CN1970550A - Carabrane type sesquiterpene lactone compound with sterilization activity separated from Carpesium macrocephalum Franch.et Sav and its application - Google Patents
Carabrane type sesquiterpene lactone compound with sterilization activity separated from Carpesium macrocephalum Franch.et Sav and its application Download PDFInfo
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Abstract
The invention discloses a calacane-typed sesquiterpene lactone compoundwith sterilizing activity separated from leptosin and application in the pesticide agent to prevent plant disease induced by plant pathogenic fungi, which comprises the following parts: carpesia lactone ketone, carpesia lactone alcohol, 13-methoxy carpesia lactone alcohol, 11, 13-dihydromethoxy carpesia lactone ketone and calacane-3(4)-olefin-12,8 beta-lactone.
Description
Technical field
The present invention relates to the tool Fungicidal active compound, particularly from the isolating bactericidal carabrane type sesquiterpene lactones compound of Herba Carpesii macrocephali and this compound thereof as sterilant in the application aspect the controlling plant diseases.
Background technology
Phytopathogen has very big harm to the growth of plant, and all cause tremendous loss to agriculture production every year.Generation for controlling plant diseases, minimizing is by its loss that causes, people have worked out the compound of big measurer sterilization and bacteriostatic activity, be used to prevent and treat Plant diseases that causes by plant pathogenic fungi and the generation that alleviates Plant diseases, Chinese patent application 200410073073.X as the applicant discloses a kind of bactericidal compound and uses thereof.
Herba Carpesii macrocephali is the smart platymiscium of composite family daybreak, Nuisanceless Pesticide Research Service Center, Xibei Agroforestry Science and T is in botanical fungicide research, find that it has very high inhibition activity to plant pathogenic fungi, and apply for a patent " Herba Carpesii macrocephali sterilant and preparation method thereof ", number of patent application 02139350.8.On this basis, the applicant has carried out systematic study to the bacteriostatic active ingredients in the Herba Carpesii macrocephali, has therefrom obtained having the compound of bacteriostatic activity.
Summary of the invention
The objective of the invention is to, provide a kind of from isolating bactericidal carabrane type sesquiterpene lactones compound of Herba Carpesii macrocephali and uses thereof.
In order to realize above-mentioned task, the present invention takes following technical solution:
Bactericidal carabrane type sesquiterpene lactones compound from the Herba Carpesii macrocephali extraction, it is characterized in that, this bactericidal carabrane type sesquiterpene lactones compound comprises: carpesia-lactone ketone, carpesia-lactone alcohol, 13-methoxyl group carpesia-lactone alcohol, 11, the two hydrogen carpesia-lactone ketone of 13-and carabrane-3 (4)-alkene-12,8 β-lactone, its molecular structure is respectively:
Carpesia-lactone ketone:
Carpesia-lactone alcohol:
13-methoxyl group carpesia-lactone alcohol:
11, the two hydrogen carpesia-lactone ketone of 13-:
The structural formula of carabrane-3 (4)-alkene-12,8 β-lactone is as follows:
Separating the concrete grammar that obtains carpesia-lactone ketone from the Herba Carpesii macrocephali plant is: exsiccant Herba Carpesii macrocephali plant sample is pulverized, used industrial methanol extraction, methyl alcohol is reclaimed in distillation, and enriched material is the total medicinal extract of Herba Carpesii macrocephali alcohol extract.This medicinal extract is suspended in water, with chloroform extraction 2 times, get chloroform extraction phase medicinal extract, by silica gel column chromatography, sample on the dry method, sherwood oil acetone (8: 1) wash-out, elutriant is concentrated into half, leaves standstill, and has crystallization to separate out, use the sherwood oil acetone recrystallization, get white, needle-shaped crystals and be carpesia-lactone ketone.
Carpesia-lactone ketone (compound 1) is the main chemical compositions of the smart platymiscium of composite family daybreak, and normal temperature is colourless needle crystal down, m.p.90-92 ℃, be soluble in chloroform, ether, acetone and other organic solvent at normal temperatures, and molecular formula is C
15H
20O
3, belong to carabrane type sesquiterpene lactones compounds.
The applicant is a raw material with carpesia-lactone ketone further, it is synthetic that it is derived, and therefrom filters out the higher compound of fungicidal activity, i.e. carpesia-lactone alcohol, 13-methoxyl group carpesia-lactone alcohol, 11, the two hydrogen carpesia-lactone ketone of 13-and carabrane-3 (4)-alkene-12,8 β-lactone.
Through the applicant above-claimed cpd is carried out fungicidal activity and measure, prove that this compound can be used in the pesticide preparation application that preparation prevents and treats the Plant diseases that is caused by plant pathogenic fungi.
Description of drawings
Fig. 1 is the synthetic route chart of carpesia-lactone alcohol (compound 2) and 13-methoxyl group carpesia-lactone alcohol (compound 3);
Fig. 2 is 11, the synthetic route chart of the two hydrogen carpesia-lactone ketone (compound 4) of 13-;
Fig. 3 is the synthetic route chart of carabrane-3 (4)-alkene-12,8 β-lactone (compound 5).
The present invention is described in further detail below in conjunction with accompanying drawing.
Embodiment
1, the synthetic route of carpesia-lactone ketone (compound 1) separation and derivative thereof
The preparation of synthesis material (carpesia-lactone ketone): get Herba Carpesii macrocephali and pulverize, use industrial methanol extraction, reclaim methyl alcohol, get the total medicinal extract of alcohol extract, medicinal extract is suspended in water, use chloroform extraction 2 times, get chloroform extraction phase medicinal extract, by silica gel column chromatography, sample on the dry method, sherwood oil acetone (8: 1) wash-out, elutriant is concentrated into half, leaves standstill, and has crystallization to separate out, use the sherwood oil acetone recrystallization, get white, needle-shaped crystals.
1.1 carpesia-lactone alcohol (compound 2) and 13-methoxyl group carpesia-lactone alcohol (compound 3) is synthetic
The carpesia-lactone ketone derivatives is dissolved in behind a little acetone on the wet method sample carries out rapid column chromatography and separate, TLC detects the back and merges same composition.8 to 27 cuts merge after further column chromatography obtains carpesia-lactone alcohol (compound 2), 531mg, and productive rate 53.5% gets 13-methoxyl group carpesia-lactone alcohol (compound 3) 103mg, productive rate 10.4% after the 30-41 cut merges.
1.211, the two hydrogen carpesia-lactone ketone (compound 4) of 13-synthetic
The synthetic route of compound 4 takes by weighing 248mg (1mmol) carpesia-lactone ketone and is dissolved in the 20ml methyl alcohol referring to Fig. 2, adds 50mg (2.083mmol) Mg powder again, and 10 ℃ of stirring reaction 2h behind the pressure reducing and steaming MeOH, use NH
4The unreacted Mg of Cl solution cancellation, mixture CHCl
3Extract 3 times, organic phase washes (3 * 50ml) with water.The pressure reducing and steaming solvent gets the light oyster white oily liquids, is dissolved in a little acetone and carries out the rapid column chromatography separation afterwards.2 to 13 cuts merge the further recrystallization in back and get monomeric compound 11, two hydrogen carpesia-lactone ketone (compound 4) 176.3mg of 13-, productive rate 70.9%.
1.3 carabrane-3 (4)-alkene-12,8 β-lactone (compound 5) is synthetic
The synthetic route of compound 5 is referring to Fig. 3, takes by weighing 40mg (1mmol) sodium borohydride and 248mg (1mmol) carpesia-lactone ketone joins in the round-bottomed flask of 50ml, with the dissolving of 10ml THF solution.Nitrogen protection, ice bath are stirred and are dripped 250mg (0.984mmol) I down
2Be dissolved in the solution that 10ml THF is made into, dropwise in the 10min, continue reaction 30min, the pressure reducing and steaming solvent gets orange red oily liquids, is dissolved in a little acetone and carries out column chromatography for separation fast.The 11-18 cut merges after further recrystallization gets monomeric compound 5 (carabrane-3 (4)-alkene-12,8 β-lactone 105mg, productive rate 42.3%).
2, structural formula of compound and physico-chemical property thereof and spectral data
2.1 the structural formula of compound
Carpesia-lactone ketone:
Carpesia-lactone alcohol:
13-methoxyl group carpesia-lactone alcohol:
11, the two hydrogen carpesia-lactone ketone of 13-:
The structural formula of carabrane-3 (4)-alkene-12,8 β-lactone is as follows:
2.2 compound physico-chemical property and spectral data
Carpesia-lactone ketone (compound 1): colourless rib shape crystal (ethyl acetate), m.p=90-92 ℃, IR (KBr) v
MaxCm
-1: 1765 (r-lactone), 1735,1690 (C=C), 1650,1370,1255,1150,820;
1HNMR(CDCl
3)δ
H：6.24(1H，d，J＝2.8Hz，H-13)，5.56(1H，d，J＝2.4Hz，H-13’)，4.79(1H，ddd，J＝6，9，11.4Hz，H-8)，3.15(1H，ddddd，J＝7，9，13Hz，H-7)，2.16(3H，s，H-14)，1.08(3H，s，H-15)，0.45(1H，m，H-5)，0.37(1H，m，H-1)。
Carpesia-lactone alcohol (compound 2): colourless oil liquid, m/z:250 (M
+),
1H-NMR (CDCl
3) δ
H: 6.25 (1H, d, 2.6Hz, H-13), 5.56 (1H, d, 2.4Hz, H-13), 4.80 (1H, ddd, 6,9,11.5HzH-8), 3.84 (1H, tq, 6,6Hz, H-4), 3.16 (1H, ddd, 7,9,13Hz, H-7), 1.21 (3H, d, 6Hz, H-15), 1.08 (3H, s, H-14), 0.45 (1H, m, H-5), 0.38 (1H, m, H-1).
13-methoxyl group carpesia-lactone alcohol (compound 3): colourless oil liquid, m/z:282 (M
+),
1H-NMR (CDCl
3) δ
H: 3.36 (3H, s, H-13), 3.71 (1H, d, H-11), 3.60 (1H, tq, H-4) 2.57 (1H, m, H-7), 4.80 (1H, ddd, H-8), 1.27 (3H, d, H-15), 1.06 (3H, s, H-14), 0.45 (1H, m, H-5), 0.32 (1H, m, H-1).
11, the two hydrogen carpesia-lactone ketone (compound 4) of 13-: colourless needle crystal, m/z:250 (M
+),
1H-NMR (CDCl
3) δ
H: 1.30 (3H, d, H-13), 1.54 (1H, m, H-7), 2.90 (1H, m, H-11), 4.76 (1H, ddd, H-8), 2.57 (2H, tq, H-3), 2.19 (3H, s, H-15), 1.03 (3H, s, H-14), 0.43 (1H, m, H-5).
Carabrane-3 (4)-alkene-12,8 β-lactone (compound 5): colourless oil liquid, m/z:234 (M
+),
1H-NMR (CDCl
3) δ
H: 1.04 (3H, d, H-13), 1.54 (1H, m, H-7), 4.92 (1H, ddd, H-2), 4.75 (1H, ddd, H-8), 1.20 (3H, s, H-14), 1.34 (3H, s, H-15), 0.46 (1H, m, H-5), 0.33 (1H, m, H-1).
3, the compound biocide preparation is prevented and treated the application of the Plant diseases that is caused by plant pathogenic fungi
Carabrane type sesquiterpene lactones compound comprises carpesia-lactone ketone and derivative carpesia-lactone alcohol thereof, 13-methoxyl group carpesia-lactone alcohol, 11, the two hydrogen carpesia-lactone ketone of 13-and carabrane-3 (4)-alkene-12,8 β-lactone, can make the sterilant of various preparation forms, spraying is suitable for, and is used for the control of Plant diseases.The weight percent of each material is in the various formulations:
| Formulation | Carabrane type sesquiterpene lactones compound % | Filler or solvent % | Tensio-active agent % |
| Wettable powder | 20～90 | 0～74 | 1～10 |
| |
5～50 | 40～95 | 5～15 |
| |
10～50 | 40～84 | 1～20 |
By the various preparations that carabrane type sesquiterpene lactones compound is formed, filler wherein can be one or more mixtures in the material known altogether of this area staff such as white carbon black, wilkinite, silicon bath soil; Solvent can be methyl alcohol, ethanol, (different) propyl alcohol just, ethyl acetate, one or more mixtures in the material that this area staff such as aromatic hydrocarbon know altogether; Tensio-active agent can be that those skilled in the art know and one or more mixture of commonly used all kinds of surfactants altogether, as calcium dodecylbenzene sulphonate, vinylbenzene acid Soxylat A 25-7, ethoxylated dodecyl alcohol, octyl phenol polyoxy ethyl ether draws back one or more mixture of tensio-active agents such as powder, saponin, xylogen, Sulfonates material, alkyl sulfonates material, lauryl alcohol.
Compound and the preparation thereof that this patent is related to set forth the control of plant disease effect by the following examples.
4, the biological activity determination of each compound
Choose 22 kinds of pathogenic bacterias altogether as for the examination bacterial classification, list in table 4-1 for the examination bacterial classification.All provide by Nuisanceless Pesticide Research Service Center, Xibei Agroforestry Science and T for the examination bacterial classification.
The test plant host material: wheat Triticum aestivum, Shan-451 susceptible variety is provided by Xibei Univ. of Agricultural ﹠ Forest Science ﹠ Technology wheat center; Tomato Lycopersicon esculentum fruit picks up from Yang Ling Yangchuan village township plastic greenhouse; Cucumber (grind No. seven in Tianjin), commercial; Corn (Shan 9) is susceptible variety, is provided by agricultural college of Xibei Univ. of Agricultural ﹠ Forest Science ﹠ Technology.
Standard medicament: 15% triadimefon WP (Tianmen, Hubei insecticide factory), 50% Sukeling WP (SUMITOMO CHEMICAL chemical industry Co., Ltd.).
Table 4-1 is for the examination pathogenic bacteria
Table 4-1 Agruculture fungi for test
| Classification | Pathogenic bacteria is bright | Latin is learned bright |
| Deuteromycotina Ascomycotina Mastigomycotina Basidiomycotina | Alternaria brassicae botrytis cinerea Fulvia fulva tomato early blight bacterium cucumber fusarium axysporum cucumber anthracnose verticillium dahliae cotton-wilt fusarium cotton rhizoctonia solani pumpkin wilt rice blast fungus withered germ of water-melon rhizoctonia cerealis tobacco brown spot pathogen dothiorella gregaria bacterium Exserohilum turcicum southern corn leaf blight Valsa mali apple anthrax bacteria dry rot of apple bacterium fusarium graminearum gaeumannomyces graminis Sclerotinia sclerotiorum wheat powdery mildew Phytophthora capsici germ bacterium of downy mildew of cucumber Rhizoctonia solani Kuhn | Alternaria brassicae Botrytis cinerea Fulvia fulva Alternaria solani Fusarium oxysporum f.sp.cucumerinum Colletotrichum lagenarium Verticillium dahliae Fusarium oxysporum f.sp.vasinfectum Rhizoctonia solani Fusarium bulbigenum Pyricularia oryzae Fusarium oxysporium f.sp.niveum Rhizoctonia cerealis Alternaria longipes Dothiorella gregaria Exserohilum turcicum Bipolaris maydis Valsa mali Glomerella cingulata Botryosphaeria berengeriana de Not Gibberella zeae Geaumannomyces graminis Sclerotinia sclerotiorum Erysiphe graminis Phytophthora capsici Pseudoperonospora cubensis(Berk.et Cert.)Rostr Thanatephorus cucumeris |
Growth rate method
Compound adopts growth rate method to the inhibiting mensuration of pathogenic bacteria mycelial growth, establishes acetone and blank, and every kind is a processing for examination bacterium one ware, and every processing repeats for three times.Measure colony diameter with the right-angled intersection method, calculate inhibiting rate (during the calculating inhibiting rate be contrast with the acetone treatment) by formula 4-1 and formula 4-2:
Colony diameter (mm)=bacterium colony mean diameter-4 (bacterium cake diameter) 4-1
The spore germination method
Compound to the inhibiting mensuration of germ spore germination adopt sessile drop method (method is planted disease research method [M] with reference to Fang Zhongda. Beijing: agriculture press. third edition .1995).In the test, after contrast sprouting (be sprouting with long short diameter one half of spore that surpasses of spore germ tube, if having little time microscopy, can add one in 0.5% mercuric chloride and fix) rate is greater than 80%, the sprouting situation of all processing of record check; If the contrast germination rate is lower than 80%, this test is cancelled and is reformed.Adopt formula (4-3) and (4-4) calculating spore germination inhibiting rate.
Pot experiment
Prevention effect to wheat powdery mildew, cucumber downy mildew adopts the pot experiment method to carry out.Concrete grammar is as follows:
10～15 wheats of every nutrition pot sowing or 2～3 cucumber seeds of vernalization,, treat that wheat and cucumber grow to two leaves during the phase (cucumber is a true leaf), treat with provide protection and test in hot-house culture.Carry out dispenser with conventional spray, 3 repetitions are established in each processing, establish the contrast of solvent control and clear water.
Adopt the spore dithering to carry out the inoculation of wheat white powder, it is 18 ± 1 ℃ that the wheat after the processing places temperature, cultivates under illumination/dark=8h/16h condition, according to disease a situation arises classification investigation, calculates and respectively handles disease index and prevention effect.
Gather the sick leaf of the former bacterium of band cucumber downy mildew from the field, cultivate 24h with preserving moisture after the flushing with clean water, with the pathogenic bacteria spore on the sick leaf under the writing brush brush, be configured to that 30～50 spore suspensions carry out spray inoculation under 10 * 10 power microscope visuals field, the cucumber after the processing is placed in high humidity, about 20 ℃ the environment and cultivates.
Therapeutic action at first connects the germ spore on not processed seedling, spray medicine behind the 24h again and handle, cultivate.Check test result behind 6～8d; Provide protection is at first sprayed medicine to seedling and is handled, and connects bacterium behind the 24h again, checks blade incidence and record, statistical results behind cultivation 6～8d.
The grade scale of wheat powdery mildew (is unit with the blade) ([114] Fang Zhong reaches. plant disease research method [M]. and Beijing: agriculture press. third edition .1995);
0 grade: the blade face does not have scab;
1 grade: have only a small amount of limited mycelium on the blade, no spore;
2 grades: the blade face mycelia scale of construction is medium, and some spores are arranged, and organizes slight necrosis and chlorisis;
3 grades: mycelial amount is medium or a lot, and the amount that spore produces is limited, and some necrosis and chlorisis are arranged;
4 grades: sorus is very big, produces a large amount of spores, does not have necrosis.
The grade scale of cucumber downy mildew (is unit with the blade) is as follows:
0 grade: anosis;
1 grade: lesion area accounts for below 5% of one-piece blade area;
2 grades: lesion area accounts for 6～25% of one-piece blade area;
3 grades: lesion area accounts for 26%～50% of one-piece blade area;
4 grades: lesion area accounts for more than 50% of one-piece blade area.
Calculate disease index and prevention effect by formula 5-5 and formula 5-6:
The tissue test method
The test of pesticide effectiveness to graw mold of tomato adopts tomato young fruit method to carry out.Concrete grammar is: the tamato fruit of not executing any bactericidal agent that will gather from the field, earlier with the clear water washes clean, dry, get 75% ethanol wiping fruit surface again with the absorbent cotton libation at an ancient wedding ceremony, carry out sterilising treatment.Sting out the zone of infecting of the about 5mm of diameter on the tamato fruit surface with inoculating needle, in order to infecting of ash arrhizus bacteria.Make the bacterium cake with the punch tool of diameter 4mm, the bacterium cake is tipped upside down on the tamato fruit surface.Divide protection and treat two kinds of methods processing.Provide protection is sprayed directly on fruit surface for adopt spray method will dilute good medicament earlier on the tomato surface, treats promptly to begin to connect bacterium after soup dries.Therapeutic action begins to connect bacterium for earlier the bacterium cake being connected on the tamato fruit surface behind the 4h.The cultivation of preserving moisture, check result behind the 3d.By the method among the 4.1.2.1 result is carried out statistical study.
4.1 5 kinds of compounds such as carpesia-lactone ketone are to the inhibition effect of phytopathogen mycelial growth
Adopt growth rate method to test carpesia-lactone ketone, carpesia-lactone alcohol, 13-methoxyl group carpesia-lactone alcohol, 11, the two hydrogen carpesia-lactone ketone of 13-and carabrane-3 (4)-alkene-12,5 kinds of compounds such as 8 β-lactone the results are shown in Table 4-1-1～table 4-1-5 to the virulence of several pathogenic bacterias.
Table 4-1-1 carpesia-lactone ketone is to the inhibition virulence (4d) of 12 kinds of pathogenic bacteria mycelial growths
| For the examination pathogenic bacteria | Toxicity regression line (Y=) | EC 50(95％CL) (mg/L) | Relation conefficient |
| Dry rot of apple bacterium B.berengeriana cotton-wilt fusarium F.oxysporum f.sp.vasinfectum leaf muld of tomato bacterium F.fulva *Botrytis cinerea B.cinerea Phytophthora capsici germ P.capsici cotton rhizoctonia solani R.solani pumpkin wilt F.bulbigenum cucumber anthracnose C.lagenarium fusarium graminearum G.zeae withered germ of water-melon F.oxysporium f.sp.niveum rhizoctonia cerealis R.cerealis gaeumannomyces graminis G.graminis | 2.9454+1.4780x 1.2103+2.0368x 2.3328+1.6243x 1.7347+2.1988x 1.3582+2.7650x 1.1003+2.5622x 0.6123+2.8062x 3.2909+1.1092x 2.5956+1.7271x 2.6299+1.6243x 3.0859+1.7373x 3.8821+1.6208x | 24.5542(16.6021～36.3152) 72.5487(57.6370～91.3182) 43.8569(32.6323～58.9424) 30.552(19.8285～47.0748) 20.7543(16.8793～25.5188) 33.2666(28.0202～39.4953) 36.6097(31.5517～42.4785) 34.7439(20.6758～58.3840) 24.6726(20.3009～29.9858) 28.7881(21.7669～38.0740) 12.6409(9.1983～17.3718) 4.8947(3.2842～7.2951) | 0.9598 0.9926 0.9805 0.9971 0.9695 0.9956 0.9887 0.9784 0.9815 0.9139 0.9219 0.9894 |
Annotate: band "
*" person is the 3d test-results.
Table 4-1-2 carpesia-lactone alcohol is to the inhibition virulence (4d) of 9 kinds of pathogenic bacteria mycelial growths
| For the examination pathogenic bacteria | Toxicity regression line (Y=) | EC 50(95％CL) (mg/L) | Relation conefficient |
| Cucumber anthracnose C.lagenarium *Botrytis cinerea B.cinerea Fulvia fulva F.fulva tomato early blight bacterium A.solani Phytophthora capsici germ P.capsici Valsa mali V.mali cotton-wilt fusarium F.oxysporum f.sp. vasinfectum cucumber anthracnose C.lagenarium rhizoctonia cerealis R.cerealis gaeumannomyces graminis G.graminis rice blast fungus P.oryzae | -1.2031+2.6905x 1.1552+1.6396x -0.4183+2.4772x 2.6549+1.2814x 0.2774+3.4810x 2.4806+1.2798x 2.5679+1.2293x -1.3442+2.8373x 0.8192+2.1423x 1.4294+3.5795x 1.0474+2.2980x | 202.1013(173.3711～235.5926) 221.2609(128.8787～379.8640) 198.4500(104.5314～226.63.08) 67.6224(32.2070～141.9811) 22.7330(11.9703～43.1726) 93.0132(66.0117～131.0594) 95.1512(67.1340～134.8609) 172.1967(137.9540～214.9391) 89.4369(50.5756～158.1584) 9.9428(6.6809～14.7973) 52.4808(31.2486～88.1396) | 0.9916 0.9615 0.9705 0.9674 0.9538 0.9735 0.9873 0.9884 0.9983 0.9706 0.9354 |
Table 4-1-3 13-methylol carpesia-lactone alcohol is to the inhibition virulence (4d) of 8 kinds of pathogenic bacteria mycelial growths
| For the examination pathogenic bacteria | Toxicity regression line (Y=) | EC 50(95％CL) (mg/L) | Relation conefficient |
| Cotton-wilt fusarium F.oxysporum f.sp.cucumerinum leaf muld of tomato bacterium F.fulva *Botrytis cinerea B.cinerea Phytophthora capsici germ P.capsici cucumber anthracnose C.lagenarium fusarium graminearum G.zeae rhizoctonia cerealis R.cerealis gaeumannomyces graminis G.graminis | 2.6546+1.1427x 0.1742+2.1568x 0.7064+1.8991x 3.3371+1.3438x 1.6975+1.4987x 0.6211+2.0684x 2.1401+1.6544x 4.1256+1.1064x | 112.8656(51.2063～248.7711) 172.7263(113.6597～262.6102) 182.3106(114.5279～290.2103) 17.2764(8.9562～33.3259) 159.8232(88.6715～288.0683) 130.9261(82.0177～208.9993) 53.5338(31.2835～91.6097) 6.1704(2.7260～13.9671) | 0.9487 0.9556 0.9797 0.9940 0.9728 0.9584 0.9747 0.9110 |
Table 4-1-4 13-methyl carpesia-lactone ketone is to the inhibition virulence (4d) of 8 kinds of pathogenic bacteria mycelial growths
| For the examination pathogenic bacteria | Toxicity regression line (Y=) | EC 50(95％CL) (mg/L) | Relation conefficient |
| The withered water chestnut germ of cotton F.oxysporum f.sp.cucumerinum leaf muld of tomato bacterium F.fulva *Botrytis cinerea B.cinerea Phytophthora capsici germ P.capsici cucumber anthracnose C.lagenarium fusarium graminearum G.zeae rhizoctonia cerealis R.cerealis gaeumannomyces graminis G.graminis | 1.3472+2.0327x 1.5537+2.0187x 2.6004+1.5586x 1.8349+2.0063x 3.2909+1.1092x 1.5876+2.2001x 3.1437+1.5428x 4.1800+0.9121x | 62.6717(40.5444～96.8751) 50.9550(32.8646～79.0032) 34.6376(19.6273～61.1273) 18.2458(24.3182～58.7754) 37.8602(20.6758～58.3840) 35.5620(23.7810～53.1793) 15.9651(8.9944～28.3381) 7.9428(3.0024～20.9177) | 0.9989 0.9604 0.9377 0.9745 0.9784 0.9606 0.9757 0.9666 |
Table 4-1-5 carabrane-3 (4)-alkene-12,8 β-lactone is to the inhibition virulence (4d) of 8 kinds of pathogenic bacteria mycelial growths
| For the examination pathogenic bacteria | Toxicity regression line (Y=) | EC 50(95％CL) (mg/L) | Relation conefficient |
| The cotton tangerine germ F.oxysporum f.sp.cucumerinum leaf muld of tomato bacterium F.fulva that withers *Botrytis cinerea B.cinerea Phytophthora capsici germ P.capsici cucumber anthracnose C.lagenarium fusarium graminearum G.zeae rhizoctonia cerealis R.cerealis gaeumannomyces graminis G.graminis | 0.3367+0.3877x -1.6128+3.4074x 1.3827+1.9318x 1.0534+1.9998x -1.3930+2.9636x 1.4399+3.0741x 2.2276+1.6826x 3.1463+1.2502x | 89.7536(61.9470～130.0421) 87.2415(66.8170～113.9092) 74.5535(46.5727～119.3454) 94.0775(59.7376～148.1578) 143.6116(105.7277～195.0698) 124.4085(92.5442～167.2443) 44.4332(25.8847～76.2731) 30.3831(14.6868～62.8544) | 0.9459 0.9527 0.9537 0.9659 0.9774 0.9482 0.9501 0.9551 |
4.2 5 kinds of compounds are to the inhibition effect of phytopathogen spore germination
Adopt sessile drop method to test the virulence of 5 kinds of compounds such as above-mentioned carpesia-lactone ketone, carpesia-lactone alcohol, the results are shown in Table 4-2-1～table 4-2-5 several pathogenic bacteria spore germinations.
Table 4-2-1 carpesia-lactone ketone is to the inhibition virulence of 7 kinds of pathogenic bacteria spore germinations
| For the examination pathogenic bacteria | Toxicity regression line (Y=) | EC 50(95％CL) (mg/L) | Relation conefficient |
| Cucumber anthracnose C.lagenarium Exserohilum turcicum E.turcicum Fulvia fulva F.fulva botrytis cinerea B.cinerea fusarium graminearum G.zeae tobacco brown spot pathogen A.alternata bacterium of downy mildew of cucumber P.cubensis | 2.7492+2.6880x 1.4849+1.5028x 2.0898+1.8446x 1.4174+2.5178x -2.4225+3.0880x 0.9074+2.1787x 1.3802+2.6944x | 6.8765(6.0920～7.7620) 218.2795(191.143～249.268) 37.8173(33.8036～42.3076) 26.4789(25.0903～27.9445) 253.3247(238.2644～269.3369) 75.5976(69.0411～82.7766) 22.0523(18.5908～26.6447) | 0.9998 0.9954 0.9985 0.9994 0.9952 0.9983 0.9346 |
Table 4-2-2 carpesia-lactone alcohol is to the inhibition virulence of 7 kinds of pathogenic bacteria spore germinations
| For the examination pathogenic bacteria | Toxicity regression line (Y=) | EC 50(95％CL) (mg/L) | Relation conefficient |
| Cucumber anthracnose C.lagenarium Fulvia fulva F.fulva apple anthrax bacteria G.cingulata Exserohilum turcicum E.turcicum botrytis cinerea B.cinerea fusarium graminearum G.zeae bacterium of downy mildew of cucumber P.cubensis | 2.2024+2.1164x 1.6690+2.2175x 2.2116+2.0034x 1.8123+1.9683x -1.1101+3.7352x 0.5296+3.0451x 0.5802+2.8396x | 20.9837(18.9053～23.2906) 31.7784(28.6154～35.2910) 24.6486(22.0099～27.6036) 41.6467(28.0195～66.2204) 43.2328(25.8847～76.2731) 29.3804(18.1258～36.0324) 36.0159(19.2926～56.4412) | 0.9960 0.9927 0.9984 0.9822 0.9315 0.9846 0.9399 |
Table 4-2-3 13-methylol carpesia-lactone alcohol is to the inhibition virulence of 6 kinds of pathogenic bacteria spore germinations
| For the examination pathogenic bacteria | Toxicity regression line (Y=) | EC 50(95％CL) (mg/L) | Relation conefficient |
| Cucumber anthracnose C.lagenarium Exserohilum turcicum E.turcicum Fulvia fulva F.fulva botrytis cinerea B.cinerea fusarium graminearum G.zeae bacterium of downy mildew of cucumber P.cubensis | 2.2052+1.9643x 1.8041+1.4095x 2.0646+1.6826x 2.8638+1.3514x -1.3241+2.5046x -1.9605+4.0085x | 26.4717(24.2636～28.8807) 185.1256(97.1785～352.6654) 55.5415(32.3559～95.2314) 38.0875(19.4221～74.6909) 334.9705(233.0919～481.3776) 54.5060(43.4619～68.3566) | 0.9597 0.9601 0.9501 0.9335 0.9653 0.9753 |
Table 4-2-4 13-methyl carpesia-lactone ketone is to the inhibition virulence of 6 kinds of pathogenic bacteria spore germinations
| For the examination pathogenic bacteria | Toxicity regression line (Y=) | EC 50(95％CL) (mg/L) | Relation conefficient |
| Cucumber anthracnose C.lagenarium Exserohilum turcicum E.turcicum Fulvia fulva F.fulva botrytis cinerea B.cinerea fusarium graminearum G.zeae bacterium of downy mildew of cucumber P.cubensis | 2.3119+1.6742x 2.7341+1.6826x 2.3518+1.5955x 1.6594+1.8873x 0.3619+2.2113x 1.5704+1.7761x | 40.3273(36.0802～45.0743) 22.2166(12.9424～38.1366) 45.6848(25.8596～80.7090) 58.8866(36.3672～95.3602) 125.1240(83.0006～188.6797) 85.2980(51.1703～142.1870) | 0.9523 0.9501 0.9719 0.9419 0.9679 0.9773 |
Table 4-2-5 carabrane-3 (4)-alkene-12,8 β-lactone is to the inhibition virulence of 6 kinds of pathogenic bacteria spore germinations
| For the examination pathogenic bacteria | Toxicity regression line (Y=) | EC 50(95％CL) (mg/L) | Relation conefficient |
| Cucumber anthracnose C.lagenarium Exserohilum turcicum E.turcicum Fulvia fulva F.fulva botrytis cinerea B.cinerea fusarium graminearum G.zeae bacterium of downy mildew of cucumber P.cubensis | 3.1959+1.1067x 4.0875+1.1491x 3.7452+1.1568x 1.8500+2.0259x 2.53 76+1.6050x 1.1569+2.2671x | 42.6702(35.7076～50.9904) 6.2253(2.8213～13.7362) 12.1522(5.5457～26.6288) 25.8800(22.9316～26.1398) 34.2125(19.4085～60.3083) 49.5623(33.2062～73.9749) | 0.9139 0.9449 0.9772 0.9881 0.9403 0.9708 |
4.3 5 kinds of compounds such as carpesia-lactone ketone are to the prevention effect of 3 kind of plant diseases
4.3.1 potted plant prevention effect to wheat powdery mildew
Each compound is mixed with 10% missible oil, adopts the greenhouse pot culture method to measure its drug effect, the results are shown in Table 4-3-1 wheat powdery mildew.
5 kinds of compounds such as table 4-3-1 carpesia-lactone ketone are to the potted plant test of pesticide effectiveness result (8d) of wheat powdery mildew
| Reagent agent | Concentration (mg/L) | Provide protection | Therapeutic action | ||
| Disease index | Preventive effect (%) | Disease index | Preventive effect (%) | ||
| Clear water control solvent contrast triadimefon Triadimefon carpesia-lactone ketone carpesia-lactone alcohol 13-methylol carpesia-lactone alcohol 13-methyl carpesia-lactone ketone carabrane-3 (4)-alkene-12,8 β- |
0 0 150 500 1000 500 1000 500 1000 500 1000 500 1000 | 83.95 83.30 23.00 45.48 26.49 50.16 32.24 57.31 45.67 40.31 29.65 45.63 35.13 | - - 72.6a 45.4c 68.2a 39.8cd 61.3ab 31.2d 45.2c 51.6bc 64.4a 45.2c 57.8b | 90.89 85.46 22.09 42.65 25.21 50.30 28.13 50.35 39.65 43.86 32.14 50.21 26.78 | - - 75.7a 50.1c 70.5a 37.6e 67.1ab 41.1d 53.6c 48.7cd 62.4b 41.2d 68.7a |
Annotate: 1. data are 3 multiple mean values in the table; 2. the drug effect of compound such as carpesia-lactone ketone is calculated and is adopted solvent control, the drug effect of triadimefon to calculate to use the clear water contrast; 3. in the preventive effect hurdle, be illustrated in the variance analysis (Duncan ' s method) significant difference on 0.05 level with the different lowercase persons of mark behind the column of figure.
4.3.2 potted plant prevention effect to cucumber downy mildew
Each compound is mixed with 10% missible oil, adopts the greenhouse pot culture method to measure its drug effect, the results are shown in Table 4-3-2 cucumber downy mildew.
5 kinds of compounds such as table 4-3-2 carpesia-lactone ketone are to the potted plant test of pesticide effectiveness result (6d) of cucumber downy mildew
| Reagent agent | Concentration (mg/L) | Provide protection | Therapeutic action | ||
| Disease index | Preventive effect (%) | Disease index | Preventive effect (%) | ||
| Clear water control solvent contrast fosetyl aluminium phosethyl-Al carpesia-lactone ketone carpesia-lactone alcohol 13-methylol carpesia-lactone alcohol 13-methyl carpesia-lactone ketone carabrane-3 (4)-alkene-12,8 β- |
0 0 2000 1000 2000 1000 2000 1000 2000 1000 2000 1000 2000 | 75.29 73.10 28.15 41.45 26.46 45.10 29.39 48.10 37.79 53.44 47.00 40.72 33.70 | - - 62.6a 43.3c 63.8a 38.3c 59.8a 34.2d 48.3b 26.9d 35.7cd 44.3bc 53.9ab | 64.98 60.42 26.04 38.91 23.38 41.87 26.16 44.35 30.04 46.89 38.55 40.84 32.45 | - - 59.9a 35.6c 61.3a 30.7d 56.7a 26.6d 38.7c 22.4d 36.2c 32.4cd 16.3b |
Annotate: 1. data are 3 multiple mean values in the table; 2. the drug effect of compound such as carpesia-lactone ketone is calculated and is adopted the see drug effect of aluminium of solvent control, second to calculate and use the clear water contrast; 3. in the preventive effect hurdle, be illustrated in the variance analysis (Duncan ' s method) significant difference on 0.05 level with the different lowercase persons of mark behind the column of figure.
4.3.3 prevention effect to graw mold of tomato
Adopt the fruit needle punching to measure its drug effect, the results are shown in Table 4-3-3 graw mold of tomato.
5 kinds of compounds such as table 4-3-3 carpesia-lactone ketone are to the prevention effect (3d) of graw mold of tomato
| Reagent agent tested compounds | Concentration c oncentration (mg/L) | Provide protection Protective effect | Therapeutic action Curative effect | ||
| Scab diameter Diameter (mm) | Preventive effect (%) Efficacy | Scab diameter Diameter (mm) | Preventive effect (%) Effect | ||
| Solvent control Solvent ck Sukeling Procymidone carpesia-lactone ketone carpesia-lactone alcohol 13-methylol carpesia-lactone alcohol 13-methyl Carabrone carabrane-3 (4)-alkene-12,8 β- |
0 500 500 1000 500 1000 500 1000 500 1000 500 1000 | 36.21 8.80 17.82 13.22 22.49 16.40 30.42 25.53 18.54 13.87 25.93 20.89 | - 75.7 50.8 63.5 37.9 54.7 16.0 29.5 48.8 61.7 28.4 42.3 | 36.89 12.80 22.17 18.22 32.32 22.69 32.91 27.93 21.95 17.41 27.89 23.76 | - 65.3 39.9 50.6 12.4 38.5 10.8 24.3 40.5 52.8 24.4 35.6 |
5, the preparation of the various preparations of each compound
The preparation of embodiment 1:20% carpesia-lactone ketone wettable powder.In cone-type mixer, add the carpesia-lactone ketone 20kg that is crushed to about 200 orders, the white carbon black 50kg of commercially available commodity filler, wilkinite 20kg, and draw back powder 5kg, saponin 5kg.Fully mixed, can make 20% carpesia-lactone ketone wettable powder 100kg.Dispersed in the water of preparation, stable, the cold and hot storage stability of diluent meets the commercially available agricultural chemical preparation and must ask.
The preparation of embodiment 2:50% carpesia-lactone ketone wettable powder.The former medicinal powder of 50kg carpesia-lactone ketone is broken to 300 orders, take by weighing the white carbon black 30kg of commodity filler, sodium lignosulfonate 15kg, ethoxylated dodecyl alcohol 5kg, add abundant mixing evenly in the mixing machine, can make 100kg50% carpesia-lactone ketone wettable powder.Dispersed in the water of preparation, stable, the cold and hot storage stability of diluent meets the commercially available agricultural chemical preparation and must ask.
The preparation of embodiment 3:5% carpesia-lactone ketone missible oil.With 5kg carpesia-lactone ketone, be dissolved in the 85kg ethyl acetate, vinylbenzene acid Soxylat A 25-7 10kg joins in the 200L reactor, stirs 0.5 hour under 40～50 ℃ of temperature, promptly makes 100kg5% carpesia-lactone ketone missible oil.The water dispersible of missible oil, diluent stability, cold and hot storage stability meet the commercially available agricultural chemical preparation and must ask.
The preparation of embodiment 4:40% carpesia-lactone ketone missible oil.In the 200L reactor,, be dissolved in the mixed solvent of 15kg ethyl acetate and 30kg chloroform 40kg carpesia-lactone ketone, add vinylbenzene acid Soxylat A 25-7 10kg again, octyl phenol polyoxy ethyl ether 5kg stirred 0.5 hour under 40～50 ℃ of temperature, promptly made 100kg40% carpesia-lactone ketone missible oil.The water dispersible of missible oil, diluent stability, cold and hot storage stability meet the commercially available agricultural chemical preparation and must ask.
The preparation of embodiment 5:10% carpesia-lactone alcohol microemulsion.Take by weighing the former medicine 10kg of carpesia-lactone alcohol, be dissolved in the 20kg Virahol, add the 5kg calcium dodecylbenzene sulphonate again, 10kg octyl phenol polyoxy ethyl ether, mixed under high-speed stirring, be heated to about 40 ℃; Drip deionized water 55kg under the high-speed stirring, the rate of addition of control water remains on about 40 ℃ temperature; Water droplet adds and finishes, and is warming up to 50 ℃, stirs 1 hour, makes 10% carpesia-lactone alcohol microemulsion 100kg.Stability of formulation, outward appearance etc. meet the requirement of commodity preparation.
The preparation of embodiment 6:20%13-methoxyl group carpesia-lactone alcohol microemulsion.Take by weighing the former medicine 20kg of 13-methoxyl group carpesia-lactone alcohol, be dissolved in the 20kg ethyl acetate, add the 10kg calcium dodecylbenzene sulphonate again, 10kg vinylbenzene acid Soxylat A 25-7, mixed under high-speed stirring, be heated to about 40 ℃; Drip deionized water 40kg under the high-speed stirring, the rate of addition of control water remains on about 40 ℃ temperature; Water droplet adds and finishes, and is warming up to 50 ℃, stirs 1 hour, makes 20%13-methoxyl group carpesia-lactone alcohol microemulsion 00kg.Stability of formulation, outward appearance etc. meet the requirement of commodity preparation.
Embodiment 7:40%11, the preparation of the two hydrogen carpesia-lactone ketone wettable powders of 13-.In cone-type mixer, adding is crushed to 11 about 200 orders, the two hydrogen carpesia-lactone ketone 40kg of 13-, and the white carbon black 20kg of commercially available commodity filler, wilkinite 20kg, and draw back powder 5kg, xylogen 15kg.Fully mixed, can make 40%11, the two hydrogen carpesia-lactone ketone wettable powder 100kg of 13-.Dispersed in the water of preparation, stable, the cold and hot storage stability of diluent meets the commercially available agricultural chemical preparation and must ask.
The preparation of embodiment 8:30% carabrane-3 (4)-alkene-12,8 β-Nei emulsifiable concentrate.In the 200L reactor, with 30kg carabrane-3 (4)-alkene-12,8 β-lactone, be dissolved in the 55kg methyl alcohol, add vinylbenzene acid Soxylat A 25-7 5kg again, octyl phenol polyoxy ethyl ether 10kg stirred 0.5 hour under 40～50 ℃ of temperature, promptly make 100kg30% carabrane-3 (4)-alkene-12,8 β-Nei emulsifiable concentrate.The water dispersible of missible oil, diluent stability, cold and hot storage stability meet the commercially available agricultural chemical preparation and must ask.
6, field experiment EXPERIMENTAL EXAMPLE
With the compound carpesia-lactone ketone that the present invention relates to, carpesia-lactone alcohol, 13-methoxyl group carpesia-lactone alcohol, 11, the two hydrogen carpesia-lactone ketone of 13-and carabrane-3 (4)-alkene-12,8 β-lactone use compounding method of preparation of the present invention, are mixed with 20% microemulsion, carried out the test of control grey mould fruit rot of strawberry bacterium in the land for growing field crops, with common fungicide 40% dimetachlone is the contrast medicament, and clear water is contrast, and the prevention effect behind the different concns medicine liquid spray sees Table 6-1.
In experiment, for various preparations, filler or the solvent of compound composition, the weight percent of tensio-active agent, and the per-cent that adds other Fungicidal active substances, by technical scheme preparation of the present invention, all can reach the ideal effect.
Investigation method is taked parallel lines 2 row samplings, and the incidence of the above fruit of every row investigation 1.5cm is by the generation classification of following grade scale to the fruit gray mold.Calculate prevention effect according to disease index, the significance of difference between each is handled with the analysis of DMRT method.
0 grade: fruit is not fallen ill;
1 grade: scab accounts for below 5% of whole fruit area;
3 grades: scab accounts for 6%～15% of whole fruit area;
5 grades: scab accounts for 16%～25% of whole fruit area;
7 grades: scab accounts for 26%～50% of whole fruit area;
9 grades: scab accounts for more than 50% of whole fruit area.
Table 6 20% each compound microemulsion is to the grey mould fruit rot of strawberry prevention effect
| The medicament title | Spraying medicine concentration (mg/l) | Disease refers to (%) before the medicine | After the dispenser d days | |||||
| 3d | 7d | 14d | ||||||
| Disease refers to (%) | Preventive effect (%) | Disease refers to (%) | Preventive effect (%) | Disease refers to (%) | Preventive effect (%) | |||
| Carpesia-lactone ketone carpesia-lactone alcohol 13-methoxyl group carpesia- |
100 200 100 200 100 200 100 | 1.68 1.76 1.88 1.76 1.78 1.96 1.78 | 4.60 4.09 4.53 3.89 4.63 4.29 4.57 | 69.89 82.76 71.79 85.76 66.79 71.76 72.79 | 5.47 5.62 5.17 5.52 5.47 5.72 5.37 | 76.09 78.89 79.25 80.89 76.09 76.89 77.90 | 4.37 3.58 4.37 3.68 4.57 3.87 4.37 | 84.49 89.08 84.49 88.08 80.49 79.98 84.49 |
| Carabrane-3 (4)-alkene-12,8 β-lactone 40% dimetachlone wp contrast | 200 100 200 800 | 1.96 1.78 1.96 2.10 2.26 | 4.29 4.56 4.29 5.79 17.40 | 71.76 64.77 76.66 64.36 | 5.64 5.49 5.72 7.02 28.52 | 76.89 76.09 83.89 73.53 | 3.92 4.37 3.68 5.36 35.47 | 89.78 84.49 89.38 83.83 |
Claims (4)
1. from the isolating bactericidal carabrane type sesquiterpene lactones compound of Herba Carpesii macrocephali, it is characterized in that, this bactericidal carabrane type sesquiterpene lactones compound comprises: carpesia-lactone ketone, carpesia-lactone alcohol, 13-methoxyl group carpesia-lactone alcohol, 11, the two hydrogen carpesia-lactone ketone of 13-and carabrane-3 (4)-alkene-12,8 β-lactone, its molecular structure is respectively:
Carpesia-lactone ketone:
Carpesia-lactone alcohol:
13-methoxyl group carpesia-lactone alcohol:
11, the two hydrogen carpesia-lactone ketone of 13-:
The structural formula of carabrane-3 (4)-alkene-12,8 β-lactone is as follows:
2. the described application that is used to prepare the Plant diseases pesticide preparation that control causes by plant pathogenic fungi from the isolating bactericidal carabrane type sesquiterpene lactones compound of Herba Carpesii macrocephali of claim 1.
3. application as claimed in claim 2 is characterized in that, makes the various preparations that spraying is used, and the weight percent of each raw material is in the various formulations:
The preparation wettable powder: carabrane type sesquiterpene lactones compound 20%～90%, filler or solvent: 0～74%, tensio-active agent 1%～10%, the summation of raw material is 100%;
Preparation missible oil: carabrane type sesquiterpene lactones compound 5%～50%, filler or solvent: 40～95%, tensio-active agent 5%～35%, the summation of raw material is 100%;
The preparation microemulsion: carabrane type sesquiterpene lactones compound 10%～50%, filler or solvent: 40～84%, tensio-active agent 1%～20%, the summation of raw material is 100%.
4. application as claimed in claim 2 is characterized in that, described filler is one or more mixtures in the material known altogether of white carbon black, wilkinite, silicon bath soil or this area staff;
Described solvent is one or more mixtures in the material known altogether of methyl alcohol, ethanol, positive Virahol, ethyl acetate, aromatic hydrocarbon or this area staff;
Described tensio-active agent is one or more a mixture of this area all kinds of surfactants commonly used.
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| CNB2006101048677A CN100494188C (en) | 2006-11-07 | 2006-11-07 | Carabrane type sesquiterpene lactone compound with sterilization activity separated from Carpesium macrocephalum Franch.et Sav and its application |
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| CNB2006101048677A CN100494188C (en) | 2006-11-07 | 2006-11-07 | Carabrane type sesquiterpene lactone compound with sterilization activity separated from Carpesium macrocephalum Franch.et Sav and its application |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101773532B (en) * | 2010-02-24 | 2011-08-24 | 周小江 | Carpesium abrotanoides total terpene lactones extract |
| CN103788037A (en) * | 2012-11-02 | 2014-05-14 | 西北农林科技大学 | Method for purifying carabrone |
| CN106631453A (en) * | 2016-12-21 | 2017-05-10 | 广西睿桂涵农业有限公司 | Fertilizer capable of improving survival rate of rubber tree seedlings |
-
2006
- 2006-11-07 CN CNB2006101048677A patent/CN100494188C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101773532B (en) * | 2010-02-24 | 2011-08-24 | 周小江 | Carpesium abrotanoides total terpene lactones extract |
| CN103788037A (en) * | 2012-11-02 | 2014-05-14 | 西北农林科技大学 | Method for purifying carabrone |
| CN103788037B (en) * | 2012-11-02 | 2015-06-03 | 西北农林科技大学 | Method for purifying carabrone |
| CN106631453A (en) * | 2016-12-21 | 2017-05-10 | 广西睿桂涵农业有限公司 | Fertilizer capable of improving survival rate of rubber tree seedlings |
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