CN115650962A - Fluorescent ligand compound for palladium-catalyzed coupling reaction and preparation method thereof - Google Patents
Fluorescent ligand compound for palladium-catalyzed coupling reaction and preparation method thereof Download PDFInfo
- Publication number
- CN115650962A CN115650962A CN202211344404.3A CN202211344404A CN115650962A CN 115650962 A CN115650962 A CN 115650962A CN 202211344404 A CN202211344404 A CN 202211344404A CN 115650962 A CN115650962 A CN 115650962A
- Authority
- CN
- China
- Prior art keywords
- compound
- palladium
- reaction
- fluorescent ligand
- catalyzed coupling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003446 ligand Substances 0.000 title claims abstract description 60
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 39
- 150000001875 compounds Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 12
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 6
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229960000583 acetic acid Drugs 0.000 claims abstract description 6
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010791 quenching Methods 0.000 claims abstract description 6
- XFVZSRRZZNLWBW-UHFFFAOYSA-N 4-(Diethylamino)salicylaldehyde Chemical compound CCN(CC)C1=CC=C(C=O)C(O)=C1 XFVZSRRZZNLWBW-UHFFFAOYSA-N 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- 239000012964 benzotriazole Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229940125782 compound 2 Drugs 0.000 claims description 9
- 229940126214 compound 3 Drugs 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229940125904 compound 1 Drugs 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000010898 silica gel chromatography Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 44
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 abstract description 44
- 229910052763 palladium Inorganic materials 0.000 abstract description 34
- 230000008859 change Effects 0.000 abstract description 11
- 230000000171 quenching effect Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 150000003384 small molecules Chemical class 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 28
- -1 palladium ions Chemical class 0.000 description 25
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 150000001768 cations Chemical class 0.000 description 11
- 239000011550 stock solution Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 239000007850 fluorescent dye Substances 0.000 description 9
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 7
- 230000005284 excitation Effects 0.000 description 7
- 230000004044 response Effects 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229960000956 coumarin Drugs 0.000 description 2
- 235000001671 coumarin Nutrition 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000001506 fluorescence spectroscopy Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001345 alkine derivatives Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000010651 palladium-catalyzed cross coupling reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Landscapes
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a fluorescent ligand compound for palladium-catalyzed coupling reaction and a preparation method thereof, and belongs to the technical field of organic small molecule catalysis and fluorescence. The fluorescent ligand compound has the following structural formula:
the preparation method comprises the steps of adding diethyl malonate, glacial acetic acid and piperidine into an ethanol solution of 4- (diethylamino) -salicylaldehyde, purifying, adding hydrazine hydrate, heating and the like. The palladium ion fluorescent ligand is changed into fluorescence for palladium ionsLight quenching phenomenon, high sensitivity and strong anti-interference capability. The palladium ion fluorescent ligand can be applied to palladium-catalyzed coupling reaction, and has the characteristics of high catalysis efficiency and capability of detecting the reaction process through fluorescence change.
Description
The technical field is as follows:
the invention belongs to the technical field of organic small molecule catalysis and fluorescence, and particularly relates to a novel fluorescent ligand compound for palladium-catalyzed coupling reaction and a preparation method thereof.
Background art:
in the field of organic synthetic chemistry, a coupling reaction catalyzed by metal palladium ions is a common method for constructing carbon-carbon bonds, and is widely applied to various fields such as material development, pharmaceutical synthesis and the like. Also, as a result, the study of palladium-catalyzed cross-coupling reactions achieved great promise for the chemical prize of nobel 2010. The importance of developing a palladium catalyst with high efficiency is self-evident.
The ligands of conventional palladium catalysts are typically phosphorus (P) -containing groups, such as triphenylphosphine and the like. However, these phosphorus-containing ligands generally have the disadvantages of being sensitive to air, expensive, and highly toxic. To solve this problem, in recent years, palladium ion ligand catalysts based on nitrogen-containing heterocycles have received much attention. Various documents report palladium ion ligand catalysts based on different nitrogen-containing heterocyclic molecules such as imidazole, indole, pyridine and the like. However, benzotriazole is used as a good coordination unit, and a palladium ion catalyst based on the benzotriazole is rarely reported. Due to the fact that benzotriazole has strong electron-withdrawing ability, after the benzotriazole is coordinated with palladium ions, the electronic environment outside atomic nuclei of the palladium ions can be changed, and catalytic activity of the benzotriazole is further enhanced.
At present, aiming at the process detection of the coupling reaction catalyzed by palladium ions, the main method is to sample a reaction system and carry out thin layer chromatography analysis. Impurities such as air and water which may be introduced during the sampling operation interfere with the reaction, thereby affecting the reaction. The fluorescence spectrometry can monitor the reaction process in real time on the premise of not damaging the reaction system, and has the advantages of quick response time, simple operation, no influence on the reaction process and the like. Therefore, the introduction of a catalyst with fluorescence activity, and the monitoring of the fluorescence change of the catalyst to indicate the reaction progress is a practical and effective technical method with practical production value. The coumarin is an excellent fluorescent molecule, and has the advantages of high fluorescent quantum yield, easiness in chemical modification, high chemical stability and the like, so that the coumarin has a full application potential in the field.
Based on the importance of the palladium ion catalytic coupling reaction and the limitation of the existing reaction process monitoring means, the excellent metal coordination capacity of benzotriazole and the good fluorescence activity of coumarin groups are combined, the palladium ion ligand catalyst with high catalytic activity is designed and prepared, and the research value and the application potential of the palladium ion ligand catalyst in the coupling reaction are provided.
The invention content is as follows:
aiming at the problems in the prior art, the invention provides a novel fluorescent ligand compound for palladium-catalyzed coupling reaction and a preparation method thereof. The fluorescent ligand is used in a palladium catalytic coupling system, and has the characteristics of high catalytic efficiency and capability of detecting the reaction process through fluorescence change.
The technical scheme of the invention is as follows:
a fluorescent ligand compound for use in palladium-catalyzed coupling reactions, having the formula:
a preparation method of a fluorescent ligand compound for palladium-catalyzed coupling reaction comprises the following steps:
(1) Slowly adding diethyl malonate, glacial acetic acid and piperidine into an ethanol solution of a compound 1 to obtain a reaction solution, reacting the reaction solution for 12 hours under the condition of heating at 80 ℃, and separating and purifying after the reaction is finished to obtain a compound 2, wherein the compound 1 is 4- (diethylamino) -salicylaldehyde; the molar ratio of the compound 1 to diethyl malonate, glacial acetic acid and piperidine is 1:3:0.05:0.2;
(2) Dissolving the compound 2 obtained in the step (1) in absolute ethyl alcohol, then slowly dropwise adding hydrazine hydrate to obtain a reaction solution, reacting the reaction solution for 5 hours under the condition of heating at 80 ℃, and separating and purifying after the reaction is finished to obtain a compound 3; the molar ratio of the compound 2 to the hydrazine hydrate is 1:5;
(3) Dissolving the compound 3 obtained in the step (2) in absolute methanol, adding the compound 4 under the protection of argon to obtain a reaction solution, and reacting the reaction solution under the condition of heating reflux for 12 hours; after the reaction is finished, separating and purifying to obtain a target product: a fluorescent ligand compound for palladium-catalyzed coupling reactions; the compound 4 is 5-aldehyde-benzotriazole; the molar ratio of the compound 3 to the compound 4 is 1:1.
preferably, the separation and purification in step (1) is that after the reaction is finished, distilled water is added to quench the reaction, the obtained mixture is extracted by ethyl acetate, the organic phases are combined, the solvent is removed by reduced pressure distillation, and the obtained crude product is purified by silica gel chromatography.
Preferably, the separation and purification in the step (2) and the step (3) are implemented by freezing and filtering the reaction solution after the reaction is completed, and recrystallizing and purifying the obtained crude product by ethanol.
The fluorescent ligand compound (BTANC) prepared by the method can be used in palladium ion catalytic coupling reaction, and the reaction process is monitored through fluorescence change.
The invention has the beneficial effects that:
1. the palladium ion fluorescent ligand provided by the invention has higher catalytic activity, can obtain a coupling product with the yield of 99% at most aiming at 6 different substrates, and is close to the optimal catalytic activity reported in the current literature; by monitoring the change of the fluorescence intensity of the fluorescent ligand in the reaction process, the reaction process can be sensitively and conveniently indicated.
2. The synthesis method of the palladium ion fluorescent ligand is simple, low in synthesis cost and high in practical application value.
Description of the drawings:
FIG. 1 shows the preparation of palladium ion fluorescent ligand BTANC prepared in example 3 1 H NMR spectrum (solvent deuterated chloroform);
FIG. 2 shows the palladium ion fluorescent ligand BTANC prepared in example 3 13 C NMR spectrum (solvent deuterated chloroform);
FIG. 3 is a diagram of the UV-visible absorption and fluorescence emission spectra of the fluorescent ligand BTANC of palladium ion in example 4, the BTANC concentration is 5 μ M, the test solvent is acetone, and the excitation wavelength is 430nm;
FIG. 4 is a graph showing the change of the fluorescence intensity of the palladium ion fluorescent ligand BTANC with time after the palladium ion is added in example 5. The concentration of BTANC is 5 MuM, the concentration of palladium ions is 10 MuM, the test solvent is acetone, and the excitation wavelength is 430nm;
FIG. 5 is a graph showing the change in the fluorescence intensity of the palladium ion fluorescent ligand BTANC with respect to the concentration of palladium ions after palladium ions were added in example 6. The BTANC concentration is 5 MuM, the palladium ion concentration is 0-10 MuM, the test solvent is acetone, and the excitation wavelength is 430nm;
FIG. 6 is the fluorescence emission spectra of the palladium ion fluorescent ligand BTANC mixed with different metal cations in example 7. The concentration of BTANC is 5 MuM, the concentration of metal cations is 10 MuM, the test solvent is acetone, and the excitation wavelength is 430nm;
FIG. 7 is a bar graph comparing the fluorescence intensity of the palladium ion fluorescent ligand BTANC of example 7 after mixing with different metal cations. The BTANC concentration is 5 MuM, the metal cation concentration is 10 MuM, the test solvent is acetone, and the excitation wavelength is 430nm;
FIG. 8 is a photograph comparing the response of the fluorescent ligand BTANC for palladium ions in example 7;
FIG. 9 is a histogram comparing the fluorescence intensities of the mixed palladium ion and BTANC ligand of example 8 with that of a mixture of other different metal cations. The concentration of BTANC is 5 MuM, the concentration of palladium ions is 10 MuM, the concentration of other metal cations is 100 MuM, the test solvent is acetone, and the excitation wavelength is 430nm;
FIG. 10 is a representation of the coupling reaction product of example 9 1 H NMR spectrum (solvent deuterated chloroform);
FIG. 11 is a representation of the coupling reaction product of example 9 13 C NMR spectrum (solvent deuterated chloroform);
FIG. 12 is a graph showing the fluorescence emission contrast of the reaction solution in the initial stage and the final stage of the coupling reaction in example 9.
The specific implementation mode is as follows:
the present invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In practice, the technical personnel according to the invention make improvements and modifications, which still belong to the protection scope of the invention.
The equipment and reagents used in the present invention are, unless otherwise specified, conventional commercial products in the art.
The synthetic route of the novel palladium ion fluorescent ligand BTANC based on benzotriazole is as follows:
example 1: preparation of Compound 2
4- (diethylamino) salicylaldehyde (0.97g, 5 mmol) and diethyl malonate (2.4g, 15mmol) were dissolved in ethanol (50 mL). After the starting material was completely dissolved, 1mmol of piperidine and 0.25mmol of glacial acetic acid were added dropwise to the solution. After the dropwise addition, the reaction solution was heated to 80 ℃ and stirred to react for 12 hours. After completion of the reaction, the reaction mixture was quenched by adding distilled water (100 mL), and the resulting mixture was extracted three times with ethyl acetate (50 mL), and the organic phases were combined and dried over anhydrous sodium sulfate. Removing the solvent by rotary evaporation to obtain a crude product. Purifying by silica gel column chromatography to obtain product compound 2, wherein the eluent is petroleum ether/ethyl acetate. The product was a yellow solid.
1 H NMR(400MHz,Chloroform-d)δ8.42(s,1H),7.35(d,J＝8.9Hz,1H),6.61(dd,J＝8.9,2.5Hz,1H),6.45(d,J＝2.4Hz,1H),4.37(q,J＝7.1Hz,2H),3.44(q,J＝7.1Hz,4H),1.39(t,J＝7.1Hz,3H),1.23(t,J＝7.1Hz,6H). 13 C NMR(101MHz,Chloroform-d)δ164.23,158.44,158.30,152.84,149.18,131.04,109.55,108.92,107.68,96.70,61.12,45.11,14.38,12.41.
Example 2: preparation of Compound 3
Compound 2 (0.58g, 2mmol) obtained in example 1 was dissolved in absolute ethanol, and after complete dissolution, hydrazine hydrate (85%, 10 mmol) was slowly added dropwise to the solution. After the dropwise addition, the reaction solution was heated to 80 ℃ and stirred to react for 5 hours. After completion of the reaction, the reaction mixture was placed in a refrigerator at-20 ℃ overnight. After yellow crystals are separated out from the solution, crude products are obtained by suction filtration and drying. And recrystallizing and purifying the obtained solid by ethanol to obtain a product compound 3. The product was yellow needle crystals.
1 H NMR(400MHz,DMSO-d 6 )δ9.42(s,1H),8.60(d,J＝2.6Hz,1H),7.65(dd,J＝9.2,2.4Hz,1H),6.76(dd,J＝9.0,2.7Hz,1H),6.56(d,J＝2.8Hz,1H),4.58(s,2H),3.44(d,J＝7.2Hz,4H),1.11–1.07(m,6H). 13 C NMR(101MHz,Chloroform-d)δ163.88,162.11,157.64,152.70,148.06,131.16,110.02,109.09,108.25,96.61,58.42,45.11,18.45,12.42.
Example 3: preparation of novel fluorescent ligand compound BTANC for palladium-catalyzed coupling reaction
The product compound 3 (55mg, 0.2mmol) obtained in example 2 was dissolved in anhydrous methanol, and 5-aldehyde-benzotriazole (50mg, 0.2mmol) was added to the reaction solution under an argon atmosphere. After complete dissolution, the reaction solution was heated to 95 ℃ and stirred for 12 hours. After the reaction was complete, the reaction was placed in a-20 ℃ freezer overnight. After yellow crystals are separated out from the solution, crude products are obtained by suction filtration and drying. And recrystallizing and purifying the obtained solid by ethanol to obtain the product, namely the palladium ion fluorescent ligand BTANC. The product was yellow needle crystals.
1 H NMR(400MHz,DMSO-d 6 )δ11.84(s,1H),8.79(s,1H),8.63(s,1H),8.20(s,1H),7.98(s,2H),7.77(d,J＝9.0Hz,1H),6.87(dd,J＝9.1,2.4Hz,1H),6.69(d,J＝2.4Hz,1H),3.44(d,J＝7.2Hz,4H),1.17(t,J＝7.0Hz,6H). 13 C NMR(101MHz,Chloroform-d)δ166.88,166.53,162.28,157.60,152.44,136.70,115.36,114.09,112.81,101.09,49.56,17.51.
Example 4: photophysical property test of novel fluorescent ligand compound BTANC for palladium-catalyzed coupling reaction
A stock solution of the novel palladium ion fluorescent ligand BTANC obtained in example 3 was prepared in a concentration of 1mM in acetone. 20 mu L of the palladium ion fluorescent probe compound CCB stock solution is diluted in 2mL of acetone (the concentration is 10 mu M), and ultraviolet-visible absorption and fluorescence emission spectrums are tested. In fluorescence emission spectroscopy, the excitation wavelength was 430nm.
The experimental results are as follows: as can be seen from FIG. 3, the maximum absorption wavelength of the palladium ion probe compound was 430nm and the maximum emission wavelength was 478nm.
Example 5: novel fluorescent ligand compound BTANC for palladium ion response time test for palladium catalytic coupling reaction
A stock solution of the novel palladium ion fluorescent ligand BTANC obtained in example 3 was prepared in a concentration of 1mM in acetone. mu.L of a stock solution of the palladium ion fluorescent probe compound CCB was diluted in 2mL of acetone (concentration: 10. Mu.M), and a palladium ion standard solution was added to the solution so that the concentration of palladium ions in the solution was 0.1mM. After the palladium ions are added, the fluorescence intensity of the mixed solution is recorded regularly.
The experimental results are as follows: as can be seen from FIG. 4, the addition of palladium ions to the probe solution immediately caused fluorescence quenching; the fluorescence tends to stabilize within 50 seconds. The fluorescent probe has rapid response to target detection object palladium ions, and the fluorescence change before and after the fluorescent probe is obvious.
Example 6: novel fluorescent ligand compound BTANC for palladium-catalyzed coupling reaction and response test on palladium ion concentration
A stock solution of the novel palladium ion fluorescent ligand BTANC obtained in example 3 was prepared in a concentration of 1mM in acetone. mu.L of the palladium ion fluorescent probe compound CCB stock solution is diluted in 2mL of acetone (the concentration is 10 mu M), and palladium ion standard solutions with different volumes are added into the solution, so that the concentration of the palladium ions in the solution is 0-10 mu M. The fluorescence intensity of the mixed solution was recorded one minute after the palladium ion was added, and the results are shown in FIG. 5.
The experimental results are as follows: with the increase of the concentration of palladium ions, the fluorescence emission intensity of the fluorescent ligand BTANC is gradually reduced, and the fluorescence emission intensity are in a linear relation. After the palladium ions are coordinated with the fluorescent ligand BTANC, intramolecular charge transfer can occur in the fluorescent ligand BTANC, so that the fluorescence of the probe is quenched.
Detection limit of fluorescent probe:
based on the results of the fluorescence titration test, the amount of fluorescence reduction Δ I of the probe at 478nm was plotted against the palladium ion concentration (0-10 μ M). The change of fluorescence intensity and the concentration of palladium ions are in a linear relationThe detection limit for palladium ions can be given by the formula: detection limit
And calculating, wherein the sigma is the standard deviation value of the blank sample, and the K is the slope of the straight line. The detection limit of the fluorescent probe for palladium ions is calculated to be as low as 2.25 multiplied by 10 -8 mol L -1 。
Example 7: novel fluorescent ligand compound BTANC for palladium ion selectivity test in palladium catalytic coupling reaction
A stock solution of the novel palladium ion fluorescent ligand BTANC obtained in example 3 was prepared in a concentration of 1mM in acetone. 20. Mu.L of the stock solution of the palladium ion fluorescent probe compound CCB was diluted in 2mL of acetone (10. Mu.M). Adding 15 metal cations to the solution, respectively, comprising: al (aluminum) 3+ ,Ba 2+ ,Ca 2+ ,Cd 2+ , Co 2+ ,Cu 2+ ,Fe 3+ ,Hg 2+ ,Li + ,Mg 2+ ,Mn 2+ ,Ni 2+ ,Sn 2+ ,Pb 2+ And Pd 2+ . The concentration of each metal cation was 100. Mu.M. After adding the metal ions, mixing uniformly, standing for one minute, and testing the fluorescence emission intensity of the solution.
The experimental results are as follows: from fig. 7 it can be concluded that the fluorescent ligand BTANC shows a pronounced fluorescence quenching if and only if palladium ions are present in the solution. Indicating that the fluorescent ligand btnc has excellent selectivity for palladium ions.
As can be seen from FIG. 8, the change of the fluorescence intensity of the probe before and after the addition of palladium ions is significant and easy to determine.
Example 8: anti-interference test of novel fluorescent ligand compound BTANC (BTANC) for palladium ion response for palladium catalytic coupling reaction
A stock solution of the novel palladium ion fluorescent ligand BTANC obtained in example 3 was prepared in a concentration of 1mM in acetone. 20. Mu.L of the stock solution of the palladium ion fluorescent probe compound CCB was diluted in 2mL of acetone (10. Mu.M). To this solution was added a palladium ion standard solution so that the concentration of palladium ions in the solution was 10. Mu.M. After the palladium ions are added, respectively adding 14 metalsA cation comprising: al (aluminum) 3+ ,Ba 2+ ,Ca 2+ ,Cd 2+ ,Co 2+ ,Cu 2+ ,Fe 3+ ,Hg 2+ ,Li + ,Mg 2+ ,Mn 2+ ,Ni 2+ ,Sn 2+ And Pb 2+ . The concentration of each metal cation was 100. Mu.M. After adding the metal ions, mixing uniformly, standing for one minute, and testing the fluorescence emission intensity of the solution.
The experimental results are as follows: from fig. 9, it can be concluded that the fluorescence quenching phenomenon of the palladium ion on the fluorescent ligand BTANC is less affected by other metal cations. The result shows that the fluorescent ligand BTANC has strong response and anti-interference capability to palladium ions.
Example 9: application of novel fluorescent ligand compound BTANC for palladium-catalyzed coupling reaction in palladium-catalyzed coupling reaction
The reaction route of palladium-catalyzed coupling is as follows:
phenylacetylene (1.1 mmol), 4-iodobenzene (1 mmol), cuprous iodide (10. Mu. Mol), palladium dichloride (5. Mu. Mol) and a fluorescent ligand BTANC (5. Mu. Mol) are sequentially added into a reaction bottle under the protection of argon. 10ml of tetrahydrofuran and 10ml of triethylamine are subsequently added. After the reaction flask was closed, the reaction flask was heated to 80 ℃ to react for 8 hours. After completion of the reaction, the reaction mixture was quenched by adding distilled water (20 mL), and the resulting mixture was extracted three times with ethyl acetate (20 mL), and the organic phases were combined and dried over anhydrous sodium sulfate. Removing the solvent by rotary evaporation to obtain a crude product. The coupling product is purified by chromatography on a silica gel column, the eluent being petroleum ether/ethyl acetate. The fluorescence intensity at the initial stage of the reaction was recorded
1 H NMR(400MHz,Chloroform-d)δ7.55–7.49(m,4H),7.35–7.27(m,6H). 13 C NMR(101MHz,Chloroform-d)δ131.70,128.43,128.34,123.38,89.50.
The experimental results are as follows:
the palladium-catalyzed coupling reaction obtains a target coupling product with a yield of 99%, and proves that the palladium coordination compound of the fluorescent ligand BTANC has good catalytic capability for the coupling reaction of terminal alkyne and halogenated aromatic hydrocarbon.
From fig. 12, it can be derived that the fluorescence intensity at the initial stage of the reaction system is significantly different in the coupling reaction catalyzed by the palladium complex of the fluorescent ligand BTANC. Indicating that the monitoring of the experimental progress can be realized through the change of the fluorescence intensity. The monitoring reaction does not need to destroy the anhydrous and anaerobic environment required by the coupling reaction, and has stronger practical application prospect.
The above detailed description is specific to a possible embodiment of the present invention, which is not intended to be limiting
The scope of the invention is to be determined by the appended claims.
Claims (4)
1. A fluorescent ligand compound for palladium-catalyzed coupling reaction has the following structural formula:
2. a method of preparing the fluorescent ligand compound for palladium-catalyzed coupling reaction of claim 1, comprising the steps of:
(1) Slowly adding diethyl malonate, glacial acetic acid and piperidine into an ethanol solution of a compound 1 to obtain a reaction solution, reacting the reaction solution for 12 hours under the condition of heating at 80 ℃, and separating and purifying after the reaction is finished to obtain a compound 2, wherein the compound 1 is 4- (diethylamino) -salicylaldehyde; the molar ratio of the compound 1 to diethyl malonate, glacial acetic acid and piperidine is 1:3:0.05:0.2;
(2) Dissolving the compound 2 obtained in the step (1) in absolute ethyl alcohol, then slowly dropwise adding hydrazine hydrate to obtain a reaction solution, reacting the reaction solution for 5 hours under the condition of heating at 80 ℃, and separating and purifying after the reaction is finished to obtain a compound 3; the molar ratio of the compound 2 to the hydrazine hydrate is 1:5;
(3) Dissolving the compound 3 obtained in the step (2) in absolute methanol, adding the compound 4 under the protection of argon to obtain a reaction solution, and reacting the reaction solution under the condition of heating reflux for 12 hours; after the reaction is finished, separating and purifying to obtain a target product: a fluorescent ligand compound for palladium-catalyzed coupling reactions; the compound 4 is 5-aldehyde-benzotriazole; the molar ratio of the compound 3 to the compound 4 is 1:1.
3. the method for preparing a fluorescent ligand compound for palladium-catalyzed coupling reaction according to claim 2, wherein the separation and purification in step (1) is that after the reaction is completed, distilled water is added to quench the reaction, the obtained mixture is extracted with ethyl acetate, the organic phases are combined and the solvent is removed by reduced pressure distillation, and the obtained crude product is purified by silica gel chromatography.
4. The method for preparing a fluorescent ligand compound for palladium-catalyzed coupling reaction according to claim 2, wherein the separation and purification in the step (2) and the step (3) are implemented by freezing and filtering a reaction solution after the reaction is completed, and purifying the obtained crude product by ethanol recrystallization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211344404.3A CN115650962A (en) | 2022-10-31 | 2022-10-31 | Fluorescent ligand compound for palladium-catalyzed coupling reaction and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211344404.3A CN115650962A (en) | 2022-10-31 | 2022-10-31 | Fluorescent ligand compound for palladium-catalyzed coupling reaction and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115650962A true CN115650962A (en) | 2023-01-31 |
Family
ID=84993862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211344404.3A Pending CN115650962A (en) | 2022-10-31 | 2022-10-31 | Fluorescent ligand compound for palladium-catalyzed coupling reaction and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115650962A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6438078A (en) * | 1987-08-04 | 1989-02-08 | Mitsubishi Petrochemical Co | Benzotriazolecarboxylic acid hydrazide compound |
| US5746840A (en) * | 1992-11-10 | 1998-05-05 | Janssen Pharmaceutica, N.V. | Process for preparing enantiomerically pure 6-{4-chlorophenyl) (1 H-1,2,4-triazol-1-YL) methyl}-1-methyl-1 H-benzotriazole |
-
2022
- 2022-10-31 CN CN202211344404.3A patent/CN115650962A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6438078A (en) * | 1987-08-04 | 1989-02-08 | Mitsubishi Petrochemical Co | Benzotriazolecarboxylic acid hydrazide compound |
| US5746840A (en) * | 1992-11-10 | 1998-05-05 | Janssen Pharmaceutica, N.V. | Process for preparing enantiomerically pure 6-{4-chlorophenyl) (1 H-1,2,4-triazol-1-YL) methyl}-1-methyl-1 H-benzotriazole |
Non-Patent Citations (1)
| Title |
|---|
| 任爱民, 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》/新型香豆素酰肼、三氮唑衍生物的合成及其荧光性质的研究, 15 January 2022 (2022-01-15) * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111116459B (en) | Tetraphenyl vinyl cation fluorescent probe and preparation method and application thereof | |
| CN111187256B (en) | Triazine trispyrazole compound and preparation method and application thereof | |
| CN111825655B (en) | Hg detection method2+High-sensitivity fluorescent probe and preparation method and application thereof | |
| Shaabani et al. | Synthesis, characterization and electrochemical properties of two new calix [4] arene derivatives bearing two ferrocene imine or ferrocene amine units at the upper rim | |
| CN111393461B (en) | Palladium ion fluorescent probe compound based on BODIPY and synthetic method thereof | |
| KR20110068259A (en) | Coumarin derivatives having cu(ii) ion selectivity and luminescence sensor using the same | |
| CN111423439B (en) | Coumarin conjugated heterocyclic fluorescent probe for detecting Fe (III) | |
| CN110746423B (en) | Synthesis of aryl imidazophenanthroline fluorescent dye and identification of metal ions | |
| Volkmann et al. | Synthesis of a Substituted [10] Cycloparaphenylene through [2+ 2+ 2] Cycloaddition | |
| Liu et al. | Synthesis and time-gated fluorometric application of a europium (III) complex with a borono-substituted terpyridine polyacid ligand | |
| CN115650962A (en) | Fluorescent ligand compound for palladium-catalyzed coupling reaction and preparation method thereof | |
| CN112778266B (en) | Iminoguanidine functionalized water-soluble column [5] arene and preparation method and application thereof | |
| CN110759890A (en) | Nopinanyl indazole silver ion fluorescent probe and preparation method thereof | |
| KR20110020455A (en) | Pyrene derivatives having cu(ii) ion selectivity, method for preparing therefor, detecting method using the same | |
| CN105606607B (en) | A kind of preparation method and application than colour pattern mercury ion probe of the organic iridium of cationic (III) complex | |
| CN110982515B (en) | Application of triphenylamine modified binaphthyl derivative | |
| CN109575004B (en) | Preparation method of pyrazolyl coumarin schiff base copper ion fluorescent probe | |
| CN115745965B (en) | Fluorescent molecule and preparation method and application thereof | |
| CN112920175B (en) | Coumarin-based palladium ion fluorescent probe compound and preparation method thereof | |
| CN113264893A (en) | Praseodymium ion fluorescent probe compound, and preparation method and application thereof | |
| KR100952958B1 (en) | Synthesis and anion recognition of calix[6]arene bridged bipyridine methal-complex of noble optical ionophores | |
| CN113336678B (en) | Electron-rich condensed ring aryl nitrone fluorescent probe and preparation and application thereof | |
| CN113831236B (en) | Detect Al 3+ Fluorescent probe of (2), preparation method and application thereof | |
| CN114014891B (en) | Purine ring modified fluorescent probe and application thereof in detection of cobalt ions | |
| CN113980009B (en) | AIE column aromatic fluorescent probe for diamine detection and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |