CN110759861B - Preparation method of quinoline derivative - Google Patents
Preparation method of quinoline derivative Download PDFInfo
- Publication number
- CN110759861B CN110759861B CN201810840456.7A CN201810840456A CN110759861B CN 110759861 B CN110759861 B CN 110759861B CN 201810840456 A CN201810840456 A CN 201810840456A CN 110759861 B CN110759861 B CN 110759861B
- Authority
- CN
- China
- Prior art keywords
- equal
- catalyst
- reaction
- aromatic amine
- liquid phase
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a preparation method of a quinoline derivative. The method comprises the steps of taking aromatic amine compounds and aliphatic alcohol as raw materials, taking oxygen-containing molybdenum disulfide as a catalyst, reacting for 2-12 hours in an inert atmosphere or an oxygen-containing atmosphere at 120-200 ℃, separating liquid phase components after the reaction is finished, concentrating, and separating through a silica gel column to obtain the substituted quinoline compound. The synthesis method can be applied to the synthesis of quinoline compounds.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of a quinoline derivative.
Background
Quinolines and their derivatives are an important class of organic compounds, which are widely used in the synthesis of functional drugs, pesticides, dyes, chemical agents, optical materials, functional polymers, and the like (Andries K et al science.2005; 307(5707): 223-27; Theraladanon C et al tetrahedron: asymmetry.2005; 16(4): 827-31; Roma G et al European Journal of medical chemistry.2000; 35(11): 1021-35; Zhang X J et al macromolecules.1999; 32(22): 7422-29). The synthesis methods have been receiving much attention, among which Skraup reaction (Organic reactions.1953; 7:59-98), Doebner reaction (J.chem.Soc.1934:1520-23), Doebner-Von Miller reaction (Berichte der deutschen chemischen Gesellschaft.1883; 6(2):2464-72), Combes reaction (J.chem.Soc.1927:1832-57), Conrad-Limpach reaction (chem.Rev.1942; 30(1):113-44),
reactions (chem. Rev.2009; 109(6):2652-71) and Pfitsinger reactions (J.Am. chem. Soc.1954; 76(18): 4580-84). The above methods, which mostly use substituted anilines and carbonyl compounds for the preparation of quinoline compounds, take into account that the carbonyl compounds from aliphatic alcohols are generally unstable (Catal day. 1997; 37(2):121-36), which would be a good reaction route if the in situ formation of the carbonyl compound could be reacted with aniline.
Regarding the conversion of fatty alcohol to generate the key carbonyl compound (5), fatty alcohol can generate aldehyde ketone under a dehydrogenation catalytic system and can also generate aldehyde ketone under an oxidation system, but the main problem at present is that the generated aldehyde or ketone intermediate is easier to react with aniline compound to generate imine compound, the imine compound can be further reduced to substituted amine (by-product 2), and meanwhile, in order to oxidize fatty alcohol, the oxidation performance of the oxidation system is usually too strong to easily oxidize substrate aniline compound, so that the reaction selectivity and the yield of quinoline derivative are low. By analysis, it is a challenging task to develop a method for selectively synthesizing quinoline compounds by using a cheap, easily available and stable non-noble metal heterogeneous catalyst.
The invention relates to a preparation method of a quinoline derivative. The method comprises the steps of taking aromatic amine compounds and aliphatic alcohol as raw materials, taking oxygen-containing molybdenum disulfide as a catalyst, reacting for 2-12 hours in an inert atmosphere or an oxygen-containing atmosphere at 120-200 ℃, separating liquid phase components after the reaction is finished, concentrating, and separating through a silica gel column to obtain the substituted quinoline compound. The synthesis method can be applied to the synthesis of quinoline compounds.
Disclosure of Invention
The invention relates to a preparation method of a quinoline derivative. The method comprises the steps of taking aromatic amine compounds and aliphatic alcohol as raw materials, taking oxygen-containing molybdenum disulfide as a catalyst, reacting for 2-12 hours in an inert atmosphere or an oxygen-containing atmosphere at 120-200 ℃, separating liquid phase components after the reaction is finished, concentrating, and separating through a silica gel column to obtain the substituted quinoline compound. The synthesis method can be applied to the synthesis of quinoline compounds.
For the aromatic amine compound, the aromatic amine compound is: (1) anilines and aniline substitutes Rx-(C6H5-X)-NH2(x ═ 1 to 5), wherein R represents various substituents (R ═ H, F, Cl, Br, I, CH3，OCH3，NH2，NO2CHO, Ph, etc.), X represents the number of substituents. When X is>1 is the same substituent that R may represent or different substituents; (2) aromatic amine compounds with benzene rings substituted by other aromatic condensed rings, wherein the other aromatic condensed rings can be one or more of naphthalene rings, anthracene rings and the like; (3) the aromatic amine compound with the benzene ring substituted by the aromatic heterocyclic ring can be one or more of a pyridine ring, a thiophene ring, a furan ring, an imidazole ring and the like.
Against fatty alcohols in which they are presentThe process acts as both a solvent and a reactant. The aliphatic alcohol is H (CH)2)nCH2CH3One or more of OH (n is more than or equal to 0 and less than or equal to 6). When n is>2 is, in addition to a linear alkane substituent, a substituent having a branch.
The catalyst containing molybdenum disulfide oxide is MoS2-XOyBy controlling the sulfuration and reduction degree of the molybdate precursor, x is more than or equal to 0 and less than or equal to 0.4 and y is more than or equal to 0 and less than or equal to 0.2 in the obtained catalyst. Regarding the preparation method of the molybdenum sulfide catalyst: ammonium molybdate and sodium molybdate are taken as precursors, thiourea and sodium sulfide are taken as sulfur sources according to n(Mo):n(S)Dispersing the catalyst in an aqueous solution at a ratio of 1: 3-1: 30, carrying out hydrothermal treatment at 160-240 ℃ for 6-72 h, filtering and washing to obtain the catalyst. Wherein, the effect of taking ammonium molybdate as a precursor is better than that of sodium molybdate, thiourea in the sulfur source is cheap and easy to control and decompose, and is more suitable in the process of preparing molybdenum sulfide materials, and the synthesis of the catalyst is optimized: according to n(Mo):n(S)The feeding is carried out at a ratio of 1: 6-1: 30, and the hydrothermal treatment is carried out at 160-220 ℃ for 12-48 h.
According to specific synthesis conditions, the aliphatic alcohol is used as a substrate and a reaction solvent at the same time, the concentration of the aromatic amine compound substrate is 0.001-5 mol/L, the dosage of the catalyst is 0.5-40 w% of the mass of the aromatic amine compound substrate, the reaction temperature is 100-220 ℃, and the reaction time is 1-24 h. The optimized conditions are that the concentration of the aromatic amine compound substrate is 0.05-2 mol/L, the dosage of the catalyst is 0.5-20 w% of the mass of the aromatic amine compound substrate, the reaction temperature is 120-200 ℃, and the reaction time is 2-12 h.
The reaction atmosphere may be a pure inert atmosphere, N, depending on the specific synthesis conditions2Ar or the mixed gas of the Ar and the Ar, wherein the pressure is 0.1-3 MPa; or the reaction is carried out in an oxygen-containing atmosphere, air or O2The atmosphere is under a pressure of 0.1 to 1 MPa.
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing a quinoline compound through oxidation-reduction integration.
Drawings
FIG. 1 is a possible mechanism for the reaction of aniline with fatty alcohols to produce quinine compounds;
FIG. 2 commercial MoS2 (Black 2H-MoS)2) And MoS2-xOy(180-24h) (Red O-MoS)2) Raman mapping of (a). Contrast display MoS2-xOy(180-24h) obvious crystal lattice oxygen residue or doping.
FIG. 3 MoS2-xOy(180-24h) EDX elemental analysis, the catalyst after analysis being expressed in MoS form1.73O0.1(180-24h)。
Detailed Description
In order to further explain the present invention in detail, some specific examples are given below, but the present invention is not limited to these examples.
First, for the convenience of expressing the catalyst used, the relevant catalyst will be described. MoSxThe base catalyst is synthesized hydrothermally. Commercial ammonium molybdate and thiourea according to n(Mo):n(S)The mixture was added to a 150mL stainless steel autoclave lined with tetrafluoro at 1:3 to 1:30, and 90mL deionized water was added with stirring. And then the sealed stainless steel autoclave is placed in an oven at 160-250 ℃ for treatment for 12-48 h. After the treatment is finished, the reaction kettle is naturally cooled to room temperature, and the black solid is washed by deionized water and absolute ethyl alcohol. The catalyst obtained was named MoS2-xOy(m-nh), wherein m represents the temperature of the treatment and n represents the time of the treatment. In order to verify whether the catalyst contains lattice oxygen residues or incorporation, the resulting catalyst was first characterized using Raman spectroscopy, followed by characterization of the oxygen content in the catalyst using EDX electron microscopy characterization techniques. MoS2-xOy(m-n h), the correlation results are plotted for the x and y parameters of the catalyst. With MoS2-xOy(180-24h), the Raman spectrum of the sample is shown in figure 2, and the element distribution diagram of the sample is shown in figure 3.
Reaction equation for quinoline synthesis:
example 1:
0.5mmol of aniline, 2.5mL of ethanol and 25mg of catalyst MoS1.73O0.1(180-24h), placing in a 25mL reaction kettle, replacing gas, charging 1atm of Ar gas, reacting at 180 ℃ for 8 hours, centrifuging, analyzing a liquid phase sample by using GC, then concentrating a liquid phase component, and separating a product by using a silica gel column. The conversion of aniline was 90%, and the isolation yield of alkyl-substituted quinoline (2-methylquinoline) was 50%.
Example 2:
0.5mmol of aniline, 2.5mL of ethanol and 25mg of catalyst MoS1.73O0.1(180-24h), placing in a 25mL reaction kettle, displacing gas, charging 1atm of Air gas, reacting at 180 ℃ for 6 hours, centrifuging, analyzing a liquid phase sample by using GC, then concentrating the liquid phase component, and separating the product by using a silica gel column. The conversion of aniline was 96% and the isolation yield of alkyl substituted quinoline was 71%.
Example 3:
0.5mmol of aniline, 2.5mL of ethanol and 25mg of catalyst MoS1.73O0.1(180-24h), placing in a 25mL reaction kettle, replacing gas, charging 4atm of Air gas, reacting at 160 ℃ for 4 hours, centrifuging, analyzing a liquid phase sample by using GC, then concentrating a liquid phase component, and separating a product by using a silica gel column. Conversion of aniline is>99% and the isolation yield of the alkyl-substituted quinoline was 72%.
Example 4:
0.5mmol of aniline, 2.5mL of ethanol and 25mg of catalyst MoS1.73O0.1(180-24h), placing in a 25mL reaction kettle, replacing gas, charging 4atm of Ar gas, reacting at 190 ℃ for 8 hours, centrifuging, analyzing a liquid phase sample by using GC, then concentrating a liquid phase component, and separating a product by using a silica gel column. The conversion of aniline was 80% and the isolation yield of alkyl substituted quinolines was 45%.
Example 5:
0.5mmol of aniline, 2.5mL of ethanol and 25mg of catalyst MoS1.85O0.02(200-24h), placing in a 25mL reaction kettle, replacing gas, charging 1atm of Ar gas, reacting at 190 ℃ for 8 hours, centrifuging, analyzing a liquid phase sample by using GC, then concentrating a liquid phase component, and separating a product by using a silica gel column. The conversion of aniline was 60% and the isolation yield of alkyl substituted quinoline was 39%.
Example 6:
0.5mmol of aniline, 2.5mL of ethanol and 25mg of catalyst MoS1.85O0.02(200-24h), placing in a 25mL reaction kettle, replacing gas, charging 4atm of Air gas, reacting at 160 ℃ for 8h, centrifuging, analyzing a liquid phase sample by using GC, then concentrating the liquid phase component, and separating the product by using a silica gel column. The conversion of aniline was 90% and the isolation yield of alkyl substituted quinoline was 63%.
Example 7:
0.5mmol of aniline, 2.5mL of ethanol and 25mg of catalyst MoS1.99O0(200-48h), placing in a 25mL reaction kettle, replacing gas, charging 1atm of Ar gas, reacting at 190 ℃ for 8 hours, centrifuging, analyzing a liquid phase sample by using GC, then concentrating a liquid phase component, and separating a product by using a silica gel column. The conversion of aniline was 60% and the isolation yield of alkyl substituted quinoline was 20%.
Example 8:
0.5mmol of aniline, 2.5mL of ethanol and 25mg of catalyst MoS1.95O0(200-48h), placing in a 25mL reaction kettle, displacing gas, charging 4atm of Air, reacting at 170 ℃ for 4 hours, centrifuging, analyzing a liquid phase sample by using GC, then concentrating the liquid phase component, and separating the product by using a silica gel column. The conversion of aniline was 72% and the isolation yield of alkyl substituted quinolines was 40%.
Example 9:
0.5mmol of p-methylaniline, 2.5mL of ethanol and 25mg of catalyst MoS1.73O0.1(180-24h), placing in a 25mL reaction kettle, replacing gas, charging 1atm Ar gas, reacting at 180 deg.C for 8 hr, centrifuging, analyzing liquid phase sample by GC, concentrating liquid phase component, and using silica gelThe column separates the products. The conversion of p-methylaniline was 92% and the isolation yield of alkyl substituted quinoline was 40%.
Example 10:
0.5mmol of p-methylaniline, 2.5mL of ethanol and 25mg of catalyst MoS1.73O0.1(180-24h), placing in a 25mL reaction kettle, replacing gas, charging 4atm of Air, reacting at 170 ℃ for 4 hours, centrifuging, analyzing a liquid phase sample by using GC, then concentrating a liquid phase component, and separating a product by using a silica gel column. The conversion of p-methylaniline is>99% and the isolation yield of the alkyl-substituted quinoline was 55%.
Example 11:
0.5mmol of p-chloronitroaniline, 2.5mL of ethanol and 25mg of catalyst MoS1.73O0.1(180-24h), placing in a 25mL reaction kettle, replacing gas, charging 4atm of Air gas, reacting at 190 ℃ for 4 hours, centrifuging, analyzing a liquid phase sample by using GC, then concentrating a liquid phase component, and separating a product by using a silica gel column. The conversion rate of p-chloroaniline is>99% and the isolation yield of the alkyl-substituted quinoline was 75%.
Example 12:
0.5mmol of p-chloroaniline, 2.5mL of ethanol and 25mg of catalyst MoS1.73O0.1(180-24h), placing in a 25mL reaction kettle, replacing gas, charging O of 4atm2Gas at 190 ℃ for 4 hours, centrifugation, analysis of a liquid phase sample by GC, concentration of the liquid phase components, and isolation of the product by means of a silica gel column. The conversion rate of p-chloroaniline is>99% and the isolation yield of alkyl-substituted quinoline is 65%.
Example 13:
0.5mmol of aniline, 2.5mL of n-propanol and 25mg of catalyst MoS1.73O0.1(180-24h), placing in a 25mL reaction kettle, replacing gas, charging 4atm of Air gas, reacting at 190 ℃ for 4 hours, centrifuging, analyzing a liquid phase sample by using GC, then concentrating a liquid phase component, and separating a product by using a silica gel column. Conversion of aniline is>99%, the isolation yield of the alkyl-substituted quinoline was 73%.
Example 14:
0.5mmol of aniline, 2.5mL of n-butanol and 25mg of catalyst MoS1.73O0.1(180-24h), placing in a 25mL reaction kettle, replacing gas, charging 4atm of Air gas, reacting at 190 ℃ for 4 hours, centrifuging, analyzing a liquid phase sample by using GC, then concentrating a liquid phase component, and separating a product by using a silica gel column. Conversion of aniline is>99%, the isolation yield of the alkyl-substituted quinoline was 64%.
Example 15:
0.5mmol of aniline, 2.5mL of n-pentanol and 25mg of catalyst MoS1.73O0.1(180-24h), placing in a 25mL reaction kettle, replacing gas, charging 4atm of Air gas, reacting at 190 ℃ for 4 hours, centrifuging, analyzing a liquid phase sample by using GC, then concentrating a liquid phase component, and separating a product by using a silica gel column. Conversion of aniline is>99% and the isolated yield of alkyl substituted quinoline is 55%.
Example 16:
0.5mmol of aniline, 2.5mL of n-hexanol and 25mg of catalyst MoS1.73O0.1(180-24h), placing in a 25mL reaction kettle, replacing gas, charging 4atm of Air gas, reacting at 190 ℃ for 4 hours, centrifuging, analyzing a liquid phase sample by using GC, then concentrating a liquid phase component, and separating a product by using a silica gel column. Conversion of aniline is>99% and the isolation yield of the alkyl-substituted quinoline was 58%.
Example 17:
0.5mmol aniline, 2.5mL ethanol and 25mg catalyst MoO3The reaction mixture was placed in a 25mL reaction vessel, purged with Air at 4atm, reacted at 160 ℃ for 4 hours, centrifuged, and a sample of the liquid phase was analyzed by GC, followed by concentration of the liquid phase components and separation of the product by means of a silica gel column. The conversion of aniline was 32% and the isolation yield of alkyl substituted quinoline was 12%.
Example 18:
0.5mmol aniline, 2.5mL ethanol and 25mg catalyst MoO2Placing in a 25mL reaction kettle, replacing gas, charging Air of 4atm, reacting at 160 deg.C for 4 hr, centrifugingThe liquid phase samples were analyzed by GC, the liquid phase components were subsequently concentrated and the product was isolated by silica gel column. The conversion of aniline was 26% and the isolation yield of alkyl substituted quinoline was 9%.
Claims (6)
1. A preparation method of quinoline derivatives is characterized in that: taking an aromatic amine compound and aliphatic alcohol as raw materials, taking oxygen-containing molybdenum disulfide as a catalyst, reacting for 1-24 h in an inert atmosphere or an oxygen-containing atmosphere at 100-220 ℃, separating liquid phase components after the reaction is finished, concentrating, and separating by using a silica gel column to obtain a substituted quinoline compound;
wherein, the aromatic amine compound is: anilines and aniline substitutes Rx-(C6H5-X)-NH2X represents the number of the substituent, x is 1-5, R is F, Cl, Br, I, CH3，OCH3，NO2When X is present>1, R represents the same substituent or different substituents;
the fatty alcohol is used as solvent and reactant, and the fatty alcohol is H (CH)2)nCH2CH2One or more than two of OH, wherein n is more than or equal to 0 and less than or equal to 6;
the oxygen-containing molybdenum disulfide is MoS2-xOyWherein x is more than or equal to 0.001 and less than or equal to 0.4 and y is more than or equal to 0.001 and less than or equal to 0.2.
2. The method of claim 1, wherein: the fatty alcohol is H (CH)2)nCH2CH2One or more than two of OH, wherein n is more than or equal to 0 and less than or equal to 2.
3. The method of claim 1, wherein: the oxygen-containing molybdenum disulfide is MoS2-xOyWherein x is more than or equal to 0.002 and less than or equal to 0.1, and y is more than or equal to 0.002 and less than or equal to 0.1.
4. The method of claim 1, wherein: the concentration of the aromatic amine compound is 0.001-5 mol/L, and the dosage of the catalyst is 0.5-40 wt% of the aromatic amine compound.
5. The method of claim 1, wherein: the concentration of the aromatic amine compound is 0.05-2 mol/L, the dosage of the catalyst is 0.5-20 wt% of the aromatic amine compound, the reaction temperature is 120-200 ℃, and the reaction time is 2-12 h.
6. The method of claim 1, wherein: reaction atmosphere is N2Ar or the mixed gas of the Ar and the Ar, wherein the pressure is 0.1-3 MPa; or in air or O2The reaction is carried out in an atmosphere or a mixed gas of the atmosphere and the mixed gas, and the pressure is 0.1-1 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810840456.7A CN110759861B (en) | 2018-07-27 | 2018-07-27 | Preparation method of quinoline derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810840456.7A CN110759861B (en) | 2018-07-27 | 2018-07-27 | Preparation method of quinoline derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110759861A CN110759861A (en) | 2020-02-07 |
| CN110759861B true CN110759861B (en) | 2022-05-31 |
Family
ID=69327967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810840456.7A Active CN110759861B (en) | 2018-07-27 | 2018-07-27 | Preparation method of quinoline derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110759861B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117050011B (en) * | 2023-10-11 | 2024-01-23 | 湖南工程学院 | Method for synthesizing 2-methylquinoline by using vinyl acetate as raw material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175327B (en) * | 2015-10-21 | 2017-07-14 | 南阳师范学院 | A kind of synthetic method of quinoline |
| CN106543078B (en) * | 2016-07-21 | 2019-01-11 | 中国科学院兰州化学物理研究所苏州研究院 | A kind of preparation method of quinoline |
-
2018
- 2018-07-27 CN CN201810840456.7A patent/CN110759861B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110759861A (en) | 2020-02-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Serna et al. | Selective hydrogenation of nitrocyclohexane to cyclohexanone oxime with H2 on decorated Pt nanoparticles | |
| CN110759861B (en) | Preparation method of quinoline derivative | |
| Akhmetova et al. | Multicomponent synthesis and biological activity of (sulfanylalkyl)-substituted azaheterocycles | |
| Romanowski et al. | Synthesis, structure, spectroscopic characterization and catalytic activity of chiral dioxidomolybdenum (VI) Schiff base complexes derived from R (−)-2-amino-1-propanol | |
| Ferguson et al. | Deoxyfluorination of (Hetero) aryl Aldehydes Using Tetramethylammonium Fluoride and Perfluorobutanesulfonyl Fluoride or Trifluoromethanesulfonic Anhydride | |
| CN112500361B (en) | Preparation method of (S) -4-phenyl-2-oxazolidinone | |
| CN110372653B (en) | Selenylation benzofuran compound and synthesis method thereof | |
| CN110878104B (en) | Preparation method of chiral 1, 2-bis (2, 5-diphenylphosphino) ethane | |
| CN110256401B (en) | Selenylation benzothiophene compound and synthetic method thereof | |
| CN104876850A (en) | Isoindolinone derivative synthesis method | |
| CN107501338B (en) | Preparation method of 2, 6-diaminopyridine condensed 4-carboxybenzaldehyde bis-Schiff base cobalt complex | |
| CN110759862B (en) | Method for preparing quinoline compound by oxidation-reduction integration | |
| CN111704591B (en) | Synthesis method of copper-catalyzed thionaphthothiazolone compound | |
| CN110759863B (en) | Method for preparing quinoline derivative by one-pot two-step method | |
| CN106622372B (en) | A kind of barium silica tungsten oxygen cluster catalyst, preparation method and its usage | |
| JP3899834B2 (en) | Method for producing 2- (4-pyridyl) ethanethiol | |
| CN108558785A (en) | A kind of 5- aryl -2- arylseleno -1,3- oxazole compounds and preparation method | |
| CN107513078B (en) | Preparation method of 2, 6-diaminopyridine condensed 3-carboxybenzaldehyde bis-Schiff base cobalt complex | |
| Bruno et al. | Acid-catalyzed epoxide alcoholysis in the presence of indenyl molybdenum carbonyl complexes | |
| CN108863834B (en) | Novel synthesis method of 2-fluoro-1, 3-dicarbonyl compound | |
| CN106582815A (en) | Vanadium-based oxygen cluster compound catalyst, preparation method and application | |
| Ternel et al. | Design of a well-defined, silica-supported chiral Zn scaffold for enantioselective catalysis | |
| CN106622385B (en) | A kind of double-core magnesium-germanium tungsten oxygen cluster catalyst, preparation method and its usage | |
| Kang et al. | One-pot solvent-free reductive amination with a solid ammonium carbamate salt from CO 2 and amine | |
| CN111978162A (en) | Novel synthesis method of aromatic ketone compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |