CN109081817A - CuI/ ionic liquid normal temperature and pressure catalysis converts CO2The method for synthesizing 1,3- oxazolidine -2- ketone compounds - Google Patents
CuI/ ionic liquid normal temperature and pressure catalysis converts CO2The method for synthesizing 1,3- oxazolidine -2- ketone compounds Download PDFInfo
- Publication number
- CN109081817A CN109081817A CN201811048579.3A CN201811048579A CN109081817A CN 109081817 A CN109081817 A CN 109081817A CN 201811048579 A CN201811048579 A CN 201811048579A CN 109081817 A CN109081817 A CN 109081817A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- cui
- normal temperature
- oxazolidine
- compound
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D263/36—One oxygen atom
- C07D263/38—One oxygen atom attached in position 2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention discloses a kind of CuI/ ionic liquid normal temperature and pressure catalysis to convert CO2The method for synthesizing 1,3-oxazoles alkane -2- ketone compounds, detailed process are as follows: with propiolic alcohol compound 1 be raw material, primary amine compound 2 is solvent, CuI and ionic liquid [P4444] [Im] be catalyst system, in CO under normal temperature and pressure2Obtained target product 1,3- oxazolidine -2- ketone compounds are stirred to react in atmosphere.Synthesis process of the invention is easy to operate, mild condition, and products collection efficiency height (up to 99%), catalyst system is cheap and easy to get.
Description
Technical field
The invention belongs to the synthesis technical fields of 1,3-oxazoles alkane -2- ketone compounds, and in particular to a kind of CuI/ ion
Liquid normal temperature and pressure catalysis converts CO2The method for synthesizing 1,3- oxazolidine -2- ketone compounds.
Background technique
Pass through carbon dioxide (CO2) catalytic conversion process to reduce the concentration of carbon dioxide in atmosphere be that one kind is effectively relieved
The potential method of carbon in atmosphere accumulation.By CO2It fixes and is converted by the approach of green, safety and a series of both have economic benefit
The high level organic chemicals for reducing carbon resource waste again have become the forward position focus in the field.CO2It is a kind of abundant, cheap, nothing
The biorenewable C1 structural unit of poison；But the kinetic inertness and high thermodynamic stability due to its own lead to CO2
Show lower reactivity.Therefore, optimize harsh reaction condition to select efficient catalyst system that CO occurs2Catalysis
Conversion is extremely crucial.
Ionic liquid (IL) as novel green solvent be widely used in organic synthesis, gas separation, the extraction of liquid-liquid and
The fields such as electrochemical research.Compared with conventional organic solvent, IL have it is not volatile, reusable, can design and thermostabilization
With the prominent characteristics such as nonflammable.Therefore, ionic liquid can be applicable to CO2In fixed and conversion, as activation CO2Effective catalysis
Agent and reaction medium.
1,3-oxazoles alkane -2- ketone compounds are important nitrogenous organic heterocyclic molecule, they are not only organic synthesis
Intermediate and chiral auxiliary, industrial there is in medicine, pesticide and also apparent, propagable commercial value.Currently, passing through
Propargyl alcohol, CO2Three component cycloaddition reactions synthesis 1,3- oxazolidine -2- ketone compounds with primary amine are that most have prospect, conversion
Best one of the synthetic method of efficiency.It mainly include Ag, Cu, ionic liquid in the reported catalyst system for synthesizing the target product
Body, tert-butyl phosphine and terpyridyl etc..However, these catalyst have the disadvantage in that, using noble metal, catalyst itself has
Poison, or it is related to volatile organic chemicals (VOC), catalysis needs high temperature and pressure etc. when reacting.Limitation based on above-mentioned catalyst
Property, it is expected that finding a kind of green used in a mild condition, environmental protection, safe and efficient novel catalyst with normal in room temperature
Pressure catalysis CO2Synthesis 1,3- oxazolidine -2- ketone compounds.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of CuI/ ionic liquid normal temperature and pressure catalysis to convert CO2Synthesis 1,
The method of 3- oxazolidine -2- ketone compounds, this method is easy to operate, mild condition, products collection efficiency height (up to 99%), catalysis
System is cheap and easy to get.
The present invention adopts the following technical scheme that CuI/ ionic liquid normal temperature and pressure catalysis converts to solve above-mentioned technical problem
CO2The method for synthesizing 1,3-oxazoles alkane -2- ketone compounds, it is characterised in that detailed process are as follows: be with propiolic alcohol compound 1
Raw material, primary amine compound 2 are solvent, CuI and ionic liquid [P4444] [Im] be catalyst system, in CO under normal temperature and pressure2Gas
Obtained target product 1,3-oxazoles alkane -2- ketone compounds, the reaction equation in synthesis process are stirred to react in atmosphere are as follows:
Wherein R1、R2For C1-4Straight chained alkyl or branched alkyl or naphthenic base, R3For C1-4Straight chained alkyl or branched alkyl, ring
Alkyl or phenyl, [Im] is imidazole anion in ionic liquid.
Preferably, the R1、R2For methyl, ethyl, isobutyl group or cyclohexyl, R3For normal-butyl, isobutyl group, cyclohexyl or
Phenyl.
Preferably, the molar ratio of the propargyl alcohol class compound 1 and primary amine compound 2 is 1:1.
Preferably, the propargyl alcohol class compound 1 and CuI or ionic liquid [P in catalyst system4444] feeding intake for [Im] rub
Your ratio is 1:0.1.
Compared with the prior art, the present invention has the following advantages:
1, catalyst system used is mantoquita cheap and easy to get and green solvent ionic liquid, investment in synthesis process of the present invention
Catalytic effect is significant after reaction；
2, the present invention be three component reaction of a step, it is easy to operate, avoid due in multistep reaction use plurality of reagents and
To the purification process of each step intermediate and caused by the wasting of resources and problem of environmental pollution；
3, raw material propargyl alcohol class compound is cheap and easy to get, is easy preparation；
4, product separation is relatively simple, and yield is higher；
5, reaction condition is milder, is passed through CO in 0.1MPa, 30 DEG C of conditions2?.
Therefore, the present invention provides a kind of green, environmental protection, safety, height for the synthesis of 1,3-oxazoles alkane -2- ketone compounds
Effect and the strong method of economic serviceability.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment 1
1a (0.1g, 1.2mmol) is added in the Schlenk pipe of 10mL, the 2a (1.0eqv) based on 1a, CuI
(0.1eqv) and ionic liquid [P4444] [Im] (IL, 0.1eqv), in CO2It is heated to 30 DEG C under atmosphere 0.1MPa, is stirred to react
13h is spin-dried for after completion of the reaction, obtains oil product 3a, yield 99% by silica gel post separation.
Embodiment 2
1b (0.1g, 1mmol) is added in the Schlenk pipe of 10mL, the 2b (1.0eqv) based on 1b, CuI (0.1eqv)
With ionic liquid [P4444] [Im] (IL, 0.1eqv), in CO2It is heated to 30 DEG C under atmosphere 0.1MPa, is stirred to react 12h, has reacted
Bi Hou is spin-dried for, and obtains oil product 3b, yield 99% by silica gel post separation.
Embodiment 3
1c (0.1g, 0.8mmol) is added in the Schlenk pipe of 10mL, the 2c (1.0eqv) based on 1c, CuI
(0.1eqv) and ionic liquid [P4444] [Im] (IL, 0.1eqv), in CO2It is heated to 30 DEG C under atmosphere 0.1MPa, is stirred to react
16h is spin-dried for after completion of the reaction, obtains oil product 3b, yield 99% by silica gel post separation.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (4)
1.CuI/ ionic liquid normal temperature and pressure catalysis converts CO2The method for synthesizing 1,3-oxazoles alkane -2- ketone compounds, feature
It is detailed process are as follows: with propiolic alcohol compound 1 be raw material, primary amine compound 2 is solvent, CuI and ionic liquid
[P4444] [Im] be catalyst system, in CO under normal temperature and pressure2Obtained target product 1,3- oxazolidine -2- is stirred to react in atmosphere
Ketone compounds, the reaction equation in synthesis process are as follows:
Wherein R1、R2For C1-4Straight chained alkyl or branched alkyl or naphthenic base, R3For C1-4Straight chained alkyl or branched alkyl, naphthenic base
Or phenyl, [Im] is imidazole anion in ionic liquid.
2. CuI/ ionic liquid normal temperature and pressure catalysis according to claim 1 converts CO2Synthesize 1,3- oxazolidine -2- ketone
The method of compound, it is characterised in that: the R1、R2For methyl, ethyl, isobutyl group or cyclohexyl, R3For normal-butyl, isobutyl group,
Cyclohexyl or phenyl.
3. CuI/ ionic liquid normal temperature and pressure catalysis according to claim 1 converts CO2Synthesize 1,3- oxazolidine -2- ketone
The method of compound, it is characterised in that: the molar ratio of the propargyl alcohol class compound 1 and primary amine compound 2 is 1:1.
4. CuI/ ionic liquid normal temperature and pressure catalysis according to claim 1 converts CO2Synthesize 1,3- oxazolidine -2- ketone
The method of compound, it is characterised in that: the propargyl alcohol class compound 1 and CuI or ionic liquid [P in catalyst system4444]
The molar ratio of [Im] is 1:0.1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811048579.3A CN109081817A (en) | 2018-09-10 | 2018-09-10 | CuI/ ionic liquid normal temperature and pressure catalysis converts CO2The method for synthesizing 1,3- oxazolidine -2- ketone compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811048579.3A CN109081817A (en) | 2018-09-10 | 2018-09-10 | CuI/ ionic liquid normal temperature and pressure catalysis converts CO2The method for synthesizing 1,3- oxazolidine -2- ketone compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109081817A true CN109081817A (en) | 2018-12-25 |
Family
ID=64841363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811048579.3A Pending CN109081817A (en) | 2018-09-10 | 2018-09-10 | CuI/ ionic liquid normal temperature and pressure catalysis converts CO2The method for synthesizing 1,3- oxazolidine -2- ketone compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109081817A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113416166A (en) * | 2021-06-23 | 2021-09-21 | 浙江外国语学院 | Method for preparing 4-hydroxyquinoline-2 (1H) -ketone compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237508A (en) * | 2015-10-20 | 2016-01-13 | 华东师范大学 | Method for synthesizing cyclic carbonate through CO<2> and propargyl alcohol |
| CN107118172A (en) * | 2017-05-04 | 2017-09-01 | 河南师范大学 | One kind is catalyzed CO at room temperature, at a normal2The method for synthesizing 2 Oxazolidinone derivatives |
-
2018
- 2018-09-10 CN CN201811048579.3A patent/CN109081817A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237508A (en) * | 2015-10-20 | 2016-01-13 | 华东师范大学 | Method for synthesizing cyclic carbonate through CO<2> and propargyl alcohol |
| CN107118172A (en) * | 2017-05-04 | 2017-09-01 | 河南师范大学 | One kind is catalyzed CO at room temperature, at a normal2The method for synthesizing 2 Oxazolidinone derivatives |
Non-Patent Citations (6)
| Title |
|---|
| JIKUAN QIU: ""Cu(I)/Ionic Liquids Promote the Conversion of Carbon Dioxide into Oxazolidinones at Room Temperature"", 《MOLECULES》 * |
| KAIHONG CHEN: ""Tuning the basicity of ionic liquids for efficient synthesis of alkylidene carbonates from CO2 at atmospheric pressure"", 《CHEM. COMMUN.》 * |
| YANFEI ZHAO: ""Azole-Anion-Based Aprotic Ionic Liquids:Functional Solvents forAtmospheric CO2 Transformation into Various Heterocyclic Compounds"", 《CHEM. ASIAN J.》 * |
| YANLONG GU: "" Ionic liquid as an efficient promoting medium for fixation of carbon dioxide: A clean method for the synthesis 5-methylene-1,3-oxazolidin-2-ones from propargylic alcohols"", 《J ORG CHEM》 * |
| YUNYAN WU: ""Tetrabutylphosphonium-Based Ionic Liquid Catalyzed CO2 Transformation at Ambient Conditions: A Case of Synthesis of α-Alkylidene Cyclic Carbonates"", 《ACS CATAL.》 * |
| 赵飞燕: ""离子液体催化常压CO2合成杂环化合物研究"", 《中国化学会第30届学术年会摘要集-第三十三分会：绿色化学》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113416166A (en) * | 2021-06-23 | 2021-09-21 | 浙江外国语学院 | Method for preparing 4-hydroxyquinoline-2 (1H) -ketone compound |
| CN113416166B (en) * | 2021-06-23 | 2022-08-05 | 浙江外国语学院 | Method for preparing 4-hydroxyquinoline-2 (1H) -ketone compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107376997B (en) | Preparation and application of catalyst for preparing benzaldehyde by oxidizing benzyl alcohol | |
| CN101343260A (en) | Method for synthesis epoxy cyclohexane with titanium molecular sieve catalysis | |
| CN105130778A (en) | Production process of methyl isobutyl ketone | |
| CN103664656A (en) | Synthesis and application of quaternary ammonium salt ionic liquid based on heteropolyacid | |
| CN103242158B (en) | Technological method for synthesizing ethyl acetate | |
| CN106008401A (en) | Preparation method of N-formamide compound | |
| CN109081817A (en) | CuI/ ionic liquid normal temperature and pressure catalysis converts CO2The method for synthesizing 1,3- oxazolidine -2- ketone compounds | |
| CN107118172B (en) | One kind being catalyzed CO at room temperature, at a normal2The method for synthesizing 2- Oxazolidinone derivative | |
| CN102234224A (en) | Method for catalytic synthesis of dichloropropanol by hydrogen chloride-containing industrial waste gas and glycerol | |
| CN102766032A (en) | Oxidation method of cyclohexane | |
| CN102234223A (en) | Method for synthesizing dichloropropanol by reaction of glycerol and hydrogen chloride | |
| CN102367230B (en) | Method for synthesizing nitrile from aldoxime | |
| CN103396338B (en) | Method for synthesizing nitrile from aldoxime under catalyzing of selenium-containing catalyst | |
| CN109704953B (en) | Method for preparing crotonic acid by catalytically converting poly-3-hydroxybutyrate through solid catalyst | |
| CN101993353B (en) | Method for preparing 3-methyl-3-butene-1-alcohol | |
| CN114591284B (en) | Zn-MOF-based catalyst in CO 2 Process for synthesizing cyclic carbonates | |
| CN108129260B (en) | Synthesis method of phenyl ethylene glycol | |
| CN106831595B (en) | A kind of benzyl imidazole ionic liquid and the method using its catalytically synthesizing cyclic carbonate ester | |
| CN108707132A (en) | The ionic liquid-catalyzed CO of bromination alcamines2The method of Synthesis cyclic carbonates compound | |
| CN102850299B (en) | Preparation method for (methyl)glycidyl acrylate | |
| CN104277027A (en) | Preparation method of (R)-propylene carbonate | |
| CN105170180A (en) | Application of 4,5-methylene-L-proline as catalyst in direct asymmetric Aldol reaction | |
| CN101993381A (en) | Synthetic method of 3-amino-1, 2-propanediol | |
| CN101830783A (en) | Method for preparing aldehyde by oxidizing alcohol with oxygen in presence of Schiff-base complex catalyst | |
| CN101709055A (en) | Method for synthesizing ionic liquid |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181225 |
|
| WD01 | Invention patent application deemed withdrawn after publication |