CN103254136A - Method for preparing quadri [4-(1- imidazolyl) phenyl] methane - Google Patents

Method for preparing quadri [4-(1- imidazolyl) phenyl] methane Download PDF

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CN103254136A
CN103254136A CN2013102089528A CN201310208952A CN103254136A CN 103254136 A CN103254136 A CN 103254136A CN 2013102089528 A CN2013102089528 A CN 2013102089528A CN 201310208952 A CN201310208952 A CN 201310208952A CN 103254136 A CN103254136 A CN 103254136A
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methane
imidazolyl
phenyl
crude product
quadri
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CN103254136B (en
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郎建平
李端秀
程洪见
任志刚
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Suzhou University
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Abstract

The invention discloses a method for preparing quadri [4-(1-imidazolyl) phenyl] methane. The method comprises the following specific steps of: uniformly mixing quadri[4-bromophenyl]methane, cuprous iodide, potassium carbonate and imidazole to obtain a mixture, putting the mixture in a vessel, and heating to react to obtain a crude product 1; then adding water, ethylenediamine tetraacetic acid and ammonia water to the crude product 1, soaking for 4-6 hours, filtering and washing to obtain a crude product 2; and recrystallizing the crude product 2 to obtain light yellow crystals, namely the quadri[4-(1-imidazolyl) phenyl] methane. The quadri [4-(1-imidazolyl) phenyl] methane prepared by using the method has an excellent fluorescence property and can be used for preparing a fluorescent material. The method disclosed by the invention is low in cost, mild in reaction condition, short in reaction time, simple in posttreatment of reaction, beneficial to purification and high yield of the quadri [4-(1-imidazolyl) phenyl] methane; and in addition, compared with the prior art, the method has the advantages that use of a reaction solvent is avoided, and the preparation process is environment-friendly and easy for industrial operation.

Description

A kind of method of preparation four [4-(1-imidazolyl) phenyl] methane
Technical field
The present invention relates to contain the preparation of the organic ligand of imidazole group, be specifically related to the preparation method of a kind of four [4-(1-imidazolyl) phenyl] methane.
Background technology
The ligand polymer that contains the imidazolyl part has unique optical property, magnetic, catalytic and biological activity, and possesses title complex and high molecular characteristics, is having broad application prospects aspect application novel material, molecular recognition and the supramolecule self-assembly.
The organic ligand that contains a plurality of imidazole groups is multiple tooth imidazole ligands, and it is many to have a hapto, and coordination ability is strong, and characteristics such as coordination mode is abundant.Because imidazole group has characteristic such as fluorescence, ultraviolet preferably, and the formed ligand polymer of multiple tooth imidazole ligands and metal ion has character such as good magnetic, absorption, therefore synthesizes new multiple tooth imidazole ligands and utilizes these multiple tooth imidazole ligands assembling duster compounds, ligand polymer to cause investigator's extensive concern.
In the prior art, more about the report of the part that contains two or three imidazole groups, the successful commercialization of part of compounds; But rarely have research to relate to the part that contains four imidazole groups.
Seung Uk Son research group discloses a kind of method of preparation four [4-(1-imidazolyl) phenyl] methane, referring to: Jaewon Choi, Hye Yun Yang, Dr. Hae Jin Kim, Prof. Seung Uk Son Angew. Chem. Int. Ed. 2010 49:7718-7722, this method makes by the monovalence copper catalysis Liv Ullmann linked reaction of classics.But such scheme is with traditional solution method, and long reaction time needs to reflux 2 days; Reaction process has been used methyl-sulphoxide simultaneously, the organic solvent that toxicity such as methylene dichloride are big, and harm environment and aftertreatment complexity are unfavorable for suitability for industrialized production.
Therefore seek that a kind of raw material sources are simple, product yield is high, the method for simple to operate, safety, environmental protection is necessary with effectively synthetic four [4-(1-imidazolyl) phenyl] methane.
Summary of the invention
The purpose of this invention is to provide that a kind of environmental pollution is few, the reaction times is short, the method for preparation four [4-(1-imidazolyl) phenyl] methane of convenient product separation.
To achieve the above object of the invention, the technical solution used in the present invention is:
A kind of method of preparation four [4-(1-imidazolyl) phenyl] methane may further comprise the steps:
(1) four (4-bromophenyl) methane, cuprous iodide, salt of wormwood and imidazoles are mixed, place container, obtain crude product 1 after the reacting by heating; The mol ratio of four (4-bromophenyl) methane, cuprous iodide, salt of wormwood and imidazoles is 1: 0.4: 6: 8～10;
(2) in above-mentioned crude product 1, add water, ethylenediamine tetraacetic acid (EDTA) and concentration are 25～28% ammoniacal liquor, soak 4～6 hours, filter, washing obtains crude product 2; Wherein, the mol ratio of ethylenediamine tetraacetic acid (EDTA) and cuprous iodide is 1: 0.5～1; The mol ratio of ethylenediamine tetraacetic acid (EDTA) and ammoniacal liquor is 1: 4～6;
(3) above-mentioned crude product 2 obtains pale yellow crystals behind recrystallization, i.e. described four [4-(1-imidazolyl) phenyl] methane.
Optimized technical scheme, the type of heating in the described step (1) is microwave heating; Microwave heating time is 90 seconds, and power is 720w.
Optimized technical scheme, according to mol ratio, four (4-bromophenyl) methane: cuprous iodide: salt of wormwood: imidazoles=1: 0.4: 6: 10.
In the technique scheme, the reagent that is used for crude product 2 recrystallizations in the step (3) is the methanol mixed solution; According to volume ratio, methyl alcohol: water=1: 4.
The present invention adopts solvent-free solid reaction process to prepare target product, need before the reacting by heating various raw materials are mixed all, the mode of taking is unqualified, belong to prior art, the preferred hybrid mode of this programme is for to put into crucible with each reactant, mixes after making it become powder by the mode of grinding.
Among the present invention, crude product 1 contains impurity such as cupric ion, imidazoles, salt of wormwood, add water in the crude product 1, behind ethylenediamine tetraacetic acid (EDTA) and the ammoniacal liquor, cupric ion namely is dissolved in the water with the form of title complex, imidazoles and salt of wormwood also can be water-soluble, four [4-(1-imidazolyl) phenyl] methane is then separated out with precipitation forms, obtain crude product 2 after the filtration, with the methanol mixed solution crude product 2 is carried out recrystallization, thereby obtain pure organism four [4-(1-imidazolyl) phenyl] methane, whole purification, last handling process are simple.
Technique scheme can be expressed as follows:
Figure 607827DEST_PATH_IMAGE002
Because technique scheme is used, the present invention compared with prior art has following advantage:
1. the present invention prepares four [4-(1-imidazolyl) phenyl] methane by solvent-free solid state reaction under microwave heating condition, owing to need not reaction solvent, environmental protection more the use methyl-sulphoxide in prior art;
2. method cost disclosed by the invention is low, reaction conditions is gentle, the reaction times is short, the aftertreatment of reaction is simple, is conducive to purifying, the product yield height of product, is easy to the industrialization operation;
3. the product that obtains of the present invention has good fluorescence property, be a kind of can be for the preparation of the part of fluorescent material, it can produce stronger emission peak at the 400nm place after the optical excitation of 327nm.
Description of drawings
Fig. 1 is the LC-MS liquid chromatogram of four [4-(1-imidazolyl) phenyl] methane among the embodiment one;
Fig. 2 is the LC-MS mass spectrum of four [4-(1-imidazolyl) phenyl] methane among the embodiment one;
Fig. 3 is the proton magnetic chart spectrum of four [4-(1-imidazolyl) phenyl] methane among the embodiment one;
Fig. 4 is the carbon nuclear magnetic spectrum of four [4-(1-imidazolyl) phenyl] methane among the embodiment one;
Fig. 5 is the fluorescence emission spectrum of four [4-(1-imidazolyl) phenyl] methane among the embodiment one;
Fig. 6 is the crystalline structure figure of Coordination Polymers Containing Imidazole Moieties among the embodiment three;
Fig. 7 is the fluorescence emission spectrum of Coordination Polymers Containing Imidazole Moieties among the embodiment three.
Embodiment
Be further described below in conjunction with the present invention of embodiment:
Synthesizing of one: four [4-(1-imidazolyl) phenyl] methane of embodiment
Concrete steps are as follows:
Figure 877397DEST_PATH_IMAGE003
With four (4-bromophenyl) methane 0.636g(1mmol), cuprous iodide 0.076g(0.4mmol), salt of wormwood 0.828g(6mmol) and imidazoles 0.68g(10mmol) add in the crucible, put into the normal domestic use microwave oven after with Glass rod grinding it being mixed, power with 720w, microwave heating 90 seconds, detect by TLC (thin-layer chromatography) method, the point of finding raw material four (4-bromophenyl) methane disappears, and reacts completely, and obtains crude product 1;
Figure 399514DEST_PATH_IMAGE004
Add 10mL water, ethylenediamine tetraacetic acid (EDTA) 0.117g(0.4mmol in the crude product 1) and the ammoniacal liquor of 0.15mL 25%, to soak 5 hours, filtration precipitates and washes 3 times (10mL/ time) with water, obtains crude product 2;
Figure 66119DEST_PATH_IMAGE005
With 20mL methanol (volume ratio 1: 4) crude product 2 is carried out recrystallization and obtain pale yellow crystals, be product four [4-(1-imidazolyl) phenyl] methane, quality 0.528g(overall yield 90%), product is carried out LC-MS, infrared, nuclear-magnetism, fluorometric investigation, ultimate analysis.
Accompanying drawing 1 is the LC-MS(liquid chromatograph mass spectrography of above-mentioned four [4-(1-imidazolyl) phenyl] methane) liquid chromatogram, accompanying drawing 2 is the LC-MS(liquid chromatograph mass spectrography of four [4-(1-imidazolyl) phenyl] methane) mass spectrum, accompanying drawing 3 is the proton magnetic chart spectrum of four [4-(1-imidazolyl) phenyl] methane, accompanying drawing 4 is the carbon nuclear magnetic spectrum of four [4-(1-imidazolyl) phenyl] methane, the result who analyzes accompanying drawing 1, accompanying drawing 2, accompanying drawing 3 and accompanying drawing 4 is: LC-MS:585.3,293.2,195.9; 1HNMR (300 MHz, CDCl 3, 298 K, TMS): δ=7.87 (s, 4H, Imz – H), 7.38 (s, 16H, Ph-H), 7.29 (s, 4H, Ph-H), 7.21 (s, 4H, Ph-H); 13CNMR (300 MHz, CDCl 3, 298 K): δ=144.7,135.8,135.4,132.1,130.7,120.8,117.9,63.7 ppm.
IR:v (KBr)/cm -13410m, 3111m, 1606m, 1517s, 1423w, 1305s, 1245w, 1192w, 1108m, 1057s, 963m, 818s, 737m, 658m, 559m; Ultimate analysis (%): C, 75.96; H, 4.82; N, 19.22.
The theoretical value of four [4-(1-imidazolyl) phenyl] methane: 1H NMR (300 MHz, CDCl 3): δ=7.90 (s, 4H, Imz – H), 7.39 (s, 16 H, Ph-H), 7.31 (s, 4H, Imz – H), 7.21 (s, 4H, Imz – H) 13C NMR (75 MHz, CDCl 3): δ=145.3,135.8,135.4,132.2,131.0,120.9,118.0,63.7 ppm; Ultimate analysis (%): C, 76.01; H, 4.83; N, 19.17.By analyzing, the product of the present invention's preparation is with theoretical consistent.
Accompanying drawing 5 is the fluorescence emission spectrum of four [4-(1-imidazolyl) phenyl] methane of the present invention's preparation, referring to accompanying drawing 5, product has stronger emission peak at the 400nm place after the optical excitation of 327nm, show that it has good fluorescence property, be a kind of can be for the preparation of the part of fluorescent material.
Synthesizing of two: four [4-(1-imidazolyl) phenyl] methane of embodiment
Concrete steps are as follows:
Figure 768102DEST_PATH_IMAGE003
With four (4-bromophenyl) methane 0.636g(1mmol), cuprous iodide 0.076g(0.4mmol), salt of wormwood 0.828g(6mmol) and imidazoles 0.544g(8mmol) add in the crucible, put into the normal domestic use microwave oven after with Glass rod grinding it being mixed, power with 720w, microwave heating 90 seconds, detect by TLC (thin-layer chromatography) method, the point of finding raw material four (4-bromophenyl) methane disappears, and reacts completely, and obtains crude product 1;
Figure 453030DEST_PATH_IMAGE004
Add 10mL water, ethylenediamine tetraacetic acid (EDTA) 0.117g(0.4mmol in the crude product 1) and the ammoniacal liquor of 0.15mL 28%, to soak 6 hours, filtration precipitates and washes 3 times (10mL/ time) with water, obtains crude product 2;
Figure 162360DEST_PATH_IMAGE005
With 20mL methanol (volume ratio 1: 4) crude product 2 is carried out recrystallization and obtain pale yellow crystals, be i.e. product four [4-(1-imidazolyl) phenyl] methane, quality 0.496g(overall yield 85%).
Embodiment three: Coordination Polymers Containing Imidazole Moieties synthetic
Get zinc nitrate hexahydrate Zn (NO 3) 26H 2O(0.15g, 0.5mmol), m-phthalic acid (0.13g, 0.5mmol) and four [4-(1-imidazolyl) phenyl] methane (0.14g 0.25mmol) puts into the heat-resistant glass tube of 8mL, adds 1: 1 mixed solvent acetonitrile/water rear enclosed of 3mL mass ratio.150 ℃ of isothermal reactions are 2 days in baking oven, slowly are down to room temperature with 5 ℃/speed at one hour rating, obtain yellow crystals and are the product Coordination Polymers Containing Imidazole Moieties, and molecular formula is C 53H 3N 8O 8Zn 2Product is carried out infrared analysis, and the result is as follows:
IR:v(KBr)/cm -1?3447m,?3136w,?1613s,?1561w,?1523s,?1373s,?1313w,?1270w,?1126w,?1068m,?966m,?827m,?762s,?656m,?561m。
Accompanying drawing 6 is the crystalline structure figure of above-mentioned Coordination Polymers Containing Imidazole Moieties, and by accompanying drawing 6 as seen, the polymkeric substance that obtains is single crystal structure; And utilized X-ray single crystal diffraction that its structure is analyzed, and the results are shown in Table 1, further proved conclusively the single crystal structure of product by table 1.
Accompanying drawing 7 is the fluorescence emission spectrum of above-mentioned Coordination Polymers Containing Imidazole Moieties, referring to accompanying drawing 7, polymkeric substance is the optical excitation of 284nm through wavelength, fluorescence emission peak occurs at 325nm, comparing with part tangible blue shift has taken place, is a kind of new ligand polymer with photoluminescent property.
The crystallographic parameter of table 1 Coordination Polymers Containing Imidazole Moieties
Figure 598152DEST_PATH_IMAGE007

Claims (6)

1. a method for preparing four [4-(1-imidazolyl) phenyl] methane is characterized in that, may further comprise the steps:
(1) four (4-bromophenyl) methane, cuprous iodide, salt of wormwood and imidazoles are mixed, place container, obtain crude product 1 after the reacting by heating; The mol ratio of described four (4-bromophenyl) methane, cuprous iodide, salt of wormwood and imidazoles is 1: 0.4: 6: 8～10;
(2) in above-mentioned crude product 1, add water, ethylenediamine tetraacetic acid (EDTA) and concentration are 25～28% ammoniacal liquor, soak 4～6 hours, filter, washing obtains crude product 2; Wherein, the mol ratio of ethylenediamine tetraacetic acid (EDTA) and cuprous iodide is 1: 0.5～1; The mol ratio of ethylenediamine tetraacetic acid (EDTA) and ammoniacal liquor is 1: 4～6;
(3) above-mentioned crude product 2 obtains pale yellow crystals behind recrystallization, i.e. four [4-(1-imidazolyl) phenyl] methane.
2. according to the method for the described preparation four of claim 1 [4-(1-imidazolyl) phenyl] methane, it is characterized in that: the type of heating in the described step (1) is microwave heating.
3. according to the method for the described preparation four of claim 2 [4-(1-imidazolyl) phenyl] methane, it is characterized in that: microwave heating time is 90 seconds, and power is 720w.
4. according to the method for the described preparation four of claim 1 [4-(1-imidazolyl) phenyl] methane, it is characterized in that: according to mol ratio, four (4-bromophenyl) methane: cuprous iodide: salt of wormwood: imidazoles=1: 0.4: 6: 10.
5. according to the method for the described preparation four of claim 1 [4-(1-imidazolyl) phenyl] methane, it is characterized in that: the reagent that is used for crude product 2 recrystallizations in the described step (3) is the methanol mixed solution.
6. according to the method for the described preparation four of claim 5 [4-(1-imidazolyl) phenyl] methane, it is characterized in that: according to volume ratio, methyl alcohol: water=1: 4.
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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN104098614A (en) * 2014-07-23 2014-10-15 苏州大学 Zinc coordination polymer as well as preparation method and application thereof
CN106732481A (en) * 2017-01-10 2017-05-31 苏州大学 A kind of pertechnetate adsorbent and its synthetic method and the application in radioactive wastewater is processed
CN115429088A (en) * 2022-10-10 2022-12-06 常熟新常泰汽车内饰科技有限公司 High-sound-absorption polyurethane trunk composite carpet and processing technology thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104098614A (en) * 2014-07-23 2014-10-15 苏州大学 Zinc coordination polymer as well as preparation method and application thereof
CN106732481A (en) * 2017-01-10 2017-05-31 苏州大学 A kind of pertechnetate adsorbent and its synthetic method and the application in radioactive wastewater is processed
CN106732481B (en) * 2017-01-10 2019-04-05 苏州大学 A kind of pertechnetate adsorbent and its synthetic method and the application in processing radioactive wastewater
CN115429088A (en) * 2022-10-10 2022-12-06 常熟新常泰汽车内饰科技有限公司 High-sound-absorption polyurethane trunk composite carpet and processing technology thereof
CN115429088B (en) * 2022-10-10 2024-02-27 常熟新常泰汽车内饰科技有限公司 High-sound-absorption polyurethane composite carpet for trunk and processing technology thereof

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