CN103554018B - A kind of dihydro-quinolinone alkaloid compound and its crystal, preparation method and the application as marine antifoulant - Google Patents
A kind of dihydro-quinolinone alkaloid compound and its crystal, preparation method and the application as marine antifoulant Download PDFInfo
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- CN103554018B CN103554018B CN201310503315.3A CN201310503315A CN103554018B CN 103554018 B CN103554018 B CN 103554018B CN 201310503315 A CN201310503315 A CN 201310503315A CN 103554018 B CN103554018 B CN 103554018B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
- C07D215/22—Oxygen atoms attached in position 2 or 4
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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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P17/00—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms
- C12P17/10—Nitrogen as only ring hetero atom
- C12P17/12—Nitrogen as only ring hetero atom containing a six-membered hetero ring
Abstract
A kind of dihydro-quinolinone alkaloid compound and its crystal, preparation method and the application as marine antifoulant, Spawn incubation first is carried out to fungi Scopulariopsis sp. (TA01 33) during preparation, fermented and cultured is carried out to the fungi again, it is filtered to remove thalline, after filtrate concentration, it is extracted with ethyl acetate；Normal-phase silica gel column chromatography, the gel filtration chromatographies of Sephadex LH 20, HPLC high performance liquid chromatography are carried out successively, produce compound of formula I.Compound of formula I, its pharmaceutically acceptable salt or its crystal can be used for the marine antifoulant for preparing high-efficiency low-toxicity.
Description
Technical field
The present invention relates to a kind of dihydro-quinolinone (dihydroquinolone) alkaloid compound and its crystal, preparation side
Method and application, it is more particularly to a kind of that there is extremely strong suppression to marine fouling organism barnacle Balanus amphitrite larvas
The dihydro-quinolinone alkaloid compound of activity and its crystal, preparation method and application.
Background technology
Marine biofouling is that subduction is set in ocean for organic molecule, microorganism, animal, plant and their accessory substance
Apply the harmfulness accumulation on surface.This harmfulness accumulation frequently occurs in the surface for the ocean subduction facility do not protected, including
Sea-freight and the ship of tourism, naval's warship, heat exchanger, sea sensor and aquaculture base etc..Biodeterioration causes
Huge economic loss, only by taking USN's warship as an example, every year economic loss in this respect 18 to 26 hundred million dollars it
Between, and USN's warship quantity only accounts for the 0.5% of global ships quantity, therefore marine biofouling is extremely serious nature
Harm.Barnacle is that representativeness very universal in fouling organism known today is biological because of its very strong Adhering capacity.From 2008
Year, the whole world was eliminated after the use of poisonous anti-fouling agent organotin, and the safe and efficient marine antifoulant of searching, which turns into, to be badly in need of solving in the world
Problem certainly.Marine natural products is considered as the important sources of novel sea anti-fouling agent.In fact, in the past few decades
From sponge, the compound for much having strong anti-fouling activity is found that in the marine organisms such as coral and marine alga.However, from above-mentioned
The reactive compound found in macro-organism is due to being leveraged its potential application by the limitation measured.Marine microorganism
Due in the lab can be with large scale fermentation, survivable natural environment, and as activity marine compound it is most important come
Source.However, in recent years there is not yet obtaining the dihydro-quinolinone biology alkalization of important anti-fouling activity from marine microorganism
Compound as anti-fouling agent use.(J.A.Callow, M.E.Callow, Nat.Commun.2011,2,244-253；
C.M.Kirschner, A.B.Brennan, Annu.Rev.Mater.Res.2012,42,1-19；M.Schultz,
J.Bendick, E.Holm, W.Hertel, Biofouling2011,27,87-98；N.Fusetani,
Nat.Prod.Rep.2004,21,94-104；N.Fusetani, Nat.Prod.Rep.2011,28,400-410；P.-
Y.Qian, Y.Xu, N.Fusetani, Biofouling2010,26,223-234.)
The content of the invention
It is an object of the invention to provide a kind of dihydro-quinolinone alkaloid compound and its crystalline substance from marine fungi
Body, preparation method and the application as marine antifoulant, it can meet the demand of prior art.Culture presevation information：Protect
Hide organization：China Committee for Culture Collection of Microorganisms's common micro-organisms center；Depositary institution address：Beijing is exposed to the sun
No. 3 Institute of Microorganism, Academia Sinica of institute of area North Star West Road 1；Preservation date：On December 17th, 2012；Deposit number：
CGMCC6959；Classification And Nomenclature：Scopulariopsis sp..
The present invention provides compound of formula I or its pharmaceutically acceptable salt：
Formulas I.
Another embodiment of the present invention provides the preparation method of compound of formula I, it is characterised in that first in bacterium culture medium
In to be isolated from gorgonian Carijoa sp. endogenetic fungus Scopulariopsis sp. (TA01-33) carry out Spawn incubation,
Fermented and cultured is carried out to the fungi in the fermentation medium again, then by gained filtering fermentation liquor, thalline is removed, filtrate is concentrated
Afterwards, it is extracted with ethyl acetate；Normal-phase silica gel column chromatography, Sephadex LH-20 gel filtration chromatographies are carried out respectively after extract concentration
Afterwards, then through HPLC high performance liquid preparative chromatographies, gained eluent is concentrated, colourless crystallization, as compound of formula I is obtained.
Bacterium culture medium preferably comprises glucose 0.1%-5.0% (percentage by weight, similarly hereinafter), ferment in above-mentioned preparation method
Female cream 0.01%-1%, peptone 0.01%-1%, agar 0.1%-3.0%, sodium chloride 0.05%-5%, remaining is water, training
Foster temperature is preferably 0-30 DEG C, and incubation time is preferably 3-15 days；Fermentation medium preferably comprises glucose 0.1%-5.0%
(percentage by weight, similarly hereinafter), yeast extract 0.01%-1%, peptone 0.01%-1%, sodium chloride 0.05%-5%, remaining is
Water, cultivation temperature is preferably 0-30 DEG C, and incubation time is preferably 10-60 days；The fixation that described normal-phase silica gel column chromatography is used
Phase preferably 200-300 mesh silica gel, mobile phase preferred volume ratio is 15%-40% ethyl acetate-light petrol mixed solvent；It is described
The mobile phase preferred volume ratio that Sephadex LH-20 gel filtration chromatographies are used is petroleum ether：Chloroform：Methanol=2：1：1 mixing
Solvent；The chromatographic column used in the HPLC high performance liquid preparative chromatographies is this area routine ODS C18 post, preferably
Kromasil10 × 250mm, 7 μm, flow velocity is preferably 1.0-5.0mL/min, and mobile phase preferred volume ratio is 50%-80% first
Alcohol-water mixed solvent.
Another embodiment of the present invention provides the crystal of compound of formula I, its Cu target X-ray crystal diffraction data：Space
Group P2 (1) 2 (1) 2 (1), cell parameter is α
=90 °, β=90 °, γ=90 °,Z=4, Dc=1.352g/cm3, F (000)=568, μ=
0.766mm-1, Flack constants are -0.05 (18).
Another embodiment of the present invention provides the preparation method of above-mentioned compound of formula I crystal, it is characterised in that by Formulas I
Compound is dissolved in any of methanol, ethanol, tetrahydrofuran or acetone or several, stands slow crystallization and can obtain Formulas I chemical combination
The crystal of thing.
The condition slowly crystallized is stood in the preparation method of above-mentioned crystal preferably at 0-30 DEG C, 1-30 days are stood.
The dihydro-quinolinone alkaloid compound that the present invention is obtained from marine fungi is to marine fouling organism barnacle
Balanus amphitrite larvas have extremely strong inhibitory activity, available for exploitation marine antifoulant, have a extensive future.
Another embodiment of the present invention provides compound of formula I, its pharmaceutically acceptable salt or its crystal and is preparing sea
Application in foreign anti-fouling agent.
Term " pharmaceutically acceptable salt " refers to the addition of atoxic inorganic or organic acid and/or alkali in the present invention
Salt.Reference can be made to " Salt selection for basic drugs ", Int.J.Pharm. (1986), 33,201-217.
Brief description of the drawings
Figure of description is the XRD of compound of formula I.
Embodiment
For the ease of a further understanding of the present invention, examples provided below has done more detailed description to it.But
It is that these embodiments only are not used for limiting the scope of the present invention or implementation principle, reality of the invention for being better understood from invention
The mode of applying is not limited to herein below.
Embodiment 1
(1) gorgonian endogenetic fungus Scopulariopsis sp. (TA01-33) Spawn incubation
Culture medium used in Spawn incubation contains glucose 1.0% (percentage by weight, similarly hereinafter), yeast extract 0.2%, albumen
Peptone 0.2%, agar 1.0%, sodium chloride 3.0%, remaining is water, and test tube slant is made when using, and fungal bacterial strain is trained at 30 DEG C
Support 5 days.
(2) gorgonian endogenetic fungus Scopulariopsis sp. (TA01-33) fermentation
Culture medium used in fermented and cultured contains glucose 1.0% (percentage by weight, similarly hereinafter), yeast extract 0.2%, albumen
Peptone 0.2%, sodium chloride 3.0%, remaining is water；Fungal bacterial strain is cultivated 60 days in 28 DEG C.
(3) the extraction separation of compound of formula I
The filtering fermentation liquor for taking 10L steps (2) to obtain, removes thalline, after filtrate is concentrated, with isometric ethyl acetate
Extraction 5 times；Carrying out normal-phase silica gel column chromatography after extract concentration respectively, (stationary phase is 200-300 mesh silica gel；Mobile phase is 30%
Ethyl acetate/petroleum ether mixed solvent, volume ratio), Sephadex LH-20 gel filtration chromatography (petroleum ethers：Chloroform：Methanol=2：
1：1 mixed solvent, volume ratio) after, then through HPLC high performance liquid preparative chromatographies separation (chromatographic column be Kromasil10 ×
250mm, 7 μm, flow velocity is 2.0mL/min, and mobile phase is 75% Methanol+Water, volume ratio), by gained eluent
Concentration, obtains colourless crystallization, as compound of formula I.
The structural identification data of compound of formula I：Clear crystal；Specific rotation value [α]25 D=+1.84 (c0.038, methanol)；1H
NMR (deuterated acetone, 400MHz, TMS) and13C NMR (deuterated acetone, 100MHz, TMS), are shown in Table 1；Infrared IR (KBr)
vmax3251,2920,1707,1487,1618,1308,1138, and768cm-1；UV (MeOH) λmax(logε)：210
(0.63), 253.8 (0.13), 286.9 (0.20), 287.4 (0.06) nm；Mass spectrum EIMS m/z：269[M]·+；High resolution mass spectrum
HRESIMS m/z270.1127[M+H]+(calculated value C16H16NO3, 270.1125).
Embodiment 2
(1) gorgonian endogenetic fungus Scopulariopsis sp. (TA01-33) Spawn incubation
Culture medium used in Spawn incubation contains glucose 0.1%-5.0% (percentage by weight, similarly hereinafter), yeast extract
0.01%-1%, peptone 0.01%-1%, agar 0.1%-3.0%, sodium chloride 0.05%-5%, remaining is water, when using
Test tube slant is made, fungal bacterial strain is cultivated 3-15 days at 0-30 DEG C.
(2) gorgonian endogenetic fungus Scopulariopsis sp. (TA01-33) fermentation
Culture medium used in fermented and cultured contains glucose 0.1%-5.0% (percentage by weight, similarly hereinafter), yeast extract
0.01%-1%, peptone 0.01%-1%, sodium chloride 0.05%-5%, remaining is water, and fungal bacterial strain cultivates 10- in 0-30 DEG C
60 days.
(3) the extraction separation of compound of formula I
The filtering fermentation liquor obtained by 5-50L steps (2) is taken, thalline is removed, after filtrate is concentrated, with the second of 1-3 times of volume
Acetoacetic ester is extracted 2-5 times；Carrying out normal-phase silica gel column chromatography after extract concentration respectively, (stationary phase is the conventional positive silicon in this area
Glue, mobile phase is 15%-40% ethyl acetate-light petrol mixed solvent, volume ratio), Sephadex LH-20 gel columns layer
(mobile phase is petroleum ether for analysis：Chloroform：Methanol=2：1：1 mixed solvent, volume ratio) after, then through HPLC efficient liquid phases prepare color
(chromatographic column is this area routine ODS C18 posts to spectrum, and flow velocity is 1.0-5.0mL/min, and mobile phase is 50%-80% methanol-water
Mixed solvent, volume ratio), gained eluent is concentrated, colourless crystallization, as compound of formula I is obtained.
Embodiment 3
Modus ponens I 5mg is dissolved in equipped with bottle any in 2mL methanol, ethanol, tetrahydrofuran or acetone,
After standing 30 days at 0 DEG C, slow crystallization produces the crystal of compound of formula I.
Embodiment 4
Modus ponens I 10mg is dissolved in equipped with any one or several in 5mL methanol, ethanol, tetrahydrofuran or acetone
In bottle, after standing 1 day at 30 DEG C, slow crystallization produces the crystal of compound of formula I.
The Cu target X-ray crystal diffraction data of above-mentioned crystal：Space group P2 (1) 2 (1) 2 (1), cell parameter isα=90 °, β=90 °, γ=
90 °,Z=4, Dc=1.352g/cm3, F (000)=568, μ=0.766mm-1, Flack is normal
Number is -0.05 (18).
Table 1：The nuclear magnetic data of compound of formula I
a400MHz for1HNMR and100MHz for13C NMR spectra.
Embodiment 5
The present invention compound of formula I and its crystal to barnacle Balanus amphitrite larvas attachment activity test according to
Following literature method test：Thiyagarajan, V.；Harder, T.；Qiu, J.W.；Qian, P.Y.Mar.Biol.
(Berlin) 2003,143,543-554.
The compound of formula I of the present invention and its attachment of crystal barnacle B.amphitrite larvas have extremely strong inhibitory activity,
Its EC50It is worth for 0.28 μ g/mL, and with very high security, its toxicity efficiency ratio LC50/EC50Value 89.Above-mentioned activity is much
It is better than potential natural anti-fouling compound EC as defined in USN50The μ g/mL of value 25 standard.Importantly, its poison
Property efficiency ratio (LC50/EC50) much larger than 15, and LC50/EC50It is regarded as having more than 15 and develops into the latent of safety antifouling agent
Power.This shows that compound of formula I, its pharmaceutically acceptable salt or its crystal can be used for the marine antifoulant for preparing high-efficiency low-toxicity,
And gorgonian endogenetic fungus Scopulariopsis sp. (TA01-33) can carry out large scale fermentation production, it is ensured that Formulas I
The natural origin of compound, it has broad application prospects.
Claims (2)
1. the application of compound of formula I or its pharmaceutically acceptable salt in marine antifoulant is prepared, it is characterised in that Formulas I chemical combination
Thing has following structure：
2. application of the crystal of compound of formula I in marine antifoulant is prepared, it is characterised in that compound of formula I has following knot
Structure：
The space group of its crystal is P2 (1) 2 (1) 2 (1), and cell parameter is
α=90 °, β=90 °, γ=90 °,Z=4, Dc=1.352g/cm3, F (000)=568, μ=
0.766mm-1, Flack constants are -0.05 (18).
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| CN104031955B (en) * | 2014-06-06 | 2018-03-02 | 中国海洋大学 | A kind of preparation method of dihydro-quinolinone alkaloid compound and the application as marine antifoulant |
| CN108658973A (en) * | 2017-03-28 | 2018-10-16 | 中国海洋大学 | A kind of lactam analog compound and preparation method thereof and purposes as marine antifoulant |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643468A (en) * | 2009-08-25 | 2010-02-10 | 中国海洋大学 | Quinolinone alkaloid derivant as well as preparation method and application thereof |
| CN103351369A (en) * | 2013-04-19 | 2013-10-16 | 中国海洋大学 | Methybutyrolactone II and preparation method thereof, and application of methybutyrolactone II as nature marine organism antifouling agent |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643468A (en) * | 2009-08-25 | 2010-02-10 | 中国海洋大学 | Quinolinone alkaloid derivant as well as preparation method and application thereof |
| CN103351369A (en) * | 2013-04-19 | 2013-10-16 | 中国海洋大学 | Methybutyrolactone II and preparation method thereof, and application of methybutyrolactone II as nature marine organism antifouling agent |
Non-Patent Citations (2)
| Title |
|---|
| 4‑Phenyl-3,4-dihydroquinolone Derivatives from Aspergillus nidulans MA-143, an Endophytic Fungus Isolated from the Mangrove Plant Rhizophora stylosa;Chun-Yan An et al;《Journal of Natural Products》;20131007;第76卷;1896-1901 * |
| 柳珊瑚来源的一株真菌中生物碱化合物及其生物活性;胥汝芳;《万方数据知识服务平台》;20130902;第46页图2-21，第39页第1段，第52页表3-1，第16页1.4菌种的培养与发酵，第17-19页2.1实验器材与材料、3.1化合物的分离纯化 * |
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