CN103922875A - Novel method for synthesizing functionalized ketone through reaction of aromatic ketone and primary alcohol - Google Patents
Novel method for synthesizing functionalized ketone through reaction of aromatic ketone and primary alcohol Download PDFInfo
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- CN103922875A CN103922875A CN201410190307.2A CN201410190307A CN103922875A CN 103922875 A CN103922875 A CN 103922875A CN 201410190307 A CN201410190307 A CN 201410190307A CN 103922875 A CN103922875 A CN 103922875A
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Abstract
The invention discloses a novel method for synthesizing functionalized ketone through reaction of aromatic ketone and primary alcohol. According to the technical scheme, the method includes the following processing steps that (1) the aromatic ketone and aromatic methanol or fatty alcohol are added into a reaction container according to the molar ratio of 2:1-2, [(Bt)2*Ir*P(Ph)3]C1 is added as a catalyst (Bt is phenylbenzothiazole), alkali and an organic solvent are added, and reaction is conducted for 15-24 hours under the condition that the temperature is 100-150 DEG C, wherein the amount ratio of the aromatic ketone, the aromatic methanol or the fatty alcohol, the catalyst and the alkali is 2:1-2:0.01-0.02:1-2; (2) after reaction liquid obtained in the step (1) is filtered, the reaction liquid is purified by 200-300-mesh silicagel columns; after 20-50mL of petroleum ether is used for pre-leaching the silicagel columns, leacheate is used for conducting elution, wherein the flow velocity of the leacheate is 1-2 mL/min, and the elution time is 3-6 h; after the solvent is removed, a corresponding functionalized ketone is obtained. According to studies, it is discovered that the novel method is used for catalyzing the aromatic ketone and the aromatic methanol or the fatty alcohol to synthesize the functionalized ketone, and the method has the advantages that conditions are gentle, the conversion rate is high, and no pollutant is generated.
Description
Technical field
The present invention relates to a kind of novel method of synthesizing functionalized ketone by aromatic ketone and primary alconol reaction, belong to chemical material and organic synthesis field.
Background technology
Along with environmental problem becomes increasingly conspicuous, Green Chemistry comes into one's own more, and development environment close friend's catalyst system and synthetic method more and more cause organic chemist's concern.
Selective oxidation alcohol generates corresponding aldehyde and ketone is one of purposes functional group's conversion reaction the most widely in organic synthesis, in fundamental research and industrial organic synthesis, has very important application.At present, although existing many effective ways of realizing this conversion reaction conventionally all need to adopt harsh reaction conditions or poisonous oxygenant, thereby produce a large amount of environmental pollutant.Along with the requirement of the sustainable steady progression of increase and social economy of environmental protection pressure, the drawback in traditional alcohol oxidation reaction system is self-evident.Therefore; in the research and development process of alcohol oxidation reaction; use environment amenable oxygenant; as oxygen, hydrogen peroxide replace traditional oxygenant; selection has high-performance, cheapness, clean catalyzer; be the important subject that realizes alcohol oxidation reaction greenization, significant for environment protection.
Ketone taking transition metal as catalyst and the alkylated reaction of alcohol are a kind of new reaction systems, compare with traditional alkylation (conventionally need to carry out under low temperature and anhydrous condition), the method by product is only water, operation is simple, mild condition is a kind of method of environmental protection.In recent years, some research groups have obtained gratifying progress in this catalyst field.Although the alkylated reaction of transition metal-catalyzed ketone and alcohol has many advantages, but also generate further reduzate coupling alcohol in generating target product coupling ketone, therefore how to improve the selectivity of reaction, the emphasis of recent this research of as far as possible having avoided becoming of side reaction.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of by the novel method of aromatic ketone and the synthetic functionalized ketone of primary alconol reaction.
According to technical scheme provided by the invention, the feature of described a kind of novel method by aromatic ketone and the synthetic functionalized ketone of primary alconol reaction is to comprise following processing step:
(1) aromatic ketone and aromatic methanol or fatty alcohol 2: 1 in molar ratio～2 are joined in reaction vessel, add [(Bt)
2* Ir*P (Ph)
3] Cl is as catalyzer (Bt is phenyl benzothiazole), then add alkali and organic solvent, under the condition of 100～150 DEG C, react 15～24 hours; The ratio of the amount of substance of described aromatic ketone, aromatic methanol or fatty alcohol, catalyzer, alkali is 2: 1～2: 0.01～0.02: 1～2
(2) after reacting liquid filtering step (1) being obtained, through 200～300 object silicagel column purifying, with after the pre-drip washing silicagel column of 20～50mL sherwood oil, adopt leacheate to carry out wash-out, leacheate flow velocity is 1～2mL/min, elution time is 3～6h, except after desolventizing, obtains the functionalized ketone of described correspondence.
The reaction equation of described method is:
wherein R
1, R
2for alkyl, phenyl, substituted-phenyl or substituted heterocyclic radical; Described alkyl is: n-propyl, isobutyl-, normal-butyl, n-octyl, iso-octyl, described substituted-phenyl is 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 4-chloro-phenyl-, 4-nitrophenyl, and described heterocyclic radical is 2-furyl, 2-pyridyl, 3-pyridyl, 4-pyridyl.
Described alkali is cesium carbonate, salt of wormwood or potassium tert.-butoxide; Described organic solvent is toluene or tertiary amyl alcohol; Described leacheate is that mass ratio is the ethyl acetate of 1: 10 and the mixture of sherwood oil
The consumption of described alkali is aromatic methanol or fatty alcohol consumption 1～1.2 times.
In step (1), described temperature of reaction is 100～150 DEG C.
In step (1), the described reaction times is 15～24 hours.
The mol ratio of described aromatic ketone and aromatic methanol or fatty alcohol is 1: 1.2.
Method of the present invention is by aromatic ketone and aromatic methanol or fatty alcohol, [(Bt) 2*Ir*P (Ph)
3] Cl is as catalyzer, cesium carbonate, salt of wormwood or potassium tert.-butoxide do alkali, and toluene or tertiary amyl alcohol are solvent, (100～150 DEG C) lower reaction 15～24h under gentle reaction conditions, then obtain the functionalized ketone of described correspondence through separation and purification.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
The reaction equation of the method for the invention is:
Wherein R
1, R
2for alkyl, phenyl, substituted-phenyl or substituted heterocyclic radical; Described alkyl is: n-propyl, isobutyl-, normal-butyl, n-octyl, iso-octyl, described substituted-phenyl is 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 4-chloro-phenyl-, 4-nitrophenyl, and described heterocyclic radical is 2-furyl, 2-pyridyl, 3-pyridyl, 4-pyridyl.
Embodiment mono-: a kind of by the novel method of aromatic ketone and the synthetic functionalized ketone of primary alconol reaction, comprise following processing step:
Under nitrogen protection, in 50mL Schlenk pipe, add methyl phenyl ketone (120mg, 1mmol), phenylcarbinol (130mg, 1.2mmol), [(Bt)
2* Ir*P (Ph)
3] Cl (10mg, 0.01mmol, 1.0mol%), cesium carbonate (326mg, 1.0mmol), adds 2.0mL tertiary amyl alcohol; Reaction solution is in 120 DEG C of reaction 20h, and the solution of generation separates (ethyl acetate/petroleum ether that elutriant is 1: 10) with 200～300 order silicagel columns, except after desolventizing, obtains corresponding product, and structural formula is:
white crystal, fusing point: 72-74 DEG C, productive rate: 92%.
Embodiment bis-: a kind of by the novel method of aromatic ketone and the synthetic functionalized ketone of primary alconol reaction; comprise following processing step: under nitrogen protection; in 50mL Schlenk pipe, add methyl phenyl ketone (120mg; 1mmol); 3-4-hydroxymethylpiperidine (131mg; 1.2mmol), [(Bt)
2* Ir*P (Ph)
3] Cl (10mg, 0.01mmol, 1.0mol%), cesium carbonate (326mg, 1.0mmol), adds 2.0mL tertiary amyl alcohol; Reaction solution is in 120 DEG C of reaction 20h, and the solution of generation separates (ethyl acetate/petroleum ether that elutriant is 1: 10) with 200～300 order silicagel columns, except after desolventizing, obtains corresponding product, and structural formula is:
white crystal, fusing point: 84-86 DEG C, productive rate: 86%.
Embodiment tri-: a kind of by the novel method of aromatic ketone and the synthetic functionalized ketone of primary alconol reaction; comprise following processing step: under nitrogen protection; in 50mL Schlenk pipe, add methyl phenyl ketone (120mg; 1mmol); 4-4-hydroxymethylpiperidine (131mg; 1.2mmol), [(Bt)
2* Ir*P (Ph)
3] Cl (10mg, 0.01mmol, 1.0mol%), cesium carbonate (326mg, 1.0mmol), adds 2.0mL tertiary amyl alcohol; Reaction solution is in 120 DEG C of reaction 20h, and the solution of generation separates (ethyl acetate/petroleum ether that elutriant is 1: 10) with 200～300 order silicagel columns, except after desolventizing, obtains corresponding product, and structural formula is:
white crystal, fusing point: 64-67 DEG C, productive rate: 83%.
Embodiment tetra-: a kind of by the novel method of aromatic ketone and the synthetic functionalized ketone of primary alconol reaction, comprise following processing step:
Under nitrogen protection, in 50mL Schlenk pipe, add methyl phenyl ketone (120mg, 1mmol), 2-4-hydroxymethylpiperidine (131mg, 1.2mmol), [(Bt)
2* Ir*P (Ph)
3] Cl (10mg, 0.01mmol, 1.0mol%), cesium carbonate (326mg, 1.0mmol), adds 2.0mL tertiary amyl alcohol; Reaction solution is in 120 DEG C of reaction 20h, and the solution of generation separates (ethyl acetate/petroleum ether that elutriant is 1: 10) with 200～300 order silicagel columns, except after desolventizing, obtains corresponding product, and structural formula is:
yellow liquid, productive rate: 83%.
Embodiment five: a kind of by the novel method of aromatic ketone and the synthetic functionalized ketone of primary alconol reaction, comprise following processing step:
Under nitrogen protection, in 50mL Schlenk pipe, add methyl phenyl ketone (120mg, 1mmol), 4-nitrobenzyl alcohol (184mg, 1.2mmol), [(Bt)
2* Ir*P (Ph)
3] Cl (10mg, 0.01mmol, 1.0mol%), cesium carbonate (326mg, 1.0mmol), adds 2.0mL tertiary amyl alcohol; Reaction solution is in 120 DEG C of reaction 20h, and the solution of generation separates (ethyl acetate/petroleum ether that elutriant is 1: 10) with 200～300 order silicagel columns, except after desolventizing, obtains corresponding product, and structural formula is:
faint yellow solid, fusing point: 98 DEG C of-100 DEG C of productive rates: 73%.
Embodiment six: a kind of by the novel method of aromatic ketone and the synthetic functionalized ketone of primary alconol reaction, comprise following processing step:
Under nitrogen protection, in 50mL Schlenk pipe, add methyl phenyl ketone (120mg, 1mmol), 2-furans phenylcarbinol (118mg, 1.2mmol), [(Bt)
2* Ir*P (Ph)
3] Cl (10mg, 0.01mmol, 1.0mol%), cesium carbonate (326mg, 1.0mmol), adds 2.0mL tertiary amyl alcohol; Reaction solution is in 120 DEG C of reaction 20h, and the solution of generation separates (ethyl acetate/petroleum ether that elutriant is 1: 10) with 200～300 order silicagel columns, except after desolventizing, obtains corresponding product, and structural formula is:
faint yellow solid, fusing point: 36 DEG C-38 DEG C, productive rate: 83%.
Embodiment seven: a kind of by the novel method of aromatic ketone and the synthetic functionalized ketone of primary alconol reaction, comprise following processing step: under nitrogen protection, in 50mL Schlenk pipe, add methyl phenyl ketone (120mg; 1mmol); propyl carbinol (89mg, 1.2mmol), [(Bt)
2* Ir*P (Ph)
3] Cl (10mg, 0.01mmol, 1.0mol%), cesium carbonate (326mg, 1.0mmol), adds 2.0mL tertiary amyl alcohol; Reaction solution is in 120 DEG C of reaction 20h, and the solution of generation separates (ethyl acetate/petroleum ether that elutriant is 1: 10) with 200～300 order silicagel columns, except after desolventizing, obtains corresponding product, and structural formula is:
weak yellow liquid, productive rate: 63%.
Embodiment eight: a kind of by the novel method of aromatic ketone and the synthetic functionalized ketone of primary alconol reaction, comprise following processing step: under nitrogen protection, in 50mL Schlenk pipe, add methyl phenyl ketone (120mg; 1mmol); n-Octanol (156mg, 1.2mmol), [(Bt)
2* Ir*P (Ph)
3] Cl (10mg, 0.01mmol, 1.0mol%), cesium carbonate (326mg, 1.0mmol), adds 2.0mL tertiary amyl alcohol; Reaction solution is in 120 DEG C of reaction 20h, and the solution of generation separates (ethyl acetate/petroleum ether that elutriant is 1: 10) with 200～300 order silicagel columns, except after desolventizing, obtains corresponding product, and structural formula is:
weak yellow liquid, productive rate: 78%.
Claims (7)
1. by a novel method for aromatic ketone and the synthetic functionalized ketone of primary alconol reaction, it is characterized in that, comprise following processing step:
(1) aromatic ketone and aromatic methanol or fatty alcohol 2: 1 in molar ratio～2 are joined in reaction vessel, add [(Bt)
2* Ir*P (Ph)
3] Cl is as catalyzer (Bt is phenyl benzothiazole), then add alkali and organic solvent, under the condition of 100～150 DEG C, react 15～24 hours; The ratio of the amount of substance of described aromatic ketone, aromatic methanol or fatty alcohol, catalyzer, alkali is 2: 1～2: 0.01～0.02: 1～2
(2) after reacting liquid filtering step (1) being obtained, through 200～300 object silicagel column purifying, with after the pre-drip washing silicagel column of 20～50mL sherwood oil, adopt leacheate to carry out wash-out, leacheate flow velocity is 1～2mL/min, elution time is 3～6h, except after desolventizing, obtains the functionalized ketone of described correspondence.
2. as claimed in claim 1 a kind of by the novel method of aromatic ketone and the synthetic functionalized ketone of primary alconol reaction, it is characterized in that: the reaction equation of described method is:
wherein R
1, R
2for alkyl, phenyl, substituted-phenyl or substituted heterocyclic radical; Described alkyl is: n-propyl, isobutyl-, normal-butyl, n-octyl, iso-octyl, described substituted-phenyl is 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 4-chloro-phenyl-, 4-nitrophenyl, and described heterocyclic radical is 2-furyl, 2-pyridyl, 3-pyridyl, 4-pyridyl.
3. as claimed in claim 1 a kind of by the novel method of aromatic ketone and the synthetic functionalized ketone of primary alconol reaction, it is characterized in that: described alkali is cesium carbonate, salt of wormwood or potassium tert.-butoxide; Described organic solvent is toluene or tertiary amyl alcohol; Described leacheate is that mass ratio is the ethyl acetate of 1: 10 and the mixture of sherwood oil.
4. as claimed in claim 1 a kind of by the novel method of aromatic ketone and the synthetic functionalized ketone of primary alconol reaction, it is characterized in that: the consumption of described alkali is aromatic methanol or fatty alcohol consumption 1～1.2 times.
5. as claimed in claim 1 a kind of by the novel method of aromatic ketone and the synthetic functionalized ketone of primary alconol reaction, it is characterized in that: described temperature of reaction is 100～150 DEG C.
6. as claimed in claim 1 a kind of by the novel method of aromatic ketone and the synthetic functionalized ketone of primary alconol reaction, it is characterized in that: the described reaction times is 15～24 hours.
7. as claimed in claim 1 a kind of by the novel method of aromatic ketone and the synthetic functionalized ketone of primary alconol reaction, it is characterized in that: the mol ratio of described aromatic ketone and aromatic methanol or fatty alcohol is 1.2: 1.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009137876A (en) * | 2007-12-06 | 2009-06-25 | Daicel Chem Ind Ltd | Method for producing carbonyl group-containing compound and large cyclic ketone |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009137876A (en) * | 2007-12-06 | 2009-06-25 | Daicel Chem Ind Ltd | Method for producing carbonyl group-containing compound and large cyclic ketone |
Non-Patent Citations (5)
| Title |
|---|
| CHEN XU等: "Triphenylphosphine-cyclometallated iridium(III) pyrimidine complexes: Synthesis, crystal structures and application in α-alkylation of ketones with alcohols", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 * |
| KAZUHIKO TAGUCHI等: "An Efficient Direct α-Alkylation of Ketones with Primary Alcohols Catalyzed by [Ir(cod)Cl]2/PPh3/KOH System without Solvent", 《J. AM. CHEM. SOC.》 * |
| KEN-ICHI FUJITA等: "Direct β-Alkylation of Secondary Alcohols with Primary Alcohols Catalyzed by a Cp*Ir Complex", 《ORGANIC LETTERS》 * |
| LI, JIAN等: "An Efficient α-Alkylation of Aromatic Ketones with Primary Alcohols Catalyzed by [Cp*IrCl2]2 without Solvent", 《CHIN. J. CHEM.》 * |
| 杨委: "含N、O配体在合成四元环配合物中的应用研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
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Application publication date: 20140716 |