CN101305728B - Use of double tetrahydrofuran lignans compound with fungicidal property - Google Patents

Use of double tetrahydrofuran lignans compound with fungicidal property Download PDF

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CN101305728B
CN101305728B CN2008101501312A CN200810150131A CN101305728B CN 101305728 B CN101305728 B CN 101305728B CN 2008101501312 A CN2008101501312 A CN 2008101501312A CN 200810150131 A CN200810150131 A CN 200810150131A CN 101305728 B CN101305728 B CN 101305728B
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prinsepiol
ester group
molecular structure
chemical name
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CN101305728A (en
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张秀云
冯俊涛
郭琪
马志卿
张兴
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Nuisanceless Pesticide Research Service Center Xibei Agroforestry Science And T
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Abstract

The invention discloses a double-effect tetrahydrofuran type lignan compound with fungicidal activity. The compound is taken as the fungicide and can be used for preparing the pesticide preparations for controlling the plant diseases caused by plant pathogenic fungi.

Description

Application with double tetrahydrofuran lignans compound of bactericidal activity
Technical field
The present invention relates to double tetrahydrofuran lignans compound, the double tetrahydrofuran lignans compound that particularly has a bactericidal activity is used to prepare the application of the plant disease pesticidal preparations that control causes by plant pathogenic fungi as bactericide.
Background technology
Prinsspiol is a double tetrahydrofuran lignans, and normal temperature is white needle-like crystals (CHCl down 3), m.p.123 ℃～124 ℃, be soluble in organic solvents such as acetone, ethyl acetate, chloroform at normal temperatures, water insoluble, molecular formula is C 20H 24O 8, its structural formula is as follows:
Figure S2008101501312D00011
Through applicant's data-searching, double tetrahydrofuran lignans Prinsrpiol does not have relevant report aspect controlling plant diseases.
Summary of the invention
The objective of the invention is to, provide double tetrahydrofuran lignans compound to be used to prepare the application of the plant disease pesticidal preparations that control causes by plant pathogenic fungi as bactericide with bactericidal activity.
Can be used as the application that bactericide is used to prepare the plant disease pesticidal preparations that control causes by plant pathogenic fungi through applicant's the double tetrahydrofuran lignans compound that experiment showed, bactericidal activity.
Embodiment
The present invention adopts to separate from valerian Valeriana laxiflora plant and has obtained Prinsepiol, concrete grammar is: the valerian Valeriana laxiflora plant sample of drying is pulverized, soaked 3 days with 95% industrial alcohol under the room temperature, merge total leachate, ethanol is reclaimed in distillation, and concentrate is the total medicinal extract of valerian Valeriana laxiflora alcohol extract.This medicinal extract is scattered in the hot water, with ethyl acetate extraction 2 times, get ethyl acetate extraction phase medicinal extract, by silica gel column chromatography, sample on the dry method, benzinum acetone (9: 1) wash-out, analyze to merge by TLC and to obtain 6 components, the 2nd component is placed after one day the adularescent acicular crystal and is separated out, and uses the benzinum acetone recrystallization, the gained white needle-like crystals is double tetrahydrofuran lignans Prinsepiol after testing.
With Prinsepiol is raw material, it is synthetic that it is derived, and carry out bactericidal activity and measure, therefrom filter out the higher compound of bactericidal activity: 4 '-acetate groups prinsepiol, 4,4 '-oxalic acid ester group prinsepiol, 4,4 '-dibutoxy prinsepiol and 4,4 '-DAADBSA ester group prinsepiol.
The chemical name of each compound and molecular structure are as follows respectively:
Compound I 4 '-monoacetate base prinsepiol:
Compound I I 4,4 '-oxalic acid ester group prinsepiol:
Compound III 4,4 '-dibutoxy prinsepiol:
Figure S2008101501312D00031
Compound IV 4,4 '-DAADBSA ester group prinsepiol:
Figure S2008101501312D00032
Below narrate the physicochemical property and the synthetic route of each compound:
1. the physicochemical property of compound and spectral data
4 '-acetate groups prinsepiol (Compound I): white amorphous powder, m.p.105～107 ℃; UV λ Max MeOHNm:279; [α] D 25-19.7 ° (c0.10, EtOAc); IR v Max KBr: 3393,1761,1607,1518cm -1HRMS (ESI): m/z calcd for C 22H 24O 9+ NH 4450.176 4, found450.1766; 1H-NMR (400MHz, DCCl 3) δ: 7.27 (1H, s, H-5 '), 7.05 (1H, t, J=5.2Hz, 2.0Hz, H-6 '), 6.94 (1H, s, H-2 '), 6.92 (1H, t, J=2.8Hz, 1.6Hz, H-6), 6.86 (1H, s, H-5), 6.84 (2H, s, H-2), 5.04 (1H, s, H-7 '), 5.00 (1H, s, H-7), 4.19 (1H, d, J=2.0Hz, H-9 α), 4.17 (1H, d, J=4.0Hz, H-9 ' α), 4.16 (1H, d, J=4.0Hz, H-9 β), 4.14 (1H, d, J=4.0Hz, H-9 ' β), 4.12 (3H, s, 3 '-OCH 3), 3.89 (3H, d, J=3.2Hz, 3-OCH 3), 2.32 (3H, s, R ' 2,-CH 3); 13C-NMR (100MHz, DCCl 3) δ: 169.08 (C-R ' 1), 151.22 (C-3 '), 146.81 (C-3), 145.94 (C-4), (139.63 C-1 '), 135.04 (C-4 '), 127.48 (C-1), 122.75 (C-5 '), 120.01 (C-6), 119.13 (C-6 '), 114.53 (C-5), 111.35 (C-2), 109.65 (C-2 '), 87.71 (C-8), (87.54 C-8 '), 87.12 (C-7), 86.32 (C-7 '), 76.58 (C-9,9 '), 55.96 (CH 3O-3,3 '), 20.60 (C-R ' 2).
4,4 '-oxalic acid ester group prinsepiol (Compound I I): white needle-like crystals, m.p.179～181 ℃; UV λ Max MeOHNm:273; [α] D 25-20.3 ° (c 0.10, EtOAc); IR v Max KBr: 3409,1763,1607,1514cm -1HRMS (ESI): m/z calcd for C 24H 26O 10+ NH 4492.186 4, found492.1857; 1H-NMR (400MHz, DCCl 3) δ: 7.27 (2H, s, H-5, H-5 '), 7.02 (2H, t, J=2.4Hz, 4.4Hz, H-6, H-6 '), 6.92 (2H, d, J=8.4Hz, H-2, H-2 '), 5.02 (2H, d, J=6.8Hz, H-7, H-7 '), 4.14 (2H, d, J=7.6Hz, H-9 α, H-9 ' α), 4.09 (2H, d, J=2.8Hz, H-9 β, H-9 ' β), 3.83 (6H, s, 3,3 '-OCH 3), 2.30 (6H, s, R 2, R ' 2,-CH 3); 13C-NMR (100MHz, DCCl 3) δ: 169.12 (C-R 1, R ' 1), 151.04 (C-3,3 '), 139.46 (C-1,1 '), 134.38 (C-4,4 '), 122.60 (C-5,5 '), 119.04 (C-6,6 '), 111.25 (C-2,2 '), 87.63 (C-8,8 '), 86.37 (C-7,7 '), 76.54 (C-9,9 '), 55.84 (CH 3O-3,3 '), 20.60 (C-R 2, R ' 2).
4,4 '-dibutoxy prinsepiol (compound III): yellow oily liquid, UV λ Max MeOHNm:280,238; [α] D 25-16.6 ° (c 0.10, EtOAc); IR v Max KBr: 3424,2932,2864,1760,1611,1519cm -1HRMS (ESI): m/z calcd for C 28H 38O 8+ NH 4520.2907 found 520.2921; 1H-NMR (400MHz, DCCl 3) δ: 7.28 (2H, s, H-6, H-6 '), 7.11 (2H, s, H-5, H-5 '), 6.92 (2H, m, H-2, H-2 '), 4.94 (2H, d, J=3.2Hz, H-7, H-7 '), 4.15 (2H, d, J=6.0Hz, H-9 α, H-9 ' α), 3.94 (4H, t, J=6.0Hz, H-R 1, H-R ' 1), 3.89 (6H, s, 3,3 '-OCH 3), 3.85 (4H, s, H-9 β, H-9 ' β), 1.81 (4H, m, H-R 2, H-R ' 2), 1.31 (4H, m, H-R 3, H-R ' 3), 1.10 (6H, t, J=1.2Hz, 2.4Hz, H-R 4, H-R ' 4); 13C-NMR (100MHz, DCCl 3) δ: 149.23 (C-3,3 '), 148.49 (C-4,4 '), 129.21 (C-1,1 '), 120.92 (C-6,6 '), 119.49 (C-5,5 '), 112.47 (C-2,2 '), 88.16 (C-8,8 '), 85.92 (C-7,7 '), 71.38 (C-9,9 '), 68.67 (C-R 1, R ' 1), 55.93 (CH 3O-3,3 '), 29.19 (C-R 2, R ' 2), 19.14 (C-R 3, R ' 3), 13.79 (C-R 4, R ' 4).
4,4 '-DAADBSA ester group prinsepiol (compound IV): yellow colloidal solid, UV λ Mzx MeOHNm:283,275; [α] D 25-61.3 ° (c 0.10, EtOAc); IR v Max KBr: 3450,2936,2863,1702,1604,1512cm -1HRMS (ESI): m/z calcd for C 32H 30O 12S 2+ Na 693.1076, and found 693.1107; 1H-NMR (400MHz, DCCl 3) δ: 7.86 (4H, d, J=7.6Hz, H-R 2, R 6, R ' 2, R ' 6), 7.65 (4H, d, J=7.6Hz, H-R 3, R ' 3, R 5, R ' 5), 7.50 (2H, t, J=8.0Hz, H-R 4, H-R ' 4), 7.15 (2H, t, J=7.6Hz, H-6, H-6 '), 6.95 (2H, d, J=6.0Hz, H-5, H-5 '), 6.90 (2H, m, H-2, H-2 '), 4.99 (2H, d, J=2.4Hz, H-7, H-7 '), 3.72 (6H, s, 3,3 '-OCH 3), 3.69 (2H, s, H-9 α, H-9 ' α), 3.49 (2H, d, J=2.8Hz, H-9 β, H-9 ' is β); 13C-NMR (100MHz, DCCl 3) δ: 151.73 (C-3,3 '), 151.52 (C-R 1, R ' 1), 137.76 (C-4,4 '), 135.98 (C-1,1 '), 135.72 (C-R 4, R ' 4), 128.69 (C-R 3, R ' 3, R 5, R ' 5), 128.38 (C-R 2, R ' 2, R 6, R ' 6), 123.90 (C-6,6 '), 118.93 (C-5,5 '), 114.51 (C-2,2 '), 107.72 (C-8,8 '), 87.75 (C-7,7 '), 75.25 (C-9,9 '), 55.86 (CH 3O-3,3 ').
2.prinsepiol the synthetic route of derivative
2.1 Compound I and Compound I I's is synthetic
Take by weighing prinsepiol 300mg (0.8mmol) in the round-bottomed flask of 50mL, add the CH of 20mL drying again 2Cl 2With no 1mL water pyridine, put reaction system in ice-water bath, slowly drip a certain amount of chloroacetic chloride and dry CH in the stirring 2Cl 2(Compound I adds the amount of chloroacetic chloride and the mol ratio of raw material is 1.2: 1 for mixed solution, Compound I I adds the amount of chloroacetic chloride and the mol ratio of raw material is 3.5: 1), after adding acyl chlorides, remove ice-water bath, after the question response system is warming up to room temperature maintenance 40min, 40 ℃ of following back flow reaction 2h, TLC follow the tracks of and detect to there not being raw material, add saturated Na2CO 3Aqueous solution cessation reaction, organic facies are used 0.3% hydrochloric acid successively, saturated CuSO 4The aqueous solution, saturated Na 2CO 3The aqueous solution, saturated common salt water washing, anhydrous Na 2SO 4Drying obtains white amorphous powder after volatilizing solvent.
Compound I: through silica gel column chromatography (benzinum: acetone=30: 1) separate, obtain Compound I (4 '-acetate groups prinsepiol, 198mg, productive rate 66.0%).
Compound I I: through silica gel column chromatography (benzinum: acetone=40: 1) separate, obtain Compound I I (4,4 '-oxalic acid ester group prinsepiol, 230mg, productive rate 76.7%).
The synthetic route of Compound I and Compound I I is:
Figure S2008101501312D00061
2.2 compound III is synthetic
Take by weighing prinsepiol 800mg (2mmol) in the round-bottomed flask of 100mL, add the oxolane dissolving of 60mL again through no water treatment, add a little sodium metal then, 40 ℃ of following back flow reaction 45min, adding and material molar ratio are 2.5: 1 n-butyl bromide again, continue to add hot reflux, TLC follows the tracks of and detects to there not being raw material, add the low amounts of water cessation reaction, organic facies 0.3% hydrochloric acid, saturated Na 2CO 3The aqueous solution, saturated common salt water washing, anhydrous Na 2SO 4Drying volatilizes solvent and obtains the yellow oily liquid compound, through one-level silica gel column chromatography and secondary silica gel column chromatography (benzinum: acetone=30: 1) separate after, obtain compound III (4,4 '-dibutoxy prinsepiol, 430mg, productive rate 53.8%).
The synthetic route of compound III is:
Figure S2008101501312D00071
2.3 compound IV (4,4 '-DAADBSA ester group prinsepiol) is synthetic
Take by weighing prinsepiol 600mg (1.5mmol) in the round-bottomed flask of 100mL, add the CH of 50mL drying again 2Cl 2With no 10mL water pyridine, put reaction system in ice-water bath, slowly drip benzene sulfonyl chloride and dry CH in the stirring 2Cl 2Mixed solution, adding the amount of benzene sulfonyl chloride and the mol ratio of raw material is 3.5: 1.After adding acyl chlorides, remove ice-water bath, after the question response system was warming up to room temperature maintenance 40min, 40 ℃ of following back flow reaction 36h, TLC followed the tracks of and detect to there not being raw material, add saturated Na 2CO 3Aqueous solution cessation reaction, organic facies are used 0.3% hydrochloric acid successively, saturated Na 2CO 3The aqueous solution, saturated common salt water washing, anhydrous Na 2SO 4Drying obtains yellow colloidal cpd after volatilizing solvent, through one-level silica gel column chromatography and secondary silica gel column chromatography (benzinum: acetone=40: 1) separate, obtain compound IV (4,4 '-DAADBSA ester group prinsepiol, 380mg, productive rate 63.3%).
The synthetic route of compound IV is:
Figure S2008101501312D00072
3, by the biocide preparation of compound
Double tetrahydrofuran lignans prinsepiol and derivative 4 ' thereof-acetate groups prinsepiol, 4,4 '-oxalic acid ester group prinsepiol, 4,4 '-dibutoxy prinsepiol and 4,4 '-DAADBSA ester group prinsepiol can make the bactericide of various preparation forms, spraying is suitable for, and is used for the control of plant disease.The percentage by weight of each material is in the various formulations:
Formulation Double tetrahydrofuran lignans compound % Filler or solvent % Surfactant %
Wetting powder 20～90 0～74 1～10
Missible oil 5～50 40～90 5～15
Microemulsion 10～50 40～84 1～20
By the various preparations that double tetrahydrofuran lignans compound is formed, filler wherein can be one or more mixtures in the material known altogether of this area staff such as white carbon, bentonite, diatomite; 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; Surfactant can be that those skilled in the art know and one or more mixture of commonly used all kinds of surface reactive materials altogether, as calcium dodecyl benzene sulfonate, styrene acid APEO, ethoxylated dodecyl alcohol, octyl phenol polyoxy ethyl ether draws back one or more mixture of surfactants such as powder, saponin, lignin, Sulfonates material, alkyl sulfonates material, laruyl alcohol.
Compound and the preparation thereof that the application is related to set forth the control of plant disease effect by the following examples.
4, biological activity determination data
This research is chosen 22 kinds of pathogens altogether as for the examination bacterial classification, lists in table 4-1 for the examination bacterial classification.All provide by Nuisanceless Pesticide Research Service Center, Xibei Agroforestry Science and T for the examination bacterial classification.
The test plant host material: wheat Triticum aestivum, Shan-451 susceptible variety is provided by Xibei Univ. of Agricultural ﹠ Forest Science ﹠ Technology wheat center; Tomato Lycopersicon esculentum fruit picks up from Yang Ling Yangchuan village township plastic greenhouse; Cucumber (grind No. seven in Tianjin), commercial; Corn (Shan 9) is susceptible variety, is provided by agricultural college of Xibei Univ. of Agricultural ﹠ Forest Science ﹠ Technology.
Standard medicament: 15% triadimefon WP (Tianmen, Hubei insecticide factory), 50% Sukeling WP (SUMITOMO CHEMICAL chemical industry Co., Ltd.).
Table 4-1 is for the examination pathogen
Table?4-1?Agruculture?fungi?for?test
Figure S2008101501312D00081
Figure S2008101501312D00091
Growth rate method:
Compound adopts growth rate method to the inhibiting mensuration of pathogen 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 average diameter-4 (bacterium cake diameter) 4-1
The spore germination method:
Compound adopts sessile drop method to the inhibiting mensuration of germ spore germination.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 S2008101501312D00101
Figure S2008101501312D00102
Pot experiment:
Control efficiency to wheat powdery mildew, cucumber downy mildew adopts the pot experiment method to carry out.Concrete grammar is as follows:
10～15 wheats of every nutritive cube sowing or 2～3 cucumber seeds of vernalization,, treat that wheat and cucumber grow to two leaves during the phase (cucumber is a true leaf), treat with protective effect and test in hot-house culture.Carry out dispenser with conventional spray, 3 repetitions are established in each processing, establish the contrast of solvent control and clear water.
Adopt the spore dithering to carry out the inoculation of wheat white powder, it is 18 ± 1 ℃ that the wheat after the processing places temperature, cultivates under illumination/dark=8h/16h condition, according to disease a situation arises classification investigation, calculates and respectively handles disease index and control efficiency.
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 pathogen 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.Checkout facility result behind 6～8d; Protective effect is at first sprayed medicine to seedling and is handled, and connects bacterium behind the 24h again, checks blade incidence and record, statistical results behind cultivation 6～8d.
The grade scale of wheat powdery mildew (is unit with the blade):
0 grade: the blade face does not have scab;
1 grade: have only a small amount of limited mycelium on the blade, no spore;
2 grades: the blade face mycelia scale of construction is medium, and some spores are arranged, and organizes slight necrosis and chlorisis;
3 grades: mycelial amount is medium or a lot, and the amount that spore produces is limited, and some necrosis and chlorisis are arranged;
4 grades: sorus is very big, produces a large amount of spores, does not have necrosis.
The grade scale of cucumber downy mildew (is unit with the blade):
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.
Adopt formula (4-5) and (4-6) calculating disease index and control efficiency:
Figure S2008101501312D00111
Figure S2008101501312D00112
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 sterilization treatment.Sting out the zone of infecting of the about 5mm of diameter on the tamato fruit surface with transfer needle, in order to infecting of ash arrhizus bacteria.Make the bacterium cake with the card punch of diameter 4mm, the bacterium cake is tipped upside down on the tamato fruit surface.Divide protection and treat two kinds of methods processing.Protective effect is sprayed directly on fruit surface for adopt spray-on process 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.
4.1 5 kinds of compounds such as Prinsepiol are to the inhibition effect of phytopathogen mycelial growth
Adopt growth rate method to test the virulence of 5 kinds of compounds such as Prinsepiol, 4 '-acetate groups prinsepiol, the results are shown in Table 4-1-1～table 4-1-5 several pathogens.
Table 4-1-1 prinsepiol is to the inhibition virulence (4d) of 12 kinds of pathogen mycelial growths
For the examination pathogen Toxicity regression line (Y=) EC 50(95％CL) (mg/L) Correlation coefficient
Dry rot of apple bacterium B.berengeriana 2.6299+1.6243x 43.5542(26.6021～56.3152) 0.9598
Cotton-wilt fusarium F.oxysporumf.sp.vasinfectum 1.2103+2.0368x 72.5487(57.6370～91.3182) 0.9926
Cladosporium leaf and fruit mould of tomato bacterium F.fulva 1.7347+2.1988x 43.8569(32.6323～58.9424) 0.9805
Botrytis cinerea B.cinerea 1.1003+2.5622x 31.5526(20.8285～67.0748) 0.9971
Phytophthora capsici germ P.capsici 1.3582+2.7650x 26.7543(16.8793～35.5188) 0.9695
Cotton rhizoctonia solani R.solani 2.3328+1.6243x 53.2666(38.0202～69.4953) 0.9956
Pumpkin wilt F.bulbigenum 0.6123+2.8062x 36.6097(31.5517～52.4785) 0.9887
Cucumber anthracnose C.lagenarium 3.2909+1.1092x 44.7439(30.6758～58.3840) 0.9784
Fusarium graminearum G.zeae 2.9454+1.4780x 24.6726(20.3009～29.9858) 0.9815
Withered germ of water-melon F.oxysporium f.sp.niveum 3.8821+1.6208x 28.7881(21.7669～38.0740) 0.9139
Rhizoctonia cerealis R.cerealis 3.0859+1.7373x 22.6409(19.1983～37.3718) 0.9219
Gaeumannomyces graminis G.graminis 2.5956+1.7271x 17.8947(13.2842～37.2951) 0.9894
Table 4-1-2 4 '-acetate groups prinsepiol is to the inhibition virulence (4d) of 9 kinds of pathogen mycelial growths
For the examination pathogen Toxicity regression line (Y=) EC 50(95％CL) (mg/L) Correlation coefficient
Cucumber anthracnose C.lagenarium 1.4294+3.5795x 20.1013(17.3711～28.5926) 0.9916
Botrytis cinerea B.cinerea 1.2031+2.6905x 12.2609(10.8787～29.8640) 0.9615
Cladosporium leaf and fruit mould of tomato bacterium F.fulva 0.4183+2.4772x 19.4500(10.5314～26.63.08) 0.9705
Tomato early blight bacterium A.solani 2.6549+1.2814x 27.6224(22.2070～41.9811) 0.9674
Phytophthora capsici germ P.capsici 1.0474+2.2980x 22.7330(11.9703～43.1726) 0.9538
Valsa mali V.mali 2.5679+1.2293x 43.0132(26.0117～67.0594) 0.9735
Cotton-wilt fusarium F.oxysporum f.sp. vasinfectum 2.4806+1.2798x 35.1512(17.1340～43.8609) 0.9873
Cucumber anthracnose C.lagenarium 1.1552+1.6396x 22.1967(17.9540～26.9391) 0.9884
Rhizoctonia cerealis R.cerealis 0.8192+2.1423x 19.4369(10.5756～28.1584) 0.9983
Gaeumannomyces graminis G.graminis 1.3442+2.8373x 10.9428(6.6809～16.7973) 0.9706
Rice blast fungus P.oryzae 0.2774+3.4810x 14.4808(9.2486～18.1396) 0.9354
Table 4-1-3 4,4 '-oxalic acid ester group prinsepiol is to the inhibition virulence (4d) of 8 kinds of pathogen mycelial growths
Figure S2008101501312D00131
Table 4-1-4 4,4 '-dibutoxy prinsepiol is to the inhibition virulence (4d) of 8 kinds of pathogen mycelial growths
Figure S2008101501312D00132
Table 4-1-5 4,4 '-DAADBSA ester group prinsepiol is to the inhibition virulence (4d) of 8 kinds of pathogen mycelial growths
Figure S2008101501312D00133
Figure S2008101501312D00141
4.25 plant the inhibition effect of compound to the phytopathogen spore germination
Adopt sessile drop method to test the virulence of 5 kinds of compounds such as Prinsepiol, 4 '-acetate groups prinsepiol, the results are shown in Table 4-2-1～table 4-2-5 several pathogen spore germinations.
Table 4-2-1 prinsepiol is to the inhibition virulence of 7 kinds of pathogen spore germinations
For the examination pathogen Toxicity regression line (Y=) EC 50(95％CL) (mg/L) Correlation coefficient
Cucumber anthracnose C.lagenarium 2.7492+2.6880x 22.8765(20.0920～29.7620) 0.9994
Exserohilum turcicum E.turcicum 1.4174+2.5178x 28.2795(17.1432～34.2681) 0.9952
Cladosporium leaf and fruit mould of tomato bacterium F.fulva 2.4225+3.0880x 37.8173(33.8036～42.3076) 0.9346
Botrytis cinerea B.cinerea 0.9074+2.1787x 28.4789(25.0903～37.9445) 0.9954
Fusarium graminearum G.zeae 2.0898+1.8446x 33.3247(23.2644～42.3369) 0.9983
Tobacco brown spot pathogen A.alternata 1.4849+1.5028x 45.5976(36.0411～62.7766) 0.9998
Bacterium of downy mildew of cucumber P.cubensis 1.3802+2.6944x 24.0523(18.5908～29.6447) 0.9985
Table 4-2-2 4 '-acetate groups prinsepiol is to the inhibition virulence of 7 kinds of pathogen spore germinations
Table 4-2-3 4,4 '-oxalic acid ester group prinsepiol is to the inhibition virulence of 6 kinds of pathogen spore germinations
For the examination pathogen Toxicity regression line (Y=) EC 50(95％CL) (mg/L) Correlation coefficient
Cucumber anthracnose C.lagenarium 2.2052+1.9643x 16.4717(12.2636～24.8807) 0.9501
Exserohilum turcicum E.turcicum 1.8041+1.4095x 21.1256(14.1785～32.6654) 0.9335
Cladosporium leaf and fruit mould of tomato bacterium F.fulva 2.0646+1.6826x 25.5415(22.3559～35.2314) 0.9653
Botrytis cinerea B.cinerea 1.9605+4.0085x 18.0875(14.4221～24.6909) 0.9601
Fusarium graminearum G.zeae 2.8638+1.3514x 24.9705(21.0919～34.3776) 0.9753
Bacterium of downy mildew of cucumber P.cubensis 1.3241+2.5046x 14.5060(43.4619～68.3566) 0.9597
Table 4-2-4 4,4 '-dibutoxy prinsepiol is to the inhibition virulence of 6 kinds of pathogen spore germinations
For the examination pathogen Toxicity regression line (Y=) EC 50(95％CL) (mg/L) Correlation coefficient
Cucumber anthracnose C.lagenarium 2.3119+1.6742x 21.8765(18.0920～3.7625) 0.9501
Exserohilum turcicum E.turcicum 2.7341+1.6826x 26.2795(19.1432～34.2683) 0.9773
Cladosporium leaf and fruit mould of tomato bacterium F.fulva 2.3518+1.5955x 31.8173(28.8036～40.3078) 0.9523
Botrytis cinerea B.cinerea 1.6594+1.8873x 29.4789(25.0913～34.9465) 0.9719
Fusarium graminearum G.zeae 0.3619+2.2113x 34.3247(25.2644～40.3369) 0.9419
Bacterium of downy mildew of cucumber P.cubensis 1.5704+1.7761x 37.5976(31.0411～52.7766) 0.9679
Table 4-2-5 4,4 '-DAADBSA ester group prinsepiol is to the inhibition virulence of 6 kinds of pathogen spore germinations
For the examination pathogen Toxicity regression line (Y=) EC 50(95％CL) (mg/L) Correlation coefficient
Cucumber anthracnose C.lagenarium 1.1569+2.2671x 25.6702(15.7076～34.9904) 0.9708
Exserohilum turcicum E.turcicum 4.0875+1.1491x 16.2253(12.8213～24.7362) 0.9403
Cladosporium leaf and fruit mould of tomato bacterium F.fulva 3.1959+1.1067x 22.1522(15.5457～26.6288) 0.9139
Botrytis cinerea B.cinerea 2.5376+1.6050x 25.8800(21.9316～32.1398) 0.9449
Fusarium graminearum G.zeae 3.7452+1.1568x 34.2125(29.4085～50.3083) 0.9772
Bacterium of downy mildew of cucumber P.cubensis 1.8500+2.0259x 29.5623(23.2062～43.9739) 0.9881
4.3Prinsepiol Deng the control efficiency of 5 kinds of compounds to 3 plant species diseases
4.3.1 potted plant control efficiency to wheat powdery mildew
Each compound is mixed with 10% missible oil, adopts the greenhouse pot culture method to measure its drug effect, the results are shown in Table 4-3-1 wheat powdery mildew.
5 kinds of compounds such as table 4-3-1prinsepiol are to the potted plant test of pesticide effectiveness result (8d) of wheat powdery mildew
Figure S2008101501312D00151
Annotate: 1. data are the mean value of 3 repetitions in the table; 2. the drug effect of compound such as prinsepiol ' is calculated and is adopted solvent control, and the drug effect of triadimefon is calculated and just contrasted with clear water; 3. in the preventive effect hurdle, be illustrated in the variance analysis (Duncan ' s method) significant difference on 0.05 level with the different lowercase persons of mark behind the column of figure.
4.3.2 potted plant control efficiency to cucumber downy mildew
Each compound is mixed with 10% missible oil, adopts the greenhouse pot culture method to measure its drug effect, the results are shown in Table 4-3-2 cucumber downy mildew.
5 kinds of compounds such as table 4-3-2prinsepiol are to the potted plant test of pesticide effectiveness result (6d) of cucumber downy mildew
Figure S2008101501312D00161
Annotate: 1. data are the mean value of 3 repetitions in the table; 2. the drug effect of compound such as prinsepiol is calculated and is adopted solvent control, the drug effect of ethyl phosphine aluminium to calculate to use the clear water contrast; 3. in the preventive effect hurdle, be illustrated in the variance analysis (Duncan ' s method) significant difference on 0.05 level with the different lowercase persons of mark behind the column of figure.
4.3.3 control efficiency to graw mold of tomato
Adopt the fruit needle point method to measure its drug effect, the results are shown in Table 4-3-3 graw mold of tomato.
5 kinds of compounds such as table 4-3-3prinsepiol are to the control efficiency (3d) of graw mold of tomato
Figure S2008101501312D00162
Figure S2008101501312D00171
The preparation of the various preparations of 5 each compound
The prinsepiol wetting powder preparation of EXPERIMENTAL EXAMPLE 1:20%:
In cone-type mixer, add the prinsepiol 20kg that is crushed to about 200 orders, the white carbon black 50kg of commercially available commodity filler, bentonite 20kg, and draw back powder 5kg, saponin 5kg.Fully mixed, can make 20%prinsepiol wetting powder 100kg.Dispersed in its water of the preparation that makes, stable, the cold and hot storage stability of dilution meets the commercially available agricultural chemical preparation and must ask.
The prinsepiol wetting powder preparation of EXPERIMENTAL EXAMPLE 2:50%:
The former medicinal powder of 50kg prinsepiol is broken to 300 orders, takes by weighing the white carbon black 30kg of commodity filler, sodium lignin sulfonate 15kg, ethoxylated dodecyl alcohol 5kg adds abundant mixing evenly in the mixer, can make 100kg 50% prinsepiol wetting powder.Dispersed in the preparation water that makes, stable, the cold and hot storage stability of dilution meets the commercially available agricultural chemical preparation and must ask.
The prinsepiol missible oil preparation of EXPERIMENTAL EXAMPLE 3:5%:
5kg carpesia-lactone ketone is dissolved in the 85kg ethyl acetate, and styrene acid APEO 10kg joins in the 200L reactor, stirs 0.5 hour under 40～50 ℃ of temperature, promptly makes 100kg 5% prinsepiol missible oil.The missible oil water dispersible that makes, dilution stability, cold and hot storage stability meet the commercially available agricultural chemical preparation and must ask.
4 ' of EXPERIMENTAL EXAMPLE 4:40%-acetate groups prinsepiol missible oil preparation:
In the 200L reactor, with 40kg 4 '-acetate groups prinsepiol, be dissolved in the mixed solvent of 15kg ethyl acetate and 30kg chloroform, add styrene acid APEO 10kg again, octyl phenol polyoxy ethyl ether 5kg, under 40～50 ℃ of temperature, stirred 0.5 hour, and promptly made 100kg 40% 4 '-acetate groups prinsepiol missible oil.The missible oil water dispersible that makes, dilution stability, cold and hot storage stability meet the commercially available agricultural chemical preparation and must ask.
4 ' of EXPERIMENTAL EXAMPLE 5:10%-acetate groups prinsepiol microemulsion preparation:
Take by weighing the former medicine 10kg of 4 '-acetate groups prinsepiol, be dissolved in the 20kg isopropyl alcohol, add the 5kg calcium dodecyl benzene sulfonate again, 10kg octyl phenol polyoxy ethyl ether, mixed under high-speed stirred, be heated to about 40 ℃; Drip deionized water 55kg under the high-speed stirred, 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%4 '-acetate groups prinsepiol microemulsion 100kg.The microemulsion stability that makes, outward appearance etc. meet the requirement of commodity preparation.
4 of EXPERIMENTAL EXAMPLE 6:20%, the preparation of 4 '-oxalic acid ester group prinsepiol microemulsion:
Take by weighing 4, the former medicine 20kg of 4 '-oxalic acid ester group prinsepiol is dissolved in the 20kg ethyl acetate, adds the 10kg calcium dodecyl benzene sulfonate again, and 10kg styrene acid APEO is mixed under high-speed stirred, is heated to about 40 ℃; Drip deionized water 40kg under the high-speed stirred, 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%4,4 '-oxalic acid ester group prinsepiol 100kg.The microemulsion stability that makes, outward appearance etc. meet the requirement of commodity preparation.
EXPERIMENTAL EXAMPLE 7:40% 4, the preparation of 4 '-dibutoxy prinsepiol wetting powder.In cone-type mixer, adding is crushed to 4 about 200 orders, 4 '-dibutoxy prinsepiol 40kg, and the white carbon black 20kg of commercially available commodity filler, bentonite 20kg, and draw back powder 5kg, lignin 15kg.Fully mixed, can make 40%4,4 '-dibutoxy prinsepiol wetting powder 100kg.Dispersed in the wetting powder water that makes, stable, the cold and hot storage stability of dilution meets the commercially available agricultural chemical preparation and must ask.
EXPERIMENTAL EXAMPLE 8:30% 4, the preparation of 4 '-DAADBSA ester group prinsepiol missible oil.In the 200L reactor, with 30kg 4,4 '-DAADBSA ester group prinsepiol, be dissolved in the 55kg methyl alcohol, add styrene acid APEO 5kg again, octyl phenol polyoxy ethyl ether 10kg stirred 0.5 hour under 40～50 ℃ of temperature, promptly make 100kg 30%4,4 '-DAADBSA ester group prinsepiol missible oil.The missible oil water dispersible that makes, dilution stability, cold and hot storage stability meet the commercially available agricultural chemical preparation and must ask.
6 field experiment EXPERIMENTAL EXAMPLE
With compound prinsepiol, 4 '-acetate groups prinsepiol, 4,4 '-oxalic acid ester group prinsepiol, 4,4 '-dibutoxy prinsepiol and 4,4 '-DAADBSA ester group prinsepiol, use compounding method of preparation of the present invention, being mixed with 20% microemulsion, having carried out the test of control grey mould fruit rot of strawberry bacterium in the land for growing field crops, is the contrast medicament with common fungicide 40% dimethachlon, clear water is contrast, and the control efficiency behind the variable concentrations medicine liquid spray sees Table 6-1.
In experiment, for various preparations, filler or the solvent of compound composition, the percentage by weight of surfactant, and the percentage that adds other Fungicidal active substances, by technical scheme preparation of the present invention, all can reach desirable effect.
Investigation method is taked parallel lines 2 row samplings, and the incidence of the above fruit of every row investigation 1.5cm is by the generation classification of following grade scale to the fruit gray mold.Calculate control efficiency 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 S2008101501312D00191
Table 6-1 20% each compound microemulsion is to the grey mould fruit rot of strawberry control efficiency
Figure S2008101501312D00192
Figure S2008101501312D00201

Claims (4)

1. the double tetrahydrofuran lignans compound that has a bactericidal activity is used to prepare the application of the plant disease pesticidal preparations that control causes by plant pathogenic fungi as bactericide.
2. application as claimed in claim 1 is characterized in that, described bactericidal double tetrahydrofuran lignans compound comprises following several, and their molecular structure and chemical name are respectively:
Compound 1: chemical name is Prinsepiol, and molecular structure is:
Figure S2008101501312C00011
Compound 2: chemical name is 4 '-acetate groups prinsepiol, and molecular structure is:
Figure S2008101501312C00012
Compound 3: chemical name is 4,4 '-oxalic acid ester group prinsepiol, and molecular structure is:
Figure S2008101501312C00021
Compound 4: chemical name is 4,4 '-dibutoxy prinsepiol, and molecular structure is:
Figure S2008101501312C00022
Compound 5: chemical name is 4,4 '-DAADBSA ester group prinsepiol, and molecular structure is:
Figure S2008101501312C00023
3. application as claimed in claim 2, it is characterized in that, described Compound P rinsepiol, compound 4 '-acetate groups prinsepiol, compound 4,4 '-oxalic acid ester group prinsepiol, compound 4,4 '-dibutoxy prinsepiol, compound 4,4 '-DAADBSA ester group prinsepiol makes wetting powder or missible oil or the microemulsion that is applicable to spraying, wherein:
Wetting powder, its material composition and percentage by weight thereof are: double tetrahydrofuran lignans compound: 20%～90%, filler or solvent: 0～74%, surfactant: 1%～10%;
Missible oil, its material composition and percentage by weight thereof are: double tetrahydrofuran lignans compound: 5%～50%, filler or solvent: 40%～90%, surfactant: 5%～15%, the summation of raw material is 100%;
Microemulsion, its material composition and percentage by weight thereof are: double tetrahydrofuran lignans compound: 10%～50%, filler or solvent: 40%～84%, surfactant: 1%～20%, the summation of raw material is 100%.
4. application as claimed in claim 3 is characterized in that, described filler is white carbon, bentonite, diatomite or known one or more mixtures; Described solvent be methyl alcohol, ethanol, just/isopropyl alcohol, ethyl acetate, aromatic hydrocarbon or known one or more mixtures; Described surfactant is one or more mixtures of all kinds of surface reactive materials used always.
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马春辉,李伯刚,许庆,张国林.柳叶忍冬的化学成分研究.应用与环境生物学报.2006,12(4),487～495. *

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