WO2016154705A1 - Composés méroterpénoïdes, procédés et compositions pour leur utilisation dans la lutte contre les insectes - Google Patents

Composés méroterpénoïdes, procédés et compositions pour leur utilisation dans la lutte contre les insectes Download PDF

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WO2016154705A1
WO2016154705A1 PCT/CA2015/000198 CA2015000198W WO2016154705A1 WO 2016154705 A1 WO2016154705 A1 WO 2016154705A1 CA 2015000198 W CA2015000198 W CA 2015000198W WO 2016154705 A1 WO2016154705 A1 WO 2016154705A1
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carbon
substituted
unsubstituted
alkyl
cyclic
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PCT/CA2015/000198
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English (en)
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Yasmin AKHTAR
Raymond J. Andersen
Ryan M. CENTKO
David E. Williams
Murray Bruce Isman
Dinith JAYANETTI
Edogage Dilip DE SILVA
Ravindra WIJESUNDERA
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The University Of British Columbia
University Of Colombo
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Priority to PCT/CA2015/000198 priority Critical patent/WO2016154705A1/fr
Publication of WO2016154705A1 publication Critical patent/WO2016154705A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • 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
    • C07D493/08—Bridged systems
    • 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
    • C07D493/12—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains three hetero rings
    • C07D493/14—Ortho-condensed systems
    • 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
    • C07D493/12—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains three hetero rings
    • C07D493/18—Bridged systems
    • 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
    • C07D493/12—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains three hetero rings
    • C07D493/20—Spiro-condensed systems
    • 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
    • C07D493/22—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains four or more hetero rings

Definitions

  • This invention relates to insect control. More specifically the invention relates to methods and compositions for control of insects, including the cabbage looper, Trichoplusia ni.
  • Insecticides are chemicals used against insects. They include ovicides and larvicides used against the eggs and larvae of insects, respectively, but many insecticides kill all life stages of target insects. Insecticides are used in agriculture, medicine, industry, and general home use. The use of insecticides is believed to be one of the major factors behind the increase in agricultural productivity in the 20 th century.
  • Synthetic insecticides however may cause acute or delayed health affects in humans, and other non-target organisms, including wildlife and beneficial insects, who can be exposed. Insecticide exposure can cause a variety of adverse health effects. Furthermore certain synthetic insecticides are persistent organic pollutants that contribute to environmental contamination.
  • the cabbage looper Trichoplusia ni ( ⁇ . Ni) is considered an important field and greenhouse pest in vegetable crop production.
  • This species is a generalist and attacks a variety of crops including lettuce, beets, turnip, spinach, brussel sprouts, peas, celery, tomatoes, rape, tobacco, certain ornamentals, many weedy plants, as well as cruciferous plants.
  • the mated females deposit dome-shaped, pale green eggs singly on the host-plants, chiefly at night. After hatching, the destructive larval stage reaches full development in two to four weeks; pupation then occurs and in almost 10 days the new adults emerge. In general, the larval stages damage the crop. The first two larval stages feed on the lower side of the leaf, eating through the upper epidermis, leaving "windows" in the leaf. Older larvae chew larger holes in the leaves, often resulting in extensive damage to leaves. Although this pest generally damages leaves, damage has been reported on fruits and flowers of various host plants. Three or more generations can be produced each season, depending on the latitude 2 ⁇ .
  • the loopers overwinter in the pupal stage, the pupae enclosed in flimsy silken cocoons attached to the food plants or to nearby objects.
  • Cabbage loopers do not generally overwinter in Canada and migrate in from the south. However, they can overwinter in or around greenhouses.
  • T. ni has developed resistance to a number of commercial insecticides, including early generation insecticides such as DDT, carbaryl, parathion3°, as well as more modern insecticides such as methomyl and Bt (Bacillus thuringiensis toxin), a widely used benign and specific insecticide against moth pests that are in the larval stagess 1 .
  • early generation insecticides such as DDT, carbaryl, parathion3°
  • insecticides such as methomyl and Bt (Bacillus thuringiensis toxin)
  • methomyl and Bt Bacllus thuringiensis toxin
  • Plants may harbor many epiphytic fungi that live on their surfaces or inside their cells. 1 - 2
  • 3 Fungal secondary metabolites play a variety of important roles in epiphytic relationships. ⁇ For example, it has been shown that loline alkaloids produced by the fungal epiphyte Epichloe festucae protect host Festuca and Lolium spp. grasses from insect predators such as aphids. 6
  • Epiphytic fungi are often uniquely adapted to the niche habitats of their specific plant hosts.7.8.9 Sri Lanka has a high rate of endemic speciation in both plants and microbes, 10 which offers great potential for the discovery of new epiphytic relationships that might generate novel secondary metabolites with medicinal or agricultural utility.
  • FIGURE l shows the structures of dhiloride compounds isolated from Penicilium purpurogenum.
  • FIGURE 2 shows the compounds obtained by modification of isolated dhilirolides.
  • FIGURE 3 shows a proposed biogenetic pathway for the dhilirolides showing representative examples of each of the new dhilirane, isodhilirane, 14,15-dinordhilirane, and 23,24-dinorisodhilirane skeletons, wherein the labeling pattern indicating intact acetate units shown for dhilirolide A (1) was determined from the [i,2- 1 3C2]acetate feeding study and an enormous natural abundance double quantum transfer
  • the present invention is based, in part, on the fortuitous discovery that certain meroterpenoid compounds showed significant feeding inhibition and sublethal developmental disruption in the cabbage looper, Trichoplusia ni. Furthermore, it was found that the compounds described herein may be useful in controlling insect infestations. Such compounds may therefore have important utility as an insecticide or as an insect repellent. Such compounds may have particular utility against the cabbage looper and other crop pests of the insect family Noctuidae.
  • a method of insect control including, applying an effective amount of a compound of Formula I, Formula II and/or Formula III to an edible or non-edible plant or its surroundings, wherein the compound of Formula I has the following structure: FORMULA II;
  • a method of insect control including, applying an effective amount of a compound of Formula I, to an edible or non-edible plant or its surroundings, wherein the compound of Formula I has the following structure:
  • A may be C(Me)(OH), C(R a ) 2 or C(Me), wherein when A is C(Me) there is a double bond between carbon 14 and carbon 3.
  • A may be absent wherein carbon 3 and carbon 13 are directly bonded to another to form a six membered ring.
  • bri ging moiety 1 wherein Xi may be selected from O, S, and CH 2 , X 2 may be selected from O, S, and CH 2 and R ! 7 may be H, CH 3 , or R d .
  • R4 may be linked to R 2 (carbon 10) and Rs (carbon 13) through bridging moiety 1.
  • R4 may be linked to R 11 (carbon 5) by X 3 , wherein X 3 may be O, S, or CH 2 .
  • R3 may be linked to R7 (carbon 8) throu h bridging moiety 2:
  • X may be O, S, or CH 2 .
  • Rs may be H, C(O)CH 3 , R k , or may be linked to R 2 (carbon 10) and R4 (carbon 9) through bridging moiety 1. Alternatively, Rs may be absent when there is a double bond between carbon
  • R7 may be H, OH, R M , C(O)OCH 3 or may be linked to R3 (carbon 9) through bridging moiety 2.
  • R 8 may be H or R N .
  • R9 may be H, OH, R°, or may be absent if there is a double bond between carbon 2 and carbon 3.
  • R 11 may be linked to R 12 (carbon 4) by X4, wherein X 4 may be O, S, or CH 2 , or may be linked to R4 (carbon 9) by X 3 .
  • R 11 may be absent if there is a double bond between carbon 4 and carbon 5 or between carbon 5 and carbon 6.
  • R 12 may be absent if there is a double bond between carbon 3 and carbon 4 or between carbon 4 and carbon 5.
  • R 12 may be linked to R 11 (carbon 5) via X4, wherein X4 may be O, S, or CH 2 , forming a three membered ring or R 12 may be linked to * (carbon 9) via X 5 , wherein X 5 may be O, S, or CH 2 .
  • R L8 may be H or R R .
  • R 18 may be absent if there is a double bond between carbon 5 and carbon 6.
  • R 1 ? may be H or R S .
  • R 2 ° may be H or R*.
  • R 20 may be absent if there is a double bond between carbon 13 and carbon 12.
  • R 21 may be H or R U .
  • R A may be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R B may be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R C may be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R D may be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by O to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R e may be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted l to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R f may be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R h may be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R h may be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by O to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R j may be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • Ri may be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R k may be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by 0 to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R m may be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R n may be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R° may be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • RP may be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted l to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R3 ⁇ 4 may be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R r may be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R s may be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R 1 may be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R u may be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R may be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by O to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R 1 may be -OH and R 2 is H.
  • R 1 may be OH and R 2 ma be linked to Rs (carbon 13) and R4 (carbon 9) though bridging moiety 3:
  • R3 may be OC(O)(CH 3 ) or C(O)CH 3 .
  • Rs may be
  • R4 may be H, OH or OC(O)(CH 3 ).
  • R4 and R 11 together may be O, with O bridging carbon 5 and carbon 9.
  • R4 and R 12 together may be O, with O bridging carbon 4 and carbon 9.
  • R 6 is CH 2 or an epoxide ring of form -CH2-O-.
  • R? may be C(O)(OMe).
  • R 8 may be H.
  • R may be H or OH.
  • R9 may be absent and there is a double bond between carbon 3 and carbon 2.
  • R 10 may be H.
  • R 11 may be OH.
  • R 11 and R 12 may be an O that bridges carbon 5 and carbon 4.
  • R 11 and R 12 may be absent and there may be a double bond between carbon 5 and carbon 4.
  • the compound may be independently selected from the following:
  • the compound may be a feeding deterrent.
  • the compound may be toxic to insects.
  • the toxicity or the feeding deterrence may be selective for insects.
  • the toxicity or the feeding deterrence may be selective for T. ni.
  • the toxicity or the feeding deterrence may be selective for other crop pests of the insect family Noctuidae.
  • the compounds may be applied simultaneously or sequentially.
  • the compound may be applied in combination with another compound or treatment.
  • the other compound may be a feeding deterrent, a toxicant or both.
  • the insect may be a larva or an adult.
  • the compound may form a composition with an agriculturally acceptable carrier.
  • the compound may be provided in a formulation selected from one or more of the group consisting of a spray, aerosol, solid, or liquid. In certain circumstances the compound may be not one of the
  • a method of insect control comprising, applying an effective amount of an extract from a culture of P. purpurogenum to an edible or non-edible plant or its surroundings.
  • A may be C(Me)(OH), C(R a ) 2 or C(Me).
  • A may be C(Me)(OH).
  • A may be C(Me)(OH) or C(Me).
  • A may be C(Me).
  • A may be absent wherein carbon 3 and carbon 13 are directly bonded to another to form a six membered ring as shown in Formula II.
  • R 1 may be selected from H, OH, OR b , NR b 2 , SR b , SiR b 3 , F, Cl, Br and I.
  • R 1 may be selected from H, OH, F, Cl, Br and I.
  • R 1 may be selected from H and OH.
  • R 2 may be linked to Rs (carbon 13) and R4 (carbon 9) through bridging
  • Xi may be selected from O, S, and CH 2 ;
  • X 2 may be selected from O, S, and CH 2 ; R 17 may be H, CH 3 , or R d .
  • Xi is selected from O, S, and CH 2 .
  • Xi may be selected from O and CH 2 ;
  • X 2 may be selected from O and CH 2 ;
  • R 17 may be H or CH 3 .
  • Xi may be selected from O, S, and CH 2 .
  • Xi may be O.
  • X 2 may be O.
  • R 17 may be H or CH 3 .
  • Xi may be selected from O and S.
  • Xi may be selected from O and CH 2 .
  • X 2 may be selected from O and S.
  • X 2 may be selected from O and CH 2 .
  • R3 may be H, OH, C(O)CH 3> or OC(O)CH 3 .
  • R4 may be H, OH, C(O)CH 3 , OC(O)CH 3 , or R f .
  • R4 may be H, OH, C(O)CH 3 or OC(O)CH 3 .
  • R may be H or OH.
  • R may be C(O)CH 3 or OC(O)CH 3 .
  • R4 may be H, C(O)CH 3 or OC(O)CH 3 .
  • R4 may be OH, C(O)CH 3 or
  • R4 may be linked to R 2 (carbon 10) and Rs (carbon 13) through bridging moiety 1.
  • R4 may be linked to R 11 (carbon 5) by X 3 , wherein X 3 is O, S, natively, R3 may be linked to R7 (carbon 8) through
  • X may be O, S, or CH 2 .
  • X may be O, S, or CH 2 .
  • X maybe O.
  • X maybe S.
  • X may be CH 2 .
  • Rs may be H, C(O)CH 3 , R k , or is linked to R 2 (carbon 10) and R4 (carbon 9) through bridging moiety 1.
  • Rs may be H, C(O)CH 3 , or is linked to R 2 (carbon 10) and R4 (carbon 9) through bridging moiety 1.
  • Rs may be H or C(O)CH 3 .
  • Rs may be absent when there is a double bond between carbon 13 and carbon 12.
  • R6 ma y be CH 2 .
  • R 6 may be an
  • R7 may be H, OH, R m , C(O)OCH 3 or is linked to R3 (carbon 9) through bridging moiety
  • R? may be H, OH, C(O)OCH 3 or is linked to R3 (carbon 9) through bridging moiety 2.
  • R7 may be H, OH or C(O)OCH 3 .
  • R 8 may be H or R n .
  • R 8 may be H.
  • R 8 maybe R n .
  • R9 may be H, OH, R°, or is absent if there is a double bond between carbon 2 and carbon
  • R9 may be H, OH, or is absent if there is a double bond between carbon 2 and carbon 3.
  • R9 may be H or OH.
  • R 10 may be H.
  • R 11 may be H or OH.
  • R 11 may be linked to R 12 (carbon 4) by X4, wherein X4 may be O, S, or CH 2> or may be linked to R4 (carbon 9) by X 3 .
  • R 11 may be absent if there is a double bond between carbon 4 and carbon 5 or between carbon 5 and carbon 6.
  • X4 may be O, S, or CH 2 .
  • X 4 may be O or S.
  • X4 may be O or CH 2 .
  • X4 may be O.
  • X4 may be S.
  • X4 may be CH 2 .
  • R 12 may be absent if there is a double bond between carbon 3 and carbon 4 or between carbon 4 and carbon 5.
  • R 12 may be linked to R 11 (carbon 5) via X4, wherein X4 may be O, S, or CH 2 , forming a three membered ring or R 12 is linked to R4 (carbon 9) via X 5 , wherein X 5 is O, S, or CH 2 .
  • X 5 may be O or S.
  • X 5 may be O or CH 2 .
  • X 5 may be O.
  • X 5 may be O.
  • X 5 may be S.
  • X 5 may be CH 2 .
  • R 18 may be H or R r or R l8 is absent if there is a double bond between carbon 5 and carbon 6.
  • R 18 may be H or R r .
  • R l8 maybe H.
  • R l8 maybe R r .
  • R 18 may be absent if there is a double bond between carbon 5 and carbon 6.
  • R ⁇ maybe H or R 5 .
  • R ⁇ maybe H.
  • R ⁇ maybe R 8 .
  • R 20 may be H or R l or may be absent if there is a double bond between carbon 13 and carbon 12.
  • R 2 ° may be H or may be absent if there is a double bond between carbon 13 and carbon 12.
  • R 2 ° may be R l or may be absent if there is a double bond between carbon 13 and carbon 12.
  • R 2 ° may be absent if there is a double bond between carbon 13 and carbon 12.
  • R 2 ° maybe H.
  • R ⁇ maybe R*.
  • R 1 maybe H or R u .
  • R 21 may be H.
  • R 21 maybe R u .
  • an agricultural chemical formulation comprising a compound described herein and an agriculturally acceptable carrier.
  • the insect control may be via a deterrent to feeding.
  • the insect control may be selective for insects.
  • the insect control may be selective for T. ni.
  • the insect control may be via developmental disruption.
  • R 22 may be CH 3 , OH, R a or may absent when there is a double bond between carbon 14 and carbon 3.
  • R3 ⁇ 4 may be CH 3 , OH, or R a .
  • R 2 3 maybe CH 3 .
  • R 2 3 may be OH.
  • R 3 may be Ra.
  • two or more compounds described herein may be applied simultaneously or sequentially.
  • a compound of Formula I may be applied in combination with another compound or treatment, such as one or more of an oviposition deterrent, an oviposition stimulant, a feeding deterrent, a feeding stimulant, an attractant, or a toxicant.
  • the insect may be a larva or may be an adult, e.g. a female adult or a male adult.
  • the site of interest may be a plant or part thereof such as a cultivated plant within the host range of a pest insect, such as T. ni.
  • R a u may independently be H, a substituted or an unsubstituted aryl, or a substituted or an unsubstituted l to 20 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by O to 10 oxygen, o to 10 sulfur, and O to 10 nitrogen atoms.
  • R a u may independently be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 15 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R a u may independently be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 14 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R a u may independently be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 13 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R a u may independently be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 12 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R a u may independently be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 11 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R a u may independently be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 10 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen, o to 10 sulfur, and o to 10 nitrogen atoms.
  • R a u may independently be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 10 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 3 oxygen, o to 3 sulfur, and o to 3 nitrogen atoms.
  • R a u may independently be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted l to 10 carbon linear, branched or cyclic, saturated or unsaturated alkyl, wherein alkyl carbon atoms may be replaced by o to 10 oxygen atoms.
  • R a u may independently be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted l to 10 carbon linear, branched or cyclic, saturated or unsaturated alkyl.
  • R a u may independently be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted l to 9 carbon linear, branched or cyclic, saturated or unsaturated alkyl.
  • R a u may independently be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 7 carbon linear, branched or cyclic, saturated or unsaturated alkyl.
  • R a u may independently be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 6 carbon linear, branched or cyclic, saturated or unsaturated alkyl.
  • R a u may independently be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 9 carbon linear, branched or cyclic, saturated or unsaturated alkyl.
  • R a u may independently be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 5 carbon linear, branched or cyclic, saturated or unsaturated alkyl.
  • R a u may independently be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 4 carbon linear, branched or cyclic, saturated or unsaturated alkyl.
  • R a u may independently be H, a substituted or an unsubstituted aryl, a substituted or an unsubstituted 1 to 3 carbon linear, branched or cyclic, saturated or unsaturated alkyl.
  • R a u may independently be H or a substituted or an unsubstituted 1 to 10 carbon linear, branched or cyclic, saturated or unsaturated alkyl.
  • Dhilirolides A (1) to N (14) represent the four unprecedented and rearranged dhilirane, isodhilirane, bisnordhilirane, and bisnorisodhilirane meroterpenoid carbon skeletons. Stable isotope feeding studies have confirmed the meroterpenoid biogenetic origin of the dhilirolides and provided support for a proposed genesis of the new carbon skeletons. Dhilirolide L (12) showed significant feeding inhibition and sublethal developmental disruption in the cabbage looper Trichoplusia ni, an important agricultural pest, at low concentrations.
  • the compound may have the following structure:
  • the dhilirolides were found to have promising feeding inhibition and developmental disruption activities against the cabbage looper Trichoplusia ni (Lepidoptera: Noctuidae), an economically important agricultural pest. Details of the isolation and structure elucidation of the new dhilirolides E-N (5-14), a stable isotope feeding study that has provided insight into the biogenesis of the new carbon skeletons, and the insecticidal activities of the dhilirolides are presented below.
  • applying an effective amount of a compound of Formula I to an edible or non-edible plant or its surroundings is meant to include spraying of insect pests directly, treating plants potentially infested with the insect pests, or treating surrounding soil or cultivation medium of the plants, in an amount sufficient to deter insect habitation on the plants or surroundings.
  • compositions described herein are meant to be sprayable and may be sprayed onto a desired location, or formulated as a concentrate that is sprayable on addition of agriculturally acceptable carriers and/or spray adjuvants.
  • Preferred compositions of the invention are shelf stable.
  • shelf stable is intended to mean that a composition of the invention does not separate out into separate phases or experience significant reduction in activity.
  • insects intended to include any material that facilitates application of a composition of the invention to the desired location (for example, plants, soil, insects etc.), which may for example be a plant, plant material or equipment, or that facilitates storage, transport or handling.
  • Carriers used in compositions for application to plants and plant material are preferably non-phytotoxic or only mildly phytotoxic.
  • a suitable carrier may be a solid, liquid or gas depending on the desired formulation.
  • preferred carriers include polar liquid carriers such as water, mineral oils and vegetable oils.
  • Pest insects are insects that may damage or kill agricultural crops, ornamental plants, or native plants, or may consume or damage harvested food, or may cause illness or unproductivity in agricultural animals or vector human diseases or cause pain. Some insects may be beneficial at one stage of life and a pest at another stage.
  • Pest insects of concern in agricultural applications include: Acalymma, Acyrthosiphon pisum, African armyworm, Africanized bee, Agromyzidae, Agrotis munda, Agrotis porphyricollis, Aleurocanthus woglumi, Aleyrodes proletella, Alphitobius diaperinus, Altica chalybea, Anasa tristis, Anisoplia austriaca, Anthonomus pomorum, Anthonomus signatus, Aonidiella aurantii, Apamea apamiformis, Apamea niveivenosa, Aphid, Aphis gossypii, Apple maggot, Argentine ant, Army cutworm, Arotrophora arcuatalis, Asparagus miner, Asterolecanium coffeae, Athous haemorrhoidalis, Aulacophora, Australian plague locust, Bactericera cockerelli, Bactrocera, Bac
  • Pest insects of concern in ornamental plant applications include: Acleris variegana, Acyrthosiphon pisum, Aphid, Bird-cherry Ermine, Grapeleaf Skeletonizer, Gypsy moths, Japanese beetle, Macrodactylus subspinosus, Mealybug, Otiorhynchus sulcatus, Paratachardina pseudolobata, Paysandisia archon, Sawfly, Scale insect, Scarlet lily beetle, Sciaridae, Spodoptera cilium, Stephanitis takeyai, Tenthredo scrophulariae, Yponomeuta malinellus, and Yponomeuta padella.
  • Pest insects that act as vectors of plant pathogens include: Acyrthosiphon pisum, Agromyzidae, Anthomyiidae, Aphid, Beet leafhopper, Brevicoryne brassicae, Cacopsylla melanoneura, Cicadulina, Cicadulina mbila, Common brown leafhopper, Curculionidae, Diabrotica balteata, Empoasca decedens, Eumetopina flavipes, Euscelis plebejus, Frankliniella tritici, Glassy-winged sharpshooter, Haplaxius crudus, Hyalesthes obsoletus, Hylastes ater, Jumping plant louse, Leaf beetle, Leafhopper, Mealybug, Melon fly, Molytinae ,Pegomya hyoscyami, Pissodes, Pissodes strobi, Pissodini, Planthopper, Pseudococcus viburni,
  • Pest insect that act as vectors of animal pathogens include: Alphitobius diaperinus, Calliphoridae, Cat flea, Culicoides imicola, Hippelates ,Lutzomyia shannoni, Musca autumnalis, Oriental rat flea.
  • Pest insects that act as vectors of human pathogens include: Aedes aegypti, Aedes albopictus, Anopheles, Anopheles barberi, Anopheles crucians, Anopheles culicifacies, Anopheles dirus, Anopheles earlei, Anopheles gambiae, Anopheles punctipennis, Black fly, Calliphoridae, Culex, Culex tritaeniorhynchus, Flea, Haemagogus, Hippelates, Housefly, Lutzomyia, Mosquito, Oriental rat flea, Phlebotomus, Rhodnius prolixus, Sarcophaga peregrina, Simuliinae, Simuliini, Simulium, Simulium yahense, Triatoma, Triatoma brasiliensis, Triatoma carrioni, Triatoma dimidiata, Triatoma gerstaeckeri, Triatoma Indict
  • a feeding deterrent is a compound that once probed by the insect, may cause it to stop feeding and starve to death.
  • ⁇ , X 3C, and 2D NMR spectra were recorded using a Bruker AV-600TM spectrometer with a 5 mm cryoprobe.
  • ⁇ chemical shifts are referenced to the residual DMSO-cfe signal ( ⁇ 2.49 ppm).
  • ⁇ C chemical shifts are referenced to the DMSO-cfe signal ( ⁇ 39.5 ppm).
  • High-resolution ESI-MS (HRESIMS) data were recorded on a Bruker-Hewlett PackardTM 1100 Esquire-LCTM system mass spectrometer. Sephadex LH-20TM (3 cm x 95 cm) was used for size exclusion column chromatography.
  • Penicillium purpurogenum was isolated from infected fruits oiAverrhoa bilimbi (Averrhoa bilimbi, L., (Oxalidaceae) as described previously. 1
  • P. purpurogenum was cultured on potato dextrose agar (50 Petri dishes) and the culture medium cut into small pieces and extracted with EtOAc. 1
  • the EtOAc extract was concentrated in vacuo and chromatographed on Sephadex LH20TM (3 cm x 95 cm) using 4:1 MeOH/CH 2 Cl 2 .
  • the fractions containing the compounds of interest were combined and subjected to reversed-phase Ce and ds HPLC chromatography using a CSC- InertsilTM 150A/ODS2, 5 ⁇ 25 x 0.94 cm column, with a linear gradient of 40-45% MeCN/H 2 0 over 60 min at a flow rate of 2 mL/min.
  • Dhilirolide A (1) was obtained as optically active colorless crystals (mp 267-269 °C) that gave an [M+H] + ion in the HRESIMS at m/z 473.1796 appropriate for a molecular formula of C 25 H 2 80g, requiring 12 sites of unsaturation.
  • the NMR spectrum obtained for 1 contained 25 resolved resonances in agreement with the HRESIMS data (not shown).
  • Dhilirolide B (2) was isolated as an optically active amorphous solid that gave an [M + Na] + ion at m/z 479.1725 in the HRESIMS appropriate for the molecular formula of C25H28O8, that differs from that of 1 simply by the loss of an oxygen atom. Although the ⁇ and NMR spectra of 2 were similar to those of 1, the UV spectrum was markedly different. In dhilirolide A (1), a Amax typical of a trisubstituted ⁇ , ⁇ -unsaturated lactone was observed at 235 nm, while, in 2, the Ama was shifted to 280 nm.
  • Dhilirolide C (3) was isolated as an optically active amorphous solid that gave an [M + Na] + ion at m/z 479.1746 in the HRESIMS consistent with the molecular formula C25H28O8, identical to the molecular formula of dhilirolide B (2).
  • the UV spectrum observed for 3 (Amax 239 nm) was similar to that of dhilirolide A (1) (Amax 235 nm) indicating that it did not have the dienone moiety found in 2.
  • Dhilirolide D (4) was isolated as an optically active amorphous solid that gave an [M - H]- ion at m/z 441.1967 in the HRESIMS appropriate for a molecular formula of C 2 5H 3 o0 7 .
  • the molecular formula of 4 differed from the molecular formula of 1 by the addition of two hydrogen atoms and the loss of two oxygen atoms, and it required only 11 sites of unsaturation.
  • Examination of the ⁇ and ⁇ C NMR spectra recorded for dhilirolide D (4) revealed a close relationship to dhilirolides A-C (1-3), but also several significant structural and functional group differences.
  • the UV (Ama 276 nm) and ! H/ ! sC/COSY/HSQC/HMBCNMR data (not shown) obtained for 4 identified the C-i to C-5 dienone substructure present in 2 and the ⁇ 2122 exocyclic alkene present in 3.
  • Dhilirolide E (5) Isolated as a amorphous white powder; [ ⁇ ] 2 3 ⁇ 4 +3.23 (c 0.09, MeOH); UV (MeCN) ( ⁇ ) 2 ⁇ 6 (3103), 248 (2348) nm; ⁇ NMR, see Table 1; «C NMR, see Table 3; positive ion HRESIMS [M+H] + m/z 443.1956 (calcd for C2 5 H 3 i0 7 , 443.2070).
  • Dhilirolide F (6) Isolated as a amorphous white solid; [0J20D +18.1 (c 0.03, MeOH); UV (MeCN) Amax ( ⁇ ) 204 (7859), 240 (4037) nm; ⁇ NMR, see Table 1; 13C NMR, see Table 3; positive ion HRESIMS [M+Na]+ m/z 479.2233 (calcd for C 2 6H 3 20 7 Na, 479.2046).
  • Dhilirolide G (7) Isolated as a amorphous white solid; [a] 20 D +8.9 (c 0.05, MeOH); UV (MeCN) Amax ( ⁇ ) 204 (5575), 269 (4786) nm; ⁇ NMR, see Table 1; 13C NMR, see Table 3; positive ion HRESIMS [M+Na]+ m/z 495.1982 (calcd for C 2 6H 32 0 8 Na, 495-1995).
  • Dhilirolide H (8) Isolated as a amorphous white solid; [0J20 D +2.92 (c 0.10, MeOH); UV (MeCN) Amax ( ⁇ ) 201 (1847), 240 (941) nm; ⁇ NMR, see Table 1; «C NMR, see Table 3; negative ion HRESIMS [M-H]- m/z 471.2014 (calcd for C26H31O8, 471.2019).
  • Dhilirolide I (9): Isolated as a amorphous white solid; [a] 2 °D +2.89 (c 0.09, MeOH); UV (MeCN) Amax ( ⁇ ) 203 (2700), 272 (2067) nm; ⁇ NMR, see Table 1; 3 ⁇ 4C NMR, see Table 3; positive ion HRESIMS [M+Na]+ m/z 453.1920 (calcd for C 2 4H 3 oO 7 Na, 453.1889).
  • Dhilirolide J (10): Isolated as a clear crystalline solid; mp decomposed at 223-225X5 [a] 20 D +5-94 (c 0.16, MeOH); UV (MeCN) Amax ( ⁇ ) 2 ⁇ 6 (4349), 279 (5346) nm; ⁇ NMR, see Table 2; «c NMR, see Table 3; positive ion HRESIMS [M+H]+ m/z 441.1918 (calcd for C 2 5H 2 9O7, 441.1913).
  • Dhilirolide K (11) Isolated as a amorphous white solid; [a] 20 D -2.26 (c 0.09, MeOH); UV (MeCN) Amax ( ⁇ ) 2 ⁇ 6 (883), 249 (978) nm; ⁇ NMR, see Table 2; «c NMR, see Table 3; positive ion HRESIMS [M+Na]+ m/z 479.1829 (calcd for C 25 H 2 8O8N , 479.1682).
  • Dhilirolide M (13) Isolated as a amorphous white solid; [ ⁇ ] 2 3 ⁇ 4 +59 (c 0.02, MeOH); UV (MeCN) Amax ( ⁇ ) 197 (4526), 273 (132) nm; ⁇ NMR, see Table 2; «C NMR, see Table 3; positive ion HRESIMS [M+Na]+ m/z 463.1740 (calcd for C2 5 H 2 8O 7 Na, 463.1733).
  • Dhilirolide N (14) Isolated as a amorphous white solid; [a] 2 °D -1.4 (c 0.05, MeOH); UV (MeCN) Xmax ( ⁇ ) 215 (2285) nm; ⁇ NMR, see Table 2; «C NMR, see Table 3; positive ion HRESIMS [M+Na]+ m/z 477.1570 (calcd for C 25 H 2 6O8Na, 477.1525).
  • the product 15 was isolated from the reaction of dhilirolide A (1) and NaN 3 with an HPLC retention time of 22 minutes. 15 was obtained as an amorphous white solid that gave an [M + H] + ion in the HRESIMS at m/z 431.1712 appropriate for a molecular formula of C2 3 H2 6 O 8 that requires 11 sites of unsaturation instead of the 12 found in 1. This molecular formula differs from that of 1 by the loss of two carbons, two protons, and one oxygen. A detailed analysis of the !
  • the H-13 resonance had showed gHMBC correlations to C-ll ( ⁇ 50.2) and the C-19 methyl ( ⁇ 18.4), but correlated to no carbon atoms in HSQC.
  • gCOSY6o couplings were observed between the H-13 methine proton and the olefinic H- 2 resonance ( ⁇ 6.oi) and a pair of germinal H-i2ax/H-i2eq methylene protons ( ⁇ .97/ 1.87).
  • tROESY correlations were used to facilitate the assignment of the relative configuration of 15 as illustrated in Scheme 4.
  • tROESY correlations between the H-13 methine resonance ( ⁇ 3.13) and the H-6a methylene ( ⁇ 2.96), H-i2ex methylene ( ⁇ .97), and OH-9 tertiary alcohol ( ⁇ 7.46) resonances confirmed the configuration of the key changes in this modified dhilirolide.
  • Additional tROESY correlations between the OH-9 and H-6a and H-23 oxygenated methine proton ( ⁇ 4.6i) further confirmed the structure of 15.
  • the absolute configuration configuration for 15 was assigned as 4S, 5R, 7S, 8R, 9R, 11R, 13R, 21R, and 23S.
  • Reaction product (16) from reaction with dhilirolide A (1) with perchloric acid Isolated as an amorphous yellow solid; ⁇ NMR, see Table 5; NMR, see Table 5; positive ion HRESIMS [M+H] + m/z 455.1078 (calcd for C25H2 7 O8, 455.1706).
  • perchloric acid Isolated as an amorphous white solid; ⁇ NMR, see Table 5;
  • Cabbage leaf discs of 1.5 cm diameter were painted with 10 ⁇ of the methanolic solution of fungal extract or the compounds on each side.
  • Control leaf discs were painted with the carrier solvent alone.
  • One treated and one control disc (after being dried) were placed 0.7 cm apart in each compartment [4.2/3.0 cm (length/ width)] of a plastic assay tray.
  • FDI feeding deterrence index
  • the crude fungal extract as well as the major constituents dhilirolides A (1), D (4), and L (14) were evaluated for bioactivity against the cabbage looper Trichoplusia ni (Lepidoptera: Noctuidae), an economically important agricultural pest.
  • the crude extract was a modest feeding inhibitor to third instar T. ni larvae, but an LH 2 0 fraction enriched in dhilirolides A-N (1-14), dhilirolide D (4), and dhilirolide L (12) was considerably more active in a two-choice feeding bioassay.
  • the DC 50 (concentration reducing feeding by 50%) for the LH 2 o fraction was 25 ⁇ g/cm 2 , comparable to a number of natural and synthetic anti-feedants previously tested against this pest.
  • 4- 2 7 Dhilirolide L (12) showed the highest activity of the pure compounds, giving a DC50 of 5.9 g/cm 2 .
  • Dhilirolide A (l) was isolated in sufficient quantities to acquire a 2D-INADEQUATE spectrum, which allowed the unambiguous assignment of intact acetate units as summarized in FIGURE 3.
  • a proposed biogenetic pathway to the dhilirolides that accounts for the [i,2- 1 3C 2 ] acetate incorporation data is shown in FIGURE 3. The pathway provides additional support for the earlier labeling work of the Simpson and Vederas groups.19,20,23

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Abstract

L'invention concerne en partie des composés dhilirolide pour la lutte contre les insectes, pour des insectes tels que la fausse-arpenteuse du chou, et des procédés associés. Les composés comprennent des composés de formule I
PCT/CA2015/000198 2015-03-30 2015-03-30 Composés méroterpénoïdes, procédés et compositions pour leur utilisation dans la lutte contre les insectes WO2016154705A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111892611A (zh) * 2018-12-04 2020-11-06 海南师范大学 一种混源萜类晶体化合物及其在防治农业病虫害中的应用

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CENTKO R.M. ET AL.: "Dhilirolides E-N, Meroterpenoids Produced in Culture by the Fungus Penicillium purpurogenum Collected in Sri Lanka: Structure Elucidation, Stable Isotope Feeding Studies, and Insecticidal Activity", J. ORG. CHEM., vol. 79, no. 8, 2014, pages 3327 - 3335, XP055316702 *
DE SILVA E.D. ET AL.: "Dhilirolides A-D, Meroterpenoids Produced in Culture by the Fruit-Infecting Fungus Penicillium purpurogenum Collected in Sri Lanka", J. ORG. LETT., vol. 13, no. 5, 2011, pages 1174 - 1177, XP055316721 *
GERIS R. ET AL.: "Meroterpenoids Produced by Fungi", J. NAT. REP., vol. 26, no. 8, 2009, pages 1063 - 1094, XP055316723 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111892611A (zh) * 2018-12-04 2020-11-06 海南师范大学 一种混源萜类晶体化合物及其在防治农业病虫害中的应用
CN111892611B (zh) * 2018-12-04 2022-12-20 海南师范大学 一种混源萜类晶体化合物及其在防治农业病虫害中的应用

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