CN103864549B - Method for preparing diphenyl ketone compound - Google Patents
Method for preparing diphenyl ketone compound Download PDFInfo
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- CN103864549B CN103864549B CN201210552322.8A CN201210552322A CN103864549B CN 103864549 B CN103864549 B CN 103864549B CN 201210552322 A CN201210552322 A CN 201210552322A CN 103864549 B CN103864549 B CN 103864549B
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Abstract
The invention relates to a method for preparing a diphenyl ketone compound. The method adopts a metal-supported oxide as a catalyst. The method comprises the specific process: after mixing a diphenyl methane compound, an oxidant, a solvent and the catalyst, refluxing at a normal pressure or putting into a reaction kettle for sealing, and stirring. The reaction temperature is higher than 50 DEG C, the reaction time is longer than 2 h, after the reaction, the catalyst is easily separated from the reaction system and can be recycled repeatedly, and the highest yield of the diphenyl ketone compound can reach 99%. The method for preparing the diphenyl ketone compound has the advantages of simple catalyst preparation, high stability, relatively mild reaction conditions, relatively high conversion rate of the diphenyl methane compound, and relatively high yield of the diphenyl ketone compound.
Description
Technical field
The present invention relates to a kind of method preparing benzophenone compound, be specifically related to oxidation ditane compounds and prepare benzophenone compound.
Background technology
Benzophenone is transparent crystals at normal temperatures and pressures, is mainly used in synthetic drugs, manufactures spices, also may be used for film production.Benzophenone compound has a wide range of applications in medicine synthesis, perfumery and macromolecular material, and can also be used for the photosensitizers etc. of film coating, be a kind of very important fine chemicals.
At present, the industrialized synthetic route of the benzophenone compound reported mainly contains carbonylation method, acylations method, nitric acid oxidation method etc.Carbonylation method generally reacts under high temperature, high pressure; Have a large amount of spent acid to generate in acylations method process, etching apparatus, catalyzer is reused more difficult; Nitric acid oxidation method long reaction time, equipment corrosion is serious, the problems such as contaminate environment.Therefore, have much new synthetic method to appear in the newspapers successively in recent years, wherein many is explore new catalytic material catalyzed oxidation ditane compounds to prepare benzophenone compound.
CN101462936A adopts oxygen to be oxygenant, and be catalyst oxidation diphenylmethanes Preparation benzophenone type oxide with Ni, Fe, Zn salt or oxide compound, yield is 89% ~ 99%.The people such as AhmadShaabani (Tetrahedron.2004,60:11415 – 11420) report is with KMnO
4/ MnO
2benzophenone prepared by oxidation ditane, and yield is 93%.The people such as Liu Zhigang (Applied Catalysis A:General.2012,413-414,30-35) prepare the supported CeO of metalloporphyrin
2@SiO
2, being applied in the oxidizing reaction of ditane, take oxygen as oxygen source, and the yield of benzophenone is about 30%.Although make great progress about the research of the catalyzer preparing benzophenone compound, these processes still also exist problem, and such as catalyst activity is lower, and preparation process is loaded down with trivial details, or need strong oxidizer, produce by product etc.The problems such as the stability of catalyzer is lower in addition also limit it and use.Therefore, exploitation has high-efficiency catalytic activity and preparation is simple, and the catalyzer of good stability has great importance and potential using value.
Summary of the invention
The object of the invention is to prepare stability carried oxide high and simple and easy to get as catalyzer, and be applied to diphenylmethanes compound oxidation and prepare benzophenone compound, realize the object that high yield prepares benzophenone compound.The preparation of this process used catalyst is simple and stability is high, and reaction conditions is comparatively gentle, and the yield of substrate conversion efficiency and product is all higher, and by product is few.
The benzophenone compound of the present invention's design is prepared by following scheme: after ditane compounds, oxygenant, solvent and catalyst mix, backflow or to put into reactor airtight under normal pressure, at a certain temperature, stirring reaction certain hour, is separated and obtains benzophenone compound; Described diphenylmethanes compounds substrate, its structure as shown in Equation 1, its corresponding product benzophenone compound structural formula as shown in Equation 2, wherein, R
1~ R
6be respectively the one in following substituting group, substituting group is-H ,-F ,-Cl ,-Br ,-Ph ,-NO
2,-NH
2,-OCH
3,-OCH
2cH
3, the alkyl of C1-C5 or substituted alkyl, the alkylene of C2-C5 or substituted olefine base; Substituting group on substituted olefine base or substituted alkyl is one or two or more kinds in-F ,-Cl ,-Br.Described oxygenant is one or more in hypochlorite, tertbutyl peroxide, hydrogen phosphide cumene, carbamide peroxide, hydrogen peroxide, oxygen; Oxygenant (except oxygen) with the mol ratio of reaction substrate is: 1:1 ~ 20:1, when oxygen makees oxygenant, its pressure is 0.2MPa ~ 1.2MPa.Described catalyzer is: and the oxide compound of metal load (M '/M
xo
y), wherein, one or more in M '=Co, Pt, Au, Ag, Pd, Cu, Fe; M
xo
y=ZrO
2, CeO
2, MnO
2, WO
3, Nb
2o
5, Al
2o
3, SiO
2, one or more in Mo-V-O, content of metal is 0.5wt% ~ 10wt%; The consumption of described catalyzer is: 0.01g (mmol substrate)
-1~ 0.5g (mmol substrate)
-1; Described temperature of reaction is 50 ° of C ~ 200 ° C, and the reaction times is: 2h ~ 48h.
Preferably diphenylmethanes compounds substrate, its structure as shown in Equation 1.Wherein, R
1~ R
6be substituting group, be respectively the one in following substituting group, substituting group is-H ,-F ,-Cl ,-NO
2,-NH
2,-OCH
3, the alkyl of C1-C5 or substituted alkyl, the substituting group on substituted alkyl is one or two or more kinds in-F ,-Cl ,-Br.Preferably oxygenant is: hypochlorite, tertbutyl peroxide, carbamide peroxide, hydrogen peroxide, one or more in oxygen; Oxygenant (except oxygen) and reaction substrate preferably mol ratio are: 1:1 ~ 8:1, when oxygen makees oxygenant, preferably pouring pressure is 0.4MPa ~ 0.8MPa.Preferably catalyzer is: and the oxide compound of metal load (M '/M
xo
y), wherein, one or more in M '=Co, Pt, Pd, Cu, Fe; M
xo
y=CeO
2, MnO
2, WO
3, Nb
2o
5, Al
2o
3, one or more in MO-V-O, preferably content of metal is 1wt% ~ 5wt%, and preferably the consumption of catalyzer is: 0.05g (mmol substrate)
-1~ 0.3g (mmol substrate)
-1; Preferably temperature of reaction is 60 ° of C ~ 160 ° C, and preferably the reaction times is: 5h ~ 30h.
Optimum diphenylmethanes compounds substrate, its structure as shown in Equation 1, wherein, R
1~ R
6be substituting group wherein, be respectively the one in following substituting group, substituting group is-H ,-F ,-Cl ,-NO
2,-OCH
3, the alkyl of C1-C3 or substituted alkyl, the substituting group on substituted alkyl is one or two or more kinds in-F ,-Cl.Optimal catalyst is: and the oxide compound of metal load (M '/M
xo
y), wherein, one or more in M '=Pt, Pd, Cu, Fe; M
xo
y=CeO
2, MnO
2, WO
3, Nb
2o
5, M
oone or more in-V-O; The optimum consumption of catalyzer is: 0.07g (mmol substrate)
-1~ 0.2g (mmol substrate)
-1; Peak optimization reaction temperature is 80 ° of C ~ 120 ° C, and the reaction times is: 5h ~ 12h.
Described solvent is: water, acetonitrile, ethanol, acetic acid, ethyl acetate, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, hexanaphthene, normal hexane, toluene, acetone, chloroform, methylene dichloride, one or two or more kinds in pyridine; Solvent load is 10mL (mmol substrate)-1 ~ 180mL (mmol substrate)-1, and the separation of catalyzer can adopt method that is centrifugal or that filter.
M '/M
xo
ycatalyzed oxidation ditane compounds is prepared benzophenone compound and is mainly divided into two processes (as shown in Equation 1): 1) catalyzer M '/M
xo
yreaction substrate is oxidized to superoxide intermediate product, self is reduced to lower valency M '/M simultaneously
x-mo
y+n, reduction-state catalyzer is oxidized to again original state M '/M in the presence of oxygenant
xo
y, complete catalytic cycle.2) the superoxide transition state direct oxidation dehydrogenation that reaction generates generates ketone, or first forms corresponding alcohol, is then further oxidized to ketone.The redox ability of catalyzer or the complexity providing active oxygen is the key determining reactive behavior.For ZrO
2, CeO
2, MnO
2, WO
3, Nb
2o
5, Al
2o
3, SiO
2, M
othe oxide compounds such as-V-O have suitable oxidation capacity, show high conversion and highly selective in the reaction; If the oxidation capacity of catalyzer is comparatively strong, then can cause the over oxidation of reaction substrate, scission of link forms two small molecules products; If the oxidation capacity of catalyzer is more weak, then can causes a large amount of generations of alcohols material, reduce the selectivity of target product ketone compounds, thus reduce yield.Adding of loaded metal can effectively active oxidation agent, produce more active oxygens, return to original state after oxide catalyst after reducing can be oxidized more easily, continue as catalyst reaction, selected loaded metal is Co, Pt, Au, Ag, Pd, one or more in Cu, Fe.
Formula 1M '/M
xo
ycatalyzed oxidation ditane compounds prepares the reaction signal of benzophenone compound.
The present invention, compared with the benzophenone compound preparation technology of announcement, has following several advantage: 1, this reaction adopts carried oxide catalyzed reaction, and material is easy to get, preparation is simple, and stability is high, and catalyzer is easily separated, repeatedly can recycle, there is wide commercial application value.
2, catalytic reaction condition is comparatively gentle, the transformation efficiency of ditane compounds and the selectivity of benzophenone compound all higher.
Embodiment
In order to be further elaborated to the present invention, provide several concrete case study on implementation below, but the invention is not restricted to these embodiments.
Embodiment 1
In the round-bottomed flask of 250ml, add 1mmol substrate respectively, 1.2g 30% hydrogen peroxide, takes the Pt/MoO of 0.3g 5wt%
3this reaction of catalysis, and add 100ml acetic acid, reflux stirring reaction 10h at 120 DEG C, and after reaction terminates, chromatogram detects product, and the yield of product is in table 1
Embodiment 2
In the reactor of the polytetrafluoro lining of 250ml, add 0.5mmol substrate respectively, 1.5mmol tertbutyl peroxide, take the Co/CeO of 0.2g 2.5wt%
2this reaction of catalysis, and add 100ml pyridine, stirring reaction 20h at 100 DEG C, after reaction terminates, chromatogram detects product, and the yield of product is in table 1
Embodiment 3
In the reactor of the polytetrafluoro lining of 250ml, add 1.5mmol substrate respectively, 6mmol hydrogen phosphide cumene, take this reaction of Cu/MO-V-O catalysis of 0.7g 5wt%, and add 100ml acetonitrile, stirring reaction 18h at 150 DEG C, after reaction terminates, chromatogram detects product, and the yield of product is in table 1
Embodiment 4
In the round-bottomed flask of 250ml, add 2mmol substrate respectively, 1.2g 30% hydrogen peroxide, takes the Pt/MnO of 0.3g2wt%
2this reaction of catalysis, and add 120ml methylene dichloride, reflux stirring reaction 10h at 100 DEG C, and after reaction terminates, chromatogram detects product, and the yield of product is in table 1
Embodiment 5
In the reactor of the polytetrafluoro lining of 250ml, add 1mmol substrate respectively, take the Fe/WO of 0.3g3.5wt%
3this reaction of catalysis, and add 130ml pyridine, pour 0.8MP oxygen, stirring reaction 20h at 150 DEG C, after reaction terminates, chromatogram detects product, and the yield of product is in table 1
Embodiment 6
In the reactor of the polytetrafluoro lining of 250ml, add 1.3mmol substrate respectively, take the Cu/CeO of 0.13g8wt%
2this reaction of catalysis, and add 100ml acetic acid, pour 0.8MP oxygen, stirring reaction 15h at 180 DEG C, after reaction terminates, chromatogram detects product, and the yield of product is in table 1
Embodiment 7
In the round-bottomed flask of 250ml, add 1.6mmol substrate respectively, 1.5g 30% hydrogen peroxide, takes the Cu/MnO of 0.5g 1.5wt%
2this reaction of catalysis, and add 100ml acetonitrile, reflux stirring reaction 48h at 100 DEG C, and after reaction terminates, chromatogram detects product, and the yield of product is in table 1
Embodiment 8
In the round-bottomed flask of 250ml, add 1mmol substrate respectively, 5mmol carbamide peroxide, take the Au/CeO of 0.3g 5wt%
2this reaction of catalysis, and add 130ml pyridine, reflux stirring reaction 30h at 120 DEG C, and after reaction terminates, chromatogram detects product, and the yield of product is in table 1
Embodiment 9
250ml round-bottomed flask in, add 1.5mmol substrate respectively, 2.0g 30% hydrogen peroxide, takes the Fe/Al of 0.33g 10wt%
2o
3this reaction of catalysis, and add 150ml acetonitrile, stirring reaction 30h at 150 DEG C, after reaction terminates, chromatogram detects product, and the yield of product is in table 1
Embodiment 10
In the reactor of the polytetrafluoro lining of 250ml, add 1mmol substrate respectively, take the Cu/Nb of 0.20g 5wt%
2o
5this reaction of catalysis, and add 100ml acetic acid, pour 1MPa oxygen, stirring reaction 40h at 80 DEG C, after reaction terminates, chromatogram detects product, and the yield of product is in table 1
Embodiment 11
In the reactor of the polytetrafluoro lining of 250ml, add 1.3mmol substrate respectively, take the Pt/MoO of 0.23g0.5wt%
3this reaction of catalysis, and add 100ml acetic acid, pour 1MPa oxygen, stirring reaction 25h at 100 DEG C, after reaction terminates, chromatogram detects product, and the yield of product is in table 1
The evaluation result of table 1 diphenylmethanes compound oxidation benzophenone compound
Can be found out by above-described embodiment, adopt preparation process, the transformation efficiency of ditane compounds and the yield of benzophenone compound all higher (, higher than 95%, yield is higher than 90% for transformation efficiency) described in this patent.
Claims (7)
1. prepare a method for benzophenone compound, it is characterized in that:
After ditane compounds, oxygenant, solvent and catalyst mix, backflow or to put into reactor airtight under normal pressure, at a certain temperature, stirring reaction certain hour, is separated and obtains benzophenone compound;
Described oxygenant is one or more in hypochlorite, tertbutyl peroxide, hydrogen phosphide cumene, carbamide peroxide, hydrogen peroxide, oxygen; Oxygenant except for oxygen and the mol ratio of reaction substrate are: 1:1 ~ 20:1, and when oxygen makees oxygenant, its pressure pouring reactor is 0.2MPa ~ 1.2Mpa;
Described catalyzer is: the oxide compound of metal load, uses M'/M
xo
yrepresent, wherein, one or more in M'=Co, Pt, Ag, Pd, Cu, Fe; M
xo
y=ZrO
2, CeO
2, MnO
2, WO
3, Nb
2o
5, Al
2o
3, SiO
2, one or more in Mo-V-O, or M'=Au, M
xo
y=ZrO
2, MnO
2, WO
3, Nb
2o
5, SiO
2, one or more in Mo-V-O; Content of metal is 0.5wt% ~ 10wt%;
The consumption of described catalyzer is: 0.01g (mmol substrate)
-1~ 0.5g (mmol substrate)
-1;
Described temperature of reaction is 50 DEG C ~ 200 DEG C, and the reaction times is: 2h ~ 48h.
2. in accordance with the method for claim 1, it is characterized in that:
Described diphenylmethanes compounds substrate, its structure as shown in the formula shown in 1, its corresponding product benzophenone compound structural formula as shown in Equation 2:
Wherein, R
1~ R
6be respectively the one in following substituting group, substituting group is-H ,-F ,-Cl ,-Br ,-Ph ,-NO
2,-NH
2,-OCH
3,-OCH
2cH
3, the alkyl of C1-C5 or substituted alkyl, the alkylene of C2-C5 or substituted olefine base; Substituting group on substituted olefine base or substituted alkyl is one or two or more kinds in-F ,-Cl ,-Br.
3. in accordance with the method for claim 2, it is characterized in that:
Described diphenylmethanes compounds substrate, its structure is as shown in Equation 1; Wherein, R
1~ R
6be respectively the one in following substituting group, substituting group is-H ,-F ,-Cl ,-NO
2,-NH
2,-OCH
3, the alkyl of C1-C5 or substituted alkyl, the substituting group on substituted alkyl is one or two or more kinds in-F ,-Cl ,-Br;
Described oxygenant is: tertbutyl peroxide, carbamide peroxide, hydrogen peroxide, one or more in oxygen; Oxygenant except for oxygen and the mol ratio of reaction substrate are: 1:1 ~ 8:1, and when oxygen makees oxygenant, its pressure pouring reactor is 0.4MPa ~ 0.8Mpa;
Described catalyzer is: the oxide compound of metal load, uses M'/M
xo
yrepresent, wherein, one or more in M'=Co, Pt, Pd, Cu, Fe; M
xo
y=CeO
2, MnO
2, WO
3, Nb
2o
5, Al
2o
3, M
oone or more in-V-O, content of metal is 1wt% ~ 5wt%, and the consumption of described catalyzer is: 0.05g (mmol substrate)
-1~ 0.3g (mmol substrate)
-1;
Described temperature of reaction is 60 DEG C ~ 160 DEG C, and the reaction times is: 5h ~ 30h.
4. in accordance with the method for claim 2, it is characterized in that:
Described diphenylmethanes compounds substrate, its structure as shown in Equation 1, wherein, R
1~ R
6be respectively the one in following substituting group, substituting group is-H ,-F ,-Cl ,-NO
2,-OCH
3, the alkyl of C1-C3 or substituted alkyl, the substituting group on substituted alkyl is one or two or more kinds in-F ,-Cl;
Described catalyzer is: the oxide compound of metal load, uses M'/M
xo
yrepresent, wherein, one or more in M'=Pt, Pd, Cu, Fe; M
xo
y=CeO
2, MnO
2, WO
3, Nb
2o
5, M
oone or more in-V-O; The consumption of described catalyzer is: 0.07g (mmol substrate)
-1~ 0.2g (mmol substrate)
-1;
Described temperature of reaction is 80 DEG C ~ 120 DEG C, and the reaction times is: 5h ~ 12h.
5. in accordance with the method for claim 1, it is characterized in that:
Described solvent is: water, acetonitrile, ethanol, acetic acid, ethyl acetate, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, hexanaphthene, normal hexane, toluene, acetone, chloroform, methylene dichloride, one or two or more kinds in pyridine; Solvent load is 10mL (mmol substrate)
-1~ 180mL (mmol substrate)
-1.
6. in accordance with the method for claim 1, it is characterized in that:
Described solvent is: acetonitrile, acetic acid, methylene dichloride, one or two or more kinds in pyridine.
7. in accordance with the method for claim 1, it is characterized in that:
Separating catalyst adopts method that is centrifugal or that filter.
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| CN112778107B (en) * | 2019-11-06 | 2022-06-10 | 复旦大学 | Method for synthesizing acetophenone or benzoic acid compound by oxidizing toluene compound |
| CN114618570B (en) * | 2020-12-11 | 2023-04-28 | 中国科学院大连化学物理研究所 | Coating type catalyst for preparing methylamine by amination of methanol, preparation and application |
| CN112495331A (en) * | 2020-12-14 | 2021-03-16 | 江苏万隆化学有限公司 | Energy-saving and environment-friendly preparation method of benzophenone compound and special production equipment thereof |
| CN113321574B (en) * | 2021-06-03 | 2023-09-19 | 陕西延长石油（集团）有限责任公司 | Preparation method of 4,4' -difluorobenzophenone and intermediate thereof |
| CN113304759A (en) * | 2021-06-16 | 2021-08-27 | 陕西延长石油（集团）有限责任公司 | Catalyst for preparing benzophenone by catalyzing oxidation of diphenylmethane and preparation method and application thereof |
| CN113816899B (en) * | 2021-10-15 | 2023-04-14 | 浙江大学衢州研究院 | Method for generating ketone or ester by catalytic oxidation of substituted aromatic compound with carbon material |
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Non-Patent Citations (1)
| Title |
|---|
| Supported Gold Nanoparticles Catalysts for Solvent-free Selective Oxidation of Benzylic Compounds into Ketones at 1 atm O2;Sudhir E. Dapurkar et al.;《Catal Lett》;20090204;第130卷;第42-47页 * |
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