CN104829528A - Isoquinoline ionic liquid, synthesis and applications thereof - Google Patents
Isoquinoline ionic liquid, synthesis and applications thereof Download PDFInfo
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- CN104829528A CN104829528A CN201510210435.3A CN201510210435A CN104829528A CN 104829528 A CN104829528 A CN 104829528A CN 201510210435 A CN201510210435 A CN 201510210435A CN 104829528 A CN104829528 A CN 104829528A
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- Prior art keywords
- ionic liquid
- isoquinoline
- bromo
- crude product
- iloquinoline derivative
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
- C07D217/02—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines
- C07D217/10—Quaternary compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
- A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
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- Engineering & Computer Science (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses an isoquinoline ionic liquid, synthesis and applications thereof. The synthesis method comprises the following steps: rapidly adding isoquinoline and bromo n-alkane into a reactor in the absence of water and oxygen under the protection of nitrogen gas, heating under stirring to carry out reflux reactions so as to obtain a crude product after the reflux reactions; cooling the crude product to the room temperature, dissolving the crude product then, subjecting crude product to column chromatography to remove the color and impurities, carrying out rotary evaporation to obtain a sticky liquid; subjecting the sticky liquid to multiple times of washing and recrystallization, and finally removing the residual solvent to obtain the isoquinoline ionic liquid; wherein the bromo n-alkane can be bromo n-butane, bromo n-octane, or bromo n-dodecane. The isoquinoline ionic liquid can be used as a bacteriostatic agent to kill escherichia coli and plant pathogenic bacteria.
Description
Technical field
The present invention relates to a kind of iloquinoline derivative ionic liquid, synthesis preparation method and application thereof, belong to organic chemistry preparation field.
Background technology
Ionic liquid is widely used in the numerous areas such as chemical industry and life science as a kind of green solvent; Because it exists certain toxicity to microorganism, there is good application in fungistat, sterilant field.Existingly mainly concentrate on imidazoles and pyridines about ion liquid anti-virus activities Journal of Sex Research, but such ion liquid anti-virus activities is poor; Isoquinoline compound is benzo pyridine structure, also be the isomers of quinolines, the isoquinoline 99.9 had now found that, quinoline compound have many-sided biological activity, comprise antibacterium and fungi, anti-malarial, throe immunity moderation function, therefore select isoquinoline 99.9 or quinoline effectively can improve the biocidal property of ionic liquid as precursor structure.
Quinoline ionic liquid has been synthesized in people such as British scientist Alessandro Busetti in 2010; result shows that quinoline ionic liquid all has very strong biocidal property for most clinical infection pathogenic bacterium; but the building-up reactions required time of quinoline ionic liquid is longer, and must react under this hypertoxic gas shield atmosphere of nitrogen tetroxide.
Summary of the invention
The object of this invention is to provide a kind of iloquinoline derivative ionic liquid, preparation method and application thereof, this ionic liquid bactericidal property is strong.
The technical solution realizing the object of the invention is: a kind of iloquinoline derivative ionic liquid, and its general structure is:
Wherein, n is 4,8 or 12.
A preparation method for iloquinoline derivative ionic liquid, step is as follows:
Under anhydrous and oxygen-free, nitrogen protection condition, in reaction vessel, add isoquinoline 99.9 and bromo normal alkane fast, stir and be heated to back flow reaction a few hours, at the end of reaction, then can obtain crude product; Dissolved with solvent I after being cooled to room temperature, after chromatography column decolouring removal of impurities, rotary evaporation obtains thick liquid; Again through solvent II washing repeatedly, under the state again at ultralow pressure after repeatedly recrystallization, extract lower boiling residual solvent, obtain described iloquinoline derivative ionic liquid and (be called for short [C
niQuin] Br).
The further preferred version of the present invention is:
Described bromo normal alkane is bromination of n-butane, n-octane bromide or N-dodeeyl bromide.
Count in mass ratio, isoquinoline 99.9: bromination of n-butane=1: 0.9, isoquinoline 99.9: n-octane bromide=1: 1.5, isoquinoline 99.9: N-dodeeyl bromide=1: 2.2.
Temperature of reaction is between 60 ~ 120 DEG C, and the reaction times is 12 ~ 16h.
When bromo normal alkane be bromination of n-butane or n-octane bromide time, solvent I adopts chloroform, and when bromo normal alkane is N-dodeeyl bromide, solvent I adopts methylene dichloride.
When bromo normal alkane is n-octane bromide, solvent II adopts anhydrous diethyl ether, when bromo normal alkane is N-dodeeyl bromide, and solvent II employing sherwood oil.
Iloquinoline derivative ionic liquid of the present invention is realized by following reaction scheme:
Compared with prior art, advantage of the present invention is:
(1) iloquinoline derivative ionic liquid of the present invention has stronger bactericidal properties to Gram-negative bacteria intestinal bacteria, [C
4iQuin] minimal inhibitory concentration (MIC) of Br is at 256 μ about g/mL, [C
12iQuin] minimal inhibitory concentration (MIC) 32 below the μ g/mL of Br, [C
8iQuin] minimal inhibitory concentration (MIC) 128 below the μ g/mL of Br.To all kinds of phytopathogen (botrytis cinerea, Rhizoctonia solani Kuhn, rhizoctonia cerealis), [C
4iQuin] Br obtains EC50 and is greater than 500mg/L, [C
8iQuin] EC50 of Br is about 45mg/L, [C
12iQuin] EC50 of Br is about 9mg/L, compared with geramine, [C
12iQuin] Br bacteriostatic activity is stronger.
(2) because this ionic liquid all has stronger bactericidal properties to intestinal bacteria and phytopathogen, sterilization and antibacterial product can be prepared.
(3) compare with existing sterilant, the synthetic route of this ionic liquid is short, technique is simple, less demanding to synthesis device, by product is few, and products obtained therefrom is easy to separating-purifying.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described.
Embodiment 1
The synthesis of iloquinoline derivative ionic liquid
1) [C
4iQuin] synthesis of Br
Under the condition of anhydrous and oxygen-free, nitrogen protection, in the round-bottomed flask of 50mL, add 11g isoquinoline 99.9 and 10g bromination of n-butane fast, stir and reflux a few hours, at the end of reaction, then can obtain product.Dissolved with solvent I after being cooled to room temperature, after chromatography column decolouring removal of impurities, rotary evaporation obtains burgundy thick liquid.After repeatedly recrystallization, extract lower boiling residual solvent with under the state of vacuum pump at ultralow pressure again, namely obtain purer bromination N-alkyl base isoquinolinium ion liquid and (be called for short [C
4iQuin] Br).
2) [C
8iQuin] synthesis of Br
Under the condition of anhydrous and oxygen-free, nitrogen protection, in the round-bottomed flask of 100mL, add 11g isoquinoline 99.9 and 17g n-octane bromide fast, stir and be heated to more than 100 DEG C, backflow a few hours, at the end of reaction, namely obtain product.Dissolved with chloroform after being cooled to room temperature, after chromatography column decolouring removal of impurities, rotary evaporation obtains yellow thick liquid.Obtain faint yellow solid after anhydrous diethyl ether repeatedly washs, namely this faint yellow solid is obtained after repeatedly recrystallization purer bromination N-n-octyl isoquinolinium ion liquid and (be called for short [C
8iQuin] Br).
3) [C
12iQuin] synthesis of Br
In the round-bottomed flask of 50mL, 5g isoquinoline 99.9 and 12g N-dodeeyl bromide is added fast under the condition of anhydrous and oxygen-free, nitrogen protection; stir and be heated to more than 100 DEG C and reflux a few hours; both product is obtained after reaction terminates; dissolved with methylene dichloride after being cooled to room temperature, after chromatography column decolouring removal of impurities, rotary evaporation obtains red thick liquid.Obtain Off-white solid after sherwood oil repeatedly washs, namely this Off-white solid is obtained after repeatedly recrystallization purer bromination N-dodecyl isoquinolinium ion liquid and (be called for short [C
12iQuin] Br).
Characterization of compound:
[C
4iQuin]Br：
1H NMR(600MHz，CDCl
3，20℃)0.97(t，-CH3，1×3H)，1.4(m，1×2H)，2.1(m，-CH2-，1×2H)，5.1(t，1×2H)，14Hδ＝11.207(s，1×H)，13H 8.799～8.77(d，2×2H)，8.146(t，2×2H)，8.36(d，1×H)，7.96(t，1×H)。
[C
8iQuin]Br：
1H NMR(600MHz，CDCl
3，20℃)0.85(t，-CH3，1×3H)，1.2(m，CH2-，3×6H)，1.3(m，-CH2-，1×2H)，1.4(m，1×2H)，2.1(m，-CH2-，1×2H)，5.1(t，1×2H)，14Hδ＝11.141(s，1×H)，13H 8.70(d，1×H)，8.12～8.15(t，2×2H)，8.36(d，1×H)，7.96(d，1×H)。
[C
12iQuin]Br：
1H NMR(600MHz，CDCl
3，20℃)0.869(t，-CH3，1×3H)，1.426～1.214(m,-CH2-，9×2H),2.1(m，-CH2-，1×2H)，5.08(t，1×2H)，14Hδ＝11.127(s，1×H)，13H 8.79(d，1×H)，8.625(s,1×H),8.325(d，1×H)，8.13(d，1×H)，7.97(m，1×H)。
[C
nisoq] Infrared Characterization of Br: 3030cm
-1, 2920cm
-1, 2960cm
-1, 1600-1500cm
-1, 725cm
-1.
Embodiment 2
1 adopts magnanimity doubling dilution to carry out bacteriostatic activity detection to ion liquid anti-virus activities agent.
Scraped by bacterium on inclined-plane with aseptic inoculation ring, making cell concentration is 5 × 10
6the bacteria suspension of CFU/mL, cultivates activation 12h for 37 DEG C.During use, mix with appropriate amount of fluid substratum that (final bacterial concentration is 10
5cFU/mL).Testing sample doubling dilution is diluted to desired concn.Only containing bacterium is negative control; Only containing substratum is blank.In shaking table, 37 DEG C, each sample is cultivated 24h, then 24h cultivated by bed board.Visual inspection, record colony number, calculate bacteriostasis rate, the Cmin of bacteriostasis rate more than 80% is MIC.
2 adopt flat band method to measure ionic liquid to the bacteriostatic activity of phytopathogen
The bacterial strain that picking is preserved on aseptic operating platform, be inoculated in inclined-plane PDA solid medium test tube, be positioned in constant incubator, 26 DEG C activate, and cultivate 4 days.Again with transfering loop by the cultivation strain inoculation of 4 days in the culture dish of diameter 90mm, be positioned in constant incubator, 26 DEG C activate, and cultivate 4 days.Mycelial growth rate method is adopted to measure often kind of sterilant to the bacteriostatic action of phytopathogen.The bacterium colony cultivated 4 days from PDA substratum gets the mycelia block that diameter is 5mm, moves on to containing [C
4iQuin] Br, [C
8iQuin] Br, [C
12iQuin] Br fixed concentration PDA solid medium central authorities, 26 DEG C be placed in constant incubator cultivate 4 days, not adding of germicide flat board for contrast.Three repetitions are done in each process, adopt right-angled intersection method to measure colony diameter size, and obtain colony growth diameter thus, calculate the growth inhibition ratio of mycelia.
Growth inhibition ratio formula is as follows:
Growth inhibition ratio (%)=(1-process colony growth diameter/contrast colony growth diameter) × 100.
Result shows that ionic liquid has very strong bacteriostatic activity.
Table 1 isoquinolinium ion liquid is for colibacillary minimal inhibitory concentration MIC, MBC (μ g/ml)
Table 2 isoquinolinium ion liquid is to the EC of three kind of plant pathogenic bacterium
50(mg/L)
Claims (8)
1. an iloquinoline derivative ionic liquid, is characterized in that, its general structure is:
Wherein, n is 4,8 or 12.
2. a synthetic method for iloquinoline derivative ionic liquid as claimed in claim 1, is characterized in that, comprise the steps:
Under anhydrous and oxygen-free, nitrogen protection condition, add rapidly isoquinoline 99.9 and bromo normal alkane, stir and be heated to back flow reaction in reaction vessel, reaction terminates rear acquisition crude product; Dissolved by crude product after being cooled to room temperature, after chromatography column decolouring removal of impurities, rotary evaporation obtains thick liquid; Thick liquid through repeatedly washing, repeatedly removing residual solvent after recrystallization, obtains described iloquinoline derivative ionic liquid again, wherein, bromo normal alkane be in bromination of n-butane, n-octane bromide and N-dodeeyl bromide any one.
3. the synthetic method of iloquinoline derivative ionic liquid as claimed in claim 2, is characterized in that, count in mass ratio, isoquinoline 99.9: bromination of n-butane=1: 0.9, isoquinoline 99.9: n-octane bromide=1: 1.5, isoquinoline 99.9: N-dodeeyl bromide=1: 2.2.
4. the preparation method of iloquinoline derivative ionic liquid as claimed in claim 2, it is characterized in that, back flow reaction temperature is between 606120 DEG C, and reflux time is 12616h.
5. the synthetic method of iloquinoline derivative ionic liquid as claimed in claim 2, it is characterized in that, when bromo normal alkane be bromination of n-butane or n-octane bromide time, crude product adopt chloroform dissolve, when bromo normal alkane is N-dodeeyl bromide, crude product adopts methylene dichloride to dissolve.
6. the synthetic method of iloquinoline derivative ionic liquid as claimed in claim 2, it is characterized in that, when bromo normal alkane is n-octane bromide, thick liquid adopts anhydrous diethyl ether repeatedly to wash, when bromo normal alkane is N-dodeeyl bromide, thick liquid adopts sherwood oil repeatedly to wash.
7. iloquinoline derivative ionic liquid as claimed in claim 1 is as sterilant and the application pressing down agent bacterium.
8. apply as claimed in claim 7, it is characterized in that, described bacterium comprises intestinal bacteria and phytopathogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510210435.3A CN104829528A (en) | 2015-04-28 | 2015-04-28 | Isoquinoline ionic liquid, synthesis and applications thereof |
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| CN201510210435.3A CN104829528A (en) | 2015-04-28 | 2015-04-28 | Isoquinoline ionic liquid, synthesis and applications thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106337060A (en) * | 2016-08-26 | 2017-01-18 | 扬州大学 | Green gene carrier having optical activity function and preparation method thereof |
| CN111789120A (en) * | 2020-07-29 | 2020-10-20 | 湖南省植物保护研究所 | Bactericide imazalil ionic liquid, and preparation method and application thereof |
-
2015
- 2015-04-28 CN CN201510210435.3A patent/CN104829528A/en active Pending
Non-Patent Citations (4)
| Title |
|---|
| MARTA KRÓLIKOWSKA等: "Phase Equilibria Study of the Binary Systems (N-Hexylisoquinolinium Thiocyanate Ionic Liquid + Organic Solvent or Water)", 《J. PHYS. CHEM. B》 * |
| XIAOHONG ZHANG等: "Micellization behavior of the ionic liquid lauryl isoquinolinium bromide in aqueous solution", 《COLLOID POLYM SCI》 * |
| 彭新影等: "异喹唑啉类离子液体对植物病原菌抑制作用研究", 《中国化学会第十四届胶体与界面化学会议论文摘要集-第6分会：胶体与界面化学技术、应用与产品》 * |
| 彭新影等: "异喹啉基离子液体的抑菌活性", 《第八届全国化学生物学学术会议论文摘要集》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106337060A (en) * | 2016-08-26 | 2017-01-18 | 扬州大学 | Green gene carrier having optical activity function and preparation method thereof |
| CN111789120A (en) * | 2020-07-29 | 2020-10-20 | 湖南省植物保护研究所 | Bactericide imazalil ionic liquid, and preparation method and application thereof |
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Application publication date: 20150812 |