CN1944427B - Novel macro-molecular compound, its preparing method and use - Google Patents
Novel macro-molecular compound, its preparing method and use Download PDFInfo
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- CN1944427B CN1944427B CN2005100303170A CN200510030317A CN1944427B CN 1944427 B CN1944427 B CN 1944427B CN 2005100303170 A CN2005100303170 A CN 2005100303170A CN 200510030317 A CN200510030317 A CN 200510030317A CN 1944427 B CN1944427 B CN 1944427B
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Abstract
The present invention provides one kind of compound, SPRI-1218, in new structure as shown. The present invention also provides the process of culturing Streptomyces caviscabies CGMCC No. 1369 and preparing the compound. The compound may be used as farm germicide, and has excellent preventing and controlling effect on gray mold of cucumber, strawberry, grape, etc, gourd powdery mildew, downy mildew and other fungus diseases of crops.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of macromolecular cpd-SPRI-1218, its preparation method and application.
Background technology
As everyone knows, because the protection of ecotope is increased day by day, the research and development of new compound are faced with more relevant toxicity, to the security of natural biology and to the restriction of the factors such as friendly of ecotope.Therefore, make the also corresponding raising of new compound development difficulty, present generalized situations is that whenever synthetic 100,000 left and right sides compounds could occur one and possess commercial kind.In order to improve the efficient of new compound initiative, external major company sets about from the source one after another, adopts various new technical meanses to come design as much as possible and acquisition compound to find lead compound.These methods mainly contain computer aided design (CAD) compound structure, the synthetic a large amount of compounds of combination synthetic method, biotechnology and obtain natural compounds, existing structure are modified and simulated multiple means such as natural compounds structure, and diverse ways all has many successful examples.
In recent years, utilize microbial metabolites to find new compound, and then the technology that research and development become medicine (comprising medicine, agricultural chemicals, veterinary drug) is widely used, as as medical antibiotic penicillin, Streptomycin sulphate etc., the Avrmectin etc. of jingganmycin, the multiple acarid of control and the noctuid of the rice sheath blight disease of preventing and treating is arranged aspect agricultural, for animals.Usually, seek new compound, often from multiple soil, isolate microorganism and produce microbial metabolites with certain purposes by microbial metabolites, then to these meta-bolitess make with extra care respectively, evaluation and Application and Development.
Summary of the invention
Purpose of the present invention just is to provide a kind of new macromolecular cpd-SPRI-1218.
Another object of the present invention is to provide a kind of preparation method of SPRI-1218.
Another purpose of the present invention is to provide a kind of SPRI-1218 to be used for the application of disinfectant use in agriculture.
The present inventor separates from the geographic soil in Zhangjiajie, China Hunan Province and has obtained a strain streptomycete, cultivate through this bacterial strain being carried out preliminary laboratory ferment, be the preliminary biological activity determination test of carrying out of target to the fermenting culture that obtains with entomogenous fungi grass etc. then, find that crop gray mold, cucurbits powdery mildew, oidium etc. such as Plant diseases, particularly cucumber that this culture causes fungal pathogens due to illness, strawberry, eggplant have good prevention effect.
By the deep research of carrying out, be streptomyces Streptomycescaviscabies with its category attribution to above-mentioned streptomycete.And submit Chinese common micro-organisms preservation center preservation on May 16th, 2005, preserving number is CGMCCNo.1369.
Simultaneously,, set out by the culture of above-mentioned gained for the active substance in the fermenting culture of clear and definite mentioned microorganism,
Also make with extra care the pure product that obtained this active compound by some appropriate means separation and Extraction, and it is numbered SPRI-1218.According to UV spectrum (UV), mass spectrum (MS), hydrogen spectrum (
1HNMR), carbon spectrum (
13CNMR) etc. detection means is carried out molecular structure to this active compound and is identified and analyze, and finds that compound S PRI-1218 is a new macromolecular cpd that does not appear in the newspapers.Determine that this compound molecule formula is C
39H
64N
4O
16, its molecular structure is as follows:
Relevant materialization data are as follows:
Molecular formula: C
39H
64N
4O
16
Molecular weight: 844
Chemical name
Chinese: 14-methyl-15-2-olefin(e) acid { 2-(3-acetamido-4,5-dihydroxyl-6-methylol-tetrahydrochysene-pyrans-2-oxygen)-5-[6-(2,4-dioxy-3,4-dihydro-2H-pyrimidine-1)-4,5-dihydroxyl-tetrahydropyrans-3-oxygen]-4-hydroxyl-6-methylol-tetrahydrochysene-pyrans-3} acid amides
English: 14-Methyl-pentadec-2-enoic acid{2-(3-acetylamino-4,5-dihydroxy-6-hydroxymethyl-tetrahydro-pyran-2-yloxy)-5-[6-(2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-4,5-dihydroxy-tetrahydro-pyran-3-yloxy]-4-hydroxy-6-hydroxymethyl-tetrahydro-pyran-3-yl}-amide
Physico-chemical property: normal temperature is white powder crystallization, water soluble, methyl alcohol, ethanol, acetone, ethyl acetate, chloroform, acetonitrile etc. down.
Above-mentioned extraction treating process mainly utilizes compound and impurity to carry out in the difference of aspects such as solubleness, ionic bond power, partition ratio, absorption avidity and molecular weight.These methods can be used separately, also can suitably cooperate or use repeatedly.Specifically, compound S PRI-1218 is present in fermented liquid and the mycelium simultaneously, after organic solvent broken wall extractions such as mycelium acetone, ethanol, after the fermented liquid merging, with organic solvent extractions such as propyl carbinol, isopropylcarbinol, isoamyl glycol, ethyl acetate, isoamyl acetate, N-BUTYL ACETATEs, organic phase obtains crude extract after concentrating; Crude extract passes through silica gel column chromatography again, just can obtain flaxen half highly finished product.Utilize compound S PRI-1218 and the small amount of impurities different solubility in different solvents at last, carry out recrystallization and obtain pure product.
In order to adapt to the needs of industrialization, the present inventor has carried out further research and development to the fermentative preparation of compound S PRI-1218 and the application on disinfectant use in agriculture.
At first, the generation bacterium of this streptomyces has been carried out the further research of fermentation culture conditions, to improve its fermentation unit.Find to make compound S PRI-1218 of the present invention by conventional production of antibiotics method.Its cultural method both can be deep-layer liquid and had cultivated, and also can be solid culture.In order to help payable cultivation, above-mentioned production bacterium should be inoculated on the substratum, the gas mixing that works of going forward side by side is mixed.
Nutrition source in the substratum be there is no special regulation, can make and contain carbon source, nitrogenous source and other nutrition sources that is usually used in microorganism culturing in the substratum.Wherein carbon source can be starch, dextrin, glucose, glycerine, sucrose, N.F,USP MANNITOL etc., and nitrogenous source can be meat peptone, soybean cake powder, peanut powder, yeast, meat extract, rice bran, corn steep liquor, wheat skin, ammonium salt, urea, nitrate and other organic or inorganic nitrogenous compounds.Other nutrition sources can suitably add some inorganic salts, for example metal-salts such as salt, phosphoric acid salt and potassium, calcium, manganese, iron.Can add in case of necessity that some move, plant, the mineral wet goods is as defoamer.
Culture condition such as temperature, PH, time be there is no strict restriction, be as the criterion with the production that is suitable for producing bacterium, and to select the highest condition of compound output for well.For example, the PH scope of substratum can be 6-8, with near neutral for well; Culture temperature is at 20-35 ℃, and air flow is with (ventilation ratio: refer to that per minute passes through the volume of air of nutrient solution and the ratio of nutrient solution volume) between the ventilation ratio 1: 0.3 to 1 to 4.The component of these substratum, PH, culture temperature, aeration condition etc. all should carry out suitable adjustment according to practical situation, to obtain best effect.
Secondly, the biological activity of compound S PRI-1218 of the present invention has been carried out deep research.Find that it can be used to prevent and treat various crop pests as disinfectant use in agriculture on agricultural, and it has prevention and therapeutic action concurrently to crop pest.Specifically, but control of leaf spot of corn, gray mold, rice sheath blight disease, rice blast, black spot, pears black heart, black soya bean disease, reed-pope wind instrument stem wilt, black rot of pear, target, cotton wilt, melon anthrax, bacterial blight of rice.
At last, to of the present invention be that the disinfectant use in agriculture of effective ingredient is studied with SPRI-1218.Preparation can use equally during this sterilant known agricultural chemicals in this technical field general various carriers such as solid phase, liquid phase and emulsifying dispersant, and can be mixed with formulation arbitrarily such as granule, pulvis, emulsion, wettable powder, tablet, microcapsule, finish, sprays, suspension concentrate.Simultaneously, in various preparations, generally some auxiliary agents can be suitably added,, but alkaline auxiliary can not be added as dispersion agent, emulsifying agent, wetting agent, permeate agent, spreader-sticker, tackiness agent, defoamer, whipping agent, tackifier, stablizer etc.
The proportioning of effective ingredient in the various preparations can suitably increase and decrease according to different application targets.In general, the effective ingredient scope of pulvis, wettable powder, granule, tablet is usually at 5-70%, and the effective ingredient scope of emulsion, finish, suspension concentrate, sprays is at 2-30%, and microcapsule is at 10-80%.
Description of drawings
Fig. 1 is the ultraviolet absorpting spectrum of compound S PRI-1218, shows that this compound has absorption at the 258nm place.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of compound S PRI-1218.
Fig. 3 is the hydrocarbon graph of a relation of multikey (HMBC) of the hydrocarbon relevant spectrum of nucleus magnetic resonance of compound S PRI-1218.
Fig. 4 is the single quantum relation figure (HSQC) of heteronuclear of the hydrocarbon relevant spectrum of nucleus magnetic resonance of compound S PRI-1218.
Fig. 5 is the mass spectrum of compound S PRI-1218.
Embodiment
Below by specific embodiment, further specify the present invention.
The starting material that below relate to are all commercially available obtaining, and the concentration that relates to is weight concentration.
One, preparation embodiment
The preparation of embodiment 1, compound S PRI-1218
Ratio with glucose 2%, starch 1%, soybean cake powder 2%, sodium-chlor 0.2%, extractum carnis 0.1%, dipotassium hydrogen phosphate 0.05% is made substratum, and PH is adjusted to 7.2, sterilization.The bacterial classification inoculation of streptomycete 1218 Streptomyces caviscabiesCGMCC No.1369 in this substratum, was cultivated 36-40 hour down at 28 ± 2 ℃.
With this culture is seed, ratio with 5-20% is inoculated in the fermentation culture of forming with glucose 2%, starch 1%, soybean cake powder 2.5%, sodium-chlor 0.2%, extractum carnis 0.1%, dipotassium hydrogen phosphate 0.05%, and 28 ± 2 ℃ of aeration-agitations were cultivated 90-96 hour.
With 100 liters of cultured fermented liquids, behind Plate Filtration, mycelium soaked 5 hours with 50 liter of 80% acetone, and concentrating under reduced pressure merges with supernatant liquor after removing acetone, and 120 liters obtain amalgamation liquid; The concentrating under reduced pressure amalgamation liquid obtains 12 liters of concentrated solutions, with 16 liters of isoamyl glycol extractions three times.The concentrating under reduced pressure organic phase obtains 270 gram oily matter I; With 500 ml methanol dissolving oily matter I, remove by filter insolubles.Concentrating under reduced pressure is removed methyl alcohol, obtains crude extract---65 gram tawny oily matter II; The crude extract II that obtains is dissolved in the 650ml methyl alcohol, with solution add silicagel column (350 * 30mm) chromatographies, use methyl alcohol: ten different gradient washing lotions of chloroform=10: 90～90: 10 (weight ratio) are carried out wash-out, obtain the elutriant of ten different componentss; Respectively these ten elutriants are carried out biological activity then and follow the tracks of to detect (method is with embodiment 10), will have the elutriant of fungicidal activity to collect and combine, concentrating under reduced pressure is sloughed solvent and is obtained 18 gram faint yellow solid III; Crystallization in the ethanolic soln of 50-80% obtains 12 gram pale solid IV, and recrystallization in the ethanolic soln of 50-80% obtains 11 gram white solid V once more.
Embodiment 2: the ultraviolet absorpting spectrum of compound S PRI-1218 is measured
Getting the compound V0.5mg that obtains among the embodiment 1 is dissolved in the 50ml methyl alcohol, getting 3ml adds in the cell, make blank with methyl alcohol, at ultraviolet full wavelength scanner instrument (UV-2501PC, day island proper Tianjin company) measures on, measure wavelength from 400nm to 200nm, obtain the ultraviolet absorpting spectrum of this compound, as seen from Figure 1, ultraviolet shows that this compound has absorption at the 258nm place.
Embodiment 3: the nuclear magnetic resonance hydrogen spectruming determining of compound S PRI-1218
Getting the compound V 10mg that obtains among the embodiment 1, be dissolved in the 0.5ml deuterochloroform, is the primary standard of measuring chemical shift with tetramethylsilane TMS, in BRUKERAC 400 nuclear magnetic resonance analyser (Switzerland, BRUKER company) enterprising line scanning obtains this compound proton nmr spectra shown in Figure 2
1H NMR shows 10 groups of different H, and its integration shows that its ratio is 2: 1: 1: 2: 1: 9: 2: 12: 1: 40.
Embodiment 4: the hydrocarbon relevant spectrum of the nucleus magnetic resonance of compound S PRI-1218 (HMBC and HSQC) is measured
Get the compound V 10mg that obtains among the embodiment 1, be dissolved among the 0.5mlDMSO, with tetramethylsilane TMS is the primary standard of measuring chemical shift, in BRUKER AC 600 nuclear magnetic resonance analyser (Switzerland, BRUKER company) enterprising line scanning, obtain the hydrocarbon relation of multikey (HMBC) (Fig. 3) and the single quantum relation of heteronuclear (HSQC) (Fig. 4).
Embodiment 5: the mass spectroscopy of compound S PRI-1218
Get the compound V25mg that embodiment 1 obtains and be dissolved in the 1.5ml deuterochloroform, measure on high frequency plasma mass spectrograph (ICPM-8500, day island proper Tianjin company), obtain the mass spectrum of this compound, see Fig. 5, the result of atlas analysis is as follows:
MS, m/z:230,244,308,428,456,486,534,557,612,646,724,755,867 (sodium salts), 883 (sylvite), 945 (triethylamine salts).
Result by Fig. 5 shows that the molecular weight of the compound of the present invention's preparation is 867-23=883-39=945-101=844.
The compound that can draw the present invention's preparation according to above analytical results has following structural formula:
Chemical name is: 14-methyl-15-2-olefin(e) acid { 2-(3-acetamido-4,5-dihydroxyl-6-methylol-tetrahydrochysene-pyrans-2-oxygen)-5-[6-(2,4-dioxy-3,4-dihydroxyl-2H-pyrimidine-1)-4,5-dihydroxyl-tetrahydropyrans-3-oxygen]-4-hydroxyl-6-methylol-tetrahydrochysene-pyrans-3} acid amides.
The molecular weight that calculates according to above structural formula is 844, matches with the result of embodiment 5.
Two, Application Example
Embodiment 6, contain the wettable powder preparation of compound S PRI-1218
Get 40 parts of III, IV that embodiment 1 obtains or V (weight ratio, down with) and 2 parts of sodium lignosulfonates, 4 parts draw back powder, 2 parts for the treatment of compound LS and 52 parts of diatomite and mix, pulverize, promptly get 100 parts of content and be 40% wettable powder.
Embodiment 7, contain the missible oil preparation of compound S PRI-1218
Get I or II28 part that embodiment 1 obtains and mix, promptly get 100 parts of content and be 28% missible oil with 10 parts of ethylene glycol, 20 parts of dimethyl formamides, 10 parts of dimethylbenzene and 32 parts of ethanol.
Embodiment 8, be applied to prevent gray mold
To be diluted to institute's predetermined concentration by the prepared former medicine of embodiment 1 or female medicine or embodiment 6,7 prepared preparation, evenly be sprayed on the leaf period cucumber seedling, treat to inoculate the gray mold germ in cucumber leaves central authorities after soup is done, handle drug concentration for every group and establish four groups of repetitions.Establish one group of clear water in addition as blank.Under 20 ℃, preserved moisture 72 hours, and checked incidence, calculate prevention effect.Test-results shows just can reach 78.6% preventive effect when the effective concentration of SPRI-1218 is 6.25 mg/litre.Test-results sees Table 1.
CK
1Disease index after the dispenser of-blank district
PT
1Disease index after the dispenser of-chemicals treatment district
Stage division:
0 grade: no scab;
1 grade: lesion area accounts for whole leaf area below 5%;
3 grades: lesion area accounts for whole leaf area 6%-10%;
5 grades: lesion area accounts for whole leaf area 11%-20%;
7 grades: lesion area accounts for whole leaf area 21%-50%;
9 grades: lesion area accounts for whole leaf area more than 50%.
Table 1, compound S PRI-1218 prevention gray mold of cucumber effect
| Handle drug concentration | Prevention effect (%) |
| 100 mg/litre | 100 |
| 50 mg/litre | 100 |
| 25 mg/litre | 98.6 |
| 12.5 mg/litre | 86.4 |
| 6.25 mg/litre | 78.6 |
| 3.125 mg/litre | 42.2 |
| 1.5625 mg/litre | 0 |
| Blank | -- |
Embodiment 9, be applied to prevent and treat graw mold of tomato
To be diluted to the concentration (effective ingredient is respectively 25,12.5,6.25,3.125 mg/litre) of being scheduled to by embodiment 6,7 prepared preparation, but compare medicament with 50% Sukeling wet-milling, 300 mg/litre simultaneously, clear water is made blank.Adopt the atomizer even spraying, 50 liters every mu of amount of liquid medicine.Test-results shows, every mu with about effective constituent 0.3 gram, just can reach the prevention effect 70% or more, just can reach similar prevention effect (the prevention effect method of calculation are with embodiment 8) and use every mu of need of medicament 150 at present always more than restraining.Test-results such as table 2.
Table 2, control graw mold of tomato test-results
The fungicidal spectrum of embodiment 10, compound S PRI-1218 is measured
To be diluted to institute's predetermined concentration by embodiment 1 prepared IV or V, indoor employing culture dish method (except that bacterial blight of rice with pot-culture method) test result such as table 3:
Table 3, SPRI-1218 minimum inhibitory concentration test-results
| Sequence number | Pathogenic bacteria | Minimum inhibitory concentration (mg/l) |
| 1 | Corn southern leaf blight | ＜0.05 |
| 2 | Gray mold | ＜0.05 |
| 3 | Rice sheath blight disease | ＜0.05 |
| 4 | Rice blast | ＜0.05 |
| 5 | Black spot | 0.1 |
| Sequence number | Pathogenic bacteria | Minimum inhibitory concentration (mg/l) |
| 6 | The pears black heart | 0.2 |
| 7 | The black soya bean disease | 0.4 |
| 8 | The reed-pope wind instrument stem wilt | 6.25 |
| 9 | Black rot of pear | 6.26 |
| 10 | Target | 6.25 |
| 11 | Cotton wilt | 12.5 |
| 12 | Melon anthrax | 12.5 |
| 13 | Candida albicans | 25 |
| 14 | Saccharomyces sake | 25 |
| 15 | Bacterial blight of rice | 50 |
Compound S PRI-1218 of the present invention is the brand-new macromolecular compound of structure, can be used for a kind of novel disinfectant use in agriculture with this compound, and this medicament has remarkable effect to multiple diseases such as control crop gray molds especially. Compare with existing disinfectant use in agriculture, the disinfectant use in agriculture take compound of the present invention as active ingredient has the following advantages:
1, dosage is few, and when equal prevention effect, every mu of effective ingredient consumption SPRI-1218 is the 0.3-1 gram, and other existing medicament needs the 20-500 gram;
2, the scope of application is wide, and SPRI-1218 can prevent and treat gray mold resistance bacterium and sensitive bacteria and other 15 kinds of diseases, and medicament commonly used often can only be prevented and treated a few disease at present;
3, good stability, safety and low toxicity.
When 4, utilizing the present invention to prepare to contain the disinfectant use in agriculture of compound S PRI-1218, can take full advantage of the agricultural byproducts such as soybean cake powder, corn flour, feather meal, turn waste into wealth, so it possesses the low characteristics of production cost.
Claims (7)
1. compound is characterized in that structural formula is as follows:
2. the preparation method of compound according to claim 1 is characterized in that cultivating earlier streptomycete Streptomyces caviscabies CGMCC No.1369, carries out separation and Extraction again from these cultures and obtains compound
3. application of compound according to claim 1 is characterized in that, described compound is as disinfectant use in agriculture.
4. application as claimed in claim 3 is characterized in that, the formulation of described sterilant comprises: missible oil or wettable powder.
5. application as claimed in claim 4 is characterized in that, in the described formulation, the content of compound described in the missible oil is 2-30wt%, and the content of compound described in the wettable powder is 5-70wt%.
6. application as claimed in claim 4 is characterized in that, described sterilant formulation is that the described compound of claim 1 and carrier and auxiliary agent are mixed and make.
7. as application of compound as described in each among the claim 3-6, it is characterized in that, be used to prevent and treat following crop pest: corn southern leaf blight, gray mold, rice sheath blight disease, rice blast, black spot, pears black heart, black soya bean disease, reed-pope wind instrument stem wilt, black rot of pear, target, cotton wilt, melon anthrax, bacterial blight of rice.
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| CN105820974A (en) * | 2016-03-30 | 2016-08-03 | 原巍俊 | Fermenting method of biocontrol actinomycetes and application |
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| Tsvetanova, Billyana,et.al.Liquid Chromatography-Electrospray MassSpectrometryofTunicamycin-Type Antibiotics..Analytical Biochemistry289 2.2001,147-156. * |
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