CN105272918A - 1-alkyl-3-vinyl-2,4,5-triaryl imidazole halide and preparation method and application - Google Patents
1-alkyl-3-vinyl-2,4,5-triaryl imidazole halide and preparation method and application Download PDFInfo
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- CN105272918A CN105272918A CN201510808967.7A CN201510808967A CN105272918A CN 105272918 A CN105272918 A CN 105272918A CN 201510808967 A CN201510808967 A CN 201510808967A CN 105272918 A CN105272918 A CN 105272918A
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- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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Abstract
The invention relates to 1-alkyl-3-vinyl-2,4,5-triaryl imidazole halide in the formula (I) and a synthesis method and application of the 1-alkyl-3-vinyl-2,4,5-triaryl imidazole halide which is used as ionic liquid to increase the reaction yield. The method includes the steps that 1-vinyl-2,4,5-triaryl imidazole and halogenated hydrocarbon (such as R4X and methyl iodide) are added into a solvent, heating is performed after even stirring, heat preservation is performed on reaction liquid till reaction ends, residues are washed, filtered, separated, dried in vacuum after the solvent is removed through steaming, and the 1-alkyl-3-vinyl-2,4,5-triaryl imidazole halide is obtained. The sysnthesis method of the 1-alkyl-3-vinyl-2,4,5-triaryl imidazole halide is easy to operate, and high practical value is achieved. Please see the formula in the specification.
Description
Technical field
The invention belongs to chemosynthesis technical field, particularly relate to halogenation-1-alkyl-3-vinyl-2,4,5-triarylimidazoles, such as iodate-1-methyl-3-vinyl-2,4,5-triarylimidazoles, and in a reaction system, synthesize halogenation-1-alkyl-3-vinyl-2,4, the method of 5-triarylimidazoles such as iodate-1-methyl-3-vinyl-2,4,5-triarylimidazoles and as ionic liquid for improving the purposes of reaction yield.
Background technology
Glyoxaline compound is all important organic compound, it to have in fields such as organic synthesis, pharmaceutical synthesis, agricultural chemicals, papermaking and functional materialss as intermediate or final product applies extremely widely, especially in the production of fine chemical product, is seized of very consequence.For many years, the research of the synthetic method of glyoxaline compound is one of the heat subject of educational circles of organising always.
In prior art, the method that common synthesis has substituent imidazoles is all that cyclization under the effect of amine (ammonium) generates by diketone and aldehyde.Bibliographical information is there is not yet in next step method generating imidazoles of two ketolysises simultaneously.
Summary of the invention
The technical problem that will solve of the present invention is to provide halogenation-1-alkyl-3-vinyl-2,4,5-triarylimidazoles, such as iodate-1-methyl-3-vinyl-2,4,5-triarylimidazoles and synthesize halogenation-1-alkyl-3-vinyl-2,4,5-triarylimidazoles such as iodate-1-methyl-3-vinyl-2 in a reaction system, 4, the method of 5-triarylimidazoles, the method is simple to operate, has higher practical value.
First, the invention provides a kind of N-vinyl triarylimidazoles compound, it has following general formula (II):
Wherein, R in general formula I I
1, R
2, R
3group is identical or not identical, substituent R
1, R
2, R
3hydrogen or electron-donating group or electron-withdrawing group independently of one another.Such as C1-C10 electron-donating group, or halogen electron-withdrawing group or nitro (electron-withdrawing group) or (C1-C4) electron-withdrawing group, as CN or trifluoromethyl.
Preferably, described electron-donating group is selected from amino-NH
2,-NHR
5,-N (R
6)
2, C
1-C
6alkyl, C
1-C
6alkoxyl group or C
1-C
6aminoacyl.
Preferably, described electron-withdrawing group is selected from halogen atom, C
1-C
6carboxyl, C
1-C
6ester group, cyano group, sulfonic group.
Preferably, R
5, R
6hydrogen, halogen or C1-5 alkyl independently of one another.
Preferably, substituent R
1c atomicity be 1 ~ 5, R
3and R
2the C atomic quantity of group is 1 ~ 5; Preferably, R is worked as
1c atomic quantity when being 1 ~ 5, R
1in the optional position of remaining five the position of substitution of phenyl ring a; Work as R
2c quantity when being 1 ~ 5, R
2can in the optional position of remaining five the position of substitution of phenyl ring b; And/or work as R
3c quantity when being 1 ~ 5, R
3can in the optional position of remaining five the position of substitution of phenyl ring c.
The present invention also provides the method for the N-vinyl triarylimidazoles compound of the above-mentioned general formula of preparation (II), and the method comprises:
(A) by dibenzoyl, phenyl aldehyde, ammonium acetate, thanomin and nanometer Fe
3o
4the mixture reflux in a solvent of magnetic fluid, reaction terminates rear cooling, obtains N-hydroxyethyl-2,4,5-triarylimidazoles after recrystallization;
(B) allow N-hydroxyethyl-2,4,5-triarylimidazoles and phosphorus tribromide temperature reaction, after reaction, cooling, obtains N-bromotrifluoromethane-2,4,5-triarylimidazoles after recrystallization;
(C) N-bromotrifluoromethane-2 is allowed, 4,5-triarylimidazoles) and alkali (such as potassium hydroxide or sodium hydroxide) back flow reaction, carry out being separated (such as post separation), obtain the N-vinyl triarylimidazoles compound of general formula (II).
Preferably, in step (A), the mol ratio of dibenzoyl, phenyl aldehyde, ammonium acetate, thanomin is 0.5 ~ 1.5:0.5 ~ 1.5:0.5 ~ 1.5:0.5 ~ 1.5, preferably 0.8 ~ 1.2:0.8 ~ 1.2:0.8 ~ 1.2:0.8 ~ 1.2.Nanometer Fe
3o
4the amount of magnetic fluid can alter a great deal, and can be such as the 5-80wt% based on above-mentioned four gross weights, 10 ~ 50wt%, as 30wt%.
Preferably, in step (B), the mol ratio of N-hydroxyethyl-2,4,5-triarylimidazoles and phosphorus tribromide is 1:1 ~ 4, preferred 1:1.5 ~ 2.5.
Preferably, in step (C), N-bromotrifluoromethane-2,4,5-triarylimidazoles) be 1:2 ~ 6 with the mol ratio of alkali, preferred 1:3 ~ 4.
For N-vinyl triphenylimidazolyl compound, its reaction scheme is as follows:
Technical scheme of the present invention is summarized as follows:
1, halogenation-1-alkyl-3-vinyl-2,4, the 5-triarylimidazoles of general formula (I):
Wherein, R in general formula I
1, R
2, R
3group is identical or not identical, substituent R
1, R
2, R
3hydrogen or electron-donating group or electron-withdrawing group independently of one another; R
4alkyl, such as C
1-C
8alkyl, preferred C
1-C
6alkyl, as C
1-C
6alkyl; X is fluorine, chlorine, bromine or iodine.
Preferably, described electron-donating group is selected from amino-NH
2,-NHR
5,-N (R
6)
2, C
1-C
6alkyl, C
1-C
6alkoxyl group or C
1-C
6aminoacyl.
Preferably, described electron-withdrawing group is selected from halogen atom, C
1-C
6carboxyl, C
1-C
6ester group, cyano group, sulfonic group,
Preferably, R
5, R
6hydrogen, halogen or C1-5 alkyl independently of one another.
Preferably, substituent R
1c atomicity be 1 ~ 5, R
3and R
2the C atomic quantity of group is 1 ~ 5.
Preferably, R is worked as
1c atomic quantity when being 1 ~ 5, R
1in the optional position of remaining five the position of substitution of phenyl ring a.Work as R
2c quantity when being 1 ~ 5, R
2can in the optional position of remaining five the position of substitution of phenyl ring b.Work as R
3c quantity when being 1 ~ 5, R
3can in the optional position of remaining five the position of substitution of phenyl ring c.
2, the method for halogenation-1-alkyl-3-vinyl-2,4, the 5-triarylimidazoles of above general formula (I) is prepared,
Wherein, R in general formula I
1, R
2, R
3, R
4with X as defined above;
Described method comprises:
1-vinyl-2,4,5-triarylimidazoles by following formula (II):
Wherein substituent R
1, R
2, R
3as defined above,
With halohydrocarbon R
4x (wherein R
4alkyl, such as C
1-C
8alkyl, preferred C
1-C
6alkyl, as C
1-C
6alkyl; Wherein X is fluorine, chlorine, bromine or iodine; Halohydrocarbon R
4x is such as methyl iodide) add in solvent, the post-heating that stirs (is preferably heated to reflux state, usual 50-100 DEG C, preferably 50 ~ 90 DEG C, more preferably 60 ~ 70 DEG C, more preferably 60 ~ 65 DEG C) and reaction solution is carried out insulation reaction (usual 8 ~ 12 hours) until reaction terminates, after steaming desolventizes, resistates, through washing, filtering separation, vacuum-drying, obtains the halogenation-1-alkyl-3-vinyl-2 of general formula (I), 4,5-triarylimidazoles.
Preferably, in the method described in above 2,1-vinyl-2,4,5-triarylimidazoles and halohydrocarbon R
4the molar ratio of X (as methyl iodide) is 1:0.1 ~ 10, preferred 1:0.5 ~ 5, more preferably 1:1.2 ~ 1.8, further preferred about 1:1.5.
Preferably, in the method described in above 2, described solvent is ether solvent such as tetrahydrofuran (THF), diox; Ketones solvent is acetone, butanone such as; Or varsol such as methylene dichloride; Or esters solvent such as vinyl acetic monomer; Be preferably tetrahydrofuran (THF).
3, in the method described in above 2, preferably, the N-vinyl triarylimidazoles compound of its formula of (II) is by prepared by the preparation method comprised the following steps:
(A) by dibenzoyl, phenyl aldehyde, ammonium acetate, thanomin and nanometer Fe
3o
4the mixture reflux in a solvent of magnetic fluid, reaction terminates rear cooling, obtains N-hydroxyethyl-2,4,5-triarylimidazoles after recrystallization;
(B) allow N-hydroxyethyl-2,4,5-triarylimidazoles and phosphorus tribromide temperature reaction, after reaction, cooling, obtains N-bromotrifluoromethane-2,4,5-triarylimidazoles after recrystallization;
(C) N-bromotrifluoromethane-2 is allowed, 4,5-triarylimidazoles) and alkali (such as potassium hydroxide or sodium hydroxide) back flow reaction, carry out being separated (such as post separation), obtain the N-vinyl triarylimidazoles compound of general formula (II).
4, in the method described in above 3, in step (A), the mol ratio of dibenzoyl, phenyl aldehyde, ammonium acetate, thanomin is 0.5 ~ 1.5:0.5 ~ 1.5:0.5 ~ 1.5:0.5 ~ 1.5, preferably 0.8 ~ 1.2:0.8 ~ 1.2:0.8 ~ 1.2:0.8 ~ 1.2; And/or
In step (B), the mol ratio of N-hydroxyethyl-2,4,5-triarylimidazoles and phosphorus tribromide is 1:1 ~ 4, preferred 1:1.5 ~ 2.5; And/or
In step (C), N-bromotrifluoromethane-2,4,5-triarylimidazoles) be 1:2 ~ 6 with the mol ratio of alkali, preferred 1:3 ~ 4.
5, halogenation-1-alkyl-3-vinyl-2 of the present invention, 4,5-triarylimidazoles, as iodate-1-methyl-3-vinyl-2,4,5-triarylimidazoles, effectively can improve reaction yield, and can be used as intermediate or final product is applied to the fields such as organic synthesis, pharmaceutical synthesis, agricultural chemicals, papermaking and functional materials.
For tetrahydrofuran solvent, method of the present invention comprises:
By 1-vinyl-2,4,5-triarylimidazoles and methyl iodide add in anhydrous tetrahydro furan, the post-heating that stirs to 50 ~ 70 DEG C, preferably 60 ~ 65 DEG C and reaction solution is carried out insulation reaction until reaction terminate, change reflux into water distilling apparatus, after steaming desolventizes, resistates joins in a large amount of ether and washs, and then filtering separation, vacuum drying oven drying obtain iodate-1-methyl-3-vinyl-2,4,5-triarylimidazoles.
Chemical equation is as follows:
The present invention adds acting in conjunction in solvent (preferred anhydrous tetrahydrochysene furan) with 1-vinyl-2,4,5-triarylimidazoles and methyl iodide, synthesis iodate-1-methyl-3-vinyl-2,4,5-triarylimidazoles, the method is simple to operate, has higher practical value.
The molar ratio of 1-vinyl-2,4,5-triarylimidazoles and methyl iodide is preferably 1:1.2 ~ 1.8, especially about 1 ︰ 1.5, and wherein tetrahydrofuran (THF) is as solvent, can reach best catalytic effect under this charging capacity.If charging capacity is less than this proportioning, then reaction not exclusively, or speed of response is too low; If charging capacity exceedes this proportioning, then cause unnecessary waste.
The feed ratio of 1-vinyl-2,4,5-triarylimidazoles and anhydrous tetrahydro furan is 1mol ︰ 5 ~ 30L, preferred 1mol:15L, and under this charging capacity, products collection efficiency is the highest.When the amount of anhydrous tetrahydro furan is less than this charging capacity, whole solubilize effect is bad, and reaction not exclusively; When the consumption of anhydrous tetrahydro furan exceedes this charging capacity, then when can cause aftertreatment, energy consumption is too high.
The described insulation reaction time is 8 ~ 20 hours, preferably 8 ~ 12 hours, and during deficiency of time, reaction is not thorough, and experiment shows that, within the time of 8 ~ 12 hours, products collection efficiency is the highest.
Described temperature of reaction is 60 ~ 65 DEG C, and during lower than this temperature, this speed of response is comparatively slow, and experiment shows that 60 ~ 65 DEG C for optimal reaction temperature.
Described joining in a large amount of ether with resistates is washed, and then filtering separation, vacuum drying oven drying obtain iodate-1-methyl-3-vinyl-2,4,5-triarylimidazoles.If the number of times of washing is inadequate, then can not separating-purifying product completely.
Advantage of the present invention and beneficial effect are:
1. halogenation-1-alkyl-3-vinyl-2 of the present invention, 4,5-triarylimidazoles, such as iodate-1-methyl-3-vinyl-2,4,5-triarylimidazoles, effectively can improve reaction yield as ionic liquid, and can be used as intermediate or final product is applied to the fields such as organic synthesis, pharmaceutical synthesis, agricultural chemicals, papermaking and functional materials.
2. reaction conditions of the present invention is gentle, does not need traditional strong acid or highly basic as catalyzer, simple to operate, has higher practical value.
3. the inventive method obtains halogenation-1-alkyl-3-vinyl-2,4,5-triarylimidazoles in a reaction system, such as iodate-1-methyl-3-vinyl-2,4,5-triarylimidazoles.
4. the reaction times of the inventive method is short, and reacts in anhydrous tetrahydro furan, environmentally friendly, pollution-free.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of monomer N-vinyl-2,4, the 5-triphenylimidazolyl of embodiment 1;
Fig. 2 is the nuclear-magnetism carbon spectrogram of monomer N-vinyl-2,4, the 5-triphenylimidazolyl of embodiment 1;
Fig. 3 is embodiment 2 gained compound
1h nmr spectrum.
Fig. 4 is embodiment 2 gained compound
13c nmr spectrum.
Embodiment
The present invention is further detailed explanation for following specific embodiment, but embodiment does not limit in any form the present invention.Unless stated otherwise, the present invention adopts reagent, method and apparatus are the art conventional reagent, method and apparatus.
Embodiment 1
The structural formula of monomer N-vinyl-2,4,5-triphenylimidazolyl is as follows respectively:
Monomer:
The synthetic route of above monomer
(1) N-hydroxyethyl-2,4,5-triphenylimidazolyl
42.05g (200mmol) dibenzoyl, 21.22g (200mmol) phenyl aldehyde, 15.42g (200mol) ammonium acetate, 12.22g (200mmol) thanomin and nanometer Fe is being added in 500ml round-bottomed flask
3o
4the mixture heating of magnetic fluid, uses 350mL dissolve with ethanol, reflux.After terminating with tlc tracking reaction, be cooled to room temperature.Reaction solution is slowly poured in a large amount of cold water, suction filtration.Gained solid with ethyl acetate recrystallization, obtains white solid.Then pillar layer separation (ethyl acetate: sherwood oil=7:3), productive rate: 78%.
(2) N-bromotrifluoromethane-2,4,5-triphenylimidazolyl
35.4g (87.0mmol) compound (N-hydroxyethyl-2,4,5-triphenylimidazolyl) is dissolved with 300mLDMF in the round-bottomed flask of 500mL.After ice bath to 0 DEG C, slowly drip 16.5mL (174mmol) phosphorus tribromide.Dropwise, be warming up to 80 DEG C of stirring reaction 5h.Reaction is cooled to room temperature, adds ammoniacal liquor and make reaction solution be weakly alkaline after stopping.Then reaction solution is poured in a large amount of cold water, suction filtration, solid distilled water wash.White solid 38.6g is obtained, productive rate 94.3% by after crude product re-crystallizing in ethyl acetate.
(3) N-vinyl-2,4,5-triphenylimidazolyl
With 300mL dissolve with ethanol 38.6g (82.1mmol compound (N-bromotrifluoromethane-2,4,5-triphenylimidazolyl) and 16.8g (300mmol) potassium hydroxide in the round-bottomed flask of 500mL.Back flow reaction 5h, pours in cold water by reaction solution after being cooled to room temperature, suction filtration, solid distilled water wash.Crude product was separated for eluent carries out post with ethyl acetate/petroleum ether (volume ratio is for 1:1), obtained 29.8g white solid, productive rate 93.4%.Fig. 1 is the nucleus magnetic hydrogen spectrum figure of this monomer N-vinyl-2,4,5-triphenylimidazolyl; Fig. 2 is the nuclear-magnetism carbon spectrogram of this monomer N-vinyl-2,4,5-triphenylimidazolyl.
Substituent R in the present embodiment
1, R
2, R
3be hydrogen simultaneously.
Embodiment 2: the building-up reactions of iodate-1-methyl-3-vinyl-2,4,5-triphenylimidazolyl
In 50ml round-bottomed flask, add reaction raw materials 1mmol1-vinyl-2,4,5-triphenylimidazolyl, 1.5mmol methyl iodide and 15mL anhydrous tetrahydro furan successively, the post-heating that stirs to 60 ~ 65 DEG C and insulation reaction liquid to reacting end, reaction 12h.After having reacted, change reflux into water distilling apparatus, steam except anhydrous tetrahydro furan, resistates joins in a large amount of ether and washs, and then filtering separation, vacuum drying oven drying obtain iodate-1-methyl-3-vinyl-2,4,5-triphenylimidazolyl.The productive rate of iodate-1-methyl-3-vinyl-2,4,5-triphenylimidazolyl is 87.2%.
Chemical equation of the present invention is:
Analysis and Identification is carried out to the product that above-mentioned building-up reactions obtains through thin-layer chromatography:
Wherein substituent R
1, R
2, R
3be the physico-chemical property qualification of iodate-1-methyl-3-vinyl-2,4, the 5-triarylimidazoles of the above general formula of hydrogen simultaneously:
1. white solid mp:113-115 DEG C.
2.
1h nmr analysis:
1HNMR(400MHz,DMSO-d
6,δ,ppm)8.06(d,J＝7.4Hz,2H),7.74(d,J＝6.9Hz,2H),7.45(ddd,J＝16.8Hz,6H),7.30–6.95(m,5H),6.82(dd,J＝15.7,8.5Hz,1H),5.12(d,J＝8.4Hz,1H),4.75(d,J＝15.7Hz,1H).
3.
13c nmr analysis:
13CNMR(100MHz,DMSO-d
6,δ,ppm):132.89,132.10,131.66–131.21,131.07,130.80,130.48,129.87,129.60,129.35,129.04,125.99,125.75,122.59,121.94,34.95.
Application of the present invention
0.4205g (2mmol) dibenzoyl, 0.2122g (2mmol) phenyl aldehyde, 0.1542g (2mol) ammonium acetate, 0.1222g (2mmol) thanomin, nanometer Fe is being added in 100ml round-bottomed flask
3o
4the mixture heating of magnetic fluid, uses 40mL dissolve with ethanol, reflux.After terminating with tlc tracking reaction, be cooled to room temperature.Reaction solution is slowly poured in a large amount of cold water, suction filtration.Gained solid with ethyl acetate recrystallization, obtains white solid.Then pillar layer separation (ethyl acetate: sherwood oil=7:3), productive rate: 78%.
0.4205g (2mmol) dibenzoyl, 0.2122g (2mmol) phenyl aldehyde, 0.1542g (2mol) ammonium acetate, 0.1222g (2mmol) thanomin, nanometer Fe is being added in 100ml round-bottomed flask
3o
4magnetic fluid heats with the mixture of (0.01g) iodate-1-methyl-3-vinyl-2,4,5-triphenylimidazolyl, uses 40mL dissolve with ethanol, reflux.After terminating with tlc tracking reaction, be cooled to room temperature.Reaction solution is slowly poured in a large amount of cold water, suction filtration.Gained solid with ethyl acetate recrystallization, obtains white solid.Then pillar layer separation (ethyl acetate: sherwood oil=4:1), productive rate: 83%
Add iodate-1-methyl-3-vinyl-2,4,5-triphenylimidazolyl ionic liquid in this reaction, the productive rate of reactant is increased to 83.2% from 78%.Gained compound
1h nmr spectrum and
13c nmr spectrum is respectively see Fig. 3 and Fig. 4.
Claims (10)
1. halogenation-1-alkyl-3-vinyl-2,4, the 5-triarylimidazoles of general formula (I):
Wherein, R in general formula I
1, R
2, R
3group is identical or not identical, substituent R
1, R
2, R
3hydrogen or electron-donating group or electron-withdrawing group independently of one another; R
4alkyl, such as C
1-C
8alkyl, as C
1-C
6alkyl; X is fluorine, chlorine, bromine or iodine.
2. halogenation-1-alkyl-3-vinyl-2,4,5-triarylimidazoles according to claim 1, wherein, described electron-donating group is selected from amino-NH
2,-NHR
5,-N (R
6)
2, C
1-C
6alkyl, C
1-C
6alkoxyl group or C
1-C
6aminoacyl; And/or
Described electron-withdrawing group is selected from halogen atom, C
1-C
6carboxyl, C
1-C
6ester group, cyano group, sulfonic group,
Wherein R
5, R
6hydrogen, halogen or C1-5 alkyl independently of one another.
3. halogenation-1-alkyl-3-vinyl-2,4,5-triarylimidazoles according to claim 1 and 2, wherein, substituent R
1c atomicity be 1 ~ 5, R
3and R
2the C atomic quantity of group is 1 ~ 5.
4. halogenation-1-alkyl-3-vinyl-2,4,5-triarylimidazoles according to claim 3, wherein, works as R
1c atomic quantity when being 1 ~ 5, R
1in the optional position of remaining five the position of substitution of phenyl ring a; Work as R
2c quantity when being 1 ~ 5, R
2can in the optional position of remaining five the position of substitution of phenyl ring b; And/or work as R
3c quantity when being 1 ~ 5, R
3can in the optional position of remaining five the position of substitution of phenyl ring c.
5. prepare the method for halogenation-1-alkyl-3-vinyl-2,4, the 5-triarylimidazoles of general formula according to claim 1 (I),
Wherein, substituent R
1, R
2, R
3, R
4, X be as in claim 1-4 define;
Described method comprises:
1-vinyl-2,4,5-triarylimidazoles by following formula (II):
Wherein, substituent R
1, R
2, R
3as in claim 1-4 define,
With halohydrocarbon R
4x (wherein R
4alkyl, such as C
1-C
8alkyl, as C
1-C
6alkyl; Wherein X is fluorine, chlorine, bromine or iodine; Halohydrocarbon R
4x is such as methyl iodide) add in solvent, the post-heating that stirs (is preferably heated to reflux state, usual 50-100 DEG C, preferably 50 ~ 90 DEG C, more preferably 60 ~ 70 DEG C, more preferably 60 ~ 65 DEG C) and reaction solution is carried out insulation reaction (usual 8 ~ 12 hours) until reaction terminates, after steaming desolventizes, resistates, through washing, filtering separation, vacuum-drying, obtains the halogenation-1-alkyl-3-vinyl-2 of general formula (I), 4,5-triarylimidazoles.
6. method according to claim 5, wherein, 1-vinyl-2,4,5-triarylimidazoles and halohydrocarbon R
4the molar ratio of X (as methyl iodide) is 1:0.1 ~ 10, preferred 1:0.5 ~ 5, more preferably 1:1.2 ~ 1.8, further preferred about 1:1.5.
7. the method according to claim 5 or 6, wherein, described solvent is ether solvent such as tetrahydrofuran (THF), diox; Ketones solvent is acetone, butanone such as; Or varsol such as methylene dichloride; Or esters solvent such as vinyl acetic monomer; Be preferably tetrahydrofuran (THF).
8. the method according to any one of claim 5-7, wherein, the N-vinyl triarylimidazoles compound of its formula of (II) is by prepared by the preparation method comprised the following steps:
(A) by dibenzoyl, phenyl aldehyde, ammonium acetate, thanomin and nanometer Fe
3o
4the mixture reflux in a solvent of magnetic fluid, reaction terminates rear cooling, obtains N-hydroxyethyl-2,4,5-triarylimidazoles after recrystallization;
(B) allow N-hydroxyethyl-2,4,5-triarylimidazoles and phosphorus tribromide temperature reaction, after reaction, cooling, obtains N-bromotrifluoromethane-2,4,5-triarylimidazoles after recrystallization;
(C) N-bromotrifluoromethane-2 is allowed, 4,5-triarylimidazoles) and alkali (such as potassium hydroxide or sodium hydroxide) back flow reaction, carry out being separated (such as post separation), obtain the N-vinyl triarylimidazoles compound of general formula (II).
9. preparation method according to claim 8, wherein, in step (A), the mol ratio of dibenzoyl, phenyl aldehyde, ammonium acetate, thanomin is 0.5 ~ 1.5:0.5 ~ 1.5:0.5 ~ 1.5:0.5 ~ 1.5, preferably 0.8 ~ 1.2:0.8 ~ 1.2:0.8 ~ 1.2:0.8 ~ 1.2; And/or
In step (B), the mol ratio of N-hydroxyethyl-2,4,5-triarylimidazoles and phosphorus tribromide is 1:1 ~ 4, preferred 1:1.5 ~ 2.5; And/or
In step (C), N-bromotrifluoromethane-2,4,5-triarylimidazoles) be 1:2 ~ 6 with the mol ratio of alkali, preferred 1:3 ~ 4.
10. halogenation-1-alkyl-3-the vinyl-2 according to any one of claim 1-4,4,5-triarylimidazoles or the halogenation-1-alkyl-3-vinyl-2 prepared by the method according to any one of claim 5-9,4,5-triarylimidazoles is as the purposes of ionic liquid, such as intermediate for improving the purposes of reaction yield, or be applied to the purposes in organic synthesis, pharmaceutical synthesis, agricultural chemicals, papermaking and functional materials as intermediate or final product.
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