CN110759904A - 9R-acyloxy quinine derivative and preparation method thereof, application of quinine or derivative thereof, and botanical pesticide - Google Patents
9R-acyloxy quinine derivative and preparation method thereof, application of quinine or derivative thereof, and botanical pesticide Download PDFInfo
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- C07D453/00—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids
- C07D453/02—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids containing not further condensed quinuclidine ring systems
- C07D453/04—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids containing not further condensed quinuclidine ring systems having a quinolyl-4, a substituted quinolyl-4 or a alkylenedioxy-quinolyl-4 radical linked through only one carbon atom, attached in position 2, e.g. quinine
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- 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
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Abstract
The invention relates to a 9R-acyloxy quinine derivative and a preparation method thereof, application of quinine or the derivative thereof and a botanical pesticide, and belongs to the technical field of botanical pesticides. The 9R-acyloxy quinine derivative is prepared by esterification reaction of quinine and R-COOH, has obvious insecticidal activity on lepidoptera agricultural pests and has obvious effect on preventing armyworms in lepidoptera, wherein the control effect of part of the 9R-acyloxy quinine derivative on the armyworms is better than that of a commercial botanical insecticide, namely toosendanin, and the 9R-acyloxy quinine derivative can be used for preparing a botanical agricultural pest insecticide for the lepidoptera agricultural pests. Quinine in the prior art is mainly used for treating human diseases caused by malaria, and researches show that quinine also has a good control effect on lepidoptera agricultural pests and has an obvious control effect on armyworms.
Description
Technical Field
The invention relates to a 9R-acyloxy quinine derivative and a preparation method thereof, application of quinine or the derivative thereof and a botanical pesticide, and belongs to the technical field of botanical pesticides.
Background
Quinine (Quinine), a major alkaloid in the bark of plants of the Rubiaceae family (Rubiaceae) family, cinchona japonica and congeneric plants, has a wide range of pharmacological actions and insecticidal activity (Xuhanhong, insecticidal plants and botanical insecticides, Chinese agriculture Press, Beijing: 2000, 49-50; lumeixiang, Miehe and Wang Xiaojuan, etc., the research on alkaloids for pesticides has progressed, pesticides 2004, 43 (6): 249-253).
Research shows that quinine alkaloid has activity of preventing and controlling pests. First, Mitchell studied the effect of quinine alkaloids on its olfactory sensors using potato beetles as model insects. The results show that quinine can inhibit the reaction of potato beetles to sucrose; and quinine exhibits some inhibitory effect on GABA receptors (B.K. Mitchell, Interactions of alkaloids with free chemical sensing cells of colorado potatoto beer, Journal of chemical Ecology,1987,13(10): 2009-. Secondly, Blades et al investigated the antifeedant activity of quinine alkaloids against blowfly. The results show that quinine can significantly reduce the sucrose uptake of blowfly adults and show better antifeedant activity (David Blades, B.K. Mitchell, Effect of alkaloids on feeding by Phormia regina, Entomologia excelmentalis et application, 1986,41(3): 299-304). Third, Schoonhoven et al found that quinine alkaloids inhibited feeding by one stink bug and stimulated feeding by another stink bug (Mawei Chun, L.M. Schoonhoven, front contact chemistry viruses of the large white tissue nail lasers and the upper porous roll in the obesity viewer, Entomologia expression et application, 1973,16(3): 343-) -357). In addition, Drosophila melanogaster (Drosophila melanogaster) Cytochrome P-450 mediates resistance to quinine alkaloids, while becoming more sensitive to synthetic pesticides (P.B. Danielson, S.L. gloor, R.T. Roush, J.C. Fogleman, Cytochrome P450-mediated resistance to isoquinoline analogs and surfactant to synthetic insecticides in Drosophila, Pesticide Biochemistry and Physiology, 1996,55: 172-179).
However, few studies on the agricultural activity of quinine alkaloids are currently carried out, and no report is made on the prevention effect of quinine alkaloids on lepidopteran agricultural pests.
Disclosure of Invention
The first purpose of the invention is to provide a 9R-acyloxy quinine derivative, and the 9R-acyloxy quinine derivative can effectively control lepidoptera agricultural pests.
The second object of the present invention is to provide a process for producing the above 9R-acyloxyquinine derivatives.
The third purpose of the invention is to provide the application of quinine or 9R-acyloxy quinine derivatives in the aspect of preventing and controlling lepidoptera pests.
The fourth purpose of the invention is to provide a botanical pesticide.
In order to achieve the purpose, the invention adopts the technical scheme that:
A9R-acyloxy quinine derivative has a structural formula shown in formula I;
in the formula I, R is selected from any one of alkyl with 1-6 carbon atoms, phenyl substituted by substituent, naphthalene and pyridyl; the substituent in the substituent-substituted phenyl is one or more of alkyl with 1-4 carbon atoms, alkoxy with 1-3 carbon atoms, halogen and nitro; the number of carbon atoms of the alkylene group in the naphthalene group is 1 to 3.
Preferably, in formula I, R is selected from any one of methyl, ethyl, n-propyl, n-pentyl, n-hexyl, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methoxyphenyl, 4-tert-butylphenyl, 2-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 4-bromophenyl, 2-nitrophenyl, 3-nitrophenyl, 4-chloro-3-nitrophenyl, 1-naphthylmethylene, 3-pyridyl and 4-pyridyl.
The 9R-acyloxy quinine derivatives have obvious insecticidal activity on lepidoptera agricultural pests and have obvious effect on preventing armyworms in the lepidoptera, wherein the prevention and control effect of part of the 9R-acyloxy quinine derivatives on the armyworms is better than that of a commercial botanical insecticide, namely toosendanin, and the 9R-acyloxy quinine derivatives can be used for preparing the botanical agricultural pest insecticide for the lepidoptera agricultural pests.
The preparation method of the 9R-acyloxy quinine derivative comprises the following steps: performing esterification reaction on quinine, R-COOH, a water reducing agent and a catalyst in an organic solvent to obtain the quinine-COOH-containing organic solvent;
r in the R-COOH is selected from any one of alkyl with 1-6 carbon atoms, phenyl substituted by substituent, naphthalene and pyridyl; the substituent in the substituent-substituted phenyl is one or more of alkyl with 1-4 carbon atoms, alkoxy with 1-3 carbon atoms, halogen and nitro; the number of carbon atoms of the alkylene group in the naphthalene group is 1 to 3.
The preparation method of the 9R-acyloxy quinine derivative can simply and conveniently obtain the 9R-acyloxy quinine derivative. Preferably, R — COOH is any one of glacial acetic acid, propionic acid, n-butyric acid, n-hexanoic acid, n-heptanoic acid, benzoic acid, o-methylbenzoic acid, m-methylbenzoic acid, p-methoxybenzoic acid, 4-tert-butylbenzoic acid, o-chlorobenzoic acid, p-chlorobenzoic acid, o-bromobenzoic acid, p-bromobenzoic acid, 2-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, 4-chloro-3-nitrobenzoic acid, 1-naphthylacetic acid, nicotinic acid, and isonicotinic acid.
Preferably, the molar ratio of quinine to R-COOH is 1: 1-1.5; more preferably, the molar ratio of quinine to R-COOH is 1: 1.2.
preferably, the reaction conditions of the esterification reaction are as follows: reacting at room temperature for 24-96 h.
Preferably, the amount of organic solvent per mole of quinine is 8-12 mL; more preferably, the amount of organic solvent is 10mL per mole of quinine.
Preferably, the organic solvent is dichloromethane.
Preferably, the molar ratio of quinine to water reducer is 1: 1-1.5; more preferably, the molar ratio of quinine to water-reducing agent is 1: 1.2.
preferably, the water reducing agent is N, N' -dicyclohexylcarbodiimide or 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC).
Preferably, the molar ratio of quinine to catalyst is 1: 0.1-0.3; more preferably, the molar ratio of quinine to catalyst is 1: 0.2.
preferably, the catalyst is 4- (N, N-dimethylamino) pyridine.
Specifically, after the esterification reaction of quinine and R-COOH is completed, urea in the reaction solution is removed by filtration, and the filtrate is diluted by an organic solvent; the diluted solution was washed once with hydrochloric acid, saturated sodium bicarbonate, and saturated brine, and then dried over anhydrous sodium sulfate; removing the solvent under reduced pressure, and separating and purifying by silica gel column chromatography to obtain the 9R-acyloxy quinine derivatives.
Preferably, the organic solvent for dilution and the organic solvent for esterification are the same. The volume ratio of the organic solvent for dilution, the organic solvent for esterification, hydrochloric acid, saturated sodium bicarbonate and saturated saline water is 8-12 mL: 45-55 mL: 25-35 mL: 25-35 mL: 25-35 mL. The organic solvent is dichloromethane. The hydrochloric acid is 0.08-0.12mol/L hydrochloric acid.
The principle of silica gel column chromatography separation is that the substances are separated according to different adsorption forces on silica gel, in general, substances with larger polarity are easy to be adsorbed by the silica gel, substances with weaker polarity are not easy to be adsorbed by the silica gel, and the whole chromatography process is the adsorption, desorption, re-adsorption and re-desorption processes. The silica gel used is 200-300 mesh (Qingdao ocean, China).
Application of quinine in preventing and treating lepidoptera pests is provided. Specifically, the lepidoptera pests are armyworms. Preferably, the lepidopteran pest is armyworm larvae. In the prior art, quinine is a plant secondary metabolite and is mainly used for treating human diseases caused by malaria, and researches show that quinine also has a good control effect on lepidoptera agricultural pests and has an obvious control effect on armyworms. Preferably, the quinine controls pests by inducing the teratogenic growth of lepidopteran pests.
The application of the 9R-acyloxy quinine derivatives in preventing and treating lepidoptera pests. Specifically, the lepidoptera pests are armyworms. Preferably, the lepidopteran pest is armyworm larvae. The structural formula of the 9R-acyloxy quinine derivative is shown as a formula I;
in the formula I, R is selected from any one of alkyl with 1-6 carbon atoms, phenyl substituted by substituent, naphthalene and pyridyl; the substituent in the substituent-substituted phenyl is one or more of alkyl with 1-4 carbon atoms, alkoxy with 1-3 carbon atoms, halogen and nitro; the number of carbon atoms of the alkylene group in the naphthalene group is 1 to 3.
Preferably, the 9R-acyloxy quinine derivative is used for controlling pests by inducing the abnormal growth of lepidoptera pests.
According to the invention, researches show that the 9R-acyloxy quinine derivatives have obvious insecticidal activity on lepidoptera agricultural pests and have obvious effect on mythimna separata in lepidoptera, wherein the control effect of part of the 9R-acyloxy quinine derivatives on the mythimna separata is better than that of a commercial botanical insecticide, namely toosendanin, and the 9R-acyloxy quinine derivatives can be used for preparing the botanical insecticide for the lepidoptera agricultural pests.
A botanical pesticide comprises quinine or 9R-acyloxy quinine derivatives as effective components; the structural formula of the 9R-acyloxy quinine derivative is shown as a formula I;
in the formula I, R is selected from any one of alkyl with 1-6 carbon atoms, phenyl substituted by substituent, naphthalene and pyridyl; the substituent in the substituent-substituted phenyl is one or more of alkyl with 1-4 carbon atoms, alkoxy with 1-3 carbon atoms, halogen and nitro; the number of carbon atoms of the alkylene group in the naphthalene group is 1 to 3.
According to the invention, researches show that quinine and 9R-acyloxy quinine derivatives have remarkable insecticidal activity on lepidoptera agricultural pests and have remarkable effect on preventing armyworms in lepidoptera, wherein the prevention and control effect of part of the 9R-acyloxy quinine derivatives on the armyworms is better than that of a commercial botanical insecticide, namely toosendanin, and the long-term prevention and control effect of the quinine on the armyworms is also better than that of the commercial botanical insecticide, namely the toosendanin, so that the quinine and the 9R-acyloxy quinine derivatives can be used for preparing the botanical agricultural pest insecticide for the lepidoptera agricultural pests.
Drawings
FIG. 1 is a hydrogen diagram of a 9R-acyloxyquinine derivative 3a in example 1 of the invention;
FIG. 2 is a hydrogen diagram of a 9R-acyloxyquinine derivative 3b in example 2 of the invention;
FIG. 3 is a hydrogen spectrum of a 9R-acyloxyquinine derivative 3c in example 3 of the invention;
FIG. 4 is a representative graph of the control and abnormal larval stages of the present invention in test example 1;
FIG. 5 is a representative diagram of the control group and the abnormal moth phase in test example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Examples 1-229R-acyloxyquinine derivatives 3a-v
In the general structural formula I, the substituent R corresponds to the table 1, and the 9R-acyloxy quinine derivatives 3a-v can be obtained.
Table 1: 9R-acyloxy quinine derivatives 3a-v corresponding substituent R
Example 23
The preparation of 9R-acyloxyquinine derivatives of examples 1-22 is shown below:
quinine 1(0.5mmol), the corresponding carboxylic acid 2a-v (0.6mmol), N' -dicyclohexylcarbodiimide DCC (0.6mmol) and 4- (N, N-dimethylamino) pyridine DMAP (0.1mmol) are weighed into a 50mL flask, 10mL of dichloromethane (calcium hydride is dried for later use) is added into the reaction solution, and esterification reaction is carried out at room temperature for 24-96 h.
TLC tracking detection is carried out during the esterification reaction until the raw material reaction is complete. A large amount of urea was removed from the reaction solution by filtration, and the filtrate was diluted with methylene chloride (50 mL). The diluted solution was washed once with 0.1mol/L hydrochloric acid (30mL), saturated sodium bicarbonate (30mL) and saturated brine (30mL) in this order, and dried over anhydrous sodium sulfate. Removing solvent under reduced pressure, and separating with silica gel column chromatography to obtain compounds 3 a-v.
In the preparation of the 9R-acyloxyquinine derivatives of examples 1 to 22, the eluent used in the separation and elution by silica gel column chromatography was methanol: 1-dichloromethane: 9, the eluent can achieve better separation effect on all the compounds (3 a-v). The esterification reaction time is 24-96h during preparation, all reactions can be completed after 24h, and the yield is slightly improved by prolonging the reaction time. The other parameters are the same.
The reaction formula is as follows:
in the reaction formula, r.t. is represented as room temperature.
In the reaction formula, R is respectively: a Me; b Et; c n-propyl; d n-amyl; e n-hexyl; f Ph; g (o-Me) Ph; h (m-Me) Ph; i (p-Me) Ph; j (p-OMe) Ph; k (p-tert-butyl) Ph; l (o-Cl) Ph; m (p-Cl) Ph; n (o-Br) Ph; o (p-Br) Ph; p (o-NO)2)Ph；q(m-NO2)Ph；r(p-NO2)Ph；s(p-Cl,m-NO2)Ph；t 1-naphthylmethylene；u 3-pyridyl；v 4-pyridyl.
The structural formula of the 9R-acyloxyquinine derivative in the embodiment 1 is shown as 3a, and the physicochemical property and the reaction formula of the compound are shown as follows:
1) and white solid with a melting point of 110-111 ℃ and a yield of 82%.
2) NMR spectrum of the compound (A)1H NMR, 400MHz) characteristics (as shown in figure 1):
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: δ:8.74(d, J ═ 4.8Hz,1H),8.02(d, J ═ 9.2Hz,1H),7.44(d, J ═ 2.8Hz,1H),7.34-7.38(m,2H),6.51(d, J ═ 7.2Hz,1H),5.79-5.88(m,1H),4.98-5.04(m,2H),3.96(s,3H),3.40(q, J ═ 8.0Hz,1H),3.08-3.14(m,1H),3.07(dd, J ═ 14.0Hz,10.0Hz,1H),2.58-2.69(m,2H),2.26-2.30(m,1H),2.12(s,3H), 1.85-1.76 (m,1H), 1.59-1H, 1.50 (m, 1H).
3) HRMS (ESI) of the compound Calcd for C22H27N2O3([M+H]+),367.2016；found,367.2020。
4) The reaction formula is as follows:
the structural formula of the 9R-acyloxyquinine derivative in the embodiment 2 is shown as 3b, and the physicochemical property and the reaction formula of the compound are shown as follows:
1) and white solid with melting point of 126-127 ℃ and yield of 82%.
2) NMR spectrum of the compound (A)1H NMR, 400MHz) characteristics (as shown in figure 2):
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: δ:8.74(d, J ═ 4.4Hz,1H),8.02(d, J ═ 9.2Hz,1H),7.45(d, J ═ 2.8Hz,1H),7.34-7.38(m,2H),6.51(d, J ═ 7.2Hz,1H),5.79-5.88(m,1H),4.98-5.04(m,2H),3.96(s,3H),3.41(q, J ═ 8.4Hz,1H),3.10-3.15(m,1H),3.07(dd, J ═ 14.0Hz,10.0Hz,1H),2.58-2.70(m,2H),2.37-2.44(m,2H),2.28(s,1H), 1.84-1.84 (m,1H), 89.76 (m,1H), 1.49-1H, 1H),1.49 (t, 1H), 1.49-1H), 1H, 1.
3) HRMS (ESI) of the compound Calcd for C23H29N2O3([M+H]+),381.2173；found,381.2175。
4) The reaction formula is as follows:
the structural formula of the 9R-acyloxyquinine derivative in the embodiment 3 is shown as 3c, and the physicochemical property and the reaction formula of the compound are shown as follows:
the physicochemical properties of the compound are as follows:
1) and white solid with a melting point of 62-63 ℃ and a yield of 74%.
2) NMR spectrum of the compound (A)1H NMR, 400MHz) characteristics (as shown in figure 3):
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: δ:8.74(d, J ═ 4.8Hz,1H),8.02(d, J ═ 9.2Hz,1H),7.45(d, J ═ 2.4Hz,1H),7.34-7.38(m,2H),6.52(d, J ═ 7.2Hz,1H),5.79-5.88(m,1H),4.98-5.04(m,2H),3.96(s,3H),3.40(q, J ═ 8.4Hz,1H),3.09-3.15(m,1H),3.07(dd, J ═ 14.0Hz,10.0Hz,1H),2.58-2.70(m,2H),2.33-2.37(m,2H),2.27-2.31(m,1H), 1.88(m, 1.85H), 1.63-2.59 (m,1H), 1.93-2H), 1.93(m,1H), 1H, 3.31 (d, 1H).
3) HRMS (ESI) of the compound Calcd for C24H31N2O3([M+H]+),395.2329；found,395.2333。
4) The reaction formula is as follows:
the structural formula of the 9R-acyloxyquinine derivative in the embodiment 4 is shown as 3d, and the physicochemical property and the reaction formula of the compound are shown as follows:
1) the product is light yellow solid, the melting point is 55-56 ℃, and the yield is 66%.
2) NMR spectrum of the compound (A)1H NMR, 400MHz) characteristics:
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: δ:8.74(d, J ═ 4.4Hz,1H),8.02(d, J ═ 9.2Hz,1H),7.45(d, J ═ 2.8Hz,1H),7.34-7.38(m,2H),6.50(d, J ═ 7.6Hz,1H),5.80-5.88(m,1H),4.98-5.04(m,2H),3.96(s,3H),3.40(q, J ═ 8.4Hz,1H),3.08-3.15(m,1H),3.07(dd, J ═ 14.0Hz,10.0Hz,1H),2.58-2.69(m,2H),2.34-2.39(m,2H),2.25-2.31(m,1H),1.85 (m, 1.85H), 1.70-1.83 (m,1H), 1.83-2.83 (m,1H), 1.83-2H), 1.70(m,1H), 1.83-1.52H).
3) HRMS (ESI) of the compound Calcd for C26H35N2O3([M+H]+),423.2642；found,423.2645。
4) The reaction formula is as follows:
the structural formula of the 9R-acyloxy quinine derivative in the embodiment 5 is shown as 3e, and the physicochemical property and the reaction formula of the compound are shown as follows:
1) light yellow oily liquid, yield 74%.
2) NMR spectrum of the compound (A)1H NMR, 400MHz) characteristics:
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: δ 8.73(d, J ═ 4.4Hz,1H),8.02(d, J ═ 9.2Hz,1H),7.45(d, J ═ 2.8Hz,1H),7.34-7.38(m,2H),6.51(d, J ═ 7.2Hz,1H),5.79-5.88(m,1H),4.99-5.04(m,2H),3.96(s,3H),3.40(q, J ═ 8.4Hz,1H),3.11-3.15(m,1H),3.08(dd, J ═ 14.0Hz,10.0Hz,1H),2.58-2.70(m,2H),2.35-2.39(m,2H),2.28(s,1H),1.85-1.87(m,2H),1.70-1.73(m,1H),1.58-1.63(m,2H),1.50-1.57(m,2H),1.21-1.26(m,6H),0.83-0.87(m,3H)。
3) HRMS (ESI) of the compound Calcd for C27H37N2O3([M+H]+),437.2799；found,437.2801。
4) The reaction formula is as follows:
the structural formula of the 9R-acyloxyquinine derivative in the embodiment 6 is shown as 3f, and the physicochemical property and the reaction formula of the compound are shown as follows:
1) white solid, melting point 178-179 ℃, yield 21%.
2) NMR spectrum of the compound (A)1H NMR, 400MHz) characteristics:
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: δ:8.73(d, J ═ 4.4Hz,1H),8.08-8.11(m,2H),8.03(d, J ═ 9.2Hz,1H),7.58-7.62(m,1H),7.48-7.52(m,3H),7.39-7.43(m,2H),6.74(d, J ═ 6.8Hz,1H),5.80-5.89(m,1H),4.98-5.05(m,2H),3.98(s,3H),3.47-3.51(m,1H),3.18-3.25(m,1H),3.12 (m, ddh), J ═ 14.0Hz,10.0Hz,1H),2.64-2.74(m,2H),2.30-2.32(m,1H), 1.90-1H (m,1H), 1.60-1H, 62-1H, and 1H.
3) HRMS (ESI) of the compound Calcd for C27H29N2O3([M+H]+),429.2173；found,429.2177。
4) The reaction formula is as follows:
the structural formula of the 9R-acyloxyquinine derivative in the embodiment 7 is shown as 3g, and the physicochemical property and the reaction formula of the compound are shown as follows:
1) white solid with melting point 118-119 deg.c and yield 78%.
2) NMR spectrum of the compound (A)1H NMR，400MHz) characteristics:
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: δ:8.74(d, J ═ 4.4Hz,1H),8.01-8.04(m,2H),7.53(d, J ═ 2.4Hz,1H),7.41-7.45(m,2H),7.39(dd, J ═ 9.2Hz,2.4Hz,1H),7.28-7.31(m,1H),7.18-7.24(m,1H),6.74(d, J ═ 6.8Hz,1H),5.80-5.89(m,1H),4.98-5.04(m,2H),3.97(s,3H),3.52(q, J ═ 8.0Hz,1H),3.17-3.25(m,1H),3.11(dd, J ═ 13.6, 10.0, 1H), 1.63-3.53 (m,1H),1.7, 1H), 1.58-3.25 (m,1H),3.11(dd, J ═ 13.6, 10.0, 1H), 1H, and 1H.
3) HRMS (ESI) of the compound Calcd for C28H31N2O3([M+H]+),443.2329；found,443.2325。
4) The reaction formula is as follows:
the structural formula of the 9R-acyloxy quinine derivative in the embodiment 8 is shown as 3h, and the physicochemical property and the reaction formula of the compound are shown as follows:
1) the product is light yellow solid, the melting point is 105-106 ℃, and the yield is 71%.
2) NMR spectrum of the compound (A)1H NMR, 400MHz) characteristics:
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: δ:8.72(d, J ═ 4.8Hz,1H),8.02(d, J ═ 9.2Hz,1H),7.88-7.91(m,2H),7.53(d, J ═ 2.8Hz,1H),7.36-7.43(m,4H),6.75(d, J ═ 6.4Hz,1H),5.80-5.89(m,1H),4.98-5.04(m,2H),3.98(s,3H),3.48-3.51(m,1H),3.18-3.21(m,1H),3.12(dd, J ═ 14.0Hz,10.0Hz,1H),2.64-2.74(m,2H),2.41(s,3H),2.30(s,1H), 1.95(m, 1.95H), 1.75(m, 1H), 1H).
3) HRMS (ESI) of the compound Calcd for C28H31N2O3([M+H]+),443.2329；found,443.2328。
4) The reaction formula is as follows:
the structural formula of the 9R-acyloxyquinine derivative in example 9 is shown in fig. 3i, and the physicochemical properties and the reaction formula of the compound are shown as follows:
1) white solid, 9R: 1 for 9S: 1, yield 69%.
2) NMR spectrum of the compound (A)1H NMR, 400MHz) characteristics:
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: δ 8.71(d, J ═ 4.4Hz,0.5H),8.02(d, J ═ 9.2Hz,0.5H),7.97-7.99(m,1H),7.51(d, J ═ 2.8Hz,0.5H),7.41-7.45(m,2H),7.38(dd, J ═ 9.2Hz,2.8Hz,0.5H),7.18-7.28(m,3.5H),6.73(d, J ═ 6.4Hz,0.5H),6.27(d, J ═ 8.0Hz,1H),5.80-5.88(m,0.5H),4.98-5.04(m,1H),4.03-4.11(m,1H),3.98(s,1.5H), 3.44-5H (m, 3.3.5H), 3.3.3.3-5H), 3.3.3.3.3.3-5H, 3.3.3.3 (m, 3.3.3, 3.3-2H), 3.3.3.3, 3.5H, 3.3.3.3, 3.3.5H, 3, 2H, 3.3.3.3, 3, 3.5H, 3, 2H, 3, 2H, 3, 2.5H),1.81-1.83(m,1H),1.66-1.71(m, 2H).
3) The reaction formula is as follows:
the structural formula of the 9R-acyloxyquinine derivative in the embodiment 10 is shown as 3j, and the physicochemical property and the reaction formula of the compound are shown as follows:
1) white solid, 9R: 1 for 9S: 1, yield 53%.
2) NMR spectrum of the compound (A)1H NMR, 400MHz) characteristics:
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: δ:8.71(d, J ═ 4.4Hz,0.5H),8.03-8.07(m,1H),8.02(d, J ═ 9.2Hz,0.5H),7.53-7.55(m,2H),7.51(d, J ═ 2.8Hz,0.5H),7.42(d, J ═ 4.4Hz,0.5H),7.38(dd, J ═ 9.2Hz,2.8Hz,0.5H),6.93-9.97(m,1H),6.87-6.91(m,2H),6.72(d, J ═ 6.4Hz,0.5H),6.05(d, J ═ 8.0Hz,1H),5.80-5.88(m,0.5H),4.98-5 (m,1H), 3.3.53-3.3H, 3.3.53H, 3.3.3H, 3.3H, 3.3, 3H, 3.3, 3.5H), 3.3.3H, 3.3H, 3, 3.5H, 3, 3.7 (d, 3.7H), 3.7H, 3.6, 3z,10.0Hz,0.5H),2.63-2.73(m,1H),2.29-2.30(m,0.5H),2.02-2.09(m,1.5H),1.90-1.94(m,2.5H),1.81-1.83(m,1H),1.70-1.74(m,2H)。
3) The reaction formula is as follows:
the structural formula of the 9R-acyloxyquinine derivative in the embodiment 11 is shown as 3k, and the physicochemical property and the reaction formula of the compound are shown as follows:
1) white solid with melting point of 72-74 ℃ and yield of 21%.
2) NMR spectrum of the compound (A)1H NMR, 400MHz) characteristics:
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: δ:8.70(d, J ═ 4.8Hz,1H),8.01-8.06(m,3H),7.49-7.53(m,3H),7.36-7.41(m,2H),6.82(d, J ═ 5.2Hz,1H),5.77-5.86(m,1H),4.98-5.05(m,2H),3.99(s,3H),3.45-3.51(m,1H),3.23-3.30(m,1H),3.18(dd, J ═ 14.0Hz,10.0Hz,1H),2.69-2.79(m,2H),2.31-2.34(m,1H),1.91-1.93(m,1H),1.81-1.88(m,2H),1.50-1.70(m, 1H), 1.9H, 1H).
3) HRMS (ESI) of the compound Calcd for C31H37N2O3([M+H]+),485.2799；found,485.2800。
4) The reaction formula is as follows:
the structural formula of the 9R-acyloxyquinine derivative in the embodiment 12 is shown in 3l, and the physicochemical property and the reaction formula of the compound are shown as follows:
1) white solid with a melting point of 137-138 ℃ and a yield of 69%.
2) NMR spectrum of the compound (A)1H NMR, 400MHz) characteristics:
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: δ 8.76(d, J ═ 4.4Hz,1H),8.04(d, J ═ 9.2Hz,1H),7.85(dd,J＝8.0Hz,1.6Hz,1H),7.32-7.53(m,6H),6.77(d,J＝7.2Hz,1H),5.80-5.89(m,1H),4.98-5.04(m,2H),3.97(s,3H),3.54(q,J＝8.4Hz,1H),3.15-3.23(m,1H),3.09(dd,J＝14.0Hz,10.0Hz,1H),2.62-2.72(m,2H),2.29(s,1H),1.94-2.02(m,1H),1.87-1.91(m,1H),1.66-1.71(m,2H),1.53-1.59(m,1H)。
3) HRMS (ESI) of the compound Calcd for C27H28ClN2O3([M+H]+),463.1783；found,463.1787。
4) The reaction formula is as follows:
the structural formula of the 9R-acyloxyquinine derivative in example 13 is shown in fig. 3m, and the physicochemical properties and the reaction formula of the compound are shown as follows:
1) white solid with a melting point of 157-158 ℃ and a yield of 72%.
2) NMR spectrum of the compound (A)1H NMR, 400MHz) characteristics:
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: δ 8.73(d, J ═ 4.4Hz,1H),8.00-8.03(m,3H),7.49-7.51(m,1H),7.43-7.46(m,2H),7.36-7.41(m,2H),6.73(d, J ═ 6.8Hz,1H),5.80-5.89(m,1H),4.99-5.05(m,2H),3.98(s,3H),3.46-3.52(m,1H),3.14-3.22(m,1H),3.11(dd, J ═ 14.0Hz,10.0Hz,1H),2.63-2.73(m,2H),2.30(s,1H),1.91-1.97(m,2H),1.65-1.70(m, 1H), 1.59-1H (m, 1H).
3) HRMS (ESI) of the compound Calcd for C27H28ClN2O3([M+H]+),463.1783；found,463.1785。
4) The reaction formula is as follows:
the structural formula of the 9R-acyloxyquinine derivative in example 14 is shown in fig. 3n, and the physicochemical properties and the reaction formula of the compound are shown as follows:
1) and white solid with a melting point of 142-143 ℃ and a yield of 47%.
2) NMR spectrum of the compound (A)1H NMR, 400MHz) characteristics:
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: δ:8.77(d, J ═ 4.8Hz,1H),8.04(d, J ═ 9.2Hz,1H),7.78-7.80(m,1H),7.66-7.68(m,1H),7.53(d, J ═ 2.8Hz,1H),7.50(d, J ═ 4.4Hz,1H),7.32-7.40(m,3H),6.77(d, J ═ 7.6Hz,1H),5.81-5.89(m,1H),4.99-5.05(m,2H),3.97(s,3H),3.55(q, J ═ 8.4Hz,1H),3.15-3.22(m,1H),3.09 (ddd, 14.0Hz,10.0, 1H), 2.62-1H, 62, 1H),1.73 (m,1H), 1.73-5.70H, 1H), 1H.
3) HRMS (ESI) of the compound Calcd for C27H28BrN2O3([M+H]+),507.1278；found,507.1275。
4) The reaction formula is as follows:
the structural formula of the 9R-acyloxyquinine derivative in example 15 is shown in fig. 3o, and the physicochemical properties and the reaction formula of the compound are shown below:
1) white solid, melting point 176-177 ℃, yield 54%.
2) NMR spectrum of the compound (A)1H NMR, 400MHz) characteristics:
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: δ:8.73(d, J ═ 4.4Hz,1H),8.03(d, J ═ 9.2Hz,1H),7.93-7.95(m,2H),7.60-7.62(m,2H),7.50(d, J ═ 2.8Hz,1H),7.36-7.40(m,2H),6.73(d, J ═ 7.2Hz,1H),5.80-5.89(m,1H),4.99-5.05(m,2H),3.98(s,3H),3.46-3.52(m,1H),3.14-3.21(m,1H),3.11(dd, J ═ 14.0Hz,10.0Hz,1H),2.64-2.72(m,2H),2.31(s,1H),1.90 (m,1H), 1.97, 1H, 1(m,1H), 1H, and 1H.
3) HRMS (ESI) of the compound Calcd for C27H28BrN2O3([M+H]+),507.1278；found,507.1285。
4) The reaction formula is as follows:
the structural formula of the 9R-acyloxyquinine derivative in the embodiment 16 is shown as 3p, and the physicochemical property and the reaction formula of the compound are shown as follows:
1) and silver solid, the melting point is 75-76 ℃, and the yield is 30%.
2) NMR spectrum of the compound (A)1H NMR, 400MHz) characteristics:
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: δ:8.79(d, J ═ 4.4Hz,1H),8.05(d, J ═ 9.2Hz,1H),7.88-7.92(m,1H),7.59-7.66(m,3H),7.49(d, J ═ 2.8Hz,1H),7.43(d, J ═ 4.4Hz,1H),7.40(dd, J ═ 9.2Hz,2.8Hz,1H),6.68(d, J ═ 8.4Hz,1H),5.81-5.90(m,1H),4.98-5.04(m,2H),3.95(s,3H),3.49(q, J ═ 8.4Hz,1H),3.08-3.16(m,1H),3.04(dd, J ═ 0, 10.0, 1H),1.49 (q, J ═ 8.4Hz,1H),3.08-3.16(m,1H),3.04(dd, 0, 1.57, 1H), 1.1H, 1H),1.71, 1H, 2H, 1.
3) HRMS (ESI) of the compound Calcd for C27H28N3O5([M+H]+),474.2023；found,474.2025。
4) The reaction formula is as follows:
the structural formula of the 9R-acyloxyquinine derivative in example 17 is shown in fig. 3q, and the physicochemical properties and reaction formula of the compound are shown below:
1) and the silver solid has a melting point of 89-90 ℃ and a yield of 53%.
2) NMR spectrum of the compound (A)1H NMR, 400MHz) characteristics:
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: δ 8.91(t, J ═ 2.0Hz,1H),8.75(d, J ═ 4.8Hz,1H),8.43-8.46(m,1H),8.37-8.40(m,1H),8.04(d, J ═ 9.2Hz,1H),7.70(t,J＝8.0Hz,1H),7.53(d,J＝2.8Hz,1H),7.44(d,J＝4.4Hz,1H),7.41(dd,J＝9.2Hz,2.8Hz,1H),6.77(d,J＝7.2Hz,1H),5.83-5.92(m,1H),5.05-5.07(m,1H),5.02(d,J＝1.6Hz,1H),4.01(s,3H),3.61(q,J＝8.0Hz,1H),3.15-3.22(m,1H),3.12(dd,J＝14.0Hz,10.0Hz,1H),2.65-2.75(m,2H),2.32(s,1H),1.97-2.05(m,1H),1.91-1.94(m,1H),1.75-1.82(m,1H),1.57-1.67(m,2H)。
3) HRMS (ESI) of the compound Calcd for C27H28N3O5([M+H]+),474.2023；found,474.2023。
4) The reaction formula is as follows:
the structural formula of the 9R-acyloxyquinine derivative in example 18 is shown in 3R, and the physicochemical properties and the reaction formula of the compound are shown as follows:
1) and white solid with a melting point of 162-163 ℃ and a yield of 42%.
2) NMR spectrum of the compound (A)1H NMR, 400MHz) characteristics:
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: δ:8.79(d, J ═ 4.8Hz,1H),8.05(d, J ═ 9.2Hz,1H),7.88-7.92(m,1H),7.59-7.66(m,3H),7.48(d, J ═ 2.8Hz,1H),7.43(d, J ═ 4.4Hz,1H),7.40(dd, J ═ 9.2Hz,2.4Hz,1H),6.67(d, J ═ 8.4Hz,1H),5.82-5.90(m,1H),4.98-5.04(m,2H),3.95(s,3H),3.43-3.48(m,1H),3.08-3.16(m,1H),3.04(dd, 13.6, 6.88, 6.56 (s,1H), 1.43-3.48 (m,1H),3.08-3.16(m,1H),3.04 (13.6, 6, 6.56, 6, 6.6H), 1H), 1.79(m,1H), 1H).
3) HRMS (ESI) of the compound Calcd for C27H28N3O5([M+H]+),474.2023；found,474.2030。
4) The reaction formula is as follows:
the structural formula of the 9R-acyloxyquinine derivative in example 19 is shown in fig. 3s, and the physicochemical properties and reaction formula of the compound are shown below:
1) and yellow solid, the melting point is 132-133 ℃, and the yield is 55%.
2) NMR spectrum of the compound (A)1H NMR, 400MHz) characteristics:
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: δ:8.75(d, J ═ 4.4Hz,1H),8.54(d, J ═ 2.0Hz,1H),8.18(dd, J ═ 8.4Hz,2.0Hz,1H),8.04(d, J ═ 9.2Hz,1H),7.68(d, J ═ 8.4Hz,1H),7.49(d, J ═ 2.4Hz,1H),7.38-7.41(m,2H),6.74(d, J ═ 7.6Hz,1H),5.82-5.91(m,1H),5.05-5.07(m,1H),5.02(d, J ═ 1.6Hz,1H),3.99(s,3H),3.58(q, J ═ 8.4, 1H), 3.02 (d, J ═ 1.6H), 3.65 (m,1H),1.65 (m,1H), 1.19 (m,1H),1.65 (m, 1.85H), 1.14.2H, 1H), 1H.
3) HRMS (ESI) of the compound Calcd for C27H27ClN3O5([M+H]+),508.1634；found,508.1639。
4) The reaction formula is as follows:
the structural formula of the 9R-acyloxyquinine derivative in example 20 is shown in fig. 3t, and the physicochemical properties and the reaction formula of the compound are shown as follows:
1) yellow oily liquid, yield 28%.
2) NMR spectrum of the compound (A)1H NMR, 400MHz) characteristics:
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: δ:8.53(d, J ═ 4.4Hz,1H),7.98(d, J ═ 9.2Hz,1H),7.88(dd, J ═ 8.0Hz,1.6Hz,2H),7.83(dd, J ═ 7.2Hz,2.0Hz,1H),7.38-7.50(m,4H),7.34(dd, J ═ 9.2Hz,2.4Hz,1H),7.25-7.26(m,1H),6.95(d, J ═ 4.4Hz,1H),6.48(d, J ═ 6.0Hz,1H),5.63-5.72(m,1H),4.90-4.95(m,2H),4.13(s,2H),3.82(s,3H), 3.3.15-5.72 (m,1H), 5.90-4.95 (m,2H),4.13(s,2H),3.82(s,3H), 3.15.65 (m,1H),1.65 (m, 1.5.78H), 1.5 (m,1H), 1.49-2H), 1.78(m,1H), 1H, 1.78-2H), 1H,1H),1.22-1.37(m,3H)。
3) HRMS (ESI) of the compound Calcd for C32H33N2O3([M+H]+),493.2486；found,493.2488。
4) The reaction formula is as follows:
the structural formula of the 9R-acyloxyquinine derivative in example 21 is shown in fig. 3u, and the physicochemical properties and the reaction formula of the compound are shown as follows:
1) white solid with a melting point of 134-135 ℃ and a yield of 44%.
2) NMR spectrum of the compound (A)1H NMR, 400MHz) characteristics:
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: δ:8.81-8.82(m,2H),8.74(d, J ═ 4.8Hz,1H),8.04(d, J ═ 9.2Hz,1H),7.87-7.88(m,2H),7.49(d, J ═ 2.8Hz,1H),7.38-7.41(m,2H),6.74(d, J ═ 7.2Hz,1H),5.81-5.90(m,1H),5.01-5.06(m,2H),3.98(s,3H),3.55(q, J ═ 8.0Hz,1H),3.12-3.20(m,1H),3.11(dd, J ═ 14.0Hz,10.0, 1H),2.64-2.74(m,2H),2.28-2.34(m,1H),1.90 (m,1H), 1.78-5.78 (m,2H), 3.1H).
3) HRMS (ESI) of the compound Calcd for C26H28N3O3([M+H]+),430.2125；found,430.2122。
4) The reaction formula is as follows:
the structural formula of the 9R-acyloxyquinine derivative in example 22 is shown in fig. 3v, and the physicochemical properties and reaction formula of the compound are shown below:
1) and white solid with a melting point of 155-156 ℃ and a yield of 24 percent.
2) NMR spectrum of the compound (A)1H NMR, 400MHz) characteristics:
substituted by deuteriumCDCl3TMS is an internal standard, where the peak assignments are: δ 9.32(dd, J ═ 2.4Hz,1.2Hz,1H),8.82(dd, J ═ 4.8Hz,1.6Hz,1H),8.75(d, J ═ 4.8Hz,1H),8.29-8.32(m,1H),8.04(d, J ═ 9.2Hz,1H),7.50(d, J ═ 2.8Hz,1H),7.37-7.44(m,3H),6.75(d, J ═ 6.8Hz,1H),5.81-5.90(m,1H),5.00-5.06(m,2H),3.99(s,3H),3.56(q, J ═ 8.0Hz,1H),3.15-3.22(m,1H),3.11 (J ═ 11, 10.0Hz,1H), 1.81-10.70 (m,1H), 1.14H), 3.14.14.70 (m,1H), 3.73-2H, 1H, 3.14.81-2H), 3.14.14 (m,1H), 3.73-2H).
3) HRMS (ESI) of the compound Calcd for C26H28N3O3([M+H]+),430.2125；found,430.2130。
4) The reaction formula is as follows:
example 24
A botanical pesticide is prepared from the compound 3a in example 1 and acetone, wherein the concentration of the compound 3a is 1 mg/mL.
In other examples of the plant pesticide, the active ingredient may include any one of the compounds 3b to v in examples 2 to 22.
In other embodiments of the botanical insecticide, the active ingredient comprises quinine.
The pesticide can be prepared into powder, spray and the like by referring to the application mode of the prior botanical pesticide, and can also be compounded with other types of pesticides.
The botanical insecticide has small influence on the natural environment, and can be used alternately with other types of insecticides to improve the insecticidal effect.
The application of quinine and 9R-acyloxy quinine derivatives in the aspect of preventing and controlling lepidoptera pests is realized in the following test examples.
Test example 1 Activity for measuring armyworm-killing activity of lepidopteran pests
1. Test compounds: quinine and 9R-acyloxyquinine derivatives 3 a-v.
2. Positive control: a commercial botanical insecticide, Toosendanin (Toosendanin).
3. Test organisms: three-year old pre-armyworm (Mythimna seperate Walker).
4. The determination method comprises the following steps: feeding poison by adopting a small leaf dish adding method, changing normal corn leaves after 48 hours for feeding until eclosion, wherein the detailed method comprises the following steps:
① the test insect is early armyworm of three ages, and is prepared by adding small leaf disc, with toosendanin as positive control and acetone as blank control, and the concentration of the sample is 1 mg/mL;
② repeating each sample for three times, selecting 10 healthy and uniform early-stage armyworms of three ages, and breeding in a culture dish with diameter of 9cm, spreading a layer of filter paper at the bottom of the culture dish for keeping moisture;
③ cutting fresh corn leaves into 1 × 1cm2Soaking the small leaf disk in the prepared sample liquid medicine and the reference liquid medicine for 3 seconds, naturally airing, feeding the test insects, adding the small leaf disk in time after the test insects eat the small leaf disk, and feeding the normal leaves until emergence after 48 hours;
④ breeding conditions comprise 25 + -2 deg.C of temperature, 65-80% of relative humidity, 12h of illumination time and 12h of dark time;
⑤ the feeding amount, the number of live mouths and the expression symptoms of the test insects are recorded regularly, and the corrected death rate (%) of the test insects in different periods is calculated according to the following formula:
5. insecticidal Activity measurement results (see Table 2)
Table 2: determination result of activity of 9R-acyloxy quinine derivatives 3a-v in killing armyworm at concentration of 1mg/mL
aThe experiment was repeated three times.
6. Conclusion
The appearance forms of the armyworms of each group are photographed at a larval stage, a pupal stage and a moth stage respectively, wherein the representative diagrams of the control group and the abnormal larval stage are shown in figure 4, and the representative diagrams of the control group and the abnormal moth stage are shown in figure 5.
The result shows that the short-term effect of quinine on armyworm is equivalent to that of toosendanin, and the long-term effect is better than that of toosendanin; the 9R-acyloxy quinine derivatives disclosed by the invention have obvious effect on preventing armyworms, wherein the control effect of the compounds 3m and 3v on the armyworms is better than that of a commercial botanical insecticide, namely toosendanin, and the control effect of the compound 3k on the armyworms is equal to that of the toosendanin, and the compounds can be used for preparing the botanical insecticides.
Claims (10)
1. A9R-acyloxy quinine derivative is characterized in that the structural formula of the 9R-acyloxy quinine derivative is shown as a formula I;
in the formula I, R is selected from any one of alkyl with 1-6 carbon atoms, phenyl substituted by substituent, naphthalene and pyridyl; the substituent in the substituent-substituted phenyl is one or more of alkyl with 1-4 carbon atoms, alkoxy with 1-3 carbon atoms, halogen and nitro; the number of carbon atoms of the alkylene group in the naphthalene group is 1 to 3.
2. The 9R-acyloxyquinine derivative according to claim 1, wherein in formula I, R is selected from any one of methyl, ethyl, n-propyl, n-pentyl, n-hexyl, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methoxyphenyl, 4-tert-butylphenyl, 2-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 4-bromophenyl, 2-nitrophenyl, 3-nitrophenyl, 4-chloro-3-nitrophenyl, 1-naphthylmethylene, 3-pyridyl and 4-pyridyl.
3. The process for preparing a 9R-acyloxyquinine derivative according to claim 1, characterized by comprising the following steps: performing esterification reaction on quinine, R-COOH, a water reducing agent and a catalyst in an organic solvent to obtain the quinine-COOH-containing organic solvent;
r in the R-COOH is selected from any one of alkyl with 1-6 carbon atoms, phenyl substituted by substituent, naphthalene and pyridyl; the substituent in the substituent-substituted phenyl is one or more of alkyl with 1-4 carbon atoms, alkoxy with 1-3 carbon atoms, halogen and nitro; the number of carbon atoms of the alkylene group in the naphthalene group is 1 to 3.
4. The process for the preparation of a 9R-acyloxyquinine derivative according to claim 3, characterized in that the molar ratio of quinine to R-COOH is 1: 1-1.5.
5. The process for preparing a 9R-acyloxyquinine derivative according to claim 3 or 4, characterized in that the esterification reaction is carried out under the following reaction conditions: reacting at room temperature for 24-96 h.
6. The application of quinine or 9R-acyloxy quinine derivatives in preventing and treating lepidoptera pests is characterized in that the structural formula of the 9R-acyloxy quinine derivatives is shown as a formula I;
in the formula I, R is selected from any one of alkyl with 1-6 carbon atoms, phenyl substituted by substituent, naphthalene and pyridyl; the substituent in the substituent-substituted phenyl is one or more of alkyl with 1-4 carbon atoms, alkoxy with 1-3 carbon atoms, halogen and nitro; the number of carbon atoms of the alkylene group in the naphthalene group is 1 to 3.
7. Use of quinine or a 9R-acyloxyquinine derivative according to claim 6, for the control of lepidopteran pests, characterized in that said lepidopteran pest is a mythimna.
8. Use of quinine or a 9R-acyloxyquinine derivative according to claim 7, for the control of lepidopteran pests, characterized in that said lepidopteran pests are armyworm larvae.
9. Use of quinine or a 9R-acyloxyquinine derivative according to claims 6 or 7 for the control of lepidopteran pests, characterized in that said quinine or 9R-acyloxyquinine derivative controls pests by inducing the abnormal growth of lepidopteran pests.
10. The botanical pesticide is characterized in that the active ingredient of the botanical pesticide comprises quinine or 9R-acyloxy quinine derivatives; the structural formula of the 9R-acyloxy quinine derivative is shown as a formula I;
in the formula I, R is selected from any one of alkyl with 1-6 carbon atoms, phenyl substituted by substituent, naphthalene and pyridyl; the substituent in the substituent-substituted phenyl is one or more of alkyl with 1-4 carbon atoms, alkoxy with 1-3 carbon atoms, halogen and nitro; the number of carbon atoms of the alkylene group in the naphthalene group is 1 to 3.
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