CN101691368B - Dehydration methylate of quinolinone alkaloid derivative and preparation method and application - Google Patents
Dehydration methylate of quinolinone alkaloid derivative and preparation method and application Download PDFInfo
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- CN101691368B CN101691368B CN2009100183213A CN200910018321A CN101691368B CN 101691368 B CN101691368 B CN 101691368B CN 2009100183213 A CN2009100183213 A CN 2009100183213A CN 200910018321 A CN200910018321 A CN 200910018321A CN 101691368 B CN101691368 B CN 101691368B
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- quinolinone
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- carboxyl
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Abstract
The invention relates to a dehydration methylate of a quinolinone alkaloid derivative and a preparation method and application. The preparation method is characterized by first carrying out strain culture on marine fungi in a strain medium, then carrying out fermentation culture in a fermentation medium, filtering obtained fermentation liquid to obtain thalli and extracting the obtained thalli by an organic solvent; carrying out chromatographic separation on extraction liquid after the extraction liquid is concentrated, concentrating obtained eluent to obtain yellow powder, namely 2-pyrrolyl-3-carboxyl-4-quinolinone; and adding a methylation reagent and a catalyst into acetone solution in which the 2-pyrrolyl-3-carboxyl-4-quinolinone is dissolved for reaction, and then obtaining the dehydration methylate of the quinolinone alkaloid derivative after reaction. The compound of the invention has strong effect on killing cotton aphids, plutella xylostella and heliothis virescens, can be used as a microbial pesticide and has extensive application prospect. In addition, the raw materials of the compound can be produced in large scale.
Description
Technical field
The present invention relates to the dehydration methylate penicinotam and preparation method thereof of a kind of quinolinone alkaloid derivant that from the thalline of ocean endogenetic fungus, extracts (2-pyrryl-3-carboxyl-4-quinolinone) and as the application of microbial pesticide sterilant.
Background technology
Since nineteen twenty-nine was prepared penicillin from fungi since, the meta-bolites of fungi had become the abundant source of medicine, and the microbiotic of most clinical applications all derives from fungi and bacterium.The meta-bolites of fungi also has other pharmaceutical use, as antitumor, and treatment cardiovascular disorder, enzyme inhibitors etc.Because the singularity of ocean environment and microorganism are in the function of the ecosystem, marine microorganism has developed the metabolic way that uniqueness, the meta-bolites that also provides the Lu Sheng microorganism to provide, people are sent in very big hope to seek new specific medicament from marine microorganism.Yet up to the present, do not see the microbial pesticide sterilant that obtains to have pharmaceutical use by thalassiomycetes as yet.
Summary of the invention
The object of the present invention is to provide a kind of dehydration methylate and preparation method thereof of the quinolinone alkaloid derivant that derives from thalassiomycetes and application as microbial pesticide, it can satisfy the demand of prior art.
A kind of dehydration methylate of quinolinone alkaloid derivant is characterized in that molecular formula is C
15H
10N
2O
2, structural formula is
The preparation method of the dehydration methylate of above-mentioned quinolinone alkaloid derivant, it is characterized in that earlier in bacterium culture medium thalassiomycetes being carried out spawn culture, fermentation culture in fermention medium again is with the gained filtering fermentation liquor, obtain thalline, with gained thalline organic solvent extraction; Extracting solution concentrates laggard circumstances in which people get things ready for a trip spectrum to be separated, and the gained elutriant is concentrated, and gets yellow powder, is 2-pyrryl-3-carboxyl-4-quinolinone; In the acetone soln that is dissolved with 2-pyrryl-3-carboxyl-4-quinolinone, add methylating reagent and catalyzer, obtain the dehydration methylate of quinolinone alkaloid derivant after the reaction.
The application of the dehydration methylate of above-mentioned quinolinone alkaloid derivant in preparation microbial pesticide sterilant.
The dehydration methylate of quinolinone alkaloid derivant of the present invention has the very strong effect of killing cotten aphid, small cabbage moth and Heliothis virescens, can be used as the microbial pesticide sterilant, and raw material can carry out scale operation, has a extensive future.
Embodiment
When preparing compound of the present invention, take following each step:
(1) in bacterium culture medium, thalassiomycetes (Penicillium sp.ZZF32#) is carried out spawn culture earlier, used substratum contains glucose 1.0% (weight percentage, down with), yeast extract paste 0.1%, peptone 0.2%, agar 1.0%, sodium-chlor 0.3%, all the other are water.Be made into the test tube slant substratum during use, above-mentioned fungal bacterial strain was cultivated 5 days down at 30 ℃.
Described bacterium culture medium contains glucose 0.1%-5.0%, yeast extract paste 0.01%-1%, peptone 0.01%-1%, agar 0.1%-3.0%, sodium-chlor 0.05%-5%, and all the other are water.Culture temperature is 15-35 ℃, and incubation time is 3-10 days.
(2) fungi strain of above-mentioned cultivation gained carries out fermentation culture, and used fermention medium contains glucose 1.0%, yeast extract paste 0.1%, peptone 0.2%, sodium-chlor 0.3%, and all the other are water, and fungal bacterial strain was cultivated 30 days in 28 ℃.
Described fermention medium contains glucose 0.1%-5.0%, yeast extract paste 0.01%-1%, peptone 0.01%-1%, sodium-chlor 0.05%-5%, and all the other are water.Culture temperature is 15-35 ℃, and incubation time is 7-40 days.
(3) extraction separation of compound 2-pyrryl-3-carboxyl-4-quinolinone
With previous step gained filtering fermentation liquor, obtain thalline; Thalline is with organic solvent methanol extraction 5 times, with the gained extracting solution merge concentrate after, carry out column chromatography or thin-layer chromatography and separate, with elutriant concentrate yellow powder, be 2-pyrryl-3-carboxyl-4-quinolinone.
Described organic solvent methyl alcohol can be used propyl carbinol, chloroform, ethanol or ethyl acetate instead.
(4) preparation of the dehydration methylate penicinotam of 2-pyrryl-3-carboxyl-4-quinolinone
0.05mol exsiccant 2-pyrryl-3-carboxyl-4-quinolinone is dissolved in the 25mL exsiccant acetone, add 0.25g exsiccant salt of wormwood, be added drop-wise to the 0.20mol methyl iodide in the reaction soln gradually under the room temperature, after stirring 24 hours at ambient temperature, with TLC detect raw material consumption fully after, in reactant, add the frozen water termination reaction, extract with chloroform, after extraction liquid concentrates, separate with silica gel column chromatography method, as eluent, obtain compound penicinotam with ethyl acetate after the separation.
Described acetone can be used chloroform or ethyl acetate instead; Described salt of wormwood can be used pyridine, diethylamine, triethylamine, imidazoles, 4-aminopyridine, 4-Dimethylamino pyridine, piperazine, morpholine, yellow soda ash, potassium hydroxide, sodium hydroxide or calcium hydroxide instead; Described methylating reagent methyl iodide can change methyl-sulfate into.
The spectral data of gained compound penicinotam and monocrystalline data
Penicinotam：a?yellow?needle?crystal；mp?323-325℃；UV(CH
3OH)λ
max(logε)191.1(5.4)，213.4(4.20)，287.6(3.30)，339.8(1.90)nm；IR(KBr)v
max?2930，2872，1737，1674，1608，1544，1496，1458，1403，1377，1232，1094，763cm
-1；
1H?NMR(DMSO-d
6，500MHz)δ8.20(1H，dd，J＝8.0，1.6Hz，H-5)，7.89(1H，dd，J＝8.0，1.6Hz，H-8)，7.78(1H，ddd，J＝8.0，8.0，1.6Hz，H-7)，7.51(1H，ddd，J＝8.0，8.0，1.6Hz，H-6)，7.47(1H，dd，J＝3.0，1.0Hz，H-5’)，7.09(1H，dd，J＝3.5，1.0Hz，H-3’)，6.43(1H，dd，J＝3.5，3.0Hz，H-4’)，3.99(3H，s，1’-NCH
3)；
13C?NMR(DMSO-d
6，125MHz)δ169.9(C，C-4)，159.5(C，3-CONH)，153.8(C，C-2)，140.4(C，C-9)，132.7(CH，C-7)，128.7(C，C-10)，125.9(CH，C-5)，125.6(CH，C-6)，125.6(C，C-2’)，120.2(CH，C-5’)，117.7(CH，C-8)，116.6(CH，C-3’)，111.6(CH，C-4’)，104.3(C，C-3)，36.6(CH
3，1’-NCH
3)；EIMS(pos.)m/z?250[M]
+，222，194，166，140，80；HREIMS?m/z?250.0733(calcd?for?C
15H
10N
2O
2，250.0737).Crystallizes?in?monoclinic，space?group?P2(1)/n?with?a＝7.3216(16)?
，b＝22.498(5)?
，c＝14.536(3)?
，α＝90°，β＝103.416(3)°，γ＝90°，C
15H
10N
2O
2，Mr＝250.07，V＝2329.1(9)?
，Z＝4，D
c＝1.476g/cm
3，F(000)＝1076，μ＝0.103mm
-1，the?final?R＝0.1380?and?wR＝0.3376?for?4332?observed?reflections(I＞2σ(I)).The?paragraph?crystallographic?data?for?1a?have?been?deposited?at?theCambridge?Crystallographic?Data?Centre(CCDC?No.734744).
The structural formula of the penicinotam compound that present embodiment makes is:
The single crystal structure formula of compound penicinotam is:
The application of compound of the present invention in preparation microbial pesticide sterilant
The insecticidal activity test of compound of the present invention
Insecticidal activity experiment parallel testing three times, the disease and insect of test is respectively cotton aphid (Aphis gossypii), diamondback moth larvae (Plutella xylost) and Heliothis virescens larva (Heliothis virescens).The initial concentration of three kinds of specimen is 1000ppm, and equal dilute with water is 500ppm during test, and each sample is joined respectively in 96 orifice plates, and each larva was all cultivated 5-9 days.Penicinotam of the present invention is diluted with water to the concentration of 1000ppm, adds 0.5ml to above-mentioned orifice plate respectively, measurement result shows, the lethality rate of cotton aphid is 100%, and the Heliothis virescens larva is also shown strong deadly activity; Penicinotam of the present invention is diluted with water to the concentration of 500ppm, diamondback moth larvae is had 100% deadly activity.
Experiment shows, the dehydration methylate of 2-pyrryl of the present invention-3-carboxyl-4-quinolinone has clearly deadly activity to cotton aphid, diamondback moth larvae and Heliothis virescens larva, therefore can be used as the microbial pesticide sterilant, and raw material can carry out scale operation, has a extensive future.
Claims (3)
1. the dehydration methylate of a quinolinone alkaloid derivant is characterized in that molecular formula is C
15H
10N
2O
2,
Structural formula is
2. the preparation method of the dehydration methylate of the described quinolinone alkaloid derivant of claim 1, it is characterized in that in bacterium culture medium, thalassiomycetes being carried out spawn culture earlier, fermentation culture in fermention medium again, with the gained filtering fermentation liquor, obtain thalline, with gained thalline methanol extraction; Carry out silica gel column chromatography after methanol extract liquid concentrates and separate, the gained elutriant is concentrated, get yellow powder, be 2-pyrryl-3-carboxyl-4-quinolinone; In the acetone soln that is dissolved with 2-pyrryl-3-carboxyl-4-quinolinone, add methyl-sulfate and salt of wormwood, obtain the dehydration methylate of quinolinone alkaloid derivant after the reaction; Described bacterium culture medium contains glucose 0.1%-5.0%, yeast extract paste 0.01%-1%, peptone 0.01%-1%, agar 0.1%-3.0%, sodium-chlor 0.05%-5%, and all the other are water; Described fermention medium contains glucose 0.1%-5.0%, yeast extract paste 0.01%-1%, peptone 0.01%-1%, sodium-chlor 0.05%-5%, and all the other are water.
3. the dehydration methylate of the described quinolinone alkaloid derivant of claim 1 is preparing the microbial pesticide sterilant to the application in cotton aphid, diamondback moth larvae and the Heliothis virescens larva.
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| CN106967061A (en) * | 2016-01-13 | 2017-07-21 | 常州方楠医药技术有限公司 | Handkerchief wins the salt in XiLin, crystal formation and preparation method thereof |
| CN108623588A (en) * | 2017-03-24 | 2018-10-09 | 中国海洋大学 | A kind of tetracyclic and its preparation method and application containing lactams |
| CN108623581B (en) * | 2017-03-24 | 2021-10-22 | 中国海洋大学 | Method for preparing paninula compound |
| CN106962377A (en) * | 2017-05-02 | 2017-07-21 | 山东省农业科学院蔬菜花卉研究所 | Compound Q uinolactacide application |
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