CN104292096A - Method for preparing p-benzoquinone compound through selective catalytic oxidation of phenol compound - Google Patents
Method for preparing p-benzoquinone compound through selective catalytic oxidation of phenol compound Download PDFInfo
- Publication number
- CN104292096A CN104292096A CN201410452657.1A CN201410452657A CN104292096A CN 104292096 A CN104292096 A CN 104292096A CN 201410452657 A CN201410452657 A CN 201410452657A CN 104292096 A CN104292096 A CN 104292096A
- Authority
- CN
- China
- Prior art keywords
- compound
- group
- phenol
- replacement
- aromatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 *c1cc(*)c(*)c(O)c1* Chemical compound *c1cc(*)c(*)c(O)c1* 0.000 description 2
Classifications
-
- 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
Abstract
The invention provides a method for preparing a p-benzoquinone compound through selective catalytic oxidation of a phenol compound. The method is characterized in that the p-benzoquinone compound is highly selectively prepared through a reaction of a raw material the phenol compound in a liquid medium under mild conditions under the action of a transition metal compound primary catalyst and a stellate molecule cocatalyst with oxygen or an oxygen-containing gas as an oxidant.
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) and be entitled as " a kind of method that para benzoquinone compound is prepared in oxybenzene compound direct oxidation " (application number: 201410449008.6, on September 5th, 2014 submits) Chinese patent expansion and supplement, and the former has the right of priority to the latter.
Technical field
The present invention relates to a kind of method that gating catalytic oxidation oxybenzene compound prepares 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 compound is synthetic pesticide, dyestuff, rubber, plastics, the important source material of fine chemicals, intermediate and auxiliary agent, is mainly used in the association areas such as photographic developer, dyestuff, rubber antioxidant and high polymer monomer stopper, antioxidant.
Due to the importance of para benzoquinone compound, various synthetic route is developed in succession.Aniline oxidation style realizes industrialized technique the earliest, and namely aniline becomes para benzoquinone through high price metal salts such as Manganse Dioxide in sulfuric acid medium, is then separated through stripping process and obtains para benzoquinone product.But, this raw materials technology high cost, and there is serious pollution problem.
As a kind of possible alternative techniques, the method using dioxygen oxidation phenol to prepare para benzoquinone is developed.Such as: the article (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; Article (oxygen Direct Catalytic Oxidation phenol synthesis para benzoquinone, Song Wei etc., Speciality Petrochemicals, 2008,25(3): 55-58) report and use cupric chloride and lithium chloride (mol ratio=1:3) as catalyzer, be para benzoquinone by oxidation of phenol under catalyzer and phenol mass ratio are the condition of 1:2.CN102336643A and CN102351656B also discloses similar techniques.But above method 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 synthesizes benzoquinone compound under alkane nitrile, aromatic nitriles or the effect of organic amide class promotor.But this technological line adds promotor in a solvent.
Therefore, develop a kind of lower-cost para benzoquinone compound for catalysis method for oxidation become this area in the urgent need to.
Summary of the invention
The present invention discloses at this kind of method that gating catalytic oxidation oxybenzene compound prepares para benzoquinone compound, the method comprises: added by oxybenzene compound in liquid medium, under the transistion metal compound Primary Catalysts and the existence of starlike molecule 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 base 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)-trimethylammonium (ethyl, sec.-propyl or the tertiary butyl) phenol, 2,3, the mixture of 4,5-tetramethyl phenol or above-mentioned oxybenzene compound.
Transistion metal compound Primary Catalysts of the present invention is selected from the combination of one or more in V, Mn, Fe, Co, Ni, Cu, Rh, Ce, Ag, Pt, Pd, can be the halogenide of metal, vitriol, (Asia) nitrate, (halo) soap, (halo) fragrant hydrochlorate, succinate, 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, Ce, Cu, Ag, and the anhydrous or hydrated form of transistion metal compound can as catalyzer.
Starlike molecule promotor of the present invention can represent with following structural formula:
Wherein R is independently selected from containing heteroatoms aromatic ring, C, P, Si, N, and described can be pyridyl, pyrryl, indyl, isoquinolyl, quinolyl containing heteroatoms aromatic ring, R
1, R
2and R
3independently be selected from hydrogen and hydrocarbyl group, and wherein at least one is hydrocarbyl group, three can be identical or different, hydrocarbyl group can be comprise 6 to about 16 carbon atom (replacement) aromatic groups or (replacement) alkyl aromatic group, comprise about 4 to about 14 carbon atoms containing heteroatoms aromatic group or (replacement) straight or branched alkane group comprising 1 to about 10 carbon atom.Further, described (replacement) aromatic group or (replacement) alkyl aromatic group are selected from the group comprising 6 to 10 carbon atoms, be the group comprising 4 to 10 carbon atoms containing heteroatoms (replacement) aromatic group, (replacement) alkane group comprises the straight or branched group of 1 to 8 carbon atom.Preferably, but infinite example comprises, and alkane group can be C
1-C
8straight or branched alkyl, aromatic group or alkyl aromatic group can be phenyl, naphthyl, anthryl, xenyl, phenmethyl, styroyl, benzyl, (adjacent// to) xylyl, (adjacent// to) diethyl phenyl, (adjacent// partially) trimethylphenyl, (adjacent// to) triethyl-benzene base, can be pyrryl, indyl, pyridyl, quinolyl, isoquinolyl containing heteroatoms aromatic ring.
Reaction medium of the present invention is liquid, it can be the halogenated alkane containing 1-3 carbon atom, comprise the alkane nitrile of about 2 to about 8 carbon atoms, aromatic nitriles, halogenated aromatic compound or organic amide, or straight chain, side chain or the ring-type Organic Alcohol containing 1 to 8 carbon atom, or the combination of aforementioned solvents.
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, temperature of reaction, reaction times and oxygen pressure, 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's starlike molecule promotor used 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 1-30%.
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 20-120
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, mixed gas 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 1-120atm, and preferably, pressure is 1-80atm.
The present invention's reaction times used, preferably, the time was 30 minutes to 3 hours usually at 10 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 catalytic capability of catalyzer is strong.
There is following reaction process in a kettle.:
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, 10.0mmol), triphenylphosphine (2.62g, 10mmol), phenol (9.4g is added in 250mL reactor, 100mmol) and DMF(94.0g, 100mL), after mixing, off-response still is also filled with 20atm oxygen, stirs and is heated to 60
oc, reacts and is cooled to room temperature after 1 hour, takes out mixture and analyze after exhaust, obtains remaining phenol: 7.4g, para benzoquinone: 1.9g.
Embodiment 2-8:
Other transistion metal compound of Cobaltous nitrate hexahydrate in embodiment 1 is replaced, as shown in the table on the impact of result:
| Project | Primary Catalysts (g, mmol) | Phenol (g) | Para benzoquinone (g) |
| 1. | -- | 9.3 | 0 |
| 2. | Nitric acid vanadium (1.82,10) | 8.3 | 0.6 |
| 3. | Iron trichloride (1.62,10) | 8.6 | 0.6 |
| 4. | Manganous acetate (1.73,10) | 5.7 | 3.4 |
| 5. | Ruthenium trichloride (2.07,10) | 5.1 | 4.0 |
| 6. | Four water cerous sulfates (4.04,10) | 6.8 | 2.3 |
| 7. | Palladous chloride (1.77,10) | 7.2 | 2.0 |
Embodiment 9-17:
The different Star-shaped of triphenylphosphine in embodiment 1 is replaced, as shown in the table on the impact of result:
| Project | Promotor (g, mmol) | Phenol (g) | Para benzoquinone (g) |
| 1. | -- | 8.7 | 0.4 |
| 2. | Triphenylamine (2.45,10) | 8.2 | 0.9 |
| 3. | Triethylamine (1.01,10) | 8.5 | 0.6 |
| 4. | Trioctylamine (3.53,10) | 8.6 | 0.5 |
| 5. | Dibenzylamine (1.97,10) | 8.1 | 1.1 |
| 6. | Trimethylchlorosilane (1.08,10) | 8.3 | 0.6 |
| 7. | Isopropyl pyridine (1.21,10) | 6.2 | 2.5 |
| 8. | Toluquinoline (1.4,10) | 6.5 | 2.5 |
| 9. | Phenylbenzene-2-pyridyl phosphine (2.63,10) | 7.6 | 1.6 |
Embodiment 18-23:
Phenol concentration in embodiment 1, catalyst molar ratio are changed, as shown in the table on the impact of reaction result:
Embodiment 24-30:
Other solvent of DMF in embodiment 1 is replaced, as shown in the table on the impact of reaction result:
| Project | Solvent (g, mL) | Phenol (g) | Para benzoquinone (g) |
| 1. | Methylene dichloride (130.1,100) | 8.6 | 0.5 |
| 2. | Acetonitrile (78.5,100) | 6.2 | 3.9 |
| 3. | Cyanophenyl (197.0,100) | 6.9 | 2.4 |
| 4. | Chlorobenzene (110.3,100) | 8.8 | 0.4 |
| 5. | Methyl alcohol (78.5,100) | 8.5 | 0.7 |
| 6. | Virahol (77.8,100) | 7.9 | 1.3 |
| 7. | Octanol (83,100) | 8.1 | 1.1 |
Embodiment 31-33:
Oxygen pressure in embodiment 1 and component are changed, as shown in the table on the impact of reaction result:
| Project | Gas (atm) | Phenol (g) | Para benzoquinone (g) |
| 1. | O 2 (1) | 9.3 | 0.1 |
| 2. | O 2 (120) | 5.9 | 3.2 |
| 3. | Air (100) | 7.9 | 2.2 |
Embodiment 34-36:
Temperature in embodiment 1 is changed, as shown in the table on the impact of reaction result:
| Project | Temperature ( oC） | Phenol (g) | Para benzoquinone (g) |
| 1. | 20 | 9.3 | 0.1 |
| 2. | 80 | 6.9 | 2.3 |
| 3. | 120 | 5.8 | 3.4 |
Embodiment 37-40:
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 at this kind of method that gating catalytic oxidation oxybenzene compound prepares para benzoquinone compound, it is characterized in that: in liquid medium, using oxybenzene compound as raw material, under the effect of transistion metal compound Primary Catalysts and starlike molecule promotor, 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, Mn, Fe, Co, Ni, Cu, Rh, Ce, Ag, Pt, Pd, can be the halogenide of metal, vitriol, (Asia) nitrate, (halo) soap, (halo) fragrant hydrochlorate, succinate, 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, Ce, Ag, and the anhydrous or hydrated form of transistion metal compound can as catalyzer.
5. method according to claim 1, described starlike molecule promotor can represent with following structural formula:
Wherein R is independently selected from C, P, Si, N or contains heteroatoms aromatic ring, and described can be pyridyl, pyrryl, indyl, isoquinolyl, quinolyl containing heteroatoms aromatic ring, R
1, R
2and R
3independently be selected from hydrogen and hydrocarbyl group, and wherein at least one is hydrocarbyl group, three can be identical or different, hydrocarbyl group can be comprise 6 to about 16 carbon atom (replacement) aromatic groups or (replacement) alkyl aromatic group, comprise about 4 to about 14 carbon atoms containing heteroatoms aromatic group or (replacement) straight or branched alkane group comprising 1 to about 10 carbon atom; Further, described (replacement) aromatic group or (replacement) alkyl aromatic group are selected from the group comprising 6 to 10 carbon atoms, be the group comprising 4 to 10 carbon atoms containing heteroatoms (replacement) aromatic group, (replacement) alkane group comprises the straight or branched group of 1 to 8 carbon atom; Preferably, but infinite example comprises, and alkane group can be C
1-C
8straight or branched alkyl, aromatic group or alkyl aromatic group can be phenyl, naphthyl, anthryl, xenyl, phenmethyl, styroyl, benzyl, (adjacent// to) xylyl, (adjacent// to) diethyl phenyl, (adjacent// partially) trimethylphenyl, (adjacent// to) triethyl-benzene base, can be pyridyl, pyrryl, indyl, isoquinolyl, quinolyl containing heteroatoms aromatic ring.
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; Starlike molecule promotor and transistion metal compound Primary Catalysts mole ratio at 10-0.01, preferably, mole ratio at 2-0.2.
7. method according to claim 1, described reaction medium is liquid, it can be the halogenated alkane containing 1-3 carbon atom, comprise the alkane nitrile of about 2 to about 8 carbon atoms, aromatic nitriles, halogenated aromatic compound or organic amide, or straight chain, side chain or the ring-type Organic Alcohol containing 1 to 8 carbon atom, or the combination of aforementioned solvents.
8. method according to claim 1, described oxygen can be pure oxygen, also the gas mixture containing oxygen can be used, 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 1-120atm, and preferably, pressure is 1-80atm.
9. method according to claim 1, described temperature of reaction is usually at 20-120
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, and do not observe other adjacent benzoquinones class product, the single-minded catalytic capability of catalyzer is strong.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410452657.1A CN104292096A (en) | 2014-09-09 | 2014-09-09 | Method for preparing p-benzoquinone compound through selective catalytic oxidation of phenol compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410452657.1A CN104292096A (en) | 2014-09-09 | 2014-09-09 | Method for preparing p-benzoquinone compound through selective catalytic oxidation of phenol compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104292096A true CN104292096A (en) | 2015-01-21 |
Family
ID=52312090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410452657.1A Pending CN104292096A (en) | 2014-09-09 | 2014-09-09 | Method for preparing p-benzoquinone compound through selective catalytic oxidation of phenol compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104292096A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146276A (en) * | 2015-04-02 | 2016-11-23 | 中国科学院金属研究所 | A kind of method of phenol compound catalysis oxidative synthesis benzoquinone compound |
| CN110433862A (en) * | 2019-08-30 | 2019-11-12 | 中南大学 | A kind of preparation method and application of the porous catalyst based on waste plastic |
| US11168068B2 (en) | 2016-07-18 | 2021-11-09 | Janssen Pharmaceutica Nv | Tau PET imaging ligands |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4478752A (en) * | 1981-07-20 | 1984-10-23 | Sun Tech, Inc. | Process for oxidizing phenol to p-benzoquinone |
| EP0369823A1 (en) * | 1988-11-18 | 1990-05-23 | THE STATE OF JAPAN, as Represented by the DIRECTOR GENERAL of the AGENCY of INDUSTRIAL SCIENCE and TECHNOLOGY | Method for the preparation of 2,3,5-trimethylbenzoquinone |
| CN1293182A (en) * | 1999-10-15 | 2001-05-02 | 德古萨－于尔斯股份公司 | Method of preparing 2,3,5-frimethyl-p-benzoquinone |
| CN104292095A (en) * | 2014-09-05 | 2015-01-21 | 中国科学院青岛生物能源与过程研究所 | Method for direct oxidation of phenol compound to prepare p-benzoquinone compound |
| CN104557487A (en) * | 2014-09-03 | 2015-04-29 | 中国科学院青岛生物能源与过程研究所 | Preparation method of p-benzoquinone compound |
-
2014
- 2014-09-09 CN CN201410452657.1A patent/CN104292096A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4478752A (en) * | 1981-07-20 | 1984-10-23 | Sun Tech, Inc. | Process for oxidizing phenol to p-benzoquinone |
| EP0369823A1 (en) * | 1988-11-18 | 1990-05-23 | THE STATE OF JAPAN, as Represented by the DIRECTOR GENERAL of the AGENCY of INDUSTRIAL SCIENCE and TECHNOLOGY | Method for the preparation of 2,3,5-trimethylbenzoquinone |
| CN1293182A (en) * | 1999-10-15 | 2001-05-02 | 德古萨－于尔斯股份公司 | Method of preparing 2,3,5-frimethyl-p-benzoquinone |
| CN104557487A (en) * | 2014-09-03 | 2015-04-29 | 中国科学院青岛生物能源与过程研究所 | Preparation method of p-benzoquinone compound |
| CN104292095A (en) * | 2014-09-05 | 2015-01-21 | 中国科学院青岛生物能源与过程研究所 | Method for direct oxidation of phenol compound to prepare p-benzoquinone compound |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146276A (en) * | 2015-04-02 | 2016-11-23 | 中国科学院金属研究所 | A kind of method of phenol compound catalysis oxidative synthesis benzoquinone compound |
| CN106146276B (en) * | 2015-04-02 | 2019-04-09 | 中国科学院金属研究所 | A kind of method of phenol compound catalysis oxidation synthesis benzoquinone compound |
| US11168068B2 (en) | 2016-07-18 | 2021-11-09 | Janssen Pharmaceutica Nv | Tau PET imaging ligands |
| CN110433862A (en) * | 2019-08-30 | 2019-11-12 | 中南大学 | A kind of preparation method and application of the porous catalyst based on waste plastic |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104744229A (en) | Synthetic method of p-benzoquinone | |
| Huguet et al. | Nickel‐catalyzed direct carboxylation of olefins with CO2: One‐pot synthesis of α, β‐unsaturated carboxylic acid salts | |
| Hu et al. | Room temperature aerobic oxidation of alcohols using CuBr2 with TEMPO and a tetradentate polymer based pyridyl-imine ligand | |
| Li et al. | Iron‐Catalyzed Ligand‐Free Three‐Component Coupling Reactions of Aldehydes, Terminal Alkynes, and Amines | |
| Das et al. | Silver catalyzed C–C and C–S coupling of aryl halides and thiols with boronic acids | |
| CN104557487A (en) | Preparation method of p-benzoquinone compound | |
| CN100349832C (en) | Method for the telomerisation of non-cyclic olefins | |
| CN104292095A (en) | Method for direct oxidation of phenol compound to prepare p-benzoquinone compound | |
| CN104292096A (en) | Method for preparing p-benzoquinone compound through selective catalytic oxidation of phenol compound | |
| Nemoto et al. | Efficient nickel-catalyzed hydrocyanation of alkenes using acetone cyanohydrin as a safer cyano source | |
| CN105085329A (en) | Preparation method for aromatic-azoxybenzene by oxidizing aromatic amine | |
| CN108017557A (en) | A kind of Process for the cyanation for preparing nitrile compounds | |
| BRPI0714196A2 (en) | Process for the production of substituted or unsubstituted 1,7-diolefins by hydrodimerization | |
| Guo et al. | Oxa‐Michael Addition to α, β‐Unsaturated Nitriles: An Expedient Route to γ‐Amino Alcohols and Derivatives | |
| Adak et al. | Gold‐Catalyzed Highly Chemo‐and Regioselective C‐H Bond Functionalization of Phenols with Haloalkynes | |
| CN111909038A (en) | Preparation method of phenylenediamine | |
| Caselli et al. | From homogeneously to heterogeneously catalyzed cyclopropanation reactions: New polymeric membranes embedding cobalt chiral schiff base complexes | |
| JP6879523B2 (en) | Method for Producing Transition Metal-Isocyanide Complex | |
| Li et al. | A green and recyclable ligand-free copper (I) catalysis system for amination of halonitrobenzenes in aqueous ammonia solution | |
| CN103272644A (en) | Schiff base metal catalyst used in liquid phase epoxidation reaction and preparation method of schiff base metal catalyst | |
| CN109836457A (en) | A kind of high steric-hindrance amino chirality P, N, N ligand and its preparation method and application | |
| CN105017520B (en) | The manufacture method of polyphenylene oxide | |
| CN107913739A (en) | Catalyst for synthesis of alkyl aromatic aldehyde | |
| Tsuruya et al. | Copper (II)-catalyzed oxidative coupling of 2, 6-dimethylphenol | |
| CN105566034B (en) | Alkynes polymerization inhibitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150121 |