CN1298877A - Tacca chantrieri andre ketonic internal ester and its use - Google Patents

Tacca chantrieri andre ketonic internal ester and its use Download PDF

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CN1298877A
CN1298877A CN 99127275 CN99127275A CN1298877A CN 1298877 A CN1298877 A CN 1298877A CN 99127275 CN99127275 CN 99127275 CN 99127275 A CN99127275 A CN 99127275A CN 1298877 A CN1298877 A CN 1298877A
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hydroxyl
spp
hydrogen
group
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A·米尔鲍尔
M·格林
R·维尔滕
W·安德施
C·埃尔德伦
A·哈德
P·马尔曹克
R·瑙恩
A·图尔贝格
T·V·松
G·亚当
刘吉开
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Kunming Institute of Botany of CAS
Bayer AG
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Kunming Institute of Botany of CAS
Bayer AG
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Priority to CN 99127275 priority Critical patent/CN1298877A/en
Priority to PCT/EP2000/011846 priority patent/WO2001040256A1/en
Priority to AU26692/01A priority patent/AU2669201A/en
Publication of CN1298877A publication Critical patent/CN1298877A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/93—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems condensed with a ring other than six-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J71/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton is condensed with a heterocyclic ring
    • C07J71/0005—Oxygen-containing hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J71/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton is condensed with a heterocyclic ring
    • C07J71/0005—Oxygen-containing hetero ring
    • C07J71/001—Oxiranes

Abstract

The present invention relates to a netural compound with partly new compound, its preparation method and derivatives of these natural compounds and their use in contiolling insect pest.

Description

Arrow root ketone lactone and uses thereof
Wherein some is the natural compounds of new compound to the present invention relates to a class, obtains and prepare their method, the derivative of these natural compoundss, and they are used to control the purposes of animal pest.
Natural compounds of the present invention can be subordinated in the arrow root potato platymiscium of arrow root potato section and separate.At present, about 50 kinds of arrow root potato platymiscium (Tacca aspera have been found; Tacca bibracteata; Taccacardenasianum; Tacca caudatum; Tacca chanteraeri; Tacca chantrieri (arrow root potato); Tacca cheancer; Tacca cristata (cockscomb arrow root potato) Tacca cylindricum; Tacca dubium; Tacca hasslerianum; Tacca josephinae; Tacca laevis; Taccaleontopetaloides; Tacca madagascariensis; Tacca minor; Tacca oceanica; Tacca palmata; Tacca parkeri; Tacca paxiana; Tacca peregrinum; Taccaplantaginea (dehiscent fruit potato); Tacca quanzensis; Tacca samoensis; Taccasubflabellata; Tacca ulei; Tacca umbrarum; Tacca variable; Taccaviridis; Tacca warmingii; Tacca weddelianum) (referring to IndexKewensis, Oxford Unversity Press1933).They grow in the torrid zone and subtropical zone, particularly the area, Asia.In the medicinal plant among the people of Africa, use the ethanol extraction of Tacca leontopetaloides to kill slug and snail.In addition, the aqueous extract of Tacca leontopetaloides stem tuber control roundworm (A.Abdel-Aziz et al.Phytotheraphy Research, 1990,4,62-65).
13 kinds of compounds from Tacca plantaginea, have been isolated at present, according to its source, with its called after arrow root ketone lactone (Z.Chen, B.Wang, M.Chen, Tetrahedron lett.1987,28,1673; Z.Chen, J.Shen, Y.Gao Heterocycles 1989,29,2103; S.Vasanth, R.Hamsaveni Gopal, R.B.Rao, J.Scient.Ind.Res.1990,49,68; Z.Chen, B.Wang, J.Shen Phytochemistry 1,988 27, and 2999; S.Chen, Z.Gao, Y.SengChin.J.Chem.1991,1,92, Z.Chen, J.Shen, Y.Gao, M.Wichtl PlantaMedica 1997,63,40-43; J.Shen, Z.Chen, Y.Gao Phytochemistry 1996,42,891).But whether above-mentioned document has biological activity about these compounds, and perhaps, if having, which type of biological activity is not done open in detail up to today.
Now be surprisingly found out that Tacca paxiana, Tacca subflabellata, the extract of Taccaplantaginea and Tacca chanteraeri stem tuber has nematicide, kills insect and kills the epizoa activity.By the separation method of biological assay-control, can obtain 4 and have insect extremely, nematicide, anthelmintic kills mollusk and the active component of combatting ectoparasites.Be surprisingly found out that these active ingredients belong to arrow root ketone lactone, now from Tacca plantaginea, be separated to 13 different arrow root ketone lactones (A-M) (see above and show I A).Also reported the derivative of arrow root ketone lactone in the document; But do not report its biological activity (seeing Table I B) equally.
Now, we are successfully from Tacca paxiana, and Tacca subflabellata is separated to arrow root ketone lactone A among Taccaplantaginea and the Tacca chanteraeri, B, E and new arrow root ketone lactone N.Thereby the anthelmintic of the extract described in the plant amedica among the people and mollusk are killed actively linked together for the first time with these compounds.
Therefore, the present invention relates to logical formula I compound
Figure 9912727500081
R wherein 1The expression acetoxyl group, hydroxyl, hydrogen, C 1-C 4-alkoxyl group or glycoloyl oxygen base, R 2The expression acetoxyl group, hydroxyl, hydrogen, C 1-C 4-alkoxyl group or glycoloyl oxygen base, R 3The expression acetoxyl group, hydroxyl, hydrogen, C 1-C 4-alkoxyl group or glycoloyl oxygen base, R 4Expression hydrogen, R 5Expression hydrogen, or R 4And R 5Represent a carbon bond together, form a two key, R 6Expression hydrogen, or R 5And R 6Represent carbonyl with the carbon atom that they connected, or R 6And R 7Expression-OCOC (OH) (CH together 3)-group, wherein Sauerstoffatom is connected band
R is arranged 6On the carbon atom of group, or R 7And R 8Expression-C (OH) (CH together 3) the COO-group, wherein carbon atom is connected band
R is arranged 7On the carbon atom of group, or R 8The expression acetoxyl group, hydroxyl, hydrogen, glycoloyl oxygen base, C 1-C 4-alkoxyl group or
Doubly linked oxygen, R 9Expression hydrogen, R 10Expression hydrogen, or R 9And R 10Represent a carbon bond together, form a two key, R 11The expression acetoxyl group, hydrogen, glycoloyl oxygen base, C 1-C 4-alkoxyl group or hydroxyl,
Or R 10And R 11Represent carbonyl with the carbon atom that they connected, R 12The expression acetoxyl group, hydroxyl, hydrogen, glycoloyl oxygen base, C 1-C 4-alkoxyl group or
Doubly linked oxygen, R 13The expression acetoxyl group, hydroxyl, glycoloyl oxygen base, C 1-C 4-alkoxyl group or hydrogen, R 14Expression hydrogen, hydroxyl, acetoxyl group, C 1-C 4-alkoxy or halogen, R 15Expression hydrogen, hydroxyl, acetoxyl group, C 1-C 4-alkoxy or halogen, or R 14And R 15Represent oxygen together, thereby form epoxy group(ing), and all possible steric isomer of formula I compound, in agricultural, forestry, product and material are preserved, Pest Control such as nematode in animal health and the hygiene department, insect, mollusk, the purposes of combatting ectoparasites and worm.
Preferred formula I compound is formula (I A) steric isomer
In the context in the structural formula preferred substituted or group range be defined as follows.R 1Preferably represent acetoxyl group, hydroxyl, methoxyl group or hydrogen.R 2Preferably represent acetoxyl group, hydroxyl, methoxyl group, hydrogen or glycoloyl oxygen
Base.R 3Preferably represent acetoxyl group, hydroxyl, methoxyl group or hydrogen.R 8Preferably represent acetoxyl group, hydroxyl, methoxyl group, hydrogen or doubly linked
Oxygen.R 11Preferably represent acetoxyl group, methoxyl group or hydroxyl.R 12Preferably represent acetoxyl group, hydroxyl, methoxyl group, hydrogen or doubly linked oxygen.R 13Preferably represent hydroxyl, methoxyl group, acetoxyl group or hydrogen.R 14Preferably represent hydrogen, hydroxyl, acetoxyl group, methoxyl group or chlorine.R 15Preferably represent hydrogen, hydroxyl, acetoxyl group, methoxyl group or chlorine.R 1Particularly preferably represent acetoxyl group or hydroxyl.R 2Particularly preferably represent acetoxyl group, hydroxyl, glycoloyl oxygen base or hydrogen.R 3Particularly preferably represent acetoxyl group or hydroxyl.R 8Particularly preferably represent acetoxyl group, hydroxyl, hydrogen or doubly linked oxygen.R 11Particularly preferably represent hydroxyl or acetoxyl group.R 12Particularly preferably represent acetoxyl group, hydroxyl or doubly linked oxygen.R 13Particularly preferably represent acetoxyl group, hydroxyl or hydrogen.R 2Very particularly preferably represent acetoxyl group, hydroxyl or hydrogen.R 8Very particularly preferably represent acetoxyl group or hydroxyl.R 11Very particularly preferably represent hydroxyl.R 12Very particularly preferably represent doubly linked oxygen.R 13Very particularly preferably represent hydrogen.
Most preferred is the formula II compound
Figure 9912727500111
R wherein 2And R 8Definition as preferred, especially preferably or definition very particularly preferably.
The compound that the present invention specifically emphasizes is the formula III compound
Figure 9912727500112
The present invention also relates to formula I, the derivative of (II) or (III) compound, i.e. formula IV compound R wherein 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 14And R 15Define as above R 16The expression formyl radical, carboxyl or carboxyl methyl ester, R 17The expression formyl radical, carboxyl or carboxyl methyl ester, and R 18Expression hydrogen, acetoxyl group, hydroxyl or C 1-C 4-alkoxyl group, and all possible steric isomer of formula IV compound, in agricultural, forestry, product and material are preserved, Pest Control such as nematode in animal health and the hygiene department, insect, mollusk, the purposes of combatting ectoparasites and worm.
The preferred substituted of formula IV compound or scope such as above-mentioned R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 14And R 15Preferred, especially preferably or definition very particularly preferably.R 18Preferably represent hydrogen, acetoxyl group, hydroxyl methoxyl group.
Particularly preferably be formula (IV A) compound
Figure 9912727500131
Above-mentioned general or preferred group definition or explain arbitrarily combination mutually promptly comprises the combination between the scope and preferable range separately.
The present invention preferably includes the bonded formula I of above-mentioned preferred definition, (II) and (IV) compound.
The present invention preferably includes the bonded formula I of above-mentioned special preferred definition especially, (II) and (IV) compound.
The present invention very particularly preferably comprises the above-mentioned very particularly preferably bonded formula I of definition, (II) and (IV) compound.
The present invention is formula II most preferably, (III) and (IV A) compound.
Formula I, (II), (III), can there be different steric isomers in (IV) with (IV A) compound.These different steric isomers all comprise within the scope of the invention.
Formula III compound and their steric isomer are new, have formed the part of theme of the present invention, and here, formula III is particularly preferred steric isomer.
In contextual structural formula, simpler in order to make it, there is not signify hydrogen on the hydroxyl.
By with the crushed material of organic solvent extraction arrow root potato platymiscium and make spissated extracting solution carry out substep liquid chromatography (LC) purifying, can obtain formula I of the present invention, (II) and (III) compound.Suitable organic solvent and chromatography method are well known by persons skilled in the art, or can be by Literature Consult (Z.Chen, B.Wang, M.Chen, Tetrahedron lett.1987,28,1673; Z.Chen, B.Wang, J.Shen Phytochemistry 1988,27,2999; S.Chen, Z.Gao, Y.SengChin.J.Chem.1991,1,92, Z.Chen, J.shen, Y.Gao, M.Wichtl, Planta Medica1997,63,40-43; J.Shen, Z.Chen, Y.Gao, Phytochemistry 1996,42, and 891).
Formula IV of the present invention and (IV A) compound can be by currently known methods by formula I, (II) and (III) compound obtain (Z.Chen etc., Heterocycles 1989,29,2103).Formula IV and (IV A) compound preferably obtain (table I A) by compound (arrow root ketone lactone) A to N.Under particularly preferred situation, formula IV and (IV A) compound be by compound (arrow root ketone lactone) A, B, and E and N obtain.
The invention still further relates to preparation (I), the method of (II) and (III) compound, it is characterized in that at first with the organic solvent extraction arrow root potato platymiscium powder that randomly contains water, extract is absorbed on the solid carrier also by the vacuum liquid phase chromatography enrichment, carry out liquid liquid then and distribute, carry out the liquid chromatography (LC) purifying at last.
In this method, preferably at first extract arrow root potato platymiscium stem tuber powder with the Fatty Alcohol(C12-C14 and C12-C18) that randomly contains water, spissated extract is absorbed on the silica gel, use to increase polar solvent wash-out extract components continuously from the solid carrier, concentrate eluant changes in the water then, contrary solvent polarity carries out liquid liquid and distributes, carry out the liquid chromatography (LC) purifying by method known to those skilled in the art at last, obtain (I), (II) and (III) compound.
The invention still further relates to second kind and prepare (I), the method of (II) and (III) compound, it is characterized in that at first with the organic solvent extraction arrow root potato platymiscium powder that randomly contains water, extract partly is dissolved in the solvent-laden water, extract continuously with increasing polar water insoluble solvent, carry out the liquid chromatography (LC) purifying by method known to those skilled in the art at last.
In this method, preferably at first with the lower aliphatic ethanol-extracted arrow root potato platymiscium powder that contains water, extract partly is dissolved in the water that contains small amount of methanol, extract continuously with hydrocarbon and ether, by method known to those skilled in the art ether is carried out the liquid chromatography (LC) purifying mutually at last, obtain formula I, (II) and (III) compound.
The invention still further relates to the method for preparing arrow root ketone lactone by other arrow root ketone lactones, be characterised in that arrow root ketone lactone is stirred in weak caustic solution.
For example, arrow root ketone lactone (B) and (N)
Figure 9912727500151
Can be by natural arrow root ketone lactone (A) and (E) preparation
Arrow root ketone lactone B can obtain by stir arrow root ketone lactone A in weak caustic solution.
Arrow root ketone lactone N can be by identical method, and E obtains from arrow root ketone lactone.
Formula I (II) or (III) compound can prepare similarly from the different sites of arrow root potato platymiscium, and it comprises the ground of plant, the organ of underground part and plant, for example, bud, stem, leaf, flower, do, seed, root or stem tuber.Preferred root or the stem tuber that uses arrow root potato platymiscium.The preparation formula I, the method 1. solid phase enrichments (method 1) of (II) and (III) compound
Preparation (I), the general feature of the method for (II) and (III) compound randomly contains the organic solvent of water (methyl alcohol for example, ethanol for usefulness at first, propyl alcohol, Virahol, acetone, ethyl acetate, ether, normal-butyl methyl ether, tetrahydrofuran (THF), acetonitrile) extracts arrow root potato platymiscium powder, spissated extract is absorbed in the solid absorbing material (natural materials of Fen Suiing for example, as kaolin, clay, talcum, chalk, quartz, the synthetic materials of polynite and pulverizing, as microgranular silica gel, aluminum oxide, silicate or polymeric adsorbent, as resol or polyamide resin) on, (order for example: 1. heptane, hexane, pentane use to increase the polar solvent, hexanaphthene, sherwood oil; 2. ether, toluene, benzene, t-butyl methyl ether, chloroform, methylene dichloride, ethyl methyl ketone ， diox, tetrahydrofuran (THF); 3. ethyl acetate or acetone; 4. propyl carbinol, n-propyl alcohol, Virahol, acetonitrile, methyl alcohol or ethanol) the wash-out extract components makes its enrichment continuously from the solid carrier, and concentrate eluant changes in the water then, and contrary solvent polarity is (for example: 1. heptane, hexane, pentane, hexanaphthene, sherwood oil or tetracol phenixin; 2. ether, toluene, benzene, t-butyl methyl ether, chloroform, methylene dichloride, ethyl methyl ketone ， diox, tetrahydrofuran (THF); 3. ethyl acetate or acetone) carry out liquid liquid and distribute, carry out the liquid chromatography (LC) purifying by method known to those skilled in the art at last.
Arrow root ketone lactone A, B, E and N can be by the method preparations that exemplifies below.
Extract
With 5 kilograms of dried arrow root potato platymiscium stem tubers of methanol extraction.Solvent evaporated under reduced pressure obtains methanol crude extract (700 gram).The vacuum liquid chromatography
Methanol crude extract is dissolved in 2.1 liters of methyl alcohol and is absorbed in 4.2 kilograms of silica gel 60 (Macherey ﹠amp; Nagel, 0.04-0.063mm) on.Solvent evaporated under reduced pressure is packed exsiccant extract/silica gel in a large amount of frits into, carries out four step gradient elution (heptane: 10 liters; T-butyl methyl ether: 10 liters; 10 liters of ethyl acetate; Water/methyl alcohol 50: 50).Obtain 3.6 gram heptane phases, 45.8 gram t-butyl methyl ether phases, 36.7 gram ethyl acetate restrain water/methyl alcohol mutually with 121.8 mutually.Referring to Hostettmann et al. (1998), Preparative Chromatography Techniques, pp.39-47, Spinger Verlag, ISBN 3-540-62459-7.Liquid liquid distributes
Be dissolved in t-butyl methyl ether in 700 ml waters mutually and usefulness normal heptane (2.5 liters), ether (2 liters) and ethyl acetate (1.5 liters) are extracted continuously.Evaporating solvent obtains 14.1 grams mutually from heptane, obtains 4 grams mutually from ether, obtains 3.1 grams mutually from ethyl acetate, obtains 20.1 gram residues from water.Silica gel medium pressure chromatography (MPLC), the reverse chromatography of preparation of silica gel HPLC and silica gel (RP18)
Ether is dissolved in the methylene dichloride mutually, carries out silica gel column chromatography (Biotage KP-SIL 32-63 μ m; (the mobile phase A: methylene dichloride of column dimension:160 * 40mm); Mobile phase B: methyl alcohol; Flow velocity 14 ml/min; Gradient: beginning: 100%A; 1 minute: 100%A; 121 minutes: 95%A; 131 minutes: 95%A; 141 minutes: 90%A; 151 minutes: 80%A; 191 minutes: 80%A; Detect 210nm).
By reusing following instrument parameter: hardware Gilson Abimed HPLC (UV detector, binary pump system); Software Unipoint 1.71 (Gilson); 1. stationary phase: Macherey ﹠amp; Nagel Nucleosil C18 (7 μ m; 250 * 20mm); Flow velocity: 25 ml/min; Mobile phase A: 0.1% contains TFA water; Mobile phase B: acetonitrile+0.1%TFA; Gradient: beginning: 85%A; 1 minute 85%A; 30 minutes: 25%A; 35 minutes: 25%A; 2. stationary phase: Macherey ﹠amp; Nagel Nucleosil C18 (7 μ m; 250 * 20mm); Flow velocity: 25 ml/min; Mobile phase A: 0.1% contains TFA water; Mobile phase B: acetonitrile+0.1%TFA; Gradient: beginning: 70%A; 1 minute 70%A; 30 minutes: 25%A; 35 minutes: 25%A; 3. stationary phase: Macherey ﹠amp; Nagel Nucleosil C18 (7 μ m; 250 * 10mm); Flow velocity: 12.5 ml/min; Mobile phase A: water+2 gram ammonium formiates/liter; Mobile phase B: acetonitrile+2 gram ammonium formiates/liter; Gradient: beginning: 80%A; 40 minutes 40%A; 41 minutes: the preparation HPLC of 0%A, by 30 to 70 minutes, stream part that preferred 34 to 58 minutes wash-outs go out obtained pure arrow root ketone lactone B and N.
By reusing following instrument parameter: hardware Gilson Abimed HPLC (UVdetector, binary pump system); Software Unipoint 1.71 (Gilson); Stationary phase: Macherey ﹠amp; Nagel Nucleosil 50-7 (250 * 21mm); Flow velocity: 25 ml/min; Mobile phase A: methylene dichloride; Mobile phase B: methyl alcohol; Gradient: beginning: 100%A; 1 minute: 100%A; 41 minutes 98%A; 42 minutes: 80%A; 61 minutes: the SiO2 of 80%A prepared HPLC or by reverse chromatography (RP), and by 50 to 70 minutes, stream part that preferred 59 to 63 minutes wash-outs go out obtained pure arrow root ketone lactone A and E.
Other embodiment of material, instrument and the step of using in the aforesaid method 1 and preferably other embodiment exemplify as follows.
Pure in order to prepare, single formula I of the present invention, (II) or (III) compound need carry out final preparation phase HPLC separation and purification.
Optionally, suitable separation system is, for example 1. stationary phase=Nucleosil C18; Acetonitrile or methyl alcohol gradient that water/Mobile phase B=0.1% that mobile phase A=0.1% contains trifluoroacetic acid or formic acid or formate damping fluid or acetate buffer contains trifluoroacetic acid or formic acid or formate damping fluid or acetate buffer are beginning: 0%-10%B is increased to 100%B in 45-90 minute; 2. stationary phase=silica gel; Mobile phase A=methylene dichloride/Mobile phase B=methyl alcohol; Gradient is beginning: 0%-10%B was increased to 50%B in 60 to 200 minutes.
Preferred solvent is aqueous methanol (95%) or aqueous ethanol (95%) during extraction.Very thin silica gel, aluminum oxide or the resol of preferred solid carrier material for pulverizing.Preferably use 1. heptane or sherwood oil and 2. ether or t-butyl methyl ether when taking off absorption.Preferred solvent was followed successively by 1. heptane or sherwood oil and 2. ether or tertbutyl ether during liquid liquid distributed subsequently.
For purifying formula I of the present invention, (II) or (III) compound need carry out final preparation phase HPLC and separate, and preferred separation system is the first step: 1. stationary phase=Nucleosil C18; Water/Mobile phase B=0.1% that mobile phase A=0.1% contains trifluoroacetic acid contains the acetonitrile of trifluoroacetic acid; Gradient is beginning: 10%B is increased to 100%B in 60 minutes; Second step: stationary phase=silica gel; Mobile phase A=methylene dichloride/Mobile phase B=methyl alcohol; Gradient is beginning: 0%B was increased to 50%B in 160 minutes.
Except that methyl alcohol, also can use ethanol, propyl alcohol, Virahol, acetone, ethyl acetate, ether, t-butyl methyl ether, tetrahydrofuran (THF), acetonitrile and other solvent extractions well known by persons skilled in the art and the dissolving of use solid carrier material fore portion.
Remove the very thin silica gel of pulverizing and improve thing, for example, C2, C4, C8, C18, DIOL, outside phenyl and the aminoderivative, suitable solid carrier material also can be the natural materials that ground, as kaolin, clay, talcum, chalk, quartz, polynite and the synthetic materials that ground, as aluminum oxide, silicate or polymeric adsorbent such as resol or polyamide resin.
Use 1. sherwood oils or heptane serially in order to dissociate from solid support material continuously; 2. ether or ethyl acetate; 3. acetone or propyl carbinol or isopropylcarbinol; 4. methyl alcohol or ethanol or Virahol.In order to increase the intensity of solvent, also can use the mixture of these solvents.
Formula I of the present invention, (II) or (III) compound also can pass through with 1. sherwood oils or heptane; 2. t-butyl methyl ether; 3. n-butanol extraction is in the enrichment of liquid liquid allocation step.
In preparation phase HPLC purifying subsequently, also can use other stationary phase by those skilled in the art, as RF8, phenyl, DIOL, C2, C4 or aminoderivative carry out.The moving phase mixture also can contain other acid (for example formic acid) or other damping fluid (for example ammonium acetate).The organic constituent of moving phase also can be, and for example, is methyl alcohol when separating with C18, is chloroform when separating with silica gel.Also but the first step is carried out different fixing phase chromatography in second step of silica gel on C18.2. liquid liquid enrichment (method 2)
Preparation (I), the general feature of the second method of (II) and (III) compound randomly contains the organic solvent of water (methyl alcohol for example, ethanol for usefulness at first, propyl alcohol, Virahol, acetone, ethyl acetate, ether, t-butyl methyl ether, tetrahydrofuran (THF), acetonitrile, methylene dichloride, chloroform) extracts arrow root potato platymiscium powder, spissated extract partly is dissolved in water-containing solvent (methyl alcohol for example, ethanol, propyl alcohol, Virahol, acetone, acetonitrile or other and the miscible solvent of water), with increasing polar and the immiscible solvent of water (1. heptane in proper order for example, hexane, pentane, hexanaphthene, sherwood oil; 2. ether, toluene, benzene, t-butyl methyl ether, chloroform, methylene dichloride, ethyl methyl ketone ， diox, tetrahydrofuran (THF); 3. ethyl acetate) extract continuously, carry out liquid phase-chromatography purification by this area standard method subsequently.
Arrow root ketone lactone A, B, E can separate by the method for describing in detail below with N.
Extract
With 1.8 kilograms of dried arrow root potato platymiscium stem tubers of methanol extraction.Solvent evaporated under reduced pressure obtains 248 gram methanol crude extract.
Liquid liquid distributes
In the container that stirs, 248 gram arrow root potato platymiscium crude extracts are dissolved in 500 ml waters/methyl alcohol (95: 5), extract four times, use 200 milliliters of normal heptanes and t-butyl methyl ether at every turn., obtain 16.4 gram normal heptanes and restrain t-butyl methyl ether mutually with 2.6 mutually except that desolvating with rotatory evaporator.
Silica gel medium pressure chromatography (MPLC)
T-butyl methyl ether is dissolved in methyl alcohol mutually, is adsorbed on 30 milliliters of silica gel 60 (Macherey; Nagel, 0.04-0.063mm) on.Removal of solvent under reduced pressure, with exsiccant extract/silica-gel mixture pack into Biotage Flash 40unit syringe (Hertford, UK).Chromatography is at silica gel (Biotage KP-SIL 32-63 μ m; Carry out on the post size 80 * 40mm), condition is: mobile phase A: methylene dichloride; Mobile phase B: methyl alcohol; Flow velocity 14 ml/min; Gradient: beginning: 100%A; 1 minute: 100%A; 121 minutes: 95%A; 131 minutes: 95%A; 141 minutes: 90%A; 151 minutes: 80%A; 191 minutes: 80%A; Detect 210nm.At 45 to 75 minutes, preferred 54 to 64 minutes wash-outs went out to contain stream part (413mg) of arrow root ketone lactone, obtained pure arrow root ketone lactone A, B, E and N by method 1 described further separation.
Optionally and preferably be used for the material of method 1, instrument and step exemplify as follows.
In order to prepare single formula I of the present invention, (II) or (III) compound need carry out final preparation phase HPLC separation and purification.Optionally, suitable separation system is, for example 1. stationary phase=Nucleosil C18; Water/Mobile phase B=0.1% that mobile phase A=0.1% contains trifluoroacetic acid or formic acid or formate damping fluid or acetate buffer contains the acetonitrile or the methyl alcohol of trifluoroacetic acid or formic acid or formate damping fluid or acetate buffer; Gradient is beginning: 0%-10%B is increased to 100%B in 45-90 minute; 2. stationary phase=silica gel; Mobile phase A=methylene dichloride/Mobile phase B=methyl alcohol; Gradient is beginning: 0%B was increased to 50%B in 60 to 200 minutes.
Preferred solvent is aqueous methanol (95%) or aqueous ethanol (95%) during extraction.Preferred methanol (5: the 95) mixture that uses is partly dissolved spissated crude extract.It is 1. heptane or sherwood oil and 2. ether or tertbutyl ether that liquid liquid distributes preferred solvent.
For final purifying formula I of the present invention, (II) or (III) compound need be prepared phase HPLC and separate, and preferred separation system is the first step: 1. stationary phase=Nucleosil C18; Water/Mobile phase B=0.1% that mobile phase A=0.1% contains trifluoroacetic acid contains the acetonitrile of trifluoroacetic acid; Gradient is beginning: 10%B is increased to 100%B in 60 minutes; Second step: stationary phase=silica gel; Mobile phase A=methylene dichloride/Mobile phase B=methyl alcohol; Gradient is beginning: 0%B was increased to 50%B in 160 minutes.
Except that methyl alcohol, also can use ethanol, propyl alcohol, Virahol, acetone, ethyl acetate, ether, t-butyl methyl ether, tetrahydrofuran (THF), acetonitrile and other solvent extractions well known by persons skilled in the art.
Formula I of the present invention, (II) or (III) compound also can pass through with 1. sherwood oils or heptane; 2. t-butyl methyl ether or ethyl acetate; 3. propyl carbinol is in the enrichment of liquid liquid allocation step.
In final preparation phase HPLC purifying, also can use other stationary phase by those skilled in the art, as RP8, phenyl, DIOL, C2, C4 or aminoderivative carry out.The moving phase mixture also can contain other acid (for example formic acid) or other damping fluid (for example ammonium acetate).The organic constituent of moving phase also can be, and for example, is methyl alcohol when separating with C18, is chloroform when separating with silica gel.Also but the first step is carried out different fixing phase chromatography in second step of silica gel on C18.3. the method (method 3) for preparing arrow root ketone lactone
A prepares B by arrow root ketone lactone
Under 0 to 50 ℃ temperature, with 10 milligrams of arrow root ketone lactone A, add 1-10 milliliter solubilizing agent if desired, as, methyl alcohol, ethanol or acetone stirred 5-160 hour in 1-20 milliliter alkali aqueous solution (pH7.5-10).Evaporating solvent, with water with solvent as, chloroform, methylene dichloride, ether, t-butyl methyl ether or ethyl acetate extraction three times.Remove and desolvate, obtain 6.7 milligrams of colorless solid shape arrow root ketone lactone B.
E prepares N by arrow root ketone lactone
Under 0 to 50 ℃ temperature, with 10 milligrams of arrow root ketone lactone E, add 1-10 milliliter solubilizing agent if desired, as, methyl alcohol, ethanol or acetone stirred 5-160 hour in 1-20 milliliter alkali aqueous solution (pH7.5-10).Evaporating solvent, with water with solvent as, chloroform, methylene dichloride, ether, t-butyl methyl ether or ethyl acetate extraction three times.Remove and desolvate, obtain 6.7 milligrams of colorless solid shape arrow root ketone lactone N.
This reaction is preferably at pH7.5-9, and preferred especially 8.0-8.5 very particularly preferably carries out in 0.05 mole of sodium hydrogen carbonate solution (pH=8.2).Preferred stablizer is a methyl alcohol.Preferred temperature of reaction is 10-30 ℃, preferred especially room temperature (20 ℃).Under this temperature, the preferred reaction times is 20-90 hour, preferred 40-45 hour especially.Preferred extraction solvent is ether or methylene dichloride.
Formula I; (II), (III), (IV) and (IV A) compound is suitable for preventing and treating animal pest; particularly agriculture; forestry, product and the protection of goods and materials storage, the nematode that animal health and hygiene department face; insect; mollusk, vermin and worm, they have good plant tolerance and warm-blooded animal toxicity.They are all effective with the insect with resistance for general susceptibility, and all effective in all stages and part stage that insect grows.Formula I, (II), (III), (IV) and (IV A) compound preferably is applicable to nematicide, insect and worm.Formula I, (II), (III), (IV) and (IV A) compound particularly preferably is applicable to anti-insect and nematode.Formula I, (II), (III), (IV) can separate from plant with (IV A) compound, also can complete synthesisly or semi-synthetic obtain.Compound in the context both can act on separately, and the use that can cooperatively interact also can be applicable to the control animal pest with other, compound of microorganism or fungi or preparation synergy.The present invention also provides and has contained a kind of formula I at least, and the arrow root potato genus plants extract of (II) or (III) compound is used for the purposes of Pest Control.This extract also can be applicable to the control animal pest with other, compound of microorganism or fungi or preparation synergy.
This extract 1 and 2 described general methods as stated above obtains, and can be suitable for the extract of various purity, formula I in the extract, and (II) or (III) compound concentrations is 0.01-2%, preferred 0.1-1% (w/w).
The present invention also provides arrow root potato platymiscium partly to be used for the purposes of Pest Control.Preferred any exsiccant part of using plant powder, for example suspension is stuck with paste particle, powder, powder or chip.Preferably use the leaf of plant, root and stem tuber preferably use root and stem tuber very especially.The powder of plant also can be applicable to the control animal pest with other, compound of microorganism or fungi or preparation synergy.
Above-mentioned insect comprises:
Isopoda (Isopoda), Oniscus asells for example, Armadillidium vulgare (pillworm) and Porrcellio scaber.
Diplopoda (polypody order), for example Blaniulus guttulatus.
Chilopoda (Chcilopoda order), for example Geophilus carpophagus and Scutigeraspec.
Symphyla (comprehensive detailed outline), for example Scutigerella immaculata.
Thysanra (Thysanura), for example Lepisma saccharina (silverfiss).
Collembola (Collembola), for example Onychiurus armatus.
Orthoptera (Orthoptera), Blatta orienralis (the non-Lian in east) for example, Periplanetaamericana (periplaneta americana), Leucophaea maderae (the non-Lian in Madeira), Blattellagermanica (Groton bug), Acheta domesticus (house cricket found in a kitchen), Gryllotlpa spp. (Gryllotalpa spp), Locusta migratoria (tropical migratory locusts), Melanoplus differentialis (long volume is born locust) and Schistocerca gregaria.
Deermaptera (Dermaptera), for example Forficula auricularia (European ball sister-in-law).
Isoptera (Isoptera), for example Reticulitermes spp. (Cryptotermes).
Anoplura (Anoplura), for example Pediculus humanus cirporis (head louse), Haematopinus spp. (blind lice belongs to) and Linognathus spp. (long Anoplura).
Mallophaga (Mallophaga), for example Trichodectes spp. (Trichodectes) and Damalineaspp..
Thysanoptera (Thysanoptera), for example Hercinothrips femoralis (greenhouse Hercinothrips spp) and Thrips tabaci (cotton thrips).
Heteroptera (Heteroptera), Eurygaster spp. (brown scutteleerid belong to) for example, Dysdercusintermedius, Piesma quadrata (beet is intended lace bug), Cimex lectularius (bedbug), Rhodnius prolixus and Triatoms spp. (triatoma sanguisuga genus).
Homoptera (Homoptera), Aleirpdes brassicae for example, Bemisia tabaci (whitefly in bt cotton), Trialeurodes vaporariorum (Trialeurodes vaporariorum Westwood), Aphis gossypii (cotten aphid), Brevicoryne brassicae (brevicoryne brassicae), Cryptomyzus ribis (the tea deer conceals knurl volume aphid), Aphis fabae (black bean aphid), Aphis pomi, Eriosoma lanigerum (apple aphid), Hyalopterus arundinis (mealy plum aphid), Phylloxera vastatrix, Pemphigus spp., Macrosihum avenae, Myzus spp. (knurl volume aphid), Phorodon humuli (hops knurl volume aphid), Rhopalosiphum padi (grain Rhopalosiphum spp), Empoasca spp. (leafhopper genus), Euscelisbilobatus, Nephotettix cincticeps (rice green leafhopper), Lecanium corni (brown apricot scale), Saissetia oleae (Fructus oleae europaeae helmet), Laodelphax striatellus (rice small brown rice planthopper), Nilaparvatalugens (brown back rice plant hopper), Aonidiella aurantii (California red scale), Aspidiotus hederae, Pseudococcus spp. (mealybug genus) and Psylla spp. (Psylla spp).
Lepidoptera (lepidopteran), Pectinopohora gossypiella (pink bollworm) for example, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella (cherry ermine moth), Plutella maculipennis (small cabbage moth), Malacosoma neustria (tent caterpillar), Euproctis chrysorrhoea, Lymantria spp. (Euproctis), Bucculatrix thurberiella (cotton shot hole of leaf lyonetid), Phyllocnistis citrella, Agrotis spp. (cutworm), Euxoa spp. (cutworm), Feltia spp. (brown noctuid), Eariasinsulana (earias insulana), Heliothis spp. (Noctua), Laphygma exigua, Mamestra brassicae (lopper worm), Panolis flammea, Prodenia litura (prodenia litura), Spodoptera spp. (Noctua), Trichoplusiani (cabbage looper), Carpocapsapomonella (carpocapsa pononella), Pieris spp. (Pier), Chilo spp. (snout moth's larva), Pyraustanubilllalis, Ephestia kuehniella, Galleria mellonella (rheum officinale snout moth's larva), Tineapellionella (bag casemaking clothes moth), Hofmannophila pseudospretella (etting moth), Cacoeciapodana, Capua reticulana, Choristoneura fumiferana (choristoneura fumigerana), Clysiaambiguella (grape codling moth (Clysia ambiguella)), Homona magnama (tea yellow leaf curl moth) Tortrixviridana (the green leaf roller of oak).
Coleoptera (Coleoptera), Anobium punctatum (furniture death watch beetle) for example, Rhizoopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus (bean weevil), Hylotrupes bajulus (house longhorn beetle), Agelastica alni, Leptinotarsadecemlineata (colorado potato bug), Phaedon cochleariae, Diabrotica spp. (chrysomelid genus), Psylliodes chrysocephala (the blue flea beetle of rape), Epilachna varivestis (mexican bean ladybird), Atomaria spp., Oryzaephilus surinamesis (saw chest ostomatid), Anthonomus spp. (weevil genus), Sitophilus spp. (Sitophilus), Otiorrhynchussulcatus, Cosmopolites sordidus (banana spider base weevil), Ceuthorrhynchusassimilis, Hypera postica (alfalfa weevil), Dermestes spp. (khapra beetle genus), Trogoderma spp., Anthrenus spp., Attagnus spp. (attagenus piceus), Lyctus spp. (powder moth), Meligethes aeneus, Ptinus spp. (Ptinus), Niptus hololeucus (golden yellow ptinid), Gibbium psylloides (wheat ptinid), Tribolium spp. intends the paddy Oryza), Tenebriomolitor (bloom first), Agriotes spp. (click beetle genus), Conoderus spp. (acupuncture needle Eimeria), Melolontha melolontha, Amphimallon solstitialis (chafer in June) and Costelytra zealandica.
Hymenoptera (Hymenoptera), Diprion spp. (Neodiprion spp genus), Hoplocampa spp. (tenthredinidae), Lasius spp. (ant), Monomorium pharaonis (kitchen ant) and Vespa spp. (wasp).
Diptera (Diptera), Aedes spp. (yellow-fever mosquito), Anopheles spp. (spot Anopheles), Culex spp. (culex), Drosophila melanogaster (drosophila yellow gorilla), Musca spp. (housefly), Fannia spp. (stable fly), Calliphora erythrocephala (calliphora erythrocephala), Lucilia spp. (lucilia sericata), Cuterebra spp. (cuterbrid genus), Gastrophilus spp., Hyppobosca spp., Stomoxys spp. (chela fly genus), Oscinella frit (Sweden's wheat stem chloropid fly), Phorbia spp. (wheat fly), Pegomyia hyoscyami (beet leaf mining flower), Ceratitis capitata (Mediterranean fruitfly), Dacus oleae (dacus oleae) and Tipula paludosa (European daddy-longlegs).
Siphonaptera (Siphonaptera), for example Xenopsylla cheopis (Xenopsyllacheopis) and Ceratophyllus spp. (Ceratophyllus).
Arachnida (Arachnida), for example Scorpio maurus and Latrodectua mactans (black widow).
Acarina (acarina), Acams siro (Acarus siro), Argas spp. (latent beak ant), Ornithodoros spp. (beak tick genus), Dermanyssus gallinae (Dermanyssus gallinae), Eriophyesribis, Phyllocoptruta oleivora (citrus rust mite), Boophilus spp. (Boophilus), Rhipicephalus spp. (carrapato genus), Sarcoptes spp. (itch mite), Tarsonemus spp. (line mite genus), Bryobia praetiosa (Bryobia praetiosa), Panonychus spp. (red spider) and Tetranychus spp. (tetranychus telarius genus).
Plant nematode comprises, Pratylenchus spp. (Pratylenchidae genus) for example, Radopholus similis (similar similes thorne), Dityklenchus dipsaci (fuller's teasel Ditylenchus dipsaci), Tylenchlus semipenetrans (nematode of partly puncturing), Heterodera spp. (Heterodera), Globodera spp. (ball Heterodera), Meloidogyne spp. (root nematode genus), Aphelenchoides spp. (Aphelenchoides), Longidorus spp. (minute hand Turbatrix), Xiphinema spp. (Xiphinema), Trichoddorus spp. (burr Turbatrix) and Bursaphelelnchus spp. (Bursaphelenchus).
Formula of the present invention (I), (II), (III), (IV) and (IV A) compound is to horseradish ape chrysomelid (Phaedoncochleariae) larva, small cabbage moth (Plutella maculipennis) caterpillar, spodoptera (Spodoptera frugiperda) caterpillar, rice green leafhopper (Nephotettix cincticeps) larva, the T.urticae Koch (Tetranychus urticae) in black peach aphid (Myzus persicae) and each stage is effective especially.
Active compound, and arrow root potato genus plants extract and powder can be converted to conventional formulation, as solution, emulsion, wettable powder, suspension, powder, pulvis, paste, soluble powder, granule, the suspension emulsion enriched material is soaked with the natural and synthetic of active compound, microcapsule and polymeric material.
These preparations can prepare with currently known methods, for example, active compound are mixed with the expansion agent that comprises liquid solvent and/or solid carrier, if desired, can use the tensio-active agent that comprises emulsifying agent and/or dispersion agent and/or pore forming material.
If the expansion agent is a water, also can use, for example, organic solvent is as solubility promoter.Suitable liquid solvent mainly contains: aromatic compound, and as dimethylbenzene, toluene, or alkylnaphthalene, chlorinated aromatic compound and chloro aliphatic hydrocarbon compound, as chlorobenzene, vinylchlorid or methylene dichloride, aliphatic hydrocrbon, as hexanaphthene or paraffin, mineral oil fraction for example, mineral oil or vegetables oil, alcohols, as butanols or ethylene glycol, and ether and ester, ketone, as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) or pimelinketone, intensive polar solvent, as dimethyl formamide and methyl-sulphoxide, and water.
Suitable solid carrier is:
Ammonium salt for example, the natural materials of pulverizing, as kaolin, clay, talcum, chalk, quartz, attapulgite, polynite or diatomite, and the synthetic materials of pulverizing are as the silica of pulverizing, aluminum oxide and silicate; The suitable solid carrier that is used for granule is: for example crushing or that smash natural rock such as calcite, marble, float stone, sepiolite and rhombspar, and synthetic is inorganic and the particle of organic materials, the organic materials particle, as wood sawdust, coconut husk, corn cob and tobacco rods; Suitable emulsifying agent and/or pore forming material are: for example nonionic and anionic emulsifier, and as polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether, alkylaryl polyglycol ether for example, alkylsulfonate, alkyl-sulphate, arylsulphonate and protein hydrolysate; Suitable dispersion agent is: for example lignin sulfite waste liquor and methylcellulose gum.
Tackiness agent such as carboxymethyl cellulose and powder, the natural synthetic polymer of particle or latex form, as gum arabic, polyvinyl alcohol and polyvinylacetate, and natural phospholipid such as kephalin and Yelkin TTS, and synthetic phospholipid also can be used in the preparation.Other additives can be mineral oil and vegetables oil.
Also can use pigment such as mineral dye in the preparation, ferric oxide for example, titanium oxide and Prussian orchid and and organic dye, as alizarine dyestuff, azoic dyestuff and metalphthelein cyanogen dyestuff, and micro-nutrients such as iron, manganese, boron, copper, cobalt, aluminum and zinc salt.
Generally speaking, contain 0.01%-95% in the preparation, the active compound of preferred 0.1-90% weight ratio.
The compounds of this invention or its preparation both can use separately, also can with known mycocide, antibiotic, miticide, nematocides or insecticide mix and use, can, for example, enlarge sphere of action or prevent that resistance from producing.Can produce synergy under many circumstances, promptly the activity of mixture surpasses the activity of one-component.
The example of particularly preferred blending ingredients is as follows: mycocide:
Aldimorph, ampropylfos (ammonia third phosphoric acid), ampropylfos potassium (ammonia third potassiumphosphate), andoprim, anliazine (anilazine), azaconazole (encircling penta azoles), azoxystrobin,
Benalaxyl (M 9834), benodanil (adjacent iodoxy aniline), benomyl (F-1991), benzamacril, benzamacril-isobutyl, bialaphos (two alanyl phosphorus), binapacryl (Niagara 9044), biphenyl (biphenyl), bitertanol (Bitertanol), blasticidinS (miewensu), bromuconazole (bromuconazole), bupirimate (bupirimate), buthiobate (fourth Saite)
Calcium polysulphide (calcium polysulfide), capsmycin, capsimycin, captafol (Difolatan), captan (Vancide 89), carbendazim (derosal), carboxin (carboxin), carvon, quinomethionate, chlobenthiazone, chlorfenazole, chloroneb, chloropicrin (trichloronitromethane), chlorothalonil (m-tetrachlorophthalodinitrile), chlozolinate (chlozolinate), clozylacon, cufraneb, cymoxanil (white urea cyanogen), cyproconazole (SN-108266), cyprodindl (cyprodinil), cyprofuram (cyprofuram)
Debacarb (debacarb), dichlorophen (dichlorophen), diclobutrazole (diclobutrazol), diclofluanid, diclomezine (diclomezin), dicloran (dicloran), diethofencarb (the mould prestige of second), difenoconazole (difenoconazole), dimethirimol (dimethirimol), dimethomorph (dimethomorph), diniconazole (alkene azoles alcohol), diniconazoleM, dinocap, diphenylamine (pentanoic), dipyrithione, ditalimfos (ditalimfos), dithianon (dihydro-anthraquinone), dodemorph (dodemorph), dodine (dodine), drazoxolon (drazoxolon)
Ediphenphos (edifenphos), epoxiconazole, etaconazole (etaconazole), ethirimol (the phonetic phenol of second), etridiazole (etridiazole),
Famoxadon, fenapanil (fenapanil), fenarimol (fenarimol), fenbuconazole (RH-7592), fenfuram (first furan anilide), fenitropan (planting the clothing ester), fenpiclonil (fenpiclonil), fenpropidin (fenpropidin), fenpropimorph, fentin acetate (triphen tin acetate), fentin hydroxide (fentin hydroxide), ferbam (Karbam Black), ferimzone (ferimzone), fluazinam (fluazinam), flumetover, fluoromide (fluoromide), fluquinconazole (fluquinconazole), flurprimidol (flurprimidol), flusilazole (fluzilazol), flusulfamide, flutolanil (fultolanil), flutriafol (flutriafol), folpet (Phaltan), fosetyl-aluminium (three second aluminum phosphates), fosetyl sodium (three second sodium phosphates), fthalide, fuberidazole (fuberidazole), furalaxyl (furalaxyl), furametpyr, furcarbonil, furconazole (furconazole), furconazole-cis, furmecyclox
Guazatine (biguanides suffering),
Hexachlorobenzene (hexachlorophen), hexaconazole (own azoles alcohol), the spirit of hymexazole (Evil bacterium),
Imazalil (pressing down mould azoles), imibenconazole (imibenconazole), iminoctadine (biguanides suffering), iminoctadine albesilate, iminoctadine triacetate (guazatine acetate), iodocarb, ipconazole (planting the bacterium azoles), iprobenfos (IBP) (iprobenfos), iprodione (RP-26019), irumamycin, isoprothiolane (isoprothiolane), isovaledione
Kasugamycin (kasugamycin), kresoxim-methyl, copper preparations (copper agent), as: copper hydroxide, alkanoic acid copper, COPPER OXYCHLORIDE 37,5, copper sulfate, cupric oxide, oxinecopper and Bordeaux mixture,
Mancopper (mancopper), mancozeb (zinc manganese ethylenebisdithiocarbamate), maneb (maneb), meferimzone, mepanipyrim (mepanipyrim), mepronil (mebenil), metalaxyl (metaxanin), metconazole (metconazole), methasulfocarb (methasulfocarb), methfuroxam (methuroxam), metiram, metomeclam, metsulfovax, mildiomycin, myclobutanil (nitrile bacterium azoles), myclozolin (myclozolin)
Nickel dimethyldithiocarbamate (Sankel), nitrothal-isopropyl, nuarimol (nuarimol),
Ofurace (ofurace), the spirit of oxadixyl (Evil frost), oxamocarb, oxolinic acid (oxolinic acide,, oxucarboxim, oxyfenthiin,
Paclobutrazole (paclobutrazol), pefurazoate (pefurazoate), penconazole (Topaze), pencycuron (pencycuron), phosdiphen (phosdiphen), pimaricin (myprozine), piperalin (piperlin), polyoxin (polyoxin), polyoxorim, probenazole (probenazole), prochloraz (prochloraz), procymidone (procymidone), propamocarb (Propamocarb), propanosine-sodium, propiconazole (Wocosin 50TK), propineb (zinc 1,2-propylene bisdithiocarbamate), pyrazophos (pyrazophos), pyrifenox (pyrifenox), pyrimethanil (phonetic mould amine), pyroquilon (pyroquilon), pyroxyfur (chlorine pyrrole furan ether)
Quinconazole, quintozene (PCNB) (quintozene),
Sulphur and sulphur preparation,
Tebuconazole (tebuconazole), tecloftalam (tecloftalam), tecnazene (tecnazene), tetcyclacis (tetcyclacis), tetraconazole (tertraconazole), thiabendazole (thiabendazole), thicyofen (thicyofen), thifluzamide, thiophanatemethyl (thiophanate_methyl), the thiram thiram), tioxymid, tolclofos-methyl (tolclofosmethyl), tolylfluanid (Tolylfluanid), triadimefon (triazolone), triadimenol (triadimenol), triazbutil, triazoxide (triazoxide), trichlamide (trichlamide), tricyclazole (tricyclazole), tridemorph (tridemorph), triflumizole (fluorine bacterium azoles), triforine (triforine), triticonazole (triticonazole)
Uniconazole (uniconazole),
Validamycin A (validamycin), vinclozolin (Vinclozoline), and viniconazole (alkene frost benzyl azoles),
Zarilamide (nitrile bacterium amine), zineb (zineb), ziram (ziram) and
Dagger?G,
OK-8705,
OK-8801,
α-(1, the 1-dimethyl ethyl)-β-(2-phenoxy group ethyl)-1H-1,2,4-triazole-1-ethanol,
α-(2,4 dichloro benzene base)-β-fluoro-b-propyl group-1H-1,2,4-triazole-1-ethanol,
α-(2,4 dichloro benzene base)-'beta '-methoxy-a-methyl isophthalic acid H-1,2,4-triazole-1-ethanol,
α-(5-methyl isophthalic acid, 3-diox-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene radical]-1H-1,2,4-triazole-1-ethanol,
(5RS, 6RS)-6-hydroxyl-2,2,7,7-tetramethyl--5-(1H-1,2,4-triazol-1-yl)-3-octanone,
(E)-a-(methoxyimino)-N-methyl-2-phenoxy group-phenyl-acetamides,
1-{2-methyl isophthalic acid-[[[1-(4-aminomethyl phenyl)-ethyl]-amino]-carbonyl]-propyl group }-carbamic acid isopropyl ester,
1-(2,4 dichloro benzene base)-2-(1H-1,2,4-triazol-1-yl) ethyl ketone O-(phenyl methyl)-oxime,
1-(2-methyl isophthalic acid-naphthyl)-1H-pyrroles-2, the 5-diketone,
1-(3, the 5-dichlorophenyl)-3-(2-propenyl)-2, the 5-pyrrolidine-diones,
The 1-[(diiodomethyl)-alkylsulfonyl]-4-toluene,
1-[[2-(2,4 dichloro benzene base)-1,3-dioxolane-2-yl]-methyl]-the 1H-imidazoles,
1-[[2-(4-chloro-phenyl-)-3-phenyl ethylene oxide base]-methyl]-1H-1,2, the 4-triazole,
1-[1-[2-[(2, the 4-dichlorophenyl) methoxyl group] phenyl] vinyl]-the 1H-imidazoles,
1-methyl-5-nonyl-2-(phenyl methyl)-3-pyrrolidinol,
2 ', 6 '-two bromo-2-methyl-4 '-trifluoromethoxy-4 '-Trifluoromethyl-1s, 3-thiazole-5-formylaniline,
2,2-two chloro-N-[1-(4-chloro-phenyl-)-ethyl]-1-ethyl-3-methyl-cyclopropane carboxamide,
2,6-two chloro-5-(methyl sulfenyl)-4-pyrimidyl thiocyanide,
2,6-two chloro-N-(4-trifluoromethyl benzyl)-benzamide,
2,6-two chloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,
2-(2,3,3-three iodos-2-propenyl)-2H-tetrazolium,
The 2-[(1-methylethyl)-alkylsulfonyl]-5-(trichloromethyl)-1,3, the 4-thiadiazoles,
2-[[6-deoxidation-4-O-(4-O-methyl-β-D-glucopyranosyl)-a-D-glucopyranosyl]-amino]-4-methoxyl group-1H-pyrrolo-[2,3-d] pyrimidine-5-nitrile,
The 2-aminobutane,
2-bromo-2-(brooethyl)-trimethylene cyanide,
2-chloro-N-(2,3-dihydro-1,1,3-trimethylammonium-1H-indenes-4-yl)-3-pyridine carboxamide,
2-chloro-N-(2, the 6-3,5-dimethylphenyl)-N-(isothiocyano methyl)-ethanamide,
2-phenylphenol (OPP),
3,4-two chloro-1-[4-(difluoro-methoxy)-phenyl]-1H-tetramethyleneimine-2, the 5-diketone,
3,5-two chloro-N-[amino [(1-methyl-2-propynyl)-oxygen]-methyl]-benzamide,
3-(1,1-dimethyl propyl-1-oxo-1H-indenes-2-nitrile,
3-[2-(4-chloro-phenyl-)-5-oxyethyl group-3-isoxazole alkyl]-pyridine,
4-chlorine 2-cyano group-N, N-dimethyl-5-(4-aminomethyl phenyl)-1H-imidazoles-1-sulphonamide,
4-methyl-tetrazolo [1,5-a] quinazoline-5 (4H)-ketone,
8-(1, the 1-dimethyl ethyl)-N-ethyl-N-propyl group-1,4-dioxo spiral shell [4.5] decane-2-methylamine,
Oxine vitriol,
9H-xanthene-2-[(phenyl amino)-carbonyl]-the 9-formyl hydrazine,
Two-(1-methylethyl)-3-methyl-4-[(3-methyl benzoyl)-oxygen]-2,5-thiophene dicarboxylic acid esters,
Suitable-1-(4-chloro-phenyl-)-2-(1H-1,2,4-triazol-1-yl)-suberyl alcohol,
Suitable-4-[3-[4-(1, the 1-dimethyl propyl)-phenyl-2-methyl-propyl]-2,6-dimethyl-morpholine hydrochloride,
[(4-chloro-phenyl-)-azo] ethyl cyanacetate,
Saleratus,
First four mercaptan sodium salts,
1-(2,3-dihydro-2,2-dimethyl-1H-indenes-1-yl)-1H-imidazoles-5-methyl-formiate,
N-(2, the 6-3,5-dimethylphenyl)-N-(5-isoxazolyl carbonyl)-DL-alanine methyl ester,
N-(chloracetyl)-N-(2, the 6-3,5-dimethylphenyl)-DL-alanine methyl ester,
N-(2,3-two chloro-4-hydroxy phenyls)-1-methyl-cyclohexyl alkane methane amide,
N-(2, the 6-3,5-dimethylphenyl)-2-methoxyl group-N-(tetrahydrochysene-2-oxo-3-furyl)-ethanamide,
N-(2, the 6-3,5-dimethylphenyl)-2-methoxyl group-N-(tetrahydrochysene-2-oxo-3-thienyl)-ethanamide,
N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzsulfamide,
N-(4-cyclohexyl phenyl)-1,4,5,6-tetrahydrochysene-2-PYRIMITHAMINE,
N-(4-hexyl phenyl)-1,4,5,6-tetrahydrochysene-2-PYRIMITHAMINE,
N-(5-chloro-2-aminomethyl phenyl)-2-methoxyl group-N-(2-oxo-3-oxazolidinyl)-ethanamide,
N-(6-methoxyl group-3-pyridyl)-cyclopropane carboxamide,
N-[2,2,2-three chloro-1-[(chloracetyl)-amino]-ethyl]-benzamide,
N-[3-chloro-4,5-two (the 2-third anoxic base)-phenyl]-N '-methoxy methyl imines acid amides,
N-formyl radical-N-hydroxyl-DL-L-Ala sodium salt,
O, O-diethyl [2-(dipropyl amino)-2-oxoethyl]-ethylenebis dithiocarbamate phosphoramidate,
The amino thiophosphatephosphorothioate of O-methyl S-phenyl propyl group,
S-methyl 1,2,3-diazosulfide-7-thiocarboxylic and
Spiral shell [2H]-1-chromene-2,1 ' (3 ' H)-isobenzofuran]-3 '-ketone, bactericide: bronopol (bronopol), dichlorophen (dichlorophen), nitrapyrin (chloromethylpyridine), nickel dimethyldithiocarbamate (Sankel), kasugamycin (kasugamycin), octhilinone (zinc thiophene ketone), furancarboxylic acid (furancarboxylic acid), oxytetracyclin (terramycin), probenazole (thiabendazole), streptomycin (Streptomycin sulphate), tecloftalam (tecloftalam), copper sulfate and other copper agents.Insecticide/miticide/nematocides:
Abamectin (Avrmectin), acephate (acephate), acetamiprid (pyridine worm miaow), acrinathrin (the good fortune third chrysanthemum ester), alanycarb (alanycarb), aldicarb (aldicarb), aldoxycarb (aldoxycarb), alphacypermethrin (alphacypermethrin, alphamethrin (struggle), amitraz (worm mite miaow), avermectin (avermectin), AZ60541, azadirachtin, azamethiphos (Jia Ji Bi Evil phosphorus), azinphos A (R-1582 A), azinphos M (R-1582 M), azocyclotin (azoles ring tin)
Bacillus popilliae (Japanese beetle genus bacillus), Bacillus sphaericus (Bacillus sphaericus), Bacillus subtilis (subtilis), Bacillus thuringiensis (Su Yun genus bacillus), baculoviruses, Beauveria bassiana (silkworm muscardine), Beauveria tenella (beauveria tenella), bendiocarb (Evil worm prestige), benfuracarb (benfuracarb), bensultap (bensultap), benzoximate (benzoximate), betacyfluthrin (betacyfluthrin), bifenazate, bifenthrin (bifenthrin), bioethanomethrin, biopermethrin (biopermethrin, BPMC, bromophosA (bromofos), bufencarb (bufencarb), butathiofos (Buprofezin), butocarboxim (fourth fork prestige), butylpyridaben
Cadusafos (cadusafos), carbaryl (carbaryl), carbofuran (carbofuran), carbophenothion (carbophenothion), carbosulfan (carbosulfan), cartap (cartap), chloethocarb, chlorethoxfos (chlorethoxyfos), chlorfenapyr, chlorfenvinphos (poisonous insect prestige), chlorfluazuron (chlorflurazole), chlormephos (chlormephos), chlorpyrifos (Chlorpyrifos 94), chlorpyrifos M (Chlorpyrifos 94 M), chlovaporthrin, cis-resmethrin, cispermethrin, clocythrin, cloethocarb (cloethocarb), clofentezine (four mite piperazines), cyanophos (cynock), cycloprene, cycloprothrin (cycloprothrin), cyfluthrin (cyfloxylate), cyhalothrin (cyhalothrin), cyhexatin (cyhexatin), cypermethrin (Cypermethrin), cyromazine (fly eradication amine)
Deltamethrin (Deltamethrin), demeton M (Systox M), demeto S (Systox S), demeton-S-methyl (demeton_S_methyl), diafenthiuron (butyl ether urea), diazinon (diazinon), dichlorvos (SD-1750), diflubenzuron (diflubenzuron), dimethoat (Rogor), dimethylvinphos (methyl poisonous insect prestige), diofenolan (difenolan), disulfoton (thiodemeton), docusat-sodium, dofenapyn
Eflusilanate (Hinosan), emamectin, empenthrin (empenthrin), endosulfan (5a,6,9,9a-hexahydro-6,9-methano-2,4), Entomopfthora spp., esfenvalerate (coming the good fortune spirit), ethiofencarb (ethiofencarb), ethion (Nialate), ethoprophos (the line spirit of going out), etofenprox (ether chrysanthemum ester), etoxazole, etrimfos (second miaow sulphur phosphorus)
Fenamiphos (spirit of benzene line), femazaquin (fenazaquin), fenbutatin oxide (fenbutatin oxide), fenitrothion (fenitrothion 95), fenothiocarb, fenoxacrim, fenoxycarb (fenoxycarb), fenpropathrin (Fenvalerate), fenpyrad, fenpyrithrin, fenpyriximate, fenvalerate (fenvalerate), fipronil (fluorine worm nitrile), fluazinam (fluazinam), fluazuron (fluazuron), flubrocythrinate, flucycloxuron, flucythrinate (flucythrinate), flufenoxuron (flufenoxuron), flutenzine, fluzvalinate, fonophos (N-2790), fosmethilan (fosmethilan), fosthiazate (lythidathion), fubfenprox, furathiocarb (furathiocarb)
granulosis?viruses,
Halofenozide, HCH (phenyl-hexachloride), heptenophos (heptenopos), hexaflumuron (fluorine bell urea), hexythiazox (hexythiazox), hydroprene (hydroprene),
Imidacloprid (Provado), isazofos (isazofos), isofenphos (isofenphos), isoxathion (oxazole phosphorus), ivermectin,
nuclear?polyhedrosis?viruses,
Lambda-cyhalothrin (lambda-cyhalothrin), lufenuron (Acarus tritici urea),
Malathion (Malathion), mecarbam (bud phosphorus goes out), metaldehyde (methaldehyde), methamidophos (acephatemet), Metharhizium anisopliae, Metharhizium flavoviride, methidathion (methidathion), methiocarb (methiocarb), methomyl (methomyl), methoxyfenozide, metolcarb (meta-tolyl-N-methylcarbamate (MTMC)), metoxadiazone (Evil worm ketone), mevinphos (Phosdrin), milbemectin, monocrotophos (monocrotophos)
Naled (naled), nitenpyram (Ti304), nithiazine, novaluron,
Omethoat (omethoate), oxamyl (oxamyl), oxydemethon M (oxydemeton_methyl),
Paecilomyces fumosoroseus, parathion A (thiophos A), parathion M (thiophos M), permethrin (permethrin), phenthoat (Tsidial), phorat (phorate), phosalone (Phosalone), phosmet (R-1504), phosphamidon (phosphamidon), phoxim (Volaton), pirimicarb (Aphox), pirimiphos A (Pyrimithate A), pirimiphos M (Pyrimithate), profenofos (Profenofos), promecarb (promecarb), propoxur (Propoxur), prothiofos (Toyodan), prothoat (prothoate), pymetrozine (pyrrole aphid ketone), pyraclolos (pyraclofos), pyresmethrin, pyrethrum (pyrethrin), pyridaben (pyridaben), pyridathion, pyrimidifen (pyrimidifen), pyriproxyfen (pyrrole propyl ether)
Quinalphos (Resitox),
ribavirin,
Salithion (salithion), sebufos, silafluofen (salifluofen), spinosad, sulfotep (dithione), sulprofos (second Toyodan),
Tau-fluvalinate (taufluvalinate), tebufenozide (worm hydrazides), tebufenpyrad (tebufenpyrad), tebupirimiphos, teflubenzuron (fluorobenzene urea), tefluthrin (tefluthrin), temephos (temephos), temivinphos (metmercapturon), terbufos (terbufos), tetrachlorvinphos (tetrachlorvinphos), theta-cypermethrin, thiofanox (thiofanox), thuringiensin, tralocythrin (tralocythrin), tralomethrin (tralomethrin), triarathene (triarathene), triazamate (triaxamate), triazophos (triazophos), triazuron, trichlophenidine (chlorine imidazoles), trichlorfon (Trichlorphon), triflumuron (killing the bell urea), trimethacarb (trimethacarb)
Vamidothion (vamidothion), vaniliprole, Verticillium lecanii,
YI?5302,
zeta-cypermethrin,zolaprolos,
(1R-is suitable)-[5-(phenyl methyl)-3-furyl]-methyl 3-[(dihydro-2-oxo--3 (2H)-furans subunit)-and methyl]-2,2-dinethyl cyclopropane carboxylic acid ester,
(3-Phenoxyphenyl)-methyl 2,2,3,3-tetramethyl-ring propane manthanoate,
1-[(2-chloro-5-thiazolyl) methyl] tetrahydrochysene-3,5-dimethyl-N-nitro-1,3,5-triazines-2 (1H)-imines,
2-(2-chloro-6-fluorophenyl)-4-[4-(1, the 1-dimethyl ethyl) phenyl]-4,5-dihydro-oxazoles,
2-(acetoxyl group)-3-dodecyl-1, the 4-naphthalenedione,
2-chloro-N-[[[4-(1-phenyl ethoxy)-phenyl]-amino]-carbonyl]-benzamide,
2-chloro-N-[[[4-(2,2-two chloro-1,1-difluoroethoxy)-phenyl]-amino]-carbonyl]-benzamide,
3-aminomethyl phenyl propyl carbamate,
4-[4-(4-ethoxyl phenenyl)-4-aminomethyl phenyl]-1-fluoro-2-phenoxy group benzene,
4-chloro-2-(1, the 1-dimethyl ethyl)-5-[[2-(2,6-dimethyl-4-phenoxy group phenoxy group) ethyl] sulphur]-3 (2H)-pyridazinones,
4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl) methoxyl group]-3 (2H)-pyridazinones,
4-chloro-5-[(6-chloro-3-pyridyl) methoxyl group]-2-(3, the 4-dichlorophenyl)-3 (2H)-pyridazinones,
Bacillus?thuringiensis?strain?EG-2348，
[2-benzoyl-1-(1, the 1-dimethyl ethyl)-hydrazino-benzoic acid,
2,2-dimethyl-3-(2,4 dichloro benzene base)-2-oxo-1-oxaspiro [4.5] last of the ten Heavenly stems-3-alkene-4-base butyric ester,
[3-[(6-chloro-3-pyridyl) methyl]-2-thiazolidine subunit]-cyanamide,
Dihydro-2-(Nitromethylene)-2H-1,3-thiazine-3 (4H)-formaldehyde,
[2-[[1,6-dihydro-6-oxo-1-(phenyl methyl)-4-pyridazinyl] oxygen] ethyl]-urethanum,
N-(3,4,4-three fluoro-1-oxo-3-butenyls)-glycine,
N-(4-chloro-phenyl-)-3-[4-(difluoro-methoxy) phenyl]-4,5-dihydro-4-phenyl-1H-pyrazoles-1-methane amide,
N-[(2-chloro-5-thiazolyl) methyl]-N '-methyl-N "-nitro-guanidine,
N-methyl-N '-(1-methyl-2-propenyl)-1,2-hydrazine dithio methane amide,
N-methyl-N '-2-propenyl-1,2-hydrazine dithio methane amide,
O, O-diethyl [2-(dipropyl amino)-2-oxoethyl]-ethylenebis dithiocarbamate phosphoramidate,
Also can use the compound with other known activity, as weedicide, or the mixture of fertilizer and growth regulator gained.
In addition, when being used for sterilant, active compound of the present invention can also exist with its commercial preparation, also can become type of service to exist by these formulation preparation, for example as with the mixture of synergistic agent.Synergistic agent is to increase the active compound of active compound, and itself can not have activity.
The amount of the active compound in the type of service of being made by the commercial preparation can change in very wide scope, and the concentration of active compound can be 0.0000001-95% in the type of service, preferred 0.0001-1% weight ratio.
This type of service can use in the usual way.
When being used to control health field and product stock field insect, active compound has residual activity on timber.Arthropods
The compounds of this invention is the may command plant not only, and health and product stock field insect also can be used for field of veterinary, control zooparasite (epizoa), and as hard tick, soft ticks, psoroptes equi, trombiculid, fly (sting and suck), tachinid larva, lice, head louse, bird lice and flea.Such parasite comprises:
Anoplurida (Anoplura), Haematopinus spp. (Haematopinus) for example, Linognathusspp. (Linognathus spp), Pediculus spp. (lice genus) and Solenopotes spp. (lice belongs to pipe).
Mallooophagida (Mallophaga) and Amblycerina (Amblycera) and Ischnocerina (thin angle suborder), Trimenopon spp. (hair Trichodectes) for example, Menoponspp., Trinoton spp. (huge Trichodectes), Bovicola spp. (Bovicola), Werneckiellaspp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp..
Diptera (Diptera) and Nematocerina (Nemocera) and Brachycerina (Brachycera), Aedes spp. (yellow-fever mosquito) for example, Anopheles spp. (spot Anopheles), Culex spp. (Culex), Simulium spp. (receive genus), Eusimulium spp. (all woolen is really received), Phlebotomusspp. (sand fly), Lutzomyia spp. (Lutzomyia), Culicoides spp. (storehouse midge), Chrysopsspp. (spot horsefly), Hybomitra spp. (knurl horsefly), Atylotus spp., Tabanus spp. (Gadfly), Haematopota spp. (Chrysozona), Philipomyia spp., Braula spp., Muscaspp., Hydrotaea spp. (Hydrotaea), Stomoxys spp. (chela fly), Haematobiaspp., Morellia spp., Fannia spp. (latrine fly), Glossina spp., Calliphora spp., Luciliaspp., Chrysomyia spp., Wohlfahrtia spp., Sarcoophaga spp. (other sarcophagids), Oestrusspp., Hypoderma spp. (torsalo), Gasterophilus spp., Hippobosca spp. (hippoboscid), Lipoptena spp. and Melopagus spp..
Siphonapterida (Siphonaptera), Pulex spp. (flea genus) for example, Ctenocephalides spp., Xenopsylla spp. (mouse flea) and Ceratophyllus spp. (c. leaf flea).
Heteropterida (Heteroptera), Cimex spp. (Cimex) for example, Triatoma spp. (stinkbug of sucking blood genus), Rhodnius spp. and Panstrongylus spp. (Panstrongylus).
Blattarida (non-Lian order), Blatta orientalis (the non-Lian in east) for example, Periplanetaamericana (periplaneta americana), Blattela germanica (Groton bug) and Supella spp..
Acaria (mite subclass), and Meta-Mesostigmata (back-mesostigma order), Argas spp. (latent beak tick belong to) for example, Ornithodorus spp. (beak tick genus), Otobius spp. (ear tick), Ixodes spp. (hard tick), Amblyomma spp. (Amblyomma), Boophilus spp. (Boophilus), Dermacentor spp. (giant's tick), Haemophysalis spp., Hyalomma spp. (glass eye tick), Rhipicephalus spp. (carrapato genus), Dermanyssus spp. (Dermanyssus gallinae), Raillietia spp. (auspicious upright tapeworm), Pneumonyssus spp., Stemostoma spp. and Varroaspp.
Actinedida (Trombidiformes) and Acaridida, Acarapis spp. for example, Cheyletiellaspp. (Cheyletiella), Ornithocheyletia spp., Myobia spp., Psorergates spp. (itch mite), Demodex spp. (crawling mite), Trombicula spp. (trombiculid), Listrophorus spp., Acarus spp. (Acarus siro), Tyrophagus spp. (junket mite), Caloglyphus spp. (having a liking for wooden mite), Hypodectes spp., Pterolichus spp. (wing clothing mite genus), Psoroptes spp. (trombiculid), Chorioptes spp. (trombiculid), Otodectes spp., Sarcoptes spp. (itch mite), Notoedresspp., Knemidocoptes spp. (sufficient mite), Cytodites spp. and Laminosioptes spp..
Formula I of the present invention, (II), (III), (IV) and (IV A) active compound and arrow root potato genus plants extract also are suitable for controlling the animal of infringement agriculturally useful, for example, ox, sheep, goat, horse, pig, donkey, camel, buffalo, rabbit, chicken, turkey, duck, goose, honeybee and other pets, for example, dog, cat, raise in cages bird and cylinder are breeded fish, and so-called laboratory animal, for example, hamster, cavy, the arthropods of rat and mouse.By controlling these arthropodss, avoid animal dead, improve agricultural output (as meat, milk, hair, skin, egg, honey etc.), therefore, use active compound of the present invention can make animal feeding more economical, easier.
In field of veterinary, active compound of the present invention and extract can be by known through the enteral administration modes, for example, and tablet, capsule, draught, Haust, granule, paste, bolus, feeding agent and suppository are by the administered parenterally mode, for example, and injection (muscle, subcutaneous, vein, intraperitoneal etc.), implant, by nasal feeding, by the percutaneous dosing mode, for example, dipping, spray, the Shi Hedian that falls executes bathing and powder, administration also can be by the formed article that contains active compound, for example, neck ring, ear pendant, tailpiece, the leg hoop, halter, administrations such as marker.
When being used for livestock, poultry during pet etc., can be used of the present invention formula I of active compound content as the 1-80% weight ratio, (II), (III), the preparation of (IV) and (IV A) active compound and extract, (for example pulvis, emulsion, fluid composition), both can directly use, also can dilute 100-10,000 times of use, form that perhaps can chemical bath is used.
Active compound of the present invention and extract also are applicable to the useful animal of control, pet, and the endoparasite that runs in laboratory animal and the game farming, particularly worm are as fluke
Monogenea (Helerocolylea), for example Gyrodactylus spp., Dactylogyrus spp. (Dactylogyrus) and Polystoma spp. (Polystoma).
Digenea (Digenea), Diplostomum spp. (Diplostomum) for example, Schistosoma spp. (stem Diplostomum), Trichobilharzia spp. (Trichobilharzia), Omithobilharzia spp. (Ornithobilharzia), Austrobilharzia spp. (Austrobilharzia), Gigantobilharzia spp. (Gigantobilharzia), Echinostoma spp. (Echinostoma), Fasciola spp. (liver fluke genus), Fasciolides spp., Fasciolopsis spp. (Fasciolopsis), Paramphistomum spp. (belonging to) with amphistome, Dicrocoelium spp. (Dicrocoelium), Troglotrema spp., Paragonismus spp., Opisthrochis spp. (Opisthorchis), Chonorchis spp., Metorchis spp. (Meotrchis) and Heterophyes spp..Tapeworm
Pseudophyllidea (Pseudophyllidea), Diphyllobothrium spp. (Bothriocephalus) for example, Ligula spp. (Ligula), Mesocestodes spp. (Mesocestoides), Anoplocephala spp. (intending Anaplocephala), Monieazoa spp. (covering the Buddhist nun tapeworm belongs to), Thysanosoma spp. (flint body tapeworm genus), Thysaniezia spp., Avitellina spp. (no yolk line tapeworm belongs to), Stilesia spp. (this is the tapeworm genus too), Cittotaenia spp. (tin Hydatigena), Taenia spp., Echinococcus spp. (Echinococcus), Hydatigera spp., Davaineaspp. (wearing the dimension tapeworm belongs to), Raillietina spp. (Raillietina), Hymenolepsis spp. (Hymenolepis) and Dipylidium spp. nematode
Enopliida (Enoplida), for example Trichuris spp. (Trichocephalus), Capillaria spp. (Hepaticola) and Trichinella spp. (trichinella).
Rhabditida (Rhabditia), for example Strongyloides spp. (Strongyloides).
Strongylida (circle line order), Strongylus spp. (strongylid) for example, Trichonemaspp. (three tooth trace worms), Oesophgostomum spp. (esophagus tooth trace Eimeria), Chabertia spp. (summer uncle Turbatrix), Stephanurus spp. (kidney Turbatrix), Ancyclostoma spp., Uncinaria spp (curved mouth nematode belongs to)., Bunostomum spp., Syngamus spp. (Syngamus), Metastrongylus spp. (Metastrongylus), Dictyocaulus spp. (Dictyocaulus), Muellerius spp. (Miu Shi Turbatrix), Protostrngylus spp. (former round lung worm), Neostrongylus spp., Angiostrongylus spp. (mouse lungworm genus), Filaroides spp., Parafilaroides spp., Trichostrongylus spp. (the hair circle belongs to), Heamonchus spp. (blood hair genus), Ostertagia spp. (oersted genus), Cooperia spp. (ancient uncle belongs to), Nematodirus spp. (Nematodirus), Hyostrongylus spp. (the pig circle belongs to), Amidostomum spp. and Ollulanus spp. (kettle anus genus).
Oxyurida (fine stern order), Oxyuris spp. (fine stern genus) for example, Enterobius spp. (living intestines belongs to), Passalums spp. (the nail tail belongs to), Syphacia spp. (pipeline genus), Aspiculuris spp. (stingless genus) and Heterakis spp. (Heterakis).
Ascaridida (Ascaridina), Ascaris spp. (ascarid genus) for example, Toxascaris spp. (ascarid belongs to bow), Toxocara spp. (bow is first to be belonged to), Parascaris spp. (secondary ascarid belongs to), Ansiakis spp. (not having decorations belongs to) and Ascaridia spp. (ascarid type genus).
Spiruida (Spirurata), Gnathostoma spp. (E Kou genus) for example, Thelazia spp. (male prominent the genus), Gongylonema spp. (the tube line belongs to), Habronema spp. (gentle line belongs to), Parabronema spp. (secondary gentle line belongs to), Draschia spp. (Draschia) and Dracunculusspp. (Dracunculus).
Filariida (nematode order), Stephanofilaria spp. for example, Parafilaria spp. (Parafilaria), Setaria spp. (thread genus), Loa spp. (Loa), Dirofilaria spp. (Evil Filaria), Litomosoides spp., Brugia spp., Wuchereria spp. (Wu Ce genus) and Onchocercaspp (Onchocerca).
Gigantnorhynchida (Gigantorhynchusgigas family), for example Macraconthorhynchusspp..
For example, they have outstanding activity to Trichinella spiralis and Nippostrongylus brasiliensis.
Useful animal, pet, laboratory animal or wildlife preferably include the animal of agriculturally useful, for example, ox, sheep, goat, horse, pig, donkey, camel, buffalo, rabbit, chicken, turkey, duck, goose, honeybee.
Pet comprises, for example, dog, cat, raise in cages bird and cylinder are breeded fish.
Laboratory animal comprises, for example, and hamster, cavy, rat and mouse.
The wildlife that wildlife is preferably raised, for example population of tawny fawn, some antelopes, ostrich.
When control arthropods or worm, active compound of the present invention both can be used for prevention, also can be used for treatment.By controlling these arthropodss or worm, can avoid the animal dead and the underproduction (as meat, milk, hair, skin, egg, honey etc.), therefore, use active compound of the present invention can make animal feeding more economical.
In field of veterinary, active compound of the present invention can be by known through the enteral administration mode, for example, and tablet, capsule, draught, Haust, granule, paste, bolus, feeding agent and suppository are by the administered parenterally mode, for example, and injection (muscle, subcutaneous, vein, intraperitoneal etc.), implant, by nasal feeding, by the percutaneous dosing mode, for example, dipping, spray, the Shi Hedian that falls executes bathing and powder, administration also can be by the formed article that contains active compound, for example, neck ring, ear pendant, tailpiece, the leg hoop, halter, administrations such as marker.
In addition, formula I of the present invention, (II), and (III), (IV) and (IV A) compound has strong insecticidal action to the insect of destroying Industrial materials.
Exemplify preferred insect below, but be not limited to this:
Beetle, for example
Hylotrupes bajulus (North America house longhorn beetle), Chloropphorus pilosis (longicorn becomes mildewed), Anobium punctatum (tool spot death watch beetle), Xestobium rufovillosum (reporting dead death watch beetle), Ptilinus pecticomis (Ptilinus pectinicornis), Dendrobium pertinex, Ernobiusmollis (loose death watch beetle), Priobium carpini, Lyctus brunneus (Lyctus brunneus Stephens), Lyctusafricaanus (African powder moth), Luctus planicollis (southern powder moth), Lyctus linearis (small wooden raft powder moth), Lyctus pubescens (pubescence powder moth), Trogoxylon aequale, Minthes rugicollis (minthea rugicollis), Xyleborus spec. (material bark beetle) Tryptodendron spec.Apatemonachus (coffee is black long moth-eaten), Bostrychus capucins (Mongolian oak is long moth-eaten), Heterobostrychusbrunneus (dun long moth-eaten), Sinoxylon spec. (long moth-eaten) and Dinoderus minutus (dinoderus minutus).
Hymenoptera, for example
Sirex juvencus (the blue or green wood wasp of little steel), Urocerus gigas (big wood wasp), Urocerus gigastaignus and Urocerus augur
Termite, for example
Kalotermes flavicollis ((kalotermitid), Cryptotermes brevis (a fiber crops heap sand termite), Heterotermes indicola (the different termite of ash point), Reticulitermes flavipes (eastern subterranean termite), Reticultermes santonensis, Reticulitermes lucifugus (lucifuge reticulitermes flavipe), Mastotermes darwiniensis (Darwin Australia termite), Zootermopsis nevadensis (damp-wood termite) and Coptoternes formosanus (Coptotermes formosanus Shtrari).
Bristletails (silverfish), for example
Lepisma saccarina (silverfiss)
The Industrial materials that relate among the application are interpreted as non-living material, for example, and preferred plastics, tackiness agent, glue, paper and cardboard, leather, timber and timber-work and coating composition.
Need preferred especially timber and timber-work in the material of pest control.
Available reagent of the present invention or the timber and the timber-work that contain the mixture protection of this reagent are interpreted as, for example, and the construction timber goods; wooden frame, railway sleeper, bridge timber-work; the harbour timber-work, wooden launch vehicle, wooden case; pallet, cootle, electric pole; the wood veneer, timber window, timber; glued board, chipboard, the timber-work that joinery or building construction or joinery are commonly used.
Active compound of the present invention can itself, its conc forms or conventional formulation, as powder, granule, solution, suspension agent, the form of emulsion or paste is used.
Above-mentioned preparation can prepare with known method itself, for example, with active compound and at least a solvent or thinner, emulsifying agent, dispersion agent and/or tackiness agent or fixing agent, water-resisting agent, if desired, siccative and UV stablizer, if desired, tinting material and pigment and other processing aids are mixed.
Being used for the insecticides of timber and timber-work protection or the concentration of enriched material active compound of the present invention is 0.0001-95%, special 0.001-60% weight ratio.
The consumption of composition or enriched material depends on the kind of insect and a situation arises, depends on medium.Optimum amount can be done the campaign decision as the case may be.But in general, based on protected material, the consumption of active compound is the 0.0001-20% weight ratio, preferred 0.001-10% weight ratio.
Employed solvent and/or thinner are organic chemistry solvent or solvent mixture and/or low-volatile oil or oily organic chemistry solvent or solvent mixture and/or polar organic solvent or solvent mixture and/or water, if desired, also have emulsifying agent and/or wetting agent.
The preferred organic chemistry solvent that uses is to volatilize number greater than 35, and flash-point is higher than 30 ℃, preferably is higher than 45 ℃ oil or oil-like solvent.The material that is suitable for use as above-mentioned low volatility water-immiscible solvent is mineral oil or its aromatic hydrocarbon fraction, or contains the solvent mixture of mineral oil, preferred petroleum solvent, oil and/or alkylbenzene.
The preferred boiling point that uses is 170-220 ℃ mineral oil, and boiling point is 170-220 ℃ a petroleum solvent, and boiling point is 250-350 ℃ a spindle oil, and boiling point is 160-280 ℃ of oil and aromatic hydrocarbon, the turpentine wet goods.
In preferred version, use boiling point to be 180-220 ℃ the high boiling aromatic hydrocarbon and the mixture and/or the naphthalene monochloride of aliphatic hydrocrbon, preferred α-naphthalene monochloride as 180-210 ℃ liquid aliphatic hydrocarbon or boiling point.
The volatilization number is greater than 35, flash-point is higher than 30 ℃, the low volatility organic oil or the oil-like solvent that preferably are higher than 45 ℃ can be learned the solvent replacement by high or middle volatile organic, condition is that the volatilization number of this solvent mixture is also greater than 35, flash-point also is higher than 30 ℃, preferably be higher than 45 ℃, and the insecticide/fungicides mixture can dissolve or emulsification in this solvent mixture.
According to preferred version, some organic chemistry solvent or solvent mixture or aliphatic polar organic are learned solvent or solvent mixture can be replaced.The preferred aliphatic organic chemistry solvent that uses hydroxyl and/or ester group and/or ether, for example, glycol ether, ester, etc.
The organic chemistry tackiness agent that uses among the present invention is known for itself, dilutable water and/or in employed organic chemistry solvent dissolving or dispersion or emulsive synthetic resins and/or bonding siccative oil, particularly by acrylic resin, ethenoid resin, polyvinyl acetate for example, vibrin, polycondensation or polyaddition resin, polyurethane resin, Synolac or modified resin, resol, hydrocarbon resin, as indene-coumarone resin ying, silicone resin, dry vegetable oil and/or siccative oil and/or based on the physical dryness tackiness agent of natural and/or synthetic resins.
Synthetic resins as tackiness agent can be emulsion, dispersed system or solution.Pitch or bituminous substances that consumption is 10% weight ratio to the maximum also can be used as tackiness agent.In addition, also can the known tinting material of use itself, pigment, water-resisting agent, odor masking agent and inhibitor or corrosion inhibitor.
Comprise as the organic chemistry tackiness agent in the preferred present composition, at least a Synolac or modified resin and/or a kind of dry vegetable oil.The present invention preferably uses oil-contg to be higher than 45%, the Synolac of preferred 50%-68% weight ratio.
Can be fixed agent (mixture) or softening agent (mixture) of above-mentioned all or part of tackiness agent replaces.These additives can prevent active compound volatilization and crystallization or precipitation.Tackiness agent preferably is replaced 0.01-30% (based on employed 100% tackiness agent).
Softening agent is from phthalate, as the dibutyl of phthalic acid, dioctyl, or the benzyl butyl ester, phosphoric acid ester is as the tricresyl phosphate butyl ester, adipic acid ester, as hexanodioic acid two (2-ethylhexyl) ester, stearate is as butyl stearate or amyl stearate, oleic acid ester, as butyl oleate, glyceryl ether or high molecular glycol ether, glyceryl ester and p-toluenesulfonic esters.
Fixing agent chemically is the polyvinyl alkyl oxide, as polyvinyl methyl ether, or ketone, as benzophenone or ethylene benzophenone.
Specially suitable solvent or thinner are water, if suitable, can make water and one or more above-mentioned organic chemistry solvent or thinner, the mixture of emulsifying agent and dispersion agent.
By heavy industrialization dipping, vacuum for example, double vacuum or pressurization dipping can be protected timber especially effectively.
If suitable, the instant composition can further comprise other sterilants, or further comprises one or more mycocides.
Addible blending ingredients is preferably described sterilant of WO94/29268 and mycocide.The described compound of this document can be directly as the application's integral part.
The particularly preferred mixing element that can mention is a sterilant, as chlorpuriphos (Chlorpyrifos 94), phoxim (phoxim), silafluofin (salifluofen), alphamethrin (alphacypermethrin), cyfluthrin (cyfloxylate), cypermethrin (Cypermethrin), deltamethrin (Deltamethrin), permethrin (permethrin), imidacloprid (Provado), NI-25, flufenoxuron (flufenoxuron), hexaflumuron (fluorine bell urea) and triflumuron (killing the bell urea), mycocide, as epoxyconazole, hexaconazole (own azoles alcohol), azaconzaole (oxygen ring azoles), propiconazole (Wocosin 50TK), tebuconazole (tebuconazole), metconazole (metconazole), hexaconazole (own azoles alcohol), dichlorfluanid, tolyfluanid (Tolylfluanid), 3-iodo-2-propynyl butyl carbamate, N-octyl group-isothiazoline-3-ketone and 4,5-two chloro-N-octyl group-isothiazoline-3-ketone.
The compounds of this invention also can be used for preventing the object, particularly hull that contact with seawater or brackish water, screen cloth, fishing net, building, the infecting of harbour and telltale.
Oligochaetae (Oligochaeta), for example Serpulidae (imperial coccid) and aquatic shell and Ledamorpha (goose barnacle), for example Lepas and Scalpellum (triumphant Lepas), or Balanomorpha (symmetrical barnacle), Balanus (Balanus) or Pollicipes infect ship and water stone roller friction resistance, because therefore the number of times that has increased energy expenditure and overhauled at graving dry dock has obviously increased working expense.
Remove and to be subjected to marine alga, for example, outside the infecting of Ectocarpus sp. and Ceramiumsp., particularly importantly be referred to as the infecting of Entomostraca (Malacostraca) of Cirripedia (Cirripedia).
Astoundingly, the mixture formed of The compounds of this invention itself or itself and other active compound has good anti-dissemination.
The mixture that the application of the invention compound itself or itself and other active compound are formed; can avoid using heavy metal compound; as two (trialkyltin) sulfide; the tri-n-butyl tin lauroleate; the tri-n-butyl tin muriate; cupric oxide (I), triethyltin muriate, three normal-butyls (2-phenyl-4-chlorophenoxy) tin; the tributyl tin oxide compound; molybdenumdisulphide, weisspiessglanz, poly(tributoxy titanium); phenyl (two pyridines) bismuth muriate; the tri-n-butyl tin fluorochemical, ethylene thiocarbamate magnesium, ziram; the ethylidene zinc dithiocarbamate; the zinc or the mantoquita of 2-pyridine mercaptan 1-oxide compound, two Methyl disulfide are for formamyl zinc ethylene thiocarbamate, zinc oxide; ethylene thiocarbamate copper (I); cupric thiocyanide, copper naphthenate and tributyl tin halogenide perhaps reduce these compound concentrations greatly.
If suitable, anti-the infecting in the coating of instant can be contained other active compounds, preferred algicide, mycocide, weedicide, invertebrate poison or other anti-active compounds that infects.
The present invention is anti-to be infected the preferred plural components of composition and is: algicide, as
The 2-tertiary butyl-4-cyclopropyl amino-6-methylthio group-1,3, the 5-triazine, dichlorophen (dichlorophen), diuron (Diuron Tech), endothal (endothal), fentin acetate (acetate fentin), isoproturon, methabnzthiazuron (methabenzthiazuron), oxyfluorfen (oxyfluorfen), quinoclamine (quinoclamine) and terbutryn (special butyronitrile); Mycocide, as
Cyclohexyl-benzo [b] thenoyl amine S, the S-dioxide, dichlofluanid, fluor-folpet, 3-iodo-2-propynyl butyl carbamate, tolyfluanid (Tolylfluanid) and azole are as azaconazole (oxygen ring azoles), cyproconazole (SN-108266), epoxyconazole, hexaconazole (own azoles alcohol), metconazole (metconazole), propiconazole (Wocosin 50TK) and tebuconazole (tebuconazole); Invertebrate poison, as
Fentin acetate (acetate fentin), metaldehyde (methaldehyde), methiocarb (methiocarb), niclosamid (niclosamide), thiodicarb and trimethacarb (trimethacarb); Or the conventional anti-active compound that infects, as 4,5-two chloro-2-octyl groups-4-isothiazoline-3-ketone, diiodomethyl paratryl sulfone; 2-(N, N-dimethylamino thiocarbonyl thio)-5-octyl group thiazole, the sylvite of 2-pyridine sulfur alcohol 1-oxide compound, mantoquita; sodium salt and zinc salt, pyridine triphenylborane, the tetrabutyl two stannanes, 2; 3,5,6-tetrachloro-4-(methyl sulphonyl)-pyridine, 2; 4,5,6 ,-daconil M; tetramethyl-thiuram disulfide and 2,4,6-trichlorine maleimide.
The used anti-composition that infects comprises and accounts for present composition 0.001-50% weight ratio, the particularly active compound of 0.01-20% weight ratio.
The present invention is anti-to be infected composition and also comprises, for example, and Ungerer, Chem.Ind.1985,37,730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973 described conventional components.
Remove algicide, mycocide, invertebrate poison and sterilant and active ingredient beyond the region of objective existence of the present invention anti-ly infect coating composition and also comprise tackiness agent especially.
The example of known binders is the polyvinyl chloride in the solvent systems, chlorinated rubber in the solvent systems, solvent systems is the acrylic resin in the aqueous system particularly, contains the vinylchlorid/vinyl acetate copolymer system in aqueous dispersion or the organic solvent system form, Butadiene/acrylic-nitrile rubber, siccative oil, as Toenol 1140, with tar or pitch bonded resin ester or modification hardened resin, pitch and epoxy compounds, a small amount of chlorinated rubber, Chlorinated Polypropylene III and ethenoid resin.
This coating composition also can comprise mineral dye, and pigment dyestuff or tinting material wherein preferably are insoluble to brinish pigment.This coating composition also can comprise the material of controlling release active compound, as rosin.This coating also can comprise softening agent, influences properties-correcting agent and other conventional components of rheological property.Also The compounds of this invention and said mixture can be sneaked into certainly-the anti-system that infects of polishing.
Active compound of the present invention also is suitable for controlling the room of closing, as the apartment, and factory building, office, the animal pest that runs into, particularly insect are waited, spider and mite in cabin in the launch vehicle.Both can use separately, the active compound and the auxiliary that also itself and other can be used for controlling the family expenses desinsection product of these insects are used in combination.They are to responsive or insensitive kind, and all effective to all growth phases of insect.These insects comprise:
Scorpionidea (Scorpionida), for example Buthus occitanus.
Acarina (acarina), Argas persicus (adobe tick), Argas reflexus (anti-edge sharp-edged tick), Bryobia spp. (Bryobia), Dermanyssus gallinae (Dermanyssus gallinae), Glyciphagus domesticus (the sweet food mite of family), Omithodorus moubat, Rhipicephalussanguineus (brown dog tick), Trombicula alfreddugesi, Neutrombiculaautumnalis, Dermatophagoides pteronissimus, Dermatophagoides forinae.
Araneae (Araneae), Aviculariidae for example, Araneidae (spider).
Opiliones, Pseudoscorpiones chelifer for example, Pseudoscorpionescheiridium, Opiliones phalangium.
Isopoda (Isopoda), Oniscus asellus for example, Porcellio scaber.
Diplopoda (polypody order), Blaniulus guttulatus for example, Polydesmus spp..
Chilopoda (Chcilopoda order), for example Geophilus spp..
Zygentoma, Ctenolepisma spp. for example, Lepisma saccharina, Lepismodes inquilinus.
Blattaria (non-Lian order), Blatta orientalies (the non-Lian in east) for example, Blattellagermanica (Groton bug), Blattella asahinai, Leucophaea maderae, Panchloraspp. (non-Lian belongs to), Parcoblatta spp., Peripaneta australasiae, Periplanetaamericana, Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa (the non-Lian of long palpus).
Saltatoria (saltaroria), for example Acheta dimesticus (cricket).
Dermaptera (Dermaptera), for example Forficula auricularia (European ball sister-in-law).
Isoptera (Isoptera), Kalotermes spp. for example, Reticulitermes spp. (Cryptotermes).
Psocoptera (Corrodentia), Lepinstus spp. for example, Liposcelis spp. (family letter louse).
Coleptera (Coleoptera), Anthrenus spp. for example, Attagenus spp., Dermestes spp. (khapra beetle genus), Latheticus oryzae (a long ostomatid), Necrobia spp., Ptinusspp. (ptinid), Rhizopertha dominica, Sitophilus granarius (grain weevil), Sitophilus oryzae (rice weevil), Sotoophilus zeamais, Stegobium paniceum (medicinal material ostomatid).
Diptera (Diptera), Aedes aegypti for example, Aedes albopictus (northwest seashore yellow-fever mosquito), Aedes taeniorhynchus, Anopheles spp. (spot Anopheles), Calliphoraerythrocephala (calliphora erythrocephala), Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens (northern house), Culex tarsalis, Drosophila spp. (Drosophila), Fanniacanicularis (yellow abdomen stable fly), Musca domestica (housefly), Phlebotomusspp., Sarcophaga camaria (sarcophagid), Simulium spp., Stomoxys calcitrans (matting chela fly), Tipula paludosa (European daddy-longlegs).
Lepidoptera (lepidopteran), Achroia grisella (lesser wax-moth) for example, Galleriamellonella (greater wax moth), Plodia interpunctella (Indian meal moth), Tinea cloacella (rain moth), Tinea pellionella (etting moth), Tineola bisselliella (bag casemaking clothes moth).
Siphonaptera (Siphonaptera), Ctenocephalides canis (dog comb head flea) for example, Ctenocephalides felis (ctenocephalides felis), Pulex irritans (Pulex irritans), Tunga penetrans (chigo), Xenopsylla cheopis (Xenopsyllacheopis).
Hymenoptera (Hymenoptera), Camponotus herculeanus (Binzhou polyrhachis) for example, Lasius fuliginosus (black careless ant), Lasius niger (common black ant), Lasius umbratus, Monomorium pharaonis (kitchen ant), Paravespula spp., Tetramorium caespitum (Pavement Ant).
Anoplura (Anoplura), Pediculus humanus capiti (head louse) for example, Pediculushumanus corporis, Phthirus pubis (crab louse).
Heteroptera (Heteroptera), Cimex hemipterus, Cimex lectularius (bedbug), Rhodinus prolixus, Triatoma infestans (triatoma sanguisuga).
In the family expenses field of pesticides, they both can use separately, also can with other suitable active compounds, as phosphoric acid ester, carbamate, pyrethroid, growth regulator or the known active compound of other field of pesticides are used in combination.
Concrete type of service is an aerosol, does not have the spraying of pressure, for example pump and atomizer spray, spraying gun, moistener, foam, gel has the vaporization product of the vaporizing tube of being made by Mierocrystalline cellulose or plastics, the vaporizing liquid device, gel and film vaporizer, angle of rake vaporizer is housed, and noenergy or passive vaporizer system are removed moth-eaten paper, remove moth-eaten sachet and remove moth-eaten gel, as granule or the pulvis of sowing or placing with bait.
Following embodiment illustrates the preparation and the purposes of active compound of the present invention.Preparation EXAMPLE Example 1 (method 1 or 2)
For example, press general method 1,2 or 3 and separate arrow root ketone lactone N.
Arrow root ketone lactone N physical parameter is as follows: LC-MS (ESI neg.): m/z=601[M-H] -LC-MS (ESI pos.): m/z=603[M+H] -HPLCR t=25.81 minutes [column materials: Lichrospher C18; 5 μ m; Post size: 2 * 125mm; Mobile phase A: water+25mmol NH 4OAc; Mobile phase B: MeOH+25mmol NH 4OAc; Gradient: beginning 20%B; 30 minutes 60%B; 31 minutes: 100%B; 40 minutes 100%B; Flow velocity: 0.4ml/min; Detect at 210nm] 1H NMR data (500MHz, CDCl 3), referring to Fig. 1:
?δ H
C-1 ?4.65(d,J=5.12Hz)
C-2 ?3.55(dd,J=4.0Hz)
C-3 ?3.43(m)
C-4 ?2.18(m) ?2.29(m)
C-5 ?2.74(dd,J=4.55,11.4Hz)
C-6
C-7 ?4.03(d,J=10.3Hz)
C-8 ?1.74(m)
C-9 ?2.13(m)
C-10
?δ H
C-11 ?1.71(m)
C-12 ?5.01(m,brd.)
C-13
C-14 ?2.10(m)
C-15 ?4.41(dd,J=9.6,9.6Hz)
C-16 ?2.42(m)
C-17 ?2.03(m)
C-18 ?0.86(s)
C-19 ?0.78(s)
C-20 ?2.23(m)
C-21 ?0.98(d,J=6.7Hz)
C-22 ?5.05(s,brd.)
C-23
C-24
C-25
C-26
C-27 ?1.70(s)
C-28 ?1.40(s)
C-29 ?2.11(s)
C-30 ?2.12(s)
Embodiment 2
For example, press general method 1,2 or 3 and separate arrow root ketone lactone B.
Arrow root ketone lactone B physical parameter is as follows: LC-MS (ESI neg.): m/z=719[M-H+HOAc] - 2659[M-H] - 2631[M-H-CO] -HPLCR t=24.51 minutes [column materials: Lichrospher C18; 5 μ m; Post size: 2 * 125mm; Mobile phase A: water+25mmol NH 4OAc; Mobile phase B: MeOH+25mmol NH 4OAc; Gradient: beginning 20%B; 30 minutes 60%B; 31 minutes: 100%B; 40 minutes 100%B; Flow velocity: 0.4ml/min; Detect at 210nm] 1H and 13C NMR data, referring to Fig. 2:
?δ c?DMSO ?δ H?DMSO
C-1 ?72.50 4.60(d,J=4.6Hz)
C-2 ?51.66 3.34(m)
C-3 ?52.99 2.10(m)
C-4 ?21.08 1.96(m) 2.05(m)
C-5 ?41.65 2.68(m)
C-6 ?208
C-7 ?75.90 4.20(d,J=10.8Hz)
C-8 ?41.36 1.80(m)
C-9 ?39.55 2.62(m)
C-10 ?42.59
C-11 ?70.62 5.13(dd,J=14.7, 2.2Hz)
C-12 ?73.44 5.04(d,J=2.2Hz)
C-13 ?43.37
C-14 ?57.13 2.00(m)
C-15 ?75.90 4.27(dd,J=9.0, 9.4Hz)
C-16 ?40.08 2.40(dd,J=10Hz, 13Hz)
C-17 ?47.50 1.68(m)
C-18 ?12.82 0.84(s)
C-19 ?12.48 0.67(s)
C-20 ?30.34 2.13(m)
C-21 ?19.69 0.75(d)
?δ c?DMSO ?δ H?DMSO
C-22 ?110.55 ?4.96(s,brd.)
C-23 ?154.10
C-24 ?49.92
C-25 ?78.71
C-26 ?175.16
C-27 ?21.73 ?1.51(s)
C-28 ?24.76 ?1.16(s)
C-29 ?20.48 ?1.80(s)
C-30 ?20.50 ?2.05(s)
C-31 ?20.50 ?2.05(s)
C-32 ?170.04
C-33 ?169.63
C-34 ?169.63
C-35 ?5.73(s,brd.)
Embodiment 3
For example, press general method 1 or 2 and separate arrow root ketone lactone E.
Arrow root ketone lactone E physical parameter is as follows: LC-MS (ESI neg.): m/z=703[M-H+HOAc] -, 643[M-H], -2601[M-H-CO 2] -HPLCR t=22.96 minutes [column materials: Lichrospher C18; 5 μ m; Post size: 2 * 125mm; Mobile phase A: water+25mmol NH 4OAc; Mobile phase B: MeOH+25mmol NH 4OAc; Gradient: beginning 20%B; 30 minutes 60%B; 31 minutes: 100%B; 40 minutes 100%B; Flow velocity: 0.4ml/min; Detect at 210nm] 1H and 13C NMR data, referring to Fig. 3:
?δ c?CDCl 3 ?δ H?CDCl 3
C-1 ?71.37 ?4.61(d,J=5.4Hz)
C-2 ?50.08 ?3.51(dd,J=3.7Hz)
C-3 ?53.32 ?3.39(m)
C-4 ?21.39 ?2.21(m)
C-5 ?43.72 ?2.68(dd,J=7.3Hz)
C-6 ?210.54
C-7 ?77.18 ?3.89(d,J=9.8Hz)
C-8 ?43.44 ?1.71(m)
C-9 ?37.38 ?2.13(m)
C-10 ?41.16
C-11 ?25.50 ?1.70(m)
C-12 ?74.34 ?5.01(s.brd.)
C-13 ?43.52
C-14 ?54.88 ?2.40(m)
C-15 ?72.29 ?5.49(dd,J=9.3,9.3Hz)
C-16 ?54.99 ?2.40(m)
C-17 ?48.44 ?1.70
C-18 ?13.67 ?0.86(s)
C-19 ?13.52 ?0.71(s)
C-20 ?30.86 ?2.20(m)
C-21 ?20.27 ?0.97(d,J=6.8Hz)
C-22 ?111.84 ?5.10(d,J=1.2Hz)
C-23 ?154.83
C-24 ?50.36
C-25 ?79.56
C-26 ?178.57
C-27 ?20.90 ?1.65(s)
C-28 ?25.69 ?1.36(s)
C-29 ?22.89 ?1.99(s)
C-30 ?21.28 ?2.10(s)
?δ c?CDCl 3 ?δ H?CDCl 3
?C-31 ?21.28 ?2.10(s)
?C-32 ?169.32
?C-33 ?169.73
?C-34 ?172.37
Embodiment 4
For example, press general method 1 or 2 and separate arrow root ketone lactone A.
Arrow root ketone lactone A physical parameter is as follows: LC-MS (ESI neg.): m/z=761[M-H+HOAc] -, 701[M-H] -, 659[M-H-CO 2] -HPLCR t=23.36 minutes [column materials: Lichrospher C18; 5 μ m; Post size: 2 * 125mm; Mobile phase A: water+25mmol NH 4OAc; Mobile phase B: MeOH+25mmol NH 4OAc; Gradient: beginning 20%B; 30 minutes 60%B; 31 minutes: 100%B; 40 minutes 100%B; Flow velocity: 0.4ml/min; Detect at 210nm] 1H and 13C NMR data, referring to Fig. 4:
?δ C?CDCl 3 ?δ H?CDCl 3
C-1 ?73.18 4.73(d,J=5.4Hz)
C-2 ?49.59 3.49(dd,J=5.1,3.9Hz)
C-3 ?52.12 3.39(m)
C-4 ?21.05 2.23(m) 2.20(m)
C-5 ?41.97 2.77(m)
C-6 ?209
?δ c?CDCl 3 ?δ H?CDCl 3
C-7 ?75.01 ?4.00(d,J=10.2Hz)
C-8 ?43.03 ?1.71(m)
C-9 ?40.03 ?2.72(m)
C-10 ?42.87
C-11 ?70.89 ?5.32(dd,J=11.7,2.5Hz)
C-12 ?73.76 ?5.27(d,J=2.5Hz)
C-13 ?43.32
C-14 ?54.28 ?2.45(dd,J=9,9Hz)
C-15 ?71.37 ?5.54(dd,J=9.7,9.7Hz)
C-16 ?51.04 ?2.42(dd,J=9,9Hz)
C-17 ?48.62 ?1.78(m)
C-18 ?13.29 ?0.99(s)
C-19 ?12.97 ?0.78(s)
C-20 ?30.63 ?2.21(m)
C-21 ?20.07 ?0.92(d,J=7.1Hz)
C-22 ?111.21 ?5.08(s.brd.)
C-23 ?154.46
C-24 ?49.73
C-25 ?79.28
C-26 ?178.20
C-27 ?20.57 ?1.64(s)
C-28 ?25.20 ?1.35(s)
C-29 ?21.06 ?1.99(s)
C-30 ?22.57 ?2.00(s)
C-31 ?20.79 ?2.13(s)
C-32 ?20.79 ?2.18(s)
C-33 ?172.17
C-34 ?170.56
C-35 ?169.27
C-36 ?169.44
Embodiment 5 is prepared the method for arrow root ketone lactone B by arrow root ketone lactone A
Under the room temperature, 10 milligrams of arrow root ketone lactone A were stirred 44 hours in 2 milliliters 0.05 mole sodium hydrogen carbonate solution (pH=8.2) and 1 ml methanol.Blow out solvent,, use 2 milliliters of ether at every turn residue ether extraction three times.Remove and desolvate, obtain 6.7 milligrams of colorless solid shape arrow root ketone lactone B.Embodiment 6 is prepared the method for arrow root ketone lactone N by arrow root ketone lactone E
Under the room temperature, 10 milligrams of arrow root ketone lactone E were stirred 44 hours in 2 milliliters 0.05 mole sodium hydrogen carbonate solution (pH=8.2) and 1 ml methanol.Blow out solvent,, use 2 milliliters of ether at every turn residue ether extraction three times.Remove and desolvate, obtain 6.7 milligrams of colorless solid shape arrow root ketone lactone N.Table 1A
Figure 9912727500581
Figure 9912727500591
Table 1B
Figure 9912727500611
Purposes EXAMPLE Example 1Meloidogyne (root nematode) tests (nematocidal effect) solvent: the acetone emulsifying agent of 4 parts of weight ratios: the alkylaryl polyglycol ether of 1 part of weight ratio
In order to prepare the active compound appropriate formulation,, and be diluted with water to required concentration with the solvent and the emulsifier mix of the active compound and the specified rate of 1 part of weight ratio.
Add sand in the container, active compounds solution, Meloidogyne incognita (southern root nematode)-ovum-larva suspension and lactuca sativa seeds.Lactuca sativa seeds is sprouted, the seedling growth.At root, the insect gall growth.
Behind the certain hour, with the % mensuration nematocidal effect of insect gall growth.Insect gall is not found in 100% expression; The insect gall number of the processed plant of 0% effect expression is suitable with the plant of being untreated.
Active compound, usage ratio and result are as shown in the table:
Figure 9912727500641
Figure 9912727500651
Figure 9912727500661
Embodiment 2Heterakis spumosa tests (anthelmintic effect)
This test uses the strain SPF/CFW1 male mice of body weight 16-18 gram to carry out.Animal is closed in the Makrolon cage, give water, Sniff mouse food, the 13cm piller, arbitrarily.
From infecting the ovum that mouse colon after 35 to 42 days separates negative worm Heterakis spumosa.This ovum was cultivated for 3 weeks at 27 ℃.With the Heterakis spumosa ovum of 90 embryonizations through the oral infecting mouse of pharyngeal canal.Infect after 46 days and handle (arrow root ketone lactone A/E compound is used in this test) with arrow root ketone lactone.At last, substances is dissolved in or is suspended in solvating agent Cremophor EL (0.2ml), add 0.3ml water then.Make oral 0.5ml solution of mouse or suspension.After 8 days, put to death mouse, separate Heterakis spumosa worm from caecum/colon.From infecting mouse in the same manner, only organize in contrast with Cremophor EL/ water treatment rather than with arrow root ketone lactone.
According to Plant et al. (1996) Pesticide Science 48, described assessment of 351-358 and the effect of mensuration anthelmintic.
In the mouse model, when oral administration dosage was 100mg/kg, arrow root ketone lactone is the interior nematode Heterakis spumosa of control volume fully in vivo.Embodiment 3Phaedon (daikon leaf beetle) larva test (anti-harm plant insect kills the insect effect) solvent: the dimethyl formamide emulsifying agent of 30 parts of weight ratios: the alkylaryl polyglycol ether of 1 fen weight ratio
In order to prepare the active compound appropriate formulation,, and be diluted to required concentration with the water that contains emulsifying agent with the solvent and the emulsifier mix of the active compound and the specified rate of 1 part of weight ratio.
The preparation increase of cabbage leaves (Brassica oleracea) being immersed the active compound of desired concn is handled, and the parasitic horseradish daikon leaf beetle of standby (Phaedoncochleariae) infects when leaf wets.
Behind the certain hour, measure the % kill ratio.100% all daikon leaf beetle larvas of expression all are killed; 0% expression does not have the daikon leaf beetle larva to be killed.
In this test, for example, the compound exhibits excellent activity among the following preparation embodiment:
Figure 9912727500681
Embodiment 4Plutella (diamond-back moth) test (anti-harm plant insect kills the insect effect) solvent: the dimethyl formamide emulsifying agent of 30 parts of weight ratios: the alkylaryl polyglycol ether of 1 fen weight ratio
In order to prepare the active compound appropriate formulation,, and be diluted to required concentration with the water that contains emulsifying agent with the solvent and the emulsifier mix of the active compound and the specified rate of 1 part of weight ratio.
The preparation increase of cabbage leaves (Brassica oleracea) being immersed the active compound of desired concn is handled, and the caterpillar of standby diamond-back moth (Plutella xylostella) infects when leaf wets.
Behind the certain hour, measure the % kill ratio.100% all caterpillars of expression all are killed; 0% expression does not have caterpillar to be killed.
In this test, for example, the compound exhibits excellent activity among the following preparation embodiment:
Figure 9912727500701
Embodiment 5Spodoptera frugiperda (noctuid is coveted on the meadow) test (anti-harm plant insect kills the insect effect) solvent: the dimethyl formamide emulsifying agent of 30 parts of weight ratios: the alkylaryl polyglycol ether of 1 fen weight ratio
In order to prepare the active compound appropriate formulation,, and be diluted to required concentration with the water that contains emulsifying agent with the solvent and the emulsifier mix of the active compound and the specified rate of 1 part of weight ratio.
The preparation increase of cabbage leaves (Brassica oleracea) being immersed the active compound of desired concn is handled, and the caterpillar of the greedy noctuid (Spodoptera frugiperda) in standby meadow infects when leaf wets.
Behind the certain hour, measure the % kill ratio.100% all caterpillars of expression all are killed; 0% expression does not have caterpillar to be killed.
In this test, for example, the compound exhibits excellent activity among the following preparation embodiment:
Figure 9912727500721
Embodiment 6Spodoptera exigua test (anti-harm plant insect kills the insect effect) solvent: the dimethyl formamide emulsifying agent of 30 parts of weight ratios: the alkylaryl polyglycol ether of 1 fen weight ratio
In order to prepare the active compound appropriate formulation,, and be diluted to required concentration with the water that contains emulsifying agent with the solvent and the emulsifier mix of the active compound and the specified rate of 1 part of weight ratio.
The preparation increase of cabbage leaves (Brassica oleracea) being immersed the active compound of desired concn is handled, and the caterpillar of garden beet noctuid (Spodoptera exigua) infects when leaf is wet.
Behind the certain hour, measure the % kill ratio.100% all caterpillars of expression all are killed; 0% expression does not have caterpillar to be killed.
In this test, for example, the compound exhibits excellent activity among the following preparation embodiment: Embodiment 7Heliothis virescens (bollworm) test (anti-harm plant insect kills the insect effect) solvent: the dimethyl formamide emulsifying agent of 30 parts of weight ratios: the alkylaryl polyglycol ether of 1 fen weight ratio
In order to prepare the active compound appropriate formulation,, and be diluted to required concentration with the water that contains emulsifying agent with the solvent and the emulsifier mix of the active compound and the specified rate of 1 part of weight ratio.
The preparation increase of soya bean seedling (Glycine max) being immersed the active compound of desired concn is handled, and the caterpillar of standby bollworm (Heliothis virescens) infects when leaf wets.
Behind the certain hour, measure the % kill ratio.100% all caterpillars of expression all are killed; 0% expression does not have caterpillar to be killed.
In this test, for example, the compound exhibits excellent activity among the following preparation embodiment:

Claims (18)

1. logical formula I compound and all possible steric isomer thereof are used for the purposes of Pest Control,
Wherein
R 1The expression acetoxyl group, hydroxyl, hydrogen, C 1-C 4-alkoxyl group or glycoloyl oxygen base,
R 2The expression acetoxyl group, hydroxyl, hydrogen, C 1-C 4-alkoxyl group or glycoloyl oxygen base,
R 3The expression acetoxyl group, hydroxyl, hydrogen, C 1-C 4-alkoxyl group or glycoloyl oxygen base,
R 4Expression hydrogen,
R 5Expression hydrogen, or
R 4And R 5Represent a carbon bond together,
R 6Expression hydrogen, or
R 5And R 6Represent carbonyl with the carbon atom that they connected, or
R 6And R 7Expression-OCOC (OH) (CH together 3)-group, wherein Sauerstoffatom is connected band
R is arranged 6On the carbon atom of group, or
R 7And R 8Expression-C (OH) (CH together 3) the COO-group, wherein carbon atom is connected band
R is arranged 7On the carbon atom of group, or
R 8The expression acetoxyl group, hydroxyl, hydrogen, glycoloyl oxygen base, the C1-C4-alkoxyl group or
Doubly linked oxygen,
R 9Expression hydrogen,
R 10Expression hydrogen, or
R 9And R 10Represent a carbon bond together, form a two key,
R 11The expression acetoxyl group, hydrogen, glycoloyl oxygen base, C 1-C 4-alkoxyl group or hydroxyl,
Or
R 10And R 11Represent carbonyl with the carbon atom that they connected,
R 12The expression acetoxyl group, hydroxyl, hydrogen, glycoloyl oxygen base, C 1-C 4-alkoxyl group or
Doubly linked oxygen,
R 13The expression acetoxyl group, hydroxyl, glycoloyl oxygen base, C 1-C 4-alkoxyl group or hydrogen,
R 14Expression hydrogen, hydroxyl, acetoxyl group, C 1-C 4-alkoxy or halogen,
R 15Expression hydrogen, hydroxyl, acetoxyl group, C 1-C 4-alkoxy or halogen, or
R 14And R 15Represent oxygen together, thereby form epoxy group(ing).
2. claim 1 compound is used for the purposes of Pest Control, it is characterized in that
R 1The expression acetoxyl group, hydroxyl, methoxyl group or hydrogen,
R 2The expression acetoxyl group, hydroxyl, methoxyl group, hydrogen or glycoloyl oxygen base,
R 3The expression acetoxyl group, hydroxyl, methoxyl group or hydrogen,
R 8The expression acetoxyl group, hydroxyl, methoxyl group, hydrogen or doubly linked oxygen,
R 11The expression acetoxyl group, methoxyl group or hydroxyl,
R 12The expression acetoxyl group, hydroxyl, methoxyl group, or doubly linked oxygen,
R 13The expression hydroxyl, methoxyl group, acetoxyl group or hydrogen,
R 14Expression hydrogen, hydroxyl, acetoxyl group, methoxyl group or chlorine,
R 15Expression hydrogen, hydroxyl, acetoxyl group, methoxyl group or chlorine.
3. claim 1 or 2 formula I compounds are used for the purposes of Pest Control, it is characterized in that
R 1Expression acetoxyl group or hydroxyl,
R 2The expression acetoxyl group, hydroxyl, glycoloyl oxygen base or hydrogen,
R 3Expression acetoxyl group or hydroxyl,
R 8The expression acetoxyl group, hydroxyl, hydrogen or doubly linked oxygen,
R 11Expression hydroxyl or acetoxyl group,
R 12The expression acetoxyl group, hydroxyl or doubly linked oxygen,
R 13Expression acetoxyl group, hydroxyl or hydrogen.
4. each formula I compound of claim 1 to 3 is used for the purposes of Pest Control, it is characterized in that
R 2The expression acetoxyl group, hydroxyl or hydrogen,
R 8Expression acetoxyl group or hydroxyl,
R 11The expression hydroxyl,
R 12Represent doubly linked oxygen,
R 13Expression hydrogen.
5. the formula II compound is used for the purposes of Pest Control,
Wherein
R 2And R 8Such as in one of claim 1 to 4 definition.
6. formula III compound
7. formula IV compound and all possible steric isomer thereof are used for the purposes of Pest Control,
Figure 9912727500051
Wherein
R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 14And R 15Such as in one of claim 1 to 5 definition, and
R 16The expression formyl radical, carboxyl or carboxyl methyl ester,
R 17The expression formyl radical, carboxyl or carboxyl methyl ester, and
R 18Expression hydrogen, acetoxyl group, hydroxyl or C 1-C 4-alkoxyl group.
8. the purposes of claim 7 formula IV compound is characterized in that
R 18Preferably represent hydrogen, acetoxyl group, hydroxyl or methoxyl group.
9. formula (IV A) compound is used for the purposes of Pest Control,
10. prepare the formula I of one of claim 1 to 6, the method for (II) and (III) compound is characterized in that
A) with the organic solvent extraction arrow root potato platymiscium powder that randomly contains water,
B) extract is absorbed on the solid carrier,
C) carry out vacuum liquid phase chromatography,
D) carry out liquid liquid then and distribute,
E) carry out the liquid chromatography (LC) purifying.
11. the formula I of one of preparation claim 1 to 6, the method for (II) and (III) compound is characterized in that
A) with the organic solvent extraction arrow root potato platymiscium powder that randomly contains water,
B) extract is changed in the solvent-laden water,
C) this mixture is extracted continuously with increasing polar water insoluble solvent,
D) carry out the liquid chromatography (LC) purifying.
12., it is characterized in that arrow root ketone lactone is stirred in weakly alkaline solution from the derive method of arrow root ketone lactone of another kind of arrow root ketone lactone.
13. sterilant is characterized in that containing the formula I of one of at least a claim 1 to 9, (II), (III), (IV) or (IV A) compound.
14. contain the formula I that wherein contains one of at least a claim 1 to 6, the sterilant of the arrow root potato genus plants extract of (II) or (III) compound.
15. contain the sterilant of arrow root potato platymiscium powder, it is characterized in that wherein containing the formula I of one of at least a claim 1 to 6, (II) or (III) compound.
16. the method for Pest Control is characterized in that the formula I with one of claim 1 to 9, (II), (III), (IV) or (IV A) compound effects is in insect and/or its habitat.
17. the method for Pest Control is characterized in that the arrow root potato genus plants extract of claim 14 is acted on insect and/or its habitat.
18. prepare the method for sterilant, it is characterized in that formula I with one of at least a claim 1 to 9, (II), and (III), (IV) or (IV A) compound mixes with expansion agent and/or tensio-active agent.
CN 99127275 1999-12-03 1999-12-03 Tacca chantrieri andre ketonic internal ester and its use Pending CN1298877A (en)

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CN102265898A (en) * 2004-01-23 2011-12-07 石原产业株式会社 Pest control composition and method of controlling pest
CN105343888A (en) * 2015-11-03 2016-02-24 石家庄以岭药业股份有限公司 Taccalonolide cyclodextrin inclusion compound, preparation method of inclusion compound and pharmaceutical composition

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US6878699B1 (en) 1999-05-21 2005-04-12 University Of Hawaii Taccalonolide microtubule stabilizing agents
WO2000071563A2 (en) * 1999-05-21 2000-11-30 University Of Hawaii Taccalonolide microtubule stabilizing agents
JP2014516078A (en) * 2011-06-06 2014-07-07 ザ ボード オブ レゲンツ オブ ザ ユニバーシティ オブ テキサス システム A novel talcaronolide microtubule stabilizer.

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DE1249272B (en) * 1964-07-13 1967-09-07 Schermg Aktiengesellschaft, Berlin Process for the production of a new 14a hydroxy steroid
WO2000071563A2 (en) * 1999-05-21 2000-11-30 University Of Hawaii Taccalonolide microtubule stabilizing agents

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CN102265898A (en) * 2004-01-23 2011-12-07 石原产业株式会社 Pest control composition and method of controlling pest
CN102265898B (en) * 2004-01-23 2013-11-06 石原产业株式会社 Pest control composition and method of controlling pest
CN105343888A (en) * 2015-11-03 2016-02-24 石家庄以岭药业股份有限公司 Taccalonolide cyclodextrin inclusion compound, preparation method of inclusion compound and pharmaceutical composition
CN105343888B (en) * 2015-11-03 2018-05-29 石家庄以岭药业股份有限公司 Taccalonolide cyclodextrin inclusion compound and preparation method thereof and a kind of pharmaceutical composition

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