CN101050209B - Compound of eudesmane type sesquiterpene lactone with insecticidal activity extracted from Carpesium macrocephalum, and application - Google Patents

Compound of eudesmane type sesquiterpene lactone with insecticidal activity extracted from Carpesium macrocephalum, and application Download PDF

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CN101050209B
CN101050209B CN200610104885A CN200610104885A CN101050209B CN 101050209 B CN101050209 B CN 101050209B CN 200610104885 A CN200610104885 A CN 200610104885A CN 200610104885 A CN200610104885 A CN 200610104885A CN 101050209 B CN101050209 B CN 101050209B
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lactone
compound
alpha
alkene
eucalyptus alkane
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CN101050209A (en
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冯俊涛
王俊儒
李广泽
何军
王智辉
张兴
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Fuji Biological Technology Development Shanghai Co ltd
Research & Development Center Of Biorational Pesticide Yangling Nongkeda
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Nuisanceless Pesticide Research Service Center Xibei Agroforestry Science And T
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Abstract

This invention discloses antibacterial eudesmane-type sesquiterpenoid compounds extracted from Carpesium macrocephalum, which include: 2alpha-acetoxy-5alpha-hydroxyl-11alphaH-eudesmane-4(15)-ene-12,8beta-lactone, 5alpha, 6alpha-dihydroxyl-4alpha, 11alphaH-eudesmane-12,8beta-lactone,5alpha-hydroxyl-eudesmane-4(15),11(13)-diene-12,8beta-lactone, 2alpha-hydroxyl-5alphaH-eudesmane-4(15),11(13)-diene-12,8beta-lactone, 2alpha,5alpha-hydroxyl-11alphaH-eudesmane-4(15)-ene-12,8beta-lactone, 5alphaH-eudesmane-4(15),11(13)-diene-12,8beta-lactone, 5alpha,11alphaH-eudesmane-4(15)-ene-12,8beta-lactone, 5alpha-hydroxyl-11alphaH-eudesmane-4(15)-ene-12,8beta-lactone, 2alpha-O-beta-D-glucopyranoside-5alpha,11alphaH-eudesmane-4(15)-ene-12,8beta-lactone, and 2alpha-O-beta-D-glucopyranoside-5alphaH-eudesmane-4(15),11(13)-diene-12,8beta-lactone. Experiments show that the eudesmane-type sesquiterpenoid compounds have high inhibitive activity on plant pathogenic fungi.

Description

Bactericidal compound of eudesmane type sesquiterpene lactone thing that extracts from Herba Carpesii macrocephali and uses thereof
Technical field
Patent of the present invention relates to compound and preparation thereof, particularly bactericidal compound of eudesmane type sesquiterpene lactone thing and this compound thereof as sterilant in the application aspect the controlling plant diseases.
Background technology
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 bactericidal compound of eudesmane type sesquiterpene lactone thing that from Herba Carpesii macrocephali, extracts and this compound thereof as sterilant in the application aspect the controlling plant diseases.
In order to realize above-mentioned task, the technical scheme that the present invention takes is: a kind of from the isolating bactericidal compound of eudesmane type sesquiterpene lactone thing of Herba Carpesii macrocephali, it is characterized in that, isolating this bactericidal compound of eudesmane type sesquiterpene lactone thing comprises: 2 α-acetoxyl group-5 Alpha-hydroxy-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone; 5 α, 6 alpha-dihydroxy-s-4 α, 11 α H-eucalyptus alkane-12,8 β-lactones; 5 Alpha-hydroxies-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones; 2 Alpha-hydroxies-5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones; 2 α, 5 Alpha-hydroxies-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone; 5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones; 5 α, 11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone; 5 Alpha-hydroxies-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone; 2 α-O-β-D-glucopyanoside-5 α, 11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone; 2 α-O-β-D-glucopyanoside-5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones;
Its molecular structure is respectively:
Compound I: 2 α-acetoxyl group-5 Alpha-hydroxy-11 α-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone:
Figure G2006101048855D00011
Compound I I:2 α-acetoxyl group-11 α H-eucalyptus alkane-4-alkene-12,8 β-lactone
Figure G2006101048855D00021
Compound III: 5 α, 6 alpha-dihydroxy-s-4 α, 11 α H-eucalyptus alkane-12,8 β-lactones:
Figure G2006101048855D00022
Compound IV: 5 Alpha-hydroxies-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones
Figure G2006101048855D00023
Compound V:2 Alpha-hydroxy-5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones
Figure G2006101048855D00024
Compound VI: 2 α, 5 Alpha-hydroxies-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone:
Figure G2006101048855D00031
Compound VI I:5 Alpha-hydroxy-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone:
Figure G2006101048855D00032
Compound VIII: 5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones:
Compound I X:5 Alpha-hydroxy-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone:
Figure G2006101048855D00034
Compound: X; 2 α-O-β-D-glucopyanoside-5 α, 11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone:
Figure G2006101048855D00041
Compounds X I:2 α-O-β-D-glucopyanoside-5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones:
Main bacteriostatic activity compound is terpene and sesquiterpene lactones compound in the Herba Carpesii macrocephali, and by constructional feature, the sesquiterpene lactones compound is divided into carabrane type sesquiterpene lactones and eudesmane type sesquiterpene lactone again.
The bactericidal compound of eudesmane type sesquiterpene lactone thing that the present invention obtains separation has carried out the bacteriostatic activity of system and has measured, proof above-claimed cpd I～XI has higher inhibition activity to the phytopathogen for examination, and the pesticide preparation that can be used in the Plant diseases that control causes by plant pathogenic fungi is used.
Description of drawings
Fig. 1 is bactericidal compound of eudesmane type sesquiterpene lactone thing molecular structure, in (a)～(k) represent Compound I～XI respectively.
Fig. 2 is a sesquiterpene lactones separation and purification schema;
The present invention is described in further detail below in conjunction with drawings and Examples.
Embodiment
Discover that the compound of eudesmane type sesquiterpene lactone species that contains in the Herba Carpesii macrocephali is more, wherein phytopathogen is had active mainly containing: Compound I 2 α-acetoxyl group-5 Alpha-hydroxy-11 α-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone; Compound I I 2 α-acetoxyl group-11 α H-eucalyptus alkane-4-alkene-12,8 β-lactone; Compound III 5 α, 6 alpha-dihydroxy-s-4 α, 11 α H-eucalyptus alkane-12,8 β-lactones; Compound IV 5 Alpha-hydroxies-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones; Compound V2 Alpha-hydroxy-5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones; Compound VI 2 α, 5 Alpha-hydroxies-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone; Compound VI I 5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones; Compound VIII 5 α, 11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone; Compound I X 5 Alpha-hydroxies-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone; Compounds X 2 α-O-β-D-glucopyanoside-5 α, 11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone; Compounds X I2 α-O-β-D-glucopyanoside-5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones.The molecular structure of each compound is referring to Fig. 1.
1, the sepn process of compound
The Herba Carpesii macrocephali plant sample is pulverized, extracted 6 times with heavily steaming to soak under the industrial methanol room temperature (about 25 ℃), each 2 days, extracting solution concentrating under reduced pressure behind activated carbon decolorizing got total medicinal extract.Carry out silica gel column chromatography with silica gel mixed sample, use sherwood oil, chloroform, chloroform successively: methyl alcohol (1: 1) and methyl alcohol gradient elution get sherwood oil wash-out part, chloroform wash-out part, chloroform: methyl alcohol (1: 1) wash-out part, methanol-eluted fractions part.Chloroform wash-out part is through column chromatography and recrystallization obtain Compound I～IV repeatedly; Chloroform: methyl alcohol (1: 1) wash-out part is through column chromatography and recrystallization obtain compound V～XI repeatedly.Fig. 2 is seen in the concrete sepn process of each compound.
2, the physico-chemical property of each compound and spectral data
After separation obtains each compound, its physico-chemical property and molecular structure are identified the physico-chemical property and the spectral data that obtain each compound are as follows:
Compound I: 2 α-acetoxyl group-5 Alpha-hydroxy-11 α-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone, colourless needle crystal, refractive index is+77.0 °, and (c 0.44, CHCl 3).Be dissolved in chloroform, ethyl acetate, methyl alcohol and aromatic solvents.M/z:308 (M +), 1H-NMR (CDCl 3) δ H: 1.95 (1H, dd, 12,12, H-1), 1.40 (1H, dd, 5,12.5, H-1 '), 4.98 (1H, dddd, 5,6,11,12, H-2), 2.64 (1H, ddd, 2,11,12, H-3), 2.58 (1H, ddd, 2,6,12, H-3 '), 1.65 (1H, dd, 6,14, H-6), 1.56 (1H, dd, 12,14, H-6 '), 2.86 (1H, dddd, 5,6,7,12, H-7), 4.58 (1H, ddd, 2,4.6,5, H-8), 2.02 (1H, dd, 4.6,15, H-9), 1.83 (1H, dd, 2,15, H-9), 2.97 (1H, dq, 7,7, H-13), 1.16 (3H, s, H-13), 4.93 (1H, brs, H-15), 4.78 (1H, brs, H-15 '), 2.04 (s, 2 ' H) 13The chemical shift of C-NMR sees Table 1.
Compound I I:2 α-acetoxyl group-11 α H-eucalyptus alkane-4-alkene-12,8 β-lactone, colourless needle crystal is dissolved in chloroform, ethyl acetate, methyl alcohol and aromatic solvents.M.p=128-130 ℃, refractive index is+68.8 ℃ of (c0.46, CHCl 3) .m/z:292 (M +), 1H-NMR (CDCl 3) δ H: 1.99 (1H, dd, 12,12, H-1), 1.40 (1H, dd, J=5,12.5, H-1 '), 4.98 (1H, dddd, 5,6,11,12, H-2), 2.08 (1H, ddd, 2,11,12, H-3), 2.38 (1H, ddd, 2,6,12, H-3 '), 1.75 (1H, dd, 6,14, H-6), 2.50 (1H, dd, 12,14, H-6 '), 2.34 (1H, dddd, 5,6,7,12, H-7), 4.44 (1H, ddd, 2,4.6,5, H-8), 1.54 (1H, dd, 4.6,15, H-9), 2.28 (1H, dd, 2,15, H-9), 2.81 (1H, dq, 7,7, H-11), 1.25 (1H, d, 7, H-13), 1.23 (3H, s, H-13), 1.68 (brs, H-15), 2.04 (s, 2 ' H) 13The chemical shift of C-NMR sees Table 1.
Compound III: 5 α, 6 alpha-dihydroxy-s-4 α, 11 α H-eucalyptus alkane-12,8 β-lactones, colourless needle crystal is dissolved in chloroform, ethyl acetate, methyl alcohol and aromatic solvents.M.p=178-180 ℃, refractive index is-22 °, and (c 0.36, CHCl 3).M/z:268 (M +), 1H-NMR (CDCl 3) δ H: 1.43 (1H, ddd, 13,12,4.5, H-1), 1.18 (1H, ddd, 13,4,2, H-1 '), 1.78 (1H, m, H-2), 1.92 (1H, ddd, 5.5,11,12, H-3), (1.66 1H, m, H-3 '), 2.04 (1H, m, H-3 '), 3.90 (1H, dd, 6,9, H-6), 2.60 (1H, ddd, 5,9,7.5, H-7), 4.56 (1H, ddd, 2,4.5,5, H-8), 2.03 (1H, dd, 4.5,15, H-9), 1.62 (1H, dd, 2,15, H-9), 2.91 (1H, dq, 7,7.5, H-11), 1.39 (1H, d, 7, H-13), 1.10 (3H, s, H-13), 1.08 (d, 7.5, H-15) 13The chemical shift of C-NMR sees Table 1.
Compound IV: 5 Alpha-hydroxies-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones, the crystallization of colourless rib shape, m.p=156-158 ℃, refractive index is+196 °, and (c 0.2, CHCl 3).Be dissolved in chloroform, ethyl acetate, methyl alcohol and aromatic solvents.M/z:248 (M +), 1H-NMR (CDCl 3) δ H: 6.13 (1H, d, 1.2, H-13), 5.58 (1H, d, 1.2, H-13 '), 4.85 (1H, brs, H-15), 4.68 (1H, brs, H-15 '), 4.56 (1H, td, 1.2,5,5, H-8), 3.34 (1H, ddd, 5,8,11.8, H-7), 0.94 (3H, S, 14-CH 3), 13The chemical shift of C-NMR sees Table 1.
Compound V:2 Alpha-hydroxy-5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones, colourless rib shape crystal, m.p=134-135 ℃, refractive index is+142 °, and (c 1.0, CHCl 3).Be dissolved in chloroform, ethyl acetate, methyl alcohol and aromatic solvents.M/z:248 (M +), 1H-NMR (CDCl 3) δ H: 6.15 (1H, d, 3.0, H-13a), 5.62 (1H, d, 3.0, H-13b), 4.89 (1H, brs, H-15a), 4.57 (1H, brs, H-15b), 4.49 (1H, ddd, H-8), 3.83 (1H, m, H-2), 3.03 (1H, m, H-7), 2.65 (2H, dd, 12.3, H-3), 2.23 (2H, dd, 15.6, H-9), 2.00 (1H, t, H-5), 1.82 (2H, m, H-1), 1.79 (2H, d, 6.9, H-6), 0.84 (3H, s, H-14) 13The chemical shift of C-NMR sees Table 1.
Compound VI: 2 α, 5 Alpha-hydroxies-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone, colourless granule crystal (methyl alcohol), m.p=108-110 ℃, refractive index is+68.0 ° of (c0.74, CH 3OH).Be dissolved in chloroform, ethyl acetate, methyl alcohol and aromatic solvents.M/z:266 (M +), 1H-HMR (CDCl 3) δ H: 1.81 (1H, dd, 12,12, H-1), 1.40 (1H, dd, 5,12.5, H-1 '), 3.79 (1H, dddd, 5,5.5,11.5,12, H-2), 2.59 (1H, ddd, 2,11.5,12, H-3), 2.42 (1H, ddd, 2.5,5,12, H-3 '), 1.69 (1H, dd, 6,13.8, H-6), 1.42 (1H, dd, 12,13.8, H-6 '), 2.86 (1H, dddd, 5,6,7,12, H-7), 4.58 (1H, ddd, 2,4.6,5, H-8), 2.02 (1H, dd, 4.6,15, H-9), 1.83 (1H, dd, 2,15, H-9), 2.97 (1H, dq, 7.7, H-13), 0.9 (3H, s, H-13), 4.93 (1H, brs, H-15), 4.78 (1H, brs, H-15 ') 13The chemical shift of C-NMR sees Table 1.
Compound VI I:5 Alpha-hydroxy-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone, colourless needle crystal, m.p=106-108 ℃, refractive index is+168 ° of (c1.43, CHCl 3).Be dissolved in chloroform, ethyl acetate, methyl alcohol and aromatic solvents.M/z:232 (M +), 1H-NMR (CDCl 3) δ H: 6.14 (1H, brs, H-13), 5.60 (1H, brs, H-13 '), 4.78 (1H, brs, H-15), 4.45 (1H, brs, H-15 '), 4.51 (1H, ddd, 1.5,5,5Hz, H-8), 2.98 (1H, ddd, 5,6.8,13.5Hz, H-7), 0.83 (3H, S, 14-CH 3), 13The chemical shift of C-NMR sees Table 1.
Compound VIII: 5 α, 11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone, colourless needle crystal, m.p=172-173 ℃, refractive index is+18.5 ° of (c0.70, CHCl 3).Be dissolved in chloroform, ethyl acetate, methyl alcohol and aromatic solvents.M/z:234 (M +), 1H-NMR (CDCl 3) δ H: 2.80 (1H, dq, H-11), 1.23 (3H, d, 7.4, H-13), 4.78 (1H, brs, H-15), 4.48 (1H, brs, H-15 '), 4.47 (1H, ddd, 2,5,5Hz, H-8), 2.38 (1H, m, H-7), 0.83 (3H, S, 14-CH 3), 13The chemical shift of C-NMR sees Table 1.
Compound I X:5 Alpha-hydroxy-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone, colourless needle crystal, m.p=188-190 ℃, refractive index is+130.8 ° of (c0.37, CHCl 3).Be dissolved in chloroform, ethyl acetate, methyl alcohol and aromatic solvents.M/z:250 (M +), 1H-NMR (CDCl 3) δ H: 4.88 (1H, brs, H-15), 4.73 (1H, brs, H-15 '), 4.56 (1H, td, J=1.2,5,5, H-8), 2.84 (1H, dq, H-11), 2.48 (1H, m, H-7), 1.21 (3H, d, J=7, H-13), 0.94 (3H, S, H-14), 13The chemical shift of C-NMR sees Table 1.
Compounds X: 2 α-O-β-D-glucopyanoside-5 α, 11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone, colourless needle crystal, m.p.206-208 ℃ (methyl alcohol).Be dissolved in chloroform, ethyl acetate, methyl alcohol and aromatic solvents.Refractive index is+17.9 °, and (c 0.56, CH 3OH).M/z:412 (M +), 1HNMR (CH 3OH) δ: 1.25 (1H, br, dd, 12.5,12.5,1 α H), 1.99 (1H, ddd, 2,5,12.5,1 β H), 3.87 (1H, m, 2 β H), 2.11 (1H, t, 12.5,12.5,3 α H), 2.79 (1H, ddd, 2,5,12.5,3 β H), 1.88 (1H, brs, d, 12.5,5 α H), 1.63 (1H, m, 6 α H), 1.06 (1H, ddd, 12.5,12.5,12.5,6 β H), (2.49 1H, m, 7 α), 4.52 (1H, ddd, 2,4,4.5,8 α), 1.58 (1H, dd, 4.5,15.5,9 α), (2.16 1H, dd, 2,15.5,9 β), 2.93 (1H, m, 11 α), 1.18 (3H, m, 13H), 0.78 (3H, s, 14H), (4.89 1H, br.s, 15 α H), 4.62 (1H, br.s, 15 β H) 13The chemical shift of C-NMR sees Table 1.
Compounds X I:2 α-O-β-D-glucopyanoside-5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones, colourless needle crystal, m.p.176-178 ℃ (methyl alcohol); Refractive index is+13.0 °, and (c 0.69, CH 3OH).Be dissolved in chloroform, ethyl acetate, methyl alcohol and aromatic solvents.M/z:410 (M +), 1HNMR (CH 3OH) δ: 1.24 (1H, br, dd, 12,4,12.4,1 α H), 1.99 (1H, ddd, 2,5,12.4,1 β H), 3.84 (1H, m, 2 β H), (2.12 1H, t, 12,12,3 α H), 2.79 (1H, ddd, 2,6,13,3 β H), 1.95 (1H, brs, d, 13,5 α H), (1.82 1H, m, 6 α H), 1.26 (1H, ddd, 13,13,13,6 β H), 3.10 (1H, m, 7 α), 4.55 (1H, ddd, 2,4,5,8 α), 1.63 (1H, dd, 5,15.5,9 α), 2.16 (1H, dd, 2,15.5,9 β), 6.06,5.70 (2H, br.s, 13H), 0.78 (3H, s, 14H), (4.89 1H, br.s, 15 α H), 4.56 (1H, br.s, 15 β H) 13The chemical shift of C-NMR sees Table 1.
3, the biocide preparation of compound
Above-mentioned 11 kinds of compounds that the compound of eudesmane type sesquiterpene lactone thing comprises can be made the sterilant of various preparation forms, and spraying is used, and are used for the control of plant epiphyte venereal disease evil.The weight percent of each material is in the various formulations:
Formulation Compound of eudesmane type sesquiterpene lactone thing % Filler or solvent % Tensio-active agent %
Wettable powder 20～90 0～74 1～10
Missible oil 5～60 40～95 5～35
Microemulsion 10～40 40～84 1～20
By the various preparations that the compound of eudesmane type sesquiterpene lactone thing 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.
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 6 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: tomato Lycopersicon esculentum fruit, pick up from Yang Ling Yangchuan village township plastic greenhouse; Cucumber (grind No. seven in Tianjin), commercial.
Standard medicament: 50% ethyl phosphine aluminium WP, 50% Sukeling WP.
Table 4-1 is for the examination pathogenic bacteria
Figure G2006101048855D00101
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
Figure G2006101048855D00102
The spore germination method
Above-claimed cpd adopts sessile drop method to the inhibiting mensuration of germ spore germination [114]([114] Fang Zhongda plants disease research method [M], Beijing agricultural press, the 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.
Figure G2006101048855D00103
Figure G2006101048855D00104
Pot experiment
Described each compound that the present invention relates to is mixed with cream preparation, carries out potted plant and rules of organization mensuration.
The prevention effect of cucumber downy mildew adopts the pot experiment method to carry out.Concrete grammar is as follows:
Sow 2～3 cucumber seeds of vernalization at every nutrition pot,, treat that cucumber grows to two leaves (true leaf), treats with provide protection and tests 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.
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 cucumber downy mildew (is unit with the blade) (Fang Zhongda plants disease research method [M], Beijing agricultural press, the third edition, 1995):
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:
Figure G2006101048855D00111
Figure G2006101048855D00112
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 11 kinds of compounds see table the inhibition virulence of pathogenic bacteria spore germination:
Compound I is to the inhibition virulence of 4 kinds of pathogenic bacteria spore germinations
For the examination pathogenic bacteria Toxicity regression line (Y=) EC 50(95％CL)(mg/L) Relation conefficient
Apple anthrax bacteria G.cingulata 2.3778+2.0970x 17.8021(11.5148～27.5222) 0.9840
Leaf muld of tomato bacterium F.fulva 1.4542+2.3002x 34.7943(23.3609～51.8236) 0.9397
Botrytis cinerea B.cinerea -1.0154+3.5476x 49.6167(38.3351～64.2183) 0.9552
For the examination pathogenic bacteria Toxicity regression line (Y=) EC 50(95％CL)(mg/L) Relation conefficient
Bacterium of downy mildew of cucumber P.cubensis 0.5400+2.6654x 47.1279(33.4081～66.4821) 0.9291
Compound I I is to the inhibition virulence of 4 kinds of pathogenic bacteria spore germinations
For the examination pathogenic bacteria Toxicity regression line (Y=) EC 50(95％CL)(mg/L) Relation conefficient
Apple anthrax bacteria G.cingulata 2.662+1.8231x 19.0591(11.5393～31.4795) 0.9712
Leaf muld of tomato bacterium F.fulva 0.8817+2.5620x 40.4974(28.4014～57.7450) 0.9508
Botrytis cinerea B.cinerea 1.2595+2.0790x 62.9726(40.1882～98.6745) 0.9933
Bacterium of downy mildew of cucumber P.cubensis 1.5506+2.1601x 39.5261(25.6130～60.9967) 0.9126
Compound III is to the inhibition virulence of 4 kinds of pathogenic bacteria spore germinations
For the examination pathogenic bacteria Toxicity regression line (Y=) EC 50(95％CL)(mg/L) Relation conefficient
Apple anthrax bacteria G.cingulata 0.9274+2.0627x 94.2832(59.9759～148.2149) 0.9732
Leaf muld of tomato bacterium F.fulva 0.8170+2.1729x 84.1527(54.7661～129.3075) 0.9589
Botrytis cinerea B.cinerea 1.5451+1.7113x 104.4494(60.4951～180.3400) 0.9453
Bacterium of downy mildew of cucumber P.cubensis 1.2660+2.2623x 44.7251(29.6112～67.5533) 0.9629
Compound IV 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
Apple anthrax bacteria 0.2091+3.0457x 37.4109(29.0193～48.6124) 0.9315
Exserohilum turcicum 1.4465+2.1536x 44.6755(36.1154～54.7728) 0.9751
The leaf muld of tomato bacterium 0.1987+3.1439x 33.6680(28.6193～39.8670) 0.9849
Botrytis cinerea -1.1849+3.6682x 48.5385(40.5962～56.0456) 0.9189
Fusarium graminearum 0.4131+3.0320x 32.5689(26.1188～38.8401) 0.9812
Bacterium of downy mildew of cucumber 0.9074+2.1787x 75.5976(45.6655～112.0908) 0.9983
Compound V 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
Apple anthrax bacteria 1.1613+2.2128x 54.2947(48.2315～60.4928) 0.9228
Exserohilum turcicum 2.3104+1.6906x 38.9828(30.5392～49.0900) 0.9445
The leaf muld of tomato bacterium 2.1788+2.0443x 23.9907(17.1101～28.6083) 0.9377
Botrytis cinerea -0.2453+3.5812x 29.1524(20.2391～37.8928) 0.9276
Fusarium graminearum 0.7920+2.7861x 32.3838(28.4444～40.6623) 0.9900
Bacterium of downy mildew of cucumber 0.3061+2.9457x 39.2176(30.9190～59.7073) 0.9487
Compound VI is to the inhibition virulence of 4 kinds of pathogenic bacteria spore germinations
For the examination pathogenic bacteria Toxicity regression line (Y=) EC 50(95％CL)(mg/L) Relation conefficient
Apple anthrax bacteria G.cingulata 0.7309+2.6205x 42.5718(29.7988～60.8199) 0.9378
Leaf muld of tomato bacterium F.filva 0.6652+2.4505x 58.7446(40.1275～85.9992) 0.9482
Botrytis cinerea B.cinerea 2.4655+1.7479x 28.1881(16.4894～48.1868) 0.9088
Bacterium of downy mildew of cucumber P.cubensis 1.8065+2.0373x 36.9393(23.3254～58.4991) 0.9150
Compound VI I is to the inhibition virulence of 4 kinds of pathogenic bacteria spore germinations
For the examination pathogenic bacteria Toxicity regression line (Y=) EC 50(95％CL)(mg/L) Relation conefficient
Apple anthrax bacteria G.cingulata -0.4950+3.0528x 63.0925(46.4862～85.6309) 0.9771
Leaf muld of tomato bacterium F.fulva 1.2660+2.2623x 44.7251(29.6112～67.5533) 0.9629
Botrytis cinerea B.cinerea 1.4135+2.0357x 57.7856(36.7471～91.3664) 0.9732
Bacterium of downy mildew of cucumber P.cubensis 0.3883+2.3687x 88.4945(59.6522～131.2825) 0.9517
Compound VIII is to the inhibition virulence of 4 kinds of pathogenic bacteria spore germinations
For the examination pathogenic bacteria Toxicity regression line (Y=) EC 50(95％CL)(mg/L) Relation conefficient
Apple anthrax bacteria G.cingulata -1.8664+3.6199x 78.8546(60.9410～102.0339) 0.9950
Leaf muld of tomato bacterium F.fulva 1.4495+1.9756x 62.6795(39.0181～100.6897) 0.9282
For the examination pathogenic bacteria Toxicity regression line (Y=) EC 50(95％CL)(mg/L) Relation conefficient
Botrytis cinerea B.cinerea 1.2808+1.8413x 104.6707(62.9447～174.0568) 0.9200
Bacterium of downy mildew of cucumber P.cubensis 1.3295+1.7008x 143.9223(83.0383～249.4503) 0.9320
Compound I X is to the inhibition virulence of 4 kinds of pathogenic bacteria spore germinations
For the examination pathogenic bacteria Toxicity regression line (Y=) EC 50(95％CL)(mg/L) Relation conefficient
Apple anthrax bacteria G.cingulata 0.9074+2.2082x 71.3391(46.7072～108.9613) 0.9306
Leaf muld of tomato bacterium F.fulva 0.2004+2.4653x 88.4743(60.5995～129.1709) 0.9696
Botrytis cinerea B.cinerea 1.1230+1.9397x 99.7242(61.5829～161.4883) 0.9370
Bacterium of downy mildew of cucumber P.cubensis 1.9824+1.4407x 124.3197(64.8314～238.3936) 0.9009
Compounds X is to the inhibition virulence of 4 kinds of pathogenic bacteria spore germinations
For the examination pathogenic bacteria Toxicity regression line (Y=) EC 50(95％CL)(mg/L) Relation conefficient
Apple anthrax bacteria G.cingulata 0.5394+2.116x 129.5559(83.2338～201.6577) 0.9447
Leaf muld of tomato bacterium F.fulva 0.9927+2.0922x 82.2832(52.6493～128.5966) 0.9488
Botrytis cinerea B.cinerea 1.0886+1.8353x 135.2704(81.1646～225.4440) 0.9035
Bacterium of downy mildew of cucumber P.cubensis 0.7440+2.3528x 64.3979(43.3036～95.7677) 0.9628
Compounds X I is to the inhibition virulence of 4 kinds of pathogenic bacteria spore germinations
For the examination pathogenic bacteria Toxicity regression line (Y=) EC 50(95％CL)(mg/L) Relation conefficient
Apple anthrax bacteria G.cingulata 1.5465+2.0940x 44.5839(28.5191～69.6978) 0.9290
Leaf muld of tomato bacterium F.fulva -0.9289+3.2303x 68.4535(51.2466～91.4379) 0.9369
Botrytis cinerea B.cinerea 1.6731+1.9626x 49.5650(30.7734～79.8317) 0.9303
Bacterium of downy mildew of cucumber p.cubensis 0.6085+2.1572x 108.5691(70.3659～167.5138) 0.9318
4.2 11 kinds of compounds see the following form to the inhibition virulence of botrytis cinerea mycelial growth:
11 kinds of compounds are to the restraining effect (72h) of botrytis cinerea mycelial growth
Compound number The virulence curve Correlation coefficient r EC 50(mg/L) EC 5095% fiducial limit
I Y＝0.406+1.2356X 0.9547 45.6247 27.5641～69.1358
II Y＝1.3762+2.3014X 0.9106 70.8619 43.3672～96.3857
III Y＝1.73.3+2.6985X 0.9387 86.3923 60.2315～106.7148
IV Y＝0.9269+1.7386X 0.9016 42.0125 23.6720～68.2347
V Y＝1.4561+2.2038X 0.9425 31.2953 19.3402～45.6910
VI Y＝1.5171+2.2317X 0.9637 26.8604 15.6947～36.2638
VII Y＝0.3217+1.1659X 0.9217 48.7892 25.3182～69.2354
VIII Y＝0.6843+1.7346X 0.9630 126.0836 76.3826～168.5371
IX Y＝1.6169+2.5866X 0.9754 86.9614 59.3576～103.5637
X Y＝0.5492+1.6462X 0.9156 156.3021 86.3217～215.6804
XI Y＝1.076+2.0235X 0.9461 78.5364 42.5103～100.8427
Annotate: the blank colony diameter is 68.37mm.
4.3 11 kinds of compounds see the following form to the prevention effect of graw mold of tomato and cucumber downy mildew:
11 kinds of compounds are to the prevention effect (7d) of gray mold on the tamato fruit
Figure G2006101048855D00151
11 kinds of compounds are to the potted plant prevention effect of cucumber downy mildew
Figure G2006101048855D00161
5, the preparation of the various preparations of each compound
The preparation of embodiment 1:15%2 α-acetoxyl group-5 Alpha-hydroxy-11 α-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone (Compound I) wettable powder.In cone-type mixer, add 2 α-acetoxyl group-5 Alpha-hydroxy-11 α-eucalyptus alkane-4 (15)-alkene-12, the 8 β-lactone 15kg that is crushed to about 200 orders, the white carbon black 50kg of commercially available commodity filler, wilkinite 25kg, and draw back powder 7.5kg, saponin 2.5kg.Fully mixed, can make 15%2 α-acetoxyl group-5 Alpha-hydroxy-11 α-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone 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 2:55%2 α-acetoxyl group-5 Alpha-hydroxy-11 α-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone (Compound I) wettable powder.With 55kg2 α-acetoxyl group-5 Alpha-hydroxy-11 α-eucalyptus alkane-4 (15)-alkene-12, the former medicinal powder of 8 β-lactone (Compound I) is broken to 300 orders, take by weighing the white carbon black 30kg of commodity filler, sodium lignosulfonate 10kg, ethoxylated dodecyl alcohol 5kg, add abundant mixing evenly in the mixing machine, can make 55%2 α-acetoxyl group-5 Alpha-hydroxy-11 α-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone 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.
Embodiment 3:5%2 α-acetoxyl group-5 Alpha-hydroxy-11 α-eucalyptus alkane-4 (15)-alkene-12, the preparation of 8 β-lactone (Compound I) missible oil. with 5kg2 α-acetoxyl group-5 Alpha-hydroxy-11 α-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone, be dissolved in the 80kg ethyl acetate, vinylbenzene acid Soxylat A 25-7 15kg, join in the 200L reactor, under 40～50 ℃ of temperature, stirred 0.5 hour, promptly make 100kg 5%2 α-acetoxyl group-5 Alpha-hydroxy-11 α-eucalyptus alkane-4 (15)-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.
The preparation of embodiment 4:50%2 α-acetoxyl group-5 Alpha-hydroxy-11 α-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone (Compound I) missible oil.In the 200L reactor, with 50kg carpesia-lactone ketone, be dissolved in the mixed solvent of 25kg ethyl acetate and 10kg chloroform, add vinylbenzene acid Soxylat A 25-7 5kg again, octyl phenol polyoxy ethyl ether 10kg, under 40～50 ℃ of temperature, stirred 0.5 hour, promptly make 100kg50%2 α-acetoxyl group-5 Alpha-hydroxy-11 α-eucalyptus alkane-4 (15)-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.
The preparation of embodiment 5:10%2 α-acetoxyl group-11 α H-eucalyptus alkane-4-alkene-12,8 β-lactone (Compound I I) microemulsion.Take by weighing 2 α-acetoxyl group-5 Alpha-hydroxy-11 α H-eucalyptus alkane-4 (15)-alkene-former medicine 10kg of 12,8 β-lactone, be dissolved in the 15kg Virahol, add the 10kg 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%2 α-acetoxyl group-5 Alpha-hydroxy-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone microemulsion 100kg.Stability of formulation, outward appearance etc. meet the requirement of commodity preparation.
Embodiment 6:20%5 α, 6 alpha-dihydroxy-s-4 α, the preparation of 11 α H-eucalyptus alkane-12,8 β-lactone (compound III) microemulsion.Take by weighing 5 α, 6 alpha-dihydroxy-s-4 α, the 11 α H-eucalyptus alkane-former medicine 20kg of 12,8 β-lactone are dissolved in the 30kg ethyl acetate, add the 15kg calcium dodecylbenzene sulphonate again, and 5kg vinylbenzene acid Soxylat A 25-7 is mixed under high-speed stirring, is heated to about 40 ℃; Drip deionized water 30kg 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%5 α, 6 alpha-dihydroxy-s-4 α, 11 α H-eucalyptus alkane-12,8 β-lactone microemulsion 100kg.Stability of formulation, outward appearance etc. meet the requirement of commodity preparation.
The preparation of embodiment 7:40%2 Alpha-hydroxy-5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones (compound V) wettable powder.In cone-type mixer, add 2 Alpha-hydroxies-5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12, the 8 β-lactone 40kg that is crushed to about 200 orders, the white carbon black 20kg of commercially available commodity filler, wilkinite 20kg, and draw back powder 5kg, xylogen 15kg.Fully mixed, can make 40%2 Alpha-hydroxies-5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactone 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 8:30%5 Alpha-hydroxy-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactone (compound VI) missible oil.In the 200L reactor, with 30kg 2 α, 5 Alpha-hydroxies-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone is dissolved in the mixed solvent of 30kg methyl alcohol and 25kg toluene, 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 100kg 30%2 α, 5 Alpha-hydroxies-11 α H-eucalyptus alkane-4 (15)-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.
Embodiment 9:10%5 Alpha-hydroxy-11 α H-eucalyptus alkane-4 (15)-alkene-12, the preparation of 8 β-lactone (compound VI I) microemulsion. take by weighing 5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12, the former medicine 10kg of 8 β-lactone, be dissolved in the 30kg 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 55 ℃, stirs 1 hour, makes the requirement that 10%5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactone microemulsion 100kg. stability of formulation, outward appearance etc. meet the commodity preparation.
Embodiment 10:35%2 α-O-β-D-glucopyanoside-5 α, the preparation of 11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone (compounds X) missible oil.In the 200L reactor, with 35kg 2 α-O-β-D-glucopyanoside-5 α, 11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone are dissolved in the 55kg toluene solvant, add vinylbenzene acid Soxylat A 25-7 15kg again, under 40～50 ℃ of temperature, stirred 1.0 hours, promptly make 100kg 35%2 α-O-β-D-glucopyanoside-5 α, 11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-Nei emulsifiable concentrates.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 11:15%5 Alpha-hydroxy-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactone (compound IV) microemulsions.Take by weighing 5 Alpha-hydroxies-former medicine 15kg of eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones, be dissolved in the 30kg Virahol, add the 5kg 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 55 ℃, stirs 1 hour, makes 15%5 Alpha-hydroxies-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactone microemulsion 100kg.Stability of formulation, outward appearance etc. meet the requirement of commodity preparation.
Embodiment 12:20%5 α, the preparation of 11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone (compound VIII) wettable powder.In cone-type mixer, add 5 α that are crushed to about 200 orders, 11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone 20kg, the white carbon black 30kg of commercially available commodity filler, wilkinite 30kg, and draw back powder 15kg, xylogen 5kg.Fully mixed, can make 20%5 α, 11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone 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 13:25%5 Alpha-hydroxy-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone (Compound I X) missible oil.In the 200L reactor, with 25kg 5 Alpha-hydroxies-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone, be dissolved in the 60kg xylene solvent, add vinylbenzene acid Soxylat A 25-7 15kg again, under 40～50 ℃ of temperature, stirred 1.0 hours, promptly make 100kg 25%5 Alpha-hydroxies-11 α H-eucalyptus alkane-4 (15)-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.
The preparation of embodiment 14:10%2 α-O-β-D-glucopyanoside-5 α H-eucalyptus alkane-4 (15), 11 (13) diene-12,8 β-lactone (compounds X I) microemulsions.Take by weighing 2 α-O-β-D-glucopyanoside-5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12, the former medicine 10kg of 8 β-lactone, be dissolved in the 20kg Virahol, 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 50kg 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 55 ℃, stirs 1 hour, makes 10%2 α-O-β-D-glucopyanoside-5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactone microemulsion 100kg.Stability of formulation, outward appearance etc. meet the requirement of commodity preparation.
6, field experiment EXPERIMENTAL EXAMPLE
With the above-mentioned 11 kinds of compound of eudesmane type sesquiterpene lactone things that the present invention relates to, use compounding method of preparation of the present invention, be mixed with 15% microemulsion, carried out the test of pesticide effectiveness of control graw mold of tomato, cowpea gray mold, gray mold of cucumber and grey mould fruit rot of strawberry in the land for growing field crops, clear water is contrast, and the prevention effect behind the different concns medicine liquid spray sees Table 6-1～table 6-4.
In experiment,,, all can reach the ideal effect by technical scheme preparation of the present invention for various preparations, filler or the solvent of compound composition, the weight percent of tensio-active agent.
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.
Figure G2006101048855D00201
Table 6-1 compound VI I～XI microemulsion is to the graw mold of tomato prevention effect
Table 6-2 15% Compound I and Compound I I microemulsion are to the prevention effect of gray mold of cucumber
Figure G2006101048855D00203
Annotate: extract ill fruit before the dispenser.
Table 6-3 15% compound III and compound IV microemulsion are to the prevention effect of cowpea gray mold
Figure G2006101048855D00204
Figure G2006101048855D00211
Annotate: extract ill fruit before the medicine.
Table 6-4 15% compound V and compound VI microemulsion are to the prevention effect of grey mould fruit rot of strawberry
Figure G2006101048855D00212

Claims (5)

1. be used to prepare the application of control from the isolating bactericidal compound of eudesmane type sesquiterpene lactone thing of Herba Carpesii macrocephali by the sterilant of the microbial Plant diseases of pathogenic;
Described bactericidal compound of eudesmane type sesquiterpene lactone thing is: 2 α-acetoxyl group-5 Alpha-hydroxy-11 α-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone; 2 α-acetoxyl group-11 α H-eucalyptus alkane-4-alkene-12,8 β-lactone; 5 α, 6 alpha-dihydroxy-s-4 α, 11 α H-eucalyptus alkane-12,8 β-lactones; 5 Alpha-hydroxies-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones; 2 Alpha-hydroxies-5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones; 2 α, 5 Alpha-hydroxies-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone; 5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones; 5 α, 11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone; 5 Alpha-hydroxies-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone; 2 α-O-β-D-glucopyanoside-5 α, 11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone; 2 α-O-β-D-glucopyanoside-5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones; Its molecular structure and chemical name are respectively:
Figure F2006101048855C00011
Compound I 2 α-acetoxyl group-5 Alpha-hydroxies-Compound I I 2 α-acetoxyl group-11 α H-eucalyptus alkane-4-alkene
11 α-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone-12,8 β-lactone
Figure F2006101048855C00012
Compound III 5 α, 6 alpha-dihydroxy-s-4 α, 11 α H-compound IV, 5 Alpha-hydroxies-eucalyptus alkane-4 (15),
Eucalyptus alkane-12,8 β-lactone 11 (13)-diene-12,8 β-lactone
Figure F2006101048855C00021
Compound V 2 Alpha-hydroxies-5 α H-eucalyptus hydride compounds VI 2 α, 5 Alpha-hydroxies-11 α H-eucalyptus alkane-
-4 (15), 11 (13)-diene-12,8 β-lactone 4 (15)-alkene-12,8 β-lactone
Figure F2006101048855C00022
Compound VI I 5 α H-eucalyptus alkane-4 (15), compound VIII 5 α, 11 α H-eucalyptus alkane-4 (15)-
11 (13)-diene-12,8 β-lactone alkene-12,8 β-lactone
Figure F2006101048855C00023
Compound I X 5 Alpha-hydroxies-11 α-eucalyptus alkane-compounds X 2 α-O-β-D-glucopyanoside
4 (15)-alkene-12,8 β-lactone-5 α, 11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone
Figure F2006101048855C00024
Compounds X I 2 α-O-β-D-glucopyanoside-5 α H-
Eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones;
Described phytopathogen is botrytis cinerea (Botrytis cinerea), leaf muld of tomato bacterium (Fulvia fulva), Exserohilum turcicum (Exserohilum turcicum), apple anthrax bacteria (Glomerella cingulata), fusarium graminearum (Gibberella zeae) or bacterium of downy mildew of cucumber (Pseudoperonospora cubensis (Berk.et Cert.) Rostr).
2. application as claimed in claim 1 is characterized in that, described compound of eudesmane type sesquiterpene lactone thing is mixed with microemulsion; The raw material of microemulsion and weight percent thereof are: compound of eudesmane type sesquiterpene lactone thing, 10～40%; Filler or solvent, 40～84%; Tensio-active agent, 1～20%; The summation of raw material is 100%.
3. application as claimed in claim 1 is characterized in that, described compound of eudesmane type sesquiterpene lactone thing is mixed with wettable powder; The raw material of wettable powder and weight percent thereof are: compound of eudesmane type sesquiterpene lactone thing, 20～90%; Filler or solvent, 0～74%; Tensio-active agent, 1～10%; The summation of raw material is 100%.
4. as claim 2 or 3 described application, it is characterized in that described solvent is one or more mixtures in methyl alcohol, ethanol, n-propyl alcohol, Virahol, ethyl acetate, the aromatic hydrocarbon.
5. as claim 2 or 3 described application, it is characterized in that described filler is one or more mixtures in white carbon black, wilkinite or the diatomite.
CN200610104885A 2006-11-10 2006-11-10 Compound of eudesmane type sesquiterpene lactone with insecticidal activity extracted from Carpesium macrocephalum, and application Expired - Fee Related CN101050209B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101919841A (en) * 2010-09-06 2010-12-22 福建医科大学 Application of eudesmane-type sesquiterpenoids

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101624387B (en) * 2008-07-10 2011-07-20 河北医科大学 Method for purifying and preparing isoalantolactone and application thereof in preparing antineoplastic medicaments
CN102533600B (en) 2011-12-30 2013-02-27 中国科学院南海海洋研究所 Marine streptomyces/pyranosesquiterpene compound and preparation method and application thereof
CN103788037B (en) * 2012-11-02 2015-06-03 西北农林科技大学 Method for purifying carabrone
CN104945361B (en) * 2015-06-19 2017-06-13 中国医学科学院药用植物研究所 Germacrane Sesquiterpenoids derivative and preparation method and application
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

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
Chao Yang,et.al..A New Eudesmanoilde from Carpesium macrocephalum.Chinese Chemical Letters13 9.2002,13(9),855-856.
Chao Yang,et.al..A New Eudesmanoilde from Carpesium macrocephalum.Chinese Chemical Letters13 9.2002,13(9),855-856. *
Chao Yang,et.al..Sesquiterpene Lactones and other Constituents fromtheAerial Parts of Carpesium macrocephalum.Aust.J.Chem.56.2003,56621-624.
Chao Yang,et.al..Sesquiterpene Lactone GlycosidesfromCarpesiummacrocephalum.Chinese Chemical Letters13 3.2002,13(3),247-248.
Chao Yang,et.al..Sesquiterpene Lactone GlycosidesfromCarpesiummacrocephalum.Chinese Chemical Letters13 3.2002,13(3),247-248. *
Chao Yang,et.al..Sesquiterpene Lactones and other Constituents fromtheAerial Parts of Carpesium macrocephalum.Aust.J.Chem.56.2003,56621-624. *
杨超 等.烟管头草地上部分化学成分的研究.兰州大学学报(自然科学版)38 4.2002,38(4),61-67.
杨超等.烟管头草地上部分化学成分的研究.兰州大学学报(自然科学版)38 4.2002,38(4),61-67. *
郭启雷 等.旋覆花属植物中倍半萜类成分及药理活性研究进展.天然产物研究与开发17 6.2005,17(6),804-809.
郭启雷等.旋覆花属植物中倍半萜类成分及药理活性研究进展.天然产物研究与开发17 6.2005,17(6),804-809. *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101919841A (en) * 2010-09-06 2010-12-22 福建医科大学 Application of eudesmane-type sesquiterpenoids
CN101919841B (en) * 2010-09-06 2012-05-30 福建医科大学 Application of eudesmane-type sesquiterpenoids

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