CN107176898A - A kind of method that aldehyde ketone is prepared as catalyst efficient catalytic molecular oxygen oxidation alcohol using houghite - Google Patents
A kind of method that aldehyde ketone is prepared as catalyst efficient catalytic molecular oxygen oxidation alcohol using houghite Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/46—Oxygen atoms
- C07D213/48—Aldehydo radicals
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen 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
The invention belongs to liquid phase catalytic oxidation technical field, there is provided a kind of method for preparing aldehyde ketone as catalyst efficient catalytic molecular oxygen oxidation alcohol using houghite.The catalyst is represented by An–‑NixM‑LDHs(An–=OH–、CO3 2–、CH3COO–And PO4 3–；M=Ga or In；Ni/M=(2~4) ︰ 1).In the presence of the catalyst, without any auxiliary agent, group compounds of aldehydes and ketones is prepared in the aerobic oxidation reaction that alcohol is carried out under temperate condition.Hydrotalcite-like materials in the present invention can be synthesized largely, and recoverable；The method has the selectivity and high income of aldehyde ketone, reaction condition is gentle, cost is low, be easy to industrialization the advantages of.
Description
Technical field
The invention belongs to liquid phase catalytic oxidation field, and in particular to one kind is using houghite as catalyst efficient catalytic molecule
The method that oxygen oxidation alcohol prepares aldehyde ketone.
Technical background
Aldehyde and ketone are important chemical intermediates, are widely used in the synthesis and production of medicine, dyestuff and agricultural chemicals.By
Alcohol direct oxidation is to prepare one of important method of aldehyde compound, and traditional alcohol oxidation, which prepares aldehyde and the method for ketone, generally to be made
Use a large amount of oxidants, such as manganese dioxide, chromium oxide and periodate.Easily make aldehyde product using the oxidant of metering in industry
Generation over oxidation, the selectivity of reaction is often relatively low, and these metal oxide toxicity are big, produce a large amount of solid wastes
Thing, pollution weight, it is difficult to large-scale application.From gentle oxidant, such as oxygen or air, it is using the method for catalysis oxidation
Solve the important method of this problem.Although efficiently synthesizing for aldehyde ketone can be realized using homogeneous catalysis systems such as Fe/TEMPO,
It is that the additive in these homogeneous catalysts and course of reaction makes the separating-purifying of product become complicated.At present, it is a variety of heterogeneous
Catalyst system and catalyzing, Pd, Pt, Au and Ru catalyst of such as load is developed to the efficient oxidation of alcohol, but these are based on expensive
The catalyst system and catalyzing of metal often limits its extensive commercial Application.Advantage of the non-precious metal catalyst in cost makes it more
It is with potential applications.At present, potassium manganese ore octahedron molecular screen (OMS-2) (Makwana, V.D.；et al.J.Catal.2002,
210,46-52), MnGa oxides (Amini, M.；et al.J.Mol. Catal.A:Chem.2014,394,303-308) and
NiAl houghites (Choudhary, B.M.；et al.Angew.Chem.Int.Ed.Engl. 2001,40,763–
766.Kawabata,T.；et al.J.Mol.Catal.A:Chem.2005,236,206-215) etc. heterogeneous catalysis by
For this reaction, but the conversion ratio of reaction and selectivity are low, and reaction efficiency still has much room for improvement.
Therefore, based on the efficient catalyst system and catalyzing of developing material cheap and easy to get, the height for realizing the alcohol under temperate condition
Effect oxidation has huge application potential.It is contemplated that exploitation one kind is using houghite as catalyst efficient catalytic molecular oxygen
The method that oxidation alcohol prepares aldehyde ketone.
The content of the invention
It is an object of the invention to develop one kind by catalyst efficient catalytic molecular oxygen oxidation alcohol of houghite to prepare aldehyde
The method of ketone.The method has the features such as energy consumption is low, pollution is small, reaction is efficient, operation is simple.
Catalytic oxidation comprises the following steps：Under liquid-phase condition, in organic solvent, using houghite as catalyst,
Oxygen-containing gas is oxidant, and carrying out oxidation reaction to alcohol is made one or both of aldehyde and ketone；Reaction temperature is 20~80
DEG C, the reaction time is 0.5~12 hour.Reaction equation is：
Wherein, R1It is phenyl, substituted aryl, substituted alkenyl or alkyl；R2It is H, phenyl, substituted aryl or alkyl；
In the reaction of the present invention, the houghite catalyst is represented by：An–-NixM-LDHs(An–=OH–、CO3 2–、
CH3COO–Or PO4 3–；M=Ga or In；Ni/M=(2~4) ︰ 1)；
In the reaction of the present invention, reaction substrate and Ni in catalyst molar ratio are 5~50；
In the reaction of the present invention, the solvent of reaction is mesitylene, toluene, acetonitrile, dioxane and normal octane；
The present invention has the following advantages that and effect relative to prior art：
(1) method provided by the present invention for preparing aldehyde ketone for alcohol oxidation, using heterogeneous catalysis system, in gentle bar
Alcohol can be achieved under part and efficiently aoxidize generation aldehydes or ketones class compound.Solve catalyst activity under temperate condition it is low and need
The problem of adding various auxiliary agents.
(2) catalytic reaction method of the present invention has good substrate applicability, can be reacted with the various alcohol of efficient catalytic
Generate corresponding aldehyde and ketone compounds.
Brief description of the drawings
Catalyst OH–-Ni3The structure of Ga-LDH samples is illustrated by Fig. 1 and Fig. 2.Fig. 1 OH–-Ni3Ga-LDH samples
XRD；Fig. 2 OH–-Ni3The SEM figures of Ga-LDH samples.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
The catalyst A of the present invention that aldehydes or ketones class compound is prepared for alcohol oxidationn–-NixM-LDHs, can be according to as follows
It is prepared by embodiment 1~3：
Embodiment 1
0.16mol/L Nickelous nitrate hexahydrate and 0.08mol/L gallium nitrate mixing salt solution 200mL are prepared, it is another to prepare
0.2mol/L sodium hydroxide and 0.2mol/L ammoniacal liquor mixed ammonium/alkali solutions mixed ammonium/alkali solutions 200mL.In N2Under protection, in 25 DEG C
Down while the above-mentioned two kinds of mixed solutions prepared are slowly added dropwise into 100mL water.During dropwise addition, it is stirred vigorously, and controls
The pH value of system is maintained in the range of 10.0 ± 0.2, continues to stir after being added dropwise to complete after 6h with being aged 12h at 70 DEG C, taking out
Filter, is washed with deionized to neutrality, in 70 DEG C of dry 24h, is ground into powder.Obtain OH–-Ni2Ga-LDH samples.
Embodiment 2
0.16mol/L Nickelous nitrate hexahydrate and 0.08mol/L gallium nitrate mixing salt solution 200mL are prepared, it is another to prepare
0.2mol/L sodium hydroxide and 0.04mol/L sodium carbonate mixed ammonium/alkali solutions 200mL.Under the conditions of 25 DEG C, at the same it is slow to
The above-mentioned two kinds of mixed solutions prepared are added dropwise in 100mL water.During dropwise addition, it is stirred vigorously, and the pH value dimension of control system
Hold in the range of 10.0 ± 0.2, continue to stir after 6h and in being aged 12h at 70 DEG C after being added dropwise to complete, suction filtration uses deionized water
Washing, in 70 DEG C of dry 24h, is ground into powder to neutrality.Obtain CO3 2–-Ni2Ga-LDH samples.
Embodiment 3
0.16mol/L Nickelous nitrate hexahydrate and 0.08mol/L indium nitrate mixing salt solution 200mL are prepared, it is another to prepare
0.2mol/L sodium hydroxide and 0.04mol/L sodium carbonate mixed ammonium/alkali solutions 200mL.Under the conditions of 25 DEG C, at the same it is slow to
The above-mentioned two kinds of mixed solutions prepared are added dropwise in 100mL water.During dropwise addition, it is stirred vigorously, and the pH value dimension of control system
Hold in the range of 9.5~10.0, continue to stir after 6h and in being aged 12h at 70 DEG C after being added dropwise to complete, suction filtration uses deionized water
Washing, in 70 DEG C of dry 24h, is ground into powder to neutrality.Obtain CO3 2–-Ni2In-LDH samples.
The method of the present invention for preparing aldehyde ketone as catalyst alcohol molecular oxygen oxidation using houghite can be by reality
Example 4~10 is applied to illustrate：
The catalytic activity of the different catalyst of houghite containing Ni of embodiment 4
Typical reaction step is as follows：By 0.108g (1mmol) phenmethylol, a certain amount of catalyst is (in phenmethylol and catalyst
Ni molar ratio is 10), mesitylene 5mL is added in reactor, is passed through oxygen, synthesis under normal pressure, 60 DEG C of stirring reactions
5h.Removing solid catalyst is separated by filtration, analyzing benzaldehyde in liquid using gas chromatogram fixative (chlorobenzene makees internal standard) contains
Amount, calculated yield is 83%.
Reaction result is shown in Table 1.
The catalytic reaction result of the inhomogeneity hydrotalcite catalyst of table 1
| Sequence number | Catalyst | Reaction time/h | Conversion ratio/% | Selectivity/% |
| 1 | CO3 2–-Ni2Ga-LDH | 5 | 62 | 100 |
| 2 | OH–-Ni2Ga-LDH | 5 | 82 | 100 |
| 3 | OH–-Ni3Ga-LDH | 5 | 98 | 100 |
| 4 | OH–-Ni4Ga-LDH | 5 | 90 | 100 |
| 5 | CO3 2–-Ni2In-LDH | 5 | 72 | 100 |
| 6 | OH–-Ni2In-LDH | 5 | 81 | 100 |
| 7 | OH–-Ni3In-LDH | 5 | 86 | 100 |
| 8 (comparing results) | CO3 2–-Ni2Al-LDH | 8 | 26 | 100 |
| 9 (comparing results) | CO3 2–-Ni2Fe-LDH | 8 | 38 | 100 |
From table 1, in atmospheric conditions, NiGa and NiIn houghites aoxidize the anti-of alcohol aldehyde ketone in catalytic molecular oxygen
There is excellent catalytic activity in answering.With OH–-Ni3When Ga-LDH is catalyst, the conversion ratio of phenmethylol reaches in 5h
98%, the selectivity of benzaldehyde is 100%.Compared with comparing result, catalyst system and catalyzing of the invention has a clear superiority.
Embodiment 5
By 0.108g (1mmol) phenmethylol, OH–-Ni3Ga-LDH 2.8mg (the molar ratios of phenmethylol and Ni in catalyst
For 50), mesitylene 5mL is added in reactor, oxygen, synthesis under normal pressure, 60 DEG C of stirring reaction 5h are passed through.It is separated by filtration and removes
Solid catalyst is removed, the content of benzaldehyde in liquid is analyzed using gas chromatogram fixative (chlorobenzene makees internal standard), calculated yield is
58%.
Embodiment 6
By 0.108g (1mmol) phenmethylol, OH–-Ni3Ga-LDH 28mg (the molar ratios of phenmethylol and Ni in catalyst
For 5), mesitylene 5mL is added in reactor, oxygen, synthesis under normal pressure, 60 DEG C of stirring reaction 2h are passed through.It is separated by filtration removing
Solid catalyst, the content of benzaldehyde in liquid is analyzed using gas chromatogram fixative (chlorobenzene makees internal standard), and calculated yield is
100%.
Embodiment 7
By 0.108g (1mmol) phenmethylol, OH–-Ni3Ga-LDH 14mg, normal octane 5mL is added in reactor, is passed through
Oxygen, synthesis under normal pressure, 60 DEG C of stirring reaction 5h.Removing solid catalyst is separated by filtration, using gas chromatogram fixative (chlorobenzene
Make internal standard) analysis liquid in benzaldehyde content, calculated yield is 91%.
Application of the method for embodiment 8 in other alcohol aoxidize aldehyde ketone reaction processed
Typical reaction step is as follows：The raw alcohol that reactant shown in 1mmol tables 2 is arranged, OH–-Ni3In-LDH 14mg,
Mesitylene 5mL is added in reactor, is passed through oxygen, synthesis under normal pressure, 60 DEG C of stirring reaction certain times.It is separated by filtration and removes
Solid catalyst is removed, the content of product in liquid, calculated yield are analyzed using gas chromatogram fixative (chlorobenzene makees internal standard).
It the results are shown in Table 2.
The oxidation reaction result of the differential responses substrate alcohol of table 2
Continued
Above example is merely to illustrate present disclosure, in addition, and the present invention also has other embodiment.But it is all
The technical scheme formed using equivalent substitution or equivalent deformation mode is all fallen within protection scope of the present invention.
Claims (4)
1. a kind of method that aldehyde ketone is prepared as catalyst efficient catalytic molecular oxygen oxidation alcohol using houghite, catalytic oxidation bag
Include following steps：Under liquid-phase condition, in organic solvent, using houghite as catalyst, oxygen-containing gas is oxidant, and alcohol is entered
Aldehyde or ketone is made in row oxidation reaction；Reaction temperature is 20~80 DEG C, and the reaction time is 0.5~12h, and reaction equation is：
Wherein, R1It is phenyl, substituted aryl, substituted alkenyl or alkyl；R2It is H, phenyl, substituted aryl or alkyl.
2. in accordance with the method for claim 1, it is characterised in that：The houghite catalyst is represented by：An–-NixM-
LDHs(An–=OH–, CO3 2–, CH3COO–Or PO4 3–；M=Ga or In；Ni/M=(2~4) ︰ 1).
3. in accordance with the method for claim 1, it is characterised in that：In reaction substrate and catalyst Ni molar ratio for 5~
50。
4. in accordance with the method for claim 1, it is characterised in that：The solvent of reaction is mesitylene, toluene, acetonitrile, dioxy
Six rings or normal octane.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836315A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of catalysis preparation method of veratraldehyde |
| CN111701608A (en) * | 2020-07-09 | 2020-09-25 | 中国科学院过程工程研究所 | Method for preparing vanadium-phosphorus-oxygen catalyst with assistance of hydrotalcite |
| CN114426467A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing glutaraldehyde based on heterogeneous catalysis technology |
| CN114684873A (en) * | 2022-05-10 | 2022-07-01 | 合肥工业大学 | Nickel-indium layered double-metal hydroxide nanosheet catalyst and preparation method and application thereof |
| CN114920645A (en) * | 2022-05-09 | 2022-08-19 | 常州大学 | Synthetic method of alpha-methoxy methyl acetate derivative |
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2017
- 2017-04-27 CN CN201710288268.3A patent/CN107176898A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836315A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of catalysis preparation method of veratraldehyde |
| CN109836315B (en) * | 2017-11-29 | 2021-10-29 | 中国科学院大连化学物理研究所 | Catalytic preparation method of veratraldehyde |
| CN111701608A (en) * | 2020-07-09 | 2020-09-25 | 中国科学院过程工程研究所 | Method for preparing vanadium-phosphorus-oxygen catalyst with assistance of hydrotalcite |
| CN111701608B (en) * | 2020-07-09 | 2021-08-31 | 中国科学院过程工程研究所 | Method for preparing vanadium-phosphorus-oxygen catalyst with assistance of hydrotalcite |
| CN114426467A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing glutaraldehyde based on heterogeneous catalysis technology |
| CN114920645A (en) * | 2022-05-09 | 2022-08-19 | 常州大学 | Synthetic method of alpha-methoxy methyl acetate derivative |
| CN114684873A (en) * | 2022-05-10 | 2022-07-01 | 合肥工业大学 | Nickel-indium layered double-metal hydroxide nanosheet catalyst and preparation method and application thereof |
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