CN104557487A - Preparation method of p-benzoquinone compound - Google Patents
Preparation method of p-benzoquinone compound Download PDFInfo
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- CN104557487A CN104557487A CN201410443854.7A CN201410443854A CN104557487A CN 104557487 A CN104557487 A CN 104557487A CN 201410443854 A CN201410443854 A CN 201410443854A CN 104557487 A CN104557487 A CN 104557487A
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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
- C07C46/08—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring with molecular oxygen
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Abstract
The invention provides a preparation method of a p-benzoquinone compound. The preparation method is characterized in that the p-benzoquinone compound is prepared from a phenol compound with high selectivity under a mild condition by taking oxygen or oxygen-containing gas in a liquid solvent as an oxidizing agent in the presence of a transitional metal compound serving as a main catalyst and N-substituted hydrocarbon oxy-compound serving as an assistant catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of para benzoquinone compound, specifically relate to a kind ofly to prepare the catalyzer of para benzoquinone compound by highly selective catalysis of phenol compound under an oxygen-containing atmosphere.
Background technology
Para benzoquinone, i.e. benzoquinones, Isosorbide-5-Nitrae-benzoquinones, be a kind of important industrial chemicals, be widely used in the fields such as analysis, dyestuff, macromolecular material, organic synthesis, fine chemistry industry.At present, para benzoquinone is mainly for the manufacture of Resorcinol 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.
Method for the preparation of para benzoquinone is more, and aniline oxidation style is the maturation process realizing suitability for industrialized production the earliest, and namely aniline becomes para benzoquinone through high price metal salts such as Manganse Dioxide in sulfuric acid medium, then with iron powder reducing para benzoquinone synthesis Resorcinol in water.The shortcoming of this method is that equipment corrosion is serious, and raw materials cost is high, and environmental pollution is serious.
Using phenol as raw material, the method using oxygen to prepare para benzoquinone as oxygenant also has report.Document (the two-step process of phenol catalytic oxidation Resorcinol, Hu Yucai etc., chemical reaction engineering and technique, 2006,22(6): 544-548) report and use cupric nitrate and SODIUMNITRATE (mol ratio=1:3) as catalyzer, can be para benzoquinone by oxidation of phenol under catalyzer and phenol mass ratio are the condition of 1:2.Document (oxygen Direct Catalytic Oxidation phenol synthesis para benzoquinone, Song Wei etc., Speciality Petrochemicals, 2008,25(3): 55-58) report similar results, use cupric chloride and lithium chloride (mol ratio=1:3) as catalyzer, under catalyzer and phenol mass ratio are the condition of 1:2, also can prepare para benzoquinone.CN102336643A and CN102351656B also discloses similar catalyst system.But above-mentioned technique needs almost stoichiometric catalyzer, and catalyst levels is excessive.
CN1918101A discloses a kind of method preparing benzoquinones and Resorcinol, is no more than 0.1 at the molar equivalent of copper containing catalyst and phenol compound, and forms benzoquinone compound under alkane nitrile, aromatic nitriles or the effect of organic amide class promotor.This technological line adds promotor in a solvent.
Therefore, develop a kind of catalyst system simple, and can the highly selective method that oxybenzene compound is converted into para benzoquinone compound become this area in the urgent need to.
Summary of the invention
The present invention discloses a kind of novel method preparing para benzoquinone compound at this, the method comprises: added by oxybenzene compound in liquid reaction medium, under the transistion metal compound Primary Catalysts and the existence of N-replacement-oxyl promotor of catalytic amounts, oxygen or oxygen-containing gas is used to prepare the technique of para benzoquinone compound as oxygenant highly selective.
Oxybenzene compound used in the present invention has 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 grp comprising 1 to about 8 carbon atom, the alkene comprising about 6 to about 12 carbon atoms or aromatic group.Preferably, 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.Preferred, oxybenzene compound can be phenol, naphthyl alcohol, 2(3 or 5 or 6)-methyl (ethyl, sec.-propyl or the tertiary butyl) phenol, 2-phenylphenol, 2-benzylphenol, 2-vinylphenol, 2,6(2,3,2,5 or 3,5)-dimethyl (ethyl, sec.-propyl or the tertiary butyl) phenol, 2,3,5(2,3,6,2,5,6 or 3,5,6) mixture of-trimethylammonium (ethyl, sec.-propyl or the tertiary butyl) phenol, 2,3,45-tetramethyl phenols or above-mentioned oxybenzene compound.
The Primary Catalysts that the method for the invention uses is transistion metal compound, metal ion is selected from the combination of one or more in V, Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Pt, can be the simple substance of metal, oxide compound, boride, sulfide, halogenide, vitriol, carbonate, nitrate, nitrite, subsalt, (halo) soap, (halo) fragrant hydrochlorate, succinate, dicarboxylate, amino acid salt, schiff base complex, phthalocyanine complex.Preferably, but be not limited to this, suitable transistion metal compound can be selected from the combination of one or more in V, Mn, Fe, Co, Cu, Ru, and the anhydrous or hydrated form of transistion metal compound can as catalyzer.
The N-that the method for the invention uses replaces hydrocarbon oxy compound promotor and can represent with following structural formula:
Wherein R
1, R
2and R
3independently be selected from hydrocarbyl group and hydrogen, three can be identical or different, wherein hydrocarbyl group be selected from the straight or branched alkane group comprising 1 to about 12 carbon atom, the aromatic group comprising about 6 to about 12 carbon atoms or alkylaryl group, comprise about 4 to about 10 carbon atoms containing heteroatoms (N, O, S) cyclic hydrocarbon group, R
1and R
2also (replacement) alkyl or the aromatic base of ring-type can be formed.Preferably, infinite example, alkane group can be the straight chain/branched paraffin group containing 1 to 8 carbon atom, aromatic group or alkylaryl can be benzyl, phenyl, naphthyl, phenmethyl and styroyl, containing heteroatoms (N, O, S) cyclic hydrocarbon group can be pyrryl, indyl, pyridyl, quinolyl, isoquinolyl, R
1and R
2(replacement) alkyl or the aromatic base that form ring-type can be (hydroxyl/alkyl replaces) cyclopentyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, xenyl.
Being liquid for reaction medium of the present invention, can be comprise the straight or branched halogenated alkane of 1 to 6 carbon atom, the straight chain comprising 2 to about 12 carbon atoms, side chain or ring-type organic ether, the alkane nitrile comprising 2 to about 12 carbon atoms, aromatic nitriles or organic amide or the straight chain containing 1 to 12 carbon atom, side chain or ring-type Organic Alcohol.Preferably, but be not limited thereto, suitable solvent comprises the halogenated alkane of 1 to 4 carbon atom, the straight chain of the alkane nitrile of the straight chain of 2 to 8 carbon atoms, side chain or ring-type organic ether, 2 to 8 carbon atoms, aromatic nitriles or organic amide or 1 to 8 carbon atom, side chain or ring-type Organic Alcohol, or the combination of aforementioned several solvent.In addition, described solvent also can be water, protonic acid, Lewis acid or aforementioned several combination.The Non-limiting examples of suitable protonic acid solvent comprises nitric acid, hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, heteropolyacid, sulfuric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, tosic acid.The Non-limiting examples of suitable Lewis acid solvent comprises boron trifluoride, titanium tetrachloride.Further, described solvent also can be the above-mentioned inorganic combination with organic solvent.
In order to realize the object of foregoing invention, the present invention adopts following operation steps: after oxybenzene compound, Primary Catalysts, promotor and solvent fully being mixed, add autoclave, off-response device is also filled with oxygen-containing gas and reaches specified pressure, react after certain hour at a certain temperature and be cooled to room temperature, be vented and measure the amount of para benzoquinone and the complete oxybenzene compound of unreacted.Wherein, all there is material impact to reaction result in the mol ratio of catalyst levels, Primary Catalysts and promotor, the concentration of oxybenzene compound, temperature of reaction, reaction times and oxygen pressure, and these factors are also the technology contents that this preparation method relates to.
Wherein, the present invention's transistion metal compound Primary Catalysts used and oxybenzene compound mole ratio at 0.01-0.5, preferably, mole ratio at 0.01-0.2.Further, the present invention N-used replace hydrocarbon oxy compound and transistion metal compound Primary Catalysts mole ratio at 10-0.1, preferably, mole ratio at 2-0.2.
In the present invention, described oxybenzene compound and the mass ratio of solvent react in the scope of 1-50%.
One of feature of the present invention is that reaction conditions is gentle, and the present invention's temperature of reaction used is usually at 20-150
oc, preferably, temperature is 30-80
oc.
The oxygen that the present invention uses can be pure oxygen, and also can use the gas mixture containing oxygen, wherein not have particular requirement to oxygen content, the gas as blending ingredients can be the combination of nitrogen, argon gas, helium, neon or above-mentioned gas.Further, when the present invention's reactant gases used is pure oxygen, pressure is usually at 1-150atm, and preferably, pressure is 1-70atm.Further, the present invention uses mixed gas as reaction gas, needs corresponding raising pressure condition, usually at 5-200atm according to oxygen partial pressure.
The present invention's reaction times used, preferably, the time was 30 minutes to 3 hours usually at 20 minutes to 5 hours.
In addition, one of feature of present method is that the selectivity of para benzoquinone class product is high, and do not observe other adjacent benzoquinones class product, the single-minded katalysis ability of catalyzer is strong.
There is following reaction process in a kettle.:
Accompanying drawing explanation
Fig. 1 is the para benzoquinone that the embodiment of the present invention 1 prepares
1h NMR spectrogram,
1h NMR (CDCl
3, 600 MHz) and δ: 6.81 (s, 4H).
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:
Cobaltous nitrate hexahydrate (2.91g is added in 250mL reactor, 10.0mmol), N, N-diethyl ethoxy amine (1.18g, 10mmol), phenol (9.4g, 100mmol) with acetonitrile (78.5g, 100mL), after mixing, off-response still is also filled with 30atm oxygen, stirs and is heated to 60
oc, reacts and is cooled to room temperature after 3 hours, takes out mixture and analyze after exhaust, obtains remaining phenol: 5.4g, para benzoquinone: 3.8g.
Embodiment 2-9:
Other transistion metal compound of Cobaltous nitrate hexahydrate in embodiment 1 is replaced, as shown in the table on the impact of reaction result:
| Project | Primary Catalysts (g, mmol) | Phenol (g) | Para benzoquinone (g) |
| 1. | -- | 9.2 | 0 |
| 2. | Vanadium Pentoxide in FLAKES (1.82,10) | 5.7 | 2.6 |
| 3. | Manganous sulfate monohydrate (1.69,10) | 4.4 | 4.8 |
| 4. | FePC (5.68,10) | 5.8 | 3.4 |
| 5. | Cupric iodide (1.9,10) | 6.9 | 2.3 |
| 6. | Ruthenium trichloride (2.1,10) | 3.5 | 5.7 |
| 7. | Rhodium trichloride hydrate (2.1,10) | 5.7 | 2.4 |
| 8. | Potassium platinichloride (4.86,10) | 5.0 | 4.0 |
Embodiment 10-18:
N in embodiment 1, N-diethyl ethoxy amine is replaced hydrocarbon oxy compound with different N-replace, as shown in the table on the impact of reaction result:
| Project | Promotor (g, mmol) | Phenol (g) | Para benzoquinone (g) |
| 1. | -- | 8.4 | 0.9 |
| 2. | N, N-dimethyl Methoxyamine (0.75,10) | 6.0 | 3.1 |
| 3. | N, N-dipropyl propoxy-amine (1.59,10) | 7.3 | 2.0 |
| 4. | N, N-di-isopropyl isopropoxy amine (1.59,10) | 3.1 | 6.0 |
| 5. | N, N-dioctyl octyloxy amine (3.7,10) | 6.5 | 2.7 |
| 6. | Azanol (0.33,10) | 6.9 | 2.1 |
| 7. | 2,2,6,6-tetramethyl piperidine-N-hydroxyl (1.6,10) | 8.4 | 0.9 |
| 8. | 4-hydroxyl-2,2,6,6-tetramethyl piperidine-N-hydroxyl (1.73,10) | 8.9 | 0.3 |
| 9. | N, N-phenylbenzene Methoxyamine (2.0,10) | 5.1 | 4.1 |
Embodiment 19-33:
Phenol quality in embodiment 1 changed, the impact of material concentration on reaction result is as shown in the table:
Embodiment 34-51:
Acetonitrile all kinds of SOLVENTS in embodiment 1 is replaced, as shown in the table on the impact of catalyzed reaction result:
Embodiment 52-60:
The different oxygen-containing gas of oxygen in embodiment 1 is replaced, as shown in the table on the impact of catalyzed reaction result:
| Project | Gas (atm) | Phenol (g) | Para benzoquinone (g) |
| 1. | O 2 (1) | 9.1 | 0.2 |
| 2. | O 2 (70) | 2.0 | 7.0 |
| 3. | O 2 (150) | 0.3 | 6.1 |
| 4. | Air (5) | 9.2 | 0.1 |
| 5. | Air (200) | 2.2 | 7.1 |
| 6. | O 2:N 2=1:1（100） | 3.2 | 6.0 |
| 7. | O 2:N 2=3:1（80） | 2.8 | 6.4 |
| 8. | O 2:Ar=3:1（80） | 2.7 | 6.3 |
| 9. | O 2:He=3:1（80） | 2.8 | 6.3 |
Embodiment 61-63:
Temperature in embodiment 1 is changed, as shown in the table on the impact of catalyzed reaction result:
| Project | Temperature ( oC） | Phenol (g) | Para benzoquinone (g) |
| 1. | 20 | 8.9 | 0.4 |
| 2. | 80 | 4.1 | 5.1 |
| 3. | 150 | 1.1 | 7.8 |
Embodiment 64-66:
Reaction times in embodiment 1 is changed, as shown in the table on the impact of catalyzed reaction result:
| Project | Time (minute) | Phenol (g) | Para benzoquinone (g) |
| 1. | 20 | 8.3 | 1.2 |
| 2. | 60 | 7.0 | 2.2 |
| 3. | 300 | 0.5 | 7.0 |
Embodiment 67-75:
Replaced by other oxybenzene compound of phenol in embodiment 1, reaction result is as shown in the table:
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 (10)
1. the present invention discloses a kind of preparation method of para benzoquinone compound at this, and described method comprises:
In liquid solvent, using oxybenzene compound as raw material, replace the effect of hydrocarbon oxy compound promotor at transistion metal compound Primary Catalysts and N-under, with oxygen or oxygen-containing gas as oxygenant, highly selective prepares the technology of para benzoquinone compound.
2. method according to claim 1, described oxybenzene compound has 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, described oxybenzene compound is selected from phenol, naphthyl alcohol, 2(3 or 5 or 6)-methyl (ethyl, sec.-propyl or the tertiary butyl) phenol, 2-phenylphenol, 2-benzylphenol, 2-vinylphenol, 2,6(2,3,2,5 or 3,5)-dimethyl (ethyl, sec.-propyl or the tertiary butyl) phenol, 2,3,5(2,3,6,2,5,6 or 3,5,6)-trimethylammonium (ethyl, sec.-propyl or the tertiary butyl) phenol, 2,3, the mixture of 4,5-tetramethyl phenol or above-claimed cpd.
4. method according to claim 1, described transistion metal compound Primary Catalysts is selected from the combination of one or more in V, Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Pt, can be the simple substance of metal, oxide compound, boride, sulfide, halogenide, vitriol, carbonate, nitrate, nitrite, subsalt, (halo) soap, (halo) fragrant hydrochlorate, succinate, dicarboxylate, amino acid salt, schiff base complex, phthalocyanine complex
,preferably, suitable transistion metal compound can be selected from the combination of one or more in V, Mn, Fe, Co, Cu, Ru, and the anhydrous or hydrated form of transistion metal compound can as catalyzer.
5. method according to claim 1, described N-replaces hydrocarbon oxy compound promotor and can represent with following structural formula:
Wherein R
1, R
2and R
3independently be selected from hydrocarbyl group and hydrogen, three can be identical or different, wherein hydrocarbyl group be selected from the straight or branched alkane comprising 1 to about 12 carbon atom, the aromatic group comprising about 6 to about 12 carbon atoms or alkyl aromatic group, comprise about 4 to about 10 carbon atoms containing heteroatoms (N, O, S) cyclic hydrocarbon group, R
1and R
2also (replacement) alkyl or the aromatic base of ring-type can be formed, preferably, alkane group is the straight or branched alkane group containing 1 to 8 carbon atom, aromatic group or alkylaryl comprise benzyl, phenyl, naphthyl, phenmethyl and styroyl, containing heteroatoms (N, O, S) cyclic hydrocarbon group comprises pyrryl, indyl, pyridyl, quinolyl, isoquinolyl, R
1and R
2(replacement) alkyl or the aromatic base that form ring-type comprise hydroxyl/alkyl substituted ring amyl group, cyclopentyl, cyclohexyl, phenyl, naphthyl, xenyl.
6. method according to claim 1, is characterized in that: transistion metal compound Primary Catalysts and oxybenzene compound mole ratio at 0.01-0.5, preferably, mole ratio at 0.01-0.2; N-replace hydrocarbon oxy compound promotor and transistion metal compound Primary Catalysts mole ratio at 10-0.01, preferably, mole ratio at 2-0.2; The mass ratio of oxybenzene compound and solvent is in the scope of 1-50%.
7. method according to claim 1, described reaction medium is liquid, it can be the straight or branched halogenated alkane comprising 1 to 6 carbon atom, comprise the straight chain of 2 to about 12 carbon atoms, side chain or ring-type organic ether, comprise the alkane nitrile of 2 to about 12 carbon atoms, aromatic nitriles or organic amide or the straight chain containing 1 to 12 carbon atom, side chain or ring-type Organic Alcohol, preferably, but be not limited thereto, suitable solvent comprises the halogenated alkane comprising 1 to 4 carbon atom, comprise the straight chain of 2 to 8 carbon atoms, side chain or ring-type organic ether, comprise the alkane nitrile of 2 to 8 carbon atoms, aromatic nitriles or organic amide or comprise the straight chain of 1 to 8 carbon atom, side chain or ring-type Organic Alcohol, or the combination of aforementioned several solvent
,described solvent also can be water, protonic acid, Lewis acid or aforementioned several combination, preferably, the Non-limiting examples of suitable protonic acid comprises nitric acid, hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, heteropolyacid, sulfuric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, tosic acid, preferably, the Non-limiting examples of suitable Lewis acid solvent comprises boron trifluoride, titanium tetrachloride, in addition, described solvent also can be the above-mentioned inorganic combination with organic solvent.
8. method according to claim 1, described oxygen can be pure oxygen, also can use the gas mixture containing oxygen, the gas as blending ingredients can be the combination of nitrogen, argon gas, helium, neon or above-mentioned gas, when reactant gases is pure oxygen, pressure is usually at 1-150atm, preferably, pressure is 1-70atm, when gas is mixed gas, corresponding raising pressure condition is needed, usually at 5-200atm according to oxygen partial pressure.
9. method according to claim 1, described temperature of reaction is usually at 20-150
oc, preferably, temperature is 30-80
oc.
10. method according to claim 1, one of feature of present method is that the selectivity of para benzoquinone product is high, does not observe adjacent benzoquinones class product, and the single-minded katalysis ability of catalyzer is strong.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104292096A (en) * | 2014-09-09 | 2015-01-21 | 中国科学院青岛生物能源与过程研究所 | Method for preparing p-benzoquinone compound through selective catalytic oxidation of phenol compound |
| CN107185571A (en) * | 2017-05-18 | 2017-09-22 | 南京工业大学 | Cobalt catalyst, preparation method thereof and application thereof in catalytic synthesis of 2,3, 5-trimethylbenzoquinone |
| CN107365243A (en) * | 2017-07-21 | 2017-11-21 | 中南民族大学 | A kind of method of one pot process benzoquinone class compound |
| CN109942388A (en) * | 2019-04-18 | 2019-06-28 | 绍兴市上虞沿江生物科技有限公司 | The preparation method of 1,4- cyclohexanedione |
| CN115611719A (en) * | 2022-09-14 | 2023-01-17 | 大连理工大学 | Preparation method and application of sec-butyl p-benzoquinone |
| CN116102414A (en) * | 2023-02-07 | 2023-05-12 | 浙江大学 | Preparation method of benzoquinone compound and 2-methyl-1, 4-naphthoquinone |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104292096A (en) * | 2014-09-09 | 2015-01-21 | 中国科学院青岛生物能源与过程研究所 | Method for preparing p-benzoquinone compound through selective catalytic oxidation of phenol compound |
| CN107185571A (en) * | 2017-05-18 | 2017-09-22 | 南京工业大学 | Cobalt catalyst, preparation method thereof and application thereof in catalytic synthesis of 2,3, 5-trimethylbenzoquinone |
| CN107185571B (en) * | 2017-05-18 | 2019-12-24 | 南京工业大学 | Cobalt catalyst, preparation method thereof and application thereof in catalytic synthesis of 2,3, 5-trimethylbenzoquinone |
| CN107365243A (en) * | 2017-07-21 | 2017-11-21 | 中南民族大学 | A kind of method of one pot process benzoquinone class compound |
| CN107365243B (en) * | 2017-07-21 | 2020-11-06 | 中南民族大学 | Method for synthesizing p-phenylene benzoquinone compound by one-pot method |
| CN109942388A (en) * | 2019-04-18 | 2019-06-28 | 绍兴市上虞沿江生物科技有限公司 | The preparation method of 1,4- cyclohexanedione |
| CN115611719A (en) * | 2022-09-14 | 2023-01-17 | 大连理工大学 | Preparation method and application of sec-butyl p-benzoquinone |
| CN116102414A (en) * | 2023-02-07 | 2023-05-12 | 浙江大学 | Preparation method of benzoquinone compound and 2-methyl-1, 4-naphthoquinone |
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