CN104761440A - Separation / purification method of p-benzoquinone compound - Google Patents
Separation / purification method of p-benzoquinone compound Download PDFInfo
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- CN104761440A CN104761440A CN201410472324.5A CN201410472324A CN104761440A CN 104761440 A CN104761440 A CN 104761440A CN 201410472324 A CN201410472324 A CN 201410472324A CN 104761440 A CN104761440 A CN 104761440A
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- Prior art keywords
- para benzoquinone
- group
- compound
- bromine
- iodine
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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 separation / purification method of a p-benzoquinone compound. The method is characterized in that an accelerator for promoting aggregation / self assembly of the p-benzoquinone compound is added to a mixed liquid containing p-benzoquinone compound, so as to realize precipitation of the p-benzoquinone compound at or below room temperature and separation / purification of the p-benzoquinone compound.
Description
The cross reference of related application
This application is entitled as " a kind of preparation method of para benzoquinone compound " (application number: 201410443854.7, on September 3rd, 2014 submits), " method of para benzoquinone compound is prepared in a kind of oxybenzene compound direct oxidation " (application number: 201410449008.6, on September 5th, 2014 submits) and " a kind of gating catalytic oxidation oxybenzene compound prepares the method for para benzoquinone compound " (application number: 201410452657.1, on September 9th, 2014 submits) Chinese patent expansion and supplement.
Technical field
The present invention relates to a kind of separation/purification method of para benzoquinone compound, particularly relate to a kind of para benzoquinone compound that realizes from the method comprising Precipitation metal ion, oxybenzene compound and organic solvent mixed system.
Background technology
Para benzoquinone compound, such as: Isosorbide-5-Nitrae-benzoquinones, 2-methylbenzoquinone, 2-tertiary butyl benzoquinones, 2,3,5-trimethylbenzoquinones etc., are the important industrial chemicals of a class, are widely used in dyestuff, macromolecular material, organic synthesis, fine chemistry industry, agricultural chemicals, medicine and other fields.At present, para benzoquinone compound is mainly for the manufacture of Resorcinol compound and dyestuff intermediate, rubber antioxidant, vinyl cyanide and vinyl acetate between to for plastic polymerization starter and chlorizating agent etc., also be used as the stopper of the monomers such as vinylbenzene, vinyl-acetic ester, methyl methacrylate, unsaturated polyester resin, also be the initiator of vinyl cyanide and vinyl acetate polymerization simultaneously, be also used as natural rubber, synthetic rubber, food and other organic oxidation inhibitor in addition.
Para benzoquinone compound due to the solubleness in cold water lower, solubleness is in the hot water higher, so a lot of enterprise adopts the steam stripped method of water vapor to carry out the separating-purifying of para benzoquinone compound.Such as: in aniline oxidation style (namely aniline is oxidized in the technique of para benzoquinone through high-valency metal salt in sulfuric acid medium), after mother liquor adopts the reverse stripping of water vapor after reaction, can be separated by steps such as cooling, crystallizations and obtain para benzoquinone product.But this stripping process energy consumption is too high, and produce a large amount of containing quinone waste water, in addition, because the chemical property of para benzoquinone is relatively more active, in stripping tower, charing coking phenomenon easily occurs, not only reduce the yield of para benzoquinone, and can quality product be affected.
For the shortcomings existed in current para benzoquinone production of chemicals technique, develop a kind of efficient, succinct para benzoquinone separating technology become this area in the urgent need to.
Summary of the invention
The sixties in last century, Pearson proposes hsab theory, molecule can be roughly divided into " soft " and " firmly " two class: " firmly " refers to that those have the molecule of higher charge density, small radii, and namely the ratio of electric density and ionic radius is larger; " soft " refers to that those have the molecule compared with low charge density and relatively large radius, and namely the ratio of electric density and ionic radius is larger.Afterwards, this theory expanded to organic chemistry filed gradually, and with absolute hardness degree divide organic molecule (R. G. Pearson,
j. Org. Chem.,1989,54,1423-1430).
Material solubleness in media as well depends on the solvent environment residing for it.Under certain condition, (instead) aromatic series or the reactive force of condensed ring compounds between the organic solvent Middle molecule that absolute hardness degree is high stronger, there will be gathering/self-assembly phenomenon, and cause the corresponding reduction of its solubleness, sometimes with Precipitation phenomenon, so this principle can be used for realizing the separating-purifying of material.Such as: document (H. Sugiura et al.,
j. Am. Chem. Soc.2004,126,14858-14864) report condensed ring molecule State-dependence in a solvent in used type of solvent, especially with the aromatic solvent of different substituents group, use the higher aromatic solvent of absolute hardness degree can realize the intermolecular gathering of condensed ring, soft aromatic solvent is then beneficial to the dispersion of condensed ring molecule.
The object of the present invention is to provide a kind of separation method of para benzoquinone compound, to solve current stripping process Problems existing.To achieve these goals, the present invention is according to hsab theory, by using the promotor that absolute hardness degree is higher to promote the gathering/self-assembly in a solvent of para benzoquinone compound, realizing para benzoquinone compound in room temperature or lower than the Precipitation under room temperature condition, reaching the object of separation.
In patent (Chinese Patent Application No.: 201410443854.7,201410449008.6 and 201410452657.1) in early stage, we disclose a series of method preparing para benzoquinone compound, namely using oxybenzene compound as raw material, oxygen is used to prepare the method for para benzoquinone compound.After the reaction that the present invention obtains using aforesaid method, mixture is as research object, can realize the simple and easy separation of para benzoquinone compound.
The present invention the para benzoquinone compound that is suitable for there is following structural formula:
Wherein R
1, R
2, R
3and R
4independently be selected from hydrogen, hydrocarbyl group, four can be identical or different, and wherein hydrocarbyl group is selected from the straight or branched alkane group comprising 1 to about 8 carbon atom, the straight or branched alkoxy base comprising 1 to about 8 carbon atom, the alkene comprising about 6 to about 12 carbon atoms or aromatic group.Further, alkyl is the alkyl containing 1 to 4 carbon atom, and alkoxyl group is the alkoxyl group containing 1 to 4 carbon atom, and aromatic series base is containing the phenyl of 6 to 12 carbon atoms, naphthyl or xenyl.Preferably, para benzoquinone compound can be para benzoquinone, naphthoquinones, anthraquinone, 2-ethyl-anthraquinone, 2(3 or 5 or 6)-methyl (ethyl, sec.-propyl or the tertiary butyl) para benzoquinone, 2-phenyl para benzoquinone, 2,6(2,3,2,5 or 3,5)-dimethyl (ethyl, sec.-propyl or the tertiary butyl) para benzoquinone, 2,3,5(2,3,6,2,5,6 or 3,5,6)-trimethylammonium (ethyl, sec.-propyl or the tertiary butyl) para benzoquinone, 2,3, the mixture of 4,5-duroquinone or above-claimed cpd.
Promotor used in the present invention can be the compound with following structural formula:
Wherein R
1be selected from the one in C, N, O, R
2and R
3independently be selected from hydrogen, amino, nitro, carboxylic acid group's (salt), ester group, aldehyde radical, sulfonic group (salt), ketone group, hydroxyl, itrile group, sulfydryl, halogen and alkyl, R
2and R
3can be identical or different, described halogen is selected from F, Cl, described alkyl is selected from the straight or branched alkane/halogenated alkane group comprising 1 to about 6 carbon atom, the straight or branched alkoxy base comprising 1 to about 6 carbon atom, the alkene comprising 6 to about 12 carbon atoms or aromatic group, further, alkane group is selected from the straight or branched alkane containing 1 to 4 carbon atom, alkoxyl group is the alkoxyl group containing 1 to 3 carbon atom, and the part that halogenated alkane group comprises containing 1 to 4 carbon atom replaces or the full halohydrocarbon replaced.
Promotor used in the present invention can also extend to the liquified Halon hydrocarbon comprising 1 to about 8 carbon atom.Preferably, but be not limited to, halogenated alkane is the halohydrocarbon containing the part replacement of 2 to 4 carbon atoms or replacement entirely.Preferred, can be 1,2-dichloro (bromine or iodine) ethane, 1,1,2,2-tetrachloro (bromine or iodine) ethane, perchloro-(bromine or iodine) are for ethane, 1,2-dichloro (bromine or iodine) propane, 1,3-dichloro (bromine or iodine) propane, 1,1,2,2-tetrachloro (bromine or iodine) butane, perchloro-(bromine or iodine) for propane, perchloro-(bromine or iodine) for a kind of or above-mentioned several combination in butane.
Promotor used in the present invention also can be the combination of above-mentioned two class promotor.
In order to realize the object of foregoing invention, the present invention adopts following operation steps: a certain amount of promotor is added liquid form mixt after the reaction containing para benzoquinone compound, stir 30 minutes in room temperature or lower than under room temperature condition, after hold over night, para benzoquinone compound is separated out with precipitation forms, and simple filtration or centrifugation can realize being separated object.Wherein, all there is material impact to separation in the amount of promotor, dwell temperature and metallic impurity ion, these factors are also the technology contents that present method relates to.
In order to reach the object of separation, the add-on of promotor of the present invention is equivalent to the 1-60% of para benzoquinone mixture quality, preferred 1-50%.
One of feature of the present invention is also that separation method is simple, can at-50-50
ocarry out under C, lesser temps promotes to be separated.Preferably, separation temperature is at-30-30
oc.
Further, separation method of the present invention is hardly by the impact of foreign metal ion, these metal ions comprise one or more in Li, Na, K, Co, Cr, V, Ni, Mn, Fe, Pd, Pt, Ir, Au, Ru, Rh, so the separation method that the present invention announces has suitability widely, can be generalized to other catalyst system.
Accompanying drawing explanation
Fig. 1 is the para benzoquinone photo in kind obtained after being separated.
Embodiment
Below in conjunction with embodiment, the specific embodiment of the present invention is described in further detail.To contribute to understanding the present invention by following embodiment, but not limit technical scheme of the present invention in any form.
Embodiment 1:
Step one: step is carried out according to the Chinese patent embodiment 1 being entitled as " a kind of preparation method of para benzoquinone compound " (application number: 201410443854.7, on September 3rd, 2014 submits).
Step 2: add benzenesulfonamide trifluoroacetate methane 8.6g(and be equivalent to 10% of mixture quality in the reaction mixture that step one obtains), at room temperature stir hold over night after 30 minutes, para benzoquinone is separated out with precipitation forms, obtains para benzoquinone 1.2g after filtration, yield 32%.
Embodiment 2-4:
Experimental procedure is identical with embodiment 1, and only the add-on of benzenesulfonamide trifluoroacetate methane carried out changing and investigating separating effect, result is as shown in the table:
| Project | Amount (g) | Yield (%) |
| 1. | 15 | 38 |
| 2. | 30 | 55 |
| 3. | 45 | 63 |
Embodiment 5-8:
Step one is identical with embodiment 1, add in step 2 benzenesulfonamide trifluoroacetate methane 45g(be equivalent to mixture quality ~ 50%), hold over night under following differing temps, result is as shown in the table:
| Project | Temperature ( oC） | Yield (%) |
| 1. | 50 | 35 |
| 2. | 10 | 65 |
| 3. | -30 | 72 |
| 4. | -50 | 73 |
Embodiment 9-14:
In order to investigate the impact of other metal ion on separating effect, respectively to the acetate (10-30mmol) adding various metal in the mixture that embodiment 1 step one obtains, in step 2, add benzenesulfonamide trifluoroacetate methane 45g, and-30
oleft overnight under C, result is as shown in the table:
| Project | Metal ion (mmol) | Yield (%) |
| 1. | Li +（30） | 70 |
| 2. | Na +（30） | 73 |
| 3. | Co 2+（10） | 65 |
| 4. | Mn 2+（10） | 68 |
| 5. | Fe 2+（10） | 65 |
| 6. | Rh 2+（10） | 70 |
Embodiment 15-24:
Step one is identical with embodiment 1, replaces the benzenesulfonamide trifluoroacetate methane in embodiment 1 step 2 in step 2 with other promotor, and-30
oleft overnight under C, separating resulting is as shown in the table:
| Project | Organic solvent (g) | Yield (%) |
| 1. | Pyridine (8.6) | 15 |
| 2. | 4-trifluoromethy pyridine (8.6) | 82 |
| 3. | Between trifluoro-benzene (8.6) | 71 |
| 4. | Between trimethylbenzene (8.6) | 36 |
| 5. | Inclined trifluoro-benzene (8.6) | 62 |
| 6. | Sym.-tetrachloroethane (2.0)+fluorobenzene (6.6) | 89 |
| 7. | 1,1,3,3-tetrachloroethane (2.0)+phenyl-difluoride (6.6) | 76 |
| 8. | 1,2-dibromopropane (2.0)+4-trifluoromethy pyridine (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 carried out according to the embodiment 67 of Chinese patent or embodiment 68 being entitled as " a kind of preparation method of para benzoquinone compound " (application number: 201410443854.7, on September 3rd, 2014 submits).
B) step is carried out according to the embodiment 70 of the Chinese patent being entitled as " a kind of preparation method of para benzoquinone compound " (application number: 201410443854.7, on September 3rd, 2014 submits).
C) step is carried out according to the embodiment 73 of Chinese patent or embodiment 74 being entitled as " a kind of preparation method of para benzoquinone compound " (application number: 201410443854.7, on September 3rd, 2014 submits).
D) step is carried out according to the embodiment 75 of the Chinese patent being entitled as " a kind of preparation method of para benzoquinone compound " (application number: 201410443854.7, on September 3rd, 2014 submits).
Step 2: add benzenesulfonamide trifluoroacetate methane 8.6g in the reaction mixture that step one obtains, at room temperature stirs after 30 minutes, and-30
oc hold over night, separating resulting is as shown in the table:
| Project | Yield (%) |
| a. | 78 |
| b. | 85 |
| c. | 83 |
| d. | 91 |
Because of length restriction, the present invention does not illustrate one by one to all examples, but the technical scheme adopting the mode of carrying out equivalent replacement or equivalent transformation to the key element of this technology to obtain all is in protection scope of the present invention.
Claims (9)
1. the invention provides a kind of separation/purification method of para benzoquinone compound, it is characterized in that: the promotor adding the gathering/self-assembly of para benzoquinone compound in the liquid form mixt containing para benzoquinone compound, realize para benzoquinone compound in room temperature or lower than the Precipitation under room temperature condition, reach the object of para benzoquinone compound separation/purification.
2. method according to claim 1, the present invention the para benzoquinone compound that is suitable for there is following structural formula:
Wherein R
1, R
2, R
3and R
4independently be selected from hydrogen, hydrocarbyl group, four can be identical or different.
3. the description of method according to claim 1 and claim 2, para benzoquinone compound of the present invention can be para benzoquinone, naphthoquinones, anthraquinone, 2-ethyl-anthraquinone, 2(3 or 5 or 6)-methyl (ethyl, sec.-propyl or the tertiary butyl) para benzoquinone, 2-phenyl para benzoquinone, 2,6(2,3,2,5 or 3,5)-dimethyl (ethyl, sec.-propyl or the tertiary butyl) para benzoquinone, 2,3,5(2,3,6,2,5,6 or 3,5,6)-trimethylammonium (ethyl, sec.-propyl or the tertiary butyl) para benzoquinone, 2,3, the mixture of 4,5-duroquinone or above-claimed cpd.
4. method according to claim 1, promotor used in the present invention can be the compound with following structural formula:
Wherein R
1be selected from the one in C, N, O, R
2and R
3independently be selected from hydrogen, amino, nitro, carboxylic acid group's (salt), ester group, aldehyde radical, sulfonic group (salt), ketone group, hydroxyl, itrile group, sulfydryl, halogen and alkyl, R
2and R
3can be identical or different, described halogen is selected from F, Cl, and described alkyl is selected from the straight or branched alkane/halogenated alkane group comprising 1 to about 6 carbon atom, the straight or branched alkoxy base comprising 1 to about 6 carbon atom, the alkene comprising 6 to about 12 carbon atoms or aromatic group; Preferably, but infinite, and alkane group is selected from the straight or branched alkane containing 1 to 4 carbon atom, and alkoxyl group is the alkoxyl group containing 1 to 3 carbon atom, and the part that halogenated alkane group comprises containing 1 to 4 carbon atom replaces or the full halohydrocarbon replaced.
5. method according to claim 1, promotor used in the present invention can also extend to the liquified Halon hydrocarbon comprising 1 to about 8 carbon atom; Preferably, but be not limited to, halogenated alkane is the halohydrocarbon containing the part replacement of 2 to 4 carbon atoms or replacement entirely, can be 1,2-dichloro (bromine or iodine) ethane, 1,1,2,2-tetrachloro (bromine or iodine) ethane, perchloro-(bromine or iodine) are for ethane, 1,2-dichloro (bromine or iodine) propane, 1,3-dichloro (bromine or iodine) propane, 1,1,2,2-tetrachloro (bromine or iodine) butane, perchloro-(bromine or iodine) for propane, perchloro-(bromine or iodine) for the combination of one or more in butane.
6. the description of method according to claim 1 and claim 4 and claim 5, promotor used in the present invention can be the combination of compound described in claim 4 and 5.
7. method according to claim 1, the amount of the promotor that the present invention uses is equivalent to the 1-60% of para benzoquinone mixture quality, preferred 1-50%.
8. method according to claim 1, one of feature of present method is can at-50-50
ocarry out under C, preferred separation temperature is at-30-30
oc.
9. method according to claim 1, the existence of other foreign metal ion does not have a significant effect to separation method of the present invention, and these metal ions comprise one or more in Li, Na, K, Co, Cr, V, Ni, Mn, Fe, Pd, Pt, Ir, Au, Ru, Rh.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410472324.5A CN104761440B (en) | 2014-09-17 | 2014-09-17 | A kind of separation/purification method of 1,4-benzoquinone compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410472324.5A CN104761440B (en) | 2014-09-17 | 2014-09-17 | A kind of separation/purification method of 1,4-benzoquinone compound |
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| Publication Number | Publication Date |
|---|---|
| CN104761440A true CN104761440A (en) | 2015-07-08 |
| CN104761440B CN104761440B (en) | 2017-06-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106631685A (en) * | 2016-08-18 | 2017-05-10 | 江苏扬农化工集团有限公司 | Separation method of phenol and p-benzoquinone |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087729C (en) * | 1999-11-12 | 2002-07-17 | 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 |
| DE102010038774A1 (en) * | 2010-08-02 | 2012-02-02 | Evonik Goldschmidt Gmbh | Modified alkoxylation products having at least one non-terminal alkoxysilyl group, with increased storage stability and increased extensibility 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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106631685A (en) * | 2016-08-18 | 2017-05-10 | 江苏扬农化工集团有限公司 | Separation method of phenol and p-benzoquinone |
| CN106631685B (en) * | 2016-08-18 | 2019-06-04 | 江苏扬农化工集团有限公司 | A kind of separation method of phenol and quinone mixture |
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