CN106279084B - A kind of method that aromatic ketone oxicracking prepares phthalic anhydride and its cyclosubstituted derivative of virtue - Google Patents
A kind of method that aromatic ketone oxicracking prepares phthalic anhydride and its cyclosubstituted derivative of virtue Download PDFInfo
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- CN106279084B CN106279084B CN201510249485.2A CN201510249485A CN106279084B CN 106279084 B CN106279084 B CN 106279084B CN 201510249485 A CN201510249485 A CN 201510249485A CN 106279084 B CN106279084 B CN 106279084B
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- Prior art keywords
- aromatic ketone
- oxicracking
- oxygen
- phenyl ring
- phthalic anhydride
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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
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention provides a kind of preparation methods of new cyclosubstituted derivative of phthalic anhydride and its benzene.For this method using aromatic ketone as substrate, air or oxygen is oxygen source, and under the action of catalyst, under liquid-phase condition, oxicracking occurs for aromatic ketone, generates acid anhydrides.The method mild condition, oxidation efficiency is high, and product yield is high；Using air or oxygen as oxygen source, economic, environmental protection is had a good application prospect.
Description
Technical field
The present invention relates to chemical fields, and in particular to a kind of aromatic ketone oxicracking prepare phthalic anhydride and its
The cyclosubstituted derivative method of virtue.
Background technique
Acid anhydrides is a kind of important Organic Chemicals, is widely used in organic synthesis and pharmacy etc..Acid anhydrides synthesis is main
It is using the method being dehydrated between two carboxylic acid molecules.Industrial phthalic anhydride production method is usually used with five oxidations two
Vanadium series catalyst based on vanadium carries out the gaseous oxidation of ortho-xylene at 400~460 DEG C.Another method is also using high temperature
Gas phase reaction, using naphthalene as raw material, oxidation prepares phthalic anhydride.These methods are all using vapour phase oxidation process, reaction condition
Harshness, high energy consumption.Inventor provide a kind of synthetic method of new acid anhydrides.Using aromatic ketone as substrate molecule, liquid phase low temperature item
Under part, oxygen or air are oxygen source, generate phthalic anhydride and its cyclosubstituted derivative of virtue by oxicracking.
Summary of the invention
The present invention provides a kind of synthetic method of new acid anhydrides, this method uses aromatic ketone for substrate, oxygen or sky
Gas is oxygen source, and under the action of catalyst, aromatic ketone is oxidized cracking, generates phthalic anhydride and its cyclosubstituted derivative of benzene；
The aromatic ketone is indone and its phenyl ring substitutive derivative, tetralone and its phenyl ring substitutive derivative, benzo ring
Heptanone and its phenyl ring substitutive derivative.
The substituent group is OCH3、F、Cl、Br、I、NO2、CH3One or more of.The number of substituent group is 1-6
It is a.
According to the present invention, use environmental-friendly oxygen or air for oxygen source.The oxygen molecule of three forms wave not living enough, needs
It wants catalyst to carry out activating oxygen and forms active oxygen.The present invention uses transition metal V, Fe, Co, Mn, Cu, Cr, Mo, Ce, Nb, W oxygen
One of compound or metal salt or it is two or more carry out activating oxygen molecule for catalyst, realize that the oxidation of aromatic ketone is split
Solution, prepares acid anhydrides.
According to the present invention, catalytic performance is related with the dosage of catalyst, the too low activity that will affect catalysis reaction, dosage mistake
Height will increase the cost of catalyst；Therefore it needs to select dosage appropriate.In order to guarantee the activity of catalyst, while can reduce again
The molar ratio of catalyst cost, used catalyst and aromatic ketone are as follows: 0.1-30mol%, preferably 1-20mol%.
According to the present invention, aromatic ketone oxidation effectiveness is related with oxygen pressure, reaction temperature and time, and wherein oxygen partial pressure is
0.1-2MPa, reaction temperature are 60-180 DEG C, reaction time 1-48h；It is preferred that oxygen partial pressure 0.4-1MPa, reaction temperature 100-
160 DEG C, reaction time 6-24h.
According to the present invention, which needs to carry out in a solvent, especially solid aromatic ketone substrate molecule, needs to be dissolved in
Can be evenly dispersed in solvent, be conducive to the contact with catalyst.It is toluene, chlorobenzene, DMF, just that tertiary amine, which aoxidizes solvent for use,
One of octane, THF, dioxane, methanol, ethyl alcohol, acetonitrile, DMSO are two or more.Matter of the aromatic ketone in solvent
Measure concentration 1-80wt%, preferably 1-40wt%.
Specific embodiment
The following example will be helpful to understand the present invention, but the content of present invention is not limited thereto.
Embodiment 1:
By 0.01g MnO2Stainless steel autoclave, interior agglomeration four is added in catalyst, 1mmol 1- indone and 2g chlorobenzene
Vinyl fluoride liner.Using automatic temperature control instrument temperature programming to 100 DEG C of reaction temperature, 0.6MPa oxygen is added, reacts 4h, reacted
Keep pressure constant in journey.Reaction product is analyzed using GC-MS, and phthalic anhydride yield is 80%.
Embodiment 2-23:
In addition to catalyst and dosage, pressure, reaction time difference, catalyst activity evaluation are same as Example 1.React item
Part and catalysis reaction result are shown in Table 1.Catalyst and dosage, oxygen pressure, reaction temperature and reaction time are to urging as can be seen from Table 1
Change effect to have an impact.With reaction temperature (embodiment 2 and 3), catalyst amount (embodiment 2 and 5), oxygen pressure (3 He of embodiment
5) increase with (embodiment 5 and 6) in reaction time, yield increases.Catalyst amount increase oxygen pressure increase, acid anhydrides yield also with
Increase.Transition metal V, Fe, Co, Mn, Cu, Cr, Mo, Ce, Nb, W oxide or metal salt all show preferable effect.
1 1- indone oxicracking of table prepares phthalic anhydride
Embodiment 24-36:
In addition to substrate difference, catalyst activity evaluation is same as Example 1.Reaction condition and catalysis reaction result are shown in Table 2.
Oxicracking can occur for the 1- indone that different kinds of aromatic ring replaces, and generate corresponding anhydride compound.
The oxicracking of 2 distinct fragrance ketone of table
Oxidation efficiency of the present invention is high, and product yield is high；Using air or oxygen as oxygen source, economic, environmental protection has good
Application prospect.
Claims (1)
1. a kind of method that aromatic ketone oxicracking prepares phthalic anhydride and its substituted derivative of phenyl ring, feature exist
In: with one of air or oxygen or two kinds for oxygen source, under the action of catalyst, oxicracking occurs for aromatic ketone, generates
Phthalic anhydride or the substituted derivative of its phenyl ring；
Catalyst be transition metal V, Fe, Co, Mn, Cu, Cr, Mo, Ce, Nb, W oxide or one of metal salt or
It is two or more；
The aromatic ketone is that indone or its phenyl ring are substituted derivative, tetralone or the substituted derivative of its phenyl ring, benzo
Cycloheptanone or the substituted derivative of its phenyl ring；
Substituent group in the above-mentioned substituted derivative of phenyl ring is selected from OCH3、F、Cl、Br、I、NO2、CH3One of or two
Kind or more；
Wherein oxygen partial pressure is 0.1-2MPa, and reaction temperature is 60-180 DEG C, reaction time 1-48h；
In terms of metal, used catalyst dosage is the 0.1-30mol% of aromatic ketone；
Aromatic ketone oxicracking solvent for use be toluene, chlorobenzene, DMF, normal octane, tetrahydrofuran, dioxane, methanol, ethyl alcohol,
One of dimethyl sulfoxide is two or more, mass concentration 1-80wt% of the aromatic ketone in solvent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510249485.2A CN106279084B (en) | 2015-05-15 | 2015-05-15 | A kind of method that aromatic ketone oxicracking prepares phthalic anhydride and its cyclosubstituted derivative of virtue |
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| CN201510249485.2A CN106279084B (en) | 2015-05-15 | 2015-05-15 | A kind of method that aromatic ketone oxicracking prepares phthalic anhydride and its cyclosubstituted derivative of virtue |
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| CN106279084A CN106279084A (en) | 2017-01-04 |
| CN106279084B true CN106279084B (en) | 2019-01-22 |
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| CN115819384B (en) * | 2022-11-29 | 2024-04-26 | 大连理工大学 | Method for preparing phthalic anhydride and derivatives thereof by catalyzing and oxidizing aromatic ketone by V-N-C material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1671470A (en) * | 2002-06-19 | 2005-09-21 | 隆萨公开有限公司 | Titaniun-vanadium-tin comprising catalyst and process for the preparation of phthalic anhydride |
| CN101448810A (en) * | 2006-05-19 | 2009-06-03 | 巴斯夫欧洲公司 | Production of phthalic anhydride by gas phase oxidation of o-xylol |
| WO2011051102A1 (en) * | 2009-10-26 | 2011-05-05 | Exxonmobil Chemical Patents Inc. | Improved phthalic anhydride process |
-
2015
- 2015-05-15 CN CN201510249485.2A patent/CN106279084B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1671470A (en) * | 2002-06-19 | 2005-09-21 | 隆萨公开有限公司 | Titaniun-vanadium-tin comprising catalyst and process for the preparation of phthalic anhydride |
| CN101448810A (en) * | 2006-05-19 | 2009-06-03 | 巴斯夫欧洲公司 | Production of phthalic anhydride by gas phase oxidation of o-xylol |
| WO2011051102A1 (en) * | 2009-10-26 | 2011-05-05 | Exxonmobil Chemical Patents Inc. | Improved phthalic anhydride process |
Non-Patent Citations (3)
| Title |
|---|
| Cuprous Oxide Catalyzed Oxidative C-CBond Cleavage for C-N Bond Formation:Synthesis of Cyclic Imides from Ketones and Amines;Min Wang et al;《Angew.Chem. Int.Ed.》;20151023;第54卷;第14061-14065页 * |
| Nermin Sımsek Kus.One-step synthesis of substituted isobenzofuran-1(3H)-ones and isobenzofuran-1,3-diones from indane derivatives in subcritical media.《Monatsh Chem》.2013,第144卷第1183-1186页. * |
| 催化氧化制备生物基有机二元酸研究进展;刘俊霞等;《中国科学：化学》;20150312;第45卷(第5期);第526-532页 * |
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| CN106279084A (en) | 2017-01-04 |
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