CN101337968A - Carboxylic acid rotenonoxime ester, method for preparing same and applications - Google Patents
Carboxylic acid rotenonoxime ester, method for preparing same and applications Download PDFInfo
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Abstract
The invention discloses carboxylate elliptone oxime ester which has a following chemical structural formula. Carboxylate elliptone oxime ester 1 has a preparation method that elliptone oxime reacts with acylating agent through acid-binding agent and phase transfer catalyst, and carboxylate elliptone oxime ester is obtained through filtering, washing and drying after the reaction is completed. Carboxylate elliptone oxime ester which is a novel compound can be used for preparing pesticide.
Description
Technical field
The present invention relates to new compound of a class and its production and application, specifically is carboxylic acid rotenonoxime ester and its production and application.
Background technology
Tubatoxin (Rotenone) is a kind of natural botanical insecticide and miticide, and it is easy to degraded, and accumulation toxicity is little in environment, does not pollute agroecological environment and agricultural-food, helps promoting the eubiosis.Yet also there are some problems in the use of tubatoxin, as: tubatoxin is easy to oxygenolysis under field conditions (factors) and lost efficacy, thereby the formulation concentrations instability, is difficult for stdn during use.And tubatoxin itself has biological activity preferably, is a kind of ten minutes valuable compounds therefrom.This project has been grasped the tubatoxin structure and has been concerned on the basis with stability, biological activity, tubatoxin is carried out chemical structure transformation and modification, utilize principle of hybridization that the active group oxime ester of agricultural chemicals is incorporated on the molecule of tubatoxin, the carboxylic acid rotenonoxime ester of the synthetic a series of novel structures of design, and the gained compound carried out structural characterization, activity and stability test, expectation obtains biological activity height, the compound of stable performance.Preliminary bioactivity research result shows: the carboxylic acid rotenonoxime ester compounds has insecticidal activity and stability preferably.
Summary of the invention
The object of the present invention is to provide a class carboxylic acid rotenonoxime ester class new compound preparation method and the application of carboxylic acid rotenonoxime ester class new compound in sterilant.
The chemical formula that carboxylic acid rotenonoxime ester class new compound of the present invention has structure shown in the formula I:
Wherein, R is selected from: C
1～C
17Alkyl; X (CH
2)
n, X=Cl, Br, I, F, CN, Ph, n=1～6; Phenyl ring, substituted benzene ring.
The preparation method of described carboxylic acid rotenonoxime ester is that rotenone oxime reacts in appropriate solvent with acylating agent in the presence of acid binding agent, phase-transfer catalyst.Reaction finishes, and filters washing, the dry carboxylic acid rotenonoxime ester that gets.
Described carboxylic acid rotenonoxime ester class new compound has insecticidal activity, can be used for preparing sterilant.
Preparation method of the present invention is undertaken by following chemical equation:
The present invention compared with prior art has following advantage:
Based on nadh dehydrogenase in the tubatoxin pair cell mitochondrial respiratory chain to the structure activity relationship of ubiquinone oxide-reductase enzyme inhibition, a series of carboxylic acid rotenonoxime esters of the synthetic biologically active of design first; New compound has higher biological activity, good stability.The present invention is grasping the tubatoxin structure and stability, biological activity concerns on the basis, kept the necessary structure of biological activity, utilize C=N to substitute and have the acidity that the electrical C=O of strong suction reduces 12a-H, the oxidative degradation that suppresses the 12a position improves the stability of whole molecular structure, according to the principle of hybridization of medicinal design, having preferably in the introducing agricultural chemicals, the oxime ester structure of bactericidal and insecticidal activity improves its biological activity and stability simultaneously.The designed compound of the present invention all has the oxime ester structure with respect to existing tubatoxin.
2. different with tubatoxin, synthetic carboxylic acid rotenonoxime ester good stability.Carboxylic acid rotenonoxime ester needs to become tubatoxin dehydrogenation to form dehydrorotenone through esterase hydrolyzed:
3. She Ji new compound is novel, synthetic operation convenient.Reaction times is short, the yield height.
4. utilize synthetic active carboxylic acid rotenonoxime ester exploitation environment friendly agricultural, be used to prepare sterilant.
Embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
Synthesizing of embodiment 1 propionic acid rotenonoxime ester (1)
20mL acetone, 1.00g rotenone oxime, 0.70g salt of wormwood, 0.05g phase-transfer catalyst 4 bromide stir, and drip the 0.93g propionic anhydride, stirring reaction under the frozen water, and TLC follows the tracks of, and the 2h reaction finishes.Reacting liquid filtering, the filter cake washing with acetone merges organic phase, and evaporated under reduced pressure gets solid, washing, dry white solid 1.10g, the yield 96.5% of getting.m.p.206～210℃；[α]
D 25+231.3(AcOEt)。
1H?NMR(CDCl
3)，δ：1.25(t，J＝7.6Hz，1H，CH
3)，1.76(s，3H，8’-CH
3)，2.53(2×q，J＝7.6Hz，1H，COCH
2)，2.92(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.28(dd，J＝10.0Hz，J＝16Hz，1H，4’-H)，3.69(s，3H，OCH
3)，3.81(s，3H，OCH
3)，4.28(d，J＝12Hz，1H，6-H)，4.58(t，J＝2.8Hz，1H，12a-H)，4.62(dd，J＝12Hz，J＝2.4Hz，1H，6-H)，4.75(d，J＝2.4Hz，1H，6a-H)，4.91(s，1H，7’-H)，5.06(s，1H，7’-H)，5.17(t，J＝8.8Hz，1H，5’-H)，6.39(s，1H，4-H)，6.45(s，1H，1-H)，6.48(d，J＝8.4Hz，1H，10-H)，7.97(d，J＝8.4Hz，1H，11-H)。Ultimate analysis (calculated value): C, 67.10% (67.09%); H, 5.63% (5.85%); N, 3.04% (3.01%).IR (KBr compressing tablet) v/cm
-1: 3063,2963,2934,2879,2856,1780,1620,1514,1199,739.
Synthesizing of embodiment 2 propionic acid rotenonoxime esters (1)
20mL N, dinethylformamide, 1.00g rotenone oxime, 0.4g pyridine stir 30min and drip the 0.27g propionic acid, 150 ℃ of stirring reactions, TLC follows the tracks of, and the 2h reaction finishes.Reacting liquid filtering, the filter cake washing with acetone merges organic phase, and evaporated under reduced pressure gets solid, washing, dry white solid, m.p.206～209 ℃; [α]
D 25+ 231.3 (AcOEt), spectral data is consistent with embodiment 1.
Synthesizing of embodiment 3 propionic acid rotenonoxime esters (1)
20mL chloroform, 1.00g rotenone oxime, 0.50g yellow soda ash, 0.05g phase-transfer catalyst tetramethyl ammonium chloride drip the 0.93g propionic anhydride, 60 ℃ of stirring reactions, and TLC follows the tracks of, and the 2.5h reaction finishes.Reacting liquid filtering, the filter cake washing with acetone merges organic phase, and evaporated under reduced pressure gets solid, washing, dry white solid 8.8g, the yield 77.2% of getting.M.p.206～210 ℃; [α]
D 25+ 231.3 (AcOEt), spectral data is consistent with embodiment 1.
Synthesizing of embodiment 4 propionic acid rotenonoxime esters (1)
5mL tetrahydrofuran (THF), 15mL acetone, 1.00g rotenone oxime, 0.60g sodium bicarbonate stir, and drip the 0.33g propionyl chloride ,-20 ℃ of stirring reactions, and TLC follows the tracks of, and the 1.5h reaction finishes.Reacting liquid filtering, the filter cake washing with acetone merges organic phase, and evaporated under reduced pressure gets solid, washing, dry white solid 1.0g, the yield 92.3% of getting.M.p.206～210 ℃; [α]
D 25+ 231.3 (AcOEt), spectral data is consistent with embodiment 1.
Synthesizing of embodiment 5 propionic acid rotenonoxime esters (1)
20mL ethyl acetate, 1.00g rotenone oxime, 0.75g saleratus, 0.05g phase-transfer catalyst tetramethyl-monoammonium sulfate stir, and drip the 0.93g propionic anhydride, 15 ℃ of stirring reactions, and TLC follows the tracks of, and the 1.5h reaction finishes.Reacting liquid filtering, the filter cake washing with acetone merges organic phase, and evaporated under reduced pressure gets solid, washing, dry white solid 0.65g, the yield 62.7% of getting.M.p.206～210 ℃; [α]
D 25+ 231.3 (AcOEt), spectral data is consistent with embodiment 1.
Synthesizing of embodiment 6 propionic acid rotenonoxime esters (1)
20mL acetone, 1.00g rotenone oxime, 0.70g salt of wormwood, 0.05g phase-transfer catalyst benzyltriethylammoinium chloride drip the 0.93g propionic anhydride, 10 ℃ of stirring reactions, and TLC follows the tracks of, and the 1.5h reaction finishes.Reacting liquid filtering, the filter cake washing with acetone merges organic phase, and evaporated under reduced pressure gets solid, washing, dry white solid 0.70g, the yield 65.1% of getting.M.p.206～210 ℃; [α]
D 25+ 231.3 (AcOEt), spectral data is consistent with embodiment 1.
Synthesizing of embodiment 7 propionic acid rotenonoxime esters (1)
20mL methyl-sulphoxide, 1.00g rotenone oxime, 0.70g salt of wormwood, stirring drip the 0.93g propionic anhydride, back flow reaction, and TLC follows the tracks of, and the 1h reaction finishes.Reacting liquid filtering, the filter cake washing with acetone merges organic phase, and evaporated under reduced pressure gets solid, washing, dry white solid 0.87g, the yield 76.7% of getting.M.p.206～210 ℃; [α]
D 25+ 231.3 (AcOEt), spectral data is consistent with embodiment 1.
Synthesizing of embodiment 8 Mono Chloro Acetic Acid rotenonoxime esters (2)
20mL acetone, rotenone oxime 1.00g, pyridine 0.40g and chloroacetyl chloride 0.90g stir 0.5h, and normal temperature reaction TLC is down followed the tracks of, and the 4h reaction finishes.Reacting liquid filtering, filter cake washing with acetone three times merge organic phase, and evaporated under reduced pressure gets solid, washing, the dry solid 1.1g of reddish-brown, the yield 92.4% of getting.m.p.：168～172℃；[α]
D 25+246(AcOEt)。
1H?NMR(CDCl
3)，δ：1.76(s，3H，8’-CH
3)，2.92(dd，J＝8.4Hz，J＝16Hz，1H，4’-H)，3.28(dd，J＝10.0Hz，J＝16Hz，1H，4’-H)，3.71(s，3H，OCH
3)，3.81(s，3H，OCH
3)，4.28(m，3H，12a-H，CH
2Cl)，4.62(dd，J＝12Hz，J＝2.8Hz，2H，6-H)，4.75(d，J＝2.8Hz，1H，6a-H)，4.92(s，1H，7’-H)，5.06(s，1H，7’-H)，5.18(t，J＝8.8Hz，1H，5’-H)，6.37(d，J＝8.4Hz，1H，10-H)，6.42(s，1H，4-H)，6.45(s，1H，1-H)，7.93(d，J＝8.4Hz，1H，11-H)。Ultimate analysis (calculated value): C, 61.96% (61.79%); H, 5.01% (4.98%); N, 2.92% (2.88%).IR (KBr compressing tablet) v/cm
-1: 3006,2964,2920,2850,1783,1620,1511,1197,772,740.
Synthesizing of embodiment 94-chloro-butyric acid rotenonoxime ester (3)
20mL acetone, 1.50g rotenone oxime, 0.6g pyridine and 1.5g chlorobutanoylchloride, the ice bath stirring reaction, TLC follows the tracks of, and the 3h reaction finishes.Reacting liquid filtering, the filter cake washing with acetone merges organic phase, and evaporated under reduced pressure gets solid, washing, dry orange red solid 1.63g, the yield 86.2% of getting.m.p.179～190℃；[α]
D 25+230(AcOEt)。
1HNMR(CDCl
3)，δ：1.76(s，3H，8’-CH
3)，2.22(m，2H，CH
2)，2.74(m，2H，COCH
2)，2.92(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.27(dd，J＝10.0Hz，J＝16Hz，1H，4’-H)，2.74(t，J＝6.0Hz，2H，CH
2Cl)，3.70(s，3H，OCH
3)，3.81(s，3H，OCH
3)，4.28(d，J＝12Hz，1H，6-H)，4.59(t，J＝2.8Hz，1H，12a-H)，4.62(dd，J＝12Hz，J＝2.4Hz，1H，6-H)，4.75(dJ＝2.4Hz，1H，6a-H)，4.91(s，1H，7’-H)，5.06(s，1H，7’-H)，5.17(t，J＝8.8Hz，1H，5’-H)，6.38(s，1H，4-H)，6.45(s，1H，1-H)，6.48(d，J＝8.4Hz，1H，10-H)，7.96(d，J＝8.4Hz，1H，11-H)。Ultimate analysis (calculated value): C, 63.96% (63.10%); H, 5.54% (5.49%); N, 2.83% (2.73%).IR (KBr compressing tablet) v/cm
-1: 3062,2965,2934,2877,2855,1777,1619,1513,1199,770,738.
Synthesizing of embodiment 10 isopropylformic acid rotenonoxime esters (4)
1.0g rotenone oxime, 20mL benzene, stirring and dissolving adds the 0.13g piperidines, drip the benzole soln 15mL of isobutyryl chloride 0.32g, room temperature reaction 30min, reaction finishes, the saturated common salt washing is told organic phase, ethyl acetate extraction water (15mL * 2), merge organic phase, anhydrous sodium sulfate drying, suction filtration, revolve the steaming precipitation, recrystallization obtains white solid 0.98g, m.p.210～214 ℃, yield 89.0%; [α]
D 25+ 242.5 (AcOEt).
1H-NMR(CDCl
3，400MHz)δ：1.26，1.28(2×d，J＝5.2Hz，6H，2×CH
3)，1.76(s，3H，8’-CH
3)，2.75(sep，J＝6.8HZ，1H，CH)，2.91(dd，J＝8.0HZ，J＝16HZ，1H，4’-H)，3.28(dd，J＝10.0Hz，J＝16Hz，1H，4’-H)，3.70(s，3H，OCH
3)，3.81(s，3H，OCH
3)，4.29(d，J＝12Hz，1H，6-H)，4.54(d，J＝2.8Hz，1H，12a-H)，4.62(dd，J＝12Hz，J＝2.8Hz，1H，6-H)，4.73(d，J＝2.8Hz，1H，6a-H)，4.91(s，1H，7’-H)，5.06(s，1H，7’-H)，5.17(t，J＝8.0Hz，1H，5’-H，)，6.39(s，1H，4-H)6.45(s，1H，1-H)，6.47(d，J＝8.4Hz，1H，10-H)，7.99(d，J＝8.4Hz，1H，11-H)。
Synthesizing of embodiment 11 isopropylformic acid rotenonoxime esters (4)
1.0g rotenone oxime, 20mL N-Methyl pyrrolidone drip ethyl isobutyrate 0.54g, back flow reaction 2h, reaction finishes, and organic phase is told in the saturated common salt washing, ethyl acetate extraction water (15mL * 2), merge organic phase, anhydrous sodium sulfate drying, suction filtration, revolve the steaming precipitation, recrystallization obtains white solid 0.88g, m.p.210～214 ℃, yield 80.2%; [α]
D 25+ 242.5 (AcOEt), spectral data is consistent with embodiment 10.
Synthesizing of embodiment 12 laurostearic acid rotenonoxime esters (5)
1.5g rotenone oxime, 20mL benzene, stirring and dissolving adds the 0.3g Tributylamine, drip the benzole soln 15mL of lauroyl chloride 0.98g, continue reaction 30min, reaction finishes, the saturated common salt washing is told organic phase, ethyl acetate extraction water (15mL * 2), merge organic phase, anhydrous sodium sulfate drying, suction filtration, revolve the steaming precipitation, recrystallization obtains white solid 1.61g, m.p.110～113 ℃, yield 70.1%; [α]
D 25+ 241 (AcOEt).
1H-NMR(CDCl
3，400MHz)δ：0.87(t，J＝6.8Hz，3H，CH
3)，1.24(m，18H，9×CH
2)，1.76(s，3H，8’-CH
3)，2.49(t，J＝6.8Hz，2H，COCH
2)2.92(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.27(dd，J＝10.0Hz，J＝16HZ，1H，4’-H)，3.70(s，3H，OCH
3)，3.81(s，3H，OCH
3)，4.28(d，J＝11.6HZ，1H，6-H)4.61(m，2H，6-H，12a-H)，4.74(s，1H，6a-H，)，4.91(s，1H，7’-H)，5.06(s，1H，7’-H)，5.17(t，J＝8.8HZ，1H，5’-H)，6.39(s，1H，4-H)，6.45(s，1H，1-H)，6.47(d，J＝8.4HZ，1H，10-H)，7.97(d，J＝8.8Hz，1H，11-H)。
Synthesizing of embodiment 13 stearic acid rotenonoxime esters (6)
1.5g rotenone oxime, 20mL benzene, stirring and dissolving adds the 0.3g triethylamine, drip stearyl chloride 1.4g benzole soln 15mL, reaction 30min, reaction finishes, the saturated common salt washing is told organic phase, ethyl acetate extraction water (15mL * 2), merge organic phase, anhydrous sodium sulfate drying, suction filtration, revolve the steaming precipitation, recrystallization obtains white solid 1.52g, m.p.110～115 ℃, yield 60.4%; [α]
D 25+ 246 (AcOEt).
1H-NMR(CDCl
3，400MHz)δ：0.88(t，J＝6.8HZ，3H，CH
3)，1.25～1.36(m，30H，15×CH
2)，1.76(s，3H，8’-CH
3)，2.49(t，J＝6.8HZ，2H，COCH
2)，2.92(dd，J＝8.4Hz，J＝16HZ，1H，4’-H)，3.27(dd，J＝10.0Hz，J＝16Hz，1H，4’-H)，3.69(s，3H，OCH
3)，3.81(s，3H，OCH
3)，4.28(d，J＝12.4Hz，1H，6-H)，4.58(d，J＝4.0Hz，1H，12a-H)，4.60(dd，J＝12.6Hz，J＝2.0Hz，1H，6-H)，4.74(d，J＝2.4Hz，1H，6a-H)，4.91(s，1H，7’-H)，5.06(s，1H，7’-H)，5.17(t，J＝9.2Hz，1H，5’-H，)，6.39(s，1H，4-H)，6.45(s，1H，1-H)，6.47(d，J＝8.8Hz，1H，10-H)，7.97(d，J＝8.8HZ，1H，11-H)。
Synthesizing of embodiment 14 vinylformic acid rotenonoxime esters (7)
With 1.5g rotenone oxime, 20mL benzene, stirring and dissolving adds the 0.5g triethylamine, drip the benzole soln 15mL of acrylate chloride 0.33g, reaction 0.5h is after reaction finishes, washing is told organic phase, ethyl acetate extraction (15mL * 2), merge organic phase, anhydrous sodium sulfate drying, suction filtration, revolve the steaming precipitation, recrystallization obtains white solid 1.47g, m.p.185～187 ℃, yield 81.5%; [α]
D 25+ 240 (AcOEt).
1H-NMR(CDCl
3，400MHz)δ：1.76(s，3H，8’-CH
3)，2.93(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.28(dd，J＝9.6Hz，J＝16Hz，1H，4’-H)，3.68(s，3H，OCH
3)，3.81(s，3H，OCH
3)，4.29(d，J＝12.0Hz，1H，6-H)，4.61(dd，J＝2.4Hz，J＝5.6Hz，1H，6-H)，4.65(d，J＝3.2Hz，1H，12a-H)，4.78(d，J＝3.2Hz，1H，6a-H)，4.92(s，1H，7’-H)，5.06(s，1H，7’-H)，5.18(t，J＝8.8Hz，1H，5’-H)，5.96(dd，J＝1.2Hz，J＝10.4Hz，1H，＝CH
2)，6.28(dd，J＝10.4Hz，J＝17.6Hz，1H，-CH＝)，6.42(s，1H，4-H)，6.45(s，1H，1-H)，6.49(d，J＝8.8HZ，1H，10-H)，6.57(dd，J＝0.8Hz，J＝17.6HZ，1H，＝CH
2)，8.01(d，J＝8.8Hz，1H，11-H)。
Synthesizing of embodiment 15 phenylformic acid rotenonoxime esters (8)
1.5g rotenone oxime, 20mL toluene, stirring and dissolving adds the 0.3g triethylamine, drip the toluene solution 15mL of Benzoyl chloride 0.62g, continue reaction 30min, reaction finishes, the saturated common salt washing is told organic phase, ethyl acetate extraction water (15mL * 2), merge organic phase, anhydrous sodium sulfate drying, suction filtration, revolve the steaming precipitation, recrystallization obtains white solid 1.70g, m.p.180～182 ℃, yield 85.9%; [α]
D 25+ 237.5 (AcOEt).
1H-NMR(CDCl
3，400MHz)δ：1.77(s，3H，8’-CH
3)，2.95(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.30(dd，J＝9.6Hz，J＝16Hz，1H，4’-H)，3.64(s，3H，OCH
3)，3.83(s，3H，OCH
3)，4.32(d，J＝11.6HZ，1H，6-H)，4.66(m，2H，12a-H，6-H)，4.86(d，J＝2.0HZ，1H，6a-H)，4.92(s，1H，7’-H)，5.08(s，1H，7’-H)，5.19(t，J＝9.2HZ，1H，5’-H，)，6.48(s，1H，4-H)，6.51(d，J＝8.8Hz，1H，10-H)，6.59(s，1H，1-H)，7.45(t，J＝7.6HZ，2H，C
6H
5?3，5-H)，7.60(t，J＝7.6Hz，1H，C
6H
5?4-H)，8.07(m，3H，C
6H
52，6-H，11-H)。
Synthesizing of embodiment 16 toluylic acid rotenonoxime esters (9)
1.5g rotenone oxime, 20mL toluene, stirring and dissolving adds the 0.2g piperidines, drip the benzole soln 15mL of phenyllacetyl chloride 0.56g, continue reaction 40min, reaction finishes, the saturated common salt washing is told organic phase, ethyl acetate extraction water (15mL * 2), merge organic phase, anhydrous sodium sulfate drying, suction filtration, revolve the steaming precipitation, recrystallization obtains white solid 1.2g, m.p.188～192 ℃, yield 65%.
1H-NMR(CDCl
3，300MHz)δ：1.75(s，3H，8’-CH
3)，2.90(dd，J＝8.1Hz，J＝15.6HZ，1H，4’-H)，3.30(dd，J＝9.9Hz，J＝15.6HZ，1H，4’-H)，3.50(s，3H，OCH
3)，3.72(d，J＝4.8HZ，1H，CH
2)，3.79(d，J＝4.8Hz，1H，CH
2)，3.81(s，3H，OCH
3)，4.21(d，J＝12.3Hz，1H，6-H)，4.53(m，2H，12a-H，6-H)，4.63(d，J＝4.5Hz，1H，6a-H)，4.92(s，1H，7’-H)，5.05(s，1H，7’-H)，5.16(t，J＝9.0Hz，1H，5’-H)，6.23(s，1H，4-H)，6.44(d，J＝8.4Hz，1H，10-H)，6.46(s，1H，1-H)，7.22～7.36(m，5H，C
6H
5)，7.94(d，J＝8.4HZ，1H，11-H)。
Embodiment 17 carboxylic acid rotenonoxime esters are to the mensuration of housefly poisoning
The mixture that accurately takes by weighing earlier 1g white sugar and milk powder is that 2.5cm, height are in the test tube of 7.5cm in diameter, with the carboxylic acid rotenonoxime ester acetone solution, get 1mL carboxylic acid rotenonoxime ester solution in the test tube that white sugar and milk powder are housed, shake up, make testing compound dry up standby with fan equably attached on white sugar and the milk powder.Select the housefly of 3～4d neat and consistent health of sprouting wings, use etherization, in every pipe, insert 10 boss flies rapidly.Make blank with acetone and handle 24h, observe the reaction of examination worm, and write down dead borer population, calculate mortality ratio.
Mortality ratio (%)=(dead borer population/confession examination worm sum) * 100%
When carboxylic acid rotenonoxime ester concentration is 300mg/L, observe the interior poisoning situation of 24h to housefly.
Carboxylic acid rotenonoxime ester is to the poisoning result of housefly: propionic acid rotenonoxime ester (1), Mono Chloro Acetic Acid rotenonoxime ester (2) and chloro-butyric acid rotenonoxime ester (3) are when 300mg/L, and the mortality ratio of housefly being handled 24h is respectively 80%, 90% and 95%.
Embodiment 18 carboxylic acid rotenonoxime esters are measured the poisoning of worms such as beet armyworm, prodenia litura
Beet armyworm and prodenia litura are adopted and soak the leaf feeding method, select fresh, clean cabbage leaves for use, and cleaning, airing are made the leaf dish of some amount with punch tool (d=1cm).With acetone carboxylic acid rotenonoxime ester is diluted respectively, be configured to 100mg/L.Fresh cabbage leaves dish is flooded 5s in each solution, the nature airing, to handle the leaf dish place the bottom with a filter paper of the same size preserve moisture, diameter is the 10cm culture dish, 6 leaf dish of each culture dish are built lid, carry out mark, and in contrast with acetone dipping leaf dish, picking examination worm, each culture dish 10 cephalont is put in 25 ± 1 ℃ the observation ward.Per 10 is 1 treatment group, repeats 3 times.Treat its get the food finish, add fresh, clean cabbage leaves.Respectively at 4d, 6d observes record examination worm death condition.Touch polypide with cotton swab, that touches motionlessly is the death standard of larva, calculates mortality ratio.When carboxylic acid rotenonoxime ester concentration is 100mg/L, handle the poisoning situation of observing beet armyworm in 4 days.
Carboxylic acid rotenonoxime ester is to the poisoning result of beet armyworm: propionic acid rotenonoxime ester (1), Mono Chloro Acetic Acid rotenonoxime ester (2) and chloro-butyric acid rotenonoxime ester (3) are respectively 57.1%, 60% and 73.3% to the lethality rate of beet armyworm.
Embodiment 19 carboxylic acid rotenonoxime esters are measured the poisoning of mythimna separata, aphid, leafhopper, red spider
Mythimna separata is adopted the Potter spray method, and concentration is 1.0g/L; Green rice leafhopper is adopted pickling process, and concentration is 0.5g/L; Black bean aphid adopts pickling process, and concentration is 0.5g/L; Two-spotted spider mite is adopted pickling process, and concentration is 0.5g/L; Handle 48h.
Insecticidal activity result: Mono Chloro Acetic Acid rotenonoxime ester (2) is when 1.0g/L, and processing 48h reaches 86.36% to the lethality rate of mythimna separata; When 0.50g/L, processing 48h reaches 71.80% to the lethality rate of leafhopper.Propionic acid rotenonoxime ester (1) is when 0.5g/L, and processing 48h reaches 54.17% to the lethality rate of leafhopper.Chloro-butyric acid rotenonoxime ester (3) processing 48h reaches 100% to the lethality rate of mythimna separata; The carboxylic acid rotenonoxime ester compounds all has certain poisoning ability to leafhopper.Mono Chloro Acetic Acid rotenonoxime ester and chloro-butyric acid rotenonoxime ester show very high poisoning ability to leafhopper in the carboxylic acid rotenonoxime ester compounds.
Claims (8)
1, a class carboxylic acid rotenonoxime ester is characterized in that described compound has chemical structural formula shown in the formula I:
Wherein, R is selected from: C
1～C
17Alkyl; X (CH
2)
n, X=Cl, Br, I, F, CN, Ph, n=1～6; Phenyl ring, substituted benzene ring.
2, the preparation method of the described carboxylic acid rotenonoxime ester of claim 1 is characterized in that, the preparation method with compound of structural formula shown in the formula I is that rotenone oxime reacts in appropriate solvent with acylating agent in the presence of acid binding agent, phase-transfer catalyst.Reaction finishes, and filters washing, the dry carboxylic acid rotenonoxime ester that gets.
According to the preparation method of the described carboxylic acid rotenonoxime ester of claim 2, it is characterized in that 3, described acid binding agent is one or more in yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, triethylamine, Tributylamine, piperidines and the pyridine.
4, according to the preparation method of the described carboxylic acid rotenonoxime ester of claim 2, it is characterized in that phase-transfer catalyst is one or more in tetramethyl ammonium chloride, tetraethylammonium bromide, Tetrabutyl amonium bromide, 4-butyl ammonium hydrogen sulfate, benzyltriethylammoinium chloride, the tetrabutylammonium iodide.
According to the preparation method of the described carboxylic acid rotenonoxime ester of claim 2, it is characterized in that 5, acylating agent is a kind of in acyl chlorides, carboxylic acid, carboxylicesters, the carboxylic acid anhydride.
According to the preparation method of the described carboxylic acid rotenonoxime ester of claim 2, it is characterized in that 6, temperature of reaction is-20 ℃～150 ℃.
7, according to the preparation method of the described carboxylic acid rotenonoxime ester of claim 2, it is characterized in that, reaction solvent is acetone, benzene, substituted benzene, ethyl acetate, chloroform, tetrahydrofuran (THF), N-Methyl pyrrolidone, N, one or more in dinethylformamide, the methyl-sulphoxide.
8, the application of the described carboxylic acid rotenonoxime ester of claim 1 is characterized in that, the compound of structural formula shown in the formula I be used to prepare sterilant.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805333A (en) * | 2010-04-16 | 2010-08-18 | 湖南大学 | Cyclorotenoid, preparation method and application thereof |
| CN102295650A (en) * | 2011-06-30 | 2011-12-28 | 湖南大学 | Rotenone oxime allyl / propargyl ether and application of the same as insecticide |
| CN102336764A (en) * | 2011-06-21 | 2012-02-01 | 兰州大学 | Spin-labeling rotenone oxime ester, its preparation method and application |
| CN103288810A (en) * | 2013-06-20 | 2013-09-11 | 湖南大学 | Cyclopropyl derris hydrazide, and preparation method and application thereof |
| CN105566022A (en) * | 2014-10-08 | 2016-05-11 | 中国石油化工股份有限公司 | Method for synthesizing oxime ester through transesterification |
-
2008
- 2008-08-27 CN CN2008100321736A patent/CN101337968B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805333A (en) * | 2010-04-16 | 2010-08-18 | 湖南大学 | Cyclorotenoid, preparation method and application thereof |
| CN102336764A (en) * | 2011-06-21 | 2012-02-01 | 兰州大学 | Spin-labeling rotenone oxime ester, its preparation method and application |
| CN102336764B (en) * | 2011-06-21 | 2013-10-30 | 兰州大学 | Spin-labeling rotenone oxime ester, its preparation method and application |
| CN102295650A (en) * | 2011-06-30 | 2011-12-28 | 湖南大学 | Rotenone oxime allyl / propargyl ether and application of the same as insecticide |
| CN103288810A (en) * | 2013-06-20 | 2013-09-11 | 湖南大学 | Cyclopropyl derris hydrazide, and preparation method and application thereof |
| CN103288810B (en) * | 2013-06-20 | 2015-03-25 | 湖南大学 | Cyclopropyl derris hydrazide, and preparation method and application thereof |
| CN105566022A (en) * | 2014-10-08 | 2016-05-11 | 中国石油化工股份有限公司 | Method for synthesizing oxime ester through transesterification |
| CN105566022B (en) * | 2014-10-08 | 2017-07-11 | 中国石油化工股份有限公司 | A kind of ester exchange synthesizes the method for oxime ester |
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