CN104710290A - Green synthesis method of alpha, beta-unsaturated ketone compound - Google Patents
Green synthesis method of alpha, beta-unsaturated ketone compound Download PDFInfo
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- CN104710290A CN104710290A CN201310676114.3A CN201310676114A CN104710290A CN 104710290 A CN104710290 A CN 104710290A CN 201310676114 A CN201310676114 A CN 201310676114A CN 104710290 A CN104710290 A CN 104710290A
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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Abstract
The invention discloses a green synthesis method of an alpha, beta-unsaturated ketone compound. The method comprises the following steps: fully reacting substrates comprising saturated alkyl ketone and aromatic aldehyde in a catalysis system formed by an amino functionalized ionic liquid and water at 20-150DEG C under microwave conditions to obtain a mixture, carrying out extracting separation, purifying, and drying to obtain the alpha, beta-unsaturated olefin ketone compound. The preparation method has the advantages of high efficiency, simplicity, mild reaction conditions, high yield, environmentally friendly catalysis reaction system, good repeatability, green ionic liquid preparation process and very good atom economy.
Description
Technical field
The present invention relates to a kind of green synthesis method of alpha, beta-unsaturated ketone compound
Background technology
α, alpha, beta-unsaturated ketone is the conjugation beta-unsaturated carbonyl compounds that a class has extensive utility value in organic synthesis, containing a difunctional structural unit, namely 1, Isosorbide-5-Nitrae-conjugated system that 2-carbon-oxygen carbonyl and 3,4-carbon-carbon double bond are formed, be present in widely in the structure of many necessary critical function molecule of organism, and play the effect wanted emphatically.In addition, alpha, beta-unsaturated ketone is the important organic synthesis precursor compound of a class and crucial intermediate equally, is widely used in the fields such as medicine, agricultural chemicals, spices.Therefore, in decades, be subject to the extensive concern of numerous chemist, to in the study on the synthesis of alpha, beta-unsaturated ketone, many new organic reactions having universal significance and theory value are found, and be devoted to improve, innovate α, the synthetic method of alpha, beta-unsaturated ketone, expects with more economically, easy and green chemical synthesis process obtains alpha, beta-unsaturated ketone.
Utilizing aldol to react is one of effective way of synthesis alpha, beta-unsaturated ketone.Classical Adol reaction is the aldehyde with α-H, and Formed negative ion under base catalysis, then carries out nucleophilic addition(Adn) using carbanion as nucleophilic reagent to aldehyde ketone, and generate beta-hydroxy aldehyde, beta-hydroxy aldehyde thermal dehydration becomes unsaturated aldehyde.Adol reaction also can under sour existent condition, and aldehyde ketone occurs from condensation or Cross-condensation reaction, obtains dehydrating condensation product alpha, beta-unsaturated ketone.Aldol condensation is also the earliest for the synthetic method of alpha, beta-unsaturated ketone, and in order to avoid by product is too much, the not high factor being unfavorable for synthesizing of productive rate, this method is gone through and repeatedly improved.Such as TeruakiMukaiyama in 1973 has invented the method carrying out stable enol in aldol reaction by the form of silicon ether: the silyl ether of enol replaces ketone and aldehyde generation cross-condensation, thus avoid the self-condensation of ketone, or aldehyde is made acetal activated, or utilize the different-phase catalysts such as enol metal-salt in addition to silicon, be all suitable for improving reaction preference and the reaction in complex system.
But, in these methods, although make moderate progress, but still there is the deficiencies such as the loaded down with trivial details or aftertreatment of such as expensive catalyst, poisonous, long reaction time, operation is complicated.Now along with the fast development of Green Chemistry and organic synthesis technology, the environmental consciousness of people is all the more strong, and the application of green catalysis system more and more causes the interest of investigator.Green catalysis system is showing high reaction activity and optionally under prerequisite, is avoiding toxic, danger, the high in cost of production shortcoming with an organic solvent brought with traditional catalyst.Organic reaction under green catalysis system is simple and environmental friendliness and gaining great popularity with its safety, reaction unit, is desirable synthetic method.(reference: 1.S.Hu, T.Jiang, Z.Zhang, A.Zhu, B.Han, J.Song, Y.Xie and W.Li, Tetrahedron Lett., 2007,48,5613.; 2.Y.Zhang, M.G.Wang, J.Liang and Z.C.Shang, Lett.Org.Chem., 2010,7,27.; 3.R.Fernandez-Lopez, J.Kofoed, M.Machuqueiro and T.Darbre, Eur.J.Org.Chem., 2005,5268.; 4.B.Wang, X.W.Liu, L.Y.Liu, W.X.Chang and J.Li, Eur.J.Org.Chem., 2010,5951.; 5.R.Hart, P.Pollet, D.J.Hahne, E.John, V.Llopis-Mestre, V.Blasucci, H.Huttenhower, W.Leitner, C.A.Eckert and C.L.Liotta, Tetrahedron, 2010,66,1082)
Summary of the invention
For solving alpha, beta-unsaturated ketone compound the deficiencies in the prior art, the invention provides a kind of green synthesis method of alpha, beta-unsaturated ketone compound, adopting the green catalysis reaction system of amino functional ionic liquid and water.
For realizing the object of the invention, it adopts concrete technical scheme to be:
A kind of α, the green synthesis method of alpha, beta-unsaturated ketone compound, described α, shown in the structure formula III of alpha, beta-unsaturated ketone compound, it is characterized in that: described synthetic method is for substrate with the alkane ketone shown in the aromatic aldehyde shown in structure formula I and structure formula II, fully react under 20 ~ 120 DEG C of microwave heating conditions in the system of amino functional and water, gained mixture obtains product alpha, beta-unsaturated ketone through separation and purification;
Wherein, Ar be by any one, the phenyl that replaces at 2 ~ 6 of two kinds or three kinds of groups, substituted radical refers to C1 ~ C4 alkyl, C1 ~ C4 alkoxyl group, nitro, halogen (fluorine, chlorine, bromine, iodine); R is H or C1 ~ C6 alkyl.
Shown in described amino functional ionic liquid structural formula formula IV:
R
0, R
1be respectively the alkyl of independently C1 ~ C12 separately; R
2, R
3, R
4, R
5be respectively the alkyl of independently C1 ~ C8 separately; M=1 or 2.
Described alkane ketone is 1:2 ~ 4 with the ratio of the amount of substance of aromatic aldehyde; Described alkane ketone is 1:0.1 ~ 0.25 with the ratio of the amount of substance of described amino functional.
Described amino functional ionic liquid and the mass ratio of water are 1:0.1 ~ 10.
Described reaction microwave heating condition is: temperature 40 ~ 150 DEG C, power 100 ~ 600W, time 5 ~ 50min, the separation of gained mixture extraction, purifying, is drying to obtain described alpha, beta-unsaturated ketone compound.
Described reaction mixture is separated or filters gained filtrate after the drying that dewaters, and continues in the reaction to use.
Concrete steps are as follows:
The preparation of the first step amino functional ionic liquid
Get alkyl sultone and excessive alkylamine, at room temperature stir 24 ~ 48h, after the drying that dewaters, obtain white solid salt, after organic solvent (methyl alcohol, ethanol or sherwood oil etc.) recrystallization, suction filtration, vacuum-drying; Then take equimolar oven dry solid salt, at room temperature stir 1h with alkali, dewater dry following ionic liquid:
In said structure, R
0, R
1for the alkyl of respective independently C1 ~ C12; R
2, R
3, R
4, R
5for the alkyl of respective independently C1 ~ C8; M=1,2.
Second step Adol condensation reaction
Under the catalyst system of amino functional ionic liquid and water, in the microwave silica tube of 50mL, add the alkane ketone of 7.5mmol and the aromatic aldehyde of 2.5mmol and seal with polytetrafluoro lid, microwave heating temperature is at 40 ~ 120 DEG C, and power is under 100 ~ 600W, stirs 5 ~ 50min.
Reaction formula is as follows:
Ar be by any one, the phenyl that replaces at 2 ~ 6 of two kinds or three kinds of groups, substituted radical refers to C1 ~ C4 alkyl, C1 ~ C4 alkoxyl group, nitro, halogen (fluorine, chlorine, bromine, iodine); R is H or C1 ~ C6 alkyl.
The separation of the 3rd step ionic liquid and the purifying of product
Reaction terminates, and extracting and separating after said mixture cooling is obtained target product, by nucleus n-ness spectrum reference determination structure.The transformation efficiency of aromatic aldehyde and the productive rate of target product are by reaction mixture
1h NMR carries out quantitative analysis.As need purifying be continued, available silica gel column chromatography treating product.After extracting and separating product, aqueous phase mixed solution reclaims, and dewater drying, obtains ionic liquid and can continue to recycle.
The method beneficial effect that amino functional ionic liquid of the present invention and water prepare alpha, beta-unsaturated ketone compound as catalytic reaction system is mainly reflected in following four aspects:
1) catalyst system of amino functional ionic liquid and water, has the dual function of catalysts and solvents concurrently, effectively can reduce the impact on environment;
2) the amino functional ionic liquid preparation process described in is simple, and atom is efficient, cheaper starting materials;
3) working method is efficiently simple, and reaction conditions is gentle, and product yield is high;
4) described ionic liquid can reuse, and product yield is unaffected.
To sum up, alpha, beta-unsaturated ketone compou nd synthesis method of the present invention is a kind of green synthesis method, environmentally friendly.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, but protection scope of the present invention is not limited in this.
Embodiment 1
The preparation of the first step ionic liquid
Get 1,3-propane sultone (6.11g, 50mmol) with excessive ethylamine solution (mass concentration 60% ~ 70%, 12mL), at room temperature stir 48h, after the drying that dewaters white solid salt (5.80g), to be greater than in the methyl alcohol of 99% after recrystallization in concentration, suction filtration vacuum-drying, obtains white needles salt; Then take equimolar oven dry solid salt and the tetraethyl ammonium hydroxide aqueous solution (mass concentration 20%) at room temperature stirs 1h, 80 DEG C of vacuum-drying 12h, obtain ionic liquid [N (C
2h
5)
4] [C
2h
5nH (C
2h
2)
3sO
3].
Second step Adol condensation reaction
Amino functional ionic liquid [N (C
2h
5)
4] [C
2h
5nH (C
2h
2)
3sO
3] (1.00g, 3.3mmol) add 50mL microblogging silica tube with water 1mL, stirred at ambient temperature to homogeneous phase, acetone (0.30g, 7.5mmol) and phenyl aldehyde (0.26g, 2.5mmol) join successively in this reaction vessel, microwave polytetrafluoro lid seals, under microwave condition (temperature 60 C, power 400W), stir 30min, be cooled to room temperature.The reaction mixture that takes a morsel does
1h NMR characterizes, and acquired results is: phenyl aldehyde transformation efficiency 99%, and target product productive rate is 98%.By 10mL chloroform extraction reaction product, re-extract step 3 time, removing chloroform also obtains target product by dried over mgso, and product structure formula is:
The separation of the 3rd step ionic liquid and the purifying of product
Reaction terminates, and suction filtration after said mixture cooling is obtained solid product, and be washed till filtrate with distilled water colourless in neutral, solid product can continue purifying (in ethanol recrystallization).Filtrate is reclaimed, and dewater drying, obtains ionic liquid and can continue to recycle.
Embodiment 2-5
Microwave temperature according to described in table 1, other reaction response condition: amino functional ionic liquid [N (C
2h
5)
4] [C
2h
5nH (C
2h
2)
3sO
3], water consumption, reaction times, reactant consumption and product yield calculate with the aldol condensation reaction in embodiment 1.
Table 1
Embodiment 6-11
Reaction times according to described in table 2, other reaction response condition: amino functional ionic liquid [N (C
2h
5)
4] [C
2h
5nH (C
2h
2)
3sO
3], water consumption, reaction times, reactant consumption and product yield calculate with the aldol condensation reaction in embodiment 1.
Table 2
Embodiment 12-14
By the amino functional ionic liquid (3.3mmol) described in table 3 and water (plasma liquid mass) stirred at ambient temperature to homogeneous phase, reactant consumption, reaction conditions and product yield calculate with the aldol condensation reaction in embodiment 1.
Table 3
Embodiment 15-19
The consumption of ionic liquid and water, reaction conditions and product yield calculate with the aldol condensation reaction in embodiment 1.Wherein alkane ketone (7.5mmol), aromatic aldehyde (2.5mmol), reaction result is in table 4.
Table 4
Embodiment 20-25
The amino functional ionic liquid of separation and purification in embodiment 1, carries out repeating to test (table 5) according to the aldol condensation reaction condition of embodiment 1.Described amino functional ionic liquid is reused 5 times and is had no reduced activity.
Table 5
The inventive method is efficiently simple, and reaction conditions is gentle, and building-up process is environmentally friendly, productive rate is high, reproducible, and, ionic liquid preparation method in this system is simple, cheap, and catalystic converter system is environmentally friendly, and process is green and have good Atom economy.
Alpha, beta-unsaturated ketone characterization of compound
Product in embodiment 1
4-Phenylbut-3-en-2-one
1H NMR(400MHz,CDCl
3)δ(ppm):7.54(m,2H),7.50(d,1H),7.39(m,3H),6.70(d,J=16.3Hz,1H),2.37(s,3H)。
The product of embodiment 15-19
4-(2-Chlorophenyl)but-3-en-2-one
1H NMR(400MHz,CDCl
3)δ(ppm):7.93(d,J=16.4Hz,1H),7.63(q,J=1.6Hz,1H),7.43(q,J=0.8Hz,1H),7.34-7.26(m,2H),6.67(d,J=16.4Hz,1H),2.42(s,3H)；
4-(3-Bromophenyl)but-3-en-2-one
1H NMR(400MHz,CDCl
3),δ(ppm):7.68(s,1H)7.52-7.41(m,3H),7.27(q,J=3.2Hz,1H),6.70(d,J=16.3Hz,1H),2.38(s,3H)；
4-(4-Methylphenyl)but-3-en-2-one
1H NMR(400MHz,CDCl
3)δ(ppm):7.49(d,J=16.3Hz,1H),7.44(d,J=8.0Hz,2H),7.20(d,J=8.0Hz,2H),6.98(d,J=16.2Hz,1H),2.38(s,3H),2.37(s,3H)；
4-(4-Methoxyphenyl)but-3-en-2-one
1H NMR(400MHz,CDCl
3)δ(ppm):7.54-7.49(m,3H),6.95(d,J=8.4Hz,2H),6.64(d,J=16.2Hz,1H),3.87(s,3H),2.39(s,3H)；
4-phenyl-3-methyl-3-buten-2-one
11H NMR(400MHz,DMSO-d
6)δ(ppm):7.59(s,1H),7.45-7.3(m,4H),2.37(s,3H),1.87(d,3H)。
Claims (6)
1. a α, the green synthesis method of alpha, beta-unsaturated ketone compound, α, the structure of alpha, beta-unsaturated ketone compound is as shown in formula III, it is characterized in that: described synthetic method is for substrate with the alkane ketone shown in the aromatic aldehyde shown in structure formula I and structure formula II, fully react under 20 ~ 150 DEG C of microwave heating under the system of amino functional ionic liquid and water, gained mixture obtains described alpha, beta-unsaturated ketone compound through separation and purification;
Wherein, Ar be by any one, the phenyl that replaces at 2 ~ 6 of two kinds or three kinds of groups, substituted radical refers to C1 ~ C4 alkyl, C1 ~ C4 alkoxyl group, nitro, halogen (fluorine, chlorine, bromine, iodine); R is H or C1 ~ C6 alkyl.
2. green synthesis method as claimed in claim 1, is characterized in that: described amino functional ionic liquid structural formula is as shown in formula IV:
R
0, R
1for the alkyl of respective independently C1 ~ C12;
R
2, R
3, R
4, R
5for the alkyl of respective independently C1 ~ C8;
M=1 or 2.
3. green synthesis method as claimed in claim 1, is characterized in that: described alkane ketone is 1:2 ~ 4 with the ratio of the amount of substance of described aromatic aldehyde; Described alkane ketone is 1:0.1 ~ 0.25 with the ratio of the amount of substance of described amino functional ionic liquid.
4. the green synthesis method as described in claim 1,2 or 3, is characterized in that: described amino functional ionic liquid and the mass ratio of water are 1:0.1 ~ 10.
5. green synthesis method as claimed in claim 1, is characterized in that: described reaction carries out 1 ~ 12h under 20 ~ 150 DEG C of microwave heating conditions, product extraction separation, purifying, be drying to obtain described alpha, beta-unsaturated ketone compound.
6. the green synthesis method as described in claim 1 or 5, is characterized in that: after described reaction mixture extracting and separating, and gained aqueous phase solution, after the drying that dewaters, continues to use in the reaction.
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|---|---|---|---|---|
| CN113480419A (en) * | 2021-05-31 | 2021-10-08 | 温州大学 | Method for synthesizing alpha, beta unsaturated ketone |
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|---|---|---|---|---|
| CN103012087A (en) * | 2011-09-23 | 2013-04-03 | 中国科学院大连化学物理研究所 | Green synthetic method of alpha, alpha'-double benzylidene cycloalkanone compound |
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|---|---|---|---|---|
| CN103012087A (en) * | 2011-09-23 | 2013-04-03 | 中国科学院大连化学物理研究所 | Green synthetic method of alpha, alpha'-double benzylidene cycloalkanone compound |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113480419A (en) * | 2021-05-31 | 2021-10-08 | 温州大学 | Method for synthesizing alpha, beta unsaturated ketone |
| CN113480419B (en) * | 2021-05-31 | 2023-07-25 | 温州大学 | Method for synthesizing alpha, beta unsaturated ketone |
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Application publication date: 20150617 |