CN103342675A - Preparation method of diindolylmethane derivative through catalysis - Google Patents
Preparation method of diindolylmethane derivative through catalysis Download PDFInfo
- Publication number
- CN103342675A CN103342675A CN2013101858674A CN201310185867A CN103342675A CN 103342675 A CN103342675 A CN 103342675A CN 2013101858674 A CN2013101858674 A CN 2013101858674A CN 201310185867 A CN201310185867 A CN 201310185867A CN 103342675 A CN103342675 A CN 103342675A
- Authority
- CN
- China
- Prior art keywords
- reaction
- catalyzer
- methyl hydride
- preparation
- aromatic aldehyde
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Indole Compounds (AREA)
Abstract
The invention provides a preparation method of diindolylmethane derivative through catalysis, belonging to the technical field of organic chemistry synthesis. During a reaction of preparing the diindolylmethane derivative, a mole ratio of indole and aromatic aldehyde is 2-5 : 1, a molar amount of a catalyst is 1-3 % of the amount of aromatic aldehyde, a volume amount (mL) of a reaction solvent water is 2-10 times of a molar amount (mmol) of the aromatic aldehyde, a reaction temperature is 25-30 DEG C, a reaction time is 2-30 minutes, and a reaction pressure is an atmospheric pressure. After the reaction, the product is filtered through pumping, and filter residues are recrystallized by 98 % aqueous ethanol and then dried to obtain the pure diindolylmethane derivative. The catalyst contained in the filtrate can be recycled without any treatment. Compared with preparation methods using traditional proton acid and Lewis acid as catalysts, the method provided by the invention is little in reaction time, mild in reaction conditions and few in catalyst amount, and the catalyst can be recycled.
Description
Technical field
The invention belongs to the organic chemical synthesis technical field, be specifically related to a kind of method of catalytic preparation di-indole methyl hydride derivative.
Background technology
The di-indole methyl hydride derivative is as very important a kind of in numerous indole derivativeses, and it extensively is present in the natural product, and has many pharmacology and physiologically active.Can promote the metabolism of female hormone in the human body such as it, can regulate the hormone metabolism thing of some cancer cells secretion, be a kind of effective cancer therapy drug.Therefore, synthetic people's the extensive concern that caused of di-indole methyl hydride derivative.The most preparation of this compounds at present mainly is to carry out in traditional organic solvent, will use the bigger Lewis acid of costliness or toxicity usually as catalyzer, has shortcomings such as long reaction time, productive rate is low, environmental pollution is serious simultaneously.Therefore, the catalytic preparation method of development of new just become synthetic family the research focus.
The acidic ion liquid that has acidic functionality is because it has thermostability preferably, non-easy volatile, organic and mineral compound are had good solubility and advantage such as the acidic site that is evenly distributed and being applied in the catalytic preparation of di-indole methyl hydride derivative.As Hojat Veisi etc. with lewis acidity ionic liquid [BTBAC] Cl-FeCl
3As catalyzer, can high productivity catalysis aldehydes or ketones under the condition of no solvent and indole reaction prepare di-indole methyl hydride and derivative (Highly efficient method for synthesis of bis (indolyl) methanes catalyzed by FeCl3-based ionic liquid thereof, Journal of the Chinese Chemical Society, 2009,56:240-245).Thereby meet water and take place to decompose and cause the shortcoming that can not recycle in order to solve above-mentioned lewis acidity ionic liquid, uses such as A.Rajendran are relatively large contains HSO
4 -Acidic ion liquid [Et
3NH] [HSO
4] as the green solvent of the preparation di-indole methyl hydride derivative catalyzer of holding concurrently, under mild conditions, can recycle (A domino green synthesis of bis (indolyl) methanes catalyzed by ionic liquid[Et
3NH] [HSO
4], International Journal of ChemTech Research, 2011,3:298-302).For the acidity that improves acidic ion liquid and then reduce the consumption of acidic ion liquid in the preparation process, utilizations such as Seyed Mohammad Vahdat synthesize contains four-SO
3The acidic ion liquid of H is made catalyzer, can successfully " one kettle way " condensation reaction be taken place for various alkanoics, fragrant aldehydes or ketones and indoles and generate corresponding di-indole methyl hydride derivative, this preparation process has characteristics such as reaction conditions gentleness, time spent weak point, productive rate height.But the preparation of this acidic ion liquid is complexity and higher (An efficient one-pot synthesis of bis (indolyl) the methanes catalyzed by ionic liquid with multi-SO of expense comparatively
3H groups under ambient temperature in water, World Applied Science Journal, 2011,15 (6): 877-884).
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide that a kind of cost is low, productive rate is high, technology is simple and the method for eco-friendly catalytic preparation di-indole methyl hydride derivative.
Catalyst structure formula used in the present invention is:
The method of a kind of catalytic preparation di-indole methyl hydride derivative provided by the present invention, its reaction formula is:
Wherein indoles (I) is 2～5:1 with aromatic aldehyde (II) mol ratio in the reaction, the molar weight of catalyzer is 1～3% of used aromatic aldehyde, the volume of reaction solvent water (mL) is 2～10 times of aromatic aldehyde molar weight (mmol), temperature of reaction is 25～30 ℃, reaction times is 2～30min, and reaction pressure is a normal atmosphere.After reaction finished, suction filtration, gained filter residue obtained pure di-indole methyl hydride derivative (III) after with 98% aqueous ethanolic solution recrystallization, drying.
The used aromatic aldehyde of the present invention is phenyl aldehyde, 4-chloro-benzaldehyde, Ortho Nitro Benzaldehyde, paranitrobenzaldehyde, p-tolyl aldehyde, p-Hydroxybenzaldehyde, aubepine, to cyanobenzaldehyde, p-Fluorobenzenecarboxaldehyde, p-bromobenzaldehyde, 2,4-dichlorobenzaldehyde, 2, any in the 4-dimethylbenzaldehyde.
In the above-mentioned preparation feedback, the catalyzer that contains in the suction filtration rear filtrate need not any processing and is directly used in reaction next time, can reuse repeatedly, and the catalytic efficiency of catalyzer does not have obvious decline.
The preparation method of catalyst system therefor of the present invention sees pertinent literature (Synthesis of a novel multi – SO
3H functionalized ionic liquid and its catalytic activities for biodiesel synthesis, Green Chemistry, 12 (2010), 201-204; A kind of preparation method of multi-sulfonic functional ion liquid, CN101348487A).
The present invention compares with the synthetic method of traditional protonic acid, Louis's acid as catalyst, has following characteristics:
1, the acidity height of catalyzer, catalytic activity is good, and the reaction time spent is few, the productive rate height;
2, catalyzer can recycle, and catalytic activity almost remains unchanged in recycling;
3, make water as reaction solvent, can alleviate the problem of environmental pollution because using the volatile organic solvent to bring;
4, the Preparation of catalysts process is comparatively simple and the preparation expense is lower.
Embodiment
Below in conjunction with specific embodiment technical solution of the present invention is described further, but protection scope of the present invention is not limited thereto.
Embodiment 1: 2mmol indoles, 1mmol phenyl aldehyde, 0.01mmol catalyzer and 2mL water are joined 25mL have in the single port bottle of stirrer.25 ℃ of following vigorous stirring reactions, (developping agent is normal hexane: ethyl acetate=4:1) is followed the tracks of extent of reaction to thin-layer chromatography (TLC).Reaction time spent 6min, reaction pressure is a normal atmosphere.Reaction finishes the back suction filtration, and the gained filter residue obtains pure two indoles phenylmethanes after with 98% aqueous ethanolic solution recrystallization, drying, and productive rate is 93%.Filtrate (comprising the intact raw material of catalyzer and unreacted) need not any processing and is directly used in reaction next time.
Embodiment 2: 2mmol indoles, 1mmol 4-chloro-benzaldehyde, 0.01mmol catalyzer and 2mL water are joined 25mL have in the single port bottle of stirrer.25 ℃ of following vigorous stirring reactions, (developping agent is normal hexane: ethyl acetate=4:1) is followed the tracks of extent of reaction to thin-layer chromatography (TLC).Reaction time spent 8min, reaction pressure is a normal atmosphere.Reaction finishes the back suction filtration, and the gained filter residue obtains pure rubigan di-indole methyl hydride after with 98% aqueous ethanolic solution recrystallization, drying, and productive rate is 94%.Filtrate (comprising the intact raw material of catalyzer and unreacted) need not any processing and is directly used in reaction next time.
Embodiment 3: 2mmol indoles, 1mmol paranitrobenzaldehyde, 0.01mmol catalyzer and 4mL water are joined 25mL have in the single port bottle of stirrer.27 ℃ of following vigorous stirring reactions, (developping agent is normal hexane: ethyl acetate=4:1) is followed the tracks of extent of reaction to thin-layer chromatography (TLC).Reaction time spent 3min, reaction pressure is a normal atmosphere.Reaction finishes the back suction filtration, and the gained filter residue obtains pure p-nitrophenyl di-indole methyl hydride after with 98% aqueous ethanolic solution recrystallization, drying, and productive rate is 97%.Filtrate (comprising the intact raw material of catalyzer and unreacted) need not any processing and is directly used in reaction next time.
Embodiment 4: with 3mmol indoles, 1mmol2,4-dichlorobenzaldehyde, 0.02mmol catalyzer and 6mL water join 50mL and have in the single port bottle of stirrer.30 ℃ of following vigorous stirring reactions, (developping agent is normal hexane: ethyl acetate=4:1) is followed the tracks of extent of reaction to thin-layer chromatography (TLC).Reaction time spent 10min, reaction pressure is a normal atmosphere.Reaction finishes the back suction filtration, and the gained filter residue obtains pure 2,4 dichloro benzene base di-indole methyl hydride after with 98% aqueous ethanolic solution recrystallization, drying, and productive rate is 94%.Filtrate (comprising the intact raw material of catalyzer and unreacted) need not any processing and is directly used in reaction next time.
Embodiment 5: with 4mmol indoles, 1mmol2,4-dimethylbenzaldehyde, 0.03mmol catalyzer and 8mL water join 50mL and have in the single port bottle of stirrer.30 ℃ of following vigorous stirring reactions, (developping agent is normal hexane: ethyl acetate=4:1) is followed the tracks of extent of reaction to thin-layer chromatography (TLC).Reaction time spent 18min, reaction pressure is a normal atmosphere.Reaction finishes the back suction filtration, and it is pure 2 that the gained filter residue obtains after with 98% aqueous ethanolic solution recrystallization, drying, and 4-3,5-dimethylphenyl di-indole methyl hydride, productive rate are 95%.Filtrate (comprising the intact raw material of catalyzer and unreacted) need not any processing and is directly used in reaction next time.
Embodiment 6: 3mmol indoles, the cyanobenzaldehyde of 1mmol, 0.01mmol catalyzer and 2mL water are joined 25mL have in the single port bottle of stirrer.25 ℃ of following vigorous stirring reactions, (developping agent is normal hexane: ethyl acetate=4:1) is followed the tracks of extent of reaction to thin-layer chromatography (TLC).Reaction time spent 5min, reaction pressure is a normal atmosphere.Reaction finishes the back suction filtration, and the gained filter residue obtains after with 98% aqueous ethanolic solution recrystallization, drying pure to the cyano-phenyl di-indole methyl hydride, and productive rate is 95%.Filtrate (comprising the intact raw material of catalyzer and unreacted) need not any processing and is directly used in reaction next time.
Embodiment 7: 2mmol indoles, 1mmol Ortho Nitro Benzaldehyde, 0.01mmol catalyzer and 2mL water are joined 25mL have in the single port bottle of stirrer.25 ℃ of following vigorous stirring reactions, (developping agent is normal hexane: ethyl acetate=4:1) is followed the tracks of extent of reaction to thin-layer chromatography (TLC).Reaction time spent 4min, reaction pressure is a normal atmosphere.Reaction finishes the back suction filtration, and the gained filter residue obtains pure Chloro-O-Phenyl di-indole methyl hydride after with 98% aqueous ethanolic solution recrystallization, drying, and productive rate is 96%.Filtrate (comprising the intact raw material of catalyzer and unreacted) need not any processing and is directly used in reaction next time.
Embodiment 8: be probe reaction with embodiment 1, make the active replica test of catalysts, catalyzer is reused 6 times, and its catalysis productive rate changes and sees Table 1.
Catalyst activity replica test result among table 1 the present invention
| The catalyst recirculation access times | Two indoles phenylmethane productive rates (%) |
| 1 | 93 |
| 2 | 93 |
| 3 | 91 |
| 4 | 90 |
| 5 | 91 |
| 6 | 91 |
| 7 | 89 |
Can draw such conclusion by table 1 data: the productive rate of catalyzer two indoles phenylmethanes in recycling process has reduction slightly, but the reduction amplitude is less, proves that it can recycle in preparation di-indole methyl hydride derivatives reaction.
Claims (3)
1. the method for a catalytic preparation di-indole methyl hydride derivative, it is characterized in that, indoles and aromatic aldehyde mol ratio are 2～5:1 in the reaction of described preparation di-indole methyl hydride derivative, the molar weight of catalyzer is 1～3% of used aromatic aldehyde, the volume of reaction solvent water (mL) is 2～10 times of aromatic aldehyde molar weight (mmol), temperature of reaction is 25～30 ℃, reaction times is 2～30min, reaction pressure is a normal atmosphere, after reaction finishes, suction filtration, gained filter residue obtain pure di-indole methyl hydride derivative after with 98% aqueous ethanolic solution recrystallization, drying;
The structural formula of described catalyzer is:
2. the method for a kind of catalytic preparation di-indole methyl hydride derivative as claimed in claim 1, it is characterized in that, described aromatic aldehyde is phenyl aldehyde, 4-chloro-benzaldehyde, Ortho Nitro Benzaldehyde, paranitrobenzaldehyde, p-tolyl aldehyde, p-Hydroxybenzaldehyde, aubepine, to cyanobenzaldehyde, p-Fluorobenzenecarboxaldehyde, p-bromobenzaldehyde, 2,4-dichlorobenzaldehyde, 2, any in the 4-dimethylbenzaldehyde.
3. the method for a kind of catalytic preparation di-indole methyl hydride derivative as claimed in claim 1 is characterized in that, the catalyzer that contains in the filtrate behind the described suction filtration need not any processing and can directly reuse.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310185867.4A CN103342675B (en) | 2013-05-17 | 2013-05-17 | Preparation method of diindolylmethane derivative through catalysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310185867.4A CN103342675B (en) | 2013-05-17 | 2013-05-17 | Preparation method of diindolylmethane derivative through catalysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103342675A true CN103342675A (en) | 2013-10-09 |
| CN103342675B CN103342675B (en) | 2015-01-21 |
Family
ID=49277516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310185867.4A Expired - Fee Related CN103342675B (en) | 2013-05-17 | 2013-05-17 | Preparation method of diindolylmethane derivative through catalysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103342675B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880728A (en) * | 2014-03-21 | 2014-06-25 | 台州学院 | Method for preparing diindolylmethane compound |
| CN104193718A (en) * | 2014-08-14 | 2014-12-10 | 安徽工业大学 | Catalytic preparation method of bishydroxycoumarin derivatives |
| CN104592089A (en) * | 2015-01-05 | 2015-05-06 | 内蒙古工业大学 | Catalytic synthesis of 3-amino-alkylindole by using [HMim] BF4 ionic liquid in water |
| CN104592088A (en) * | 2015-01-05 | 2015-05-06 | 内蒙古工业大学 | Method for preparing 3-amino alkyl indole through catalyzing by lauric acid |
| CN106567104A (en) * | 2016-10-31 | 2017-04-19 | 华南理工大学 | Electrochemical synthesis method of 1,1'-diindolylmethane derivatives |
| CN107827804A (en) * | 2017-11-27 | 2018-03-23 | 菏泽海诺知识产权服务有限公司 | A kind of preparation method of diindolylmethane derivative |
| CN110016042A (en) * | 2019-05-09 | 2019-07-16 | 马鞍山市泰博化工科技有限公司 | A kind of method that catalysis prepares Isosorbide-5-Nitrae-dihydro pyrido [3,2-c] [5,6-c] bicoumarin derivative |
| CN113880748A (en) * | 2021-11-15 | 2022-01-04 | 西安久中生物科技有限公司 | Green preparation process of 3, 3-diindolylmethane |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3527517A (en) * | 1965-09-01 | 1970-09-08 | Kalle Ag | Bis-indolyl-aryl-methane light sensitive compositions |
| WO2006025889A2 (en) * | 2004-05-21 | 2006-03-09 | The Texas A & M University System | Inhibition of atherosclerosis by diindolylmethane analogs |
| CN1837193A (en) * | 2006-04-26 | 2006-09-27 | 浙江大学 | Process for preparing diindolylmethane derivatives |
| CN101348487A (en) * | 2008-09-04 | 2009-01-21 | 华东师范大学 | Preparation of multi-sulfonic functional ion liquid |
| CN102153500A (en) * | 2011-03-02 | 2011-08-17 | 河北大学 | Method for synthesizing diindolylmethane derivative |
-
2013
- 2013-05-17 CN CN201310185867.4A patent/CN103342675B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3527517A (en) * | 1965-09-01 | 1970-09-08 | Kalle Ag | Bis-indolyl-aryl-methane light sensitive compositions |
| WO2006025889A2 (en) * | 2004-05-21 | 2006-03-09 | The Texas A & M University System | Inhibition of atherosclerosis by diindolylmethane analogs |
| CN1837193A (en) * | 2006-04-26 | 2006-09-27 | 浙江大学 | Process for preparing diindolylmethane derivatives |
| CN101348487A (en) * | 2008-09-04 | 2009-01-21 | 华东师范大学 | Preparation of multi-sulfonic functional ion liquid |
| CN102153500A (en) * | 2011-03-02 | 2011-08-17 | 河北大学 | Method for synthesizing diindolylmethane derivative |
Non-Patent Citations (1)
| Title |
|---|
| SEYED MOHAMMAD VAHDAT，等: "An Efficient One-Pot Synthesis of Bis (Indolyl)methanes Catalyzed by Ionic Liquid with Multi-SO3H Groups under Ambient Temperature in Water", 《WORLD APPLIED SCIENCES JOURNAL》, vol. 15, no. 6, 31 December 2011 (2011-12-31), pages 877 - 884 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880728A (en) * | 2014-03-21 | 2014-06-25 | 台州学院 | Method for preparing diindolylmethane compound |
| CN103880728B (en) * | 2014-03-21 | 2016-03-30 | 台州学院 | A kind of method preparing di-indole methyl hydride compounds |
| CN104193718B (en) * | 2014-08-14 | 2016-03-30 | 安徽工业大学 | The method of temparin analog derivative is prepared in a kind of catalysis |
| CN104193718A (en) * | 2014-08-14 | 2014-12-10 | 安徽工业大学 | Catalytic preparation method of bishydroxycoumarin derivatives |
| CN104592088B (en) * | 2015-01-05 | 2019-01-01 | 内蒙古工业大学 | The method that laurel acid catalysis prepares 3- amine alkyl-indol |
| CN104592088A (en) * | 2015-01-05 | 2015-05-06 | 内蒙古工业大学 | Method for preparing 3-amino alkyl indole through catalyzing by lauric acid |
| CN104592089A (en) * | 2015-01-05 | 2015-05-06 | 内蒙古工业大学 | Catalytic synthesis of 3-amino-alkylindole by using [HMim] BF4 ionic liquid in water |
| CN104592089B (en) * | 2015-01-05 | 2019-04-16 | 内蒙古工业大学 | [HMim] BF in water4Ionic liquid-catalyzed synthesis 3- amine alkyl-indol |
| CN106567104A (en) * | 2016-10-31 | 2017-04-19 | 华南理工大学 | Electrochemical synthesis method of 1,1'-diindolylmethane derivatives |
| CN106567104B (en) * | 2016-10-31 | 2018-12-11 | 华南理工大学 | The electrochemical method for synthesizing of 1,1 '-di-indole methyl hydride analog derivatives |
| CN107827804A (en) * | 2017-11-27 | 2018-03-23 | 菏泽海诺知识产权服务有限公司 | A kind of preparation method of diindolylmethane derivative |
| CN110016042A (en) * | 2019-05-09 | 2019-07-16 | 马鞍山市泰博化工科技有限公司 | A kind of method that catalysis prepares Isosorbide-5-Nitrae-dihydro pyrido [3,2-c] [5,6-c] bicoumarin derivative |
| CN110016042B (en) * | 2019-05-09 | 2020-09-04 | 马鞍山市泰博化工科技有限公司 | Method for preparing 1, 4-dihydropyrido [3, 2-c ] [5, 6-c ] dicoumarin derivative through catalysis |
| CN113880748A (en) * | 2021-11-15 | 2022-01-04 | 西安久中生物科技有限公司 | Green preparation process of 3, 3-diindolylmethane |
| CN113880748B (en) * | 2021-11-15 | 2023-06-23 | 西安久中生物科技有限公司 | Green preparation process of 3, 3-diindolylmethane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103342675B (en) | 2015-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103342675B (en) | Preparation method of diindolylmethane derivative through catalysis | |
| Li et al. | Asymmetric transfer hydrogenation of ketones and imines with novel water-soluble chiral diamine as ligand in neat water | |
| Lee et al. | Can a ketone be more reactive than an aldehyde? Catalytic asymmetric synthesis of substituted tetrahydrofurans | |
| EP2431353B1 (en) | Process for preparing amine compound | |
| US20130338359A1 (en) | Novel organic metal complex and process for preparing amine compound | |
| Zhu et al. | Modular design of chiral conjugate-base-stabilized carboxylic acids: catalytic enantioselective [4+ 2] cycloadditions of acetals | |
| CN103232426A (en) | Method for preparing benzopyran derivative by choline chloride functional ion liquid catalysis | |
| Kobayashi et al. | Iridium complex-catalyzed C2-extension of primary alcohols with ethanol via a hydrogen autotransfer reaction | |
| CN108516937B (en) | Method for preparing chiral alpha-hydroxy-beta-keto ester compound by visible light-initiated aerobic Salan-copper catalyst | |
| CN102010447B (en) | Preparation method and application of ruthenium and rhodium transition metal complex functional ionic liquid | |
| Guin et al. | N-Alkylation of Amines by C1–C10 Aliphatic Alcohols Using A Well-Defined Ru (II)-Catalyst. A Metal–Ligand Cooperative Approach | |
| Liu et al. | Asymmetric transfer hydrogenation of ketones catalyzed by thermoregulated ionic liquid-regulating ruthenium complexes | |
| CN104193718A (en) | Catalytic preparation method of bishydroxycoumarin derivatives | |
| CN104610163A (en) | Method for catalytic synthesis of benzimidazole derivatives | |
| Wang et al. | [3, 3]‐Sigmatropic Rearrangements of Naphthyl 1‐Propargyl Ethers: para‐Propargylation and Catalytic Asymmetric Dearomatization | |
| CN102766081A (en) | Method for synchronizing diindolylmethane derivatives | |
| Jose et al. | Ruthenium‐Catalyzed Direct Reductive Amination of Carbonyl Compounds for the Synthesis of Amines: An Overview | |
| CN102631916A (en) | Mesoporous carbon catalyst with load palladium (Pd) and application of mesoporous carbon catalyst | |
| CN102153500A (en) | Method for synthesizing diindolylmethane derivative | |
| Liu et al. | Dimeric Manganese-Catalyzed Direct Nucleophilic Addition of C (sp2)–H Bonds to Inert Aldehydes | |
| CN102153434A (en) | Method for preparing aryl ketone | |
| Vyas et al. | Ru–Prolinamide‐Catalyzed Asymmetric Transfer Hydrogenation of Racemic β‐Heterosubstituted Cycloalkanones Driven by Dynamic Kinetic Resolution | |
| Yanagisawa et al. | Enantioselective protonation of alkenyl trifluoroacetates catalyzed by chiral tin methoxide. | |
| EP2865446B1 (en) | Process for producing optically active secondary alcohol | |
| Scalambra et al. | Photo-generation of H 2 by heterometallic complexes |
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: 20150121 Termination date: 20150517 |
|
| EXPY | Termination of patent right or utility model |