CN104437621B - Catalyst system and catalyzing for alkynol hydration reaction synthesis alpha-alcohol ketone - Google Patents
Catalyst system and catalyzing for alkynol hydration reaction synthesis alpha-alcohol ketone Download PDFInfo
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Abstract
The invention discloses a kind of catalyst system and catalyzing for alkynol hydration reaction synthesis α hydroxy ketone compounds.This catalyst system and catalyzing is by ionic liquid and CO2Gas forms；Described ionic liquid is selected from following formula IaFormulas IeAt least one in shown ionic liquid, in described catalyst system and catalyzing, the amount of the material of described ionic liquid is 0.01 0.5mol, and the pressure of described gas is 0.1 8MPa；Present invention also offers a kind of method utilizing described catalyst system and catalyzing to prepare α hydroxy ketone compounds.This catalyst system and catalyzing is applicable to be catalyzed the reaction system of alkynol hydration reaction synthesis α hydroxy ketone compounds；This catalyst system and catalyzing has higher catalysis activity, and reaction condition is gentle, participates in without metal；Major catalyst ionic liquid is readily synthesized and reclaims, and has stronger using value.
Description
Technical field
The invention belongs to catalyst field, be specifically related to a kind of catalytic body for alkynol hydration reaction synthesis alpha-alcohol ketone
System.
Background technology
Alpha-hydroxy ketones is a very important organic compound of class, and it is widely present in bioactive compound
With (Y.F.Liang, N.Jiao, Angew.Chem.Int.Ed.2014,53,548) among the molecular skeleton of synthetic drug；
Therefore, development efficiently synthesizes the method for alpha-hydroxy ketones and catalyst system and catalyzing is significant.
Alkynol hydration reaction is the method for the synthesis alpha-hydroxy ketones that a kind of simple, Atom economy is good,
Meet the requirement of Green Chemistry and sustainable development.Various metals catalyst is had been developed at present, such as platinum (Pt), gold
(Au), silver (Ag) etc. replace traditional poisonous hydrargyrum (Hg) catalyst system and catalyzing, for the synthesis of alkynol hydration reaction
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 typically requires strong acid or highly basic and organic ligand
Deng, and the side reactions such as Meyer-Schuster and Rupe rearrangement can occur.Therefore, development gentleness, green high-efficient,
Catalyst system and catalyzing without metal remains the core of this repercussion study.
Summary of the invention
It is an object of the invention 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 CO2Gas forms；Described ionic liquid is selected from following formula
Ia-Formulas IeAt least one in shown ionic liquid, in described catalyst system and catalyzing, the amount of the material of described ionic liquid is
0.01-0.5mol, the pressure of described gas is 0.1-8MPa.
In above-mentioned catalyst system and catalyzing, the amount of the material of described ionic liquid can be 0.3-0.5mol further, most preferably 0.3
mol。
The pressure of described gas can be 0.1-1MPa further, most preferably 0.1 or 1MPa.
In above-mentioned catalyst system and catalyzing, described Formulas Ia-IeShown ionic liquid plays major catalyst and molten in whole catalyst system and catalyzing
The effect of agent.Described CO2Gas plays the effect of promoter.
Further object is that above-mentioned catalyst system and catalyzing is used for alkynol and synthesizes α-hydroxyl by hydration reaction by offer
The method of base ketone compounds, comprises the steps: under conditions of described catalyst system and catalyzing exists, by alkynol and H2O
Carry out hydration reaction, prepare alpha-hydroxy ketones.
In said method, described alkynol is 1:(0.1-5 with the mol ratio of described catalyst system and catalyzing intermediate ion liquid), enter one
Step can be 1:(3-5), most preferably 1:3.
The mol ratio of described alkynes alcohol and water is (1:1)-(1:30), preferably 1:2.
Described alkynol 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-Hexalin.
The reaction temperature of described hydration reaction is 30-100 DEG C, preferably 80 DEG C.
The response time of described hydration reaction is 1-48h, concretely 24-48h, preferably 24h or 48h.
Described alpha-hydroxy ketones 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 catalysis activity, and it has been reported that (H.T.He, C.R.Qi, X.
H.Hu, Y.Q.Guan, H.F.Jiang, Green chem., 2014,16,3729) optimum catalyst system and catalyzing catalysis alkynol obtains
Suitable to the productivity of alpha-hydroxy ketones, but reaction condition more green, gentle (< 100 DEG C), without metal participation；
Major catalyst ionic liquid is readily synthesized and reclaims；This catalyst system and catalyzing is widely applicable, can be used for the synthesis of alkynol hydration reaction
Alpha-hydroxy ketones, has stronger using value.
Detailed description of the invention
Below in conjunction with specific embodiment, the method for the present invention is illustrated, but the invention is not limited in this, all at this
Any amendment, equivalent and the improvement etc. made within the spirit of invention and principle, should be included in the guarantor of the present invention
Within the scope of protecting.
Experimental technique described in following embodiment, if no special instructions, is conventional method；Described reagent and material,
If no special instructions, the most commercially obtain.
Ionic-liquid catalyst used in the present invention, except [Bu4P] outside [BenzTriz] can be bought by commercial sources, its
Remaining ionic liquid all can be prepared according to the method that following document provides: C.M.Wang, et al；Angew.Chem.
Int.Ed.2011,50,4918。
Concrete preparation method is as follows: first with anion exchange resin, by tetrabutyl phosphonium bromide phosphine ([Bu4P] [Br]) hand over
It is changed to tetrabutylammonium hydroxide phosphine ([Bu4P] [OH]), it is stored in ethanol solution, standby after concentration titrations；Second
Step, respectively at [Bu4P] [OH] ethanol solution adds equimolar imidazoles, 1,2,4-triazole, benzimidazole or acetic acid
Etc. weak proton donor.Then mixture is stirred at room temperature 24h.Subsequently, boil off except ethanol at 60 DEG C of decompression backspins
And water.Carry out the ionic liquid obtained at 60 DEG C being vacuum dried 48h.
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, it is sequentially added into 2-methyl-3-butyne-2-alcohol (8.41g, 0.1mol), H2O(3.60
G, 0.2mol) and Formulas Ia[Bu4P] [Im] (97.89g, 0.3mol), use CO2Replace air therein；Then keep
CO2Pressure is at 0.1MPa, and at 80 DEG C, condensing reflux stirs 24 hours.After question response terminates, with the tert-butyl alcohol as internal standard,
Pass through1H NMR detection by quantitative, utilizes conventional internal standard method to calculate, obtains the product of 3-hydroxy-3-methyl-2-butanone
Rate is 90%.
Product is used1H and13C 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-d6,100MHz)δ213.64,75.76,26.15,24.11。
From the foregoing, it will be observed that this product structure is correct, for 3-hydroxy-3-methyl-2-butanone.
Embodiment 2, catalysis 2-methyl-3-butyne-2-alcohol hydration reaction generate 3-hydroxy-3-methyl-2-butanone
Use and the identical reaction condition of embodiment 1 and detection method, only by [Bu4P] [Im] amount change 163.15g into
(0.5mol) productivity, 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
Use and the identical reaction condition of embodiment 1 and detection method, only by [Bu4P] [Im] amount change 65.26g into
(0.2mol), CO2Gas pressure becomes 1MPa, and the response time becomes 24h, obtains 3-hydroxy-3-methyl-2-fourth
The productivity of ketone is 86%.
Embodiment 4, catalysis 2-methyl-3-butyne-2-alcohol hydration reaction generate 3-hydroxy-3-methyl-2-butanone
Use and the identical reaction condition of embodiment 1 and detection method, only by [Bu4P] [Im] amount change 32.63g into
(0.1mol), CO2Gas pressure becomes 1MPa, and the response time becomes 40h, obtains 3-hydroxy-3-methyl-2-fourth
The productivity of ketone is 83%.
Embodiment 5, catalysis 2-methyl-3-butyne-2-alcohol hydration reaction generate 3-hydroxy-3-methyl-2-butanone
Use and the identical reaction condition of embodiment 1 and detection method, only ionic liquid is become
[Bu4P] [Triz], in an amount of from 98.19g (0.3mol), the productivity 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
Use and the identical reaction condition of embodiment 1 and detection method, only ionic liquid is become
[Bu4P] [BenzTriz], in an amount of from 113.19g (0.3mol), CO2Gas pressure becomes 1MPa, and the response time becomes
For 48h, the productivity 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
Use and the identical reaction condition of embodiment 1 and detection method, only ionic liquid is become
[Bu4P] [BenzIm], in an amount of from 112.89g (0.3mol), the productivity 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
Use and the identical reaction condition of embodiment 1 and detection method, only ionic liquid is become [Bu4P] [Ac],
In an amount of from 95.48g (0.3mol), CO2Gas pressure becomes 1MPa, and the response time becomes 24h, obtains 3-hydroxyl
The productivity of base-3-methyl-2-butanone is 85%.
Embodiment 9, catalysis 2-methyl-3-butyne-2-alcohol hydration reaction generate 3-hydroxy-3-methyl-2-butanone
Use and the identical reaction condition of embodiment 1 and detection method, only ionic liquid is become [Bu4P][Mi]
[Bu4P] [Triz], its amount is respectively 48.94g (0.15mol) and 49.09g (0.15mol), obtains 3-hydroxyl-3-
The productivity of methyl-2-butanone is 84%.
Embodiment 10, catalysis methylpentynol hydration reaction generate 3-hydroxy-3-methyl-2 pentanone
Use with the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become 3-methyl isophthalic acid-
Pentyne-3-alcohol, the response time becomes 48h, and the productivity obtaining 3-hydroxy-3-methyl-2 pentanone is 91%.
Product is used1H and13C nuclear magnetic spectrogram determines its structure:
1H NMR(DMSO-d6,400MHz)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-d6,100MHz)δ214.18,78.54,31.76,25.09,24.13,7.87。
From the foregoing, it will be observed that this product structure is correct, for 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
Use and the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become 3,5-dimethyl
-1-hexin-3-alcohol, the response time becomes 40h, obtains 3-hydroxyl-3, and the productivity of 5-dimethyl-methyl-n-butyl ketone is 60%.
Product is used1H and13C nuclear magnetic spectrogram determines its structure:
1H NMR(DMSO-d6,400MHz)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-d6,100MHz)δ214.27,78.46,25.91,25.05,24.21,23.67。
From the foregoing, it will be observed that this product structure is correct, for 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
Use and the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become 3,5-dimethyl
-1-hexin-3-alcohol, CO2Gas pressure becomes 1MPa, obtains 3-hydroxyl-3, and the productivity of 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
Use and the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become 3-ethyl-1-
Pentyne-3-alcohol, the productivity obtaining 3-ethyl-3-hydroxyl-2 pentanone is 65%.
Product is used1H and13C nuclear magnetic spectrogram determines its structure:
1H NMR(DMSO-d6,400MHz)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-d6,100MHz)δ213.99,81.43,30.36,25.95,7.63。
From the foregoing, it will be observed that this product structure is correct, for 3-ethyl-3-hydroxyl-2 pentanone.
Embodiment 14, catalysis 3-ethyl-1-pentyne-3-alcohol hydration reaction generate 3-ethyl-3-hydroxyl-2 pentanone
Use and the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become 3-ethyl-1-
Pentyne-3-alcohol, the response time becomes 48h, and the productivity obtaining 3-ethyl-3-hydroxyl-2 pentanone is 90%.
Embodiment 15, catalysis 3-methyl isophthalic acid-n-heptylacetylene-3-alcohol hydration reaction generate 3-hydroxy-3-methyl-methyl n-heptyl ketone
Use with the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become 3-methyl isophthalic acid-
N-heptylacetylene-3-alcohol, the response time becomes 40h, and the productivity obtaining 3-hydroxy-3-methyl-methyl n-heptyl ketone is 50%.
Product is used1H and13C nuclear magnetic spectrogram determines its structure:
1H NMR(DMSO-d6,400MHz)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-d6,100MHz)δ214.03,78.21,39.11,31.14,29.07,24.98,24.60,
22.99,21.98,13.88。
From the foregoing, it will be observed that this product structure is correct, for 3-hydroxy-3-methyl-methyl n-heptyl ketone.
Embodiment 16, catalysis 3-methyl isophthalic acid-n-heptylacetylene-3-alcohol hydration reaction generate 3-hydroxy-3-methyl-methyl n-heptyl ketone
Use with the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become 3-methyl isophthalic acid-
N-heptylacetylene-3-alcohol, CO2Gas pressure becomes 1MPa, and the response time becomes 40h, obtains 3-hydroxy-3-methyl-methyl n-heptyl ketone
Productivity be 90%.
Embodiment 17, catalysis 2-phenyl-3-butyne-2-alcohol hydration reaction generate 3-hydroxyl-3-Phenyl 2 butanone
Use and the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become 2-phenyl-3-
Butyne-2-alcohol, the response time becomes 40h, and the productivity obtaining 3-hydroxyl-3-Phenyl 2 butanone is 68%.
Product is used1H and13C nuclear magnetic spectrogram determines its structure:
1H NMR(DMSO-d6,400MHz)δ7.45-7.26(m,5H),6.04(s,1H),2.02(s,3H),1.52(s,
3H)。
13C NMR(DMSO-d6,100MHz)δ210.22,143.25,128.14,127.09,124.97,79.67,
26.00,24.18。
From the foregoing, it will be observed that this product structure is correct, for 3-hydroxyl-3-Phenyl 2 butanone.
Embodiment 18, catalysis 2-phenyl-3-butyne-2-alcohol hydration reaction generate 3-hydroxyl-3-Phenyl 2 butanone
Use and the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become 2-phenyl-3-
Butyne-2-alcohol, CO2Gas pressure becomes 1MPa, and the productivity obtaining 3-hydroxyl-3-Phenyl 2 butanone is 90%.
Embodiment 19, catalysis 1-acetenyl-1-Hexalin hydration reaction generate 1-acetyl cyclohexanol
Use and the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become 1-acetenyl-1-
Hexalin, CO2Gas pressure becomes 1MPa, and the response time becomes 48h, obtains the productivity of 1-acetyl cyclohexanol
It is 88%.
Product is used1H and13C nuclear magnetic spectrogram determines its structure:
1H NMR(DMSO-d6,400MHz)δ5.05(s,1H),2.14(s,3H),1.58-1.40(m,9H),
1.27-1.11(m,1H)。
13C NMR(DMSO-d6,100MHz)δ214.07,76.84,32.84,25.03,24.38,20.79。
From the foregoing, it will be observed that this product structure is correct, for 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
Use and the identical reaction condition of embodiment 1 and detection method, only reaction substrate is become 2-methyl-4-
Phenyl-3-butyne-2-alcohol, CO2Gas pressure becomes 1MPa, and the response time becomes 48h, obtains 3-hydroxy-3-methyl
The productivity of-1-Phenyl 2 butanone is 90%.
Product is used1H and13C nuclear magnetic spectrogram determines its structure:
1H NMR(DMSO-d6,400MHz)δ7.99-7.96(t,2H),7.64-7.47(m,3H),3.10(s,2H),
1.24(s,6H)。
13C NMR(DMSO-d6,100MHz)δ199.64,137.94,132.82,128.44,128.35,69.12,
50.31,29.74。
From the foregoing, it will be observed that this product structure is correct, for 3-hydroxy-3-methyl-1-Phenyl 2 butanone.
Claims (8)
1. for a catalyst system and catalyzing for alkynol hydration reaction synthesis alpha-alcohol ketone, by Formulas Ia-IeShown ionic liquid
At least one in body and CO2Gas forms, wherein, in described catalyst system and catalyzing, and described Formulas Ia-IeShown ion
The amount of total material of liquid is 0.01-0.5mol, described CO2The pressure of gas is 0.1-8MPa；
Catalyst system and catalyzing the most according to claim 1, it is characterised in that: described Formulas Ia-IeShown ionic liquid
The amount of total material of body is 0.3-0.5mol；
Described CO2The pressure of gas is 0.1-1MPa.
3. utilize the method that the catalyst system and catalyzing described in claim 1 or 2 prepares alpha-alcohol ketone, including as follows
Step: under conditions of described catalyst system and catalyzing exists, by alkynol and H2O carries out hydration reaction, prepare α-
Hydroxy-ketone.
Method the most according to claim 3, it is characterised in that: in described alkynol and described catalyst system and catalyzing from
The mol ratio of sub-liquid is 1:(0.1-5)；
The mol ratio of described alkynes alcohol and water is (1:1)-(1:30).
5. according to the method described in claim 3 or 4, it is characterised in that: described alkynol is selected from following at least one
Kind: 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-Hexalin.
6. according to the method described in claim 3 or 4, it is characterised in that: the reaction temperature of described hydration reaction
For 30-100 DEG C；
The response time of described hydration reaction is 1-48h.
Method the most according to claim 6, it is characterised in that: the response time of described hydration reaction is 24
-48h。
Method the most according to claim 4, it is characterised in that: described alpha-alcohol ketone is selected from following at least one
Kind: 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-benzene
Base-2-butanone and 1-acetyl cyclohexanol.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN101412667A (en) * | 2008-11-06 | 2009-04-22 | 浙江工业大学 | Preparation of 2-pimelie kelone compound |
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| CN1817841A (en) * | 2006-03-17 | 2006-08-16 | 浙江大学 | Production of unsaturated ketone |
| CN101412667A (en) * | 2008-11-06 | 2009-04-22 | 浙江工业大学 | Preparation of 2-pimelie kelone compound |
Non-Patent Citations (1)
| Title |
|---|
| Efficient synthesis of tertiary α-hydroxy ketones through CO2-promoted regioselective hydration of propargylic alcohols;Haitao He,et al;《Green Chemistry》;20140605;第16卷(第8期);第3729-3733页 * |
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