CN102532100A - 1-alkyl-2-(quinolone-8-yl) benzimidazole derivative - Google Patents
1-alkyl-2-(quinolone-8-yl) benzimidazole derivative Download PDFInfo
- Publication number
- CN102532100A CN102532100A CN2011104162656A CN201110416265A CN102532100A CN 102532100 A CN102532100 A CN 102532100A CN 2011104162656 A CN2011104162656 A CN 2011104162656A CN 201110416265 A CN201110416265 A CN 201110416265A CN 102532100 A CN102532100 A CN 102532100A
- Authority
- CN
- China
- Prior art keywords
- benzoglyoxaline
- quinoline
- alkyl
- ethyl
- instance
- 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
Images
Landscapes
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a 1-alkyl-2-(quinolone-8-yl) benzimidazole derivative, which is a novel benzimidazole ligand and can be combined with transition metal, rare earth and the like to form metal coordination compounds. Meanwhile, the derivative has excellent fluorescent (blue light) performance and the relative fluorescence intensity is enhanced along with the increase of concentration in a range of 0.01-1.00mM. The 1-alkyl-2-(quinolone-8-yl) benzimidazole derivative can be used for developing fluorescent probes, blue luminescent materials and fluorescent brightener.
Description
Technical field
The present invention relates to a kind of 1-alkyl-2-(quinoline-8-yl) benzimidizole derivatives, they have good fluorescence property.The present invention also relates to the crystalline structure of 1-ethyl-2-(2-ethyl quinoline-8-yl) benzoglyoxaline.
Background technology
Benzimidazoles compound is widely used in fields such as chemical, life science, material, weaving and agricultural because of its diversity structure, good biology, reactive behavior and optical property etc.Can be used as the treatment agent of catalyzer, curing agent for epoxy resin and some metallic surface and the midbody of organic reaction etc. at chemical field.In the life science field, benzimidazoles compound can be used as molecular probe, is applied to the fluorometric assay of gene and cell.In high-performance organic materials field, benzimidazoles compound and metal complexes have good fluorescence or phosphorescent characteristics, are the hole mobile material and the luminescent materials of important organic electroluminescent LED (OLED).In addition, some benzimidazoles compounds can be used as wetting agent, whitening agent, pore forming material, tenderizer, dispersion agent, control agent etc., are widely used in industries such as weaving, photograph, daily-use chemical industry, agricultural.Therefore, the research synthetic and that use of benzoglyoxaline and verivate thereof in decades never is interrupted, and new compound, new purposes constantly are in the news.
The present invention designs and has synthesized 6 kinds of 1-alkyl-2-(quinoline-8-yl) benzimidizole derivatives, and has tested their fluorescence property, and these compounds have good fluorescence.
Summary of the invention
This patent is at first with anthranilic acid and α, and beta-unsaturated aldehyde is that raw material prepares basic material 2-alkyl 8-quinolinecarboxylic acid through addition, condensation reaction; 2-alkyl 8-quinolinecarboxylic acid and O-Phenylene Diamine condensation get midbody 2-(quinoline-8-yl) benzoglyoxaline under the catalysis of polyphosphoric acid (PPA) and microwave radiation then; Use alkane iodide and 2-(quinoline-8-yl) benzoglyoxaline to carry out electrophilic substitution reaction at last and make final product 1-alkyl-2-(quinoline-8-yl) benzimidizole derivatives.
The fluorescence property test result of 1-alkyl-2-(quinoline-8-yl) benzimidizole derivatives is following:
The fluorescence property of table 1 1-alkyl-2-(quinoline-8-yl) benzimidizole derivatives
Annotate: concentration is the ethanol solution of 1.0mmol/L, the fluorescence emission spectrum of 1-alkyl-2-under the exciting light of room temperature measuring 355nm (quinoline-8-yl) benzimidizole derivatives.
Visible by table 1,1-alkyl-2-(quinoline-8-yl) benzimidizole derivatives has good fluorescence property.
Description of drawings
Fig. 1 is the IR spectrogram of the product (1-methyl-2-(2-toluquinoline-8-yl) benzoglyoxaline) of instance 7.
Fig. 2 is the product (1-methyl-2-(2-toluquinoline-8-yl) benzoglyoxaline) of instance 7
1H MNR spectrogram.
Fig. 3 is the mass spectrum of the product (1-methyl-2-(2-toluquinoline-8-yl) benzoglyoxaline) of instance 7.
Fig. 4 is the crystalline structure figure of the product (1-ethyl-2-(2-ethyl quinoline-8-yl) benzoglyoxaline) of instance 10.
Fig. 5 is the relation of 1-methyl-2-(2-methyl-8-quinolyl) benzoglyoxaline ethanolic soln concentration and emitting fluorescence intensity.
Embodiment
Synthesizing of instance 1:2-methyl-8-quinolinecarboxylic acid
Get anthranilic acid 13.71g (100mmol), the HCl 240mL of 6M joins in the there-necked flask of 500mL successively, slowly drips crotonic aldehyde 12mL (145mmol), and 110 ℃ of back flow reaction are after 10 hours.Reaction solution is cooled to room temperature, with ammoniacal liquor adjust pH to 5, obtains head product with the dichloromethane extraction reaction solution then.(leacheate is V through column chromatography
ETHYLE ACETATE: V
Sherwood oil=1: 3) purifying, get white solid 14.11g, productive rate is 75.4%.
Synthesizing of instance 2:2-ethyl-8-quinolinecarboxylic acid
By routine 1 method Synthetic 2-ethyl-8-quinolinecarboxylic acid, productive rate is 74.7%.
Synthesizing of instance 3:2-propyl group-8-quinolinecarboxylic acid
By routine 1 method Synthetic 2-propyl group-8-quinolinecarboxylic acid, productive rate is 73.9%.
Synthesizing of instance 4:2-(2-toluquinoline-8-yl) benzoglyoxaline
2-methyl-8-quinolinecarboxylic acid 3.74g (20mmol) is mixed with the O-Phenylene Diamine of 1.5eq and the PPA of 10.0g (30mmol); Then mixture is placed microwave oven; Thawing, reacting respectively 2,3 and 3 minutes under the moderate heat, three kinds of patterns of middle high fire successively, dark green solution.Reaction solution is cooled to 80 ℃, pours in the frozen water, adds KOH it is neutralized to pH=10～11, separates out deposition.Suction filtration is dispersed to filter cake in the water, uses CH
2Cl
2Extraction obtains thick product.(leacheate is V to column chromatography then
ETHYLE ACETATE: V
Sherwood oil=1: 3) separation and purification gets product 2-(2-toluquinoline-8-yl) benzoglyoxaline 3.76g, and productive rate is 72.4%.
Synthesizing of instance 5:2-(2-ethyl quinoline-8-yl) benzoglyoxaline
By routine 4 method Synthetic 2s-(2-ethyl quinoline-8-yl) benzoglyoxaline, productive rate is 71.4%.
Synthesizing of instance 6:2-(2-propyl group-8-quinolyl) benzoglyoxaline
By routine 4 method Synthetic 2s-(2-propyl group-8-quinolyl) benzoglyoxaline, productive rate is 69.4%.
Synthesizing of instance 7:1-methyl-2-(2-toluquinoline-8-yl) benzoglyoxaline
Get 2-(2-toluquinoline-8-yl) benzoglyoxaline of 5mmol and the CH of 1.5eq
3ONa is mixed in the CH of 20mL
3Among the CN, after refluxing 5 hours, at room temperature drip CH
3I (5mmol), after 50 ℃ 24h was reacted in continuation down, rotary evaporation removed and desolvates, and (leacheate is V to residuum through column chromatography
ETHYLE ACETATE: V
Sherwood oil=1: 5) purifying gets 1-methyl-2-(2-toluquinoline-8-yl) benzoglyoxaline 0.87g, and productive rate is 71.8%.
Product structure characterizes:
mp.135-136℃；FT-IR(KBr?disc，cm
-1)：3050(v?CH(Ph))，2960，2930(v?CH
2，CH
3)，1620(vC＝N)，1600，1580(v?C＝C)，1500(v?CH)，1460，1440，1430(v?C-N)，1390，1370(δCH
3)；
1HNMR(400MHz，CDCl
3)δ：8.15(d，J＝8.4Hz，1H)，8.08(d，J＝6.2Hz，1H)，7.98(d，J＝8.1Hz，1H)，7.90(d，J＝7.3Hz，1H)，7.64(t，J＝7.6Hz，1H)，7.50(d，J＝7.3Hz，1H)，7.42-7.31(m，3H)，3.67(s，3H)，2.66(s，3H).Anal.Calc.for?C
18H
15N
3：C，79.10；H，5.53；N，15.37％；found?C，?79.21；H，5.74；N，15.57％；HRMS(EI)calcd?for?C
18H
15N
3273.1266，found?273.1301.
Synthesizing of instance 8:1-ethyl-2-(2-methyl-8-quinolyl) benzoglyoxaline
By synthetic 1-ethyl-2-(2-methyl-8-quinoline) benzoglyoxaline of routine 7 methods, productive rate is 67.3%.
Product structure characterizes:
mp.125-126℃；FT-IR(KBr?disc，cm
-1)：3060(v?CH(Ph))，2970，2930，2870(v?CH
2，CH
3)，1610(v?C＝N)，1600，1580(v?C＝C)，1530，1500，1480(v?CH)，1460，1440，1430(v?C-N)，1390(δCH
3)；
1H?NMR(400MHz，CDCl
3)δ：8.14(d，J＝8.3Hz，1H)，7.98(t，J＝7.5Hz，2H)，7.90(d，J＝7.0Hz，1H)，7.62(t，J＝7.5Hz，1H)，7.53(d，J＝7.2Hz，1H)，7.42-7.31(m，3H)，4.10(q，J＝7.2Hz，2H)，2.63(s，3H)，1.34(t，J＝7.1Hz，3H).Anal.Calc.for?C
19H
17N
3：C，79.41；H，5.96；N，14.62％；found?C，79.33；H，5.93；N，14.39％；HRMS(EI)calcd?for?C
19H
17N
3287.1423，found287.1426.
Synthesizing of instance 9:1-methyl-2-(2-ethyl-8-quinoline) benzoglyoxaline
By synthetic 1-methyl-2-(2-ethyl-8-quinoline) benzoglyoxaline of routine 7 methods, productive rate is 67.3%.
Product structure characterizes:
mp.121-122℃；FT-IR(KBr?disc，cm
-1)：3050(v?CH(Ph))，2960，2930(v?CH
2，CH
3)，1620(vC＝N)，1600，1580(v?C＝C)，1500(v?CH)，1460，1440，1430(v?C-N)，1390，1370(δCH
3)；
1HNMR(400MHz，CDCl
3)δ：8.14(d，J＝8.4Hz，1H)，8.07(d，J＝7.0Hz，1H)，7.95(d，J＝8.0Hz，1H)，7.88(d，J＝7.0Hz，1H)，7.62(t，J＝7.6Hz，1H)，7.47(d，J＝7.5Hz，1H)，7.37-7.28(m，3H)，3.65(s，3H)，2.90(q，J＝7.5Hz，2H)，1.27(t，J＝7.5Hz，3H).Anal.Calc.for?C
19H
17N
3：C，79.41；H，5.96；N，14.62％；found?C，79.77；H，5.94；N，14.79％；HRMS(EI)calcd?for?C
19H
17N
3287.1423，found?287.1398.
Synthesizing of instance 10:1-ethyl-2-(2-ethyl-8-quinoline) benzoglyoxaline
By synthetic 1-ethyl-2-(2-ethyl-8-quinoline) benzoglyoxaline of routine 7 methods, productive rate is 61.3%.
Product structure characterizes:
mp.119-120℃；FT-IR(KBr?disc，cm
-1)：3060(CH(Ph))，2970，2930，2870(v?CH
2，CH
3)，1610(vC＝N)，1600，1580(v?C＝C)，1500(v?CH)，1460，1440，1430(v?C-N)，1380，1370(v?CH
3)；
1HNMR(400MHz，CDCl
3)δ：8.15(d，J＝8.5Hz，1H)，7.99(dd，J＝14.4and?7.6Hz，2H)，7.90(d，J＝7.4Hz，1H)，7.63(t，J＝7.6Hz，1H)，7.53(d，J＝7.4Hz，1H)，7.43-7.30(m，3H)，4.14(q，J＝7.2Hz，2H)，2.90(q，J＝7.6Hz，2H)，1.27(m，6H).Anal.Calc.for?C
20H
19N
3：C，79.70；H，6.35；N，13.94％；found?C，79.01；H，6.42；N，13.55％；HRMS(EI)calcd?for?C
20H
19N
3301.1579，found?301.1598.
Synthesizing of instance 11:1-methyl-2-(2-propyl group-8-quinoline) benzoglyoxaline
By synthetic 1-methyl-2-(2-propyl group-8-quinoline) benzoglyoxaline of routine 7 methods, productive rate is 64.3%.
Product structure characterizes:
mp.105-106℃；FT-IR(KBr?disc，cm
-1)：3060(v?CH(Ph))，2960，2930，2870(v?CH
2，CH
3)，1610(v?C＝N)，1600，1570(v?C＝C)，1530，1500，1480(v?CH)，1460，1440，1430(v?C-N)，1390，1370(v?CH
3)；
1H?NMR(400MHz，CDCl
3)δ：8.13(d，J＝8.4Hz，1H)，8.05(d，J＝7.1Hz，1H)，?7.94(d，J＝8.1Hz，1H)，7.87(d，J＝7.7Hz，1H)，7.61(t，J＝7.6Hz，1H)，7.47(d，J＝7.3Hz，1H)，7.39-7.28(m，3H)，3.64(s，3H)，2.84(t，J＝7.6Hz，2H)，1.75(m，2H)，0.92(t，J＝7.4Hz，3H).Anal.Calc.for?C
20H
19N
3：C，79.70；H，6.35；N，13.94％；found?C，78.68；H，6.93；N，13.56％；HRMS(EI)calcd?for?C
20H
19N
3301.1579，found?301.1602.
Synthesizing of instance 12:1-ethyl-2-(2-propyl group-8-quinoline) benzoglyoxaline
By synthetic 1-ethyl-2-(2-propyl group-8-quinoline) benzoglyoxaline of routine 7 methods, productive rate is 61.8%.
Product structure characterizes:
mp.93-94℃；FT-IR(KBr?disc，cm
-1)：3060(v?CH(Ph))，2960，2930，2860(v?CH
2，CH
3)，1610(vC＝N)，1600，1570(v?C＝C)，1500，1470(v?CH)，1460，1440，1430(v?C-N)，1380，1370(δCH
3)；
1HNMR(400MHz，CDCl
3)δ：8.12(d，J＝8.5Hz，1H)，7.97(d，J＝7.1Hz，1H)，7.94(d，J＝8.2Hz，1H)，7.87(d，J＝6.3Hz，1H)7.59(t，J＝7.6Hz，1H)，7.49(d，J＝7.0Hz，1H)，7.33(m，3H)，4.10(q，J＝7.2Hz，2H)，2.86-2.78(m，2H)，1.71(m，2H)，1.25(t，J＝7.2Hz，3H)，0.90(t，J＝7.4Hz，3H).Anal.Calc.for?C
21H
21N
3：C，79.97；H，6.71；N，13.32％；found?C，79.93；H，6.96；N，13.52％；HRMS(EI)calcd?for?C
21H
21N
3315.1736，found?315.1729.
The crystalline preparation and the test of instance 13:1-ethyl-2-(2-ethyl quinoline-8-yl) benzoglyoxaline
1-ethyl-2-(2-ethyl quinoline-8-yl) benzoglyoxaline that normal hexane takes by weighing 25mg be dissolved in 50ml in, heating for dissolving obtains saturated solution, is cooled to room temperature; There is small amount of solid to separate out; Filtration obtains filtrating, places refrigerator and cooled but filtrating, obtains white transparent crystals.
The crystalline structure data are following:
The crystallographic data of table 2 1-ethyl-2-(2-ethyl quinoline-8-yl) benzoglyoxaline
The fluorescence property test of instance 14:1-alkyl-2-(quinoline-8-yl) benzimidizole derivatives
With the absolute ethyl alcohol is solvent; Compound concentration is the ethanolic soln of 1-alkyl-2-(2-alkyl quinoline-8-yl) benzoglyoxaline of 0.01mM; And concentration is respectively 1-methyl-2-quinoline 3 benzoglyoxaline ethanolic solns of 0.01mM, 0.05mM, 0.10mM, 0.50mM, 1.00mM, 1.00mM and 1.50mM; Measure fluorescence property with U.S. Edinburgh 920 Analytical Instruments XRFs, the result sees table 1 and Fig. 3.As can beappreciated from fig. 3, the relative intensity of fluorescence of 1-methyl-2-(quinoline-8-yl) benzoglyoxaline ethanolic soln strengthens along with the increase of concentration in 0.01mM～1.00mM scope.
Claims (2)
1. a 1-alkyl-2-(quinoline-8-yl) benzimidizole derivatives is characterized in that chemical structural formula is following:
2.1-the single crystal structure of ethyl-2-(2-ethyl quinoline-8-yl) benzoglyoxaline; This crystal belongs to rhombic system; P 21 21 21 spacers; Lattice parameter a, b and c are that
and
unit cell volume are 4 for
Z value, and α, β and γ value are 90.000 °, 90.000 ° and 90.000 °.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104162656A CN102532100A (en) | 2011-11-24 | 2011-11-24 | 1-alkyl-2-(quinolone-8-yl) benzimidazole derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104162656A CN102532100A (en) | 2011-11-24 | 2011-11-24 | 1-alkyl-2-(quinolone-8-yl) benzimidazole derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102532100A true CN102532100A (en) | 2012-07-04 |
Family
ID=46340273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011104162656A Pending CN102532100A (en) | 2011-11-24 | 2011-11-24 | 1-alkyl-2-(quinolone-8-yl) benzimidazole derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102532100A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050839A (en) * | 2009-10-30 | 2011-05-11 | 中国科学院化学研究所 | Coordination compound for catalyzing vinyl polymerization and preparation method of coordination compound as well as catalyst containing coordination compound and application of catalyst |
-
2011
- 2011-11-24 CN CN2011104162656A patent/CN102532100A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050839A (en) * | 2009-10-30 | 2011-05-11 | 中国科学院化学研究所 | Coordination compound for catalyzing vinyl polymerization and preparation method of coordination compound as well as catalyst containing coordination compound and application of catalyst |
Non-Patent Citations (1)
| Title |
|---|
| TIANPENGFEI XIAO, ET AL.,: "Bidentate Iron(II) Dichloride Complexes Bearing Substituted 8-(Benzimidazol-2-yl)quinolines: Synthesis, Characterization, and Ethylene Polymerization Behavior", 《ORGANOMETALLICS》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103058942B (en) | One-pot synthetic method for 1,2,3-triazole compounds | |
| CN101811919B (en) | Method for preparing amino acid schiff base metal complexes without solvent | |
| CN110818743B (en) | Preparation method and application of cyclometalated platinum complex with aggregation-induced emission property | |
| Zhang et al. | Polymorphic Ln (iii) and BPTC-based porous metal–organic frameworks with visible, NIR photoluminescent and magnetic properties | |
| CN102827087A (en) | Synthetic method of erlotinib | |
| CN108129435B (en) | Novel iron ion fluorescent probe and preparation method thereof | |
| Shi et al. | Synthesis and crystal structure of metal-organic frameworks [Ln2 (pydc-3, 5) 3 (H2O) 9] n3nH2O (Ln= Sm, Eu, Gd, Dy; pydc-3, 5= pyridine-3, 5-dicarboxylate) along with the photoluminescent property of its europium one | |
| CN108017618B (en) | Novel compound pyrazole aldehyde pyridine amine Schiff base and preparation method and application thereof | |
| CN104177321B (en) | A kind of copper ion fluorescence probe based on chromene diketone and preparation method thereof | |
| CN103408525B (en) | A kind of synthetic method of flavonoid compound and application thereof | |
| CN110746423B (en) | Synthesis of aryl imidazophenanthroline fluorescent dye and identification of metal ions | |
| Yang et al. | Novel flavonoid derivatives and their corresponding rare earth complexes: Synthesis and luminescent properties | |
| CN102532100A (en) | 1-alkyl-2-(quinolone-8-yl) benzimidazole derivative | |
| CN109988108B (en) | Preparation method of cabozantinib | |
| CN102532101B (en) | 2-(quinoline-8-yl)benzimidazole derivative | |
| CN103232478A (en) | Metal complex based on bis-benzimidazole ligand and preparation method and purpose thereof | |
| CN110922338B (en) | Anthraquinone derivative and synthesis method and application thereof | |
| CN103773360B (en) | Schiff base fluorescent polymer and preparation method thereof | |
| CN103254217B (en) | Metal complexes with durene-bridged bibenzimidazole as ligand, and preparation method and application thereof | |
| CN109928955A (en) | A kind of synthesis of urea groups pyrimidone derivatives fluorescent material | |
| CN114685530B (en) | Aggregation-induced emission molecule based on isoquinoline and preparation method thereof | |
| AU2021103937A4 (en) | A method for synthesizing a Schiff base ligand-lanthanides | |
| CN103059001B (en) | Quinazolinone Schiff base containing triazole and preparation method thereof | |
| CN102659666B (en) | Novel carbazole derivatives and preparation method and application thereof | |
| CN105566270A (en) | 3-aryl coumarin derivatives and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120704 |