CN103864549A - Method for preparing diphenyl ketone compound - Google Patents
Method for preparing diphenyl ketone compound Download PDFInfo
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- CN103864549A CN103864549A CN201210552322.8A CN201210552322A CN103864549A CN 103864549 A CN103864549 A CN 103864549A CN 201210552322 A CN201210552322 A CN 201210552322A CN 103864549 A CN103864549 A CN 103864549A
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- 0 Cc1c(*)c(CC2=CC=C(*)C(C3CC3)C(*)=C2*)ccc1* Chemical compound Cc1c(*)c(CC2=CC=C(*)C(C3CC3)C(*)=C2*)ccc1* 0.000 description 2
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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 of preparing benzophenone compound, be specifically related to be oxidized 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 can be for film production.Benzophenone compound is synthetic at medicine, have a wide range of applications aspect perfumery and macromolecular material, can also be used for the photosensitizers of film coating etc., is a kind of very important fine chemicals.
At present, the industrialized synthetic route of benzophenone compound of having reported mainly contains carbonylation method, acylations method, nitric acid oxidation method etc.Carbonylation method generally reacts under high temperature, high pressure; In acylations method process, there are a large amount of spent acid to generate, etching apparatus, catalyzer is reused more difficult; Nitric acid oxidation method long reaction time, the problem such as equipment corrosion is serious, contaminate environment.Therefore, have in recent years a lot of new synthetic methods to appear in the newspapers successively, wherein many is to explore new catalytic material catalyzed oxidation ditane compounds to prepare benzophenone compound.
It is oxygenant that CN101462936A adopts oxygen, with Ni, and Fe, Zn salt or oxide compound are catalyst oxidation diphenylmethanes Preparation benzophenone type oxide, yield is 89% ~ 99%.The people such as AhmadShaabani (Tetrahedron.2004,60:11415 – 11420) report with KMnO
4/ MnO
2oxidation ditane is prepared benzophenone, 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, be applied in the oxidizing reaction of ditane, take oxygen as oxygen source, the yield of benzophenone is 30% left and right.Although the research about the catalyzer of preparing benzophenone compound makes great progress, these processes still exist problem, and for example catalyst activity is lower, and preparation process is loaded down with trivial details, or need strong oxidizer, produce by product etc.In addition the stability of catalyzer is lower etc., and problem also limits its 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 is prepared benzophenone compound.This process used catalyst preparation 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: by after ditane compounds, oxygenant, solvent and catalyst mix, under normal pressure, reflux or to put into reactor airtight, at a certain temperature, stirring reaction certain hour, separates and obtains benzophenone compound; Described ditane 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-F ,-Cl, one or two or more kinds in-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, M '=Co, Pt, Au, Ag, Pd, Cu, one or more in 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 ditane 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-F ,-Cl, one or two or more kinds in-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, M '=Co, Pt, Pd, Cu, one or more in 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%, 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 ditane 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-F, one or two or more kinds in-Cl.Optimal catalyst is: and the oxide compound of metal load (M '/M
xo
y), wherein, M '=Pt, Pd, Cu, one or more in 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 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 that provides active oxygen are the keys that determines 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 reaction; If the oxidation capacity of catalyzer is stronger, can cause the over oxidation of reaction substrate, scission of link forms two small molecules products; If the oxidation capacity of catalyzer a little less than, can cause a large amount of generations of alcohols material, reduced the selectivity of target product ketone compounds, thereby reduce yield.Loaded metal add effectively active oxidation agent, produce more active oxygens, make the oxide catalyst after reduction return to original state after can being oxidized more easily, continue as catalyst reaction, selected loaded metal is Co, Pt, Au, Ag, Pd, Cu, one or more in Fe.
Formula 1M '/M
xo
ycatalyzed oxidation ditane compounds is prepared the reaction signal of benzophenone compound.
The present invention compares 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, can repeatedly recycle, there is wide commercial application value.
2, catalytic reaction condition is comparatively gentle, and the transformation efficiency of ditane compounds and the selectivity of benzophenone compound are all higher.
Embodiment
For the present invention is further elaborated, provides several concrete case study on implementation below, but the invention is not restricted to these embodiment.
Embodiment 1
In the round-bottomed flask of 250ml, add respectively 1mmol substrate, 1.2g 30% hydrogen peroxide, takes the Pt/MoO of 0.3g 5wt%
3this reaction of catalysis, and add 100ml acetic acid, the stirring reaction 10h that refluxes at 120 ℃, after reaction finishes, chromatogram detects product, and the yield of product is in table 1
Embodiment 2
In the reactor of the polytetrafluoro lining of 250ml, add respectively 0.5mmol substrate, 1.5mmol tertbutyl peroxide, takes the Co/CeO of 0.2g 2.5wt%
2this reaction of catalysis, and add 100ml pyridine, stirring reaction 20h at 100 ℃, after reaction finishes, chromatogram detects product, and the yield of product is in table 1
Embodiment 3
In the reactor of the polytetrafluoro lining of 250ml, add respectively 1.5mmol substrate, 6mmol hydrogen phosphide cumene, take this reaction of Cu/MO-V-O catalysis of 0.7g 5wt%, and adding 100ml acetonitrile, stirring reaction 18h at 150 ℃, after reaction finishes, chromatogram detects product, and the yield of product is in table 1
Embodiment 4
In the round-bottomed flask of 250ml, add respectively 2mmol substrate, 1.2g 30% hydrogen peroxide, takes the Pt/MnO of 0.3g2wt%
2this reaction of catalysis, and add 120ml methylene dichloride, the stirring reaction 10h that refluxes at 100 ℃, after reaction finishes, chromatogram detects product, and the yield of product is in table 1
Embodiment 5
In the reactor of the polytetrafluoro lining of 250ml, add respectively 1mmol substrate, 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 ℃, after reaction finishes, chromatogram detects product, and the yield of product is in table 1
Embodiment 6
In the reactor of the polytetrafluoro lining of 250ml, add respectively 1.3mmol substrate, 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 ℃, after reaction finishes, chromatogram detects product, and the yield of product is in table 1
Embodiment 7
In the round-bottomed flask of 250ml, add respectively 1.6mmol substrate, 1.5g 30% hydrogen peroxide, takes the Cu/MnO of 0.5g 1.5wt%
2this reaction of catalysis, and add 100ml acetonitrile, the stirring reaction 48h that refluxes at 100 ℃, after reaction finishes, chromatogram detects product, and the yield of product is in table 1
Embodiment 8
In the round-bottomed flask of 250ml, add respectively 1mmol substrate, 5mmol carbamide peroxide, takes the Au/CeO of 0.3g 5wt%
2this reaction of catalysis, and add 130ml pyridine, the stirring reaction 30h that refluxes at 120 ℃, after reaction finishes, chromatogram detects product, and the yield of product is in table 1
Embodiment 9
250ml round-bottomed flask in, add respectively 1.5mmol substrate, 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 ℃, after reaction finishes, chromatogram detects product, and the yield of product is in table 1
Embodiment 10
In the reactor of the polytetrafluoro lining of 250ml, add respectively 1mmol substrate, 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 ℃, after reaction finishes, chromatogram detects product, and the yield of product is in table 1
Embodiment 11
In the reactor of the polytetrafluoro lining of 250ml, add respectively 1.3mmol substrate, 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 ℃, after reaction finishes, chromatogram detects product, and the yield of product is in table 1
The evaluation result of table 1 diphenylmethanes compound oxidation benzophenone compound processed
Can find out by above-described embodiment, adopt the preparation process described in this patent, the transformation efficiency of ditane compounds and the yield of benzophenone compound be higher (transformation efficiency is higher than 95%, and yield is higher than 90%) all.
Claims (7)
1. a method of preparing benzophenone compound, is characterized in that:
By after ditane compounds, oxygenant, solvent and catalyst mix, under normal pressure, reflux or to put into reactor airtight, at a certain temperature, stirring reaction certain hour, separates and obtains benzophenone compound;
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, and when oxygen makees oxygenant, its pressure that pours reactor is 0.2MPa ~ 1.2Mpa;
Described catalyzer is: and the oxide compound of metal load (M '/M
xo
y), wherein, M '=Co, Pt, Au, Ag, Pd, Cu, one or more in 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.
2. in accordance with the method for claim 1, it is characterized in that: described ditane compounds substrate, its structure is as shown in the formula shown in 1, its corresponding product benzophenone compound structural formula as shown in Equation 2:
(structural formula 1) (structural formula 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-F ,-Cl, one or two or more kinds in-Br.
3. according to the method described in claim 1 or 2, it is characterized in that:
Described ditane compounds substrate, its structure is 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-F ,-Cl, one or two or more kinds in-Br;
Described oxygenant is: tertbutyl peroxide, carbamide peroxide, hydrogen peroxide, one or more in oxygen; Oxygenant (except oxygen) with the mol ratio of reaction substrate is: 1:1 ~ 8:1, and when oxygen makees oxygenant, its pressure that pours reactor is 0.4MPa ~ 0.8Mpa;
Described catalyzer is: and the oxide compound of metal load (M '/M
xo
y), wherein, M '=Co, Pt, Pd, Cu, one or more in 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%, the consumption of described catalyzer is: 0.05g (mmol substrate)
-1~ 0.3g (mmol substrate)
-1;
Described temperature of reaction is 60 ° of C ~ 160 ° C, and the reaction times is: 5h ~ 30h.
4. according to the method described in claim 1 or 2, it is characterized in that:
Described ditane 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-F, one or two or more kinds in-Cl;
Described catalyzer is: and the oxide compound of metal load (M '/M
xo
y), wherein, M '=Pt, Pd, Cu, one or more in 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 ° of C ~ 120 ° C, and the reaction times is: 5h ~ 12h.
5. it is characterized in that in accordance with the method for claim 1:
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. it is characterized in that in accordance with the method for claim 1:
Described solvent is: acetonitrile, acetic acid, methylene dichloride, one or two or more kinds in pyridine.
7. according to described in claim 1, it is characterized in that:
Described separating catalyst can adopt method centrifugal or that filter.
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|---|---|---|---|
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| CN103864549B CN103864549B (en) | 2015-07-15 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112778107A (en) * | 2019-11-06 | 2021-05-11 | 复旦大学 | Method for synthesizing acetophenone or benzoic acid compound by oxidizing toluene compound |
| 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 |
| CN113321574A (en) * | 2021-06-03 | 2021-08-31 | 陕西延长石油（集团）有限责任公司 | Preparation method of 4, 4' -difluorobenzophenone and intermediate thereof |
| CN113816899A (en) * | 2021-10-15 | 2021-12-21 | 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 |
| CN114618570A (en) * | 2020-12-11 | 2022-06-14 | 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 thereof |
-
2012
- 2012-12-18 CN CN201210552322.8A patent/CN103864549B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| SUDHIR E. DAPURKAR ET AL.: "Supported Gold Nanoparticles Catalysts for Solvent-free Selective Oxidation of Benzylic Compounds into Ketones at 1 atm O2", 《CATAL LETT》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778107A (en) * | 2019-11-06 | 2021-05-11 | 复旦大学 | Method for synthesizing acetophenone or benzoic acid compound by oxidizing toluene compound |
| CN112778107B (en) * | 2019-11-06 | 2022-06-10 | 复旦大学 | Method for synthesizing acetophenone or benzoic acid compound by oxidizing toluene compound |
| CN114618570A (en) * | 2020-12-11 | 2022-06-14 | 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 thereof |
| 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 |
| CN113321574A (en) * | 2021-06-03 | 2021-08-31 | 陕西延长石油（集团）有限责任公司 | Preparation method of 4, 4' -difluorobenzophenone and intermediate 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 |
| CN113816899A (en) * | 2021-10-15 | 2021-12-21 | 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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|---|---|
| CN103864549B (en) | 2015-07-15 |
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