CN106188014A - The preparation of the c h bond Anion Recognition receptor of a kind of neutrality and application - Google Patents
The preparation of the c h bond Anion Recognition receptor of a kind of neutrality and application Download PDFInfo
- Publication number
- CN106188014A CN106188014A CN201510226098.7A CN201510226098A CN106188014A CN 106188014 A CN106188014 A CN 106188014A CN 201510226098 A CN201510226098 A CN 201510226098A CN 106188014 A CN106188014 A CN 106188014A
- Authority
- CN
- China
- Prior art keywords
- compound
- anion
- receptor
- dissolved
- chloride ion
- 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.)
- Withdrawn
Links
Landscapes
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
The invention discloses a kind of new compound that may be used for detection identification chloride ion, be specifically related to preparation and the application of the c h bond Anion Recognition receptor of a kind of neutrality, belong to supramolecular chemistry molecular recognition technical field.This receptor structural formula of compound is as follows:.This miazines acceptor compound based on neutral c h bond has improvement greatly to the recognition performance of anion, and forms the stable comple of 1:1 with chloride ion.This compound selectivity is good, and binding ability is strong, highly sensitive, can be used for the detection identification of chloride ion in biology or environmental sample, has good application prospect.
Description
Technical field
The present invention relates to chemical analysis detection technique field, be specifically related to preparation method and the application in terms of detection chloride ion of this receptor compound of a kind of neutral c h bond Anion Recognition receptor.
Background technology
This inorganic anion of chloride ion occupies extremely important effect in daily life and biotic environment, if chloride ion is the main anion of extracellular fluid, can maintain extracellular fluid osmotic balance, and then maintain the balance of human internal environment；Chloride ion and carbonic acid hydrogen ion regulate electric charge and acid-base balance by carrying out ion exchange between blood plasma and erythrocyte；Chloride ion is the activator etc. of pancreatic amylase and ptyalin.Therefore, identification and the detection of chloride ion has very important Research Significance.Therefore a kind of high sensitivity of synthesis, high selectivity, it is possible to quickly the chloride ion identification receptor in detection ecological environment and sample is significant and practical value.
Summary of the invention
One of the object of the invention is to provide one and synthesizes simple, reaction condition Anion Recognition gentle, lower-cost receptor synthetic method；The two of purpose be to provide a kind of highly sensitive, selectivity good, binding ability is strong, it is possible to realize the Anion Recognition acceptor compound of Fluorometric assay chloride ion.
The present invention uses Fluorometric assay chloride ion, and using pyrimidine group as rigid backbone group, with 1, the 2-position C-H proton of 3-disubstituted imidazole and pyrimidine 2-position C-H proton are as recognition site.
The present invention solves the technical scheme that problem takes, the acceptor compound of a kind of fluorescence titrimetric method detection chloride ion, and its molecular structural formula is,.The synthetic route of this Anion Recognition receptor is as follows,
Concrete preparation method comprises the following steps: 1) by imidazoles, bromododecane, Anhydrous potassium carbonate is placed in round-bottomed flask, adds acetone stirring and dissolving, and mixed solution is heated to reflux 7 h.Rotary evaporation carries out column chromatography for separation after removing acetone solvent, and vacuum rotary steam is also vacuum dried, the N-dodecyl imidazole after being purified.2) by Amidinobenzene hydrochloride, diethyl malonate is dissolved in dehydrated alcohol；Feldalat NM is dissolved in methanol, the methanol solution constant pressure funnel of Feldalat NM is added slowly in dehydrated alcohol reactant liquor, is heated to reflux 3 h.After question response terminates, it is carefully added into hydrochloric acid solution by system pH regulator to 3 ~ 4, has white depositions to separate out, the precipitation of precipitation is filtered and washes with water obtain for several times middle producing 2 and directly carrying out next step reaction.3) adding in round-bottomed flask by intermediate product 2, be carefully added into phosphorus oxychloride, oil bath 110 DEG C is reacted, thin layer chromatography detection extent of reaction.After 3 h, reaction terminates, and careful dropping frozen water, till precipitation precipitation no longer increases, will be cooled to the decompression sucking filtration of the reaction system after room temperature, and the precipitation crude product recrystallization in ethanol of gained purifies and obtains light yellow solid 3.4) Weigh Compound 3 and 1 is placed in three-neck flask, adds toluene stirring and dissolving, is heated to reflux 24 h.After reaction terminates so that it is naturally cool to room temperature, Precipitation, decompression sucking filtration is had to obtain white crude.Then carry out recrystallization white waxy solid with dichloromethane, be the hydrochlorate of double imidazoles pyrimidine, be directly used in next step ion exchange.4) upper step product being dissolved in methanol, dropwise drip the aqueous solution of boron lithium fluoride, reactant mixture is stirred at room temperature 30 min.Washing for several times by the white precipitate sucking filtration separated out and by ethyl acetate, obtaining the product after ion exchange is white waxy solid, illustrate in greater detail synthesis and the detection method of this receptor compound in the embodiment of this specification.
The using method of the Anion Recognition acceptor compound of the present invention is as follows, in being dissolved in dry dichloromethane by this compound molecule, tests under room temperature.When adding chloride ion, owing to the hydrogen bond recognition site of this compound can form hydrogen bond with chloride ion, fluorescence is made to produce quencher in various degree.Identification receptor molecule is as follows with chloride ion action principle,
The specific features of the chloride ion identification receptor compound of the present invention is as follows: in non-polar non-protic solvent dichloromethane solution, acceptor compound has strong identification ability and bond strength to chloride ion, and binding constant reaches 1.6 × 108 M-1.After adding chloride ion, the maximum emission wavelength of system is blue shifted to l=350 about nm by l=361 nm, and the fluorescence intensity of system occurs quencher in various degree.Job curve shows compound and various anion (F-, Cl-, Br-, I-,
H2PO4 -, HSO4 -, AcO-) all can form the stable comple of 1:1.
Acceptor compound molecule synthesis of the present invention is simple, and cost is relatively low, good to the selectivity of chloride ion, bond strength is high, fast response time makes this chloride ion identification receptor at biochemistry, and the field such as environmental science has the using value of reality.
Accompanying drawing explanation
Fig. 1 is the Anion Recognition receptor of the present invention identification situation to fluorion, acceptor molecule (5.0 × 10-6 Mol/L) in dichloromethane solution, adding the fluorescence spectrum of system and scatterplot at maximum emission wavelength (361 nm) place after the fluorion of variable concentrations, built-in figure is Job curve.
Fig. 2 is the Anion Recognition receptor of the present invention identification situation to chloride ion, acceptor molecule (5.0 × 10-6Mol/L) in dichloromethane solution, adding the fluorescence spectrum of system and scatterplot at maximum emission wavelength (361 nm) place after the chloride ion of variable concentrations, built-in figure is Job curve.
Fig. 3 is the Anion Recognition receptor of the present invention identification situation to bromide ion, acceptor molecule (5.0 × 10-6 Mol/L) in dichloromethane solution, adding the fluorescence spectrum of system and scatterplot at maximum emission wavelength (361 nm) place after the bromide ion of variable concentrations, built-in figure is Job curve.
Fig. 4 is the Anion Recognition receptor of the present invention identification situation to iodide ion, acceptor molecule (5.0 × 10-6
Mol/L) in dichloromethane solution, adding the fluorescence spectrum of system and scatterplot at maximum emission wavelength (361 nm) place after the iodide ion of variable concentrations, built-in figure is Job curve.
Fig. 5 is the identification situation of Anion Recognition receptor Dichlorodiphenyl Acetate radical ion of the present invention, acceptor molecule (5.0 × 10-6 Mol/L) in dichloromethane solution, adding the fluorescence spectrum of system and scatterplot at maximum emission wavelength (361 nm) place after the acetate ion of variable concentrations, built-in figure is Job curve.
Fig. 6 is the Anion Recognition receptor of the present invention identification situation to hydrogen sulfate ion, acceptor molecule (5.0 × 10-6 Mol/L) in dichloromethane solution, adding the fluorescence spectrum of system and scatterplot at maximum emission wavelength (361 nm) place after the hydrogen sulfate ion of variable concentrations, built-in figure is Job curve.
Fig. 7 is the Anion Recognition receptor of the present invention identification situation to dihydrogen phosphate ions, acceptor molecule (5.0 × 10-6 Mol/L) in dichloromethane solution, adding the fluorescence spectrum of system and scatterplot at maximum emission wavelength (361 nm) place after the dihydrogen phosphate ions of variable concentrations, built-in figure is Job curve.
Fig. 8 is that Anion Recognition receptor of the present invention is to various anion (F-, Cl-, Br-, I-,
H2PO4 -, HSO4 -, AcO-) binding constant, binding constant Ks is to be calculated by acceptor compound fluorescence titration in dichloromethane and obtain, coefficient R2It is, by method of least square, fluorescence titration curve is carried out nonlinear fitting gained.
Detailed description of the invention
Embodiment
1
: compound
1
Synthesis
Weigh imidazoles 1(0.68 g, 10 mmol), bromododecane (2.5 g, 10 mmol), Anhydrous potassium carbonate (2.76 g, 20 mmol) is placed in 50 mL round-bottomed flasks, adds 20 mL acetone stirring and dissolving, and mixed solution is heated to reflux 7h.Rotary evaporation carries out column chromatography for separation (ethyl acetate is eluant) after removing acetone solvent, vacuum rotary steam removes ethyl acetate solvent, and is vacuum dried, N-dodecyl imidazole 2.12 g after being purified, and productivity is 90%.Compound 1 is characterized as below:1HNMR
(400 MHz, CDCl3) δ(ppm): 0.81 (t, 3H), 1.22 (s (br), 18H), 1.70 (m, 2H), 3.85
(t, 2H), 6.86 (s, 1H), 6.99 (s, 1H), 7.42 (s, 1H).
Embodiment
2
: compound
2
Synthesis
Weighing Amidinobenzene hydrochloride (3.92 g, 25 mmol), diethyl malonate (4.28 g, 27 mmol) is placed in 100 mL cleaning round-bottomed flasks, adds 40 mL absolute ethyl alcohol and stirring and dissolves；Weigh Feldalat NM (5.61 g, 91 mmol) to be dissolved in 24 mL methanol.The methanol solution constant pressure funnel of Feldalat NM is added slowly in dehydrated alcohol reactant liquor, is heated to reflux 3 h.After question response terminates, it is carefully added into hydrochloric acid solution by system pH regulator to 3 ~ 4, has white depositions to separate out, the precipitation of precipitation is filtered and washes with water obtain intermediate product for several times and directly carry out next step reaction.
Embodiment
3
: compound
3
Synthesis
Adding in 100 mL round-bottomed flasks by intermediate product (1.75 g, 9.30 mmol), be carefully added into phosphorus oxychloride (3.57 g, 23.23 mmol), oil bath 110 DEG C is reacted, thin layer chromatography detection extent of reaction.After 3 h, reaction terminates, and the careful frozen water that drips, till precipitation precipitation no longer increases, will be cooled to the decompression sucking filtration of the reaction system after room temperature, and it is 1.79 g that the precipitation crude product recrystallization in ethanol purification of gained obtains light yellow solid 5, and productivity is 86.06%.Compound 3 is characterized as below:1HNMR (400 MHz,
CDCl3) δ(ppm): 8.40 (m, 2H),
7.54 (m, 3H), 7.30 (s, 1H).
Embodiment
4
: the synthesis of identification receptor molecule
Weigh Compound 3(1.13 g, 5 mmol) and 1(2.60 g, 11 mmol) be placed in 100 mL three-neck flasks, add 40 mL toluene stirring and dissolving, under argon shield, be heated to reflux 24 h.After reaction terminates so that it is naturally cool to room temperature, Precipitation, decompression sucking filtration is had to obtain white crude.Then carry out being recrystallized to give 1.98 g white waxy solid with dichloromethane, be the hydrochlorate of double imidazoles pyrimidine, be directly used in next step ion exchange, productivity 56.9%.Intermediate product is characterized as below:1HNMR (400 MHz, CDCl3): δ (ppm) 11.65 (s, 2H), 9.66
(s, 1H), 9.37 (s, 1H), 8.55 (s, 2H), 7.64 (s, 2H),7.45(s, 2H) 4.48 (t, J = 7.2
Hz, 4H), 2.11−2.04 (m, 4H), 1.46−1.20 (m, 36H), 0.87 (t, J =7.2 Hz, 6H)
Weighing step product 0.70 g (1 mmol) to be dissolved in 20 mL methanol, dropwise the aqueous solution (10 mL) of dropping boron lithium fluoride (0.21 g, 2.21 mmol), reactant mixture is stirred at room temperature 30 min.Washing for several times by the white precipitate sucking filtration separated out and by ethyl acetate, obtaining the product P2 after ion exchange is white waxy solid, weighs to obtain 0.74 g, productivity 92.5%.Identification receptor characterization of compound is as follows:1HNMR (400 MHz, d6-DMSO): δ (ppm) 10.52(s, 2H),
8.80(d, 2H), 8.71(d, 2H), 8.63(s, 1H), 8.22(d, 2H)7.70(m, 3H), 4.40(t, 4H),
1.95(s, 4H), 1.30(d, 36H), 0.84(d, 6H). 13CNMR (100MHz, DMSO-d6): δ (ppm) 164.6, 156.5,
136.8, 134.4, 133.7, 129.4, 124.9, 119.7, 97.7, 50.5, 31.7, 29.6, 29.5, 29.4,
29.4, 29.3, 29.1, 28.9, 26.0, 22.5, 14.4.
Embodiment
5
: the application of phenylmercaptan. fluorescent probe of the present invention
Anion Recognition acceptor compound is dissolved in dry dichloromethane and is configured to 5.0 × 10-6The solution of mol/L, weighs the anion (F of respective quality respectively-, Cl-, Br-, I-,
H2PO4 -, HSO4 -, AcO-) 4-butyl ammonium, add dilution after host compound solution dissolve, preparation anion solubility be 5 × 10-5 The identification system of mol/L.Use accumulative sampling system to be sequentially added into the anion solutions of certain volume with microsyringe, observe and record each fluorescence emission spectrum.After adding different aniones all there is blue shift in various degree in maximum emission wavelength (l=361 nm), about 350 nm are gradually moved to by 361 nm, the fluorescence intensity of system gradually weakens along with the addition of anion simultaneously, illustrates to define the complex of hydrogen bond action.When anion concentration is continuously increased to time a certain amount of, and the fluorescence intensity of system is constant, reaches poised state.Learning that by Job curve the coordination ratio of acceptor compound and various anion is 1:1, utilize formula that fluorescence titration result is carried out least square fitting and can obtain corresponding binding constant, the strong and weak order of various anion binding abilities is followed successively by by it: Cl- > HSO4 -
> H2PO4 - >Br- > F-
> AcO- > I- .Binding constant to chloride ion is 1.6 × 108 M-1, it being far longer than other aniones, this anion receptor compound has the strongest binding ability to chloride ion, and selectivity is good, highly sensitive.
Claims (3)
1. the preparation of neutral c h bond Anion Recognition receptor and an application, its structure is:
。
2. the preparation method of miazines anion receptor as claimed in claim 1, it is characterised in that be prepared according to the following steps:
A imidazoles, bromododecane, Anhydrous potassium carbonate are dissolved in acetone by (), be heated to reflux carrying out column chromatography for separation after 7 h. rotary evaporations remove acetone solvent, obtain product 1；
B () takes Amidinobenzene hydrochloride, diethyl malonate is dissolved in dehydrated alcohol；Feldalat NM is dissolved in 24 mL methanol；
The methanol solution of Feldalat NM is added slowly in dehydrated alcohol reactant liquor, is heated to reflux after 3 h. question responses terminate, being carefully added into hydrochloric acid solution by system pH regulator to acid；
The precipitation of precipitation is filtered and washes with water and obtains compound 2 for several times；
C compound 2 is added in round-bottomed flask by (), being carefully added into phosphorus oxychloride, oil bath 110 DEG C is reacted, and after 3 h, reaction terminates, careful dropping frozen water is till separating out precipitation no longer increase, and the crude product being filtrated to get recrystallization in ethanol purifies and obtains compound 3；
D compound 1 and compound 3 are dissolved in toluene by (), be heated to reflux under argon shield 24 h. reaction terminate after, room temperature cooling separate out precipitation, be then recrystallized to give compound 4 with dichloromethane；
E compound 4 is dissolved in methanol by (), dropwise in the aqueous solution of dropping boron lithium fluoride；Reactant mixture is stirred at room temperature 30 min；
By separate out precipitation sucking filtration and with ethyl acetate washing obtain ion exchange after product be target recipient compound.
The purposes of Anion Recognition receptor the most according to claim 1, it is characterised in that the detection of this pyrimidine neutrality c h bond anion receptor chloride ion in environmental and biological materials and analysis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510226098.7A CN106188014A (en) | 2015-05-06 | 2015-05-06 | The preparation of the c h bond Anion Recognition receptor of a kind of neutrality and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510226098.7A CN106188014A (en) | 2015-05-06 | 2015-05-06 | The preparation of the c h bond Anion Recognition receptor of a kind of neutrality and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106188014A true CN106188014A (en) | 2016-12-07 |
Family
ID=57459040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510226098.7A Withdrawn CN106188014A (en) | 2015-05-06 | 2015-05-06 | The preparation of the c h bond Anion Recognition receptor of a kind of neutrality and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106188014A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111103249A (en) * | 2019-12-30 | 2020-05-05 | 南阳师范学院 | Bis-thiourea anion recognition receptor and preparation method thereof |
| CN111220611A (en) * | 2020-02-18 | 2020-06-02 | 北京工业大学 | Application of triazine trispyrazole compound in anion detection |
| CN115677596A (en) * | 2022-12-10 | 2023-02-03 | 江苏莱科化学有限公司 | Preparation process of herbicidal safener fenclorim |
-
2015
- 2015-05-06 CN CN201510226098.7A patent/CN106188014A/en not_active Withdrawn
Non-Patent Citations (3)
| Title |
|---|
| BIN DONG, ET AL: "Ion-Based Materials Derived from Positively and Negatively Charged Chloride Complexes of π‑Conjugated Molecules", 《J. AM. CHEM. SOC.》 * |
| FABIAN SCHÜLER, ET AL: "Hyperbranched Polymeric Ionic Liquids with Onion-like Topology as Transporters and Compartmentalized Systems", 《ANGEW. CHEM. INT. ED.》 * |
| XIANG ZHANG, ET AL: "Design, Synthesis and Antifungal Activities of Novel Strobilurin Derivatives Containing Pyrimidine Moieties", 《BULL. KOREAN. CHEM. SOC.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111103249A (en) * | 2019-12-30 | 2020-05-05 | 南阳师范学院 | Bis-thiourea anion recognition receptor and preparation method thereof |
| CN111220611A (en) * | 2020-02-18 | 2020-06-02 | 北京工业大学 | Application of triazine trispyrazole compound in anion detection |
| CN111220611B (en) * | 2020-02-18 | 2022-05-10 | 北京工业大学 | Application of triazine trispyrazole compound in anion detection |
| CN115677596A (en) * | 2022-12-10 | 2023-02-03 | 江苏莱科化学有限公司 | Preparation process of herbicidal safener fenclorim |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104357044B (en) | A kind of fluorescent probe and its preparation method and application | |
| CN110194766B (en) | Double-channel two-photon fluorescence polarity probe and preparation method and application thereof | |
| CN104910316B (en) | A kind of macromolecule colorimetric nano film material and preparation method thereof and it is used for Fe3+With the application of pyrophosphate context of detection | |
| CN102863406B (en) | Receptor compound for detecting CN- by colorimetry-fluorescence two channels, synthesis thereof and application thereof | |
| CN104449669B (en) | A kind of polyaryl substituted imidazole fluorescence probe and preparation method thereof and the application in detection G-tetra-stranded structure | |
| CN105732723B (en) | A kind of ruthenium (II) multi-pyridine ligand and its preparation and application | |
| CN104860840A (en) | Preparation and application of fluorescence enhancement type hydrogen sulfide fluorescent probe | |
| CN104230813B (en) | Double glyoxaline cation temperature controlled ionic liquids of one class PEG functionalization and its preparation method and application | |
| CN106188014A (en) | The preparation of the c h bond Anion Recognition receptor of a kind of neutrality and application | |
| CN111349091B (en) | Fluorescent dye and preparation method and application thereof | |
| CN104830312B (en) | The preparation of a kind of Fluorescence Increasing type probe compound and trivalent chromic ion detection | |
| CN102818802A (en) | Method for detecting hypochlorite | |
| CN111892923A (en) | Two-photon fluorescence viscosity probe based on dinitrile vinyl group and preparation method and application thereof | |
| CN106189343B (en) | A kind of acetonitrile class dyestuff of benzothiazole 2 and its application | |
| CN103342698A (en) | Dual-fluorophore ratio fluorescence molecular probe for non-fluorescence resonance energy transfer and preparation method thereof | |
| CN104198451B (en) | A kind of sensor array and the application in metal ion auxiliary is identified thereof | |
| CN108148014B (en) | Formaldehyde fluorescent probe and preparation method and application thereof | |
| CN107382935B (en) | A kind of coumarin fluorescent probe C1 and its preparation method and application | |
| CN107253957A (en) | Rhodamine aluminium ion fluorescence probe containing glycine hydrazides structure and its preparation method and application | |
| CN105198917B (en) | A kind of organic inorganic hybridization fluorescent sensing material and its synthetic method and application | |
| CN115124519B (en) | Fluorescent reagent for detecting dimethyl chlorophosphate and preparation method thereof | |
| CN107417598B (en) | Fluorescent probe for detecting G-quadruplex DNAs (deoxyribonucleic acids) and preparation method thereof | |
| CN103901211B (en) | A kind of new method of homocysteinic acid visual recognition | |
| CN106478646A (en) | A kind of photosensitive probe of rhodamine guanidine radicals benzimidazole functionalization and its application | |
| CN113185458A (en) | Preparation method and application of trimeric indenyl conjugated 8-benzyloxy quinoline derivative |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20161207 |