not less than 10% in described vitriolated mixed acid, outside described vitriolated mixed acid sulfuric acid, possibly together with more than one in phosphoric acid, oxalic acid, benzenesulfonic acid or p-methyl benzenesulfonic acid；
Preferably, described in step (2), the time of isothermal reaction is 0.1～5.0h；
Preferably, temperature of reaction kettle described in step (2) is 75～90 DEG C；
(3) after reaction terminates, cooling down reactant liquor, precipitate out solid crystal, filter, gained filtrate retains, and gained filtering residue washes with water, then dries and obtains 2,5-di-tert-butyl hydroquinones；
Preferably, step (3) described filtering residue washes 2～8 times of the quality that consumption is filtering residue of middle water with water；
Preferably, step (3) described filtering residue wash with water in washing times be 2～5 times；
Preferably, step (3) described filtrate recycles as reaction mother liquor；
Described filtrate recycles as reaction mother liquor method particularly includes: hydroquinone, the tert-butyl alcohol and catalyst are joined in described filtrate, heating for dissolving, isothermal reaction at 75～90 DEG C, filters, and gained filtering residue is scrubbed obtains 2,5-di-tert-butyl hydroquinones；Gained filtrate preserves and carries out above-mentioned steps as reaction mother liquor circulation.
The present invention has such advantages as relative to prior art and effect:
(1) directional synthesis method of the present invention adopts vitriolated catalyst alkylated reaction, 2,5-di-tert-butyl hydroquinone's yields reach more than 90%, and raw material is close to and is completely converted into target product 2,5-di-tert-butyl hydroquinone, selectivity and Atom economy are high.
(2) building-up process of directional synthesis method of the present invention does not use the organic solvent such as aromatic hydrocarbon and ketone, it is to avoid the problem of dissolvent residual, energy-conserving and environment-protective.
(3) directional synthesis method reaction condition of the present invention is gentle, requires low to consersion unit.
(4) reactant liquor of directional synthesis method of the present invention can be recycled, and greatly reduces production cost, and decreases the pollution to environment.
(5) 2,5-di-tert-butyl hydroquinone's yield of directional synthesis method of the present invention are high, and reaction yield is more than 90%, and filtering residue is after washing, crystallization, and the purity of 2,5-di-tert-butyl hydroquinones reaches 99%.
Accompanying drawing explanation
Fig. 1 is the GC-MS detection figure of the inventive method products therefrom 2,5 di tert butyl hydroquinone.
Fig. 2 is the inventive method products therefrom 2,5 di tert butyl hydroquinone1HNMR detects figure.
Fig. 3 is the IR detection figure of the inventive method products therefrom 2,5 di tert butyl hydroquinone.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
Taking hydroquinone 2.757g to mix with oxalic acid 0.142g, be equipped with the there-necked flask of thermometer, agitator, condensing tube, constant pressure funnel, add water 2ml, stirring in there-necked flask, heating is to 82 DEG C；Being added by constant pressure funnel by tert-butyl alcohol 3.100g, to there-necked flask, solid is completely dissolved, and is mixed with concentrated sulphuric acid 2.457g by the 8.030g tert-butyl alcohol, is slowly added to there-necked flask, and keeps 82 DEG C of reaction 2h；Stopped reaction, after system cools down, filters, and solid filter residue, with 5mL water washing, repeated washing 4 times, dries, obtains crude product 2,5-di-tert-butyl hydroquinone 4.694g, yield: 84.32%.
Recrystallization obtains product 2,5-di-tert-butyl hydroquinone 3.898g, and purity reaches more than 99%, and comprehensive yield is 70.03%.
Taking the product after recrystallization, carry out GC-MS detection with acetone for solvent, detecting instrument is Japan Shimadzu GCMS-QP2010, and testing result is as shown in Figure 1.Result illustrates: the inventive method products therefrom main component 2,5-di-tert-butyl hydroquinone's content reaches 99%, has higher purity, and molecular weight is 222, is consistent with the molecular weight of 2,5-di-tert-butyl hydroquinones.
Embodiment 2
Taking hydroquinone 2.732g, be equipped with the there-necked flask of thermometer, agitator, condensing tube, constant pressure funnel, add water 2ml, stirring in there-necked flask, heating is to 83 DEG C；Being added by constant pressure funnel by tert-butyl alcohol 2.978g, to there-necked flask, solid is completely dissolved, and with concentrated sulphuric acid 1.966g, phosphoric acid 0.491g, the 8.152g tert-butyl alcohol is made into mix acid liquor, is slowly added to there-necked flask, and keeps 83 DEG C of reaction 2h；Stopped reaction, after system cools down, filters, and solid filter residue, with 5mL water washing, repeated washing 4 times, dries, obtains crude product 2,5-di-tert-butyl hydroquinone 4.637g, yield: 84.06%.
Recrystallization obtains 2,5-di-tert-butyl hydroquinone 3.887g, and purity reaches more than 99%, and comprehensive yield is 70.47%.
Take the product after recrystallization, carry out for solvent with deuterated acetone1HNMR detects, and detecting instrument is Germany Brooker company AVANCEDigital400MHzNMR, and testing result is as shown in Figure 2.Result illustrates: peak, chemical displacement value 6.7ppm place is hydrogen on phenyl ring, and peak, 1.3ppm place is methyl hydrogen, and the two integrated value ratio is about 1:9, composes information of number with the hydrogen of the chemical constitution of 2,5-di-tert-butyl hydroquinones and is consistent.
Embodiment 3
Taking hydroquinone 5.505g to mix with oxalic acid 0.228g, be equipped with the there-necked flask of thermometer, agitator, condensing tube, constant pressure funnel, add 4ml water, stirring, heating is to 86 DEG C；Being added by Dropping funnel by tert-butyl alcohol 6.044g, to there-necked flask, solid is completely dissolved, and is mixed with concentrated sulphuric acid 4.971g by the 10.704g tert-butyl alcohol, is slowly added to there-necked flask, and keeps 86 DEG C of reaction 2h；Stopped reaction, after system cools down, filters, and solid filter residue, with 10mL water washing, repeated washing 4 times, dries, obtains crude product 2,5-di-tert-butyl hydroquinone 9.277g, yield: 83.46%.
Recrystallization obtains product 2,5-di-tert-butyl hydroquinone 7.894g, and comprehensive yield: 71.32%, purity reaches more than 99%.
Taking the product after recrystallization, with KBr pressed disc method, it is carried out FT-IR detection, detecting instrument is the silent nicolet380FT-IR of U.S.'s match, and testing result is respectively as shown in Figure 3.Result illustrates: 3401cm-1For O-H stretching vibration absworption peak, 2951cm-1With 2869cm-1Locate antisymmetry and symmetrical absworption peak, the 1471cm of respectively methyl-1With 1400cm-1Locate antisymmetry bending vibration and umbrella shape bending vibration absworption peak, the 1170cm of respectively methyl-1Place is C-O stretching vibration absworption peak.Result is consistent with 2,5 di tert butyl hydroquinone characteristic group's absworption peak.
Embodiment 4
Taking hydroquinone 11.015g and be equipped with the there-necked flask of thermometer, agitator, condensing tube, constant pressure funnel, add water 8ml, stirring in there-necked flask, heating is to 83 DEG C；Being added by Dropping funnel by tert-butyl alcohol 12.082g, to there-necked flask, solid is completely dissolved, and with concentrated sulphuric acid 9.609g, phosphoric acid 0.468g, the 32.524g tert-butyl alcohol is made into mix acid liquor, is slowly added in there-necked flask, and keeps 83 DEG C of reaction 2h；Stopped reaction, after system cools down, filters, and solid filter residue, with 20mL water washing, repeated washing 4 times, dries, obtains crude product 2,5-di-tert-butyl hydroquinone 20.819g, and yield is 93.65%.
Recrystallization obtains product 2,5-di-tert-butyl hydroquinone 15.701g, and purity reaches more than 99%, and comprehensive yield is 70.63%.
Embodiment 5
Taking hydroquinone 33.402g and be equipped with the there-necked flask of thermometer, agitator, condensing tube, constant pressure funnel, add water 20ml, stirring in there-necked flask, heating is to 86 DEG C；Being added by Dropping funnel by tert-butyl alcohol 35.024g, to there-necked flask, solid is completely dissolved, and is mixed with concentrated sulphuric acid 29.741g by the 79.482g tert-butyl alcohol, is slowly added to there-necked flask, and keeps 86 DEG C of reaction 2h；Stopped reaction, after system cools down, filters, and solid filter residue, with 60mL water washing, repeated washing 4 times, dries, obtains crude product 2,5-di-tert-butyl hydroquinone 66.075g, yield: 98.07%.
Recrystallization obtains product 2,5-di-tert-butyl hydroquinone 53.025g, and purity reaches more than 99.5%, comprehensive yield: 78.70%.
Embodiment 6
Taking hydroquinone 436.462g and be equipped with the there-necked flask of thermometer, agitator, condensing tube, constant pressure funnel, add water 260ml, stirring in there-necked flask, heating is to 85 DEG C；Being added by Dropping funnel by tert-butyl alcohol 450.326g, to there-necked flask, solid is completely dissolved, and is mixed with concentrated sulphuric acid 386.123g by the 1007.917g tert-butyl alcohol, is slowly added to there-necked flask, and keeps 85 DEG C of reaction 3h；Stopped reaction, after system cools down, filters, and solid filter residue, with 800mL water washing, repeated washing 4 times, dries, obtains crude product 2,5-di-tert-butyl hydroquinone 874.382g, yield: 99.32%.
Recrystallization obtains product 2,5-di-tert-butyl hydroquinone 696.574g, and purity reaches more than 99.3%, comprehensive yield: 79.12%.
Embodiment 7
Taking hydroquinone 33.010g, be equipped with the there-necked flask of thermometer, agitator, condensing tube, constant pressure funnel, add water 24ml, stirring in there-necked flask, heating is to 83 DEG C；Being added by Dropping funnel by tert-butyl alcohol 35.193g, to there-necked flask, solid is completely dissolved, and is mixed with 28.794g concentrated sulphuric acid by the 98.523g tert-butyl alcohol, is slowly added to there-necked flask, and keeps 83 DEG C of reaction 2h；Reaction stops, and after system cools down, filters, obtains solid filter residue 63.497g, yield 95.27%；
Filtrate returns there-necked flask as mother solution, is added to 33.147g hydroquinone, tert-butyl alcohol 66.492g, concentrated sulphuric acid 28.200g, reheats to 83 DEG C, and insulation reaction 3h；After system cools down, filter, obtain solid filter residue 62.134g, yield 92.84%；Filtrate again returns to there-necked flask, adds hydroquinone 33.336g, tert-butyl alcohol 132.492g, concentrated sulphuric acid 28.764g to there-necked flask, reheats to 83 DEG C, and insulation reaction 3h, after system cools down, filters, obtains solid filter residue 62.657g, yield 93.09%；Filtrate returns there-necked flask, adds 33.171g hydroquinone, the 133.974g tert-butyl alcohol, 28.578g concentrated sulphuric acid, reheat to 83 DEG C in there-necked flask, and insulation reaction 3h, after system cools down, filters, obtains solid filter residue 60.311g, yield 90.05%.
Above-described embodiment is the present invention preferably embodiment; but embodiments of the present invention are also not restricted to the described embodiments; the change made under other any spirit without departing from the present invention and principle, modification, replacement, combination, simplification; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (4)
1. one kind 2, the directional synthesis method of 5-di-tert-butyl hydroquinone, it is characterised in that comprise the steps: with the tert-butyl alcohol and hydroquinone for raw material, with water for solvent, add catalyst, after carrying out insulation reaction, cooling, precipitate out solid crystal, filter, after filtering residue washing, dry and obtain 2,5-di-tert-butyl hydroquinones；
Concrete synthesis step is as follows:
(1) in a kettle. by hydroquinone, water and the tert-butyl alcohol mixing accounting for the total consumption 1/5～1/2 of the tert-butyl alcohol, heating for dissolving；
(2) by the remaining tert-butyl alcohol and catalyst mix, then being slowly dropped in aforesaid reaction vessel, keeping temperature of reaction kettle after being added dropwise to complete is 75～90 DEG C, isothermal reaction 0.1～5.0h；
(3) after reaction terminates, cooling down reactant liquor, precipitate out solid crystal, filter, gained filtrate retains, and gained filtering residue washes with water, then dries and obtains 2,5-di-tert-butyl hydroquinones；
The mol ratio of described hydroquinone and the total consumption of the tert-butyl alcohol is 1:3～1:7；The mass ratio of the total consumption of the described tert-butyl alcohol and water is 100:0～30:70；The mol ratio of described hydroquinone and catalyst is 2:1～1:2；Described catalyst is sulphuric acid or vitriolated mixed acid；In described vitriolated mixed acid, the molar content of sulphuric acid is not less than 10%, outside described vitriolated mixed acid sulfuric acid, possibly together with more than one in phosphoric acid, oxalic acid, benzenesulfonic acid or p-methyl benzenesulfonic acid.
2. the directional synthesis method of 2,5-di-tert-butyl hydroquinones according to claim 1, it is characterised in that: step (3) described filtering residue washes 2～8 times of the quality that consumption is filtering residue of middle water with water；Step (3) described filtering residue wash with water in washing times be 2～5 times.
3. the directional synthesis method of 2,5-di-tert-butyl hydroquinones according to claim 1, it is characterised in that: step (3) described filtrate recycles as reaction mother liquor.
4. according to claim 32, the directional synthesis method of 5-di-tert-butyl hydroquinone, it is characterized in that: described filtrate recycles as reaction mother liquor method particularly includes: hydroquinone, the tert-butyl alcohol and catalyst are joined in step (3) described filtrate, heating for dissolving, isothermal reaction at 75～90 DEG C, filters, and gained filtering residue is scrubbed obtains 2,5-di-tert-butyl hydroquinone, gained filtrate carries out above-mentioned steps as reaction mother liquor circulation.
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| CN105418383B (en) * | 2015-12-25 | 2017-10-20 | 华南理工大学 | The commercial plant and method of 2,5 di-tert-butyl hydroquinones of a kind of energy saving and environment friendly production |
| CN110878008B (en) * | 2018-09-06 | 2023-10-13 | 四川科伦药物研究院有限公司 | Preparation method of high-purity 2-tertiary butyl hydroquinone and purification method of 2-tertiary butyl hydroquinone |
| CN109865521B (en) * | 2019-03-20 | 2020-04-28 | 北京化工大学 | Mixed metal catalyst for preparing tert-butylhydroquinone and preparation method of tert-butylhydroquinone |
| CN111620763A (en) * | 2020-06-05 | 2020-09-04 | 亿如科技(北京)有限公司 | Green synthesis process of TBHQ |
| CN112876342A (en) * | 2021-02-08 | 2021-06-01 | 杉杉新材料（衢州）有限公司 | Preparation method of 2, 5-di-tert-butyl-p-xylylene ether |
| CN115073352A (en) * | 2022-06-28 | 2022-09-20 | 吉尔多肽生物制药(大连市)有限公司 | Synthetic method of 2,5, 7-tri-tert-butyl tryptophan |
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