CN104557499A - Method for synthesizing methyl ketone - Google Patents
Method for synthesizing methyl ketone Download PDFInfo
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- CN104557499A CN104557499A CN201310482691.9A CN201310482691A CN104557499A CN 104557499 A CN104557499 A CN 104557499A CN 201310482691 A CN201310482691 A CN 201310482691A CN 104557499 A CN104557499 A CN 104557499A
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- reaction
- methyl ketone
- microwave
- synthesizing methyl
- alkynes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/26—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydration of carbon-to-carbon triple bonds
Abstract
The invention discloses a method for synthesizing methyl ketone. The method comprises the following steps: adding alkyne, [(IPr)AuCl], AgOTf, a solvent, namely 1,4-dioxane and water in a reaction container, performing microwave reaction on a reaction mixture for 1h at 120 DEG C and cooling to room temperature; filtering, performing rotary evaporation to remove the solvent, and then separating by a column to obtain a target compound. The method disclosed by the invention adopts a microwave technology, and the reaction time is shortened; furthermore, the reaction only generates a byproduct, namely water, so that the reaction is in line with the requirements of green chemistry and has broad development prospects.
Description
Technical field
The invention belongs to technical field of organic synthetic chemistry, be specifically related to a kind of synthetic method of ketone.
Background technology
Methyl ketone is the very important compound of a class, presents physiology widely and pharmacologically active, is also important organic synthesis intermediate.By the important method that transition metal-catalyzed alkynes regioselective hydrolyis is a kind of synthesizing methyl ketone.In recent years, gold complex progressively instead of poisonous mercury salt and carrys out this reaction (a) of catalysis E.Mizushima, K.Sato, T.Hayashi, M.Tanaka, Angew.Chem.Int.Ed.2002,41,4563-4565; B) R.Casado, M.Contel, M.Laguna, P.Romero, S.Sanz, J.Am.Chem.Soc.2003,125,11925-11935; C) N.Marion, R.S.Ramon, S.P.Nolan, J.Am.Chem.Soc.2009,131,448-449). but reaction also needs the longer time.
Microwave technology obtains more and more many development at present, and widely uses in organic synthesis field, is characterized in shortening test period, improves speed of reaction.Microwave heating is the raw electricity of electromagnetic wave induction sent by microwave tube, after change into the kinetic energy of molecule and generate heat, to have rapidly and efficiently, the feature of safety.
Summary of the invention
The object of the present invention is to provide a kind of novel method of synthesizing methyl ketone.
The present invention is achieved through the following technical solutions: the method for a kind of synthesizing methyl ketone (formula I)
It comprises makes alkynes (formula II)
Under gold complex catalysis and microwave state, hydrolysis reacts, and its reaction expression is:
Wherein, R
1be selected from aryl, list or polysubstituted aryl or alkyl, preferable methyl phenyl, p-methoxy-phenyl, halogenophenyl or cyclopropyl.
Invention is realized by following technological method:
In reaction vessel, add alkynes, [(IPr) AuCl], AgOTf, solvent Isosorbide-5-Nitrae-dioxane and water, reaction mixture microwave reaction after 1 hour at 120 DEG C, cool to room temperature; Filter, rotary evaporation, except desolventizing, is then separated by post, obtains target compound.
Wherein, the structural formula of [(IPr) AuCl] is
Described microwave reaction instrument is that U.S. CE M DISCOVER SP focuses on single mold microwave synthesizer.
With molar ratio computing [(IPr) AuCl]: AgOTf: alkynes=1:1:100; The mol ratio of water consumption and alkynes is 2.
Compared with prior art, advantage of the present invention is: adopt microwave technology, shorten the reaction times, and reaction only generates the by product of water, and therefore, this reaction meets the requirement of Green Chemistry, has vast potential for future development.
Embodiment
Show that example is to illustrate some embodiment of the present invention, and should not be construed as and limit the scope of the invention.Simultaneously from material, method and reaction conditions can carry out many improvement to content disclosed by the invention, change and change.All these improve, and change and change fall within the spirit and scope of the present invention all definitely.
Embodiment 1: methyl phenyl ketone
Acetophenone
By catalyst A (6mg, 0.01mmol, 1.0mol%), AgOTf(2.6mg, 0.01mmol, 1.0mol%), phenylacetylene (102mg, 1mmol), Isosorbide-5-Nitrae-dioxane (1ml) and water (36ul) is added in 5ml microwave tube successively.Reaction mixture microwave reaction after 1 hour at 120 DEG C, cool to room temperature.Filter, rotary evaporation removes solvent, then obtains pure target compound, productive rate by column chromatography (developping agent: petrol ether/ethyl acetate): 92%
1H NMR(500MHz,CDCl
3)δ7.96(dd,J=7.6Hz and0.7Hz,2H,ArH),7.57(t,J=7.5Hz,1H,ArH),7.47(t,J=7.7Hz,2H,ArH),2.61(s,3H,CH
3).
Embodiment 2:4-methyl acetophenone
1-p-tolylethanone
By catalyst A (6mg, 0.01mmol, 1.0mol%), AgOTf(2.6mg, 0.01mmol, 1.0mol%), 4-methylbenzene acetylene (116mg, 1mmol), Isosorbide-5-Nitrae-dioxane (1ml) and water (36ul) are added in 5ml microwave tube successively.Reaction mixture microwave reaction after 1 hour at 120 DEG C, cool to room temperature.Filter, rotary evaporation removes solvent, then obtains pure target compound, productive rate by column chromatography (developping agent: petrol ether/ethyl acetate): 93%
1H NMR(500MHz,CDCl
3)δ7.86(d,J=7.9Hz,2H,ArH),7.27(d,J=6.4Hz,2H,ArH),2.59(s,3H,CH
3),2.42(s,3H,CH
3).
Embodiment 3:4-methoxyacetophenone
1-(4-methoxyphenyl)ethanone
By catalyst A (6mg, 0.01mmol, 1.0mol%), AgOTf(2.6mg, 0.01mmol, 1.0mol%), 4-Methoxy-phenylacetylene (132mg, 1mmol), Isosorbide-5-Nitrae-dioxane (1ml) and water (36ul) are added in 5ml microwave tube successively.Reaction mixture microwave reaction after 1 hour at 120 DEG C, cool to room temperature.Filter, rotary evaporation removes solvent, then obtains pure target compound, productive rate by column chromatography (developping agent: petrol ether/ethyl acetate): 94%
1H NMR(500MHz,CDCl
3)δ7.94(d,J=8.8Hz,2H,ArH),6.94(d,J=8.8Hz,2H,ArH),3.88(s,3H,OCH
3),2.57(s,3H,CH
3).
Embodiment 4:4-chloro-acetophenone
1-(4-chlorophenyl)ethanone
By catalyst A (6mg, 0.01mmol, 1.0mol%), AgOTf(2.6mg, 0.01mmol, 1.0mol%), 4-chlorobenzene acetylene (136mg, 1mmol), Isosorbide-5-Nitrae-dioxane (1ml) and water (36ul) are added in 5ml microwave tube successively.Reaction mixture microwave reaction after 1 hour at 120 DEG C, cool to room temperature.Filter, rotary evaporation removes solvent, then obtains pure target compound, productive rate by column chromatography (developping agent: petrol ether/ethyl acetate): 90%
1H NMR(500MHz,CDCl
3)δ7.90(d,J=8.4Hz,2H,ArH),7.44(d,J=8.3Hz,2H,ArH),2.60(s,3H,CH
3).
Embodiment 5:4-fluoro acetophenone
1-(4-fluorophenyl)ethanone
By catalyst A (6mg, 0.01mmol, 1.0mol%), AgOTf(2.6mg, 0.01mmol, 1.0mol%), 4-fluorobenzene acetylene (120mg, 1mmol), Isosorbide-5-Nitrae-dioxane (1ml) and water (36ul) are added in 5ml microwave tube successively.Microwave reaction is after 1 hour at 120 DEG C for reaction mixture, and cool to room temperature filters, and rotary evaporation removes solvent, then obtains pure target compound, productive rate by column chromatography (developping agent: petrol ether/ethyl acetate): 88%
1H NMR(500MHz,CDCl
3)δ8.01-7.97(m,2H,ArH),7.14(t,J=8.6Hz,2H,ArH),2.60(s,3H,CH
3).
Embodiment 6:4-bromoacetophenone
1-(4-bromophenyl)ethanone
By catalyst A (6mg, 0.01mmol, 1.0mol%), AgOTf(2.6mg, 0.01mmol, 1.0mol%), 4-bromobenzene acetylene (181mg, 1mmol), Isosorbide-5-Nitrae-dioxane (1ml) and water (36ul) are added in 5ml microwave tube successively.Reaction mixture microwave reaction after 1 hour at 120 DEG C, cool to room temperature.Filter, rotary evaporation removes solvent, then obtains pure target compound, productive rate by column chromatography (developping agent: petrol ether/ethyl acetate): 90%
1H NMR(500MHz,CDCl
3)δ7.82(d,J=8.0Hz,2H,ArH),7.61(d,J=8.4Hz,2H,ArH),2.95(s,3H,CH
3).
Embodiment 7:2,4-dimethyl acetophenone
1-(2,4-dimethylphenyl)ethanone
By catalyst A (6mg, 0.01mmol, 1.0mol%), AgOTf(2.6mg, 0.01mmol, 1.0mol%), 2,4-dimethyl benzene acetylene (130mg, 1mmol), Isosorbide-5-Nitrae-dioxane (1ml) and water (36ul) are added in 5ml microwave tube successively.Reaction mixture microwave reaction after 1 hour under 120oC, cool to room temperature.Filter, rotary evaporation removes solvent, then obtains pure target compound, productive rate by column chromatography (developping agent: petrol ether/ethyl acetate): 95%.
1H NMR(500MHz,CDCl
3)δ7.64(d,J=7.7Hz,1H,ArH),7.06(d,J=8.2Hz,2H,ArH),2.56(s,3H,CH
3),2.52(s,3H,CH
3),2.35(s,3H,CH
3).
Embodiment 8:1-cyclopropyl ethyl ketone
1-cyclopropylethanone
By catalyst A (6mg, 0.01mmol, 1.0mol%), AgOTf(2.6mg, 0.01mmol, 1.0mol%), ring third acetylene (66mg, 1mmol), Isosorbide-5-Nitrae-dioxane (1ml) and water (36ul) is added in 5ml microwave tube successively.Reaction mixture microwave reaction after 1 hour at 120 DEG C, cool to room temperature.Filter, rotary evaporation removes solvent, then obtains pure target compound, productive rate by column chromatography (developping agent: petrol ether/ethyl acetate): 87%.
1H NMR(500MHz,CDCl
3)δ2.35(s,3H,CH
3),1.94(quint,J=3.9Hz,1H,CH),1.02(q,J=2.5Hz,2H,CH
2),0.88(q,J=3.7Hz,2H,CH
2)。
Claims (5)
1. a method for synthesizing methyl ketone, is characterized in that described methyl ketone is by making alkynes II
Unboiled water solution building-up reactions is issued in gold complex catalysis and microwave state,
Wherein, R
1be selected from aryl, list or polysubstituted aryl or alkyl; Concrete steps are as follows:
In reaction vessel, add alkynes, [(IPr) AuCl], AgOTf, solvent Isosorbide-5-Nitrae-dioxane and water, reaction mixture microwave reaction 1 hour at 120 DEG C, cool to room temperature; Filter, rotary evaporation, except desolventizing, is then separated by post, obtains target compound.
2. the method for synthesizing methyl ketone according to claim 1, is characterized in that described R
1for aminomethyl phenyl, p-methoxy-phenyl, halogenophenyl or cyclopropyl.
3. the method for synthesizing methyl ketone according to claim 1, is characterized in that described microwave reaction instrument is that U.S. CE M DISCOVER SP focuses on single mold microwave synthesizer.
4. the method for synthesizing methyl ketone according to claim 1, is characterized in that with molar ratio computing [(IPr) AuCl]: AgOTf: alkynes=1:1:100.
5. the method for synthesizing methyl ketone according to claim 1, is characterized in that the mol ratio of described water consumption and alkynes is 2.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008499A (en) * | 2016-05-13 | 2016-10-12 | 青岛云天生物技术有限公司 | Method for preparing CDK46 kinase inhibitor Palbociclib |
| CN106478395A (en) * | 2015-08-28 | 2017-03-08 | 南京理工大学 | A kind of method of iridium catalyzed synthesizing alpha-alkyl ketone |
| CN106986754A (en) * | 2017-03-31 | 2017-07-28 | 兰州大学 | A kind of method that cobalt catalysis prepares MIBK |
| CN109384677A (en) * | 2017-08-14 | 2019-02-26 | 南京理工大学 | A method of synthesis primary amine hydrochloride |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617318A (en) * | 2012-02-20 | 2012-08-01 | 常熟理工学院 | Reaction method for oxidizing aromatic side chain by aid of oxygen |
-
2013
- 2013-10-15 CN CN201310482691.9A patent/CN104557499A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617318A (en) * | 2012-02-20 | 2012-08-01 | 常熟理工学院 | Reaction method for oxidizing aromatic side chain by aid of oxygen |
Non-Patent Citations (2)
| Title |
|---|
| GABINO A. CARRIEDO，ET AL.: ""Covalently Bonded Bis(phosphane)gold(I) Cations in a Cross-Linked Phosphazene Polymeric Matrix as Recyclable Supported Catalysts for Thermal and Microwave-Assisted Hydration of Alkynes"", 《EUR. J. INORG. CHEM.》 * |
| NICOLAS MARION，ET AL.: ""[(NHC)AuI]-Catalyzed Acid-Free Alkyne Hydration at Part-per-Million Catalyst Loadings"", 《J. AM. CHEM. SOC.》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106478395A (en) * | 2015-08-28 | 2017-03-08 | 南京理工大学 | A kind of method of iridium catalyzed synthesizing alpha-alkyl ketone |
| CN106478395B (en) * | 2015-08-28 | 2019-06-25 | 南京理工大学 | A kind of method of iridium catalyzed synthesizing alpha-alkyl ketone |
| CN106008499A (en) * | 2016-05-13 | 2016-10-12 | 青岛云天生物技术有限公司 | Method for preparing CDK46 kinase inhibitor Palbociclib |
| CN106008499B (en) * | 2016-05-13 | 2017-10-10 | 刘淑兰 | A kind of method for preparing CDK46 kinase inhibitors Pa Boxini |
| CN106986754A (en) * | 2017-03-31 | 2017-07-28 | 兰州大学 | A kind of method that cobalt catalysis prepares MIBK |
| CN109384677A (en) * | 2017-08-14 | 2019-02-26 | 南京理工大学 | A method of synthesis primary amine hydrochloride |
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Application publication date: 20150429 |