CN106565445A - Preparation method of p-fluorobenzaldehyde - Google Patents
Preparation method of p-fluorobenzaldehyde Download PDFInfo
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- CN106565445A CN106565445A CN201510655139.4A CN201510655139A CN106565445A CN 106565445 A CN106565445 A CN 106565445A CN 201510655139 A CN201510655139 A CN 201510655139A CN 106565445 A CN106565445 A CN 106565445A
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- Prior art keywords
- fluorobenzaldehyde
- preparation
- compound
- promoter
- catalyst
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- WRWPPGUCZBJXKX-UHFFFAOYSA-N Cc(cc1)ccc1F Chemical compound Cc(cc1)ccc1F WRWPPGUCZBJXKX-UHFFFAOYSA-N 0.000 description 1
- UOQXIWFBQSVDPP-UHFFFAOYSA-N O=Cc(cc1)ccc1F Chemical compound O=Cc(cc1)ccc1F UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 description 1
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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
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Belonging to the field of chemistry, in particular to the field of medicine synthesis, the invention particularly relates to a preparation method of p-fluorobenzaldehyde. Directed at the problems of low yield, high cost, pollution and other problems in existing p-fluorobenzaldehyde industrial synthesis the invention provides a brand new preparation method of p-fluorobenzaldehyde. P-fluorotoluene is adopted as the raw material for catalytic oxidation to prepare p-fluorobenzaldehyde, thus effectively controlling the oxidation degree, achieving high selective synthesis of p-fluorobenzaldehyde, reducing content of alcohol and carboxylic acid by-products in the product, and effectively reducing wastewater and waste emission at the same time. The method provided by the invention achieves high yield and high purity, and can realize industrial large-scale green synthesis of p-fluorobenzaldehyde.
Description
Technical field
The invention belongs to chemical field, especially belongs to medical synthesis field, more particularly relates to one kind
The preparation method of 4-Fluorobenzaldehyde.
Background technology
4-Fluorobenzaldehyde is a kind of very important organic synthesis intermediate, can be widely applied to medicine, pesticide,
In the synthesis of the fine chemicals such as plastic additive.The primary synthetic methods of the 4-Fluorobenzaldehyde of report are chlorine at present
For Hydrolyze method, direct chemical oxidization method, electrochemical oxidation process, dioxygen oxidation method etc..
Document " study on the synthesis of 4-Fluorobenzaldehyde. dye industry .2001,38 (3), 32～34 " report with to fluorine
Toluene is raw material, and chlorinolysis synthesis is obtained, and the method total recovery can reach 86%, but due to containing in its product
Have micro chlorine so as to apply and be restricted in some fields, and serious is caused to environment in building-up process
Pollution, is not suitable for large-scale production.
Simultaneously as aldehyde is not highest oxidation rank, it is very easy to continue oxidation formation in existing synthesis
Carboxylic acid compound, thus the substantial amounts of carboxylic acidss by-product of content in product.This selection just to 4-Fluorobenzaldehyde
Property synthesis cause very big difficulty.And this problem also causes the synthetic method of 4-Fluorobenzaldehyde raw in big industry
There is low yield, high cost in product, it is difficult to the problem of industrialization promotion.
The content of the invention
The purpose of the present invention be that for current 4-Fluorobenzaldehyde industry be combined to present in low yield, high cost,
And the problems such as cause pollution, there is provided a kind of preparation method of brand-new 4-Fluorobenzaldehyde, such that it is able to effectively
Control degree of oxidation, synthesizes 4-Fluorobenzaldehyde with high selectivity, reduces alcohol, carboxylic acid byproduct content in product,
Wastewater and waste materials discharge can be effectively reduced simultaneously.Realize in high yield, high-purity, can be extensive green with industrialization ground
Color synthesizes 4-Fluorobenzaldehyde.
In order to realize this purpose, the invention particularly discloses two kinds of synthesis techniques.
The first synthetic method is to be aoxidized to form by p-fluorotoluene under conditions of 50～150 DEG C, 1.7～2.2MPa, its
Synthetic route is as follows：
Wherein：Catalyst one kind arbitrarily in manganese compound, cobalt compound, iron compound,
Promoter is any one in bromide；
Reaction dissolvent is any one in acetic acid or acetonitrile.
Preferably, reaction temperature is 90～120 DEG C.Reaction is generally carried out 1～3 hour.
Preferably, catalyst arbitrarily selects the one kind in manganese acetate, cobaltous acetate, iron acetate, particularly preferably acetic acid
Cobalt.
Preferably, promoter is potassium bromide or the one kind in sodium bromide.
Preferably, compound ii：Catalyst：The mol ratio of promoter is 1：0.01～0.1：0.01～0.1.
It is further preferable that compound ii：Catalyst：The mol ratio of promoter is 1：0.04～0.06：0.04～0.06.
Second synthetic method is to be aoxidized to form by p-fluorotoluene under conditions of 50～100 DEG C, and its synthetic route is as follows：
Wherein：Catalyst is arbitrarily selected from 8%Cr2O3/ HMS, 7%Fe2O3In/HZSM-5,13%V-MCM-41
One kind；Especially preferably 13%V-MCM-41.Reaction dissolvent is any one in acetonitrile or acetic acid.
Preferably, hydrogen peroxide of the hydrogen peroxide for volumetric concentration 30%.
Preferably, reaction temperature is 70～90 DEG C.
Preferably, n (compound ii, mol)：M (catalyst, g)：N (promoter, mol)：V (hydrogen peroxide,
L ratio) is 1：2～6：0.01～0.1：0.5～5.
It is further preferable that n (compound ii, mol)：M (catalyst, g)：N (promoter, mol)：V is (double
Oxygen water, L) ratio be 1：4～5：0.04～0.06：1～2.
Using technology contents disclosed in this invention, the use due to avoiding chlorine, with p-fluorotoluene as initiation material,
Thus will not be a kind of environment amenable synthetic method to environmental effects.While conversion rate of products height,
High income, purity are high, and low production cost is beneficial to industrialization large-scale production.
Specific embodiment
In order to be better understood from the present invention, below we in conjunction with specific embodiments the present invention is carried out further
Illustrate.
Must state first, the reagent for arriving used in the present invention, instrument etc. unless there are specified otherwise,
Other are commercially available product.If no special instructions, all technologies herein and scientific terminology are by the present invention
The normal implication that involved industry those of ordinary skill is commonly understood by.
Embodiment 1
To in autoclave add compound ii (10mmol), acetic acid (50ml), potassium bromide (0.4mmol) with
And cobaltous acetate (0.5mmol), autoclave is sealed, and air is filled with reactor, pressure is risen to into 2.0Mpa,
System is warming up to into 120 DEG C.After stirring reaction 2.5 hours, recovery pressure to normal pressure, opening kettle cover, sucking filtration,
Filtrate pours vacuum distillation apparatus into, in 75～80 DEG C of recovered under reduced pressure acetic acid to after doing, is continuously heating to 135～140 DEG C
Fine vacuum collects I 9.5mmol of product compound, yield 95%.
Embodiment 2
To in autoclave add compound ii (10mmol), acetic acid (60ml), sodium bromide (0.5mmol) with
And manganese acetate (0.5mmol), autoclave is sealed, and air is filled with reactor, pressure is risen to into 1.9Mpa,
System is warming up to into 120 DEG C.After stirring reaction 3 hours, recover pressure to normal pressure, open kettle cover, sucking filtration point
From insoluble matter.Filtrate pours vacuum distillation apparatus into, in 75～80 DEG C of recovered under reduced pressure acetic acid to after doing, continues to heat up
I 9.0mmol of product compound, yield 90% are collected to 135～140 DEG C of fine vacuum.
Embodiment 3
To in autoclave add compound ii (10mmol), acetic acid (50ml), potassium bromide (0.5mmol) with
And iron acetate (0.5mmol), autoclave is sealed, and air is filled with reactor, pressure is risen to into 1.8Mpa,
System is warming up to into 110 DEG C.After stirring reaction 3 hours, recover pressure to normal pressure, open kettle cover, sucking filtration point
From insoluble matter.Filtrate pours vacuum distillation apparatus into, in 45～50 DEG C of recovered under reduced pressure acetonitriles to after doing, continues to heat up
I 8.3mmol of product compound, yield 83% are collected to 135～140 DEG C of fine vacuum.
Embodiment 4
Compound ii (10mmol) is added in the reaction bulb equipped with acetonitrile (60ml), after dissolving, is added
13%V-MCM-41 molecular sieves (0.05g), potassium bromide (0.5mmol), 30% hydrogen peroxide (10ml), stirring
85 DEG C are warming up to, are reacted 3 hours.Sucking filtration, filtrate pour vacuum distillation apparatus into, in 60～65 DEG C of recovered under reduced pressure
Acetonitrile and water, are continuously heating to 135～140 DEG C of fine vacuum and collect I 9.4mmol of product compound, yield 94%.
Embodiment 5
Compound ii (10mmol) is added in the reaction bulb equipped with acetonitrile (60ml), after dissolving, is added
8%Cr2O3/ HMS molecular sieves (0.05g), sodium bromide (0.5mmol), 30% hydrogen peroxide (10ml), stirring
85 DEG C are warming up to, are reacted 2.5 hours.Sucking filtration, filtrate pour vacuum distillation apparatus into, reduce pressure back at 60～65 DEG C
Acetonitrile and water are received, 145～150 DEG C of fine vacuum is continuously heating to and is collected I 8.4mmol of product compound, yield 84%.
Embodiment 6
Compound ii (10mmol) is added in the reaction bulb equipped with acetonitrile (60ml), after dissolving, is added
7%Fe2O3/ HZSM-5 molecular sieves (0.04g), sodium bromide (0.6mmol), 30% hydrogen peroxide (20ml),
Stirring is warming up to 85 DEG C, reacts 2 hours.Sucking filtration, filtrate pour vacuum distillation apparatus into, reduce pressure at 60～65 DEG C
Acetonitrile and water are reclaimed, 135～140 DEG C of fine vacuum is continuously heating to and is collected I 8.5mmol of product compound, yield
85%.
Comparative example
To in autoclave add compound ii (10mmol), acetic acid (50ml), potassium bromide (0.4mmol) with
And cobaltous acetate (0.25mmol)-manganese acetate (0.25mol) mixed catalyst system, autoclave is sealed, to anti-
Air is filled with answering kettle, pressure is risen to into 2.0Mpa, system is warming up to into 120 DEG C.Stirring reaction 2.5 hours
Afterwards, recover pressure to normal pressure, open kettle cover, sucking filtration goes out solid, and filtrate pours vacuum distillation apparatus into, at 75～80 DEG C
Recovered under reduced pressure acetic acid to after doing is continuously heating to 135～140 DEG C of fine vacuum and collects I 5.6mmol of product compound,
Yield 56%.
Claims (10)
1. the preparation method of 4-Fluorobenzaldehyde, is characterized in that, by p-fluorotoluene in 50～150 DEG C, 1.7～2.2MPa
Under conditions of aoxidize and form, its synthetic route is as follows：
Wherein：Catalyst one kind arbitrarily in manganese compound, cobalt compound, iron compound；
Promoter is any one in bromide；
Reaction dissolvent is any one in acetic acid or acetonitrile.
2. the preparation method of 4-Fluorobenzaldehyde according to claim 1, is characterized in that, catalyst is arbitrarily selected
Select the one kind in manganese acetate, cobaltous acetate, iron acetate.
3. the preparation method of 4-Fluorobenzaldehyde according to claim 1, is characterized in that, promoter is bromination
One kind in potassium or sodium bromide.
4. the preparation method of 4-Fluorobenzaldehyde according to any one of claim 1 to 3, is characterized in that, change
Compound II：Catalyst：The mol ratio of promoter is 1：0.01～0.1：0.01～0.1.
5. the preparation method of 4-Fluorobenzaldehyde according to claim 4, is characterized in that, compound ii：Catalysis
Agent：The mol ratio of promoter is 1：0.04～0.06：0.04～0.06.
6. the preparation method of 4-Fluorobenzaldehyde, is characterized in that, aoxidized under conditions of 50～100 DEG C by p-fluorotoluene and
Into its synthetic route is as follows：
Wherein：Catalyst is arbitrarily selected from 8%Cr2O3/ HMS, 7%Fe2O3In/HZSM-5,13%V-MCM-41
One kind；Promoter is any one in potassium bromide or sodium bromide；During reaction dissolvent is acetonitrile or acetic acid
Any one.
7. the preparation method of 4-Fluorobenzaldehyde according to claim 6, is characterized in that, hydrogen peroxide is that volume is dense
The hydrogen peroxide of degree 30%.
8. the preparation method of 4-Fluorobenzaldehyde according to claim 6, is characterized in that, reaction temperature is 70～90 DEG C.
9. the preparation method of 4-Fluorobenzaldehyde according to claim 6, is characterized in that, n (compound ii,
mol)：M (catalyst, g)：N (promoter, mol)：The ratio of V (hydrogen peroxide, L) is 1：2～6：
0.01～0.1：0.5～5.
10. the preparation method of 4-Fluorobenzaldehyde according to claim 9, is characterized in that, n (compound ii,
mol)：M (catalyst, g)：N (promoter, mol)：The ratio of V (hydrogen peroxide, L) is 1：4～5：
0.04～0.06：1～2.
Priority Applications (1)
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| CN201510655139.4A CN106565445A (en) | 2015-10-10 | 2015-10-10 | Preparation method of p-fluorobenzaldehyde |
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| CN201510655139.4A CN106565445A (en) | 2015-10-10 | 2015-10-10 | Preparation method of p-fluorobenzaldehyde |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655457A (en) * | 2019-09-05 | 2020-01-07 | 门希国 | Novel method for preparing p-fluorobenzaldehyde by catalytic oxidation of hydrogen peroxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4088823A (en) * | 1975-10-07 | 1978-05-09 | Phillips Petroleum Company | Promoted liquid phase oxidation of alkyl aromatic compounds |
| CN1724500A (en) * | 2005-07-22 | 2006-01-25 | 云南大学 | Method of liquid phase catalyzing oxihalogenated foluene to halogenated benzaldehyde |
-
2015
- 2015-10-10 CN CN201510655139.4A patent/CN106565445A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4088823A (en) * | 1975-10-07 | 1978-05-09 | Phillips Petroleum Company | Promoted liquid phase oxidation of alkyl aromatic compounds |
| CN1724500A (en) * | 2005-07-22 | 2006-01-25 | 云南大学 | Method of liquid phase catalyzing oxihalogenated foluene to halogenated benzaldehyde |
Non-Patent Citations (4)
| Title |
|---|
| HEMANT V. BORGAONKAR等: "Liquid Phase Oxidation of Toluene to Benzaldehyde by Air", 《IND. ENG. CHEM. PROD. RES. DEV.》 * |
| 吴娟娟: "甲苯液相双氧水选择氧化及天然苯甲醛的合成研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑（月刊）》 * |
| 姚其正: "《药物合成反应》", 31 December 2012 * |
| 方永勤等: "对氟甲苯液相氧化制备对氟苯甲醛", 《常州大学学报（自然科学版）》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655457A (en) * | 2019-09-05 | 2020-01-07 | 门希国 | Novel method for preparing p-fluorobenzaldehyde by catalytic oxidation of hydrogen peroxide |
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Application publication date: 20170419 |