CN103254136B - Method for preparing quadri [4-(1- imidazolyl) phenyl] methane - Google Patents
Method for preparing quadri [4-(1- imidazolyl) phenyl] methane Download PDFInfo
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- CN103254136B CN103254136B CN201310208952.8A CN201310208952A CN103254136B CN 103254136 B CN103254136 B CN 103254136B CN 201310208952 A CN201310208952 A CN 201310208952A CN 103254136 B CN103254136 B CN 103254136B
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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
Technical field
The present invention relates to the preparation of the organic ligand containing imidazole group, be specifically related to a kind of preparation method of four [4-(1-imidazolyl) phenyl] methane.
Background technology
The ligand polymer of Ligand containing imidazolyl, has unique optical property, magnetic, catalytic and biological activity, and possesses title complex and high molecular feature, has broad application prospects in application novel material, molecular recognition and Supramolecular self assembly.
Organic ligand containing multiple imidazole group is multiple tooth imidazole ligands, has hapto many, and coordination ability is strong, and the feature such as coordination mode is abundant.There is due to imidazole group the characteristics such as good fluorescence, ultraviolet, and the ligand polymer that multiple tooth imidazole ligands and metal ion are formed has the character such as good magnetic, absorption, therefore synthesize new multiple tooth imidazole ligands and utilize these extensive concerns that multiple tooth imidazole ligands assembles duster compounds, ligand polymer causes investigator.
In prior art, the report about the part containing two or three imidazole groups is more, and part of compounds is successful commercialization; But rarely have the part studied and relate to containing four imidazole groups.
Seung Uk Son research group discloses the method that one prepares four [4-(1-imidazolyl) phenyl] methane, see: Jaewon Choi, Hye Yun Yang, Dr. Hae Jin Kim, Prof. Seung Uk Son Angew. Chem. Int. Ed. 2010 49:7718-7722, the method is obtained by classical monovalence copper catalysis Liv Ullmann linked reaction.But, the traditional solution method of such scheme, long reaction time, need reflux 2 days; Simultaneous reactions process has used methyl-sulphoxide, the organic solvent that the toxicity such as methylene dichloride are large, and harm environment and aftertreatment is complicated, is unfavorable for suitability for industrialized production.
Therefore find that a kind of raw material sources are simple, product yield is high, simple to operate, safety, environmental protection method be necessary effectively to synthesize four [4-(1-imidazolyl) phenyl] methane.
Summary of the invention
The object of this invention is to provide that a kind of environmental pollution is few, the reaction times is short, the method for the preparation of convenient product separation four [4-(1-imidazolyl) phenyl] methane.
To achieve the above object of the invention, the technical solution used in the present invention is:
One prepares the method for four [4-(1-imidazolyl) phenyl] methane, comprises the following steps:
(1) four (4-bromophenyl) methane, cuprous iodide, salt of wormwood and imidazoles is mixed, be placed in container, after reacting by heating, obtain crude product 1; 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 the ammoniacal liquor that water, ethylenediamine tetraacetic acid (EDTA) and concentration are 25 ~ 28%, 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 after recrystallization, namely described four [4-(1-imidazolyl) phenyl] methane.
Preferred technical scheme, the type of heating in described step (1) is microwave heating; Microwave heating time is 90 seconds, and power is 720w.
Preferred technical scheme, according to mol ratio, four (4-bromophenyl) methane: cuprous iodide: salt of wormwood: imidazoles=1: 0.4: 6: 10.
In technique scheme, be methanol/water mixed solution for the reagent of crude product 2 recrystallization in step (3); According to volume ratio, methyl alcohol: water=1: 4.
The present invention adopts solvent-free solid reaction process to prepare target product, need by various raw material mixing all before reacting by heating, the mode taked does not limit, belong to prior art, the preferred hybrid mode of this programme, for each reactant is put into crucible, mixes after becoming powder by the mode of grinding.
In the present invention, crude product 1 is containing impurity such as cupric ion, imidazoles, salt of wormwood, add water, ethylenediamine tetraacetic acid (EDTA) and ammoniacal liquor in crude product 1 after, namely cupric ion 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, crude product 2 is obtained after filtration, with methanol/water mixed solution, recrystallization is carried out to crude product 2, thus obtaining pure organism four [4-(1-imidazolyl) phenyl] methane, whole purification, last handling process are simple.
Technique scheme can be expressed as follows:
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. the present invention is under microwave heating condition, prepares four [4-(1-imidazolyl) phenyl] methane by solvent-free solid state reaction, due to without the need to reaction solvent, relative to using environmental protection more 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, and the purifying, the product yield that are conducive to product are high, are easy to industrial operation;
3. the product that the present invention obtains has excellent fluorescence property, and be a kind of part that may be used for preparing fluorescent material, it is after the optical excitation of 327nm, can produce stronger emission peak at 400nm place.
Accompanying drawing explanation
Fig. 1 is the LC-MS liquid chromatogram of four [4-(1-imidazolyl) phenyl] methane in embodiment one;
Fig. 2 is the LC-MS mass spectrum of four [4-(1-imidazolyl) phenyl] methane in embodiment one;
Fig. 3 is the hydrogen nuclear magnetic spectrum of four [4-(1-imidazolyl) phenyl] methane in embodiment one;
Fig. 4 is the carbon nuclear magnetic spectrum of four [4-(1-imidazolyl) phenyl] methane in embodiment one;
Fig. 5 is the fluorescence emission spectrum of four [4-(1-imidazolyl) phenyl] methane in embodiment one;
Fig. 6 is the crystalline structure figure of Coordination Polymers Containing Imidazole Moieties in embodiment three;
Fig. 7 is the fluorescence emission spectrum of Coordination Polymers Containing Imidazole Moieties in embodiment three.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
The synthesis of embodiment one: four [4-(1-imidazolyl) phenyl] methane
Concrete steps are as follows:
by 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 crucible, normal domestic use microwave oven is put into after making it mix by Glass rod grinding, with the power of 720w, microwave heating 90 seconds, detected by TLC (thin-layer chromatography) method, find that the point of raw material four (4-bromophenyl) methane disappears, react completely, obtain crude product 1;
10mL water is added, ethylenediamine tetraacetic acid (EDTA) 0.117g(0.4mmol in crude product 1) and the ammoniacal liquor of 0.15mL 25%, soak 5 hours, filter, precipitation washes with water 3 times (10mL/ time), obtains crude product 2;
by 20mL methanol/water (volume ratio 1: 4), crude product 2 is carried out recrystallization and obtain pale yellow crystals, i.e. product four [4-(1-imidazolyl) phenyl] methane, quality 0.528g(overall yield 90%), LC-MS, infrared, nuclear-magnetism, fluorometric investigation, ultimate analysis are carried out to product.
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 hydrogen nuclear magnetic 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 analyzing 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, product prepared by the present invention is consistent with theory.
The fluorescence emission spectrum of four [4-(1-imidazolyl) phenyl] methane that accompanying drawing 5 is prepared for the present invention, see accompanying drawing 5, product is after the optical excitation of 327nm, stronger emission peak is had at 400nm place, showing that it has excellent fluorescence property, is a kind of part that may be used for preparing fluorescent material.
The synthesis of embodiment two: four [4-(1-imidazolyl) phenyl] methane
Concrete steps are as follows:
by 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 crucible, normal domestic use microwave oven is put into after making it mix by Glass rod grinding, with the power of 720w, microwave heating 90 seconds, detected by TLC (thin-layer chromatography) method, find that the point of raw material four (4-bromophenyl) methane disappears, react completely, obtain crude product 1;
10mL water is added, ethylenediamine tetraacetic acid (EDTA) 0.117g(0.4mmol in crude product 1) and the ammoniacal liquor of 0.15mL 28%, soak 6 hours, filter, precipitation washes with water 3 times (10mL/ time), obtains crude product 2;
by 20mL methanol/water (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: the synthesis of Coordination Polymers Containing Imidazole Moieties
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) put into the heat-resistant glass tube of 8mL, add the mixed solvent acetonitrile/water rear enclosed of 3mL mass ratio 1: 1.150 DEG C of isothermal reactions 2 days in baking oven, be slowly down to room temperature with 5 DEG C/h of speed, obtain yellow crystals and be product Coordination Polymers Containing Imidazole Moieties, molecular formula is C
53h
3n
8o
8zn
2.Carry out infrared analysis to product, result is as follows:
IR:v(KBr)/cm
-13447m, 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 from accompanying drawing 6, the polymkeric substance obtained is single crystal structure; And make use of X-ray single crystal diffraction its structure is analyzed, the results are shown in Table 1, confirmed the single crystal structure of product by table 1 further.
Accompanying drawing 7 is the fluorescence emission spectrum of above-mentioned Coordination Polymers Containing Imidazole Moieties, see accompanying drawing 7, polymkeric substance is the optical excitation of 284nm through wavelength, occurs fluorescence emission peak at 325nm, there occurs obvious blue shift compared with part, is a kind of ligand polymer with photoluminescent property newly.
The crystallographic parameter of table 1 Coordination Polymers Containing Imidazole Moieties
Claims (4)
1. prepare a method for four [4-(1-imidazolyl) phenyl] methane, it is characterized in that, comprise the following steps:
(1) four (4-bromophenyl) methane, cuprous iodide, salt of wormwood and imidazoles is mixed, be placed in container, after reacting by heating, obtain crude product four [4-(1-imidazolyl) phenyl] methane; 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 crude product four [4-(1-imidazolyl) phenyl] methane of step (1), the ammoniacal liquor that water, ethylenediamine tetraacetic acid (EDTA) and concentration are 25 ~ 28% is added, soak 4 ~ 6 hours, filter, washing, drying, obtains crude product four [4-(1-imidazolyl) phenyl] methane; 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) crude product four [4-(1-imidazolyl) phenyl] methane of step (2) obtains pale yellow crystals after recrystallization, i.e. four [4-(1-imidazolyl) phenyl] methane;
Type of heating in described step (1) is microwave heating; Microwave heating time is 90 seconds, and power is 720w.
2. prepare the method for four [4-(1-imidazolyl) phenyl] methane according to claim 1, it is characterized in that: according to mol ratio, four (4-bromophenyl) methane: cuprous iodide: salt of wormwood: imidazoles=1: 0.4: 6: 10.
3. prepare the method for four [4-(1-imidazolyl) phenyl] methane according to claim 1, it is characterized in that: the reagent of crude product four [4-(1-imidazolyl) phenyl] the methane recrystallization for step (2) in described step (3) is methanol/water mixed solution.
4. prepare the method for four [4-(1-imidazolyl) phenyl] methane according to claim 3, it is characterized in that: according to volume ratio, methyl alcohol: water=1: 4.
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| US4141981A (en) * | 1976-07-06 | 1979-02-27 | Bayer Aktiengesellschaft | Antimicrobial agent |
| US4720549A (en) * | 1985-11-02 | 1988-01-19 | Bayer Aktiengesellschaft | Process for the preparation of imidazolyl-methane derivatives |
| DE4333189A1 (en) * | 1993-09-29 | 1995-03-30 | Hoechst Ag | Adamantyl(imidazolyl)phenylmethanes and their salts, process for their preparation, pharmaceuticals containing these compounds and their use |
| CN1714128A (en) * | 2002-11-22 | 2005-12-28 | 东洋铝株式会社 | Powder coating composition |
| CN101193867A (en) * | 2004-12-01 | 2008-06-04 | Osi医药有限公司 | N-substituted benzimidazolyl c-Kit inhibitors and combinatorial benzimidazole library |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4141981A (en) * | 1976-07-06 | 1979-02-27 | Bayer Aktiengesellschaft | Antimicrobial agent |
| US4720549A (en) * | 1985-11-02 | 1988-01-19 | Bayer Aktiengesellschaft | Process for the preparation of imidazolyl-methane derivatives |
| DE4333189A1 (en) * | 1993-09-29 | 1995-03-30 | Hoechst Ag | Adamantyl(imidazolyl)phenylmethanes and their salts, process for their preparation, pharmaceuticals containing these compounds and their use |
| CN1714128A (en) * | 2002-11-22 | 2005-12-28 | 东洋铝株式会社 | Powder coating composition |
| CN101193867A (en) * | 2004-12-01 | 2008-06-04 | Osi医药有限公司 | N-substituted benzimidazolyl c-Kit inhibitors and combinatorial benzimidazole library |
Non-Patent Citations (1)
| Title |
|---|
| Organometallic hollow spheres bearing Bis(N-heterocyclic carbene)-palladium species: Catalytic application in three-component strecker reactions;Jaewon Choi，等;《Angew. Chem. Int. Ed.》;20100910;第49卷(第42期);第7718-7722页 * |
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