CN103787850A - A method of oxidizing hydroquinone to prepare quinone - Google Patents
A method of oxidizing hydroquinone to prepare quinone Download PDFInfo
- Publication number
- CN103787850A CN103787850A CN201210431598.0A CN201210431598A CN103787850A CN 103787850 A CN103787850 A CN 103787850A CN 201210431598 A CN201210431598 A CN 201210431598A CN 103787850 A CN103787850 A CN 103787850A
- Authority
- CN
- China
- Prior art keywords
- quinhydrones
- oxygen
- reaction
- quinone
- sodium nitrite
- 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.)
- Granted
Links
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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/02—Quinones with monocyclic quinoid structure
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/08—Quinones with polycyclic non-condensed quinoid structure
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/24—Quinones containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/26—Quinones containing groups having oxygen atoms singly bound to carbon atoms
- C07C50/28—Quinones containing groups having oxygen atoms singly bound to carbon atoms with monocyclic quinoid structure
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method of oxidizing hydroquinone to prepare quinone. According to the method, water is used as a reaction medium, sodium nitrite is used as a catalyst, a solid acid Amberlyst15 is used as a co-catalyst, oxygen is adopted as an oxidizing agent, and the hydroquinone is oxidized to obtain the quinone. The method is mild in reaction conditions, simple in operation, and free of organic solvent and metal pollution, and is a novel green method for quinone preparation by hydroquinone oxidation catalyzed by a nonmetal catalyst.
Description
Technical field
The present invention relates to catalyzed oxidation and prepare quinone, be specifically related to a kind of method that catalyzed oxidation quinhydrones is prepared quinone.
Background technology
Quinone is a kind of important organic intermediate, has a wide range of applications in pharmacy and field of fine chemical.The report that is oxidized the method for preparing quinone about quinhydrones is a lot, is mainly divided into stoichiometry oxidation and catalyzed oxidation.Stoichiometry is oxidized multiplex Fremy ' s salt, sodium dichromate 99-sulfuric acid mixture, iodo-hydrogen peroxide, diphenyl diselenide-hydrogen peroxide, tertbutyl peroxide-cerous ammonium nitrate is oxygenant, although they can be oxidized to quinone quinhydrones, these methods can produce a large amount of refuses, thereby have limited their development.Oxygen is optimal oxygen source, and transition metal-catalyzed dioxygen oxidation method has gentleer compared with traditional oxidizing reaction, and green, advantages of environment protection, cause chemist's concern.It is catalyzer that nineteen ninety-five Sakai etc. (Inorg.Chim.Acta, 1995,234,157-161) adopt the trivalent Pt complex compound of dimerization, under oxygen exists, quinhydrones can be oxidized to quinone.Pac in 1997 etc. (J.Org.Chem., 1997,62,3194-3199) have reported in butyl acetate solvent, and the copper sulfate of aluminium sesquioxide load can catalytic molecular oxygen oxidation quinhydrones, and high yield obtains quinone.Within 2005, Pan Zhi power waits (Chin.J.Chem., 2005,23,835-842) large ring N with Cu, and O complex compound is catalyzer, and oxygen is oxygenant, in methyl alcohol-acetonitrile mixing solutions, 2-methylbenzene quinhydrones can be oxidized to 2-methylbenzoquinone.Kobayashi in 2008 etc. (Angew.Chem.In.Ed., 2008,47,8093-8095) with the nanometer Pt catalytic molecular oxygen oxidation quinhydrones of Polymer-supported, obtain being greater than the quinone of 95% yield in chloroform-water solvent.Aforesaid method is all to have used a large amount of organic solvents as reaction medium, has both increased cost, not environmental protection again.Residual metal is a very large problem for pharmacy and food applications simultaneously, even if they only have minimal residue.From the viewpoint of economy and Green Chemistry, the method that quinone is prepared in quinhydrones oxidation also needs further Improvement.
Summary of the invention
It is a kind of take water as reaction medium that the problems such as the object of the invention is to overcome above-mentioned oxidation system and has metal residual, pollution provide, and the Sodium Nitrite catalyzed oxidation quinhydrones that molecular oxygen is oxygen source is produced quinone novel method.The method adopts inexpensive Green Oxidant oxygen, has reduced production cost, and environment is not polluted.Water is a kind of desirable oxidation solvent simultaneously, and it not only can avoid generating from the by product of organic solvent, and the oxidizing reaction environment of a safety can be provided again.
For achieving the above object, the technical solution used in the present invention comprises the steps: in water solvent, and take Sodium Nitrite as catalyzer, Amberlyst15 is promotor, and oxygen is that oxygenant is oxidized quinhydrones.
Oxygen pressure used in the present invention is 0.1MPa～1.0MPa, preferably 0.5MPa～1.0MPa
The suitable substrate of the present invention is quinhydrones, and molecular formula is
wherein R
1, R
2, R
3, R
4=H, OMe, C
nh
2n+1(n=1 ~ 10), Ph, Cl, Br.
The applicable temperature of reaction of the present invention is typically about 15 ℃～100 ℃.Preferably, this reaction is carried out about 30 ℃ ~ 40 ℃.
Catalyzer Sodium Nitrite of the present invention and quinhydrones react with the mol ratio of 0.5:100～15:100.Be preferably 1:100～10:100.The consumption of Sodium Nitrite is relevant with the activity of substrate, active high substrate, and the consumption of Sodium Nitrite is less, and the use of active low material Sodium Nitrite increases to some extent.Catalyzer Sodium Nitrite and promotor Amberlyst15 react with the mass ratio of 1:1～1:15.Be preferably 1:1.5 ~ 1:4.Amberlyst15 has a significant impact reaction, and its effect is to provide certain acidity for reaction.
After reaction finishes, reaction system is cooled to room temperature, filters, extraction, can obtain highly purified product after concentrating.
Due to the utilization of above-mentioned technology, the present invention compared with prior art has following advantages:
1, the oxidizing reaction of this catalyst system, using green inexpensive oxygen is oxygen source; Avoid using prior art toxic and dangerous larger oxygenant, environmentally friendly, and also cost is relatively low.
2, water does solvent environmentally safe, and product separation is simple.
3, due to oxygen, the use of catalyzer and promotor makes reaction conditions gentleness, and selectivity is high, simple to operate, and product is easily separated.
Embodiment
Describe specific embodiment of the invention step in detail below by some embodiment, should be by these embodiment as scope of the invention restriction.Reaction is carried out in the 100mL stainless steel cauldron with polytetrafluoro liner.
The investigation of embodiment 1 reaction conditions
First we investigate reaction conditions take 2-methylbenzene quinhydrones as model substrates.Reaction product 2-methylbenzoquinone,
1h NMR (CDCl
3, 500MHz) and δ 2.29 (s, 3H), 6.68 (s, 3H);
13c NMR (CDCl
3, 125MHz) and δ 125MHz) δ 2.29 (s, 3H), 6.68 (s, 3H).IR(KBr,cm
-1):3307,3264,3074,3066,3034,2960,2926,2866,2724,2671,2579,2016,1650,1600,1466,1442,1426,1376,1349,1302,1283,1231,1187,1143,1098,1039,1000,928,903,885,860,826,761,722,682。The results are shown in Table 1;
The investigation of table 1 reaction conditions
Table 1 is visible, Sodium Nitrite, and Amberlyst15, oxygen is to the vital effect of having of oxidizing reaction, indispensable.The temperature of reaction of system is in the time of 30 ℃ ~ 45 ° of C, and result is better, and the too high by product that has of temperature generates, thereby reduces the yield of product, and oxygen pressure is larger, reacts faster, and result is also better.
The oxidation of embodiment 2,2-methylbenzene quinhydrones
In the 100mL stainless steel cauldron with polytetrafluoro liner, add 12.4g (0.1mol) 2-methylbenzene quinhydrones, 0.345g (0.005mol) Sodium Nitrite, 1.0g Amberlyst 15,30mL water, sealing, is filled with 2atm oxygen.Stirring reaction 20h under 40 ° of C conditions, is cooled to reaction system room temperature and slowly bleeds off responseless oxygen, filters, and the aqueous solution is extracted with ethyl acetate 3 times, can obtain product 2-methylbenzoquinone 11.9g after steaming organic solvent.
1H?NMR(CDCl
3,500MHz)δ2.29(s,3H),6.68(s,3H);
13C?NMR(CDCl
3,125MHz)δ2.29(s,3H),6.68(s,3H)。IR(KBr,cm
-1):3307,3264,3074,3066,3034,2960,2926,2866,2724,2671,2579,2016,1650,1600,1466,1442,1426,1376,1349,1302,1283,1231,1187,1143,1098,1039,1000,928,903,885,860,826,761,722,682。
Embodiment 3,2, the oxidation of 6-dimethyl benzene quinhydrones
In the 100mL stainless steel cauldron with polytetrafluoro liner, add 13.8g (0.1mol) 2,6-dimethyl benzene quinhydrones, 0.69g(0.01mol) Sodium Nitrite, 2.0g Amberlyst 15,35mL water, sealing, is filled with 4atm oxygen.Stirring reaction 24h under 35 ° of C conditions, is cooled to reaction system room temperature and slowly bleeds off responseless oxygen, filters, and the aqueous solution is extracted with ethyl acetate 3 times, can obtain product 2,6-phlorone 12.9g after steaming organic solvent.
1H?NMR(CDCl
3,500MHz)δ2.04(s,6H),6.73(s,2H)；
13C?NMR(CDCl
3,125MHz)δ12.10,136.12,142.89,187.30。IR(KBr,cm
-1):3264,3052,3042,2996,2968,2930,1753,1673,1656,1627,1614,1442,1430,1422,1383,1376,1362,1317,1291,1206,1181,1036,1024,935,920,901,853,794,648,569,464,457。
The oxidation of embodiment 4,2-phenyl benzene quinhydrones
In the 100mL stainless steel cauldron with polytetrafluoro liner, add 18.6g (0.1mol) 2-phenyl benzene quinhydrones, 0.414g(0.006mol) Sodium Nitrite, 0.9g Amberlyst 15,35mL water, sealing, is filled with 3atm oxygen.Stirring reaction 20h under 40 ° of C conditions, is cooled to reaction system room temperature and slowly bleeds off responseless oxygen, filters, and the aqueous solution is extracted with ethyl acetate 3 times, can obtain product 2-phenyl benzoquinones 18.1g after steaming organic solvent.
1H?NMR(CDCl
3,500MHz)δ6.84(dd,1H,J=2.10,10.3Hz),6.87(m,2H),7.50(m,5H)；
13C?NMR(CDCl
3,125MHz)δ128.55,129.24,130.14,132.68,136.25,137.05,145.89,186.56,187.52。IR(KBr,cm
-1):3426,3416,3254,3076,3053,3043,1686,1659,1645,1599,1592,1573,1494,1446,1344,1329,1316,1300,1278,1256,1197,1108,1096,1078,1002,979,938,922,914,843,747,694,686,624,427。
Embodiment 5,2,3, the oxidation of 6-Three methyl Benzene quinhydrones
In the 100mL stainless steel cauldron with polytetrafluoro liner, add 15.2g (0.1mol) 2,3,6-Three methyl Benzene quinhydrones, 0.552g(0.008mol) Sodium Nitrite, 1.6g Amberlyst 15,45mL water, sealing, is filled with 5atm oxygen.Stirring reaction 15h under 40 ° of C conditions, is cooled to reaction system room temperature and slowly bleeds off responseless oxygen, filters, and the aqueous solution is extracted with ethyl acetate 3 times, can obtain product 2,3,6-trimethylbenzoquinone 14.1g after steaming organic solvent.
1H?NMR(CDCl
3,500MHz)δ1.95(s,9H),6.88(s,1H)；
13C?NMR(CDCl
3,125MHz)δ14.22,136.52,144.73,145.79,186.50,187.27。IR(KBr,cm
-1):3309,3264,3052,3042,2986,2968,2930,1753,1656,1614,1442,1430,1422,1383,1376,1362,1317,1291,1206,1181,1036,1024,935,920,901,853,794,684,567,460,454。
The oxidation of embodiment 6,2-chlorobenzene quinhydrones
In the 100mL stainless steel cauldron with polytetrafluoro liner, add 14.46g (0.1mol) 2-chlorobenzene quinhydrones, 0.483g(0.007mol) Sodium Nitrite, 1.8g Amberlyst 15,25mL water, sealing, is filled with 2atm oxygen.Stirring reaction 35h under 40 ° of C conditions, is cooled to reaction system room temperature and slowly bleeds off responseless oxygen, filters, and the aqueous solution is extracted with ethyl acetate 3 times, can obtain product 2-chloranil 13.5g after steaming organic solvent.
1H?NMR(CDCl
3,500MHz)δ6.78(s,1H),6.96(s,2H)；
13C?NMR(CDCl
3,125MHz)δ134.12,136.93,144.15,176.83,185.86。IR(KBr,cm
-1):3358,1691,1661,1656,1651,1571,1547,1491,1318,1250,1237,1210,1113,1109,907,754,713,704。
The oxidation of embodiment 7,2-bromobenzene quinhydrones
In the 100mL stainless steel cauldron with polytetrafluoro liner, add 18.9g (0.1mol) 2-bromobenzene quinhydrones, 0.276g(0.004mol) Sodium Nitrite, 0.552g Amberlyst 15,35mL water, sealing, is filled with 5atm oxygen.Stirring reaction 35h under 30 ° of C conditions, is cooled to reaction system room temperature and slowly bleeds off responseless oxygen, filters, and the aqueous solution is extracted with ethyl acetate 3 times, can obtain product 2-bromobenzene quinone 18.1g after steaming organic solvent.
1H?NMR(CDCl
3,500MHz)δ6.78(s,2H),7.23(s,1H)；
13C?NMR(CDCl
3,125MHz)δ136.91,138.53,139.20,177.66,185.88。IR(KBr,cm
-1):3364,3338,1692,1679,1665,1641,1564,1547,1478,1278,1268,1258,1218,1166,1066,1055,1030,976,868,705,695,645。
The oxidation of embodiment 8,2-tert.-butylbenzene quinhydrones
In the 100mL stainless steel cauldron with polytetrafluoro liner, add 16.6g (0.1mol) 2-tert.-butylbenzene quinhydrones, 0.138g(0.002mol) Sodium Nitrite, 0.276g Amberlyst 15,35mL water, sealing, is filled with 1atm oxygen.Stirring reaction 30h under 45 ° of C conditions, is cooled to reaction system room temperature and slowly bleeds off responseless oxygen, filters, and the aqueous solution is extracted with ethyl acetate 3 times, can obtain product 2-tertiary butyl benzoquinones 16.2g after steaming organic solvent.
1H?NMR(CDCl
3,500MHz)δ1.29(s,9H),6.60(s,1H),6.68(s,2H)；
13C?NMR(CDCl
3,125MHz)δ29.11,35.28,131.54,134.63,138.68,156.05,187.49,188.45。IR(KBr,cm
-1):3061,3000,2961,2916,2872,1657,1590,1486,1462,1390,1368,1355,1340,1289,1260,1199,1108,1047,1014,934,923,883,839,425。
Embodiment 9,2,6-2-methoxyhydroquinone's oxidation
In the 100mL stainless steel cauldron with polytetrafluoro liner, add 17.2g (0.1mol) 2,6-2-methoxyhydroquinone, 0.069g(0.001mol) Sodium Nitrite, 0.3g Amberlyst 15,35mL water, sealing, is filled with 2atm oxygen.Stirring reaction 24h under 40 ° of C conditions, is cooled to reaction system room temperature and slowly bleeds off responseless oxygen, filters, and the aqueous solution is extracted with ethyl acetate 3 times, can obtain product 2,6-dimethoxy para benzoquinone 16.8g after steaming organic solvent.
1H?NMR(CDCl
3,500MHz)δ3.89(s,6H),6.74(s,2H)；
13C?NMR(CDCl
3,125MHz)δ16.76,136.52,158.79,181.50,187.67。IR(KBr,cm
-1):3388,3224,3062,3050,2997,2966,2952,2912,2852,1696,1644,1625,1593,1524,1498,1471,1466,1447,1441,1416,1380,1322,1260,1219,1191,1109,1006,996,879,855,808,773,703,606,449。
Claims (7)
1. a method for quinhydrones oxidation quinone processed, the method comprises the steps: in the aqueous solution, and take Sodium Nitrite as catalyzer, solid acid Amberlyst15 is promotor, and oxygen is that oxygenant carries out oxidizing reaction to quinhydrones.
2. method as claimed in claim 1, is characterized in that: wherein temperature of reaction is 15 ° of C ~ 100 ° C.
3. as the method for claim 1 or 2, it is characterized in that: wherein temperature of reaction is preferably 30 ° of C ~ 40 ° C.
4. as the method for claim 1 or 2, it is characterized in that: the pressure of oxygen is 0.1Mpa～1.0MPa.
5. method as claimed in claim 1, is characterized in that: suitable substrate quinhydrones molecular formula is:
wherein R
1, R
2, R
3, R
4difference=H, OMe, C
nh
2n+1(n=1 ~ 10), Cl or Br.
6. as the method for claim 1 or 5, it is characterized in that: carry out in reaction process, the mol ratio of its Sodium Nitrite and quinhydrones is 0.5:100～15:100.
7. as the method for claim 1 or 5, it is characterized in that: carry out in reaction process, the mass ratio of its Sodium Nitrite and Amberlyst15 is 1:1～1:15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210431598.0A CN103787850B (en) | 2012-11-01 | 2012-11-01 | The method of a kind of quinhydrones oxidation quinone processed |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210431598.0A CN103787850B (en) | 2012-11-01 | 2012-11-01 | The method of a kind of quinhydrones oxidation quinone processed |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103787850A true CN103787850A (en) | 2014-05-14 |
| CN103787850B CN103787850B (en) | 2015-10-21 |
Family
ID=50663967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210431598.0A Expired - Fee Related CN103787850B (en) | 2012-11-01 | 2012-11-01 | The method of a kind of quinhydrones oxidation quinone processed |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103787850B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084006A (en) * | 2017-10-30 | 2018-05-29 | 浙江新和成药业有限公司 | A kind of preparation method of trimethylbenzoquinone and trimethylhydroquinone |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5118823A (en) * | 1990-12-13 | 1992-06-02 | Eastman Kodak Company | Oxidation of dihydroxyaromatic compounds to quinones |
| CN102108047A (en) * | 2010-12-06 | 2011-06-29 | 上海迪赛诺医药发展有限公司 | Method for preparing 2,3,5-trimethylhydroquinone |
-
2012
- 2012-11-01 CN CN201210431598.0A patent/CN103787850B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5118823A (en) * | 1990-12-13 | 1992-06-02 | Eastman Kodak Company | Oxidation of dihydroxyaromatic compounds to quinones |
| CN102108047A (en) * | 2010-12-06 | 2011-06-29 | 上海迪赛诺医药发展有限公司 | Method for preparing 2,3,5-trimethylhydroquinone |
Non-Patent Citations (2)
| Title |
|---|
| RAJENDRA RATHORE ET AL.,: "Convenient Preparation of Quincms via the Catalytic Autoxidation", 《TETRAHEDRON LETTERS》, vol. 35, no. 9, 31 December 1994 (1994-12-31), pages 1335 - 1338 * |
| ZHOU HONG ET AL.,: "Study on the Crystal Structure of a Macrocycle and Tyrosinase Activity of Its Dinuclear Copper Complexes", 《CHINESE JOURNAL OF CHEMISTRY》, vol. 23, no. 7, 31 December 2005 (2005-12-31), pages 835 - 842, XP008109280, DOI: doi:10.1002/cjoc.200590835 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084006A (en) * | 2017-10-30 | 2018-05-29 | 浙江新和成药业有限公司 | A kind of preparation method of trimethylbenzoquinone and trimethylhydroquinone |
| CN108084006B (en) * | 2017-10-30 | 2020-12-29 | 浙江新和成药业有限公司 | Preparation method of trimethylbenzoquinone and trimethylhydroquinone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103787850B (en) | 2015-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Derikvand et al. | Oxidation of hydroquinones to benzoquinones with hydrogen peroxide using catalytic amount of silver oxide under batch and continuous-flow conditions | |
| CN107803220B (en) | Supported imidazole ionic liquid catalyst and application thereof in preparation of cyclohexanone and cyclohexanol by catalytic oxidation of cyclohexane | |
| CN108148024B (en) | Method for preparing methyl furoate by oxidizing and esterifying furfural | |
| CA2715655A1 (en) | Method for producing olefinically unsaturated carbonyl compounds by oxidative dehydrogenation of alcohols | |
| CN110563590B (en) | Method for selective oxidation of toluene compounds | |
| Zhu et al. | Magnetic copper ferrite nanoparticles/TEMPO catalyzed selective oxidation of activated alcohols to aldehydes under ligand-and base-free conditions in water | |
| CN103864549B (en) | Method for preparing diphenyl ketone compound | |
| CN103787850B (en) | The method of a kind of quinhydrones oxidation quinone processed | |
| CN103467434A (en) | Method for preparing eta-caprolactone by composite catalysis | |
| CN102964230B (en) | Method for preparing benzaldehyde from methylbenzene through liquid-phase catalytic oxidation | |
| CN104151133B (en) | A kind of method of methylbenzene selective preparing benzaldehyde by oxidizing | |
| CN101613252B (en) | Method for synthesizing oxygen-containing compounds by selective oxidization of hydrocarbons in the presence of metal and quinine catalyst | |
| Stuchinskaya et al. | Novel efficient catalysts based on Ru or Pd oxide for selective liquid-phase oxidation of alcohols with nitrous oxide | |
| CN103755526A (en) | Method of preparing alpha-phenethyl alcohol compounds by catalytic oxidation of side chains of aromatic hydrocarbon by using metalloporphyrin | |
| CN110423185B (en) | Method for selectively oxidizing cumene compound | |
| Wong et al. | Controlling the selectivity of the manganese/bicarbonate/hydrogen peroxide catalytic system by a biphasic pyrrolidinium ionic liquid/n-heptane medium | |
| CN103691485B (en) | The method of hydroquinones and the catalyst of use thereof and preparation method is prepared for catalytic hydrogenation | |
| CN108144612A (en) | It is a kind of for the cobalt-base catalyst of one pot process carboxylate and its preparation and application | |
| CN110483244B (en) | Preparation method of tert-butyl alcohol | |
| CN105597830A (en) | Method for preparing ketone compound through biomimetic catalysis | |
| CN102659522A (en) | Simple preparation method of 2,3,5-trimethylhydroquinone and method for preventing 2,3,5-trimethylhydroquinone from being oxidized in production or storage process | |
| JP2013202533A (en) | Method for recovering palladium | |
| CN104860901B (en) | Preparation method of benzothiazole-2-carboxylic acid | |
| CN104437491A (en) | Activated carbon supported iron catalyst and method for catalyzing oxidative coupling of 3-tert-butyl-4-hydroxy anisole | |
| CN103030557A (en) | Method for generating phenylacetate by acetophenone in one step |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151021 Termination date: 20181101 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |