CN104437621A - Catalytic system for synthesizing alpha-hydroxy ketone by alkynol hydration reaction - Google Patents
Catalytic system for synthesizing alpha-hydroxy ketone by alkynol hydration reaction Download PDFInfo
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Abstract
The invention discloses a catalytic system for synthesizing alpha-hydroxy ketone by alkynol hydration reaction. The catalytic system consists of an ionic liquid and a CO2 gas, wherein the ionic liquid is selected from at least one of ionic liquids as shown in formulas Ia-Ie described in the specification. In the catalytic system, the amount of substances of the ionic liquid is 0.01-0.5mol, and the pressure of the gas is 0.1-8MPa. The invention further provides a method of preparing alpha-hydroxy ketone compounds by utilizing the catalytic system. The catalytic system is suitable for a reaction system for catalyzing alkynol hydration reaction to synthesize alpha-hydroxy ketone compounds. The catalytic system is relatively high in catalytic activity, mild in reaction condition, and free of metals. The main catalyst ionic liquid is easy to synthesize and recycle, and has a relatively strong application value.
Description
Technical field
The invention belongs to catalyst field, be specifically related to a kind of catalyst system and catalyzing for alkynol hydration reaction synthesis alpha-alcohol ketone.
Background technology
Alpha-hydroxy ketones is the very important organic compound of a class, among its molecular skeleton being extensively present in bioactive compound and synthetic drug (Y.F.Liang, N.Jiao, Angew.Chem.Int.Ed.2014,53,548); Therefore, the method and the catalyst system and catalyzing that develop efficient synthesis alpha-hydroxy ketones are significant.
Alkynol hydration reaction is a kind of method of simple, synthesis alpha-hydroxy ketones that Atom economy is good, meets the requirement of Green Chemistry and sustainable development.Develop various metals catalyst at present, as platinum (Pt), gold (Au), silver (Ag) etc. replace traditional poisonous mercury (Hg) catalyst system and catalyzing, for alkynol hydration reaction synthesis alpha-hydroxy ketones (W.Baidossi, M.Lahav, J.Blum, J.Org.Chem.1997,62,669; E.Mizushima, K.Sato, T.Hayashi, M.Tanaka, Angew.Chem.Int.Ed.2002,41,4563; A.Leyva, A.Corma, J.Org.Chem.2009,74,2067; R.Das, D.Chakraborty, Appl.Organometal.Chem.2012,26,722; H.T.He, C.R.Qi, X.H.Hu, Y.Q.Guan, H.F.Jiang, Green chem., 2014,16,3729).But above-mentioned catalyst system and catalyzing needs strong acid or highly basic and organic ligand etc. usually, and the side reactions such as Meyer-Schuster and Rupe rearrangement can be there is.Therefore, develop gentleness, green high-efficient, remain the core of this repercussion study without the catalyst system and catalyzing of metal.
Summary of the invention
The object of this invention is to provide a kind of catalyst system and catalyzing for alkynol hydration reaction synthesis alpha-hydroxy ketones.
Catalyst system and catalyzing provided by the present invention is by ionic liquid and CO
2gas composition; Described ionic liquid is selected from following formula I
a-Shi I
eat least one in shown ionic liquid, in described catalyst system and catalyzing, the amount of substance of described ionic liquid is 0.01-0.5mol, and the pressure of described gas is 0.1-8MPa.
In above-mentioned catalyst system and catalyzing, the amount of substance of described ionic liquid can be 0.3-0.5mol further, most preferably is 0.3mol.
The pressure of described gas can be 0.1-1MPa further, most preferably is 0.1 or 1MPa.
In above-mentioned catalyst system and catalyzing, described formula I
a-I
eshown ionic liquid plays major catalyst and solvent in whole catalyst system and catalyzing.Described CO
2gas plays co-catalyst.
Another object of the present invention is to provide and above-mentioned catalyst system and catalyzing is used for the method for alkynol by hydration reaction synthesis alpha-hydroxy ketones, comprises the steps: under described catalyst system and catalyzing existent condition, by alkynol and H
2o carries out hydration reaction, prepares alpha-hydroxy ketones.
In said method, the mol ratio of described alkynol and described catalyst system and catalyzing intermediate ion liquid is 1:(0.1-5), can be 1:(3-5 further), most preferably be 1:3.
The mol ratio of described alkynes alcohol and water is (1:1)-(1:30), is preferably 1:2.
Described alkynol is selected from following at least one: 2-methyl-3-butyne-2-alcohol, methylpentynol, 3-ethyl-1-pentyne-3-alcohol, 3,5-dimethyl-1-hexin-3-alcohol, 3-methyl isophthalic acid-n-heptylacetylene-3-alcohol, 2-phenyl-3-butyne-2-alcohol, 2-methyl 4-phenyl-3-butyne-2-alcohol and 1-acetenyl-1-cyclohexanol.
The reaction temperature of described hydration reaction is 30-100 DEG C, is preferably 80 DEG C.
The reaction time of described hydration reaction is 1-48h, specifically can be 24-48h, is preferably 24h or 48h.
Described alpha-hydroxy ketones is selected from following at least one: 3-hydroxy-3-methyl-2-butanone, 3-hydroxy-3-methyl-2 pentanone, 3-ethyl-3-hydroxyl-2 pentanone, 3-hydroxyl-3,5-dimethyl-methyl-n-butyl ketone, 3-hydroxy-3-methyl-methyl n-heptyl ketone, 3-hydroxyl-3-Phenyl 2 butanone, 3-hydroxy-3-methyl-1-Phenyl 2 butanone and 1-acetyl cyclohexanol.
Catalyst system and catalyzing provided by the present invention has higher catalytic activity, with report (H.T.He, C.R.Qi, X.H.Hu, Y.Q.Guan, H.F.Jiang, Green chem., 2014,16,3729) productive rate that optimum catalyst system and catalyzing catalysis alkynol obtains alpha-hydroxy ketones is suitable, but reaction condition is more green, gentleness (<100 DEG C), without metal superlattice; Major catalyst ionic liquid is easy to synthesis and reclaims; This catalyst system and catalyzing is widely applicable, can be used for alkynol hydration reaction synthesis alpha-hydroxy ketones, has stronger using value.
Detailed description of the invention
Be described method of the present invention below in conjunction with specific embodiment, but the present invention is not limited thereto, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Experimental technique described in following embodiment, if no special instructions, is conventional method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Ionic-liquid catalyst used in the present invention, except [Bu
4p] [BenzTriz], by outside commercial sources purchase, the method that all the other ionic liquids all can provide according to following document is prepared: C.M.Wang, et al; Angew.Chem.Int.Ed.2011,50,4918.
Concrete preparation method is as follows: first utilize anion exchange resin, by tetrabutyl phosphonium bromide phosphine ([Bu
4p] [Br]) be exchanged for tetrabutylammonium hydroxide phosphine ([Bu
4p] [OH]), be stored in ethanolic solution, for subsequent use after concentration titrations; Second step, respectively at [Bu
4p] add the weak proton donors such as equimolar imidazoles, 1,2,4-triazole, benzimidazole or acetic acid in [OH] ethanolic solution.Then mixture is at room temperature stirred 24h.Subsequently, boil off except second alcohol and water at 60 DEG C of decompression backspins.The ionic liquid obtained is carried out vacuum drying 48h at 60 DEG C.
Embodiment 1, catalysis 2-methyl-3-butyne-2-alcohol hydration reaction generate 3-hydroxy-3-methyl-2-butanone
In the single port bottle of 250 milliliters, add 2-methyl-3-butyne-2-alcohol (8.41g, 0.1mol), H successively
2o (3.60g, 0.2mol) and formula I
a[Bu
4p] [Im] (97.89g, 0.3mol), use CO
2displacement air wherein; Then CO is kept
2pressure is at 0.1MPa, and at 80 DEG C, condensing reflux stirs 24 hours.After question response terminates, be interior mark with the tert-butyl alcohol, pass through
1h NMR quantitatively detects, and utilize conventional internal standard method to calculate, the productive rate obtaining 3-hydroxy-3-methyl-2-butanone is 90%.
Product is used
1h and
13c nuclear magnetic spectrogram determines its structure:
1H NMR(DMSO-d6,400MHz)δ5.21(s,1H),2.15(s,3H),1.17(s,6H)。
13C NMR(DMSO-d
6,100MHz)δ213.64,75.76,26.15,24.11。
As from the foregoing, this product structure is correct, is 3-hydroxy-3-methyl-2-butanone.
Embodiment 2, catalysis 2-methyl-3-butyne-2-alcohol hydration reaction generate 3-hydroxy-3-methyl-2-butanone
Adopt and the identical reaction condition of embodiment 1 and detection method, only by [Bu
4p] [Im] amount change 163.15g (0.5mol) into, the productive rate obtaining 3-hydroxy-3-methyl-2-butanone is 88%.
Embodiment 3, catalysis 2-methyl-3-butyne-2-alcohol hydration reaction generate 3-hydroxy-3-methyl-2-butanone
Adopt and the identical reaction condition of embodiment 1 and detection method, only by [Bu
4p] [Im] amount change 65.26g (0.2mol) into, CO
2gas pressure becomes 1MPa, and the reaction time becomes 24h, and the productive rate obtaining 3-hydroxy-3-methyl-2-butanone is 86%.
Embodiment 4, catalysis 2-methyl-3-butyne-2-alcohol hydration reaction generate 3-hydroxy-3-methyl-2-butanone
Adopt and the identical reaction condition of embodiment 1 and detection method, only by [Bu
4p] [Im] amount change 32.63g (0.1mol) into, CO
2gas pressure becomes 1MPa, and the reaction time becomes 40h, and the productive rate obtaining 3-hydroxy-3-methyl-2-butanone is 83%.
Embodiment 5, catalysis 2-methyl-3-butyne-2-alcohol hydration reaction generate 3-hydroxy-3-methyl-2-butanone
Adopt and the identical reaction condition of embodiment 1 and detection method, only ionic liquid is become [Bu
4p] [Triz], its amount is 98.19g (0.3mol), and the productive rate obtaining 3-hydroxy-3-methyl-2-butanone is 81%.
Embodiment 6, catalysis 2-methyl-3-butyne-2-alcohol hydration reaction generate 3-hydroxy-3-methyl-2-butanone
Adopt and the identical reaction condition of embodiment 1 and detection method, only ionic liquid is become [Bu
4p] [BenzTriz], its amount is 113.19g (0.3mol), CO
2gas pressure becomes 1MPa, and the reaction time becomes 48h, and the productive rate obtaining 3-hydroxy-3-methyl-2-butanone is 85%.
Embodiment 7, catalysis 2-methyl-3-butyne-2-alcohol hydration reaction generate 3-hydroxy-3-methyl-2-butanone
Adopt and the identical reaction condition of embodiment 1 and detection method, only ionic liquid is become [Bu
4p] [BenzIm], its amount is 112.89g (0.3mol), and the productive rate obtaining 3-hydroxy-3-methyl-2-butanone is 82%.
Embodiment 8, catalysis 2-methyl-3-butyne-2-alcohol hydration reaction generate 3-hydroxy-3-methyl-2-butanone
Adopt and the identical reaction condition of embodiment 1 and detection method, only ionic liquid is become [Bu
4p] [Ac], its amount is 95.48g (0.3mol), CO
2gas pressure becomes 1MPa, and the reaction time becomes 24h, and the productive rate obtaining 3-hydroxy-3-methyl-2-butanone is 85%.
Embodiment 9, catalysis 2-methyl-3-butyne-2-alcohol hydration reaction generate 3-hydroxy-3-methyl-2-butanone
Adopt and the identical reaction condition of embodiment 1 and detection method, only ionic liquid is become [Bu
4p] [Mi] and [Bu
4p] [Triz], its amount is respectively 48.94g (0.15mol) and 49.09g (0.15mol), and the productive rate obtaining 3-hydroxy-3-methyl-2-butanone is 84%.
Embodiment 10, catalysis methylpentynol hydration reaction generate 3-hydroxy-3-methyl-2 pentanone
Adopt and the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become methylpentynol, the reaction time becomes 48h, and the productive rate obtaining 3-hydroxy-3-methyl-2 pentanone is 91%.
Product is used
1h and
13c nuclear magnetic spectrogram determines its structure:
1H NMR(DMSO-d
6,400MHz)δ5.04(s,1H),2.13(s,3H),1.64-1.55(m,1H),1.51-1.42(m,1H),1.12(s,3H),0.76-0.73(t,3H)。
13C NMR(DMSO-d
6,100MHz)δ214.18,78.54,31.76,25.09,24.13,7.87。
As from the foregoing, this product structure is correct, is 3-hydroxy-3-methyl-2 pentanone.
Embodiment 11, catalysis 3,5-dimethyl-1-hexin-3-alcohol hydration reaction generate 3-hydroxyl-3,5-dimethyl-methyl-n-butyl ketone
Adopt and the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become 3,5-dimethyl-1-hexin-3-alcohol, the reaction time becomes 40h, and the productive rate obtaining 3-hydroxyl-3,5-dimethyl-methyl-n-butyl ketone is 60%.
Product is used
1h and
13c nuclear magnetic spectrogram determines its structure:
1H NMR(DMSO-d
6,400MHz)δ4.99(s,1H),2.16(s,3H),1.69-1.55(m,2H),1.43-1.39(q,1H),1.15(s,3H),0.88-0.86(d,2H),0.79-0.78(d,2H)。
13C NMR(DMSO-d
6,100MHz)δ214.27,78.46,25.91,25.05,24.21,23.67。
As from the foregoing, this product structure is correct, is 3-hydroxyl-3,5-dimethyl-methyl-n-butyl ketone.
Embodiment 12, catalysis 3,5-dimethyl-1-hexin-3-alcohol hydration reaction generate 3-hydroxyl-3,5-dimethyl-methyl-n-butyl ketone
Adopt and the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become 3,5-dimethyl-1-hexin-3-alcohol, CO
2gas pressure becomes 1MPa, and the productive rate obtaining 3-hydroxyl-3,5-dimethyl-methyl-n-butyl ketone is 86%.
Embodiment 13, catalysis 3-ethyl-1-pentyne-3-alcohol hydration reaction generate 3-ethyl-3-hydroxyl-2 pentanone
Adopt and the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become 3-ethyl-1-pentyne-3-alcohol, the productive rate obtaining 3-ethyl-3-hydroxyl-2 pentanone is 65%.
Product is used
1h and
13c nuclear magnetic spectrogram determines its structure:
1H NMR(DMSO-d
6,400MHz)δ4.77(s,1H),2.12(s,3H),1.65-1.59(m,2H),1.49-1.44(m,2H),0.74-0.70(t,6H)。
13C NMR(DMSO-d
6,100MHz)δ213.99,81.43,30.36,25.95,7.63。
As from the foregoing, this product structure is correct, is 3-ethyl-3-hydroxyl-2 pentanone.
Embodiment 14, catalysis 3-ethyl-1-pentyne-3-alcohol hydration reaction generate 3-ethyl-3-hydroxyl-2 pentanone
Adopt and the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become 3-ethyl-1-pentyne-3-alcohol, the reaction time becomes 48h, and the productive rate obtaining 3-ethyl-3-hydroxyl-2 pentanone is 90%.
Embodiment 15, catalysis 3-methyl isophthalic acid-n-heptylacetylene-3-alcohol hydration reaction generates 3-hydroxy-3-methyl-methyl n-heptyl ketone
Adopt and the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become 3-methyl isophthalic acid-n-heptylacetylene-3-alcohol, the reaction time becomes 40h, and the productive rate obtaining 3-hydroxy-3-methyl-methyl n-heptyl ketone is 50%.
Product is used
1h and
13c nuclear magnetic spectrogram determines its structure:
1H NMR(DMSO-d
6,400MHz)δ5.03(s,1H),2.13(s,3H),1.56-1.53(m,1H),1.43-1.42(m,1H),1.30-1.18(m,8H),1.13(s,3H),0.87-0.83(t,3H)。
13C NMR(DMSO-d
6,100MHz)δ214.03,78.21,39.11,31.14,29.07,24.98,24.60,22.99,21.98,13.88。
As from the foregoing, this product structure is correct, is 3-hydroxy-3-methyl-methyl n-heptyl ketone.
Embodiment 16, catalysis 3-methyl isophthalic acid-n-heptylacetylene-3-alcohol hydration reaction generates 3-hydroxy-3-methyl-methyl n-heptyl ketone
Adopt and the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become 3-methyl isophthalic acid-n-heptylacetylene-3-alcohol, CO
2gas pressure becomes 1MPa, and the reaction time becomes 40h, and the productive rate obtaining 3-hydroxy-3-methyl-methyl n-heptyl ketone is 90%.
Embodiment 17, catalysis 2-phenyl-3-butyne-2-alcohol hydration reaction generate 3-hydroxyl-3-Phenyl 2 butanone
Adopt and the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become 2-phenyl-3-butyne-2-alcohol, the reaction time becomes 40h, and the productive rate obtaining 3-hydroxyl-3-Phenyl 2 butanone is 68%.
Product is used
1h and
13c nuclear magnetic spectrogram determines its structure:
1H NMR(DMSO-d
6,400MHz)δ7.45-7.26(m,5H),6.04(s,1H),2.02(s,3H),1.52(s,3H)。
13C NMR(DMSO-d
6,100MHz)δ210.22,143.25,128.14,127.09,124.97,79.67,26.00,24.18。
As from the foregoing, this product structure is correct, is 3-hydroxyl-3-Phenyl 2 butanone.
Embodiment 18, catalysis 2-phenyl-3-butyne-2-alcohol hydration reaction generate 3-hydroxyl-3-Phenyl 2 butanone
Adopt and the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become 2-phenyl-3-butyne-2-alcohol, CO
2gas pressure becomes 1MPa, and the productive rate obtaining 3-hydroxyl-3-Phenyl 2 butanone is 90%.
Embodiment 19, catalysis 1-acetenyl-1-cyclohexanol hydration reaction generate 1-acetyl cyclohexanol
Adopt and the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become 1-acetenyl-1-cyclohexanol, CO
2gas pressure becomes 1MPa, and the reaction time becomes 48h, and the productive rate obtaining 1-acetyl cyclohexanol is 88%.
Product is used
1h and
13c nuclear magnetic spectrogram determines its structure:
1H NMR(DMSO-d
6,400MHz)δ5.05(s,1H),2.14(s,3H),1.58-1.40(m,9H),1.27-1.11(m,1H)。
13C NMR(DMSO-d
6,100MHz)δ214.07,76.84,32.84,25.03,24.38,20.79。
As from the foregoing, this product structure is correct, is 1-acetyl cyclohexanol.
Embodiment 20, catalysis 2-methyl 4-phenyl-3-butyne-2-alcohol hydration reaction generate 3-hydroxy-3-methyl-1-Phenyl 2 butanone
Adopt and the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become 2-methyl 4-phenyl-3-butyne-2-alcohol, CO
2gas pressure becomes 1MPa, and the reaction time becomes 48h, and the productive rate obtaining 3-hydroxy-3-methyl-1-Phenyl 2 butanone is 90%.
Product is used
1h and
13c nuclear magnetic spectrogram determines its structure:
1H NMR(DMSO-d
6,400MHz)δ7.99-7.96(t,2H),7.64-7.47(m,3H),3.10(s,2H),1.24(s,6H)。
13C NMR(DMSO-d
6,100MHz)δ199.64,137.94,132.82,128.44,128.35,69.12,50.31,29.74。
As from the foregoing, this product structure is correct, is 3-hydroxy-3-methyl-1-Phenyl 2 butanone.
Claims (7)
1. for a catalyst system and catalyzing for alkynol hydration reaction synthesis alpha-alcohol ketone, by formula I
a-I
eat least one in shown ionic liquid and CO
2composition, wherein, in described catalyst system and catalyzing, described formula I
a-I
etotal amount of substance of shown ionic liquid is 0.01-0.5mol, described CO
2the pressure of gas is 0.1-8MPa;
2. catalyst system and catalyzing according to claim 1, is characterized in that: described formula I
a-I
etotal amount of substance of shown ionic liquid is 0.3-0.5mol;
Described CO
2the pressure of gas is 0.1-1MPa.
3. utilize the catalyst system and catalyzing described in claim 1 or 2 to prepare a method for alpha-alcohol ketone, comprise the steps: under described catalyst system and catalyzing existent condition, by alkynol and H
2o carries out hydration reaction, prepares alpha-alcohol ketone.
4. method according to claim 3, is characterized in that: the mol ratio of described alkynol and described catalyst system and catalyzing intermediate ion liquid is 1:(0.1-5);
The mol ratio of described alkynes alcohol and water is (1:1)-(1:30).
5. the method according to claim 3 or 4, it is characterized in that: described alkynol is selected from following at least one: 2-methyl-3-butyne-2-alcohol, methylpentynol, 3-ethyl-1-pentyne-3-alcohol, 3,5-dimethyl-1-hexin-3-alcohol, 3-methyl isophthalic acid-n-heptylacetylene-3-alcohol, 2-phenyl-3-butyne-2-alcohol, 2-methyl 4-phenyl-3-butyne-2-alcohol and 1-acetenyl-1-cyclohexanol.
6. the method according to any one of claim 3-5, is characterized in that: the reaction temperature of described hydration reaction is 30-100 DEG C;
The reaction time of described hydration reaction is 1-48h, is specially 24-48h.
7. the method according to any one of claim 4-6; it is characterized in that: described alpha-alcohol ketone is selected from following at least one: 3-hydroxy-3-methyl-2-butanone, 3-hydroxy-3-methyl-2 pentanone, 3-ethyl-3-hydroxyl-2 pentanone, 3-hydroxyl-3,5-dimethyl-methyl-n-butyl ketone, 3-hydroxy-3-methyl-methyl n-heptyl ketone, 3-hydroxyl-3-Phenyl 2 butanone, 3-hydroxy-3-methyl-1-Phenyl 2 butanone and 1-acetyl cyclohexanol.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107670663A (en) * | 2017-08-30 | 2018-02-09 | 江南大学 | A kind of compound AuAgPd catalyst and preparation method hydrolyzed for alkynol with oxidation reaction |
| CN108218742A (en) * | 2017-12-11 | 2018-06-29 | 绍兴文理学院 | A kind of preparation method of ketoxime |
| CN111349137A (en) * | 2018-12-21 | 2020-06-30 | 北京启慧生物医药有限公司 | Green synthesis method of ulipristal acetate intermediate and ulipristal acetate |
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| CN100334056C (en) * | 2006-03-17 | 2007-08-29 | 浙江大学 | Production of unsaturated ketone |
| CN101412667B (en) * | 2008-11-06 | 2012-06-27 | 浙江工业大学 | Preparation of 2-pimelie kelone compound |
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2014
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107670663A (en) * | 2017-08-30 | 2018-02-09 | 江南大学 | A kind of compound AuAgPd catalyst and preparation method hydrolyzed for alkynol with oxidation reaction |
| CN107670663B (en) * | 2017-08-30 | 2020-07-03 | 江南大学 | Composite AuAgPd catalyst for alkynol hydrolysis and oxidation reaction and preparation method thereof |
| CN108218742A (en) * | 2017-12-11 | 2018-06-29 | 绍兴文理学院 | A kind of preparation method of ketoxime |
| CN111349137A (en) * | 2018-12-21 | 2020-06-30 | 北京启慧生物医药有限公司 | Green synthesis method of ulipristal acetate intermediate and ulipristal acetate |
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