CN101050209A - Eudesmane type sesquiterpene lactone compound extracted from Carpesium macrocephalum and having antibacterial activity, and its application - Google Patents

Eudesmane type sesquiterpene lactone compound extracted from Carpesium macrocephalum and having antibacterial activity, and its application Download PDF

Info

Publication number
CN101050209A
CN101050209A CNA2006101048855A CN200610104885A CN101050209A CN 101050209 A CN101050209 A CN 101050209A CN A2006101048855 A CNA2006101048855 A CN A2006101048855A CN 200610104885 A CN200610104885 A CN 200610104885A CN 101050209 A CN101050209 A CN 101050209A
Authority
CN
China
Prior art keywords
lactone
alpha
compound
eucalyptus alkane
alkene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA2006101048855A
Other languages
Chinese (zh)
Other versions
CN101050209B (en
Inventor
冯俊涛
王俊儒
李广泽
何军
王智辉
张兴
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fuji Biological Technology Development Shanghai Co ltd
Research & Development Center Of Biorational Pesticide Yangling Nongkeda
Original Assignee
Pollution Free Pesticide Research And Service Center Of Northwest Agricultural And Forestry University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Pollution Free Pesticide Research And Service Center Of Northwest Agricultural And Forestry University filed Critical Pollution Free Pesticide Research And Service Center Of Northwest Agricultural And Forestry University
Priority to CN200610104885A priority Critical patent/CN101050209B/en
Publication of CN101050209A publication Critical patent/CN101050209A/en
Application granted granted Critical
Publication of CN101050209B publication Critical patent/CN101050209B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Landscapes

  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

The invention discloses a eudesmane type sesquiterpene lactone compound with bactericidal activity separated from golden larch, which comprises 2 alpha-acetoxyl group-5 alpha-hydroxy group-11 alpha H-eudesmane-4 (15) -alkene-12, 8 beta-lactone; 5 α, 6 α -dihydroxy-4 α, 11 α H-eudesmane-12, 8 β -lactone; 5 α -hydroxy-eudesmane-4 (15), 11(13) -diene-12, 8 β -lactone; 2 α -hydroxy-5 α H-eudesmane-4 (15), 11(13) -diene-12, 8 β -lactone; 2 α, 5 α -hydroxy-11 α H-eudesmane-4 (15) -ene-12, 8 β -lactone; 5 α H-eudesmane-4 (15), 11(13) -diene-12, 8 β -lactone; 5 α, 11 α H-eudesman-4 (15) -ene-12, 8 β -lactone; 5 α -hydroxy-11 α H-eudesman-4 (15) -ene-12, 8 β -lactone; 2 α -O- β -D-glucopyranoside-5 α, 11 α H-eudesmane-4 (15) -ene-12, 8 β -lactone; 2 α -O- β -D-glucopyranoside-5 α H-eudesmane-4 (15), 11(13) -diene-12, 8 β -lactone; the antibacterial activity determination of the compound proves that the compound has higher inhibitory activity to tested phytopathogens.

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 A20061010488500061
Compound I I:5 α, 6 alpha-dihydroxy-s-4 α, 11 α H-eucalyptus alkane-12,8 β-lactones
Figure A20061010488500071
Compound III: 5 Alpha-hydroxies-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones:
Compound IV: 5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones
Figure A20061010488500073
Compound V:2 Alpha-hydroxy-5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones
Figure A20061010488500074
Compound VI: 2 α, 5 Alpha-hydroxies-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone:
Compound VI I:5 Alpha-hydroxy-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone:
Figure A20061010488500082
Compound VIII: 5 α, 11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone:
Figure A20061010488500083
Compound I X:5 Alpha-hydroxy-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone:
Compound: X; 2 α-O-β-D-glucopyanoside-5 α, 11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone:
Figure A20061010488500091
Compounds X I:2 α-O-β-D-glucopyanoside-5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones:
Figure A20061010488500092
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 the active Compound I that mainly contains: 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-5 Alpha-hydroxy-11 α H-eucalyptus alkane-4 (15)-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 V:2 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-hydroxy-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 I:2 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-5 Alpha-hydroxy-11 α H-eucalyptus alkane-4 (15)-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-NMR (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 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones, 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.
Table 1 compound 1～XI's 13C-NMR (100MHz) data
Carbon atom sequence number Carbon number Compound C ompounds
I II III IV V VI VII VIII IX X XI
1 40.0 45.1 35.6 35.56t 46.26t 45.1t 36.83t 35.8 35.48 48.5 48.4
2 69.2 67.6 15.9 35.34t 66.96d 67.53d 17.67t 22.5 35.12 76.0 75.8
3 37.3 38.4 27.8 33.77t 50.89t 42.32t 42.22t 36.4 33.66 45.5 45.5
4 147.5 124.0 34.7 150.12s 145.94s 151.14s 148.97s 149.0 150.29 148.4 148.1
5 73.3 131.1 76.7 74.26d 45.51d 73.53d 41.41d 50.6 73.92 46.9 46.5
6 27.3 21.8 66.8 21.58t 27.22t 28.02t 27.5t 23.3 27.36 22.2 28.5
7 37.0 40.7 45.3 37.56d 40.46d 38.48d 46.26d 48.1 36.88 41.6 41.5
8 77.5 77.5 78.1 76.9d 76.38d 79.88d 76.68d 78.8 77.78 79.6 78.8
9 35.4 42.6 38.7 31.78t 41.03t 36.81t 40.56t 41.9 31.59 42.2 41.9
10 37.1 36.0 36.5 36.45s 33.92s 37.96s 34.29d 38.2 35.78 35.2 34.7
11 41.0 42.0 40.6 142.13s 141.9s 42.12d 142.25s 38.9 41.02 42.8 144.0
12 179.1 179.5 179.3 170.69s 170.46s 182.67s 170.6s 180.0 179.02 182.0 173.0
13 9.1 9.3 11.1 120.23t 120.38t 9.58q 120.0t 9.6 9.29 9.5 120.9
14 22.3 27.1 22.4 21.73q 18.67q 22.94q 22.69q 17.9 21.58 19.1 18.9
15 111.9 19.2 16.5 108.98t 109.18t 110.18t 106.62t 106.4 108.29 109.3 109.5
1’ 170.4 170.6
2’ 21.3 21.4
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
Classification Pathogenic bacteria is bright The Latin formal name used at school
Deuteromycotina Botrytis cinerea Botrytis cinerea
The leaf muld of tomato bacterium Fulvia fulva
Exserohilum turcicum Exserohilum turcicum
Ascomycotina Apple anthrax bacteria Glomerella cingulata
Fusarium graminearum Gibberella zeae
Mastigomycotina Bacterium of downy mildew of cucumber Pseudoperonospora cubensis(Berk.et Cert.) Rostr
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 A20061010488500151
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 A20061010488500152
Figure A20061010488500153
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 A20061010488500161
Figure A20061010488500162
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
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.fulva 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
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
Compound number Concentration (mg/L) Provide protection Therapeutic action
Scab diameter (mm) Prevention effect (%) Scab diameter (mm) Prevention effect (%)
I 500 32.67 38.65 40.26 28.56
1000 25.53 52.06 31.65 43.83
II 500 35.58 33.19 41.88 25.67
1000 27.41 48.52 35.21 37.52
III 500 37.95 28.74 43.87 22.14
1000 31.61 40.63 37.43 33.58
IV 500 33.28 37.51 44.04 21.84
1000 26.15 50.89 33.45 40.63
V 500 28.55 46.38 36.58 35.08
1000 19.90 62.63 28.52 49.38
VI 500 26.48 50.27 35.03 37.84
1000 16.87 68.32 16.05 71.52
VII 500 30.43 42.86 39.28 30.29
1000 24.94 53.17 32.78 41.82
VIII 500 37.98 28.67 44.76 20.57
1000 30.24 43.21 35.77 36.53
IX 500 36.99 30.53 43.69 22.46
1000 29.89 43.86 37.46 33.52
X 500 38.00 28.64 45.60 19.07
1000 31.67 40.53 40.23 28.61
XI 500 34.68 34.87 44.20 21.56
1000 26.96 49.38 34.98 37.93
Sukeling WP 500 14.24 73.26. 17.65 68.67
Contrast 53.25 —— 56.35 ——
11 kinds of compounds are to the potted plant prevention effect of cucumber downy mildew
Compound number Concentration (mg/L) Provide protection Therapeutic action
Disease index Prevention effect (%) Disease index Prevention effect (%)
I 1000 28.64 41.09 32.72 38.63
2000 22.52 53.68 26.46 50.38
II 1000 27.89 42.64 36.86 30.87
2000 21.95 54.85 27.03 49.31
III 1000 29.35 39.64 38.19 28.37
2000 24.21 50.21 32.14 39.73
IV 1000 29.32 39.70 35.95 32.58
2000 24.99 48.60 30.80 42.23
V 1000 20.24 58.37 25.58 52.03
2000 14.04 71.12 20.60 61.37
VI 1000 27.75 42.93 27.04 49.28
2000 20.13 58.59 19.82 62.83
VII 1000 32.64 32.86 38.82 27.19
2000 27.61 43.21 32.88 38.33
VIII 1000 34.34 29.38 37.19 30.26
2000 31.18 35.86 30.64 42.53
IX 1000 35.23 27.53 36.88 30.84
2000 30.99 36.26 32.01 39.97
X 1000 28.28 41.83 37.03 30.56
2000 23.74 51.17 31.55 40.83
XI 1000 32.98 32.17 37.49 29.69
2000 26.42 45.66 32.78 38.53
Ethyl phosphine aluminium WP 1000 13.54 72.16 11.59 78.26
Contrast 48.62 —— 53.32 ——
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.
The preparation of embodiment 3:5%2 α-acetoxyl group-5 Alpha-hydroxy-11 α-eucalyptus alkane-4 (15)-alkene-12,8 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-5 Alpha-hydroxy-11 α H-eucalyptus alkane-4 (15)-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.
Embodiment 8:30%2 α, the preparation of 5 Alpha-hydroxies-11 α H-eucalyptus alkane-4 (15)-alkene-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.
The preparation of embodiment 9:10%5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactone (compound VI I) microemulsions.Take by weighing the former medicine 10kg of 5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones, 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 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 requirement of 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-lactones (compounds X I) microemulsion.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 A20061010488500251
Table 6-1 compound VI I～XI microemulsion is to the graw mold of tomato prevention effect
The medicament title Spraying medicine concentration (mg/l) Disease refers to (%) before the medicine After the dispenser d days
7d 14d
Disease refers to (%) Preventive effect (%) Disease refers to (%) Preventive effect (%)
Compounds X I 100 1.88 5.17 79.25 4.37 84.49
200 1.76 5.52 80.89 3.68 88.08
Compounds X 100 1.68 5.47 76.09 4.37 84.49
200 1.76 5.62 78.89 3.58 89.08
Compound I X 100 1.78 5.47 76.09 4.57 80.49
200 1.96 5.72 76.89 3.87 79.98
Compound VIII 100 1.78 5.37 77.90 4.37 84.49
200 1.96 5.64 76.89 3.92 89.78
Compound VI I 100 1.78 5.49 76.09 4.37 84.49
200 1.96 5.72 83.89 3.68 89.38
40% dimetachlone wp 800 2.10 7.02 73.53 5.36 83.83
Contrast 2.26 28.52 35.47
Table 6-2 15% Compound I and Compound I I microemulsion are to the prevention effect of gray mold of cucumber
The medicament title Spraying medicine concentration (mg/l) After the dispenser d days
7d 14d
Disease refers to (%) Preventive effect (%) Disease refers to (%) Preventive effect (%)
Compound I 200 1.35 80.66 2.5 76.98
100 1.78 74.50 3.01 72.28
Compound I I 200 2.82 59.60 4.65 57.18
100 1.91 72.64 3.18 70.72
The clear water contrast - 6.98 - 10.86 -
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
The medicament title Spraying medicine concentration (mg/l) After the dispenser d days
7d 14d
Disease refers to (%) Preventive effect (%) Disease refers to (%) Preventive effect (%)
Compound III 200 8.32 78.40 15.12 76.84
100 9.42 75.55 17.64 73.88
Compound IV 200 9.25 75.99 17.35 73.42
100 12.43 67.73 21.45 67.14
The clear water contrast - 38.52 - 65.28 -
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
Medicament For examination concentration (mg/L) Disease refers to before the medicine After the dispenser 7 days The significance of difference After the dispenser 14 days The significance of difference
Disease refers to Preventive effect (%) 0.05 0.01 Disease refers to Preventive effect (%) 0.05 0.01
Compound V 200 13.75 4.06 76.43 a A 3.99 79.31 a A
100 7.38 3.44 63.64 a A 3.24 68.70 a A
Compound VI 100 8.05 4.25 57.68 b B 5.14 54.48 b B
200 7.47 2.98 68.03 a A 2.78 73.47 a A
Blank - 6.83 8.52 - c C 9.58 - c C

Claims (4)

1. 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:
2 α-acetoxyl group-5 Alpha-hydroxy-11 α-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone:
Figure A2006101048850002C1
5 α, 6 alpha-dihydroxy-s-4 α, 11 α H-eucalyptus alkane-12,8 β-lactones
Figure A2006101048850002C2
5 Alpha-hydroxies-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones:
Figure A2006101048850003C1
5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones
Figure A2006101048850003C2
2 Alpha-hydroxies-5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones
Figure A2006101048850003C3
2 α, 5 Alpha-hydroxies-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone:
Figure A2006101048850003C4
5 Alpha-hydroxies-11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone:
Figure A2006101048850004C1
5 α, 11 α H-eucalyptus alkane-4 (15)-alkene-12,8 β-lactone:
Figure A2006101048850004C2
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:
Figure A2006101048850004C4
2 α-O-β-D-glucopyanoside-5 α H-eucalyptus alkane-4 (15), 11 (13)-diene-12,8 β-lactones:
Figure A2006101048850005C1
2. the described pesticide preparation application that is used to prevent and treat the Plant diseases that causes by plant pathogenic fungi from the isolating bactericidal compound of eudesmane type sesquiterpene lactone thing of Herba Carpesii macrocephali of claim 1.
3. application as claimed in claim 2 is characterized in that, above-mentioned bactericidal compound of eudesmane type sesquiterpene lactone thing is made various preparation sprayings, control plant epiphyte venereal disease evil, and the weight percent of each material of various preparations is:
Formulation is a wettable powder: the compound of eudesmane type sesquiterpene lactone thing: 20%～90%, and filler or solvent: 0～74%, tensio-active agent: 1%～10%, the summation of raw material is 100%;
Formulation is a missible oil: the compound of eudesmane type sesquiterpene lactone thing: 5%～60%, and filler or solvent: 40%～95%, tensio-active agent: 5%～35%, the summation of raw material is 100%;
Formulation is a microemulsion: the compound of eudesmane type sesquiterpene lactone thing: 10%～40%, and filler or solvent: 40%～84%, tensio-active agent: 1%～20%, the summation of raw material is 100%.
4. application as claimed in claim 3 is characterized in that, described filler is one or more mixtures in white carbon black, wilkinite, silicon bath soil or the material well known in the art; Described solvent is methyl alcohol, ethanol, positive Virahol, ethyl acetate, one or more mixtures in aromatic hydrocarbon or the known material of this area staff; Described tensio-active agent is one or more a mixture of all kinds of surfactants used always.
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)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN200610104885A CN101050209B (en) 2006-11-10 2006-11-10 Compound of eudesmane type sesquiterpene lactone with insecticidal activity extracted from Carpesium macrocephalum, and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN200610104885A CN101050209B (en) 2006-11-10 2006-11-10 Compound of eudesmane type sesquiterpene lactone with insecticidal activity extracted from Carpesium macrocephalum, and application

Publications (2)

Publication Number Publication Date
CN101050209A true CN101050209A (en) 2007-10-10
CN101050209B CN101050209B (en) 2010-05-12

Family

ID=38781832

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200610104885A Expired - Fee Related CN101050209B (en) 2006-11-10 2006-11-10 Compound of eudesmane type sesquiterpene lactone with insecticidal activity extracted from Carpesium macrocephalum, and application

Country Status (1)

Country Link
CN (1) CN101050209B (en)

Cited By (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
WO2013097424A1 (en) * 2011-12-30 2013-07-04 中国科学院南海海洋研究所 Marine streptomyces sp., compound of pyranosesquiterpenes and preparation method and use thereof
CN103788037A (en) * 2012-11-02 2014-05-14 西北农林科技大学 Method for purifying carabrone
CN104945361A (en) * 2015-06-19 2015-09-30 中国医学科学院药用植物研究所 Germacrane sesquiterpenoid derivative and preparation method and application thereof
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

Families Citing this family (1)

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

Cited By (8)

* 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
WO2013097424A1 (en) * 2011-12-30 2013-07-04 中国科学院南海海洋研究所 Marine streptomyces sp., compound of pyranosesquiterpenes and preparation method and use thereof
US9200301B2 (en) 2011-12-30 2015-12-01 South China Sea Institute Of Oceanology, Chinese Academy Of Sciences Marine streptomyces, pyranosesquiterpene compound, as well as preparation method and applications thereof
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
CN104945361A (en) * 2015-06-19 2015-09-30 中国医学科学院药用植物研究所 Germacrane sesquiterpenoid derivative and preparation method and application thereof
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

Also Published As

Publication number Publication date
CN101050209B (en) 2010-05-12

Similar Documents

Publication Publication Date Title
CN101050209A (en) Eudesmane type sesquiterpene lactone compound extracted from Carpesium macrocephalum and having antibacterial activity, and its application
US20220119761A1 (en) Aspergillus niger f22 strain having nematicidal activity against plant-parasitic nematodes, and use thereof
CN108033916B (en) Preparation of amino acid ester compound and application of amino acid ester compound in preventing and treating tobacco diseases
CN101928271A (en) 3-o-methylphenyl-2-oxo-1-oxaspiro[4,4]-n-3-ene-4-alcohol and derivatives thereof
CN109234021A (en) A kind of preparation method of medical ozone carburetion
CN1281136C (en) Pesticidal disease-preventing plant growth promoter and its prepn
CN100494188C (en) Carrageenan sesquiterpene lactone compound separated from Carpesium macrocephalum with bactericidal activity and application thereof
CN108191629A (en) A kind of ferulic acid derivative and its application
CN1092106A (en) Plant hormone-dependent/non-dependent cell culture
CN110100823A (en) Panaxsaponin mixture and its application and fungicide and preparation method thereof and the method for inhibiting graw mold of tomato
CN100342787C (en) Combination of insect disinfectations containing benzoate of Avermectin in methylamine group and azadirachtin
CN1200608C (en) Medicine for resisting rice blast, its preparation method and application
CN107445933B (en) 3-coumarin formic acid compound and application thereof in preparation of phytopathogen antibacterial agent
CN1529550A (en) Plant growth regulator for increasing crop gield comprising polyprenol and extraction method thereof
CN1021906C (en) Method for the preparation of ethers
JP2514038B2 (en) Plant treatment
CN1066454C (en) Physiologically active substances of plant, process for the preparation thereof, and utilities thereof
CN101305728B (en) Use of double tetrahydrofuran lignans compound with fungicidal property
CN103554026A (en) 3-trifluoromethyl-4-formyl pyrazole compounds
CN111004208B (en) 2-cyano-3-thiophene substituted valeramide derivative and application thereof
CN102731455B (en) Carabrone derivatives having bactericidal activities, and use thereof
CN1074250C (en) Application of diniconazole emulsion in preventing and treating sigatoka
CN1293046C (en) Unsaturated oximino ether compound with fungicidal, insecticidal activity
CN114903059A (en) Thymus vulgaris oil and application of preparation thereof in preventing and treating crop soft rot
CN1433686A (en) Stress resistance plant growth regulator and preparation process and use thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
ASS Succession or assignment of patent right

Owner name: FUJI BIOTECH. (SHANGHAI) CO., LTD.

Free format text: FORMER OWNER: YANGLING NWSUAF RESEARCH + DEVELOPMENT CENTER OF BIORATIONAL PESTICIDE

Effective date: 20110929

C41 Transfer of patent application or patent right or utility model
C56 Change in the name or address of the patentee

Owner name: YANGLING NWSUAF RESEARCH + DEVELOPMENT CENTER OF B

Free format text: FORMER NAME: NUISANCELESS PESTICIDE RESEARCH SERVICE CENTER, XIBEI AGROFORESTRY SCIENCE AND T

COR Change of bibliographic data

Free format text: CORRECT: ADDRESS; FROM: 712100 XIANYANG, SHAANXI PROVINCE TO: 200443 BAOSHAN, SHANGHAI

CP03 Change of name, title or address

Address after: 712100 Yangling District, Shaanxi Province

Patentee after: RESEARCH & DEVELOPMENT CENTER OF BIORATIONAL PESTICIDE YANGLING NONGKEDA

Address before: 712100 Shaanxi Province, Xi'an city Yangling District Tai Road No. 3 demonstration

Patentee before: Pollution free pesticide research and service center of northwest agricultural and Forestry University

TR01 Transfer of patent right

Effective date of registration: 20110929

Address after: 200443 Shanghai City, Baoshan District No. 588 South Building 10C Yunlu Ji

Patentee after: FUJI BIOLOGICAL TECHNOLOGY DEVELOPMENT (SHANGHAI) CO.,LTD.

Address before: 712100 Yangling District, Shaanxi Province

Patentee before: RESEARCH & DEVELOPMENT CENTER OF BIORATIONAL PESTICIDE YANGLING NONGKEDA

CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20100512

Termination date: 20181110

CF01 Termination of patent right due to non-payment of annual fee