CN1281609C - Compound with pine wood nematode killing activity with poison and use thereof - Google Patents
Compound with pine wood nematode killing activity with poison and use thereof Download PDFInfo
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- CN1281609C CN1281609C CN 200510010693 CN200510010693A CN1281609C CN 1281609 C CN1281609 C CN 1281609C CN 200510010693 CN200510010693 CN 200510010693 CN 200510010693 A CN200510010693 A CN 200510010693A CN 1281609 C CN1281609 C CN 1281609C
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Abstract
The present invention relates to compounds with activity of poisoning pine wood nematode and applications thereof, which belongs to the technical field of biotic pesticides. The active compounds are prepared from producing strains by using the methods of conventional solid fermentation and extracting separation. The producing strains are gliocladium roseum (Gr87), and are preserved in China Committee for Culture Collection of Microorganisms on October 9th, 2002 with the preservation number of CGMCCNo. 0807. The active compounds comprises 6 compounds. The compounds can be used to effectively poison the pine wood nematode, and can be used to prepare biotic pesticides for poisoning nematode in a single mode or a combined mode.
Description
Technical field:
The present invention relates to compound and application thereof that a class has pine wood nematode poisoning activity, belong to biological pesticide technical field.
Background technology:
The pine nematode of pine tree is by pine wood nematode (Bursaphelenchus xylophilus (Steiner ﹠amp; Buhrer) Nickle) colonize in a kind of especially big destructive disease of getting food nutrition in Pinus seeds (Pinus sp.) body and causing the rapid death of trees, belong to international important Quarantine Objects, classify as first of the forest disease and pest, be called as " smokeless hill fire ".This disease now has been distributed widely in Japan, the U.S., Korea S, Canada, Mexico, Greece, Portugal and China etc. since finding, be in the news in 1934 from 1905.Japan is used for this sick expenses for prevention and control and accounts for 93.6% of forest pest control expense every year, accounts for 20% of forestry gross investment, but still reach 100 ten thousand ms because of this disease loss timber every year
3About.Since China finds this disease in nineteen eighty-two, now expanded to ground such as Jiangsu, Zhejiang, Anhui, Guangdong, Shandong, Hubei, Shanghai, Hong Kong and Taiwan, area has taken place surpassed 7.3 * 10hm
2, dead pine tree 2 * 10
7Strain causes the massive losses on economy of forestry, the forest ecology and the havoc of natural landscape, and the pine forest of the vast normal region of China is constituted a serious threat.Since the eighties, the method for preventing and treating of pine wood nematode has been mainly contained:
1. use the communication media worm that can kill pine wood nematode---the sterilant Sumithion (MEP) of Monochamus alternatus (Monochamusalternatus), Tiguvon (MPP), carbaryl (NAC) etc.This characteristics of preventing and treating method are that the passive method of preventing and treating that vector is protected pine tree is killed in a kind of dependence, and it is the big generation of disease controlling effectively, and have the pharmaceutical chemicals of certain degree to pollute to ground vegetation.
2. (mesulfenphos tartalicacid) prevents and treats pine wood nematode directly to inject nematocides in the tree body.This method only is applicable to the protection rare tree species, and effect is undesirable, and big to the person poultry toxicity.
The method of control pine nematode is mainly controlled Monochamus alternatus based on spraying insecticide at present, but because the Monochamus alternatus imago phase is long, and resistance is strong, prevention effect is very undesirable.So far still do not work out the special-purpose agricultural chemicals of the high-efficiency low-toxicity that kills pine wood nematode of energy practical application, also not seeing has the double medicament of pine wood nematode and Monochamus alternatus or the research report of method controlled.
Summary of the invention:
The object of the present invention is to provide a class to derive from compound with pine wood nematode poisoning activity and the application thereof of fresh water fungi.
Production bacterial strain of the present invention was pink sticking broom mould (Gliocladium roseum) Gr87 bacterial strain, and this bacterial strain has been deposited in China Microbial Culture Preservation Commission common micro-organisms center, preserving number: CGMCC No.0807 on October 9th, 2002
The compound that a class of the present invention has pine wood nematode poisoning activity is the compound that extraction separation obtains 6 kinds of structural similitudies from the fermenting culture of producing bacterial strain, wherein compound 1 and 2 is a new compound, and the structure of these 6 kinds of compounds is (the following compound 1-6 that abbreviates as respectively) shown in following formula 1-6:
1 R
1＝OH R
2＝CH
3 x＝3
2 R
1＝OH R
2＝CH
3 x＝4
3 R
1＝H R
2＝CH
3 x＝2
4 R
1＝OH R
2＝CH
3 x＝2
5 R
1＝OH R
2＝CH
2CH
3 x＝2
6 R
1＝OH R
2＝CH(OH)CH
3 x＝2
The physico-chemical constant of active compound 1-6 of the present invention, hydrogen spectrum data and carbon spectrum data see Table 1 respectively, table 2 and table 3.
The physico-chemical constant of table 1. compound 1-6
| 1 | 2 | 3 | 4 | 5 | 6 | |
| Molecular weight | C 30H 28N 6O 6S 5 | C 30H 28N 6O 6S 6 | C 30H 28N 6O 5S 4 | C 30H 26N 6O 6S 4 | C 31H 30N 6O 6S 4 | C 31H 30N 6O 7S 4 |
| FAB-MS | 729 | 761 | 680 | 697 | 711 | 727 |
| [α]D (CHCl 3 or pyridine) | [α] D 18.0+ 553.6°(c 0.004532 g/mL in pyridine) | [α] D 18.0+ 555.8°(c 0.004365g/mL in pyridine) | [α] D 18.2+ 548.9°(c 0.004668g/mL in pyridine) | α] D 22+727.5° (c 0.1 in CHCl 3) | α] D 22+688.2 (c 0.1 in CHCl 3) | α] D 22+768.9 (c 0.1 in CHCl 3) |
| UV(MeOH or pyridine) | 261.3，255.6， 250.1，202.4 | 261.2，255.6， 250.2，202.4 | 299.0，261.4， 255.6，250.0， 202.4 | 240，303 | 241，305 | 242，301 |
| IR(KBr) | 3441，1664， 1608，1557， 1490，1480， 753 | 3430，1678， 1611，1552， 1483，1470，749 | 3451，1676， 1484，1379， 1095，748 | 3446，1669， 1580，1483， 750 | 3390，2923，1690， 1668，1610，1469， 1349，1302，1247， 1203，1093，1065， 756 | 3412，2924，1684， 1674，1608，1469， 1351，1303，1247， 1094，1068，765 |
Table 2. compound 1-6's
1HNMR (pyridine)
| C | 1 | 2 | 3 | 4 | 5 | 6 |
| 5a | 5.72s | 6.08s | 5.82s | 5.78s | 5.77s | 5.79s |
| 7 | 6.67d(7.8) | 6.65d(7.8) | 6.58m | 6.70d(7.8) | 6.72d(7.8) | 6.70d(7.8) |
| 8 | 7.12t (7.5，7.8) | 7.05t (7.5，7.8) | 6.98m | 7.12t (7.5，7.8) | 7.15t (7.5，7.8) | 7.10t (7.5，7.8) |
| 9 | 6.77t(7.5) | 6.61m | 6.66m | 6.79t(7.5) | 6.79t(7.5) | 6.80t(7.5) |
| 10 | 8.34(7.5) | 8.37d(7.5) | 6.98m | 8.28d(7.5) | 8.27d(7.5) | 8.28d(7.5) |
| 11 | 6.27s | 6.38s | 6.93s | 6.26s | 6.26s | 6.29s |
| 12 | 2.79s | 2.86s | 2.89s | 2.83s | 2.88s | 2.82s |
| 13 | 1.77s | 1.73s | 1.97s | 1.75s | 1.81s | 1.74s |
| 5a′ | 5.78s | 5.85s | 6.95s | 5.78s | 5.77s | 5.86s |
| 7′ | 6.72d(7.8) | 6.69d(7.8) | 6.58m | 6.70d(7.8) | 6.72d(7.8) | 6.68d(7.8) |
| 8′ | 7.09t (7.7) | 6.93t (7.7) | 6.98m | 7.12t (7.5，7.8) | 7.15t (7.5，7.8) | 7.07t (7.5.7.8) |
| 9′ | 6.69(7.5) | 6.61m | 6.66m | 6.79t(7.5) | 6.79t(7.5) | 6.80t(7.5) |
| 10′ | 8.17(7.6) | 8.12(7.7) | 6.98m | 8.28d(7.5) | 8.27d(7.5) | 8.31d(7.5) |
| 11′ | 6.39s | 6.08s | 3.33brs(15.0) 5.03brs(15.0) | 6.26s | 6.24s | 6.33s |
| 12′ | 3.01s | 2.87s | 2.87s | 2.83s | 2.88s | 2.82s |
| 13′ | 1.57s | 1.61s | 1.92s | 1.75s | 2.12m | 4.99q |
| 14′ | 1.25t(7.4) | 1.52d(6.2) |
The C of table 3. compound 1-6
13NMR (pyridine)
| C | 1 | 2 | 4 | 3 | 5 | 6 |
| 1 | 166.3s | 166.1s | 166.1s | 166.6s | 166.3s | 166.1s |
| 3 | 74.1s | 74.0s | 74.3s | 74.6s | 74.5s | 74.3s |
| 4 | 162.3s | 162.2s | 162.3s | 162.7s | 162.6s | 162.3s |
| 5a | 83.6d | 83.4d | 83.3d | 83.3d | 83.5d | 83.3d |
| 6a | 150.8s | 150.9s | 150.9s | 150.6s | 151.0s | 150.9s |
| 7 | 110.5d， | 110.3d | 110.3d | 109.0d | 110.5d | 110.3d |
| 8 | 130.9d | 130.0d | 130.1d | 129.9d | 130.3d | 130.1d |
| 9 | 119.5d | 119.4d | 119.4d | 118.3d | 119.5d | 119.3d |
| 10 | 128.8d | 128.6d | 128.6d | 129.3d | 128.7d | 128.6d |
| 10a | 130.9s | 130.8s | 130.8s | 129.6s | 130.9s | 130.8s |
| 10b | 67.4s | 67.5s | 67.5s | 65.6s | 67.6s | 67.5s |
| 11 | 82.6d， | 82.8d | 82.8d | 81.3d | 83.0d | 82.8d |
| 11a | 78.5s， | 78.8s | 78.5s | 77.7s | 78.7s | 78.5s |
| 12 | 26.9q | 27.2q | 26.9q | 27.2q | 27.2q | 26.9q |
| 13 | 17.5q | 17.5q | 17.6q | 18.3q | 17.8q | 17.6q |
| 1 | 168.6s | 167.4s | 166.1s | 165.5s | 167.2s | 167.4s |
| 3′ | 72.5s | 75.3s | 74.3s | 74.7s | 74.5s | 74.3s |
| 4′ | 164.9s | 164.5s | 162.3s | 162.5s | 161.8s | 162.1s |
| 5a′ | 82.0d | 84.2d | 83.3d | 82.0d | 83.6d | 83.5d |
| 6a′ | 153.8s | 151.6s | 150.9s | 150.8s | 150.1s | 150.8s |
| 7′ | 110.6d | 110.7d | 110.3d | 109.2d | 110.5d | 110.3d |
| 8′ | 130.1d | 128.8d | 130.1d | 129.9d | 130.3d | 130.1d |
| 9′ | 118.8d | 119.0d | 119.4d | 118.2d | 119.7d | 119.5d |
| 10′ | 129.7d | 129.1d | 128.6d | 129.3 | 128.8d | 128.7d |
| 10a′ | 128.2s | 131.1s | 130.8s | 131.1s | 130.9s | 130.9s |
| 10b′ | 65.51s | 67.5s | 61.3s | 67.6s | 67.5s | |
| 11′ | 85.6d | 82.8d | 45.8t | 83.0d | 82.8d | |
| 11a′ | 86.6d | 78.5s | 74.9s | 79.1s | 78.5s | |
| 12′ | 27.9q | 28.6q | 26.9q | 26.9q | 28.2q | 29.2q |
| 13′ | 21.2q | 23.2q | 17.6q | 17.7 | 25.1t | 67.2d |
| 14′ | 9.9q | 20.0q |
Active compound of the present invention is in the nematicide active testing of soaked with liquid method, be 36 hours in the treatment time, when concentration is 1.0mg/mL, compound 1-6 is respectively 62.4%, 63.5%, 54.2%, 53.4%, 44.6% and 49.7% to the lethality rate of pine wood nematode, and the methanol crude extract of the mixing solutions of compound 4 and 1 and compound 1-6 lethality rate to pine wood nematode under same test condition and test concentrations is 75.4% and 93.2%.As seen the equal pine wood nematode poisoning effectively of compound 1-6 can be used to prepare pesticide preparation alone or in combination; Simultaneously the mixture of the crude extract of active compound or different ratios has collaborative toxic action to this compounds of statement of facts that the cytotoxicity of pine wood nematode is higher than monomeric compound to pine wood nematode.
Therefore, compound of the present invention can be used as the application of preparation agricultural chemicals nematode killing agent.
Embodiment:
Embodiment 1: the separation preparation of compound 1-6
A. the seed culture of the pink sticking broom of fungi mould (Gliocladium roseum) Gr87:
The PDA substratum: potato 200g, glucose 20g, yeast extract 1.0g, glycerine 6.0g, agar 17g, water 1000mL makes the test tube slant, and the picking bacterial strain inserts the inclined-plane, cultivates 5 days for 28 ℃;
B. the mould solid fermentation of the pink sticking broom of fungi is cultivated:
Wheat substratum (preparation process is: wheat is dipped in 48h in the tap water, cleans then, drain clear water, be respectively charged in the triangular flask of 500cm, with cotton wrapping bottleneck 15psi sterilization twice down, each 40min).
The bacterial strain that slant culture is good is chosen into the solid fermentation substratum, leaves standstill in 25 ℃ of room temperatures and cultivates 30 days;
C. with the mould mycelium freeze-drying of above-mentioned cultured pink sticking broom, use randomly organic solvent (for example methyl alcohol, ethanol, propyl alcohol again, ethyl acetate, tetrahydrofuran (THF), acetonitrile) cold soaking extracts 4 times, spissated crude extract is absorbed in the solid absorbing material, and (natural materials of Fen Suiing for example is as kaolin, clay, talcum, quartz etc.; Or the synthetic materials of pulverizing, as microgranular silica gel, aluminum oxide etc.) on, in silicagel column, carrying out chromatographic separation, sample on the dry method is the eluent gradient elution with chloroform/acetone=0-50%.
D. collect the chloroform/acetone elutriant of 1%-10%, concentrating under reduced pressure.
E. above-mentioned concentrated solution is carried out chromatographic separation once more in silicagel column, sample on the dry method is the eluent gradient elution with sherwood oil/acetone=10-80%.
F. collect on the TLC plate sulfuric acid colour developing and be the sherwood oil of orange-yellow 20-30%/acetone elutriant, concentrated Chu's yellow crystal is the mixture shown in the structural formula.Through Sephedex-LH20 and HPLC chromatography separating for several times, can obtain compound 1-6 again.
Embodiment 2:
Adopt the liquid immersed method to detect the monomer and the active test of mixture nematicide of The compounds of this invention.
1, test with medicament:
To test with sample and be dissolved in a small amount of organic reagent DMSO earlier, add the sample test solution that certain density Tween solution prepares concentration as shown in table 4 respectively again.In this solution, the final concentration of the final concentration of DMSO＜3%, tween＜5 ‰.The aqueous solution that in addition DMSO of same concentrations is dissolved in the tween 20 that contains 0.5% (V/V) in contrast.
2. cultivation of pine wood nematode and preparation
The cultural method of pine wood nematode B.xylophilus: Botrytis cinerea (Botrytis cinerea) is inserted the PDA flat board, under 25 ℃, be cultured to and cover with flat board, insert a substratum that has B.xylophilus, be cultured to mycelia and disappear under 25 ℃, nematode is covered with flat board.
The substratum that will be loaded with nematode during use is chosen, and is put in the nematode separator, and after with sterilized water nematode being washed out, centrifugal concentrating is prepared into nematode suspension (about 500 every milliliter).
3. test method
The The compounds of this invention dilution is supplied reagent liquid for 400ppm, 200ppm, 100ppm concentration, it is the culture dish of 5cm that soup 2ml is placed diameter, the suspension that adds living nematode 20ul (about 300) nematode again behind the mixing is positioned over culture dish in 25 ℃ the incubator gently.Respectively at the mortality ratio of checking the calculating nematode in 12,24 and 48 hours.And under binocular microscope, observe observation line polypide wall changing conditions.
The method of identifying nematode death is: add 1-5 and drip 5%NaCl solution in handling flat board, observe after 2 minutes, dead worm is stiff, and the worm that lives is then curled or twisting.
Mortality ratio %=dead wire borer population/bus borer population * 100
With the test soln that does not add sample is contrast, and whole experiment triplicate is got three mean value calculation and gone out average mortality.
4. test-results
Table 4. specimen is to the cytotoxicity result of pine wood nematode
| Sample test number | Sample test concentration | The different treatment time (hour) interior lethality rate (%) | ||
| 12 | 24 | 36 | ||
| Compound 1 | 1.0mg/mL 0.8mg/mL 0.5mg/mL | 0 0 0 | 53.2 27.8 15.6 | 62.4 42.1 21.3 |
| Compound 2 | 1.0mg/mL 0.8mg/mL 0.5mg/mL | 0 0 0 | 57.8 32.1 21.3 | 63.5 34.7 27.8 |
| Compound 3 | 1.0mg/mL 0.8mg/mL 0.5mg/mL | 0 0 0 | 48.5 30.6 19.6 | 54.2 34.8 25.4 |
| Compound 4 | 1.0mg/mL 0.8mg/mL 0.5mg/mL | 0 0 0 | 46.7 36.5 27.9 | 53.4 34.5 30.1 |
| Compound 4 and compound 1 | 1.0mg/mL 0.8mg/mL 0.5mg/mL | 0 0 0 | 70.4 52.8 39.1 | 75.4 54.9 42.3 |
| Compound 5 | 1.0mg/mL 0.8mg/mL 0.5mg/mL | 0 0 0 | 36.7 29.4 19.4 | 44.6 33.7 21.6 |
| Compound 6 | 1.0mg/mL 0.8mg/mL 0.5mg/mL | 0 0 0 | 46.2 32.8 22.6 | 49.7 44.5 28.7 |
| Methanol extract | 1mg/mL 0.5mg/mL | 64.5 52.3 | 88.5 57.4 | 93.2 60.2 |
| The chloroform/acetone enriched material of 1%-10% | 1mg/mL 0.5mg/mL | 58.7 32.4 | 80.6 52.0 | 85.4 57.6 |
| The sherwood oil of 20-30%/acetone enriched material | 1mg/mL 0.5mg/mL | 54.2 25.9 | 73.1 35.8 | 80.3 44.2 |
| Contrast | 3.2 | 3.8 | 4.1 | |
The result shows: compound 1-6 of the present invention has toxic action preferably to pine wood nematode, can be used for preparing the agricultural chemicals nematode killing agent and uses; Simultaneously the mixture of the crude extract of active compound or different ratios has collaborative toxic action to this compounds of statement of facts that the cytotoxicity of pine wood nematode is higher than monomeric compound to pine wood nematode.
Claims (4)
1, a kind of compound with pine wood nematode poisoning activity by producing bacterial strain, adopts the method for conventional solid fermentation and extraction separation to obtain, and it is characterized in that:
A. producing bacterial strain is pink sticking broom mould (Gliocladium roseum) Gr87, preserving number: CGMCCNo.0807;
B. the structural formula of this compound is:
Wherein: R
1=OH, R
2=CH
3, x=3;
Or: R
1=OH, R
2=CH
3, x=4.
2, a kind of composition with pine wood nematode poisoning activity by producing bacterial strain, adopts the method for conventional solid fermentation and extraction separation to obtain, and it is characterized in that:
A. the production bacterial strain of said composition is pink sticking broom mould (Gliocladium roseum) Gr87, preserving number: CGMCC No.0807;
B. said composition contains the compound 1-6 of following formula:
Compound 1:R
1=OH, R
2=CH
3, x=3;
Compound 2:R
1=OH, R
2=CH
3, x=4;
Compound 3:R
1=OH, R
2=CH
3, x=2;
Compound 4:R
1=H, R
2=CH
3, x=2;
Compound 5:R
1=OH, R
2=CH
2CH
3, x=2;
Compound 6:R
1=OH, R
2=CH (OH) CH
3, x=2.
3, the application of the described active compound of claim 1 is characterized in that this active compound is used for the preparation of pine wood nematode pesticide preparation extremely.
4, the application of the described composition of claim 2 is characterized in that said composition is used for the preparation of pine wood nematode pesticide preparation extremely.
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| CN 200510010693 CN1281609C (en) | 2005-03-16 | 2005-03-16 | Compound with pine wood nematode killing activity with poison and use thereof |
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|---|---|---|---|
| CN 200510010693 CN1281609C (en) | 2005-03-16 | 2005-03-16 | Compound with pine wood nematode killing activity with poison and use thereof |
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| CN1281609C true CN1281609C (en) | 2006-10-25 |
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| CN101805699B (en) * | 2009-02-17 | 2013-05-29 | 中国科学院微生物研究所 | Method for preparing gliocladicillin C and application thereof |
| WO2015035504A1 (en) * | 2013-09-11 | 2015-03-19 | Bee Vectoring Technology Inc. | Isolated strain of clonostachys rosea for use as a biological control agent |
| CN105506002B (en) * | 2015-12-22 | 2018-10-30 | 云南大学 | A kind of compound and its application |
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