CN110612981B - Application of quassin compounds in killing ants - Google Patents
Application of quassin compounds in killing ants Download PDFInfo
- Publication number
- CN110612981B CN110612981B CN201910991380.2A CN201910991380A CN110612981B CN 110612981 B CN110612981 B CN 110612981B CN 201910991380 A CN201910991380 A CN 201910991380A CN 110612981 B CN110612981 B CN 110612981B
- Authority
- CN
- China
- Prior art keywords
- compound
- bait
- killing
- ant
- corn flour
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- A01N43/06—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 five-membered rings
- A01N43/08—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 five-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
- A01N43/02—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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses an application of quassin compounds in killing ants, belonging to the field of ant killing medicaments. The picrasma quassioides picrin compound discovered by the invention can be applied to killing solenopsis invicta, and after the picrasma quassioides picrasp compound is prepared into an ant killing bait, the picrasma quassioides picrasp bait has good stomach toxicity activity to invasive pests solenopsis invicta, can effectively kill solenopsis invicta, is more convenient to use, and is not easily influenced by the interference of the external environment. The quassinoid compound discovered by the invention is obtained by separating and purifying natural plants, and has low toxicity, no residue and no pollution to various grain, melon, fruit, vegetable and other economic crops. Therefore, the compound has good application prospect in killing the red imported fire ant pests.
Description
Technical Field
The invention belongs to the field of termite killing medicaments, particularly relates to application of a quassin picrin compound in termite killing, and particularly provides a botanical quassin picrin compound termite killing bait and a preparation method thereof.
Background
The Solenopsis invicta (Solenopsis invicta) is an invasive pest which causes serious harm to human and animal health, agriculture and forestry production, public facilities and ecological environment, and is listed as one of the 100 most destructive pests in the world, so that the eradication of the Solenopsis invicta is a difficult and must-be-solved technical problem for human beings. The chemical prevention and control is the main method for preventing and controlling the red fire ants at present, the killing speed is high, the remarkable effect is achieved in the prevention and control of the red fire ants, but the long-term use of a large amount of chemical pesticides can cause damage to non-target organisms and cause pollution to the agriculture, urban and rural soil and water sources to different degrees. With the increasing awareness of the environmental safety of human beings, there is an urgent need for a method for controlling solenopsis invicta with low toxicity, long-lasting effect and strong selectivity. The botanical pesticide is a natural product with wide source and easy obtaining, has the characteristics of quick biodegradation, difficult generation of resistance of pests, low toxicity to environment and non-target organisms and the like, and is now the key point for developing efficient and low-toxicity medicaments for the solenopsis invicta.
The quassinoid is highly oxidized nortriterpenoid with polycyclic lactone skeleton structure, and is a characteristic component of quassiaceae plants. The compound has good anti-tumor, anti-malaria, anti-virus, anti-inflammatory and insect antifeedant effects, wherein the insect antifeedant effect is the important activity of the components, and the compound has wide prospects in the application of developing plant-derived pesticides. However, no relevant research report on the killing of solenopsis invicta by picrasma quassioides picrin compounds exists at present. Therefore, the picrasma quassioides bitter principle ant killing bait agent of plant source is a novel important research direction for killing solenopsis invicta.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the application of the quassinoid compound in killing ants. The quassin can kill Formica rufa.
The purpose of the invention is realized by the following technical scheme:
use of quassinoid compounds, or epimers, tautomers, diastereomers or mixtures thereof, or pharmaceutically acceptable salts thereof, for killing ants.
Use of quassinoid compounds, or epimers, tautomers, diastereomers or pharmaceutically acceptable salts thereof, for the preparation of an ant killing bait.
Further, the ant is a red imported fire ant.
The quassinoid compound is selected from C19Picrasma quassioides bitter principle compounds and C20At least one of quassin compounds;
said C19The quassin compounds have a structure of C19Basic skeleton structure of type C20The quassin compounds have a structure of C20The basic skeleton structure is as follows:
in the structure, at least one of C-1, C-2, C-6, C-7, C-11, C-12, C-13, C-14, C-15 and C-30 alleles is connected with an oxygen-containing group, such as a hydroxyl group, a carbonyl group, an ester group, an ether group and the like; at least one of C-2-C-3, C-3-C-4, C-4-C-29, C-4-C-5, C-5-C-6, C-12-C-13, C-13-C-18, and C-14-C-15, etc. contains a double bond, and further at least one of C-3-C-4, C-4-C-29, C-4-C-5, C-5-C-6, and C-13-C-18, etc. contains a double bond.
Further, C19In the basic skeleton structure, at least 6 of C-1, C-2, C-6, C-7, C-11, C-12 and C-15 alleles are connected with oxygen-containing groups, such as hydroxyl, carbonyl, ester, ether and the like; at least one of C-3-C-4, C-4-C-29, C-4-C-5, and C-5-C-6, etc. contains a double bond.
Further, C20In the basic skeleton structure of type C-1, C-2, C-7, C-11, C-12, C-13. At least 5 of the C-14, C-15 and C-30 alleles have oxygen-containing groups, such as hydroxyl, carbonyl, ester, ether, etc.; at least one of C-3-C-4, C-4-C-5 and C-13-C-18, etc. contains a double bond.
In a preferred embodiment of the invention, the quassinoid compounds include, but are not limited to:
the invention relates to a pharmaceutical composition, which comprises:
(1) an effective amount of the quassinoid compounds described above, or epimers, tautomers, diastereomers, or pharmaceutically acceptable salts thereof, or combinations thereof; and
(2) the ant killing bait agent can be accepted as filling bait.
Further, the ant is a red imported fire ant.
Further, the filling bait comprises at least one of corn flour, butter and yellow sugar.
The application of the pharmaceutical composition in preparing the ant killing bait is provided.
Further, the ant is a red imported fire ant.
An ant killing bait comprises the following components in percentage by weight: 0.1-10% of original medicine, 55-69.9% of corn flour, 15-25% of brown sugar and 10-20% of butter.
Further, the ant killing bait comprises the following components in percentage by weight: 0.1-10% of raw medicine, 60-69.9% of corn flour, 15-25% of brown sugar and 10-20% of butter.
Furthermore, the ant killing bait comprises the following components in percentage by weight: 0.1-10% of raw medicine, 60-69.9% of corn flour, 20% of yellow sugar and 10% of butter.
Still further, the ant killing bait comprises the following components in percentage by weight: 1-10% of original medicine, 60-69% of corn flour, 20% of yellow sugar and 10% of butter.
The technical material is a picrasma quassioides picroside compound, or an epimer, a tautomer, a diastereoisomer, a pharmaceutically acceptable salt or a combination thereof.
The preparation method of the bait for killing the ants comprises the following steps:
1) preparing filling bait: sieving corn flour with a 50-80 mesh (preferably 60 mesh) sieve according to a proportion, adding water into the corn flour, the brown sugar and the butter to prepare dough, extruding the dough, sieving the extruded dough with a 20-40 mesh (preferably 20 mesh) sieve to form particles, and drying;
2) dissolving raw materials in a solvent according to a certain proportion to prepare the ant killing medicament; and (2) infiltrating the ant killing agent into the filling bait prepared in the step 1) by using a soaking or spraying method, then drying, and crushing and screening by using a 20-50-mesh (preferably 40-mesh) screen to obtain the ant killing bait.
Preferably, the solvent in step 2) is acetone.
Preferably, the drying temperature in the step 1) and the step 2) is 30-50 ℃; further 40 ℃;
compared with the prior art, the invention has the following advantages and effects:
the picrasma quassioides picrorhizin compound can be applied to killing solenopsis invicta, and after the picrasma quassioides picrorhiza kussizin compound is prepared into an ant killing bait, the bait has good stomach toxicity activity on invasive pests solenopsis invicta, and can effectively kill the solenopsis invicta. The quassinoid compound discovered by the invention is obtained by separating and purifying natural plants, and has low toxicity, no residue and no pollution to various grain, melon, fruit, vegetable and other economic crops. Therefore, the compound has good application prospect in killing the red imported fire ant pests.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
Extraction separation and structural identification of quassinoid compounds in Eurycoma longifolia Robusta of Simaroubaceae
10kg of Eurycoma longifolia Roxb root is crushed into coarse powder, the coarse powder is extracted by cold soaking with 95% ethanol, the extracting solutions are combined and concentrated under reduced pressure to obtain 270g of total extract. Suspending the total extract with water, sequentially extracting with petroleum ether, ethyl acetate and n-butanol, and recovering solvent under reduced pressure to obtain petroleum ether fraction (40g), ethyl acetate fraction (99g), n-butanol fraction (85g) and water fraction (26 g).
Subjecting petroleum ether fraction to silica gel column chromatography, gradient eluting with chloroform-methanol system (100:0-0:100, v/v), and mixing by TLC analysis to obtain 7 main fractions (Fr.a-Fr.g).
Performing ODS column chromatography on Fr.c, performing methanol-water gradient elution (20:80-100:0, v/v), and performing TLC analysis to obtain Fr.c1-Fr.c 4. Wherein, Fr.c3 and Fr.c4 were separated and purified by repeated ODS column chromatography, Sephadex LH-20 and high performance liquid chromatography, respectively, to give compound 16(10.0mg), compound 13 (520.0mg), compound 14(2.0mg), compound 9(400.0mg), compound 10(15.5mg), compound 11(106.5mg) and compound 12(40.6 mg).
Performing ODS column chromatography on Fr.e, performing methanol-water gradient elution (20:80-100:0, v/v), and performing TLC analysis to obtain Fr.e1-Fr.e5. Wherein, compound 15(1.5g), compound 19(52.0mg), compound 18(210.5mg), compound 17(100.0mg), compound 22(85.6mg), compound 23(32.5mg), compound 20(10.0mg), compound 21(105.4mg), compound 2(25.0 mg), compound 3(42.8mg), compound 6(103.5mg), compound 7(15.3mg), compound 1(120.7 mg), compound 4(7.2mg), compound 5(200.0mg) and compound 8(5.8mg) were obtained by separation and purification by repeated ODS column chromatography, Sephadex LH-20 and high performance liquid chromatography, respectively.
The structure of each compound is identified by a wave spectrum method, and each physical and chemical data and spectrum data are as follows: compound 1
Colorless needle crystals (methanol), mp 195-196 ℃,
1.6 ° (c 0.65, methanol); UV (acetonitrile) lambdamax(logε)：235(3.99)nm；IR(KBr)vmax：3442,1774,1660,1458,1333,1261, 1178,1114,1053,964,932,875,750,600cm-1；HR-ESI-MS：m/z 373.1621[M+Na]+ (calcd for C19H26O6Na,373.1622)；1H NMR(300MHz,C5D5N)δ5.91(s,1H),4.16 (m,1H),5.76(q,J＝5.0Hz,1H),4.48(dd,J＝5.0,1.3Hz,1H),3.54(d,J＝8.6Hz, 1H),3.36(brs,1H),3.30(q,J＝7.0Hz,1H),2.53(dt,J＝12.4,4.5Hz,1H),2.45(m, 1H),2.12(dt,J＝12.4,4.5Hz,1H),1.91(s,3H),1.67(s,3H),1.22(q,J＝12.4Hz, 1H),1.04(d,J＝6.9Hz,3H),0.93(d,J＝6.4Hz,3H)；13C NMR(75MHz,C5D5N)δ 199.9,177.7,171.4,120.9,85.6,85.2,70.8,69.7,53.4,48.8,48.2,46.9,41.1,32.6, 32.1,23.1,18.6,17.8,17.2。
Compound 2
Colorless needle crystals (methanol), mp 198-,
+30.3 ° (c 0.29, methanol); UV (acetonitrile) lambdamax(logε)：203(3.98)nm；IR(KBr)vmax：3516,3416,1780,1746,1707,1655, 1462,1385,1333,1250,1173,1089,1053,962,932,883cm-1；HR-ESI-MS：m/z 373.1621[M+Na]+(calcd for C19H26O6Na,373.1622)；1H NMR(400MHz,C5D5N)δ 5.33(m,1H),4.94(brs,1H),4.52(m,1H),4.32(brs,1H),4.11(m,1H),3.72(m,1H), 3.28(brs,1H),3.17(m,1H),3.14(m,1H),2.83(dd,J＝12.5,5.7Hz,1H),2.43(dd, J＝15.4,3.7Hz,1H),2.34(t,J＝12.5Hz,1H),2.27(m 1H),2.06(d,J＝3.4Hz,1H), 1.71(s,3H),1.52(s,3H),1.05(d,J＝6.9Hz,3H)；13C NMR(100MHz,C5D5N) δ208.2,177.2,145.5,109.1,84.4,82.8,73.0,70.5,54.0,52.2,51.3,51.1,44.1,44.0, 37.8,33.2,24.0,17.2,13.1。
Compound 3
Colorless needle crystals (methanol), mp 270-,
+62.1 ° (c 0.38, methanol); UV (acetonitrile) lambdamax(logε)：194(4.51)nm；IR(KBr)vmax：3482,1746,1710,1464,1389,1325, 1281,1174,1098,1044,1015,957,875,836,753,601cm-1；HR-ESI-MS：m/z 373.1619[M+Na]+(calcd for C19H26O6Na,373.1622)；1H NMR(300MHz,C5D5N)δ 5.76(brs,1H),5.57(q,J＝5.0Hz,1H),4.67(brs,1H),4.51(d,J＝4.0Hz,1H),4.06 (d,J＝4.3Hz,1H),3.30(brs,1H),3.17(q,J＝6.9Hz,1H),2.93(t,J＝15.4Hz,1H), 2.62(dd,J＝15.4,3.9Hz,1H),2.50(d,J＝15.4Hz,1H),2.12(d,J＝3.3Hz,1H), 1.75(s,3H),1.68(s,3H),1.55(s,3H),1.04(d,J＝6.9Hz,3H)；13C NMR(75MHz, C5D5N)δ208.0,177.4,134.2,127.4,84.7,82.9,74.7,70.7,54.4,52.4,50.4,49.8, 44.7,37.5,33.3,24.6,20.9,17.3,12.1。
Compound 4
Colorless needle crystals (methanol), mp 187-,
-269.8 ° (c 0.47, methanol); UV (acetonitrile) lambdamax(logε)：241(3.67)nm；IR(KBr)vmax：3544,1769,1714,1673,1619,1465, 1396,1346,1323,1160,1120,1081,1014,968cm-1；HR-ESI-MS：m/z 389.1576 [M+Na]+(calcd for C19H26O7Na,389.1571)；1H NMR(400MHz,C5D5N)δ5.29(m, 1H),4.79(s,1H),4.64(d,J＝4.6Hz,1H),4.18(td,J＝9.7,6.0Hz,1H),3.88(d,J＝ 9.7Hz,1H),3.22(q,J＝7.0Hz,1H),3.04(s,1H),2.54(dd,J＝18.1,6.0Hz,1H), 2.31(m,1H),2.26(d,J＝3.5Hz,1H),1.68(s,3H),1.67(s,3H),1.64(s,3H),1.07(d, J＝7.0Hz,3H)；13C NMR(100MHz,C5D5N)δ206.6,178.3,140.0,134.3,85.5, 82.3,80.7,70.1,67.2,56.6,49.4,48.3,45.6,41.2,33.2,20.9,20.9,20.7,17.3。
Compound 5
Colorless needle crystals (methanol), mp 215-,
-4.0 ° (c 0.58, methanol); UV (acetonitrile) lambdamax(logε)：282(4.03)nm；IR(KBr)vmax：3481,1766,1711,1655,1581,1458, 1384,1327,1262,1174,1054,958,932,882,715,621cm-1；HR-ESI-MS：m/z 371.1460[M+Na]+(calcd for C19H24O6Na,371.1465)；1H NMR(400MHz,C5D5N)δ 6.24(brs,1H),6.11(s,1H),6.02(m,1H),4.73(brs,1H),4.54(m,1H),3.97(d,J＝ 7.3Hz,1H),3.44(d,J＝1.2Hz,1H),3.35(q,J＝6.9Hz,1H),2.63(d,J＝3.2Hz, 1H),1.92(s,3H),1.82(s,3H),1.80(s,3H),1.08(d,J＝6.9Hz,3H)；13C NMR(100 MHz,C5D5N)δ200.0,177.8,163.6,138.1,131.5,121.7,85.4,83.6,72.1,70.1,53.9, 48.3,47.3,46.1,32.8,24.1,20.3,17.3,16.8。
Compound 6
Colorless needle crystals (methanol), mp 251-,
+38.9 ° (c 0.29, methanol); UV (acetonitrile) lambdamax(logε)：240(3.97)nm；IR(KBr)vmax：3459,2952,1734,1667,1436,1381, 1261,1122,961,818,631cm-1；HR-ESI-MS：m/z 371.1461[M+Na]+(calcd for C19H24O6Na,371.1465)；1H NMR(400MHz,CDCl3)δ6.09(s,1H),4.77(m,1H), 4.35(d,J＝4.7Hz,1H),4.03(s,1H),2.92(brs,1H),2.91(m,1H),2.87(m,1H), 2.78(overlapped,2H),1.93(s,3H),1.86(d,J＝3.6Hz,1H),1.54(s,3H),1.23(s, 3H),1.14(d,J＝7.0Hz,3H)；13C NMR(100MHz,CDCl3)δ205.6,197.5,176.3, 162.3,124.5,83.2,81.3,69.9,53.0,51.2,49.4,49.1,47.0,36.3,32.4,23.7,22.0,16.7, 12.2。
Compound 7
Colorless needle crystals (methanol), mp 272-,
56.3 ° (c 0.19, methanol); UV (acetonitrile) lambdamax(logε)：243(2.76)nm；IR(KBr)vmax：3483,2974,2885,1747,1710,1463, 1324,1247,1174,1098,1045,958,836,711,601cm-1；HR-ESI-MS：m/z 387.1414 [M+Na]+(calcd for C19H24O7Na,387.1414)；1H NMR(400MHz,CDCl3)δ6.14(dd, J＝2.6,1.3Hz,1H),4.80(m,1H),4.58(d,J＝11.3Hz,1H),4.36(m,1H),3.98(s, 1H),2.92(m,1H),2.92(m,1H),2.69(m,1H),2.27(s,3H),1.83(d,J＝3.6Hz), 1.62(s,3H),1.30(s,3H),1.17(d,J＝7.0Hz,3H)；13C NMR(100MHz,CDCl3)δ 207.5,197.2,175.5,165.1,125.6,83.0,81.2,70.1,69.7,57.1,48.7,47.8,53.5,49.7, 32.0,25.0,23.3,16.6,13.8。
Compound 8
A white amorphous powder of a crystalline substance,
-4.3 ° (c 0.45, methanol); (ii) a UV (acetonitrile) lambdamax(logε)：288 (3.99)nm；IR(KBr)vmax：3422,1772,1653,1581,1456,1384,1328,1291,1264, 1212,1173,957,933cm-1；HR-ESI-MS：m/z 369.1305[M+Na]+(calcd for C19H22O6Na,369.1309)；1H NMR(400MHz,CDCl3)δ6.29(s,1H),6.24(s,1H), 4.89(m,1H),4.39(m,1H),4.19(s,1H),3.00(brs,1H),2.94(q,J＝7.0Hz,1H), 2.33(d,J＝3.7Hz,1H),2.16(s,3H),1.53(s,3H),1.45(s,3H),1.19(d,J＝7.0Hz, 3H)；13C NMR(100MHz,C5D5N)δ199.7,198.8,177.5,159.0,150.8,129.2,127.0, 84.9,76.6,67.1,53.7,47.7,45.6,38.7,32.9,22.9,20.7,20.4,17.3。
Compound 9
A colorless oily substance,
+72.8 ° (c 0.29, methanol); UV (acetonitrile) lambdamax(logε)：196(3.76) nm；IR(KBr)vmax：3406,1764,1655,1451,1393,1245,1120,1167,1057,991,971, 900,738cm-1；HR-ESI-MS：m/z 391.1726[M+Na]+(calcd for C19H28O7Na, 391.1727)；1H NMR(300MHz,C5D5N)δ6.00(brs,1H),5.81(brs,1H),5.44(brs, 1H),5.31(brs,1H),4.65(dd,J＝11.3,3.5Hz,1H),4.51(d,J＝3.5Hz,1H),4.19(m, 1H),3.86(d,J＝8.1Hz,1H),2.86(dd,J＝12.0,5.8Hz,1H),2.80(m,1H),2.73(d,J ＝11.3Hz,1H),2.62(s,1H),2.47(d,J＝5.5Hz,1H),2.22(t,J＝12.0Hz,1H),1.91 (s,3H),1.75(d,J＝7.4Hz,3H),1.60(s,3H)；13C NMR(75MHz,C5D5N)δ177.9, 142.8,111.0,88.1,83.7,76.3,74.3,73.6,65.0,57.1,53.4,45.6,45.4,44.4,43.8,28.3, 22.1,15.7,14.5。
Compound 10
Colorless needle crystals (methanol), mp 255-,
+22.7 ° (c 0.39, methanol); UV (acetonitrile) lambdamax(logε)：241(4.58)nm；IR(KBr)vmax：3488,1766,1734,1642,1453,1378, 1334,1230,1171,1117,1058,894,858,824,670cm-1；HR-ESI-MS m/z 373.1620 [M+Na]+(calcd for C19H26O6Na,373.1622)；1H NMR(400MHz,C5D5N)δ6.11(s, 1H),5.66(brs,1H),4.14(brs,1H),4.05(brs,1H),4.18(s,1H),2.78(m,1H),2.75 (m,1H),2.63(brs,1H),2.39(d,J＝5.6Hz,1H),2.31(dt,J＝15.1,3.0Hz,1H),1.90 (m,1H),1.77(s,3H),1.76(s,3H),1.75(d,J＝7.2Hz,3H),1.34(s,3H)；13C NMR (100MHz,C5D5N)δ200.2,177.5,164.2,125.3,83.4,83.3,76.2,74.0,56.5,48.4, 44.6,43.3,43.3,28.4,24.1,22.2,21.9,15.7,11.8。
Compound 11
Colorless needle crystals (methanol), mp 287-288 ℃,
+98.8 ° (c 0.43, methanol); UV (acetonitrile) lambdamax(logε)：245(3.96)nm；IR(KBr)vmax：3525,3473,2916,1755,1657,1453, 1381,1338,1260,1177,1119,1044,982,827,730,585cm-1；HR-ESI-MS m/z 389.1571[M+Na]+(calcd for C19H28O7Na,389.1571)；1H NMR(400MHz,CD3OD) δ6.08(brs,1H),4.98(m,1H),4.24(dd,J＝11.5,3.9Hz,1H),4.14(d,J＝3.9Hz, 1H),4.02(s,1H),3.63(t,J＝3.1Hz,1H),2.78(d,J＝11.4Hz,1H),2.37(overlapped, 2H),2.30(s,3H),2.07(d,J＝1.4Hz,1H),1.60(s,3H),1.41(d,J＝6.9Hz,3H), 1.12(s,3H)；13C NMR(100MHz,CD3OD)δ201.0,178.7,167.5,127.3,88.0,83.5, 76.1,73.6,65.9,57.0,50.7,51.5,44.0,42.8,28.1,25.3,21.2,14.8,12.6。
Compound 12
Colorless needle crystals (methanol), mp 186-,
+61.5 ° (c 0.45, methanol); UV (acetonitrile) lambdamax(logε)：241(3.78)nm；IR(KBr)vmax：3545,2956,2856,1766,1737,1641, 1454,1376,1335,1230,1172,1115,1072,1021,972,891,760,667,580cm-1； HR-ESI-MS m/z 431.1679[M+Na]+(calcd for C21H28O8Na,431.1676)；1H NMR (300MHz,C5D5N)δ6.21(s,1H),5.80(m,1H),5.75(dd,J＝12.1,3.9Hz,1H),4.55 (d,J＝3.8Hz,1H),4.26(s,1H),4.15(m,1H),3.23(d,J＝12.0Hz,1H),2.80(brs, 1H)2.78(m,1H),2.49(d,J＝5.5Hz,1H),2.15(s,3H),1.98(s,3H),1.88(s,3H), 1.76(d,J＝7.4Hz,3H),1.50(s,3H)；13C NMR(75MHz,C5D5N)δ199.8,176.7, 170.7,162.5,127.9,83.5,82.8,76.1,73.6,68.9,56.4,50.6,47.5,43.9,42.1,28.0, 23.8,21.7,21.5,15.6,12.9。
Compound 13
Colorless needle crystals (methanol), mp 213-,
+88.5 ° (c 0.63, methanol); UV (acetonitrile) lambdamax(logε)：205(3.85)nm；IR(KBr)vmax：3428,1721,1656,1385,1258,1122, 1071,996,967,875,822,759,687,570cm-1；HR-ESI-MS m/z 421.1829[M+Na]+ (calcd for C20H30O8Na,421.1833)；1H NMR(300MHz,C5D5N)δ5.78(s,1H),5.65 (brs,1H),4.93(brs,1H),4.40(brs,1H),4.17(td,J＝9.7,6.0Hz,1H),3.98(d,J＝ 9.7Hz,1H),3.13(dq,J＝7.3,2.9Hz,1H),2.99(dd,J＝14.9,3.3Hz,1H),2.76(d,J ＝14.8Hz,1H),2.56(brs,1H),2.44(m,1H),2.35(m,1H),2.15(s,3H),2.02(s,3H), 1.80(s,3H),1.80(d,J＝7.3Hz,3H)；13C NMR(75MHz,C5D5N)δ176.5,132.4, 125.1,83.3,83.2,78.3,78.0,74.8,71.3,68.0,47.5,47.2,44.9,41.5,37.2,28.9,20.2, 20.0,18.5,14.7。
Compound 14
Colorless needle crystals (methanol), mp 223-,
+6.3 ° (c 1.73, methanol); UV (acetonitrile) lambdamax(logε)：242(4.05)nm；IR(KBr)vmax：3459,2952,1734,1667,1436,1381, 1261,1123,961,818,631cm-1；HR-ESI-MS m/z 403.1734[M+Na]+(calcd for C20H28O7Na,403.1727)；1H NMR(300MHz,DMSO-d6)δ6.02(dd,J＝2.9,1.4Hz, 1H),4.84(m,1H),4.76(t,J＝6.2Hz,1H),4.24(s,1H),3.87(d,J＝2.4Hz,1H), 3.35(m,1H),2.86(d,J＝12.1Hz,1H),2.34(ddd,J＝7.4,5.0,2.4Hz,1H),2.11(td, J＝14.5,12.4,2.0Hz,1H),2.01(m,1H),1.94(s,3H),1.80(d,J＝2.4Hz,1H),1.51 (t,J＝5.7Hz,1H),1.42(s,3H),1.07(s,3H),1.04(d,J＝7.3Hz,3H)；13C NMR(75 MHz,DMSO-d6)δ199.1,172.7,165.1,124.0,84.0,81.9,75.3,72.2,65.3,55.0,47.9, 42.5,40.3,37.3,26.3,25.1,24.5,22.1,16.4,11.7。
Compound 15
Colorless columnar crystals (methanol), mp 267-268 ℃,
+54.3 ° (c 0.51, methanol); UV (acetonitrile) lambdamax(logε)：241(4.05)nm；IR(KBr)vmax：3425,2945,1726,1660,1435,1381, 1344,1262,1122,1064,998,964,902,818,773,698,565,525cm-1；HR-ESI-MS m/z 419.1674[M+Na]+(calcd for C20H28O8Na,419.1676)；1H NMR(400MHz, CDCl3)δ6.09(s,1H),5.36(s,1H),4.90(t,J＝2.8Hz,1H),4.63(t,J＝3.0Hz,1H), 4.03(s,1H),3.90(t,J＝2.6Hz,1H),2.88(d,J＝13.7Hz,1H),2.43(qd,J＝7.3,3.2 Hz,1H),2.29(dt,J＝14.4,2.9Hz,1H),2.11(overlapped,1H),2.10(m,1H),1.97(s, 3H),1.52(s,3H),1.23(d,J＝7.3Hz,3H),1.18(s,3H)；13C NMR(100MHz,CDCl3) δ198.2,175.9,164.5,124.4,82.7,81.5,77.0,75.9,73.7,71.2,48.2,45.0,43.6,43.1, 35.9,26.1,22.8,17.4,12.5,12.4。
Compound 16
Colorless needle crystals (methanol), mp 252-,
-17.3 ° (c 0.25, methanol); UV (acetonitrile) lambdamax(logε)：241(3.96)nm；IR(KBr)vmax：3491,2925,1733,1671,1370,1270, 1132,1033cm-1；HR-ESI-MS m/z 385.1629[M+Na]+(calcd for C20H26O6Na, 385.1622)；1H NMR(500MHz,CDCl3)δ6.05(dt,J＝2.9,1.4Hz,1H),4.39(dd,J＝ 3.6Hz,2.2,1H),4.02(s,1H),3.87(d,J＝3.1Hz,1H),3.73(s,1H),3.69(dd,J＝ 19.3,12.7Hz,1H),2.90(d,J＝11.8Hz,1H),2.70(dd,J＝19.4,6.6Hz,1H),2.29 (m,1H),2.20(dt,J＝14.4,3.1Hz,1H),2.00(m,1H),1.80(ddd,J＝12.1,6.5,4.9 Hz,1H),1.96(s,3H),1.21(s,3H),1.13(d,J＝5.9Hz,3H),1.12(s,3H)；13C NMR (125MHz,CDCl3)δ210.2,197.2,170.9,163.2,125.0,84.6,82.2,81.8,46.5,46.0, 45.2,42.7,40.1,35.3,29.1,25.3,22.9,22.6,13.5,9.7。
Compound 17
Colorless block crystals (methanol), mp 302-,
+77.7 ° (c 25, methanol); UV (acetonitrile) lambdamax(logε)：205(3.67)nm；IR(KBr)vmax：3467,1734,1649,1497,1389,1313, 1226,1125,1055,1012,965,818,766cm-1；HR-ESI-MS m/z 435.1627[M+Na]+ (calcd for C20H28O9Na,435.1626)；1H NMR(400MHz,C5D5N)δ5.51(s,1H),5.21 (brs,1H),4.69(d,J＝8.8Hz,1H),4.31(d,J＝8.8Hz,1H),4.24(td,J＝9.9,6.0Hz, 1H),4.16(brs,1H),4.02(d,J＝9.9Hz,1H),3.21(s,1H),3.03(dd,J＝15.2,3.6Hz, 1H),2.84(m,1H),2.64(d,J＝15.2Hz,1H),2.51(dd,J＝17.0,6.0Hz,1H),2.37 (dd,J＝17.0,9.9Hz,1H),1.99(s,3H),1.80(d,J＝7.2Hz,3H),1.76(s,3H)；13C NMR(100MHz,C5D5N)δ174.9,130.0,127.5,111.0,84.1,79.8,76.7,76.7,71.7, 68.2,67.5,53.7,50.9,44.8,42.5,41.8,28.3,20.1,19.0,14.2。
Compound 18
Colorless needle crystals (methanol), mp 288-,
+65.6 ° (c 39, methanol); UV (acetonitrile) lambdamax(logε)：196(3.79)nm；IR(KBr)vmax：3469,1748,1730,1497,1390,1225, 1148,1054,1009,964,815,767,711,639cm-1；HR-ESI-MS m/z 385.1629[M+Na]+ (calcd for C20H26O6Na,385.1622)；1H NMR(300MHz,C5D5N)δ6.11(d,J＝1.5Hz, 1H),5.81(brs,1H),5.65(d,J＝1.5Hz,1H),5.52(s,1H),5.18(t,J＝2.5Hz,1H), 4.81(s,1H),4.64(m,1H),4.56(d,J＝8.5Hz,1H),4.06(d,J＝8.5Hz,1H),4.05(d, J＝7.8Hz,1H),3.55(s,1H),2.82(brd,1H),2.18(dt,J＝14.7,2.7Hz,1H),1.92(m, 1H),1.74(s,3H),1.63(s,3H)；13C NMR(75MHz,C5D5N)δ174.3,148.9,135.3, 127.3,119.7,109.9,84.0,81.4,79.7,76.8,73.0,72.2,68.2,53.0,48.2,42.6,41.9, 25.9,21.6,11.1。
Compound 19
Colorless needle crystals (methanol), mp 260-,
+24.5 ° (c 0.19, methanol); UV (acetonitrile) lambdamax(logε)：200(3.60)nm；IR(KBr)vmax：3508,3304,1727,1629,1390,1308, 1246,1213,1116,1041,993,890,850,816,735,709,661cm-1；HR-ESI-MS：m/z 449.1420[M+Na]+(calcd for C20H26O10Na,449.1418)；1H NMR(400MHz,C5D5N) δ5.81(s,1H),5.70(s,1H),5.11(brs,1H),4.88(d,J＝8.9Hz,1H),4.65(brs,1H), 4.11(d,J＝8.9Hz,1H),4.08(d,J＝8.0Hz,1H),4.05(s,1H),3.81(d,J＝5.2Hz, 1H),3.56(s,1H),3.02(d,J＝5.2Hz,1H),2.84(d,J＝15.5Hz,1H),2.18(dt,J＝ 14.5,2.3Hz,1H),1.93(td,J＝14.2,13.8,2.3Hz,1H),1.76(s,3H),1.64(s,3H)；13C NMR(100MHz,C5D5N)δ174.3,135.4,127.4,110.2,84.0,82.2,76.6,75.9,73.1, 72.0,67.5,59.9,54.1,49.0,47.0,42.7,42.0,25.8,21.7,11.4。
Compound 20
Colorless needle crystals (methanol), mp 231-,
-16.9 ° (c 0.70, methanol); UV (acetonitrile) lambdamax(logε)：240(2.79)nm；IR(KBr)vmax：3492,3320,1721,1677,1429,1237, 1070,820,628cm-1；HR-ESI-MS m/z 433.1471[M+Na]+(calcd for C20H26O9Na, 433.1469)；1H NMR(400MHz,C5D5N)δ6.14(s,1H),5.18(s,1H),4.83(s,1H), 4.56(d,J＝9.0Hz,1H),4.41(s,1H),4.13(m,1H),4.09(d,J＝9.0Hz,1H),3.15(d, J＝12.6Hz,1H),3.01(dq,J＝12.1,7.2Hz,1H),2.35(dt,J＝14.9,2.8Hz,1H),2.08 (td,J＝15.1,12.9,2.7Hz,1H),1.79(s,3H),1.61(s,3H),1.51(d,J＝7.2Hz,3H),；13C NMR(100MHz,C5D5N)δ197.7,172.2,162.6,126.6,110.5,85.2,79.1,77.0, 76.3,71.3,68.1,50.3,46.2,45.7,42.8,41.5,26.3,22.8,11.0,10.5。
Compound 21
Colorless needle crystals (methanol), mp 289-,
+47.4 ° (c 0.61, methanol); UV (acetonitrile) lambdamax(logε)：241(4.07)nm；IR(KBr)vmax：3466,2952,2906,2717,1733,1653, 1496,1389,1313,1227,1126,1056,1014,966,817,766cm-1；HR-ESI-MS m/z 433.1463[M+Na]+(calcd for C20H26O9Na,433.1469)；1H NMR(300MHz,C5D5N)δ 6.13(s,1H),5.64(s,1H),5.22(d,J＝2.9Hz,1H),4.66(d,J＝9.1Hz,1H),4.40(s, 1H),4.15(brs,1H),4.06(d,J＝9.0Hz,1H),3.53(s,1H),3.18(d,J＝12.6Hz,1H), 2.86(m,1H),2.28(dt,J＝14.7,3.0Hz,1H),2.04(td,J＝15.0,12.8,2.4Hz,1H), 1.87(d,J＝6.6Hz,3H),1.77(s,3H),1.63(s,3H)；13C NMR(75MHz,C5D5N)δ 197.9,175.2,163.1,126.4,110.7,84.9,80.0,76.9,75.4,72.3,67.7,53.1,47.3,46.0, 42.6,42.5,26.1,22.8,14.5,11.0。
Compound 22
Colorless needle crystals (methanol), mp 285-,
+39.5 ° (c 0.65, methanol); UV (acetonitrile) lambdamax(logε)：241(3.46)nm；IR(KBr)vmax：3410,1737,1673,1622,1504,1435, 1385,1357,1313,1261,1230,1156,1121,943,915,866,826,765,697cm-1； HR-ESI-MS m/z 431.1314[M+Na]+(calcd for C20H24O9Na,431.1313)；1H NMR (300MHz,C5D5N)δ6.16(brs,1H),6.12(d,J＝1.8Hz,1H),5.67(s,1H),5.65(d,J ＝1.7Hz,1H),5.26(t,J＝2.9Hz,1H),4.81(s,1H),4.55(d,J＝8.6Hz,1H),4.52(s, 1H),4.02(d,J＝8.6Hz,1H),3.82(s,1H),3.26(d,J＝12.5Hz,1H),2.33(dt,J＝ 14.9,2.8Hz,1H),2.02(td,J＝15.1,12.9,2.5Hz,1H),1.78(s,3H),1.62(s,3H)；13C NMR(75MHz,C5D5N)δ197.9,174.3,162.9,148.4,126.4,119.7,109.9,84.9,81.3, 79.8,76.2,72.1,68.0,52.9,48.1,46.3,42.5,26.0,22.8,10.8。
Compound 23
Colorless columnar crystals (methanol), mp 215-,
+55.7 ° (c 0.56, methanol); UV (acetonitrile) lambdamax(logε)：211(4.05)nm；IR(KBr)vmax：3507,3304,1727,1629,1392,1309, 1248,1213,1141,992,890,850,709,659cm-1；HR-ESI-MS m/z 447.1258[M+Na]+ (calcd for C20H24O10Na,447.1262)；1H NMR(400MHz,C5D5N)δ6.17(s,1H),5.84 (s,1H),5.19(brs,1H),4.89(d,J＝8.9Hz,1H),4.56(s,1H),4.08(d,J＝8.9Hz,1H), 4.04(s,1H),3.82(s,1H),3.81(d,J＝5.1Hz,1H),3.28(d,J＝12.3Hz,1H),3.05(d, J＝5.1Hz,1H),2.34(dt,J＝14.8,2.9Hz,1H),2.04(td,J＝15.1,12.9,2.5Hz,1H), 1.80(s,3H),1.64(s,3H)；13C NMR(100MHz,C5D5N)δ197.8,174.2,162.8,126.5, 110.0,84.8,82.1,76.0,75.9,71.9,67.2,59.6,53.9,48.7,46.9,46.2,42.6,25.8,22.8, 10.8。
Example 2
Evaluation of activity of quassin compounds in killing solenopsis invicta
Preparation of eurycolactone F (compound 12) termite killing bait and research on effect of termite control
(1) Method for preparing 0.1% compound 12 ant killing bait
Dissolving a compound 12 by using acetone, wherein the components and the weight percentage of each component are as follows:
(2) preparation method of 1% compound 12 ant killing bait
Dissolving a compound 12 by using acetone, wherein the components and the weight percentage of each component are as follows:
(3) method for preparing 10% compound 12 ant killing bait
Dissolving a compound 12 by using acetone, wherein the components and the weight percentage of each component are as follows:
sieving corn flour with a 60-mesh sieve, mixing the corn flour, the brown sugar and the butter according to the proportion, adding water to prepare dough, extruding the dough, sieving the extruded dough with a 20-mesh sieve to form particles, and drying at 40 ℃ to prepare the filling bait. And (3) taking the compound 12 according to a certain proportion, dissolving the compound in acetone to prepare the ant killing medicament, infiltrating the ant killing medicament into the prepared filling bait by a spraying method, drying the filling bait in an oven at 40 ℃, and crushing and sieving the filling bait by a 40-mesh sieve to obtain the ant killing bait.
(4) Experimental methods
Indoor toxicity of solenopsis invicta was measured using the ant killing bait of compound 12 prepared in the above procedure with mass fractions of 0.1%, 1% and 10%, respectively. Adding a layer of fine sand with the thickness of about 1mm at the bottom of a cylindrical transparent plastic box with the diameter of 10cm, drying the fine sand, coating talcum powder on the periphery of the box wall to prevent the red imported fire ants from escaping, and placing a 10mL centrifuge tube and a water supply tube made of cotton. Selecting 80 heads of worker ants with the same size, putting the workers in a box, after hungry for one day, respectively putting about 1g of bait prepared according to the proportion, and taking filling bait without adding an ant killing agent as blank control. The test is carried out in a shading environment, and the control test environment is as follows: humidity is about 27 ℃, and relative humidity is about 85%. The number of deaths of solenopsis invicta was recorded, corrected mortality was calculated, and the dead workers were picked out for a total of 15 days, with 3 replicates per treatment.
Corrected mortality (%) - (treatment mortality-control mortality)/(1-control mortality) × 100%
(5) Results of the experiment
The ant killing bait prepared by taking the compound 12 as a raw material has better stomach toxicity activity on solenopsis invicta, wherein the mass fractions of the ant killing bait are respectively 0.1%, 1% and 10%. From table 1, it can be seen that the difference between the different mass percentages is not significant within 5 days of the administration of compound 12, the corrected mortality rate of the compound 12 bait to solenopsis invicta at 10% after 10 days of the administration is about 87%, and the corrected mortality rate reaches more than 90% after 15 days, which is in positive correlation with the treatment concentration.
TABLE 1 corrected mortality of Compound 12 against Solenopsis invicta
Example 3
Preparation of eurycolatone E (compound 3) termite killing bait and research on effect of termite control
(1) Preparation method of 0.1% compound 3 bait for killing ants
Dissolving a compound 3 by using acetone, wherein the components and the weight percentage of each component are as follows:
(2) preparation method of 1% compound 3 ant killing bait
Dissolving a compound 3 by using acetone, wherein the components and the weight percentage of each component are as follows:
(3) preparation method of 10% compound 3 ant killing bait
Dissolving a compound 3 by using acetone, wherein the components and the weight percentage of each component are as follows:
sieving corn flour with a 60-mesh sieve, mixing the corn flour, the brown sugar and the butter according to the proportion, adding water to prepare dough, extruding the dough, sieving the extruded dough with a 20-mesh sieve to form particles, and drying at 40 ℃ to prepare the filling bait. And (3) dissolving the compound 3 in acetone according to a certain proportion to prepare the ant killing medicament, infiltrating the ant killing medicament into the prepared filling bait by a spraying method, drying in an oven at 40 ℃, crushing and sieving by a 40-mesh sieve to obtain the ant killing bait.
(4) Experimental methods
The indoor toxicity of solenopsis invicta is measured by using the ant killing bait agent of the compound 3 prepared by the steps and respectively accounting for 0.1 percent, 1 percent and 10 percent, and the experimental design and the calculation formula are the same as those in the example 2.
(5) Results of the experiment
The ant killing bait prepared by taking the compound 3 as a raw material has better stomach toxicity activity on solenopsis invicta, wherein the mass fractions of the ant killing bait are respectively 0.1%, 1% and 10%. From table 2, it can be seen that 10% of compound 3 bait after 10 days of application has a corrected mortality rate of about 73% for solenopsis invicta, and reaches 91% after 15 days; the corrected mortality rate of 1% of the compound 3 bait to solenopsis invicta 15d is 87%, and thus the compound 3 has better activity to solenopsis invicta 10d and is positively correlated with the treatment concentration.
TABLE 2 corrected mortality of Compound 3 against Solenopsis invicta
Example 4
Preparation of 15-hydroxykalaineanone (compound 14) ant killing bait and research on effect of termite control
(1) Preparation method of 0.1% compound 14 ant killing bait
Dissolving a compound 14 by using acetone, wherein the components and the weight percentage of each component are as follows:
(2) preparation method of 1% compound 14 ant killing bait
Dissolving a compound 14 by using acetone, wherein the components and the weight percentage of each component are as follows:
(3) preparation method of 10% compound 14 ant killing bait
Dissolving a compound 14 by using acetone, wherein the components and the weight percentage of each component are as follows:
sieving corn flour with a 60-mesh sieve, mixing the corn flour, the brown sugar and the butter according to the proportion, adding water to prepare dough, extruding the dough, sieving the extruded dough with a 20-mesh sieve to form particles, and drying at 40 ℃ to prepare the filling bait. And (3) taking the compound 14 according to a certain proportion, dissolving the compound in acetone to prepare the ant killing medicament, infiltrating the ant killing medicament into the prepared filling bait by a spraying method, drying the filling bait in an oven at 40 ℃, and crushing and sieving the filling bait by a 40-mesh sieve to obtain the ant killing bait.
(4) Experimental methods
The indoor toxicity of solenopsis invicta was measured by using the ant killing bait of compound 14 prepared in the above steps in the mass fractions of 0.1%, 1% and 10%, respectively, and the experimental design and calculation formula were the same as those of example 2.
(5) Results of the experiment
The ant killing bait prepared by taking the compound 14 as a raw material has better stomach toxicity activity on solenopsis invicta, wherein the mass fractions of the ant killing bait are respectively 0.1%, 1% and 10%. It can be seen from table 3 that compound 14 has a corrected mortality rate of about 87% for solenopsis invicta for 10 days after administration of 10% of the bait formulation of compound 14 and 95% after 15 days; the 1% bait of compound 14 achieved 93% corrected mortality of solenopsis invicta 15d, and was positively correlated with treatment concentration and time.
TABLE 3 corrected mortality of Compound 14 against Solenopsis invicta
Example 5
Preparation of 13 alpha (21) -epoxynyuromanol (compound 19) ant killing bait and effect thereof for preventing and controlling solenopsis invicta
(1) Preparation method of 0.1% compound 19 ant killing bait
Dissolving a compound 19 by using acetone, wherein the components and the weight percentage of each component are as follows:
(2) preparation method of 1% compound 19 ant killing bait
Dissolving a compound 19 by using acetone, wherein the components and the weight percentage of each component are as follows:
(3) preparation method of 10% compound 19 ant killing bait
Dissolving a compound 19 by using acetone, wherein the components and the weight percentage of each component are as follows:
sieving corn flour with a 60-mesh sieve, mixing the corn flour, the brown sugar and the butter according to the proportion, adding water to prepare dough, extruding the dough, sieving the extruded dough with a 20-mesh sieve to form particles, and drying at 40 ℃ to prepare the filling bait. And (3) taking the compound 19 according to a certain proportion, dissolving the compound in acetone to prepare the ant killing medicament, infiltrating the ant killing medicament into the prepared filling bait by a spraying method, drying the filling bait in an oven at 40 ℃, and crushing and sieving the filling bait by a 40-mesh sieve to obtain the ant killing bait.
(4) Experimental methods
The indoor toxicity of solenopsis invicta was measured by using the ant killing bait of the compound 19 prepared in the above steps in mass fractions of 0.1%, 1% and 10%, respectively, and the experimental design and calculation formula were the same as those of example 2.
(5) Results of the experiment
The ant killing bait prepared by taking the compound 19 as a raw material has better stomach toxicity activity on solenopsis invicta, wherein the mass fractions of the ant killing bait are respectively 0.1%, 1% and 10%. It can be seen from table 4 that 10% of compound 19 bait after 10 days of administration gave a corrected mortality rate of 89% for solenopsis invicta and around 94% after 15 days; the 1% compound 19 bait achieves 91% corrected mortality of solenopsis invicta 15d and is positively correlated with treatment concentration.
TABLE 4 corrected mortality of Compound 19 against Solenopsis invicta
Example 6
Preparation of Eurycomanone (compound 22) termite killing bait and research on effect of Eurycomanone on preventing and controlling Solenopsis invicta
(1) Preparation method of 0.1% compound 22 ant killing bait
Dissolving a compound 22 by using acetone, wherein the components and the weight percentage of each component are as follows:
(2) preparation method of 1% compound 22 ant killing bait
Dissolving a compound 22 by using acetone, wherein the components and the weight percentage of each component are as follows:
(3) preparation method of 10% compound 22 ant killing bait
Dissolving a compound 22 by using acetone, wherein the components and the weight percentage of each component are as follows:
sieving corn flour with a 60-mesh sieve, mixing the corn flour, the brown sugar and the butter according to the proportion, adding water to prepare dough, extruding the dough, sieving the extruded dough with a 20-mesh sieve to form particles, and drying at 40 ℃ to prepare the filling bait. And (3) taking the compound 22 according to a certain proportion, dissolving the compound in acetone to prepare the ant killing medicament, infiltrating the ant killing medicament into the prepared filling bait by a spraying method, drying the filling bait in an oven at 40 ℃, and crushing and sieving the filling bait by a 40-mesh sieve to obtain the ant killing bait.
(4) Experimental methods
The indoor toxicity of solenopsis invicta was measured using the ant killing bait of compound 22 prepared in the above steps in mass fractions of 0.1%, 1% and 10%, respectively, and the experimental design and calculation formula were the same as in example 2.
(5) Results of the experiment
The ant killing bait prepared by taking the compound 22 as a raw medicine and respectively accounting for 0.1 percent, 1 percent and 10 percent of the mass fraction has better stomach toxicity activity on solenopsis invicta. From table 5, it can be seen that compound 22 has a corrected mortality rate of about 85% for solenopsis invicta at 10% of compound 22 bait 10 days after application and 96% after 15 days; the corrected mortality rate after 15d for solenopsis invicta was 90% for 1% of the compound 22 bait and was positively correlated with treatment concentration.
TABLE 5 corrected mortality of Compound 22 against Solenopsis invicta
The invention discloses application of quassin compounds in killing solenopsis invicta, which can be used for preparing solenopsis invicta bait, is more convenient to use and is not easily influenced by the interference of external environment; the invention is obtained by separating and purifying natural plants, has low toxicity, no residue and no pollution to various grain, melon and fruit, vegetable and other economic crops; the compound has higher stomach toxicity activity to the solenopsis invicta and can play a role in preventing and controlling pests.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. The application of the quassinoid compound or the pharmaceutically acceptable salt thereof in killing solenopsis invicta is characterized in that:
the quassinoid compound is selected from at least one of compounds 3, 12, 14, 19 and 22;
the structural formulae of compounds 3, 12, 14, 19, 22 are as follows:
2. a pharmaceutical composition characterized in that it comprises:
(1) the quassinoid compound of claim 1, or a pharmaceutically acceptable salt thereof, or a combination thereof; and
(2) the ant killing bait agent can be accepted as filling bait.
3. The pharmaceutical composition of claim 2, wherein:
the filling bait comprises at least one of corn flour, butter and brown sugar.
4. Use of a pharmaceutical composition according to claim 2 or 3 for the preparation of an ant killing bait.
5. An ant killing bait agent is characterized in that: comprises the following components in percentage by weight: 0.1-10% of original medicine, 55-69.9% of corn flour, 15-25% of brown sugar and 10-20% of butter;
the bulk drug is the quassinoid compound of claim 1, or a pharmaceutically acceptable salt thereof, or a combination thereof.
6. The ant-killing bait according to claim 5, wherein:
the ant killing bait comprises the following components in percentage by weight: 0.1-10% of raw medicine, 60-69.9% of corn flour, 15-25% of brown sugar and 10-20% of butter.
7. The ant-killing bait according to claim 6, wherein:
the ant killing bait comprises the following components in percentage by weight: 0.1-10% of raw medicine, 60-69.9% of corn flour, 20% of yellow sugar and 10% of butter.
8. The ant-killing bait according to claim 7, wherein:
the ant killing bait comprises the following components in percentage by weight: 1-10% of original medicine, 60-69% of corn flour, 20% of yellow sugar and 10% of butter.
9. A process for the preparation of an ant-killing bait according to claim 5 or 6 or 7 or 8, characterized by comprising the steps of:
1) preparing filling bait: sieving corn flour with a 50-80 mesh sieve according to a proportion, adding water into the corn flour, the brown sugar and the butter to prepare dough, extruding the dough, sieving the extruded dough with a 20-40 mesh sieve to form particles, and drying;
2) dissolving raw materials in a solvent according to a certain proportion to prepare the ant killing medicament; and (2) infiltrating the ant killing agent into the filling bait prepared in the step 1) by using a soaking or spraying method, then drying, crushing and sieving with a 20-50-mesh sieve to obtain the ant killing bait.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910991380.2A CN110612981B (en) | 2019-10-18 | 2019-10-18 | Application of quassin compounds in killing ants |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910991380.2A CN110612981B (en) | 2019-10-18 | 2019-10-18 | Application of quassin compounds in killing ants |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110612981A CN110612981A (en) | 2019-12-27 |
| CN110612981B true CN110612981B (en) | 2021-04-27 |
Family
ID=68925862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910991380.2A Active CN110612981B (en) | 2019-10-18 | 2019-10-18 | Application of quassin compounds in killing ants |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110612981B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818721B (en) * | 2019-11-29 | 2021-11-12 | 广西师范大学 | Lignin compound and preparation method and application thereof |
| CN112136824B (en) * | 2020-10-14 | 2022-04-26 | 广东省农业科学院果树研究所 | Application of quassin compounds in preventing and treating plant fungal diseases |
| CN112889913B (en) * | 2021-03-19 | 2023-05-02 | 广东省农业科学院果树研究所 | Application of eurycolatone F in food preservation |
| CN113975267B (en) * | 2021-10-26 | 2023-11-28 | 广东中诚生物科技有限公司 | Application of 6 alpha-hydroxyeyeurycommactone in preparation of anti-dengue virus drugs |
| CN117797141A (en) * | 2024-03-01 | 2024-04-02 | 暨南大学 | Use of inhibitors of OTUB1-ERRα -PGC1 signaling pathway |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109497066A (en) * | 2018-11-09 | 2019-03-22 | 广东省农业科学院果树研究所 | 15 β-the hydroxyklaineanone of antifeedant for insect of transporting in plant and application |
| CN109535172A (en) * | 2018-10-19 | 2019-03-29 | 广东省农业科学院果树研究所 | A kind of quassinoids class compound and its preparing the application in antifeedant for insect |
-
2019
- 2019-10-18 CN CN201910991380.2A patent/CN110612981B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535172A (en) * | 2018-10-19 | 2019-03-29 | 广东省农业科学院果树研究所 | A kind of quassinoids class compound and its preparing the application in antifeedant for insect |
| CN109497066A (en) * | 2018-11-09 | 2019-03-22 | 广东省农业科学院果树研究所 | 15 β-the hydroxyklaineanone of antifeedant for insect of transporting in plant and application |
Non-Patent Citations (6)
| Title |
|---|
| 1985－1993年苦木苦味素研究进展;于荣敏，林少霞，张惟才，李铣;《中国药物化学杂志》;19940920;第4卷(第03期);第224-230页 * |
| Glaucarubolone Glucoside,a Potential Fungicidal Agent for the Control of Grape Downy Mildew;Joseph J.Hoffmann;《J.Agric.Food Chem.》;19921231;第1056-1057页 * |
| Growth inhibitory, insecticidal and antifeedant effects of some antileukemic and cytotoxic quassinoids on two species of agricultural pests;Klocke, J. A. et.al.;《Experientia》;19851231;第41卷(第3期);第379-381页 * |
| Insect antifeedant and growth regulating activities of quassinoids from Samadera indica;T.R. Govindachari et.al.;《Fitoterapia》;20011231;第72卷;第568-571 * |
| 苦木科植物化学成分及生物活性研究进展;王琦等;《国外医学.中医中药分册》;20040930;第26卷(第05期);第279页2.3段 * |
| 苦木苦味素的化学、生源和抗癌活性;泰国伟等;《国外医学.药学分册》;19790131(第01期);第10-17页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110612981A (en) | 2019-12-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110612981B (en) | Application of quassin compounds in killing ants | |
| Itokawa et al. | Antitumour principles from Alpinia galanga | |
| Formisano et al. | Chemical constituents and biological activities of Nepeta species | |
| Roy et al. | Limonoids: overview of significant bioactive triterpenes distributed in plants kingdom | |
| Vieira et al. | Quassinoids: structural diversity, biological activity and synthetic studies | |
| JPS6110589A (en) | Novel compound, manufacture and use | |
| CN110627759B (en) | Sesquiterpenoids and preparation method and application thereof | |
| Abdel-Ghani et al. | Phytochemical and biological study of Malva parviflora L. grown in Egypt | |
| Oktiansyah et al. | Antioxidant and Antibacterial Activity of Endophytic Fungi Isolated from The Leaves of Sungkai (Peronema canescens). | |
| CN106719856B (en) | A kind of extractive of pubescent angelica root coumarin preparation method and applications with killing activity of pine wood nematode | |
| JPH01500517A (en) | Misaquinolide and its derivatives | |
| Borkosky et al. | Molluscicidal sesquiterpene lactones from species of the tribe Vernonieae (Compositae) | |
| Dar et al. | The expeditious oxidation OF arylboronic acids to phenols By tertiary butyl hydroperoxide IN green aqueous ethanol | |
| Aswar et al. | Antimicrobial activity of Ficus benghalensis | |
| Liang et al. | Chemical constituents and antibacterial activities of Aspidistra typica | |
| Sharma et al. | Optimization of lantadenes isolation and preparation of 22 β-hydroxyoleanonic acid | |
| Muñoz et al. | Phytochemistry and biological properties of Drimys winteri JR et G. Forster var chilensis (DC) A | |
| Manivannan et al. | Anti-microbial and anti-inflammatory flavonoid constituents from the leaves of Lawsonia inermis | |
| CN111777588B (en) | Pseudorufop-gracilis phenylpropanoids compound and application thereof | |
| CN103749456A (en) | Application of diterpene alkaloid compound and preparation to prevention of crop virus diseases | |
| Sasidhar | Mangrove medicinal plants and its chemistry: A review | |
| DE60029982T2 (en) | ANTIMYCOTIC ENEDIYNE | |
| Zhang et al. | Podophyllotoxin derivatives show activity against Brontispa longissima larvae | |
| US4960791A (en) | Salannin derivative insect control agents | |
| CN113200903B (en) | Pyrrole alkaloid compound with antifeedant and defensive functions on coccinella twenty-eight star in Solanum septemlobum and separation and extraction method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |