CN106810519A - A kind of method for being catalyzed aldol reaction - Google Patents
A kind of method for being catalyzed aldol reaction Download PDFInfo
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- CN106810519A CN106810519A CN201510869477.8A CN201510869477A CN106810519A CN 106810519 A CN106810519 A CN 106810519A CN 201510869477 A CN201510869477 A CN 201510869477A CN 106810519 A CN106810519 A CN 106810519A
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- carbonyls
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
A kind of method for being catalyzed aldol reaction of the present invention, belongs to organic catalysis synthesis technical field.The method with metal halide as catalyst, the condensation reaction of catalysis of carbonyl compound under certain condition.Advantage of the present invention is：Metal halide is catalyzed the reaction system of aldol condensation under certain conditions, and the side reaction that base catalysis can be avoided to cause, applicable substrate spectrum is wider, the product yield high obtained by the reaction system, and catalyst, solvent can realize circulation.
Description
Technical field
The invention belongs to organic catalysis synthesis technical field, and in particular to a kind of method of catalysis aldol reaction.
Background technology
The platform chemicals of support chemical engineering industry are mainly obtained from petroleum resources at present, as oil etc. can not be again
A large amount of consumption in production-goods source, will constantly be improved with the cost that oil is leading chemical engineering industry.Excavation can be again
Production-goods source prepares Novel platform compound, is the important method for solving current resource and energy crisis, biomass
It is that a class reserves are big, distribution is wide, the renewable resource of low cost, will by raw material production of chemicals of biomass
Alleviate to a certain extent social development to the heavy dependence of fossil resource (Chem.Rev.2007,107,
2411–2502)。
5 hydroxymethyl furfural (5-HMF), furfural, 5 methyl furfural etc. are receive much concern in recent years new flat
Platform compound, can be dehydrated by monose and obtain (Science 2007,316,1597-1600；Catal.Sci.Technol.,
2015,5,4001；Ind.Eng.Chem.Res.2015,54,8368-8373).5 hydroxymethyl furfural, furfural,
5 methyl furfural etc. is free from the carbonyls of α-H, and aldol condensation occurs through with additional carbonyls
Reaction can prepare the chemical products and fuel (Chem.Rev.2011,111,397-417) of various more added values.
Catalysis aldol reaction majority is base catalysis at present, based on NaOH, also has alkalescence in addition
Metal oxide (Journal of Molecular Catalysis A:Chemical 2008,296,18–27；
Catalysis Today2014,223,138–147；Applied Catalysis B:Environmental2012,113–
114,201–211)。
However, when existing method is with NaOH as catalyst, high to equipment requirement, catalystic converter system is limited,
Solvent is water, is not suitable for that the solubility in water is small, not alkaline-resisting carbonyls.Example furfural is acted in highly basic
Lower generation Cannizzaro reaction, generates furfuryl alcohol and furancarboxylic acid.During with metal oxide as catalyst, catalytic efficiency
It is low, and catalyst stability is bad.
The content of the invention
Regarding to the issue above, the present invention proposes a kind of method for being catalyzed aldol condensation.
A kind of method for being catalyzed aldol reaction, follows the steps below：It is catalysis with metal halide
Agent, in a solvent catalysis of carbonyl class compound occur aldol reaction.
Specific reaction condition be for：The metal halide of catalytic amount is taken, is dissolved in solvent, be added thereto to
Feedstock carbonyl compound, reacts under certain condition, can obtain the condensation product of carbonyls；
The catalyst is 0.001~1 with the mol ratio of carbonyls：1；Reaction temperature is not less than 50 DEG C；
Reaction time is 0.1-24h；The concentration of carbonyls is 0.05~4mol.L-1。
The reaction temperature preferred scope is 100-180 DEG C.
The catalyst is 0.02~0.3 with the preferred scope of carbonyls mol ratio：1.
The preferred scope in the reaction time is 0.5-12h.
The preferred scope of the carbonyl compound concentration is 0.25~0.5mol.L-1。
The metal halide is vanadium trichloride, chromium chloride (II, III), iron chloride (II, III), copper chloride
(I, II), chromic bromide (II, III), bromination vanadium, ferric bromide (II, III) or copper bromide (I, II).
The preferred vanadium trichloride of metal halide, chromium chloride (II, III).
The carbonyls is a kind of A, or the carbonyls is two kinds, as A+B；
The A is the carbonyls of-H containing α,
The B is the carbonyls of-H containing α or without α-H carbonyls
Material combination is：The carbonyls of-the H containing α+be carbonylated without α-H the carbonyls ,-H containing α
Compound+another kind-H containing α carbonyls, or the carbonyls of-H containing the α condensation of itself.
When the raw material composition of condensation reaction is for two kinds of carbonyls, the molar ratio A/B of its composition is not low
In 0.03.
When the raw material composition of condensation reaction is for two kinds of carbonyls, the molar ratio A/B of its composition is preferred
Scope is 0.2-30.
It is described without α-H carbonyls be furfural, 5 hydroxymethyl furfural, 5 methyl furfural, benzaldehyde or
Its derivative.
The carbonyls of-the H containing α is acetaldehyde, acetone, butanone, hexanone, cyclohexanone or cyclopentanone.
The solvent of the reaction system includes ionic liquid and not ionic liquids class；Ionic liquid cation has miaow
Azole, pyridines, piperidines or quaternary ammonium ionic liquid；Not ionic liquids class solvent contains ethers, lipid,
Alkanes, alkyl halide hydro carbons or other organic solvents.
The ionic liquid is imidazole radicals with cation, and anion is based on halogen ionic liquid.
The ionic liquid, the best results when anion is chlorion.
The not ionic liquids type solvent is alcohols, ether, tetrahydrofuran, methyl tertiary butyl ether(MTBE), ethylene glycol
Dimethyl ether, butyl ether, ethyl acetate, methyl formate, petroleum ether, hexamethylene, dichloromethane, chloroform or four
Chlorination carbon.
Beneficial effects of the present invention are：A kind of new catalyst system and catalyzing of present invention report catalysis aldol reaction,
Catalyst is compatible good for solvent and raw material, and can obtain product yield higher.Additive, solvent
Equal reusable edible.
Brief description of the drawings
Fig. 1 condensation product C8 GC-MS testing result figures.
Fig. 2 condensation product C13 GC-MS testing result figures.
Fig. 3 condensation product C9 GC-MS testing result figures.
Specific embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not by real
The limitation of example is applied, if the person skilled in the art in the field makes one according to the invention described above content to the present invention
A little nonessential modifications and adaptations, still fall within protection scope of the present invention.
In addition, what deserves to be explained is, each group in resulting solution or extraction phase is crossed after pillar treatment in following embodiment
Divide the assay of thing to use gas chromatograph-mass spectrometer (GC-MS), its conversion ratio calculated according to the inventory of substrate,
The yield of condensation product.
Embodiment 1
Weighing 19.6mg catalyst vanadium trichlorides, 2g [BMIM] Cl, 200mg furfural, 600mg acetone,
2g glycol dimethyl ethers (GDE), are well mixed in 20mL autoclaves, and initial nitrogen is reacted in system
Pressure is 500psi, and temperature is 120 DEG C, and the reaction time is 12h.After reaction terminates, removed using silicagel column
Deionization liquid, or extracted with extractant, thick dark brown liquid is obtained after revolving solvent, it is that condensation is produced
Thing C8, C13, yield is respectively 46%, 44%.C8 structures are：C13 structures are:
Its GC-MS testing result figure such as Fig. 1, shown in Fig. 2.
Embodiment 2
Weigh 32.7mg vanadium trichlorides, 2g dichloromethane, 200mg furfurals, 600mg acetone, 300mg
TEAC, is well mixed in 20mL autoclaves, and it is 500psi, temperature that initial nitrogen pressure is reacted in system
It it is 120 DEG C, the reaction time is 12h.After reaction terminates, chloride is removed using silicagel column, remove solvent
Afterwards thick dark brown liquid, be C8, C13 products, yield is respectively 15%, 31%.
C8 structures are：C13 structures are:
Its GC-MS testing result figure such as Fig. 1, shown in Fig. 2.
Embodiment 3
Weigh 33.9mg CrCl3.6H2O, 2g [BMIM] Cl, 200mg furfural, 600mg acetone, 2g second
Glycol dimethyl ether, is well mixed in 20mL autoclaves, and it is 500psi that initial nitrogen pressure is reacted in system,
Temperature is 120 DEG C, and the reaction time is 12h.After reaction terminates, ionic liquid is removed using silicagel column, or
Person is extracted with extractant, and thick dark brown liquid is obtained after removal solvent, is C8, C13 products, yield point
Wei not 22%, 35%.
C8 structures are：C13 structures are:
Its GC-MS testing result figure such as Fig. 1, shown in Fig. 2.
Embodiment 4
Weighing 12.5mg vanadium trichlorides, 1.5g [BMIM] Cl, 100mg 5 hydroxymethyl furfural, 900mg acetone,
It is well mixed in 10mL autoclaves, temperature is 100 DEG C, and the reaction time is 12h.After reaction terminates,
Glycol dimethyl ether extraction product, thick dark brown liquid is obtained after removal solvent, is condensation product C9, is received
Rate is up to 50%.
C9 structures are：
Its GC-MS testing result figure is as shown in Figure 3.
Embodiment 5
Weigh 19.6mg catalyst vanadium trichlorides, 500mg [BMIM] Cl, 200mg furfural, 600mg third
Ketone, 570mg ethanol is well mixed in 20mL autoclaves, and it is 500 that initial nitrogen pressure is reacted in system
Psi, temperature is 140 DEG C, and the reaction time is 1.5h.After reaction terminates, ionic liquid is removed using silicagel column,
Or extracted with extractant, thick dark brown liquid is obtained after revolving solvent, it is condensation product C8, C13,
Yield is respectively 12%, 40%.C8 structures are：C13 structures are:
Its GC-MS testing result figure such as Fig. 1, shown in Fig. 2.
Embodiment 6
Weighing 6.5mg catalyst vanadium trichlorides, 5g [BMIM] Cl, 200mg furfural, 600mg acetone,
860mg ethanol, is well mixed in 20mL autoclaves, and it is 500psi that initial nitrogen pressure is reacted in system,
Temperature is 140 DEG C, and the reaction time is 3h.After reaction terminates, ionic liquid is removed using silicagel column, or
Extracted with extractant, thick dark brown liquid is obtained after revolving solvent, be condensation product C8, C13, yield
Respectively 36%, 27%.C8 structures are：C13 structures are:
Its GC-MS testing result figure such as Fig. 1, shown in Fig. 2.
Embodiment 7
Weighing 19.6mg catalyst vanadium trichlorides, 5g [BMIM] Cl, 200mg furfural, 600mg acetone,
570mg ethanol, is well mixed in 20mL autoclaves, and it is 500psi that initial nitrogen pressure is reacted in system,
Temperature is 180 DEG C, and the reaction time is 1h.After reaction terminates, ionic liquid is removed using silicagel column, or
Extracted with extractant, thick dark brown liquid is obtained after revolving solvent, be condensation product C8, C13, yield
Respectively 31%, 48%.
C8 structures are：C13 structures are:
Its GC-MS testing result figure such as Fig. 1, shown in Fig. 2.
Claims (16)
1. it is a kind of be catalyzed aldol reaction method, it is characterised in that follow the steps below：With metal halogen
Compound is catalyst, and catalysis of carbonyl class compound occurs aldol reaction in a solvent.
2. according to a kind of method of the catalysis aldol reaction described in claim 1, it is characterised in that specific anti-
Answer condition and be for：Take catalyst to be dissolved in solvent, be added thereto to feedstock carbonyl compound, in certain condition
Under react, can obtain the condensation product of carbonyls；
The catalyst is 0.001~1 with the mol ratio of carbonyls：1；Reaction temperature is not less than 50 DEG C；
Reaction time is 0.1~24h；The concentration of carbonyls is 0.05~4mol.L-1。
3. according to a kind of method of the catalysis aldol reaction described in claim 2, it is characterised in that：It is described
The preferred scope of reaction temperature is 100-180 DEG C.
4. according to a kind of method of the catalysis aldol reaction described in claim 2, it is characterised in that：It is described
Catalyst is 0.02~0.3 with the preferred scope of carbonyls mol ratio：1.
5. according to a kind of method of the catalysis aldol reaction described in claim 2, it is characterised in that：It is described
The preferred scope in reaction time is 0.5-12h.
6. according to a kind of method of the catalysis aldol reaction described in claim 2, it is characterised in that：It is described
The preferred scope of carbonyl compound concentration is 0.25~0.5mol.L-1。
7. according to a kind of method of the catalysis aldol reaction described in claim 1, it is characterised in that：It is described
Metal halide is vanadium chloride, chromium chloride (II, III), iron chloride (II, III), copper chloride (I, II), bromine
Change chromium (II, III), bromination vanadium, ferric bromide (II, III) or copper bromide (I, II).
8. according to a kind of method of the catalysis aldol reaction described in claim 1, it is characterised in that：It is described
The preferred vanadium trichloride of metal halide, chromium chloride (II, III).
9. according to a kind of method of the catalysis aldol reaction described in claim 1, it is characterised in that：Institute
Carbonyls is stated for a kind of A, or the carbonyls is two kinds, as A+B；
The A is the carbonyls of-H containing α,
The B is the carbonyls of-H containing α or without α-H carbonyls.
10. according to the system of a kind of new catalysis aldol reaction described in claim 9, it is characterised in that：
When the raw material composition of condensation reaction is for two kinds of carbonyls, the molar ratio A/B of its composition is not less than
0.03。
11. according to a kind of new system for being catalyzed aldol reaction described in claim 9, it is characterised in that：
When the raw material composition of condensation reaction is for two kinds of carbonyls, the molar ratio A/B preferred scopes of its composition
It is 0.2-30.
12. according to a kind of new system for being catalyzed aldol reaction described in claim 9, it is characterised in that：
It is described without α-H carbonyls be furfural, 5 hydroxymethyl furfural, 5 methyl furfural, benzaldehyde or
Its derivative.
The carbonyls of-the H containing α is acetaldehyde, acetone, butanone, hexanone, cyclohexanone or cyclopentanone.
13. according to a kind of catalysis aldol reaction described in claim 1 method, it is characterised in that：Instead
Answering the solvent of system includes ionic liquid and not ionic liquids class；Ionic liquid cation has imidazoles, pyridine
Class, piperidines or quaternary ammonium ionic liquid；Not ionic liquids class solvent contains ethers, lipid, alkanes, halogen
For alkanes or other organic solvents.
14. according to a kind of catalysis aldol reaction described in claim 13 method, it is characterised in that：From
The sub- preferred imidazole radicals of liquid cationic, the preferred halogen ionic liquid of anion.
15. according to a kind of catalysis aldol reaction described in claim 13 method, it is characterised in that：From
Sub- liquid, the best results when anion is chlorion.
16. according to a kind of catalysis aldol reaction described in claim 13 method, it is characterised in that：It is non-
Ion liquid type solvent is alcohols, ether, tetrahydrofuran, methyl tertiary butyl ether(MTBE), glycol dimethyl ether, fourth
Ether, ethyl acetate, methyl formate, petroleum ether, hexamethylene, dichloromethane, chloroform or carbon tetrachloride.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107935831A (en) * | 2017-12-06 | 2018-04-20 | 福州大学 | A kind of method of mantoquita catalysis aldol reaction |
| CN114044738A (en) * | 2021-11-24 | 2022-02-15 | 万华化学集团股份有限公司 | Method for preparing pentadiene aldehyde by aldol condensation |
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| WO2007099392A2 (en) * | 2005-09-27 | 2007-09-07 | Swiss Federal Institute Of Technology | Convergent synthesis of carbohydrate building blocks |
| CN102850309A (en) * | 2012-09-25 | 2013-01-02 | 湖南中烟工业有限责任公司 | Synthesis method of menthalactone |
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2015
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1302374A (en) * | 1969-07-15 | 1973-01-10 | ||
| US4501918A (en) * | 1982-04-26 | 1985-02-26 | International Flavors & Fragrances Inc. | Substituted methyl isopropyl oxocyclohexane derivatives, organoleptic uses thereof and process for preparing same |
| WO2007099392A2 (en) * | 2005-09-27 | 2007-09-07 | Swiss Federal Institute Of Technology | Convergent synthesis of carbohydrate building blocks |
| CN102850309A (en) * | 2012-09-25 | 2013-01-02 | 湖南中烟工业有限责任公司 | Synthesis method of menthalactone |
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| Title |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107935831A (en) * | 2017-12-06 | 2018-04-20 | 福州大学 | A kind of method of mantoquita catalysis aldol reaction |
| CN114044738A (en) * | 2021-11-24 | 2022-02-15 | 万华化学集团股份有限公司 | Method for preparing pentadiene aldehyde by aldol condensation |
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Application publication date: 20170609 |