CN104761440B - A kind of separation/purification method of 1,4-benzoquinone compound - Google Patents
A kind of separation/purification method of 1,4-benzoquinone compound Download PDFInfo
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- CN104761440B CN104761440B CN201410472324.5A CN201410472324A CN104761440B CN 104761440 B CN104761440 B CN 104761440B CN 201410472324 A CN201410472324 A CN 201410472324A CN 104761440 B CN104761440 B CN 104761440B
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- benzoquinone
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- benzoquinone compound
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- accelerator
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/10—Separation; Purification; Stabilisation; Use of additives
Abstract
The invention provides a kind of separation/purification method of 1,4-benzoquinone compound, it is characterized in：To the accelerator that promotion 1,4-benzoquinone compound aggregation/self assembly is added in the liquefied mixture containing 1,4-benzoquinone compound, the Precipitation under realizing 1,4-benzoquinone compound in room temperature or less than room temperature condition realizes the purpose that 1,4-benzoquinone compound is separated/purified.
Description
Cross reference to related applications
This application is entitled " a kind of preparation method of 1,4-benzoquinone compound "（Application number：201410443854.7,2014 years
September is submitted on the 3rd）, " a kind of method that oxybenzene compound direct oxidation prepares 1,4-benzoquinone compound "（Application number：
September is submitted on the 5th within 201410449008.6,2014 years）" a kind of gating catalytic oxidation oxybenzene compound prepares 1,4-benzoquinone compound
Method "（Application number：September is submitted on the 9th within 201410452657.1,2014 years）Chinese patent extension and supplement.
Technical field
1,4-benzoquinone chemical combination is realized the present invention relates to a kind of separation/purification method of 1,4-benzoquinone compound, more particularly to one kind
Method of the thing from Precipitation comprising metal ion, oxybenzene compound and in organic solvent mixed system.
Background technology
1,4-benzoquinone compound, for example：1,4- benzoquinones, 2- methylbenzoquinones, 2- tert-butyl groups benzoquinones, 2,3,5- trimethylbenzoquinones
Deng, it is the important industrial chemicals of a class, it is widely used in dyestuff, macromolecular material, organic synthesis, fine chemistry industry, agricultural chemicals, medicine
Deng field.At present, 1,4-benzoquinone compound is mainly for the manufacture of hydroquinones compound and dyestuff intermediate, rubber antioxidant, third
Alkene nitrile and vinyl acetate polymerization initiator and chlorinating agent etc., also serve as styrene, vinyl acetate, methyl methacrylate,
The polymerization inhibitor of the monomers such as unsaturated polyester resin, while being also the initiator of acrylonitrile and vinyl acetate polymerization, also serves as in addition
The antioxidant of natural rubber, synthetic rubber, food and other organic matters.
1,4-benzoquinone compound is relatively low due to the solubility in cold water, and solubility in the hot water is higher, so many enterprises
Industry carries out the separating-purifying of 1,4-benzoquinone compound using the steam stripped method of water vapour.For example：In aniline oxidizing process（I.e. aniline is in sulphur
It is oxidized in the technique of 1,4-benzoquinone through high-valency metal salt in acid medium）In, after reaction Mother liquor is using water vapour inversely stripping,
Can be with isolated 1,4-benzoquinone product by steps such as cooling, crystallizations.But, this stripping process energy consumption is too high, and produces
Substantial amounts of waste water containing quinone, further, since the chemical property of 1,4-benzoquinone is more active, charing coking is susceptible in stripper and is showed
As not only reducing the yield of 1,4-benzoquinone, and product quality can be influenceed.
For shortcomings present in current 1,4-benzoquinone production of chemicals technique, develop a kind of efficient, succinct to benzene
Quinone separating technology turn into this area in the urgent need to.
The content of the invention
The sixties in last century, Pearson proposes hsab theory, and molecule can be roughly divided into " soft " and " hard " two
Class：" hard " refer to those have the ratio of the molecule of higher charge density, small radii, i.e. charge density and ionic radius compared with
Greatly；" soft " refer to those have molecule compared with low charge density and relatively large radius, i.e. ratios of charge density and ionic radius compared with
Greatly.Later, this theory gradually expanded to organic chemistry filed, and divided organic molecule with absolute hardness（R. G.
Pearson,J. Org. Chem., 1989,54, 1423-1430）.
Material solubility in media as well depends on the solvent environment residing for it.Under certain condition,（Instead）Aromatic series or
Active force of the thick cyclics between molecule in absolute hardness organic solvent high is stronger, it may appear that aggregation/self assembly is existing
As, and cause its solubility accordingly to reduce, sometimes with Precipitation phenomenon, so this principle can be used to realize material
Separating-purifying.For example：Document（H. Sugiura et al.,J. Am. Chem. Soc., 2004, 126, 14858-
14864）Condensed ring molecule State-dependence in a solvent is reported in the type of solvent for being used, especially with different substituents
The aromatic solvent of group, the intermolecular aggregation of condensed ring can be realized using absolute hardness aromatic solvent higher, and soft virtue
Fragrant race's solvent is then beneficial to the dispersion of condensed ring molecule.
It is an object of the invention to provide a kind of separation method of 1,4-benzoquinone compound, exist to solve current stripping process
Problem.To achieve these goals, the present invention is promoted according to hsab theory by using absolute hardness accelerator higher
Enter the aggregation/self assembly in a solvent of 1,4-benzoquinone compound, under realizing 1,4-benzoquinone compound in room temperature or less than room temperature condition
Precipitation, reaches the purpose of separation.
In early stage patent（Chinese Patent Application No.：201410443854.7th, 201410449008.6 and
201410452657.1）In, we disclose a series of methods for preparing 1,4-benzoquinone compound, i.e., using oxybenzene compound as original
Material, the method that 1,4-benzoquinone compound is prepared using oxygen.Mixture is used as research after the reaction that method described above of the present invention is obtained
Object, it is possible to achieve the simple separation of 1,4-benzoquinone compound.
The 1,4-benzoquinone compound that the present invention is applicable has following structural formula：
Wherein R1, R2, R3And R4It is independent selected from hydrogen, hydrocarbyl group, four can be with identical or difference, wherein alkyl base
Group is selected from comprising 1 to about 8 straight or branched alkane group of carbon atom, comprising 1 to the about 8 straight or branched alkane of carbon atom
Epoxide group, comprising about 6 to about 12 alkene or aromatic group of carbon atom.Further, alkyl is containing 1 to 4 carbon original
The alkyl of son, alkoxy is that, containing 1 to 4 alkoxy of carbon atom, aromatic series base is containing 6 to 12 phenyl, the naphthyls of carbon atom
Or xenyl.Preferably, 1,4-benzoquinone compound can be 1,4-benzoquinone, naphthoquinones, anthraquinone, 2- EAQs, 2（3 or 5 or 6）- methyl
（Ethyl, isopropyl or the tert-butyl group）1,4-benzoquinone, 2- phenyl 1,4-benzoquinone, 2,6（2,3rd, 2,5 or 3,5）- dimethyl（Ethyl, isopropyl
Or the tert-butyl group）1,4-benzoquinone, 2,3,5（2,3,6th, 2,5,6 or 3,5,6）- trimethyl（Ethyl, isopropyl or the tert-butyl group）1,4-benzoquinone,
The mixture of 2,3,4,5- duroquinones or above-claimed cpd.
Accelerator used in the present invention can be the compound with following structural formula：
Wherein R1Selected from the one kind in C, N, O, R2And R3It is independent selected from hydrogen, amino, nitro, carboxylic acid group（Salt）, ester group,
Aldehyde radical, sulfonic group（Salt）, ketone group, hydroxyl, itrile group, sulfydryl, halogen and alkyl, R2And R3Can be with identical or difference, the halogen
Selected from F, Cl, described alkyl is selected from comprising 1 to about 6 straight or branched alkane/halogenated alkane group of carbon atom, comprising 1
To about 6 straight or branched alkoxyl groups of carbon atom, comprising 6 to about 12 alkene or aromatic group of carbon atom, enter
One step, alkane group is selected from containing 1 to the 4 straight or branched alkane of carbon atom, and alkoxy is containing 1 to 3 alkane of carbon atom
Epoxide, halogenated alkane group is included containing 1 to 4 halogenated hydrocarbons of part substitution or the full substitution of carbon atom.
Accelerator used in the present invention can be extended to comprising 1 to about 8 liquified Halon hydrocarbon of carbon atom.It is preferred that
, but be not limited to, halogenated alkane is containing 2 to 4 halogenated hydrocarbons of part substitution or the full substitution of carbon atom.It is furthermore preferred that can
Being 1,2- dichloros（Bromine or iodine）Ethane, 1,1,2,2- tetrachloros（Bromine or iodine）Ethane, perchloro-（Bromine or iodine）For ethane, 1,2- dichloros
（Bromine or iodine）Propane, 1,3- dichloros（Bromine or iodine）Propane, 1,1,2,2- tetrachloros（Bromine or iodine）Butane, perchloro-（Bromine or iodine）Generation third
Alkane, perchloro-（Bromine or iodine）For the one kind in butane or above-mentioned several combination.
Accelerator used in the present invention can also be the combination of above-mentioned two classes accelerator.
In order to realize the purpose of foregoing invention, the present invention uses following operating procedure：A certain amount of accelerator is added containing right
Liquefied mixture after the reaction of quinone compounds, stirs 30 minutes, to benzene after standing overnight in room temperature or less than under room temperature condition
Naphtoquinone compounds are separated out with precipitation form, and simple filtering or centrifugation are to be capable of achieving to separate purpose.Wherein, the amount of accelerator,
All there is material impact in dwell temperature and metal impurities ion, these factors are also the technology contents that this method is related to separation.
In order to reach the purpose of separation, the addition of accelerator of the present invention is equivalent to 1,4-benzoquinone mixture quality
1-60%, preferably 1-50%.
One of feature of the invention also resides in separation method simply, can be in -50-50oCarried out under C, lower temperature promotes
Separate.Preferably, separation temperature is in -30-30oC。
Further, separation method of the present invention is hardly influenceed by foreign metal ion, these metal ions
Including one or more in Li, Na, K, Co, Cr, V, Ni, Mn, Fe, Pd, Pt, Ir, Au, Ru, Rh, so what the present invention was announced
Separation method has widely applicability, can be generalized to other catalyst system and catalyzings.
Brief description of the drawings
Fig. 1 is the 1,4-benzoquinone material object photo obtained after separating.
Embodiment 1：
Step one：Step is according to entitled " a kind of preparation method of 1,4-benzoquinone compound "（Application number：
September is submitted on the 3rd within 201410443854.7,2014 years）Chinese patent embodiment 1 carry out.
Step 2：To addition benzenesulfonamide trifluoroacetate methane 8.6g in the reactant mixture that step one is obtained（Equivalent to mixture quality
10%）, being stood overnight after being stirred at room temperature 30 minutes, 1,4-benzoquinone is separated out with precipitation form, and 1,4-benzoquinone is obtained after filtering
1.2g, yield 32%.
Embodiment 2-4：
Experimental procedure is same as Example 1, is only changed the addition of benzenesulfonamide trifluoroacetate methane and investigates separating effect, knot
It is really as shown in the table：
| Project | Amount（g） | Yield（%） |
| 1. | 15 | 38 |
| 2. | 30 | 55 |
| 3. | 45 | 63 |
Embodiment 5-8：
Step one is same as Example 1, and benzenesulfonamide trifluoroacetate methane 45g is added in step 2（Equivalent to mixture quality ~
50%）, stood overnight under following different temperatures, it is as a result as shown in the table：
| Project | Yield（%） | |
| 1. | 50 | 35 |
| 2. | 10 | 65 |
| 3. | -30 | 72 |
| 4. | -50 | 73 |
Embodiment 9-14：
In order to investigate influence of other metal ions to separating effect, the mixture for being obtained to the step one of embodiment 1 respectively
The acetate of the middle various metals of addition（10-30mmol）, benzenesulfonamide trifluoroacetate methane 45g is added in step 2, and -30oC is lower to be placed
Overnight, it is as a result as shown in the table：
| Project | Metal ion（mmol） | Yield（%） |
| 1. | 70 | |
| 2. | 73 | |
| 3. | 65 | |
| 4. | 68 | |
| 5. | 65 | |
| 6. | 70 |
Embodiment 15-24：
Step one is same as Example 1, and the benzenesulfonamide trifluoroacetate first in the step 2 of embodiment 1 is replaced with other accelerator in step 2
Alkane, and -30oLeft overnight under C, separating resulting is as shown in the table：
| Project | Organic solvent（g） | Yield（%） |
| 1. | Pyridine（8.6） | 15 |
| 2. | 4- trifluoromethy pyridines（8.6） | 82 |
| 3. | Between trifluoro-benzene（8.6） | 71 |
| 4. | Between trimethylbenzene（8.6） | 36 |
| 5. | Inclined trifluoro-benzene（8.6） | 62 |
| 6. | 1,1,2,2- tetrachloroethanes（2.0）+ fluorobenzene（6.6） | 89 |
| 7. | 1,1,3,3- tetrachloroethanes（2.0）+ difluoro-benzene（6.6） | 76 |
| 8. | 1,2- dibromopropanes（2.0）+ 4- trifluoromethy pyridines（6.6） | 93 |
| 9. | Perchloro- propane（6.6）+ trifluoro-benzene（2.0） | 68 |
| 10. | Perbromo- butane（3.3）+ trimethylbenzene（5.3） | 72 |
Embodiment 25-28：
Step one：a）Step is according to entitled " a kind of preparation method of 1,4-benzoquinone compound "（Application number：
September is submitted on the 3rd within 201410443854.7,2014 years）Chinese patent embodiment 67 or embodiment 68 carry out.
b）Step is according to entitled " a kind of preparation method of 1,4-benzoquinone compound "（Application number：201410443854.7,2014
On September is submitted for 3）The embodiment 70 of Chinese patent carry out.
c）Step is according to entitled " a kind of preparation method of 1,4-benzoquinone compound "（Application number：201410443854.7,2014
On September is submitted for 3）Chinese patent embodiment 73 or embodiment 74 carry out.
d）Step is according to entitled " a kind of preparation method of 1,4-benzoquinone compound "（Application number：201410443854.7,2014
On September is submitted for 3）The embodiment 75 of Chinese patent carry out.
Step 2：To benzenesulfonamide trifluoroacetate methane 8.6g is added in the reactant mixture that step one is obtained, 30 points are stirred at room temperature
Zhong Hou, and -30oC stands overnight, and separating resulting is as shown in the table：
| Project | Yield（%） |
| a. | 78 |
| b. | 85 |
| c. | 83 |
| d. | 91 |
Because of length limitation, the present invention is not illustrated one by one to all examples, but uses the key element to this technology
Technical scheme that the mode of equivalent or equivalent transformation obtained is carried out all in protection scope of the present invention.
Specific embodiment
With reference to embodiment, specific embodiment of the invention is described in further detail.By following embodiments
Will be helpful to understand the present invention, but the technical scheme that the invention is not limited in any way.
Claims (2)
1. a kind of separation/purification method of 1,4-benzoquinone compound, it is characterised in that：Mix to the liquid containing 1,4-benzoquinone compound
The accelerator of 1,4-benzoquinone compound aggregation/self assembly is added in thing, realizes that 1,4-benzoquinone compound is heavy under the conditions of -50-50 DEG C
Precipitation goes out, and the purpose that 1,4-benzoquinone compound is separated/purified is reached, wherein described 1,4-benzoquinone compound is 1,4-benzoquinone；Wherein make
Accelerator is the compound with following structural formula：
Wherein R1Selected from CH, R2And R3It is independent selected from hydrogen, halogen and alkyl, R2And R3Can be with identical or difference, the halogen
Selected from F, the alkyl is selected from comprising 1 to 6 halogenated alkane group of carbon atom；Or 1,2- dichloroethanes, 1,1,2,2- tetrachloros
Ethane, perchloro- ethane, 1,2- dichloropropanes, 1,3- dichloropropanes, the chlorobutanes of 1,1,2,2- tetra-, perchloro- propane, perchloro-
Butane；Or the mixture of above-claimed cpd.
2. method according to claim 1, wherein 1-60% of the amount of the accelerator for using equivalent to 1,4-benzoquinone quality.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1254707A (en) * | 1999-11-12 | 2000-05-31 | 中国科学院上海有机化学研究所 | C1-6 fragment compound as intermediate of esperamicin and its usage |
| JP2002284731A (en) * | 2001-03-27 | 2002-10-03 | Mitsui Chemicals Inc | Method for purifying p-quinone |
| CN102432862A (en) * | 2010-08-02 | 2012-05-02 | 赢创高施米特有限公司 | Modified alkoxylation products having at least one non-terminal alkoxysilyl group, with increased storage life and increased stretchability of the polymers prepared using them |
| CN103480176A (en) * | 2013-08-27 | 2014-01-01 | 仙桃市康化科技有限公司 | Continuous separation device for p-benzoquinone crystals |
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2014
- 2014-09-17 CN CN201410472324.5A patent/CN104761440B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1254707A (en) * | 1999-11-12 | 2000-05-31 | 中国科学院上海有机化学研究所 | C1-6 fragment compound as intermediate of esperamicin and its usage |
| JP2002284731A (en) * | 2001-03-27 | 2002-10-03 | Mitsui Chemicals Inc | Method for purifying p-quinone |
| CN102432862A (en) * | 2010-08-02 | 2012-05-02 | 赢创高施米特有限公司 | Modified alkoxylation products having at least one non-terminal alkoxysilyl group, with increased storage life and increased stretchability of the polymers prepared using them |
| CN103480176A (en) * | 2013-08-27 | 2014-01-01 | 仙桃市康化科技有限公司 | Continuous separation device for p-benzoquinone crystals |
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