CN109111354A - A kind of synthetic method of p-trifluoromethyl benzaldehyde - Google Patents
A kind of synthetic method of p-trifluoromethyl benzaldehyde Download PDFInfo
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- CN109111354A CN109111354A CN201810998519.1A CN201810998519A CN109111354A CN 109111354 A CN109111354 A CN 109111354A CN 201810998519 A CN201810998519 A CN 201810998519A CN 109111354 A CN109111354 A CN 109111354A
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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
- C07C45/42—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis
- C07C45/43—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis of >CX2 groups, X being halogen
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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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
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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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a kind of preparation methods of p-trifluoromethyl benzaldehyde, under the action of homemade catalyst, hydrolysis will occur to trifluoromethyl xylylene dichlorides and water, after reaction, reaction mass is layered through washing, the purified p-trifluoromethyl benzaldehyde product for obtaining 98.5% or more gas phase content of obtained p-trifluoromethyl benzaldehyde crude product, total yield of products reach 96% or more.The vacuum dried recycling catalyst of water layer, catalyst may be reused.Hydrochloric acid can be made through water absorption by generating hydrogen chloride in the process.The environmentally protective excellent characteristics such as method provided by the invention has technique simple and direct, and the three wastes are few, to be more suitable for industrial-scale production.
Description
Technical field
The present invention relates to the preparation methods of p-trifluoromethyl benzaldehyde, belong to technical field of organic synthesis.
Background technique
P-trifluoromethyl benzaldehyde also known as 4- trifluoromethylated benzaldehyde, English entitled α, α, α-Trifluoro-p-
Tolualdehyde, molecular formula C8H5F3O, relative molecular weight 174.12, colourless liquid.As a kind of important organic centre
Body is widely used in pesticide, medicine and organic synthesis.The use in newtype drug synthesis receives much attention in recent years.It synthesizes road
Line mainly has:
(1) to trifluoromethyl xylylene dichlorides Hydrolyze method；
(2) 1- (4- trifluoromethyl) phenyl -1- nitromethane oxidizing process；
(3) to trifluoromethylbenzonitrile reduction method；
(4) to trifluoromethyl benzoyl chloride hydrogenation method；
(5) p-trifluoromethylaniline diazonium salt Hydrolyze method；
(6) rearrangement method in 1- (4- trifluoromethyl) phenyl -1- methyl sulfoxide water.
It wherein, is the production technology of existing maturation to trifluoromethyl xylylene dichlorides Hydrolyze method, hydrolytic process is with dense
It spends higher sulfuric acid and carries out catalyzing hydrolysis, therefore a large amount of spent acid will be generated, processing pressure is larger.And other several techniques
Route is difficult to realize industrialized production because of at high cost or severe reaction conditions.
Currently, as attention degree of the country to environmental protection increasingly improves and market is to the need of p-trifluoromethyl benzaldehyde
It asks trend vigorous, it is imperative to develop a kind of environmentally protective p-trifluoromethyl benzaldehyde synthetic method.
Summary of the invention
When studying some specific ionic compounds, discovery is a kind of to be had if the ionic compound of formula (Ι) structure is to right
Trifluoromethyl xylylene dichlorides hydrolysis can play good catalytic action.
Wherein, R1, R2, R3 represent the alkylidene of C1~4；
M represents hydrogen or alkali metal；
M, n represent 0~4 natural number, and m+n=4.
The structure feature of this kind of ionic compound is: (1) R1, R2 and R3 represent the methylene or ethylidene of straight chain, or sub-
Propyl or butylidene.R1, R2 and R3 may be the same or different.(2) M represents hydrogen or a kind of alkali metal, alkali metal such as K,
Or Na or Li et al..(3) pyridine ring being connected respectively with R1, R2 and R3, their N can be neighbour with corresponding R1, R2 and R3
Position, contraposition or meta position.(4) and the N that is connected of R1, R2 and R3+With Cl-Or MSO4-An ion pair is constituted, and
The N on pyridine ring being connected with R1, R2 and R3+With Cl-Or MSO4-Three ion pairs are constituted, i.e., in a molecular structure altogether
Four ion pairs are deposited, and under certain specific environment, anion exchange recombination may occur for ion pair.This kind of ion combination
Object can use N, (pyridine alkylidene) amine of N, N- tri- and hydrochloric acid or sulfuric acid or alkali metal bisulfates reactant salt and be made, wherein N, N,
N- tri- (pyridine alkylidene) amine, which directly can be bought or synthesize, to be obtained.
Technical scheme is as follows:
A kind of preparation method of p-trifluoromethyl benzaldehyde will be to trifluoromethyl two under the action of homemade catalyst
Hydrolysis occurs for chloromethylbenzene and water, and after reaction, reaction mass is layered through washing, obtained p-trifluoromethyl benzaldehyde
Crude product is purified to obtain p-trifluoromethyl benzaldehyde product.The vacuum dried recycling catalyst of water layer, catalyst can repeat to make
With.Hydrochloric acid can be made through water absorption by generating hydrogen chloride in the process.
In above-mentioned technical proposal, the homemade catalyst structure formula is as follows.
Wherein, R1, R2, R3 represent the alkylidene of C1~4；
M represents hydrogen or alkali metal；
M, n represent 0~4 natural number, and m+n=4.
In above-mentioned technical proposal, preferably, the catalyst is with the mass ratio to trifluoromethyl xylylene dichlorides
0.02~0.1:1, more preferably 0.05~0.1:1.
In above-mentioned technical proposal, preferably, the water in the hydrolysis stage with to trifluoromethyl xylylene dichlorides
Mass ratio is 0.08~0.4:1, more preferably 0.1~0.2:1.
In above-mentioned technical proposal, preferably, reaction temperature is controlled at 100~130 DEG C, more preferably when the reaction
110~120 DEG C.
In above-mentioned technical proposal, the reaction can carry out under normal pressure, can also be in reaction system under boosting power
It carries out.
In above-mentioned technical proposal, preferably, by-product --- the chlorination that the reaction can will generate in reaction process
Hydrogen is constantly absorbed with water, and hydrochloric acid is made.
In above-mentioned technical proposal, it may be reused after the catalyst is recovered.
In above-mentioned technical proposal, further include the steps that purification of products after the reaction step, such as liquid separation, washing, mistake
Filter, dry, fractionation etc., are this field routine operation, are known to technical staff, this will not be repeated here.
The present invention using a kind of there is the ionic compound such as formula (Ι) structure to introduce as catalyst to trifluoromethyl dichloromethane
Base benzene hydrolysis is prepared in the reaction of p-trifluoromethyl benzaldehyde, and good reaction effect can be played.Show the following aspects:
(1) reaction does not generate a large amount of discarded acid
It is existing to trifluoromethyl xylylene dichlorides technology for hydrolyzing because using the sulfuric acid of a large amount of about 83% concentration to make catalyst
Cause Waste Sulfuric Acid yield big, unfavorable to environmental protection, and not only dosage is few for the catalyst that the present invention uses, and catalyst and hydrolyzes
It is immiscible between the p-trifluoromethyl benzaldehyde arrived, it is easy to recycle and reuse, the hydrogen chloride for reacting generation can all be inhaled
Receipts form by-product, so the not generation of spent acid.
(2) reaction is completed in efficient situation
In the prior art, the usage amount of sulfuric acid is usually 2~3 times to trifluoromethyl xylylene dichlorides amount quality, and
The dosage of catalyst of the invention is only 0.02~0.1 times to trifluoromethyl xylylene dichlorides amount quality, to trifluoromethyl
The yield of benzaldehyde can achieve 96% or more, this reaction result is suitable with existing sulfuric acid catalysis effect.It can be seen that this
Catalyst used by inventing shows high reactivity and selectivity.
(3) catalyst stabilization, and convenient for recycling and reuse
For compared with the prior art, ionic compound catalyst performance of the present invention is more stable.It will not
It is unstable and decompose under prolonged thermal rection condition, and because its between p-trifluoromethyl benzaldehyde it is immiscible,
This just can be easily separated the two, not easily cause ingredients from lossing.Catalyst after the recovery may be reused after dehydrating, and lead to
It crosses and reuses three times, do not have a adverse impact to product content.
In conclusion the present invention provides a kind of preparation method of p-trifluoromethyl benzaldehyde, in homemade catalyst
Under effect, hydrolysis will occur to trifluoromethyl xylylene dichlorides and water, after reaction, reaction mass is layered through washing,
The purified p-trifluoromethyl benzaldehyde product for obtaining 98.5% or more gas phase content of obtained p-trifluoromethyl benzaldehyde crude product,
Total yield of products reaches 96% or more.The vacuum dried recycling catalyst of water layer, catalyst may be reused.It generates in the process
Hydrochloric acid can be made through water absorption in hydrogen chloride.Method provided by the invention has technique simple and direct, and it is environmentally protective excellent that the three wastes are few etc.
Different feature, to be more suitable for industrial-scale production.
Detailed description of the invention
Fig. 1 is the qualitative figure of 13C NMR.
Fig. 2 is the gas chromatogram that 1 step of embodiment obtains.
Fig. 3 is the gas chromatogram that 3 step of embodiment obtains.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.In following embodiments, unless otherwise specified, used experimental method is conventional method, institute
It can be bought from biological or chemical company with other materials, the reagent etc. in addition to catalyst.
Catalyst is by one group of N, (pyridine alkylidene) amine of N, N- tri- and hydrochloric acid or sulfuric acid or alkali metal sulphuric acid hydrogen salt or alkali
Prepared by one of metal sulfate or two kinds or more reaction, specific synthetic method, will by taking the synthesis of No. 1 catalyst as an example
Amine is mixed with 200ml methanol, and is sufficiently dissolved under reflux temperature by 42g N, N, N- tri- (2- (2- pyridine) ethyl), is then instilled
50% sulfuric acid of 25g mass concentration, maintains the reflux for for 24 hours, then instills 35% hydrochloric acid of 46g mass concentration, then maintain the reflux for 36h, decompression
After drying, resulting material is washed with 100ml ether again, and washing three times, is then dried under reduced pressure, and obtains 63g1 catalyst, and mark produces
Object is confirmed by nuclear magnetic resoance spectrum and high resolution mass spectrum measurement, and 13C NMR is qualitative to be detailed in Fig. 1.2 to No. 5 catalyst
It can be made with similar method and (the difference is that only raw material replacement or reduce), these catalyst and preparation condition are shown in Table 1.
The preparation condition of 1 catalyst of table
The embodiment of the present invention uses gas chromatographic detection methyl phenyl ethers anisole, and condition is as follows:
6890 formula equivalent of GC Agilent
Fid detector, chromatographic work station
The equivalent chromatographic column of ZB-5 (30m × 0.32mm × 0.25 μm) formula
Hydrogen flow rate: 30ml/min
Air velocity: 300ml/min
Carrier gas (High Purity Nitrogen) flow velocity: 1.0ml/min
Gasify room temperature: 260 DEG C
Detector temperature: 260 DEG C
Middle control condition:
Initial column temperature: 120 DEG C
Termination column temperature: 260 DEG C
Heating rate: 20 DEG C/min
Product condition:
Column temperature: 100 DEG C of operation 20min
The preparation of 1 p-trifluoromethyl benzaldehyde of embodiment
1. hydrolysis: to the 0.5L for being furnished with thermometer, stirring, dropping funel, reflux condenser and device for absorbing tail gas
Industrial crude product is put into there-necked flask respectively to trifluoromethyl xylylene dichlorides 250g (1mol) and No. 1 catalyst 12.5g, stirring rises
50g deionized water, time for adding are slowly added dropwise into reaction system by dropping funel at this temperature to 110~120 DEG C for temperature
2.5h is added dropwise, and keeps the temperature 1h, and taking the detection of kettle sample, (gas chromatogram is detailed in trifluoromethyl xylylene dichlorides residue 0.14%
Fig. 2), reaction terminates.
2. post-processing: 1. after reaction, kettle temperature drops to 90 DEG C, and 10g deionized water is added, and abundant static 1h is separated and contained
The water layer 55g of catalyst, organic phase are washed twice with 50g deionized water, obtain p-trifluoromethyl benzaldehyde crude product 188g, washing
After water merges with the water layer containing catalyst before, decompression dehydration obtains 12.8g recycling catalyst.
3. p-trifluoromethyl benzaldehyde rectifying: the 188g p-trifluoromethyl benzaldehyde crude product 2. obtained immigration is furnished with
The 250mL rectifier unit of the rectifying column of 500mm high collects the fraction of 100~105 DEG C/- 0.098MPa, obtains 169.3g content
For 98.8% p-trifluoromethyl benzaldehyde (gas chromatogram is detailed in Fig. 3), product yield 96.1%, rectification residue 2.8g.
The preparation of 2 p-trifluoromethyl benzaldehyde of embodiment
With embodiment 1, difference from Example 1 is reaction process, by embodiment 1, with No. 2 catalyst 25g generations
For No. 1 catalyst, deionized water 25g, other constant, recycling catalyst 26g, obtains 99.2% pair of trifluoromethylbenzene after reaction
Formaldehyde 167g, product yield 95.1%, rectification residue 2.9g.
The preparation of 3 p-trifluoromethyl benzaldehyde of embodiment
With embodiment 1, difference from Example 1 is reaction process, by embodiment 1, with No. 3 catalyst 12.5g
It is other constant instead of No. 1 catalyst.Catalyst 13g is recycled after reaction, obtains 99.0% p-trifluoromethyl benzaldehyde 165.3g,
Product yield is 94.0%, rectification residue 4.2g.
The preparation of 4 p-trifluoromethyl benzaldehyde of embodiment
With embodiment 1, difference from Example 1 is reaction process, by embodiment 1, with No. 4 catalyst 15g generations
It is other constant for No. 1 catalyst.Catalyst 15.4g is recycled after reaction, obtains 99.3% p-trifluoromethyl benzaldehyde 169.5g,
Product yield is 96.7%, rectification residue 2.3g.
The preparation of 5 p-trifluoromethyl benzaldehyde of embodiment
With embodiment 1, difference from Example 1 is reaction process, by embodiment 1, with No. 5 catalyst 15g generations
It is other constant for No. 1 catalyst.Catalyst 15.3g is recycled after reaction, obtains 99.5% p-trifluoromethyl benzaldehyde 170g, is produced
Product yield is 97.1%, rectification residue 2.2g.
The preparation of 6 p-trifluoromethyl benzaldehyde of embodiment
With embodiment 1, difference from Example 1 is reaction process, by embodiment 1, with what is recycled in embodiment 5
Catalyst 15.3g replaces No. 1 catalyst, other constant.Catalyst 15.5g is recycled after reaction, obtains 99.3% pair of trifluoromethyl
Benzaldehyde 170.2g, product yield 97.0%, rectification residue 2.7g.
The preparation of 7 p-trifluoromethyl benzaldehyde of embodiment
With embodiment 1, difference from Example 1 is reaction process, by embodiment 1, with what is recycled in embodiment 6
Catalyst 15.5g replaces No. 1 catalyst, other constant.Catalyst 15.2g is recycled after reaction, obtains 99.2% pair of trifluoromethyl
Benzaldehyde 171g, product yield 97.4%, rectification residue 2.5g.
The preparation of 8 p-trifluoromethyl benzaldehyde of embodiment
With embodiment 1, difference from Example 1 is reaction process, by embodiment 1, with what is recycled in embodiment 7
Catalyst 15.2g replaces No. 1 catalyst, other constant.Catalyst 15.3g is recycled after reaction, obtains 99.3% pair of trifluoromethyl
Benzaldehyde 169.4g, product yield 96.6%, rectification residue 3.3g.
The preparation of 1 p-trifluoromethyl benzaldehyde of comparative example
1. hydrolysis: to the 0.5L for being furnished with thermometer, stirring, dropping funel, reflux condenser and device for absorbing tail gas
Industrial crude product is put into there-necked flask respectively to the sulfuric acid 187.5g of trifluoromethyl xylylene dichlorides 62.5g (0.25mol) and 83%,
Stirring is warming up to 80~90 DEG C, keeps the temperature 1h at this temperature, and kettle sample is taken to detect to trifluoromethyl xylylene dichlorides residue 0.17%,
Reaction terminates.
2. post-processing: 1. after reaction, 100g water is added, stirs 0.5h, static 1h separates the water layer of sulfur acid
289g, organic phase three times, obtain p-trifluoromethyl benzaldehyde crude product 45g with 50g water washing.
3. p-trifluoromethyl benzaldehyde rectifying: the 45g p-trifluoromethyl benzaldehyde crude product 2. obtained being moved into and is furnished with 500mm
The 250mL rectifier unit of high rectifying column collects the fraction of 100~105 DEG C/- 0.098MPa, and obtaining 40.2g content is
98.9% p-trifluoromethyl benzaldehyde, product yield 91.3%, rectification residue 1.6g.
Claims (9)
1. a kind of synthetic method of p-trifluoromethyl benzaldehyde under the effect of the catalyst will be to trifluoromethyl xylylene dichlorides
Hydrolysis occurs with water, obtains p-trifluoromethyl benzaldehyde product；
The catalyst structure formula is as follows:
Wherein, R1, R2, R3 represent the alkylidene of C1~4；
M represents hydrogen or alkali metal, preferably hydrogen；
M, n represent 0~4 natural number, and m+n=4.
2. synthetic method according to claim 1, which is characterized in that hydrolyzed to trifluoromethyl xylylene dichlorides with water
Reaction, after reaction, reaction mass are layered through washing, and obtained p-trifluoromethyl benzaldehyde crude product is purified to obtain to three
Methyl fluoride benzaldehyde product；The vacuum dried recycling catalyst of water layer, catalyst may be reused；Hydrogen chloride is generated in the process
Hydrochloric acid can be made through water absorption.
3. synthetic method according to claim 1, which is characterized in that the catalyst with to trifluoromethyl xylylene dichlorides
Mass ratio be 0.02~0.1:1,0.05~0.1:1 of preferred scope.
4. synthetic method according to claim 1, which is characterized in that the water in the hydrolysis stage with to trifluoromethyl
The mass ratio of xylylene dichlorides is 0.08~0.4:1,0.1~0.2:1 of preferred scope.
5. synthetic method according to claim 1, which is characterized in that when the reaction, reaction temperature control 100~
130 DEG C, 110~120 DEG C of preferred scope.
6. synthetic method according to claim 1, which is characterized in that the reaction can carry out under normal pressure, or can also
With carrying out under boosting power in confined reaction system.
7. synthetic method according to claim 1, which is characterized in that the pair that the reaction can will generate in reaction process
Product --- hydrogen chloride is constantly absorbed with water, and hydrochloric acid is made.
8. synthetic method according to claim 1, which is characterized in that may be reused after the catalyst is recovered.
9. synthetic method according to claim 1, which is characterized in that alkali metal is potassium or sodium.
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| WO2018081347A1 (en) * | 2016-10-26 | 2018-05-03 | Temple University-Of The Commonwealth System Of Higher Education | Polycationic amphiphiles as antimicrobial agents and methods using same |
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| CN101412694A (en) * | 2008-11-28 | 2009-04-22 | 江苏大学 | Preparation of efficient green tripyridyl methyl amine compounds |
| CN102516047A (en) * | 2011-12-13 | 2012-06-27 | 联化科技股份有限公司 | Preparation methods of 2-(trifluoromethyl)benzaldehyde and intermediate thereof |
| CN107540525A (en) * | 2016-06-27 | 2018-01-05 | 宁夏海诚电化信息科技有限公司 | A kind of p-trifluoromethyl benzaldehyde production procedure |
| WO2018081347A1 (en) * | 2016-10-26 | 2018-05-03 | Temple University-Of The Commonwealth System Of Higher Education | Polycationic amphiphiles as antimicrobial agents and methods using same |
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Application publication date: 20190101 |
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| RJ01 | Rejection of invention patent application after publication |