CN107973703A - A kind of synthetic method of aryl olefin - Google Patents
A kind of synthetic method of aryl olefin Download PDFInfo
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- CN107973703A CN107973703A CN201711252869.5A CN201711252869A CN107973703A CN 107973703 A CN107973703 A CN 107973703A CN 201711252869 A CN201711252869 A CN 201711252869A CN 107973703 A CN107973703 A CN 107973703A
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- reaction
- synthetic method
- substituted olefins
- isoesdragol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of synthetic method containing aryl-substituted olefins disclosed by the invention, it is characterized in that reacted using aliphatic acetal as alkylating agent with aromatic compound, under solid acid catalyst catalytic action, under 0.1 1.0MPa of normal pressure or low pressure, in the range of reaction temperature is 90 160 DEG C, one pot reaction directly obtains the aryl-substituted olefins such as isoesdragol.The present invention has following features：1) it is a kind of new synthetic route, reaction is one pot of completion.2) aromatic compound is not only used as reactant, but also is used as solvent, without using other organic solvents.3) catalyst is the solid acids such as H Beta molecular sieves and its Modified Molecular Sieves, and is catalytic amount.4) after the alcohol recycling produced, can be recycled when synthesizing acetal.5) reaction may be carried out batchwise, and can also be carried out in tubular reactor and fixed bed reactors.6) post processing is simple, does not have discarded object generation in reaction process, is a kind of environmentally protective synthetic route.
Description
Technical field
The invention belongs to organic synthesis field, and in particular to a kind of synthetic method of aryl olefin, especially isoesdragol
Synthesis.
Background technology
Isoesdragol (also referred to as anethole or trans-anethole), chemical name 1- methoxyl groups -4- (1- acrylic) benzene is naturally occurring
In the essential oils such as oil of badian, ennel oil, trans body is in the great majority.It is main to use with the sweet fennel fragrance of characteristic
In allotment food flavor and toothpaste essence.
The traditional preparation methods of isoesdragol be from the natural essential oil rich in isoesdragol by freezing and crystallizing, centrifuge
To the method extraction of isoesdragol crude product, then rectifying.Such as from oil of badian, ennel oil extraction (referring to CN102491884
And essence and flavoring agent cosmetics, 2013,02 phases).
Since the source of natural essential oil and quantity are restricted, the isoesdragol naturally produced can not meet growing need
Ask.Therefore, synthesis finished product has the very big market demand and commercial value.Its synthesis is widely paid attention to all the time.
CN103058835 describes a kind of synthetic method of isoesdragol, uses propionyl chloride and the friedel- of methyl phenyl ethers anisole
Crafts reacts to obtain to methoxybenzene acetone, then corresponding alcohol is obtained with sodium borohydride reduction, then in p-methyl benzenesulfonic acid
Deng acid condition under dehydration obtain trans-anethole.Due to needing, using the propionating of excessive Aluminium Trichloride as Catalyst methyl phenyl ethers anisole, to obtain
Substantial amounts of waste discharge, environmental protection side are all produced using sodium borohydride reduction and last dehydration to methoxybenzene acetone
There is not minor issue in face.
DE19742418974 reveals the method for synthesizing isoesdragol for two step of starting material using methyl phenyl ethers anisole and propionic aldehyde.
First, methyl phenyl ethers anisole produces the mixture of double (methoxyphenyl) propane under acidic catalyst effect with propionic aldehyde, and second step is above-mentioned
Condensation product occurs to eliminate anti-in the presence of the acidic catalysts such as the phosphoric acid of catalytic amount under 200-300 DEG C and certain vacuum degree
Crude product and should be steamed.Condensation product conversion ratio 67.3%, isoesdragol selectivity about 41%. crude products in contain the unreacted contracting in part
Compound, trans-anethole, the trans trans-anethole of cis isoesdragol and ortho position etc.；It is said that ortho position trans-anethole is again anti-together with methyl phenyl ethers anisole
The condensation mixture cracking that should be obtained can obtain about 8% isoesdragol.Shortcoming is that reaction needs to occur at relatively high temperatures,
The cracking for being condensed intermediate is incomplete；Also obtain a considerable amount of ortho position trans-anetholes and other accessory substances；Due to the length of cracking process
The complexity of ortho position trans-anethole process is heated and recycled to time, produce a considerable amount of accessory substances, unwanted isomers and
Other polymers etc..
CN103755533 describe it is a kind of with chavicol methyl ether oil be Material synthesis trans-anethole method, it is in basic catalyst
Under effect, chavicol methyl ether oil isomerization reaction 0.5-3h at a temperature of 140-215 DEG C, chavicol methyl ether is isomerized to isoesdragol, then leads to
Cross freezing and crystallizing, filtering and rectifying and obtain isoesdragol.
CN106103398 discloses the thermal decomposition that one kind is directed to use with corresponding 1,1- diarylpropanes, is used to prepare virtue
The method of base propylene especially 1- methoxyl groups -4- (1- acrylic) benzene (isoesdragol).By 1,1- diarylpropanes in one kind
Under boron-containing molecular sieve catalyst action, decompression and the gas phase thermal decomposition at a temperature of 300-400 DEG C, slough an aromatic hydrocarbon molecule, obtain
To isoesdragol.
Above-mentioned related process is either not readily available using expensive raw material price or process three waste discharge problem is serious,
Or the reason such as severe reaction conditions, therefore the exploration of the synthetic route of isoesdragol still arouses people's interest.
The content of the invention
It is an object of the invention to：A kind of synthetic method containing aryl-substituted olefins, especially the one of isoesdragol are provided
The new synthetic method of kind.
The present invention technical solution be：
A kind of synthetic method containing aryl-substituted olefins, it is to be used as alkylating agent and aromatic compound using aliphatic acetal
Reaction, is 90-160 DEG C of model in reaction temperature under normal pressure or low pressure 0.1-1.0MPa under solid acid catalyst catalytic action
In enclosing, one pot reaction directly obtains the aryl-substituted olefins such as isoesdragol, and specific reaction equation is as follows:
In a preferred embodiment of the invention, the aliphatic acetal is C1-C12 aliphatic acetals.
In a preferred embodiment of the invention, the solid acid catalyst is molecular sieve H-Beta.
In a preferred embodiment of the invention, the reaction temperature is 110-140 DEG C.
As a result of technical solution as above, the present invention has following features：
1) it is a kind of new synthetic route, reaction is one pot of completion.
2) aromatic compound is not only used as reactant, but also is used as solvent, without using other organic solvents.
3) catalyst is the solid acids such as H-Beta molecular sieves and its Modified Molecular Sieves, and is catalytic amount.
4) after the alcohol recycling produced, can be recycled when synthesizing acetal.
5) reaction may be carried out batchwise, and can also be carried out in tubular reactor and fixed bed reactors.
6) post processing is simple, does not have discarded object generation in reaction process, is a kind of environmentally protective synthetic route.
Embodiment
With reference to specific embodiment further illustrate the present invention technical solution, these embodiments it is not intended that
It is the limitation to technical solution.
Embodiment 1：
100ml autoclaves, oil bath, electromagnetic agitation.18g methyl phenyl ethers anisoles are added in kettle, add propionic aldehyde diformazan acetal 3.9g；Again
Add 0.78g H-Beta molecular sieve powders.120 DEG C of oil bath, when stirring reaction 3 is small；Room temperature is cooled to, material filters off catalyst, gas
Phase chromatography detects.Acetal conversion ratio 74%；Isoesdragol 52.4%, 2- of selectivity methyl-2-pentenal servings 25.3%.
Embodiment 2：
100ml autoclaves, oil bath, electromagnetic agitation.30g methyl phenyl ethers anisoles are added in kettle, add propionic aldehyde diformazan acetal 4.5g；Again
Add 1.1g Ce-Beta molecular sieve powders.When 130 DEG C of stirring reactions 4 of oil bath are small；Room temperature is cooled to, reaction mass filters off catalysis
Agent, gas chromatographic detection.Acetal conversion ratio 63.5%；Isoesdragol 61.2%, 2- of selectivity methyl-2-pentenal servings 15.1%.
Embodiment 3：
100ml autoclaves, oil bath, electromagnetic agitation.50g methyl phenyl ethers anisoles are added in kettle, add propionic aldehyde diformazan acetal 7.5g；Again
Add 3g Ni-Y molecular sieve powders.When 135 DEG C of stirring reactions 5 of oil bath are small；Room temperature is cooled to, reaction mass filters off catalyst, gas phase
Chromatography detects.Acetal conversion ratio 33.5%；Isoesdragol 24.6%, 2- of selectivity methyl-2-pentenal servings 35.1%.
Embodiment 4：
250ml there-necked flasks, oil bath, electromagnetic agitation, installation thermometer, condenser pipe.74g methyl phenyl ethers anisoles are added in bottle, add third
Two normal propyl alcohol acetal 9.5g of aldehyde；Again plus 2.8g H-Beta molecular sieve powders.When 132 DEG C of stirring reactions 4.5 of oil bath are small；It is cooled to
Room temperature, material filter off catalyst, gas chromatographic detection.Acetal conversion ratio 39.3%；Isoesdragol selectivity 36.6%, 2- first
Base -2- pentenals 27.4%.
Claims (4)
- A kind of 1. synthetic method containing aryl-substituted olefins, it is characterized in that being used as alkylating agent and aromatics using aliphatic acetal Thing reacts, and is 90-160 DEG C in reaction temperature under normal pressure or low pressure 0.1-1.0MPa under solid acid catalyst catalytic action In the range of, one pot reaction directly obtains the aryl-substituted olefins such as isoesdragol, and specific reaction equation is as follows:
- A kind of 2. synthetic method containing aryl-substituted olefins as claimed in claim 1, it is characterised in that the aliphatic acetal For C1-C12 aliphatic acetals.
- A kind of 3. synthetic method containing aryl-substituted olefins as claimed in claim 1, it is characterised in that the solid acid catalysis Agent is molecular sieve H-Beta.
- 4. a kind of synthetic method containing aryl-substituted olefins as claimed in claim 1, it is characterised in that the reaction temperature is 110-140℃。
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| CN201711252869.5A CN107973703B (en) | 2017-12-01 | 2017-12-01 | Synthetic method of aryl olefin |
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| CN201711252869.5A CN107973703B (en) | 2017-12-01 | 2017-12-01 | Synthetic method of aryl olefin |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4026951A (en) * | 1974-04-19 | 1977-05-31 | Haarmann & Reimer Gmbh | Process for the production of anethole |
| JP2014172834A (en) * | 2013-03-07 | 2014-09-22 | National Institute Of Advanced Industrial & Technology | Method for producing aromatic olefins |
| CN106103398A (en) * | 2014-01-17 | 2016-11-09 | 巴斯夫欧洲公司 | For the method producing aryl propylene |
-
2017
- 2017-12-01 CN CN201711252869.5A patent/CN107973703B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4026951A (en) * | 1974-04-19 | 1977-05-31 | Haarmann & Reimer Gmbh | Process for the production of anethole |
| JP2014172834A (en) * | 2013-03-07 | 2014-09-22 | National Institute Of Advanced Industrial & Technology | Method for producing aromatic olefins |
| CN106103398A (en) * | 2014-01-17 | 2016-11-09 | 巴斯夫欧洲公司 | For the method producing aryl propylene |
Non-Patent Citations (1)
| Title |
|---|
| 刘宁宁等: "缩醛与吲哚或苯并呋喃的烷基化反应", 《有机化学》 * |
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