CN110183318A - A kind of preparation method of chloranil - Google Patents
A kind of preparation method of chloranil Download PDFInfo
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- CN110183318A CN110183318A CN201910609060.6A CN201910609060A CN110183318A CN 110183318 A CN110183318 A CN 110183318A CN 201910609060 A CN201910609060 A CN 201910609060A CN 110183318 A CN110183318 A CN 110183318A
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- chloranil
- benzoquinone
- hydrogen peroxide
- preparation
- catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
- C07C46/06—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the preparation methods of chloranil a kind of, take chloranil, benzene, and hydrogen peroxide is added concentrated hydrochloric acid and catalyst in reaction system, temperature is made to maintain 55-65 DEG C of reaction 2-4h, then 1,4-benzoquinone powder is dried to obtain in filtering in three-neck flask.The invention avoids industrial pollution brought when conventional synthesis 1,4-benzoquinone, and can efficiently use industrial waste；Powder color is in yellow and becomes clear, and product quality is high and reliable；The yield of chloranil is high.
Description
Technical field
The present invention relates to technical field of organic synthesis, more particularly to a kind of preparation method of 1,4-benzoquinone.
Background technique
Industrially there is aniline manganese dioxide method, synthesis is reacted in sulfuric acid medium.It generates in process of production a large amount of
Manganese sulfate, ammonium sulphate waste liquor and iron cement, environmental pollution is serious；Corrosion due to containing dilute sulfuric acid in reaction material liquid, to equipment
Seriously, cost of equipment is high.
Currently, external have the research of 1,4-benzoquinone: E. I. Du Pont de Nemours and Co's patent report makees catalyst using copper bromide
Dioxygen oxidation phenol prepares 1,4-benzoquinone under the high pressure of 70 atmospheric pressure, and conversion ratio 99%, yield is up to 78%.Hus Chao-yang
Solvent selection acetonitrile is worked as in discoveries such as (Sun Tech, Inc., Philadelphia, Pa.) and water mixed solvent, cuprous iodide are
Catalyst, under the pressure of 5.2 megapascal, the selectivity of 1,4-benzoquinone is increased to 93%, and conversion ratio is 50%.It is suitble to industrialized production.
Mitsui Co., Ltd. patent report solution for oxidation of phenol with hydrogen peroxide synthesizes 1,4-benzoquinone conversion ratio 28%, selectivity 85% or so.
And the country also has relevant research to report in recent years, the report such as Hu Yucai of Shandong science and technology institute is with methanol
Solvent, molar ratio are the Cu (NO of 1 ︰ 33)2 And NaNO3 For catalyst, dioxygen oxidation, up to 90%, benzoquinones selects phenol conversion
Selecting property is up to 88%.The suitable reaction condition of the report phenol catalytic oxidation 1,4-benzoquinone such as Song Wei of domestic Inner Mongol University of Technology
Are as follows: using ethyl alcohol as solvent, CuCl2·4h2O and LiClH2O is catalyst, and at this point in the reaction, phenol conversion reaches
85%, 1,4-benzoquinone is selective up to 83%.The reports such as the Zeng Haiqiang of Hunan University are using T (p-Cl) PPCo catalyst through peroxidating
Hydroxide phenol, phenol conversion 0.3%, selectivity is up to 100%.Xu Yonghua etc. reports mesopore molecular sieve Cu/ MCM-
41 catalytic oxidation activity result of study shows that when catalyst be 100 mg, and 30mL acetic acid is solvent, 2g phenol, 6mL30%
H2O2, controlled at 80 DEG C, after reacting 8h, the conversion ratio of phenol can achieve 39%, and the selectivity of 1,4-benzoquinone can achieve
97%。
In short, the pollution to environment is very tight from the point of view of on the case where just industrially producing 1,4-benzoquinone both at home and abroad at present
Weight, can generate a large amount of waste liquid.Therefore, how a kind of green synthesis process of 1,4-benzoquinone is provided, has both been able to satisfy industrial big
The technical issues of amount demand will not pollute the environment, become those skilled in the art's urgent need to resolve.
Summary of the invention
In view of this, filling up industrial production to benzene the invention discloses the green synthesis process of chloranil a kind of
The vacancy of quinone makes industrial production greenization, prevents pollution environment, destroys production equipment, and correspondingly increase the yield of 1,4-benzoquinone.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of preparation method of chloranil, using benzene as solvent, is being urged using chloranil and 30% hydrogen peroxide as raw material
2-4h is reacted in agent and acid condition, chloranil is dried to obtain in filtering.
Preferably, the catalyst is copper chloride or copper oxide.
Preferably, the reaction temperature is 55-65 DEG C.
Preferably, the chloranil: benzene: hydrogen peroxide=1:10:10.
Preferably, the acid condition is addition concentrated hydrochloric acid, the concentrated hydrochloric acid: chloranil=1:2.
Preferably, the additive amount of the catalyst is the 1-3% of the quality of chloranil.
It can be seen via above technical scheme that compared with prior art, the present invention has the beneficial effect that:
1, the present invention using hydrogen peroxide as raw material, can be to avoid the pollution to environment, and yield is high, 1,4-benzoquinone
Powder color is golden yellow bright, and quality is good；
2, the catalyst that the present invention uses not will cause heavy metal pollution for anhydrous cupric chloride or copper oxide；
3, acid condition of the invention is provided by concentrated hydrochloric acid, because corroding the reason of sulfuric acid equipment before solving
Problem；
4, present invention process is simple, and generated waste liquid does not pollute the environment, and can greatly improve the production efficiency and effect of factory
Benefit；
5, waste material produced by the invention can efficiently use, turn waste be changed into values.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
Embodiment 1
4g hydroquinone is weighed, 40mL benzene is measured, is put into togerther in three-neck flask, measures 40mLK hydrogen peroxide and constant pressure funnel
In, 2mL concentrated hydrochloric acid is added, then weigh 0.04g CuCl2Or CuCl2·2H2O is put into three-neck flask, while controlling hydrogen peroxide
Rate of addition, 3s/d, react 4h after, be separated by solid-liquid separation, obtained solid naturally dry, yield 90.54%.
Embodiment 2
4g hydroquinone is weighed, 40mL benzene is measured, is put into togerther in three-neck flask, measures 40mL hydrogen peroxide and constant pressure funnel
In, 2mL concentrated hydrochloric acid is added, then weigh 0.04gCuCO3It is put into three-neck flask, while controlling the rate of addition of hydrogen peroxide,
3s/d after reacting 4h, is separated by solid-liquid separation, obtained solid naturally dry, yield 89.68%.
Embodiment 3
4g hydroquinone is weighed, 40mL benzene is measured, is put into togerther in three-neck flask, measures 40mL hydrogen peroxide in constant pressure funnel
In, 2mL concentrated hydrochloric acid is added, then weigh 0.04gCuSO4It is put into three-neck flask, while controlling the rate of addition of hydrogen peroxide,
3s/d after reacting 4h, is separated by solid-liquid separation, obtained solid naturally dry, yield 89.3%.
Embodiment 4
4g hydroquinone is weighed, 40mL benzene is measured, is put into togerther in three-neck flask, measures 40mL hydrogen peroxide and constant pressure funnel
In, 2mL concentrated hydrochloric acid is added, then weigh 0.04gCuCl2·2H2O is put into three-neck flask, while controlling the dropwise addition speed of hydrogen peroxide
Degree, 3s/d after reacting 4h, are separated by solid-liquid separation, obtained solid naturally dry, yield 90%.
Embodiment 5
4g chloranil is weighed, 40mL benzene is measured, is put into togerther in three-neck flask, measures 40mL hydrogen peroxide and constant pressure funnel
In, 2mL concentrated hydrochloric acid is added, then weigh 0.04g copper oxide and be put into three-neck flask, while controlling the rate of addition of hydrogen peroxide,
3s/d after reacting 4h, is separated by solid-liquid separation, obtained solid naturally dry.Obtained 1,4-benzoquinone yield is 90.54 %.
Embodiment 6
4g chloranil is weighed, 40mL benzene is measured, is put into togerther in three-neck flask, measures 40mL hydrogen peroxide and constant pressure funnel
In, 2mL concentrated hydrochloric acid is added, then weigh 0.04gCu (OH)2It is put into three-neck flask, while controlling the rate of addition of hydrogen peroxide,
3s/d after reacting 4h, is separated by solid-liquid separation naturally dry.Obtained 1,4-benzoquinone yield is 90.54%.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.For device disclosed in embodiment
For, since it is corresponded to the methods disclosed in the examples, so being described relatively simple, related place is said referring to method part
It is bright.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (6)
1. a kind of preparation method of chloranil, which is characterized in that using chloranil and hydrogen peroxide as raw material, be with benzene
Solvent, reacts 2-4h in catalyst and acid condition, and 1,4-benzoquinone is dried to obtain in filtering.
2. the preparation method of chloranil according to claim 1 a kind of, which is characterized in that the catalyst is chlorination
Copper or copper oxide.
3. the preparation method of chloranil according to claim 1 a kind of, which is characterized in that the reaction temperature is
55-65℃。
4. the preparation method of chloranil according to claim 1-3 a kind of, which is characterized in that the tetrachloro
1,4-benzoquinone: benzene: hydrogen peroxide=1:10:10.
5. the preparation method of chloranil according to claim 4 a kind of, which is characterized in that the acid condition is to add
Enriching hydrochloric acid, the concentrated hydrochloric acid: chloranil=1:2.
6. the preparation method of chloranil according to claim 4 a kind of, which is characterized in that the addition of the catalyst
Amount is the 1-3% of the quality of chloranil.
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| CN201910609060.6A CN110183318A (en) | 2019-07-08 | 2019-07-08 | A kind of preparation method of chloranil |
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| CN201910609060.6A CN110183318A (en) | 2019-07-08 | 2019-07-08 | A kind of preparation method of chloranil |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172508A (en) * | 2011-12-22 | 2013-06-26 | 中国科学院大连化学物理研究所 | Method for preparing 1,4-benzoquinone by directly oxidizing benzene |
| CN104744229A (en) * | 2015-04-13 | 2015-07-01 | 中国科学院青岛生物能源与过程研究所 | Synthetic method of p-benzoquinone |
| CN106588618A (en) * | 2016-10-28 | 2017-04-26 | 江苏扬农化工集团有限公司 | Method for catalyzing oxidation of phenol and hydrogen peroxide with selenium-containing catalyst for synthesis of p-benzoquinone |
| CN106673983A (en) * | 2017-01-03 | 2017-05-17 | 岳阳环宇药业有限公司 | Tetrachloro-1,4-benzoquinone preparation method |
| CN108689821A (en) * | 2018-06-22 | 2018-10-23 | 北京工业大学 | A kind of method of hydrogen peroxide oxidation regeneration tetrachloroquinone |
-
2019
- 2019-07-08 CN CN201910609060.6A patent/CN110183318A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172508A (en) * | 2011-12-22 | 2013-06-26 | 中国科学院大连化学物理研究所 | Method for preparing 1,4-benzoquinone by directly oxidizing benzene |
| CN104744229A (en) * | 2015-04-13 | 2015-07-01 | 中国科学院青岛生物能源与过程研究所 | Synthetic method of p-benzoquinone |
| CN106588618A (en) * | 2016-10-28 | 2017-04-26 | 江苏扬农化工集团有限公司 | Method for catalyzing oxidation of phenol and hydrogen peroxide with selenium-containing catalyst for synthesis of p-benzoquinone |
| CN106673983A (en) * | 2017-01-03 | 2017-05-17 | 岳阳环宇药业有限公司 | Tetrachloro-1,4-benzoquinone preparation method |
| CN108689821A (en) * | 2018-06-22 | 2018-10-23 | 北京工业大学 | A kind of method of hydrogen peroxide oxidation regeneration tetrachloroquinone |
Non-Patent Citations (4)
| Title |
|---|
| 刘俊峰等: "氢醒氧化加成合成四氯-1,4-苯醒", 《化学试剂》 * |
| 宋伟等: "氧气直接催化氧化苯酚合成对苯醒", 《精细石油化工》 * |
| 朱旭容等: "四氯苯醌的合成", 《南京化工大学学报》 * |
| 申利群等: "过氧化氢氧化法合成四氯苯醌的研究", 《精细化工中间体》 * |
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