CN104151332B - Based on nitrogen heterocyclic carbene silver complex and preparation method thereof and the application of double pyrazole methylenedioxy phenoxy Methylimidazole - Google Patents
Based on nitrogen heterocyclic carbene silver complex and preparation method thereof and the application of double pyrazole methylenedioxy phenoxy Methylimidazole Download PDFInfo
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- methylenedioxy phenoxy
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 52
- -1 pyrazole methylenedioxy phenoxy Methylimidazole Chemical compound 0.000 title claims abstract description 47
- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 26
- OTWSURXLBKIUNH-UHFFFAOYSA-N methylidenesilver Chemical compound [Ag]=C OTWSURXLBKIUNH-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000010668 complexation reaction Methods 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract 2
- 150000002460 imidazoles Chemical class 0.000 claims description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 6
- CKXMKCYLCNDVQF-UHFFFAOYSA-N 1-(chloromethyl)imidazole;hydrochloride Chemical compound Cl.ClCN1C=CN=C1 CKXMKCYLCNDVQF-UHFFFAOYSA-N 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- UQFQONCQIQEYPJ-UHFFFAOYSA-N N-methylpyrazole Chemical compound CN1C=CC=N1 UQFQONCQIQEYPJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 3
- HRDXJKGNWSUIBT-UHFFFAOYSA-N methoxybenzene Chemical group [CH2]OC1=CC=CC=C1 HRDXJKGNWSUIBT-UHFFFAOYSA-N 0.000 claims description 3
- 125000004353 pyrazol-1-yl group Chemical group [H]C1=NN(*)C([H])=C1[H] 0.000 claims description 3
- BJOZXBYJFDBSAF-UHFFFAOYSA-N 2-(pyrazol-1-ylmethyl)phenol Chemical compound OC1=CC=CC=C1CN1N=CC=C1 BJOZXBYJFDBSAF-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 2
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 claims description 2
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract description 2
- 150000001345 alkine derivatives Chemical class 0.000 abstract 1
- 150000001412 amines Chemical class 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- FWWIQSJJLZQJMF-UHFFFAOYSA-N 1-benzyl-2-(phenoxymethyl)imidazole Chemical class N=1C=CN(CC=2C=CC=CC=2)C=1COC1=CC=CC=C1 FWWIQSJJLZQJMF-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 4
- 238000007306 functionalization reaction Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- PQNJCOYXVMMNJK-UHFFFAOYSA-N methane;1h-pyrazole Chemical compound C.C=1C=NNC=1 PQNJCOYXVMMNJK-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical compound NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 description 1
- USPWKWBDZOARPV-UHFFFAOYSA-N pyrazolidine Chemical compound C1CNNC1 USPWKWBDZOARPV-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- Catalysts (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The present invention relates to the nitrogen heterocyclic carbene silver complex and preparation method thereof based on double pyrazole methylenedioxy phenoxy Methylimidazole and application.Wherein the preparation method of nitrogen heterocyclic carbene silver complex is: under the condition of room temperature lucifuge, is in organic solvent react 24 hour at 1: 0.7, filters methyl substituted for double pyrazole methylenedioxy phenoxy imidazole salts and silver suboxide with mol ratio, concentrated obtained.Nitrogen heterocyclic carbene silver complex of the present invention has strong fluorescent emission, and the ability of catalysis alkynes, amine and aldehyde three components linked reaction, is mainly used in fluorescent material and organic catalysis technical field.
Description
Technical field:
The invention belongs to organic synthesis and Organometallic Chemistry technical field, relating to the Synthesis and application of nitrogen heterocyclic carbene silver complex, is preparation method and application that chloro 1-[2-two (pyrazol-1-yl) methylenedioxy phenoxy methyl] imidazole salts and 1-[two (pyrazol-1-yl) methylenedioxy phenoxy methyl of 2-] limidazolium hexafluorophosphate and a tetrafluoro borate are the nitrogen heterocyclic carbene silver complex of precursor in particular.
Background technology:
Because it is successfully applied to coordination chemistry and homogeneous catalysis, N-heterocyclic carbine and transition metal complex thereof have become one of focus of people's research in recent years.In these N-heterocyclic carbine metal title complexs, nitrogen heterocyclic carbene silver complex especially receives people and pays close attention to widely.They present structure diversity, are used as Cabbeen transfering reagent widely, have potential biological activity and luminescent properties.But, utilize nitrogen heterocyclic carbene silver complex to carry out also be nowhere near at present as the research of catalyzer.On the other hand, the N-heterocyclic carbine of heteroatoms functionalization also result in increasing attention recently.Due to heteroatomic introducing, the N-heterocyclic carbine of these functionalization shows the coordination mode and reactive mode that make new advances, and its metal complexes shows relatively high stability and catalytic activity.Double pyrazole methane is the nitrogenous polydentate ligand that a class has extensive coordination ability, and research display, on end of the bridge carbon, the double pyrazole methane of functionalization often shows distinguished reactive behavior and catalytic performance.Double pyrazole methane is introduced in N-heterocyclic carbine, the N-heterocyclic carbine of design and synthesis pyrazolidine functionalization and the research of title complex also more rare.The N-heterocyclic carbine of this kind of novel structure and metal complexes thereof are that people find new efficient catalyzer and explore some new chemical reactions and open New view.
Summary of the invention:
The object of the present invention is to provide the nitrogen heterocyclic carbene silver complex and preparation method thereof based on double pyrazole methylenedioxy phenoxy Methylimidazole and application.The present invention also relates to the method preparing this type of nitrogen heterocyclic carbene silver complex precursor.The fluorescence data that the present invention further relates to this type of nitrogen heterocyclic carbene silver complex and precursor thereof measures and the application of this type of nitrogen heterocyclic carbene silver complex in catalytic field.
The synthetic method of the nitrogen heterocyclic carbene silver complex in the present invention, comprises the following steps:
(1) in ethanol two for 2-hydroxy phenyl (pyrazol-1-yl) methane and 1-chloromethyl imidazole hydrochloride are reacted under alkalescence, obtained 1-[two (pyrazol-1-yl) methylenedioxy phenoxy methyl of 2-] imidazoles; Wherein the mol ratio of two (pyrazol-1-yl) methane of 2-hydroxy phenyl and 1-chloromethyl imidazole hydrochloride is: 1: 1;
(2) 1-[2-two (pyrazol-1-yl) methylenedioxy phenoxy methyl] imidazoles that obtains of step (1) and halohydrocarbons reaction, obtained 1-[two (pyrazol-1-yl) methylenedioxy phenoxy methyl of 2-] imidazole salts; Wherein the mol ratio of 1-[two (pyrazol-1-yl) methylenedioxy phenoxy methyl of 2-] imidazoles and halohydrocarbon is: 1: 1.0-1.1;
(3) imidazole salts that obtains of step (2) is soluble in water, under agitation add the aqueous solution of Potassium Hexafluorophosphate or ammonium tetrafluoroborate, react 3 hours under room temperature, synthesize corresponding 1-[two (pyrazol-1-yl) methylenedioxy phenoxy methyl of 2-] limidazolium hexafluorophosphate and a tetrafluoro borate; Wherein the mol ratio of the imidazole salts that obtains of step (2) and Potassium Hexafluorophosphate or ammonium tetrafluoroborate is: 1: 1.0-1.3;
(4) 1-[two (pyrazol-1-yl) methylenedioxy phenoxy methyl of 2-] imidazole salts step (2) or step (3) obtained mixes with the ratio that mol ratio is 1: 0.7 with silver suboxide, add acetonitrile or N, dinethylformamide, at room temperature lucifuge reacts 24 hours.Filter, concentrated, obtain the nitrogen heterocyclic carbene silver complex based on double pyrazole methylenedioxy phenoxy Methylimidazole.
Above-mentioned halohydrocarbon is: methyl iodide, monobromethane, n-propyl chloride, 2 cbloropropane isopropyl chloride, benzyl chlorine.
The present invention adopts the means such as nucleus magnetic resonance and fluorescence spectrum to characterize the synthesized nitrogen heterocyclic carbene silver complex based on double pyrazole methylenedioxy phenoxy Methylimidazole and precursor thereof.The nitrogen heterocyclic carbene silver complex that the present invention obtains has strong fluorescent emission, efficient catalytic activity, is expected to obtain further Application and Development in organic synthesis fluorescent material and catalytic field.
Accompanying drawing illustrates:
Fig. 1, crystalline structure figure based on the N-heterocyclic carbine silver chloride title complex (1) of double pyrazole methylenedioxy phenoxy Methylimidazole
The solid state fluorescence figure of Fig. 2, chloro N-[two (pyrazol-1-yl) methyl of 2-] Phenoxymethyl-N ' benzyl imidazole salt (L1) and corresponding N-heterocyclic carbine silver chloride title complex (1)
Embodiment:
Embodiment 1
The synthesis of 1-[two (pyrazol-1-yl) methylenedioxy phenoxy methyl of 2-] imidazoles
In 100mL round-bottomed flask, add 20mL ethanol successively, two (pyrazol-1-yl) methane 2.4g (10mmol) of 2-hydroxy phenyl, 1-chloromethyl imidazole hydrochloride 1.53g (10mmol) and potassium hydroxide 1.12g (20mmol), then heated and stirred refluxes 24 hours.Be chilled to room temperature, filter, wash solid with ethanol (3 × 10mL), this solid is inorganic salt Repone K.Filtrate adds 20mL water except after desolventizing, with methylene dichloride (3 × 30mL) extraction, merges organic phase, with anhydrous sodium sulfate drying, filters.Except desolventizing, obtain faint yellow solid product 1.79g, productive rate 56%.
1HNMR(400MHz，CDCl
3)：δ5.97(s，2H)，6.32(t，2H)，6.89(s，1H)，7.73(s，1H)，7.94(s，1H)，6.87(d，1H)，7.04(t，1H)，7.32(d，1H)，7.39-7.45(m，1H)，7.12(s，1H)，7.56(d，2H)，7.66(d，2H)。
The synthesis of chloro N-[two (pyrazol-1-yl) methyl of 2-] Phenoxymethyl-N ' benzyl imidazole salt (L1)
In 100mL round-bottomed flask, add 20mL acetonitrile successively, 1-[two (pyrazol-1-yl) methylenedioxy phenoxy methyl of 2-] imidazoles 1.60g (5.0mmol) and benzyl chlorine 0.60mL (5.2mmol), stirring heating refluxes 24 hours.Be chilled to room temperature, be evaporated to 2mL, add 15mL ether, separate out oily liquids, separatory.Take off a layer oily liquids, vacuum-drying, obtain oily product 1.88g, productive rate 84%.
1HNMR(400MHz，CDCl
3)：δ5.44(s，2H)，6.26(s，2H)，6.47(s，2H)，6.87(d，1H)，7.04(d，1H)，7.60(d，1H)，7.07(s，1H)，8.08(s，1H)，7.16(s，1H)，7.35-7.43(m，6H)，7.46(d，2H)，7.54(d，2H)，10.98(s，1H)。
Based on the synthesis of the N-heterocyclic carbine silver chloride title complex (1) of double pyrazole methylenedioxy phenoxy Methylimidazole
In 100mL round-bottomed flask, add 20mL acetonitrile successively, chloro N-[two (pyrazol-1-yl) methyl of 2-] Phenoxymethyl-N ' benzyl imidazole salt (L1) 0.45g (1.0mmol) and silver suboxide 0.16g (0.7mmol).Lucifuge stirring reaction 24 hours under room temperature.Filter, filtrate reduced in volume, to 2mL, adds 10mL ethanol subsequently, separates out white solid.Filter, solid vacuum-drying, obtains product 0.50g, productive rate 91%.
1HNMR(400MHz，CDCl
3)：δ5.25(s，2H)，5.97(s，2H)，6.28(t，2H)，6.76(d，1H)，6.84-6.86(m，2H)，7.06(t，1H)，7.17-7.21(m，3H)，7.32-7.43(m，6H)，7.58(d，2H)，7.92(s，1H)。
Crystalline structure is shown in Figure of description 1.
Embodiment 2
The synthesis of N-[two (pyrazol-1-yl) methyl of 2-] Phenoxymethyl-N '-benzyl imidazole a tetrafluoro borate
In 100mL round-bottomed flask, chloro N-[two (pyrazol-1-yl) methyl of 2-] Phenoxymethyl-N '-benzyl imidazole salt (L1) 0.45g (1.0mmol) is dissolved in 10mL water, then the 10mL aqueous solution of ammonium tetrafluoroborate 0.14g (1.3mmol) is dropwise added in above-mentioned reaction mixture, adds rear room temperature and continue stirring 3 hours.With methylene dichloride (3 × 10mL) extraction, merge organic phase, use anhydrous sodium sulfate drying.Filter, except the solid phase prod 0.45g obtaining the easy moisture absorption of white after desolventizing under filtrate decompression, productive rate is 90%.
1HNMR(400MHz，CDCl
3)：δ5.24(s，2H)，6.00(s，2H)，6.23(t，2H)，6.84(d，1H)，7.15(d，1H)，6.70-7.07(m，3H)，7.31-7.37(m，6H)，7.96(s，1H)，7.42(d，2H)，7.51(d，2H)，8.97(s，1H)。
Based on the synthesis of the N-heterocyclic carbine Tetrafluoroboric acid silver complex (2) of double pyrazole methylenedioxy phenoxy Methylimidazole
In 100mL round-bottomed flask, add 10mLN successively, dinethylformamide, N-[two (pyrazol-1-yl) methyl of 2-] Phenoxymethyl-N ' benzyl imidazole a tetrafluoro borate 0.50g (1.0mmol) and silver suboxide 0.16g (0.7mmol).Lucifuge stirring reaction 24 hours under room temperature.Filter, be concentrated to 2mL under filtrate decompression, add 10mL ethanol subsequently, separate out white solid.Filter, solid vacuum-drying, obtains product 0.56g, productive rate 92%.
1HNMR(400MHz，DMSO-d
6)：δ5.27(s，2H)，6.03(s，2H)，6.20(s，2H)，6.75(d，1H)，7.09(t，1H)，7.24-7.29(m，5H)，7.33-7.38(m，3H)，7.43-7.47(m，1H)，7.52-7.54(m，2H)，7.78(s，2H)，8.18(s，1H)。
Embodiment 3
Part (L1) obtained for embodiment 1 and corresponding nitrogen heterocyclic carbene silver complex (1) are at room temperature measured solid fluorescence, and the part that the fluorescence emission spectrum strength ratio of title complex (1) is corresponding is stronger, and change in fluorescence is obvious.The excitation wavelength of part (L1) is the excitation wavelength of 295nm and corresponding title complex (1) is that under 360nm condition, solid state fluorescence figure is shown in Figure of description 2.
Embodiment 4
The general procedure of three components linked reaction: in 10mL round-bottomed flask, add phenylacetylene (1.5mmol) successively, piperidines (1.2mmol), aldehyde (1.0mmol), 2mL methylene dichloride or N, dinethylformamide, nitrogen heterocyclic carbene silver complex (nmol%).Then stir under assigned temperature and specify the reaction times.Decompression is lower, and except desolventizing, residue with ethyl acetate/sherwood oil (60 ~ 90 DEG C, volume ratio 1: 5) is eluent, crosses silicagel column, obtains corresponding propargylamine.
1 is the results are shown in Table as catalyst three components linked reaction using the nitrogen heterocyclic carbene silver complex 1 and 2 that embodiment 1 and 2 obtains.
The three components linked reaction of table 1 nitrogen heterocyclic carbene silver complex 1 and 2 catalysis
Above embodiment is only for illustration of content of the present invention, and unrestricted the present invention, knowledgeable people in same area can propose other embodiment easily within technical director's thought of the present invention, but this embodiment all comprises within the scope of the present invention.
Claims (5)
1., based on the nitrogen heterocyclic carbene silver complex of double pyrazole methylenedioxy phenoxy Methylimidazole, it is characterized in that its structural formula is as follows:
Wherein: R is for being selected from n-propyl, sec.-propyl and benzyl.
2., based on the nitrogen heterocyclic carbene silver complex of double pyrazole methylenedioxy phenoxy Methylimidazole, it is characterized in that its structural formula is as follows:
Wherein: R is for being selected from methyl, ethyl, n-propyl, sec.-propyl and benzyl; X is tetrafluoroborate or hexafluoro-phosphate radical.
3. prepare the method based on the nitrogen heterocyclic carbene silver complex of double pyrazole methylenedioxy phenoxy Methylimidazole described in claim 1 or 2, it is characterized in that synthesis technique comprises the following steps:
(1) in ethanol two for 2-hydroxy phenyl (pyrazol-1-yl) methane and 1-chloromethyl imidazole hydrochloride are reacted under alkalescence, obtained 1-[two (pyrazol-1-yl) methylenedioxy phenoxy methyl of 2-] imidazoles; Wherein the mol ratio of two (pyrazol-1-yl) methane of 2-hydroxy phenyl and 1-chloromethyl imidazole hydrochloride is: 1: 1;
(2) 1-[2-two (pyrazol-1-yl) methylenedioxy phenoxy methyl] imidazoles that obtains of step (1) and halohydrocarbons reaction, obtained 1-[two (pyrazol-1-yl) methylenedioxy phenoxy methyl of 2-] imidazole salts; Wherein the mol ratio of 1-[two (pyrazol-1-yl) methylenedioxy phenoxy methyl of 2-] imidazoles and halohydrocarbon is: 1: 1.0-1.1;
(3) imidazole salts that obtains of step (2) is soluble in water, under agitation add the aqueous solution of Potassium Hexafluorophosphate or ammonium tetrafluoroborate, react 3 hours under room temperature, synthesize corresponding 1-[two (pyrazol-1-yl) methylenedioxy phenoxy methyl of 2-] limidazolium hexafluorophosphate and a tetrafluoro borate; Wherein the mol ratio of the imidazole salts that obtains of step (2) and Potassium Hexafluorophosphate or ammonium tetrafluoroborate is: 1: 1.0-1.3;
(4) 1-[two (pyrazol-1-yl) methylenedioxy phenoxy methyl of 2-] imidazole salts step (2) or step (3) obtained mixes with the ratio that mol ratio is 1: 0.7 with silver suboxide, add acetonitrile or N, dinethylformamide, at room temperature lucifuge reacts 24 hours, filter, concentrated, obtain the nitrogen heterocyclic carbene silver complex based on double pyrazole methylenedioxy phenoxy Methylimidazole.
4. method according to claim 3, wherein said halohydrocarbon is: methyl iodide, monobromethane, n-propyl chloride, 2 cbloropropane isopropyl chloride, benzyl chlorine.
5. described in claim 1 or 2 based on the nitrogen heterocyclic carbene silver complex of double pyrazole methylenedioxy phenoxy Methylimidazole as the application in catalyzer, organic synthesis fluorescent material.
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| CN104860966B (en) * | 2015-04-29 | 2017-01-11 | 天津师范大学 | Tetradentate nitrogen-heterocyclic Carbene silver complex and preparation method and application thereof |
| CN108129497B (en) * | 2018-02-05 | 2019-07-23 | 天津师范大学 | Cyclic annular nitrogen heterocyclic carbene silver complex and the preparation method and application thereof |
| CN108276432B (en) * | 2018-02-05 | 2019-08-09 | 天津师范大学 | Cyclic annular nitrogen heterocyclic carbene silver complex of fluorenes bridging and the preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011071881A2 (en) * | 2009-12-07 | 2011-06-16 | University Of Hawaii | Microwave-assisted synthesis of n-heterocyclic carbene transition metal complexes |
| WO2012050629A1 (en) * | 2010-10-12 | 2012-04-19 | The University Of Akron | Metal complexes of n-heterocyclic carbenes |
| CN102442952A (en) * | 2011-11-07 | 2012-05-09 | 天津师范大学 | Cyclic N-heterocyclic carbene metal complex, and preparation method and application thereof |
| CN102838547A (en) * | 2012-09-14 | 2012-12-26 | 华东理工大学 | Novel method for synthesizing chirality carbene precursor with imidazolinyl and complex of chirality carbene precursor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011071881A2 (en) * | 2009-12-07 | 2011-06-16 | University Of Hawaii | Microwave-assisted synthesis of n-heterocyclic carbene transition metal complexes |
| WO2012050629A1 (en) * | 2010-10-12 | 2012-04-19 | The University Of Akron | Metal complexes of n-heterocyclic carbenes |
| CN102442952A (en) * | 2011-11-07 | 2012-05-09 | 天津师范大学 | Cyclic N-heterocyclic carbene metal complex, and preparation method and application thereof |
| CN102838547A (en) * | 2012-09-14 | 2012-12-26 | 华东理工大学 | Novel method for synthesizing chirality carbene precursor with imidazolinyl and complex of chirality carbene precursor |
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