CN107903155A - A kind of method that catalysis oxidation styrax prepares benzil - Google Patents
A kind of method that catalysis oxidation styrax prepares benzil Download PDFInfo
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- CN107903155A CN107903155A CN201711221557.8A CN201711221557A CN107903155A CN 107903155 A CN107903155 A CN 107903155A CN 201711221557 A CN201711221557 A CN 201711221557A CN 107903155 A CN107903155 A CN 107903155A
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- styrax
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- benzil
- catalysis oxidation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to prepare the technical field of benzil, provide a kind of method that catalysis oxidation styrax prepares benzil, this method is used as oxidant using oxygen or air, the composite catalyst that two kinds of oxyvanadium compound, nitrous acid ester components are formed, catalysis oxidation styrax prepares benzil at 60 120 DEG C.Compared with the stoichiometric chemistry oxidizing process such as traditional chromate oxidations method, nitric acid oxidation method, permanganate oxidation method, this method reaction condition is gentle, catalyst Cheap highly effective, environmentally protective, the styrax conversion ratio of reaction and benzil selectivity are higher, has preferable application prospect and higher practical value.
Description
Technical field
The invention belongs to prepare the technical field of benzil, and in particular to pacify to a kind of complex catalyst system catalysis oxidation
Breath perfume (or spice) prepares benzil.
Background technology
Benzil is also known as diphenylthanedione, dibenzoyl, dibenzoyl, available for synthetic drug dilantin sodium, photosensitizer,
Insecticide, the printing ink of packaging for foodstuff and the corrosion inhibiter of mild steel, are that important organic synthesis intermediate and organic chemical industry are former
Material, is widely used in the industries such as food, medicine, pesticide.
Using styrax as raw material, the method that oxidation styrax prepares benzil is divided into two kinds:One kind is non-catalytic oxidation.
Benzil is prepared using inorganic compound, metallo-organic compound, polymerizable compound etc. as oxidizing styrax, but is existed
The problems such as oxidizer is big, reaction is violent, accessory substance is more, seriously polluted.For example, Tetrahedron Letters (2017,
58,2720-2722) report ethyl acetate and aoxidize styrax system under room temperature as oxidant as solvent, 40%TCCA
Standby benzil, reacts 24h, and the yield of benzil is 100%, this reaction oxidizer is larger, and the reaction time is longer;It is another
It is catalytic oxidation, using effective catalyst, benzil is prepared as oxidizer catalytic oxidation styrax using molecular oxygen or air,
The advantages that this method has high catalytic efficiency, and environmental pollution is small, meets the new concept of Green Chemistry and clean manufacturing, has good
Application prospect.Catalysis Communications (2009,10,1931-1935) report air as oxidant, first
Benzene is solvent, Pd/SiO2For catalyst, catalysis oxidation styrax prepares benzil at 100 DEG C, reacts 0.75h, benzil
Yield is 98%, and reaction condition is gentle, the reaction time is short, the high income of benzil, but expensive catalyst, reaction cost are higher,
It is unfavorable for industrialized production.Journal ofChemical Sciences (2014,126,111-115) report room temperature condition
Under using molecular oxygen or air as oxidant, paraxylene is aoxidized as solvent, Co (Salen) complexs as catalyst
Styrax prepares benzil, reacts 2.25h, and the yield 94% of product benzil, the reaction time is short, and catalyst efficiency is high, still
Co (Salen) complex prepares cumbersome, and manufacturing cycle is longer.Tetrahedron Letters (1999,40,7657-7659) are reported
Road air is as oxidant, and acetic acid aqueous solution is solvent, 40mol%Bi (NO3)2With 4mol%Cu (OAc)2As catalyst
Catalysis oxidation styrax prepares benzil, reacts 3h, and the yield of benzil is 99%, and reaction condition is gentle, catalyst preparation letter
It is single, but the dosage of catalyst bismuth nitrate is larger, cost is higher.
Therefore, a kind of catalyst of Cheap highly effective is developed, can realize that high selectivity catalysis oxidation is pacified in a mild condition
The fragrant method for preparing benzil of breath has great importance.
The content of the invention
It is compound in this method to urge it is an object of the invention to provide a kind of method that catalysis oxidation styrax prepares benzil
Agent system is made of oxyvanadium compound, two component of nitrous acid ester, the catalyst system in a mild condition, with molecular oxygen or sky
Gas prepares benzil as oxidant, catalysis oxidation styrax.This method has that high catalytic efficiency, accessory substance be few, environmental pollution
The small, advantage such as reaction cost is low.
To realize above-mentioned target, the technical solution adopted by the present invention is:
A kind of method that catalysis oxidation styrax prepares benzil, including step are as follows:
Step 1, styrax, catalyst and reaction dissolvent is put into reaction kettle by a certain percentage, afterwards confined reaction
Kettle;Wherein, catalyst is made of two kinds of components of oxyvanadium compound and nitrous acid ester, and the dosage of oxyvanadium compound is raw material styrax
0.5~20mol%, the dosage of nitrous acid ester is the 50-200mol% of oxyvanadium compound;The dosage of the reaction dissolvent is original
Expect benzoic 50-850wt%.
Step 2, oxygen or air are filled with into reaction kettle to 0.05-2.0MPa, opens and stirs and be warming up to predetermined reaction
During 25-150 DEG C of temperature, isothermal reaction 0.5-24h, is replenished in time oxygen in reaction process or air maintains reaction system pressure not
Become.
Step 3, after reaction, cooling, revolving remove solvent, and decompression is filtered and is washed with deionized, is dried to obtain
Product benzil.
Further, in above-mentioned catalyst oxyvanadium compound for vanadic sulfate, vanadyl acetylacetonate, pyridine carboxylic acid vanadyl,
One or more in vanadyl phosphate, vanadyl oxalate, oxidation triethyl group vanadyl or vanadium oxytrichloride.
Further, in above-mentioned catalyst nitrous acid ester for nitrite tert-butyl, isoamyl nitrite, methyl nitrite,
One or more in hexyl nitrite, butyl nitrite or nitrous ether (ethyl nitrite).
Further, above-mentioned reaction dissolvent is acetonitrile, propionitrile, ethyl acetate, acetone, dimethylformamide, dimethyl Asia
One or more in sulfone or dichloromethane.
Further, the reaction pressure described in step 2 is 0.2-1.0MPa.
Further, reaction temperature described in step 2 is 60-120 DEG C.
Further, the reaction time described in step 2 is 2-12h.
Compared with prior art, the invention has the advantages that:
The present invention provides a kind of complex catalyst system of Cheap highly effective, the benzoic conversion ratio of raw material and product benzil
Selectivity it is higher.
The composite catalyst that the present invention is made of oxyvanadium compound and two component of nitrous acid ester, with loaded catalyst phase
Than eliminating cumbersome catalyst preparation flow and longer preparation time.
The present invention reacts under the conditions of molecular oxygen or air atmosphere, and reaction condition is gentle, easy to operate, reaction process green
Environmental protection.
Brief description of the drawings
Fig. 1 is benzil1HNMR schemes.
Embodiment
Styrax, catalyst, reaction dissolvent are put into reaction kettle by a certain percentage, after closed reactor, to reaction kettle
In be passed through certain pressure oxygen, under certain temperature and pressure, stirring reaction after a certain period of time, cooling, revolving remove solvent, subtract
Pressure filters and is washed with deionized, is dried to obtain product benzil.
The invention will be further described with reference to the accompanying drawings and embodiments, but protection scope of the present invention not limited to this.
Embodiment 1-9:Influence of the different catalysts species to styrax conversion ratio and benzil selectivity, specific experiment mistake
Journey is described as follows:
5mmol styraxes, 2mol% oxyvanadium compounds, 2mol% nitrous acid ester, 10ml acetonitriles are added in 25ml reaction kettles,
After closed reactor, into reaction kettle in be filled with 0.5MPaO2, 100 DEG C are warming up under stirring, and 6h is kept, it is cold after reaction
But quantitative analysis is carried out using gas-chromatography to room temperature, product analysis.
Table 1:Influence of the different catalysts species to styrax conversion ratio and benzil selectivity
Embodiment 10-15:Influence of the additive amount of catalyst to styrax conversion ratio and benzil selectivity, specific experiment
Process description is as follows:
By a certain amount of catalyst (vanadic sulfate/nitrite tert-butyl=100mol%), 5mmol styraxes, 10ml second
Nitrile add 25ml reaction kettles in, into reaction kettle in be filled with 0.5MPa O2, 100 DEG C are warming up under stirring, and 6h is kept, react
After be cooled to room temperature, product analysis using gas-chromatography carry out quantitative analysis.
Table 2:Influence of the additive amount of catalyst to styrax conversion ratio and benzil selectivity
Embodiment 16-19:The molar ratio of nitrous acid ester and oxyvanadium compound is to styrax conversion ratio and benzil selectivity
Influence, specific experiment process description is as follows:
5mmol styraxes, 2mol% vanadic sulfates, a certain amount of nitrous acid ester, 10ml acetonitriles are added in 25ml reaction kettles,
0.5MPa O are filled with into reaction kettle2, 100 DEG C are warming up under stirring, and 6h is kept, it is cooled to room temperature, produces after reaction
Thing analysis carries out quantitative analysis using gas-chromatography.
Table 3:Influence of the molar ratio of nitrous acid ester and oxyvanadium compound to styrax conversion ratio and benzil selectivity
Embodiment 20-24:Influence of the reaction temperature to styrax conversion ratio and benzil selectivity, specific experiment process are retouched
State as follows:
5mmol styraxes, 2mol% vanadic sulfates, 2mol% nitrite tert-butyls, 10ml acetonitriles add 25ml reaction kettles
In, into reaction kettle in be filled with 0.5MPa O2, 100 DEG C are warming up under stirring, and 6h is kept, it is cooled to room temperature after reaction,
Product analysis carries out quantitative analysis using gas-chromatography.
Table 4:Reaction temperature is to the influence to styrax conversion ratio and benzil selectivity
Embodiment 25-30:Influence of the reaction time to styrax conversion ratio and benzil selectivity, specific experiment process are retouched
State as follows:
5mmol styraxes, 2mol% vanadic sulfates, 2mol% nitrite tert-butyls, 10ml acetonitriles add 25ml reaction kettles
In, into reaction kettle in be filled with 0.5MPaO2, 100 DEG C are warming up under stirring, and kept for certain time, it is cooled to after reaction
Room temperature, product analysis carry out quantitative analysis using gas-chromatography.
Table 5:Influence of the reaction time to styrax conversion ratio and benzil selectivity
Found out by data in table, the benzoic optimum reacting time of catalysis oxidation is 2-12h.
Embodiment 31-37:Influence of the reaction dissolvent to styrax conversion ratio and benzil selectivity, specific experiment process are retouched
State as follows:
5mmol styraxes, 2mol% vanadic sulfates, 2mol% nitrite tert-butyls, it is anti-that 10ml reaction dissolvents add 25ml
Answer in kettle, into reaction kettle in be filled with 0.5MPa O2, 100 DEG C are warming up under stirring, and 6h is kept, it is cooled to after reaction
Room temperature, product analysis carry out quantitative analysis using gas-chromatography.
Table 6:Influence of the reaction dissolvent to styrax conversion ratio and benzil selectivity
Embodiment 38-43:Influence of the oxygen pressure to styrax conversion ratio and benzil selectivity, specific experiment process are retouched
State as follows:
5mmol styraxes, 2mol% vanadic sulfates, 2mol% nitrite tert-butyls, 10ml acetonitriles add 25ml reaction kettles
In, into reaction kettle in be filled with certain pressure O2, 100 DEG C are warming up under stirring, and 6h is kept, room is cooled to after reaction
Temperature, product analysis carry out quantitative analysis using gas-chromatography.
Table 7:Influence of the oxygen pressure to styrax conversion ratio and benzil selectivity
Embodiment 44:25mmol styraxes, 2mol% vanadic sulfates, 2mol% nitrite tert-butyls, 25ml acetonitriles add
In 50ml reaction kettles, into reaction kettle in be filled with 0.5MPaO2, 60 DEG C are warming up under stirring, and 24h is kept, it is cold after reaction
But to room temperature, the benzoic conversion ratio of gas chromatographic analysis is 98%, and the selectivity of benzil is 99%.
Embodiment 45:25mmol styraxes, 4mol% vanadic sulfates, 4mol% nitrite tert-butyls, 25ml acetonitriles add
In 50ml reaction kettles, into reaction kettle in be filled with 0.5MPaO2, 100 DEG C are warming up under stirring, and 4h is kept, it is cold after reaction
But to room temperature, the benzoic conversion ratio of gas chromatographic analysis is 99%, and the selectivity of benzil is 98%.
Embodiment 46:25mmol styraxes, 5mol% vanadic sulfates, 5mol% nitrite tert-butyls, 25ml acetonitriles add
In 50ml reaction kettles, into reaction kettle in be filled with 0.2MPaO2, 80 DEG C are warming up under stirring, and 8h is kept, it is cold after reaction
But to room temperature, the benzoic conversion ratio of gas chromatographic analysis is 99%, and the selectivity of benzil is 98%.
Claims (10)
1. a kind of method that catalysis oxidation styrax prepares benzil, it is characterised in that as follows including step:
Step 1, styrax, catalyst and reaction dissolvent is put into reaction kettle by a certain percentage, afterwards closed reactor;Its
In, catalyst is made of two kinds of components of oxyvanadium compound and nitrous acid ester, and the dosage of oxyvanadium compound is raw material benzoic 0.5
~20mol%, the dosage of nitrous acid ester are the 50-200mol% of oxyvanadium compound;The dosage of the reaction dissolvent is pacified for raw material
Cease fragrant 50-850wt%;
Step 2, oxygen or air are filled with into reaction kettle to 0.05-2.0MPa, opens and stirs and be warming up to predetermined reaction temperature
At 25-150 DEG C, isothermal reaction 0.5-24h, oxygen is replenished in time in reaction process or air maintains reaction system pressure constant;
Step 3, after reaction, cooling, revolving remove solvent, and decompression is filtered and is washed with deionized, and is dried to obtain product
Benzil.
2. the method that a kind of catalysis oxidation styrax according to claim 1 prepares benzil, it is characterised in that described to urge
Oxyvanadium compound is vanadic sulfate, vanadyl acetylacetonate, pyridine carboxylic acid vanadyl, vanadyl phosphate, vanadyl oxalate, oxidation three in agent
One or more in ethyl vanadyl or vanadium oxytrichloride.
3. the method that a kind of catalysis oxidation styrax according to claim 1 or 2 prepares benzil, it is characterised in that institute
It is nitrite tert-butyl, isoamyl nitrite, methyl nitrite, hexyl nitrite, nitrous acid fourth to state nitrous acid ester in catalyst
One or more in ester or nitrous ether (ethyl nitrite).
4. the method that a kind of catalysis oxidation styrax according to claim 1 or 2 prepares benzil, it is characterised in that institute
Reaction dissolvent is stated as one kind in acetonitrile, propionitrile, ethyl acetate, acetone, dimethylformamide, dimethyl sulfoxide (DMSO) or dichloromethane
It is or a variety of.
5. the method that a kind of catalysis oxidation styrax according to claim 3 prepares benzil, it is characterised in that described anti-
It is one kind or more in acetonitrile, propionitrile, ethyl acetate, acetone, dimethylformamide, dimethyl sulfoxide (DMSO) or dichloromethane to answer solvent
Kind.
6. the method that a kind of catalysis oxidation styrax according to claim 1 or 2 or 5 prepares benzil, it is characterised in that
Reaction pressure described in step 2 is 0.2-1.0MPa.
7. the method that a kind of catalysis oxidation styrax according to claim 3 prepares benzil, it is characterised in that step 2
The reaction pressure is 0.2-1.0MPa.
8. the method that a kind of catalysis oxidation styrax according to claim 4 prepares benzil, it is characterised in that step 2
The reaction pressure is 0.2-1.0MPa.
9. the method that a kind of catalysis oxidation styrax according to claim 1 or 2 or 5 or 7 or 8 prepares benzil, it is special
Sign is that reaction temperature described in step 2 is 60-120 DEG C.
10. the method that a kind of catalysis oxidation styrax according to claim 1 or 2 or 5 or 7 or 8 prepares benzil, it is special
Sign is that the reaction time described in step 2 is 2-12h.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108404991A (en) * | 2018-05-08 | 2018-08-17 | 宁波大学 | A kind of catalysis oxidation purposes of sulfaquinoxaline cobalt compound |
CN108752175A (en) * | 2018-07-12 | 2018-11-06 | 维思普新材料(苏州)有限公司 | A kind of continuous preparation method of benzil or derivatives thereof |
CN109809978A (en) * | 2019-03-04 | 2019-05-28 | 浙江医药高等专科学校 | A kind of preparation method of benzil |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001031616A (en) * | 1999-07-19 | 2001-02-06 | Masayuki Kirihara | Production of 1,2-dicarbonyl compound |
CN1950318A (en) * | 2004-05-20 | 2007-04-18 | 株式会社可乐丽 | Process for producing alpha-oxocarbonyl compound |
-
2017
- 2017-11-23 CN CN201711221557.8A patent/CN107903155A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001031616A (en) * | 1999-07-19 | 2001-02-06 | Masayuki Kirihara | Production of 1,2-dicarbonyl compound |
CN1950318A (en) * | 2004-05-20 | 2007-04-18 | 株式会社可乐丽 | Process for producing alpha-oxocarbonyl compound |
Non-Patent Citations (4)
Title |
---|
MASAYUKI KIRIHARA等: "Aerobic oxidation of α-hydroxycarbonyls catalysed by trichlorooxyvanadium: efficient synthesis of α-dicarbonyl compounds", 《CHEM. COMMUN.》 * |
SUBBARAYAN VELUSAMY等: "Novel Vanadium-Catalyzed Oxidation of Alcohols to Aldehydes and Ketones under Atmospheric Oxygen", 《ORGANIC LETTERS》 * |
YANGYANG MA等: "Mechanistic studies on the VO(acac)2-catalyzed oxidative cleavage of lignin model compounds in acetic acid", 《RSC ADV.》 * |
YONGKE HU等: "NHPI/tert-butyl nitrite: A highly efficient metal-free catalytic system for aerobic oxidation of alcohols to carbonyl compounds using molecular oxygen as the terminal oxidant", 《CATALYSIS COMMUNICATIONS》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108404991A (en) * | 2018-05-08 | 2018-08-17 | 宁波大学 | A kind of catalysis oxidation purposes of sulfaquinoxaline cobalt compound |
CN108752175A (en) * | 2018-07-12 | 2018-11-06 | 维思普新材料(苏州)有限公司 | A kind of continuous preparation method of benzil or derivatives thereof |
CN108752175B (en) * | 2018-07-12 | 2021-06-18 | 维思普新材料(苏州)有限公司 | Continuous preparation method of benzil or derivatives thereof |
CN109809978A (en) * | 2019-03-04 | 2019-05-28 | 浙江医药高等专科学校 | A kind of preparation method of benzil |
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