CN105218368B - A kind of method of ionic liquid-catalyzed synthesis Momo-cyclohexyl fumarte - Google Patents
A kind of method of ionic liquid-catalyzed synthesis Momo-cyclohexyl fumarte Download PDFInfo
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- CN105218368B CN105218368B CN201510759926.3A CN201510759926A CN105218368B CN 105218368 B CN105218368 B CN 105218368B CN 201510759926 A CN201510759926 A CN 201510759926A CN 105218368 B CN105218368 B CN 105218368B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
Abstract
The invention belongs to the field of chemical synthesis, a kind of method being specifically related to ionic liquid-catalyzed synthesis Momo-cyclohexyl fumarte.Described method, with maleic anhydride and Hexalin as raw material, carries out esterified isomerizedization reaction, the Momo-cyclohexyl fumarte needed for preparing under ionic-liquid catalyst is catalyzed.The method preparing Momo-cyclohexyl fumarte of the present invention attempts ionic-liquid catalyst to be applied in the compound experiment of Momo-cyclohexyl fumarte first, with maleic anhydride and Hexalin as raw material, esterified isomerizedization reaction is carried out under ionic-liquid catalyst is catalyzed, can be implemented in same reactor, realize a stepization by once charging to react, whole reaction is without secondary feeds, and the response time shorter (less than 4h), react compared to other one-step synthesis method in prior art, the product yield of the method for the invention is up to more than 80%, product yield is greatly promoted.
Description
Technical field
The invention belongs to the field of chemical synthesis, be specifically related to the side of a kind of ionic liquid-catalyzed synthesis Momo-cyclohexyl fumarte
Method.
Background technology
The outer actually used food preservative of Present Domestic is mainly benzoic acid, sorbic acid and its esters and to hydroxyl
Benzoates preservative etc., but its effect is all affected by factors such as microbe species, food composition, pH value and dissolubilities,
Largely limit their application.Fumaric acid esters preservative is the most widely used novel product, and because having
Wide spectrum, efficiently, low toxicity, the feature such as economical and practical be by people's extensive concern.Dimethyl fumarate was once considered as the most promising
Chemical preservative, be widely used in the industries such as food, leather, feedstuff.But, skin and mucosa are had by dimethyl fumarate
Strong impulse effect, can cause allergic reaction, and also limit it and applies further, people and then sight turned to rich horse
Acid is the exploitation of the preservative of parent and studies.
Fumaric monoalkylester is the important organic synthesis intermediate of a class and novel chemical preservative, and because it has low
Malicious, efficient, use is not enjoyed favor by advantages such as pH value limitation, noresidues.Wherein, Momo-cyclohexyl fumarte (momo-
Cyclohexyl fumarte, MCHF) can be used as the cross-linking agent of various polymer, it is especially useful in need the neck solidified in atmosphere
In territory, such as coating, coating, bonding and encapsulant, can be used to prepare some have because it contains a carboxyl again
The macromolecular compound of particular characteristic, therefore, MCHF is required by a lot of American-European enterprises.And antibacterial to Momo-cyclohexyl fumarte
Effect disquisition also indicates that, it all shows strong antibacterial activity in pH value 3-9, far above dimethyl fumarate, and through high temperature
After process, its bacteriostasis is without substantially reducing；Cutaneous sensibility test simultaneously shows, Momo-cyclohexyl fumarte relatively fumaric acid diformazan
Ester is much smaller to stimulation, the allergy effect of skin.Visible, Momo-cyclohexyl fumarte completely solves dimethyl fumarate in application
During the biggest obstacle that runs into, have great application prospect at food and the aspect such as fresh-keeping, be a kind of efficient novel anti-
Rotten agent.
At present, worldwide, the yield of Momo-cyclohexyl fumarte is the least, grinding about its synthesis of current document report
Study carefully the fewest.The synthesis of traditional fumarate is to use inorganic acid as catalyst, makes fumaric acid and alcohol direct esterification obtain, and this closes
Although one-tenth method has an advantage simple to operate, that product yield is higher, but shortcoming be by-product dimethyl ester there is increasing in a large number
Add the difficulty of post processing, and equipment corrosion is serious, cost of material is higher.At present, many documents report the synthesis richness of improvement
The method of two step one stills of horse acid list cyclohexyl, i.e. with maleic anhydride and Hexalin as raw material, first generates maleic acid list through esterification
Cyclohexyl, then synthesize Momo-cyclohexyl fumarte through isomerization reaction under catalyst action.During this, owing to steric effect makes
The side reaction that must generate maleic acid diester is difficult to occur, and maleic anhydride wide material sources, cheap, achieves good effect
Really.But, although the method is to carry out in same reactor, but catalyst must add the most again, namely two step
Method is prepared, although its product yield is preferable, but course of reaction is complex.
On this basis, the side that it is catalyst synthesis Momo-cyclohexyl fumarte with solid super-strong acid that Yan Peng et al. reports
Method.It is with solid super-strong acid SO4 2-/SnO2-CeO2For catalyst, utilize solid super-strong acid in acid catalyzed reaction to isomerization and
Esterification shows the highest reactivity and selective advantage, can a step complete to be esterified and the process of isomery, and its
The yield of Momo-cyclohexyl fumarte product is up to 57.65%, although the method for more aforementioned two step one stills of product yield is lower slightly, but
Research further for one-step synthesis method Momo-cyclohexyl fumarte is laid a good foundation, and simply the yield of its target product is the most relatively
Low.Subsequently, document is had again to report with SO4 2-/SnO2-Al2O3For catalyst, the yield of its Momo-cyclohexyl fumarte product up to
76.61%, although increase, but the most not satisfactory.
Summary of the invention
To this end, the technical problem to be solved is to provide a kind of course of reaction simple and product yield is high
The method of synthesis Momo-cyclohexyl fumarte.
For solving above-mentioned technical problem, the method for ionic liquid-catalyzed synthesis Momo-cyclohexyl fumarte of the present invention,
It is with maleic anhydride and Hexalin as raw material, carries out being esterified-isomerization reaction under ionic-liquid catalyst is catalyzed, prepare required
Momo-cyclohexyl fumarte, described reaction equation is as follows:
Preferably, described ionic-liquid catalyst is 1-methyl-3-N-morpholinopropanesulfonic acid imidazole bisulfate ionic-liquid catalyst.
The reaction temperature of described reaction is 80-100 DEG C, response time 2-4h.
In described reaction raw materials, the mol ratio of described Hexalin and maleic anhydride is 1-2:1.
The consumption of described catalyst accounts for described Hexalin and the 10-20wt% of maleic anhydride raw material total amount.
Optimum, the reaction temperature of described reaction is 90 DEG C, response time 3.53h, described Hexalin and maleic anhydride
Mol ratio is 1.62:1, and the consumption of described catalyst accounts for described Hexalin and the 15.4wt% of maleic anhydride raw material total amount.
Described reaction is to carry out under ultrasonic assistant, and the frequency of described ultrasonic Treatment is 20-30kHz, and power is
200mW/cm2。
Described ultrasonic Treatment mode is: initial with 20kHz frequency processing 15min in reaction, is quickly ramped up to 30kHz subsequently
Frequency processing 15min；Repeat above-mentioned ultrasonic power circular treatment to terminate to reaction.
The method of the invention also includes the step by product and separation and recovery of catalyst, particularly as follows: question response is complete
Bi Hou, addition dehydrated alcohol mixing, and filtered while hot also reclaim catalyst；Gained filtrate has been cooled to white needles material
Suspend, leach insoluble matter, vacuum dried process, obtain described Momo-cyclohexyl fumarte product.
Described ionic-liquid catalyst 1-methyl-3-N-morpholinopropanesulfonic acid imidazole bisulfate is prepared by the following method: with 1,3-third
Sultones and N-Methylimidazole. are raw material, in the presence of ethyl acetate, carry out reacting to producing white precipitate in 60-80 DEG C,
Leach precipitate and with ethyl acetate washing, drying, obtain 1-(3-sulfonic group) propyl group-3-methylimidazole salt；
Described 1-(3-sulfonic group) propyl group-3-methylimidazole salt is dissolved in water, adds concentrated sulphuric acid and carry out in 80-90 DEG C anti-
Should, remove moisture content subsequently and obtain faint yellow sticky shape product liquid, be 1-methyl-3-N-morpholinopropanesulfonic acid imidazole bisulfate ionic liquid
Body catalyst.
Ionic liquid (Ionic Liquids is called for short ILs) is also called ionic liquid at room temperature, is in ionic condition under room temperature
Salts substances, have non-volatile, do not aoxidize, highly polar, inorganic and organic compound are had the characteristics such as good dissolubility, by extensively
General for replacing the environment-friendly type solvent of volatile chemical solvent.1-methyl-3-N-morpholinopropanesulfonic acid base imidazole bisulfate is i.e. existing skill
In art, known a kind of ionic-liquid catalyst, is used in the synthetic reaction of lipid, for overcoming the solid acid etc. of routine to urge
The corrosivity that agent exists is strong, equipment investment is high, side reaction is many, pollute environment, be difficult to recycle, product is difficult with reaction system
With defects such as separation.
The method preparing Momo-cyclohexyl fumarte of the present invention attempts ionic-liquid catalyst to be applied to rich horse first
In the compound experiment of the single cyclohexyl of acid, with maleic anhydride and Hexalin as raw material, under ionic-liquid catalyst is catalyzed, carry out ester
Change-isomerization reaction, it is possible to achieve in same reactor, by once charging realize one stepization react, whole reaction without
Secondary feeds, and response time shorter (less than 4h), react compared to other one-step synthesis method in prior art, of the present invention
The product yield of method is up to more than 80%, and product yield is greatly promoted.
The method of the invention is further with ultrasonic assistant method, it is intended to shortens the time of whole reaction further and carries
The yield of high product, data show, use conventional Ultrasound processing mode to contribute to improving further the product yield of reaction, and this
Invent described method and optimize the mode obtaining using gradient-circulating ultrasonic to process further, greatly improve fumaric acid list especially
The yield of cyclohexyl product, achieves unforeseeable technique effect.
Accompanying drawing explanation
In order to make present disclosure be more likely to be clearly understood, below according to the specific embodiment of the present invention and combine
Accompanying drawing, the present invention is further detailed explanation, wherein,
Fig. 1 is the infrared spectrogram of Momo-cyclohexyl fumarte product of the present invention.
Detailed description of the invention
The ionic-liquid catalyst 1-methyl-3-N-morpholinopropanesulfonic acid imidazole bisulfate used in the following embodiment of the present invention is existing
There is technical products, only need to prepare according to existing conventional method, 1-methyl-3-the third sulphur used in the following embodiment of the present invention
The synthesis schematic diagram of imidazole acid disulfate is as follows, and prepares in accordance with the following steps:
Weigh 18.4g PS, and measure in 100mL ethyl acetate addition there-necked flask, load onto constant voltage and drip
Liquid funnel, magnetic stirring apparatus and reflux condensing tube, be heated to when 60 DEG C be slowly added to 12.3g N-methyl in water-bath
Imidazoles, after being added dropwise to complete, makes architecture heat preservation react 2h at 70-80 DEG C, to producing white precipitate；System is carried out decompression take out
Filter, and wash filter cake by ethyl acetate, put into 100 DEG C of drying in oven, products obtained therefrom is 1-(3-sulfonic group) propyl group-3-methyl
Imidazole salts (MIM-PS)；
Weigh 20.4g MIM-PS to add in 250mL there-necked flask, add water and make it be completely dissolved, will under magnetic agitation
6.1mL concentrated sulphuric acid is slowly added in flask, after being added dropwise to complete, is warming up to 90 DEG C and continues reaction 2h, then with rotation in water-bath
Turn evaporimeter and remove the moisture in reaction system, obtain faint yellow sticky shape product liquid, be required 1-methyl-3-the third sulphur
Imidazole acid hydrogen sulphate ionic liquid catalyst.
Preparing described in following each embodiment in the method for Momo-cyclohexyl fumarte, its reaction equation is as follows:
Embodiment 1
Weigh maleic anhydride 9.8g (0.1mol), measure Hexalin 10g (0.1mol) and above-mentioned ionic-liquid catalyst
1.98g (10wt%), adds in 250mL there-necked flask, loads onto the experimental provision such as reflux condensing tube, thermometer, and magnetic agitation adds
Heat, reacts 4h at a temperature of controlling 80 DEG C.Taking 10mL dehydrated alcohol after question response and add flask, stirring filtered while hot are returned
Receive catalyst.And gained filtrate is cooled and stands 12h, to there being white needles material to suspend, carry out subsequently filtering, take and leach
Insoluble matter is placed in vacuum drying oven drying, i.e. obtains product Momo-cyclohexyl fumarte.
Embodiment 2
The method preparing Momo-cyclohexyl fumarte described in the present embodiment, its raw material and catalyst amount, and reaction temperature,
Time is the most same as in Example 1, and it differs only in, and whole reaction all processes under the conditions of ultrasonic assistant, described super
The frequency of sonicated is 20kHz, and power is 200mW/cm2。
Embodiment 3
The method preparing Momo-cyclohexyl fumarte described in the present embodiment, its raw material and catalyst amount, and reaction temperature,
Time is the most same as in Example 1, and it differs only in, and whole reaction all processes under the conditions of ultrasonic assistant, described super
The frequency of sonicated is 30kHz, and power is 200mW/cm2。
Embodiment 4
The method preparing Momo-cyclohexyl fumarte described in the present embodiment, its raw material and catalyst amount, and reaction temperature,
Time is the most same as in Example 1, and it differs only in, and whole reaction all processes under the conditions of ultrasonic assistant, described super
Sonicated mode is: initial with 20kHz frequency processing 15min in reaction, is quickly ramped up to 30kHz frequency processing 15min subsequently；
Repeat above-mentioned ultrasonic power 8 circulation, process extremely reaction and terminate.
Embodiment 5
Weigh maleic anhydride 9.8g (0.1mol), measure Hexalin 20g (0.2mol) and above-mentioned ionic-liquid catalyst
2.98g (10wt%), adds in 250mL there-necked flask, loads onto the experimental provision such as reflux condensing tube, thermometer, and magnetic agitation adds
Heat, reacts 2h at a temperature of controlling 100 DEG C.Taking 10mL dehydrated alcohol after question response and add flask, stirring filtered while hot are returned
Receive catalyst.And gained filtrate is cooled and stands 12h, to there being white needles material to suspend, carry out subsequently filtering, take and leach
Insoluble matter is placed in vacuum drying oven drying, i.e. obtains product Momo-cyclohexyl fumarte.
Embodiment 6
The method preparing Momo-cyclohexyl fumarte described in the present embodiment, its raw material and catalyst amount, and reaction temperature,
Time is the most same as in Example 5, and it differs only in, and whole reaction all processes under the conditions of ultrasonic assistant, described super
The frequency of sonicated is 20kHz, and power is 200mW/cm2。
Embodiment 7
The method preparing Momo-cyclohexyl fumarte described in the present embodiment, its raw material and catalyst amount, and reaction temperature,
Time is the most same as in Example 5, and it differs only in, and whole reaction all processes under the conditions of ultrasonic assistant, described super
The frequency of sonicated is 30kHz, and power is 200mW/cm2。
Embodiment 8
The method preparing Momo-cyclohexyl fumarte described in the present embodiment, its raw material and catalyst amount, and reaction temperature,
Time is the most same as in Example 5, and it differs only in, and whole reaction all processes under the conditions of ultrasonic assistant, described super
Sonicated mode is: initial with 20kHz frequency processing 15min in reaction, is quickly ramped up to 30kHz frequency processing subsequently
15min；Repeat above-mentioned ultrasonic power 8 circulation, process extremely reaction and terminate.
Embodiment 9
Weigh maleic anhydride 9.8g (0.1mol), measure Hexalin 20g (0.2mol) and above-mentioned ionic-liquid catalyst
2.98g (10wt%), adds in 250mL there-necked flask, loads onto the experimental provision such as reflux condensing tube, thermometer, and magnetic agitation adds
Heat, reacts 2h at a temperature of controlling 100 DEG C.Taking 10mL dehydrated alcohol after question response and add flask, stirring filtered while hot are returned
Receive catalyst.And gained filtrate is cooled and stands 12h, to there being white needles material to suspend, carry out subsequently filtering, take and leach
Insoluble matter is placed in vacuum drying oven drying, i.e. obtains product Momo-cyclohexyl fumarte.
Embodiment 10
The method preparing Momo-cyclohexyl fumarte described in the present embodiment, its raw material and catalyst amount, and reaction temperature,
Time is the most the same as in Example 9, and it differs only in, and whole reaction all processes under the conditions of ultrasonic assistant, described super
The frequency of sonicated is 20kHz, and power is 200mW/cm2。
Embodiment 11
The method preparing Momo-cyclohexyl fumarte described in the present embodiment, its raw material and catalyst amount, and reaction temperature,
Time is the most the same as in Example 9, and it differs only in, and whole reaction all processes under the conditions of ultrasonic assistant, described super
The frequency of sonicated is 30kHz, and power is 200mW/cm2。
Embodiment 12
The method preparing Momo-cyclohexyl fumarte described in the present embodiment, its raw material and catalyst amount, and reaction temperature,
Time is the most the same as in Example 9, and it differs only in, and whole reaction all processes under the conditions of ultrasonic assistant, described super
Sonicated mode is: initial with 20kHz frequency processing 15min in reaction, is quickly ramped up to 30kHz frequency processing 15min subsequently；
Repeat above-mentioned ultrasonic power 8 circulation, process extremely reaction and terminate.
Embodiment 13
Weigh maleic anhydride 9.8g (0.1mol), measure Hexalin 10g (0.1mol) and above-mentioned ionic-liquid catalyst
3.96g (20wt%), adds in 250mL there-necked flask, loads onto the experimental provision such as reflux condensing tube, thermometer, and magnetic agitation adds
Heat, reacts 2h at a temperature of controlling 90 DEG C.Taking 10mL dehydrated alcohol after question response and add flask, stirring filtered while hot are returned
Receive catalyst.And gained filtrate is cooled and stands 12h, to there being white needles material to suspend, carry out subsequently filtering, take and leach
Insoluble matter is placed in vacuum drying oven drying, i.e. obtains product Momo-cyclohexyl fumarte.
Embodiment 14
The method preparing Momo-cyclohexyl fumarte described in the present embodiment, its raw material and catalyst amount, and reaction temperature,
Time is all identical with embodiment 13, and it differs only in, and whole reaction all processes under the conditions of ultrasonic assistant, described super
The frequency of sonicated is 20kHz, and power is 200mW/cm2。
Embodiment 15
The method preparing Momo-cyclohexyl fumarte described in the present embodiment, its raw material and catalyst amount, and reaction temperature,
Time is all identical with embodiment 13, and it differs only in, and whole reaction all processes under the conditions of ultrasonic assistant, described super
The frequency of sonicated is 30kHz, and power is 200mW/cm2。
Embodiment 16
The method preparing Momo-cyclohexyl fumarte described in the present embodiment, its raw material and catalyst amount, and reaction temperature,
Time is all identical with embodiment 13, and it differs only in, and whole reaction all processes under the conditions of ultrasonic assistant, described super
Sonicated mode is: initial with 20kHz frequency processing 15min in reaction, is quickly ramped up to 30kHz frequency processing 15min subsequently；
Repeat above-mentioned ultrasonic power 8 circulation, process extremely reaction and terminate.
Embodiment 17
Weigh maleic anhydride 9.8g (0.1mol), measure Hexalin 20g (0.2mol) and above-mentioned ionic-liquid catalyst
5.96g (20wt%), adds in 250mL there-necked flask, loads onto the experimental provision such as reflux condensing tube, thermometer, and magnetic agitation adds
Heat, reacts 4h at a temperature of controlling 90 DEG C.Taking 10mL dehydrated alcohol after question response and add flask, stirring filtered while hot are returned
Receive catalyst.And gained filtrate is cooled and stands 12h, to there being white needles material to suspend, carry out subsequently filtering, take and leach
Insoluble matter is placed in vacuum drying oven drying, i.e. obtains product Momo-cyclohexyl fumarte.
Embodiment 18
The method preparing Momo-cyclohexyl fumarte described in the present embodiment, its raw material and catalyst amount, and reaction temperature,
Time is all identical with embodiment 17, and it differs only in, and whole reaction all processes under the conditions of ultrasonic assistant, described super
The frequency of sonicated is 20kHz, and power is 200mW/cm2。
Embodiment 19
The method preparing Momo-cyclohexyl fumarte described in the present embodiment, its raw material and catalyst amount, and reaction temperature,
Time is all identical with embodiment 17, and it differs only in, and whole reaction all processes under the conditions of ultrasonic assistant, described super
The frequency of sonicated is 30kHz, and power is 200mW/cm2。
Embodiment 20
The method preparing Momo-cyclohexyl fumarte described in the present embodiment, its raw material and catalyst amount, and reaction temperature,
Time is all identical with embodiment 17, and it differs only in, and whole reaction all processes under the conditions of ultrasonic assistant, described super
Sonicated mode is: initial with 20kHz frequency processing 15min in reaction, is quickly ramped up to 30kHz frequency processing 15min subsequently；
Repeat above-mentioned ultrasonic power 8 circulation, process extremely reaction and terminate.
Embodiment 21
Weigh maleic anhydride 9.8g (0.1mol), measure Hexalin 16.2g (0.162mol) and above-mentioned ionic liquid is urged
Agent 4g (15.4wt%), adds in 250mL there-necked flask, loads onto the experimental provision such as reflux condensing tube, thermometer, magnetic agitation
Heating, reacts 3.53h at a temperature of controlling 90 DEG C.Take 10mL dehydrated alcohol after question response and add flask, stirring while hot mistake
Catalyst is reclaimed in filter.And gained filtrate is cooled and stands 12h, to there being white needles material to suspend, carry out subsequently filtering, taking filter
The insoluble matter gone out is placed in vacuum drying oven drying, i.e. obtains product Momo-cyclohexyl fumarte.
Embodiment 22
The method preparing Momo-cyclohexyl fumarte described in the present embodiment, its raw material and catalyst amount, and reaction temperature,
Time is all identical with embodiment 17, and it differs only in, and whole reaction all processes under the conditions of ultrasonic assistant, described super
The frequency of sonicated is 20kHz, and power is 200mW/cm2。
Embodiment 23
The method preparing Momo-cyclohexyl fumarte described in the present embodiment, its raw material and catalyst amount, and reaction temperature,
Time is all identical with embodiment 17, and it differs only in, and whole reaction all processes under the conditions of ultrasonic assistant, described super
The frequency of sonicated is 30kHz, and power is 200mW/cm2。
Embodiment 24
The method preparing Momo-cyclohexyl fumarte described in the present embodiment, its raw material and catalyst amount, and reaction temperature,
Time is all identical with embodiment 17, and it differs only in, and whole reaction all processes under the conditions of ultrasonic assistant, described super
Sonicated mode is: initial with 20kHz frequency processing 15min in reaction, is quickly ramped up to 30kHz frequency processing 15min subsequently；
Repeat above-mentioned ultrasonic power 8 circulation, process extremely reaction and terminate.
Experimental example
1, GC-MS detection
The product prepared in above-described embodiment 1-24 is carried out GC-MS analysis, and chromatographic condition is: RTX-5MS composes post
(30.0m × 0.25mm × 0.25 μm), injector temperature 330 DEG C, column temperature 100 DEG C, temperature programming rises to 150 DEG C with 6 DEG C/min,
Retain 3min, then rise to 300 DEG C with 9 DEG C/min, ion source temperature 250 DEG C.Gas chromatograph results shows, product purity is the highest
(>=99%).
Mass spectral results: m/z 199 is molecular ion peak (m+1), it was demonstrated that synthesized product is single cyclohexyl；Ester products loses
It is raw that hydroxyl generates fragment ion m/z 181, product loses carboxyl generation fragment ion m/z 153, product loses Hexalin part
Fragmentate ion m/z 99.
2, FTIR phenetic analysis
Utilize KBr crystal tabletting (cm-1) the above-mentioned product prepared is carried out infrared spectrum detection, through relative analysis
Understanding, the product prepared according to the method for the invention is Momo-cyclohexyl fumarte, is wherein prepared in embodiment 21
The infrared spectrogram of the product arrived is as shown in Figure 1.And carry out owing to the mode of Sonication assisted treatment is only acceleration reaction
Being used, it has no effect on the structure of product, therefore, the method for the invention be fully available for preparing Momo-cyclohexyl fumarte it
With.
3, product yield detection
According to prior art conventional method, product in above-described embodiment 1-24 is carried out the product receipts of Momo-cyclohexyl fumarte
Rate (product/reactant × 100%) detects, and testing result see table 1.
Table 1 each embodiment product yield situation
| Numbering | Product yield (%) | Response time (h) |
| Embodiment 1 | 79.03 | 4 |
| Embodiment 2 | 80.46 | 4 |
| Embodiment 3 | 81.33 | 4 |
| Embodiment 4 | 88.27 | 4 |
| Embodiment 5 | 78.45 | 2 |
| Embodiment 6 | 80.75 | 2 |
| Embodiment 7 | 81.28 | 2 |
| Embodiment 8 | 88.85 | 2 |
| Embodiment 9 | 78.98 | 2 |
| Embodiment 10 | 80.39 | 2 |
| Embodiment 11 | 81.40 | 2 |
| Embodiment 12 | 88.68 | 2 |
| Embodiment 13 | 78.24 | 2 |
| Embodiment 14 | 81.01 | 2 |
| Embodiment 15 | 81.54 | 2 |
| Embodiment 16 | 88.96 | 2 |
| Embodiment 17 | 77.95 | 4 |
| Embodiment 18 | 81.03 | 4 |
| Embodiment 19 | 81.69 | 4 |
| Embodiment 20 | 88.73 | 4 |
| Embodiment 21 | 82.78 | 3.53 |
| Embodiment 22 | 85.98 | 3.53 |
| Embodiment 23 | 86.27 | 3.53 |
| Embodiment 24 | 93.35 | 3.53 |
Visible, the method for the invention attempts ionic-liquid catalyst to be applied to the synthesis of Momo-cyclohexyl fumarte first
In experiment, with maleic anhydride and Hexalin as raw material, carry out being esterified-isomerization reaction under ionic-liquid catalyst is catalyzed, can
With realize in same reactor, by once charging realize one stepization react, whole reaction without secondary feeds, and reaction time
Between shorter (less than 4h), react compared to other one-step synthesis method in prior art, the product yield of the method for the invention can
Reaching more than 80%, product yield is greatly promoted.
The method of the invention is further with ultrasonic assistant method, it is intended to shortens the time of whole reaction further and carries
The yield of high product, data show, use conventional Ultrasound processing mode to contribute to improving further the product yield of reaction, and this
Invent described method and optimize the mode obtaining using gradient-circulating ultrasonic to process further, greatly improve fumaric acid list especially
The yield of cyclohexyl product, achieves unforeseeable technique effect.
Obviously, above-described embodiment is only for clearly demonstrating example, and not restriction to embodiment.Right
For those of ordinary skill in the field, can also make on the basis of the above description other multi-form change or
Variation.Here without also cannot all of embodiment be given exhaustive.And the obvious change thus extended out or
Change among still in the protection domain of the invention.
Claims (9)
1. the method for an ionic liquid-catalyzed synthesis Momo-cyclohexyl fumarte, it is characterised in that described method is with maleic anhydride
It is raw material with Hexalin, carries out being esterified-isomery under 1-methyl-3-N-morpholinopropanesulfonic acid imidazole bisulfate ionic-liquid catalyst catalysis
Changing reaction, prepare required Momo-cyclohexyl fumarte, described reaction equation is as follows:
The method of ionic liquid-catalyzed synthesis Momo-cyclohexyl fumarte the most according to claim 1, it is characterised in that described
The reaction temperature of reaction is 80-100 DEG C, response time 2-4h.
The method of ionic liquid-catalyzed synthesis Momo-cyclohexyl fumarte the most according to claim 2, it is characterised in that described
In reaction raw materials, the mol ratio of described Hexalin and maleic anhydride is 1-2:1.
The method of ionic liquid-catalyzed synthesis Momo-cyclohexyl fumarte the most according to claim 3, it is characterised in that described
The consumption of catalyst accounts for described Hexalin and the 10-20wt% of maleic anhydride raw material total amount.
The method of ionic liquid-catalyzed synthesis Momo-cyclohexyl fumarte the most according to claim 4, it is characterised in that described
The reaction temperature of reaction is 90 DEG C, and response time 3.53h, the mol ratio of described Hexalin and maleic anhydride is 1.62:1, described
The consumption of catalyst accounts for described Hexalin and the 15.4wt% of maleic anhydride raw material total amount.
6., according to the method for the arbitrary described ionic liquid-catalyzed synthesis Momo-cyclohexyl fumarte of claim 1-5, its feature exists
In, described reaction is to carry out under ultrasonic assistant, and the frequency of described ultrasonic Treatment is 20-30kHz, and power is 200mW/
cm2。
The method of ionic liquid-catalyzed synthesis Momo-cyclohexyl fumarte the most according to claim 6, it is characterised in that described
Ultrasonic Treatment mode is: initial with 20kHz frequency processing 15min in reaction, is quickly ramped up to 30kHz frequency processing subsequently
15min；Repeat above-mentioned ultrasonic power circular treatment to terminate to reaction.
The method of ionic liquid-catalyzed synthesis Momo-cyclohexyl fumarte the most according to claim 7, it is characterised in that described
Method also includes the step by product and separation and recovery of catalyst, particularly as follows: after question response, add dehydrated alcohol and mix
Even, and filtered while hot reclaim catalyst；Gained filtrate is cooled to white needles material suspend, has leached insoluble matter, through true
Empty dried, obtains described Momo-cyclohexyl fumarte product.
The method of ionic liquid-catalyzed synthesis Momo-cyclohexyl fumarte the most according to claim 8, it is characterised in that described
Ionic-liquid catalyst 1-methyl-3-N-morpholinopropanesulfonic acid imidazole bisulfate is prepared by the following method: with 1,3-propane sultone and N-
Methylimidazole. is raw material, in the presence of ethyl acetate, carries out reacting to producing white precipitate in 60-80 DEG C, leaches precipitate also
With ethyl acetate washing, dry, obtain 1-(3-sulfonic group) propyl group-3-methylimidazole salt；
Described 1-(3-sulfonic group) propyl group-3-methylimidazole salt is dissolved in water, adds concentrated sulphuric acid and react in 80-90 DEG C,
Remove moisture content subsequently and obtain faint yellow sticky shape product liquid, be 1-methyl-3-N-morpholinopropanesulfonic acid imidazole bisulfate ionic liquid
Catalyst.
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