CN101284836A - Rotenone oxime ether, preparation method and applications thereof - Google Patents

Rotenone oxime ether, preparation method and applications thereof Download PDF

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CN101284836A
CN101284836A CNA2008100314412A CN200810031441A CN101284836A CN 101284836 A CN101284836 A CN 101284836A CN A2008100314412 A CNA2008100314412 A CN A2008100314412A CN 200810031441 A CN200810031441 A CN 200810031441A CN 101284836 A CN101284836 A CN 101284836A
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rotenone
rotenone oxime
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oxime ether
ether
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CN101284836B (en
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胡艾希
王超
邹孟
欧晓明
徐汉虹
叶姣
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Hunan University
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Hunan University
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Abstract

The invention discloses a rotenone oxime-ether with chemical structural formula as showed on the right. The preparation method of rotenone oxime-ether I and II comprises the following steps of: allowing the rotenone oxime, catalyst, alkali and aldylating agent to react in solvent and to be filtered, washed and dried after the reaction; and the rotenone oxime-ether is obtained. New compounds of the rotenone oxime-ether can be used for preparing insecticide and fungicide.

Description

Rotenone oxime ether and preparation method thereof and application
Technical field
The present invention relates to new compound of a class and its production and application, specifically is rotenone oxime ether 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 ether of agricultural chemicals is incorporated on the molecule of tubatoxin, the rotenone oxime ether of the synthetic a series of novel structures of design, and the gained compound carried out structural characterization, activity and stability test, expectation obtains ideal compound, its biological activity height, stable performance.Preliminary bioactivity research result shows: the rotenone oxime ether compound has sterilization preferably, insecticidal activity and stability.
Summary of the invention
The object of the present invention is to provide a rotenoid oxime ethers new compound preparation method and the application of rotenone oxime ethers new compound in desinsection, sterilant.
Rotenone oxime ethers new compound of the present invention has the chemical formula of structure shown in formula I or the formula II:
Wherein, R is selected from: C 1～C 18Alkyl; XCH 2CH 2, X=Cl, Br, I, F, OH, CN; C 3～C 18Alkylidene group; ArCH 2, Ar=phenyl ring, substituted benzene ring, cyclohexyl biphenyl, substituted biphenyl ring, heterocycle, substituted heterocycle; CH 2YCH 2, Y=phenyl ring, substituted benzene ring, cyclohexyl biphenyl, substituted biphenyl ring, heterocycle, substituted heterocycle; EtCHCO 2Et, CH 2CO 2Pr-i, EtCHCO 2Et, EtCHCO 2H, EtCHCO 2H or
Described heterocycle is preferably from pyridine, piperidines, piperazine, morpholine, imidazoles, imidazoles, 1,2,4-triazole or furans; Substituted heterocycle is preferably from picoline or Methylimidazole; The substituted biphenyl ring is preferably from methyl diphenyl or dimethyl diphenyl.
The preparation method that the preparation method of described rotenone oxime ethers new compound comprises the steps: to have the rotenone oxime ether of structure shown in formula I or the formula II be rotenone oxime, catalyzer, alkali and alkylating agent at solvent reaction, reaction finishes.Filter washing, the dry rotenone oxime ether that gets.
Described rotenone oxime ethers new compound has desinsection, fungicidal activity function, can be used for preparing desinsection, sterilant.
Preparation method of the present invention is undertaken by following chemical equation:
Figure A20081003144100041
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, the rotenone oxime ether series of the synthetic biologically active of design first; New compound has higher biological activity, and good stability is residual little.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 in the medicinal design, having preferably in the introducing agricultural chemicals, the oxime ether structure of bactericidal and insecticidal activity improves its biological activity and stability simultaneously.The designed compound of the present invention all has oxime ether structure with respect to existing tubatoxin.
2. different with tubatoxin, synthetic rotenone oxime ether good stability, and have fungicidal activity.
3. She Ji new compound is novel, synthetic operation convenient.Reaction times is short, the yield height.
4. utilize the active rotenone oxime ether exploitation of synthetic environment friendly agricultural, be used to prepare sterilant and sterilant.
Embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
Synthesizing of embodiment 1 rotenone oxime methyl ether (2)
25mL acetone, 1.00g rotenone oxime and 0.05g 4 bromide, the 2mL50% sodium hydroxide solution stirs 30min.Drip the 5mL acetone soln of 0.38g methyl-sulfate in the time of 5 ℃.Dropwise, 0～5 ℃ of reaction, TLC follows the tracks of, and the 10h reaction finishes.Filter, filtrate decompression evaporate to dryness, raffinate are poured in the 50mL water, have solid to separate out, filter, and water washing, drying gets light yellow solid 1.01g, yield 98.06%.195～203 ℃ of fusing points. 1H?NMR(CDCl 3)，δ：1.75(s，3H，8’CH 3)，2.99(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.28(dd，J＝10.0Hz，J＝16Hz，1H，4’-H)，3.75(s，3H，OCH 3)，3.80(s，3H，OCH 3)，4.06(s，3H，NOCH 3)，4.23(d，J＝12Hz，1H，6-H)，4.49(t，J＝2.8Hz，1H，12a-H)，4.58(dd，J＝12Hz，J＝2.4Hz，1H，6-H)，4.75(d，J＝2.4Hz，1H，6a-H)，4.90(s，1H，7’-H)，5.06(s，1H，7’-H)，5.14(t，J＝8.8Hz，1H，5’-H)，6.42(s，1H，4-H)，6.43(d，J＝8.4Hz，1H，10-H)，6.52(s，1H，1-H)，7.77(d，J＝8.4Hz，1H，11-H)。Elementalanalysis(％，Calcd.)：C，68.12％(68.07％)；H，5.88％(5.95％)；N，3.39％(3.31％)。IR (KBr compressing tablet) v/cm -1: 3083,2970,2821,1620,1501,1199,735.
Embodiment 2 rattan ketoxime 1.5g, DMF 15ml, sodium hydroxide 0.2g stirs 20min, dropping contains the DMF solution 10ml of methyl iodide 7.2mmol, and room temperature reaction 3.0h slowly adds saturated aqueous common salt, standing demix to reaction solution, filter, dry cake, ethyl alcohol recrystallization obtains white solid 2.
Synthesizing of embodiment 3 rotenone oxime propyl ethers (3)
Figure A20081003144100051
20mL acetone, the 1.00g rotenone oxime, 0.70g salt of wormwood, 0.08g potassiumiodide and 0.90g N-PROPYLE BROMIDE backflow stirring reaction, TLC follows the tracks of, and the 18h reaction finishes.Reacting liquid filtering, the filter cake washing with acetone merges organic phase, and evaporated under reduced pressure gets solid, washes with water, dry white solid 1.02g, the yield 91.07% of getting.209～214 ℃ of fusing points. 1H?NMR(CDCl 3)，δ：1.01(t，J＝4.4Hz，3H，-CH 2CH 3)，1.75(m，5H，8’-CH 3，-CH 2CH 3)，2.91(dd，J＝8.0Hz，J＝15.6Hz，1H，4’-H)，3.28(dd，J＝10.0Hz，J＝15.6Hz，1H，4’-H)，3.74(s，3H，OCH 3)，3.80(s，3H，OCH 3)，4.22(m，3H，6-H，OCH 2)，4.50(s，1H，12a-H)，4.59(dd，J＝2.8Hz，J＝12.4Hz，1H，6-H)，4.78(d，J＝2.8Hz，1H，6a-H)，4.90(s，1H，7’-H)，5.05(s，1H，7’-H)，5.14(t，J＝8.8Hz，1H，5’-H)，6.42(d，J＝9.2Hz，2H，4-H，10-H)，6.55(s，1H，1-H)，7.77(d，J＝7.6Hz，1H，11-H)。Elemental?analysis(％，Calcd.)：C，69.60％(69.16％)；H，6.44％(6.47％)；N，3.17％(3.10％)。IR (KBr compressing tablet) v/cm -1: 3059,2960,2932,2874,2854,1619,1512,1199,738.
Synthesizing of embodiment 4 rotenone oxime butyl ethers (4)
Figure A20081003144100052
20mL acetone, the 1.00g rotenone oxime, 0.70g salt of wormwood, 0.08g potassiumiodide and 1.02g n-butyl bromide, the backflow stirring reaction, TLC follows the tracks of, and the 45h 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 1.08g, the yield 94.74% of getting.219～222 ℃ of fusing points. 1H?NMR(CDCl 3)，δ：0.96(t，J＝7.6Hz，3H，CH 3)，1.47(m，2H，-CH 2CH 3)，1.75(m，5H，8’-CH 3，-CH 2CH 2CH 3)，2.92(dd，J＝8.4Hz，J＝15.6Hz，1H，4’-H)，3.28(dd，J＝10.0Hz，J＝16Hz，1H，4’-H)，3.74(s，3H，OCH 3)，3.80(s，3H，OCH 3)，4.25(m，3H，6-H，NOCH 2)，4.50(s，1H，12a-H)，4.59(dd，J＝2.8Hz，J＝12.4Hz，1H，6-H)，4.78(d，J＝3.2Hz，1H，6a-H)，4.90(s，1H，7’-H)，5.05(s，1H，7’-H)，5.14(t，J＝8.8Hz，1H，5’-H)，6.40(d，J＝9.2Hz，2H，4-H，10-H)，6.54(s，1H，1-H)，7.76(d，J＝8.4Hz，1H，11-H)。Elemental?analysis(％，Calcd.)：C，69.72％(69.66％)；H，6.59％(6.71％)；N，3.06％(3.01％)。IR (KBr compressing tablet) v/cm -1: 3060,2956,2934,2874,2832,1620,1585,1199,738.
Synthesizing of embodiment 5 rotenone oxime amyl ethers (5)
Figure A20081003144100061
20mL acetone, the 1.00g rotenone oxime, 0.70g salt of wormwood, 0.08g potassiumiodide and 1.12g bromo pentane silane, the backflow stirring reaction, TLC follows the tracks of, and the 31h 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 1.08g, the yield 92.31% of getting.202～206 ℃ of fusing points. 1H?NMR(CDCl 3)，δ：0.91(t，J＝6.8Hz，3H，-CH 2CH 3)，1.38(m，4H，-CH 2CH 2CH 3)，1.76(t，J＝6.8Hz，5H，8’-CH 3，-CH 2CH 2CH 2CH 3)，2.92(dd，J＝8.4Hz，J＝16Hz，1H，4’-H)，3.28(dd，J＝9.6Hz，J＝15.6Hz，1H，4’-H)，3.74(s，3H，OCH 3)，3.80(s，3H，OCH 3)，4.25(m，3H，6-H，NOCH 2)，4.50(s，1H，12a-H)，4.58(dd，J＝2.8Hz，J＝12.4Hz，1H，6-H)，4.78(d，J＝3.2Hz，1H，6a-H)，4.90(s，1H，7’-H)，5.05(s，1H，7’-H)，5.14(t，J＝8.8Hz，1H，5’-H)，6.43(d，J＝9.2Hz，2H，4-H，10-H)，6.55(s，1H，1-H)，7.76(d，J＝8.8Hz，1H，11-H)。Elemental?analysis(％，Calcd.)：C，69.99％(70.13％)；H，6.66％(6.94％)；N，3.02％(2.92％)。IR (KBr compressing tablet) v/cm -1: 3000,2960,2930,2878,2856,1620,1512,1199,738.
Synthesizing of embodiment 6 rotenone oxime propenyl ether (6)
Figure A20081003144100062
20mL acetone, the 1.00g rotenone oxime, 0.70g salt of wormwood, 0.05g phase-transfer catalyst 4 bromide and 0.54g propenyl chloride, the backflow stirring reaction, TLC follows the tracks of, and the 15h 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 0.99g, the yield 92.52% of getting.185～192 ℃ of fusing points. 1H?NMR(CDCl 3)，δ1.75(s，3H，8’-CH 3)，2.91(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.28(dd，J＝10.0Hz，J＝16Hz，1H，4’-H)，3.75(s，3H，OCH 3)，3.80(s，3H，OCH 3)，4.23(d，J＝12Hz，1H，6-H)，4.50(t，J＝2.8Hz，1H，12a-H)，4.58(dd，J＝12Hz，J＝2.4Hz，1H，6-H)，4.72(m，1H，CH＝)，4.78(d，J＝2.4Hz，1H，6a-H)，4.90(s，1H，7’-H)，5.06(s，1H，7’-H)，5.15(t，J＝8.8Hz，1H，5’-H)，5.25(dd，J＝18.6Hz，J＝1.6Hz，1H，CH 2＝)，5.38(dd，J＝17.2Hz，J＝1.6Hz，1H，CH 2＝)，6.13(m，1H，NOCH 2)，6.41(s，1H，4-H)，6.42(d，J＝8.4Hz，1H，10-H)，6.56(s，1H，1-H)，7.77(d，J＝8.4Hz，1H，11-H)。Elemental?analysis(％，Calcd.)：C，69.12％(69.47％)；H，6.07％(6.05％)；N，3.16％(3.12％)。IR (KBr compressing tablet) v/cm -1: 3007,2972,2919,2859,1619,1512,1199,740.
Synthesizing of embodiment 7 rotenone oxime isobutenyl ethers (7)
Figure A20081003144100071
20mL acetone, the 0.80g rotenone oxime, 0.60g salt of wormwood, 0.04g 4 bromide and 0.51g isocrotyl chloride, the backflow stirring reaction, TLC follows the tracks of, and the 20h 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 0.73g, the yield 80.22% of getting.212～218 ℃ of fusing points. 1H?NMR(CDCl 3)，δ：1.75(s，3H，CH 3)，1.85(s，3H，8’-CH 3)，2.92(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.28(dd，J＝9.6Hz，J＝16Hz，1H，4’-H)，3.73(s，3H，OCH 3)，3.80(s，3H，OCH 3)，4.24(d，J＝12Hz，1H，6-H)，4.51(t，J＝2.8Hz，1H，12a-H)，4.59(dd，J＝12Hz，J＝2.4Hz，1H，6-H)，4.68(dd，J＝12.8Hz，J＝12.8Hz，2H，CH 2)，4.81(d，J＝2.4Hz，1H，6a-H)，4.89(s，1H，7’-H)，4.96(s，1H，＝CH 2)，5.06(s，2H，7’-H，＝CH 2)，5.15(t，J＝8.8Hz，1H，5’-H)，6.42(s，1H，4-H)，6.43(d，J＝8.4Hz，1H，10-H)，6.57(s，1H，1-H)，7.76(d，J＝8.4Hz，1H，11-H)。Elemental?analysis(％，Calcd.)：C，70.03％(69.96％)；H，6.28％(6.31％)；N，3.11％(3.02％)。IR (KBr compressing tablet) v/cm -1: 2997,2972,2927,2855,1620,1512,1199,739.
Synthesizing of embodiment 8 rotenone oxime benzylic ethers (8)
Figure A20081003144100072
20mL acetone, the 1.00g rotenone oxime, 0.70g salt of wormwood, 0.05g 4 bromide and 0.90g benzyl chlorine, backflow stirring reaction TLC follows the tracks of, and the 36h reaction finishes.Reacting liquid filtering, filter cake merges organic phase with washing with acetone three times, and evaporated under reduced pressure gets solid, washing, dry orange red solid 0.9g yield 73.17%.226～232 ℃ of fusing points. 1H?NMR(CDCl 3)，δ：1.75(s，3H，8’-CH 3)，2.91(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.27(dd，J＝10Hz，J＝16Hz，1H，4’-H)，3.50(s，3H，OCH 3)，3.78(s，3H，OCH 3)，4.21(d，J＝12Hz，1H，6-H)，4.48(t，J＝2.8Hz，1H，12a-H)，4.55(dd，J＝12Hz，J＝2.4Hz，1H，6-H)，4.80(d，J＝2.4Hz，1H，6a-H)，4.90(s，1H，7’-H)，5.06(s，1H，7’-H)，5.14(t，J＝8.8Hz，1H，5’-H)，5.28(dd，J＝12Hz，J＝12Hz，2H，NOCH 2)，6.39(s，1H，4-H)，6.44(d，J＝8.4Hz，1H，10-H)，6.77(s，1H，1-H)，7.38(m，3H，C 6H 53，4，5-H)，7.47(d，J＝6.4Hz，2H，C 6H 52，6-H)，7.79(d，J＝8.4Hz，1H，11-H)。Elementalanalysis(％，Calcd.)：C，71.80％(72.13％)；H，5.49％(5.85％)；N，2.80％(2.80％)。IR (KBr compressing tablet) v/cm -1: 3062,2929,2982,2852,1620,1509,1198,741.
Synthesizing of embodiment 9 rotenone oxime propylene oxide base ethers (9)
Figure A20081003144100081
20mL acetone, 1.50g rotenone oxime, 0.6g pyridine and 0.99g epoxy chloropropane, backflow stirring reaction.TLC follows the tracks of, and the 12h 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 1.65g, the yield 96.49% of getting.201～204 ℃ of fusing points. 1H NMR (CDCl 3), δ: 1.76 (s, 3H, 8 '-CH 3), 2.71 (m, 1H, oxirane ring OCH 2), 2.89 (t, J=4.4Hz, 1H, oxirane ring OCH 2), 2.92 (dd, J=8.0Hz, J=16Hz, 1H, 4 '-H), 3.28 (dd, J=10.0Hz, J=16Hz, 1H, 4 '-H), 3.38 (m, 1H, oxirane ring OCH), 3.75,3.77 (2 * s, 3H, OCH 3), 3.80 (s, 3H, OCH 3), 4.15 (m, 1H, NOCH 2), 4.23 (d, J=12Hz, 1H, 6-H), 4.50 (m, 1H, NOCH 2), 4.52 (t, J=2.8Hz, 1H, 12a-H), 4.59 (dd, J=12Hz, J=2.4Hz, 1H, 6-H), 4.81 (d, J=2.4Hz, 1H, 6a-H), 4.90 (s, 1H, 7 '-H), 5.06 (s, 1H, 7 '-H), 5.15 (t, J=8.8Hz, 1H, 5 '-H), 6.42 (s, 1H, 4-H), 6.44 (d, J=8.4Hz, 1H, 10-H), 6.55,6.58 (2 * s, 1H, 1-H), 7.75 (d, J=8.4Hz, 1H, 11-H).Elemental?analysis(％，Calcd.)：C，67.37％(67.09％)；H，5.60％(5.85％)；N，3.04％(3.01％)。IR (KBr compressing tablet) v/cm -1: 3053,2968,2928,2876,2856,1619,1512,1198,738.
Synthesizing of embodiment 10 rotenone oxime ethoxy carbonyl methyl ethers (10)
Figure A20081003144100082
20mL acetone, the 1.00g rotenone oxime, 0.70g salt of wormwood and 1.08g ethyl chloroacetate, the backflow stirring reaction, TLC follows the tracks of, and the 27h reaction finishes.Reacting liquid filtering, the filter cake washing with acetone merges organic phase, and the evaporated under reduced pressure solvent gets solid, washing, dry orange red solid 1.18g, the yield 96.72% of getting.174～175 ℃ of fusing points. 1H?NMR(CDCl 3)，δ：1.28(t，J＝7.2Hz，3H，CH 3)，1.73(s，3H，8’-CH 3)，2.89(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.25(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.77(s，3H，OCH 3)，3.79(s，3H，OCH 3)，4.23(q，J＝7.2Hz，2H，CH 2CH 3)，4.23(d，J＝4Hz，1H，12a-H)，4.55(ddd，J＝12Hz，J＝12Hz，J＝2.4Hz，2H，6-H)，4.75(s，2H，NOCH 2)，4.86(t，J＝3.0Hz，1H，6a-H)，4.87(s，1H，7’-H)，5.03(s，1H，7’-H)，5.13(t，J＝8.8Hz，1H，5’-H)，6.38(s，1H，4-H)，6.40(d，J＝8.4Hz，1H，10-H)，6.78(s，1H，1-H)，7.69(d，J＝8.4Hz，1H，11-H)。Elemental?analysis(％，Calcd.)：C，65.51％(65.44％)；H，5.94％(5.90％)；N，2.88％(2.83％)。IR (KBr compressing tablet) v/cm -1: 3066,2977,2926,2857,1759,1621,1514,1200,738.
Synthesizing of the different third oxygen carbonyl methyl ether (11) of embodiment 11 rotenone oximes
Figure A20081003144100091
Rotenone oxime 1.0g, acetone 10.0ml, salt of wormwood 0.7g heated and stirred, dissolving adds the acetone soln that 10ml contains the 0.98g isopropyl chloracetate, back flow reaction 27h, filtering reacting liquid, filtrate revolve the steaming precipitation, the white solid that washing obtains, ethyl alcohol recrystallization obtains the 1.0g white powder, 184～187 ℃ of yields 75.3% of fusing point. 1H-NMR(CDCl 3，400MHz)δ：1.29(t，J＝6.0Hz，6H，2×CH 3)，1.75(s，3H，8’-CH 3)，2.91(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.28(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.80(s，3H，OCH 3)，3.81(s，3H，OCH 3)，4.24(d，J＝12Hz，1H，6-H)，4.54(t，J＝2.4Hz，1H，12a-H)，4.59(dd，J＝12Hz，J＝2.4Hz，1H，6-H)，4.73(s，2H，OCH 2)，4.89(t，J＝3.0Hz，1H，6a-H)，4.90(s，1H，7’-H)，5.05(s，1H，7’-H)，5.13(m，2H，5’-H，OCH)，6.41(s，1H，4-H)6.42(d，J＝8.4Hz，1H，10-H)，6.80(s，1H，1-H)，7.70(d，J＝8.4Hz，1H，11-H)。
Synthesizing of embodiment 12 rotenone oxime methoxy carbonyl propyl ethers (12)
Figure A20081003144100092
Rotenone oxime 1.0g, DMF 15ml, yellow soda ash 1.5g, stir 20min, drip the DMF solution 10ml that contains 2-bromo-butyric acid methyl esters 0.65g, 80 ℃ of reactions of temperature control 8h, add saturated aqueous common salt to reaction solution, standing demix filters dry cake, ethyl alcohol recrystallization, obtain white solid 0.92g, 142～144 ℃ of fusing points, yield 60%. 1H-NMR(CDCl 3，400MHz)δ：1.01～1.09(m，3H，CH 3)，1.75(s，3H，8’-CH 3)，1.91～1.94(m，2H，CH 2)，2.92(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.28(dd，J＝10.0Hz，J＝16Hz，1H，4’-H)，3.74～3.86(3×s，9H，3×OCH 3)，4.25(d，J＝12.0Hz，1H，6-H)，4.51～4.61(m，2H，12a-H，6-H)，4.72(t，J＝6.4Hz，1H，-OCH)，4.80(d，J＝3.2Hz，1H，6a-H)，4.90(s，1H，7’-H)，5.05(s，1H，7’-H)，5.15(t，J＝9.2Hz，1H，5’-H)，6.40～6.70(m，3H，4-H，1-H，10-H)，7.68(d，J＝8.8Hz，1H，11-H)。
Embodiment 13 rotenone oximes are synthetic to vinyl benzyl oxide (13)
Figure A20081003144100101
Rotenone oxime 1.5g, DMF 15ml, sodium hydroxide 0.15g, stir 20min, dropping contains p-chloromethyl styrene 0.7g DMF solution 10ml, stops up temperature reaction 8h, slowly add saturated aqueous common salt to reaction solution, standing demix filters dry cake, ethyl alcohol recrystallization, obtain white solid 1.4g, 177～180 ℃ of fusing points, yield 68.8%. 1H-NMR(CDCl 3，400MHz)δ：1.75(s，3H，8’-CH 3)，2.91(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.27(dd，J＝9.6Hz，J＝16Hz，1H，4’-H)，3.50(s，3H，OCH 3)，3.78(s，3H，OCH 3)，4.21(d，J＝12.0Hz，1H，6-H)，4.49(d，J＝2.4Hz，1H，12a-H)，4.57(dd，J＝12.0Hz，J＝2.4Hz，1H，6-H)，4.79(d，J＝3.2Hz，1H，6a-H)，4.90(s，1H，7’-H)，5.06(s，1H，7’-H)，5.15(t，J＝9.2Hz，1H，5’-H)，5.20～5.33(m，3H，＝CH 2，OCH 2)，5.75(d，J＝17.6Hz，1H，＝CH 2)，6.39(s，1H，4-H)，6.45(m，2H，1-H，10-H)，6.71(dd，J＝10.8Hz，J＝21.6Hz，＝CH)，7.42(q，J＝8.0Hz，4H，C 6H 4)，7.79(d，J＝8.8Hz，1H，11-H)。
Synthesizing of embodiment 14 rotenone oxime 6-chloro-3-picolyl ethers (14)
Rotenone oxime 1.0g, DMF 25ml, sodium hydroxide 0.5g, stir 20min, add 2-chloro-5-chloromethylpyridine 0.6g, room temperature reaction 7.5h, slowly add saturated aqueous common salt to reaction solution, standing demix filters, dry cake, ethyl alcohol recrystallization, column chromatography, ethyl acetate: sherwood oil=1: 3 wash-out, obtain white solid 1.2g, 191～194 ℃ of fusing points, yield 75%. 1H-NMR(CDCl 3，400MHz)δ：1.75(s，3H，8’-CH 3)，2.91(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.27(dd，J＝10.0Hz，J＝16Hz，1H，4’-H)，3.58(s，3H，OCH 3)，3.79(s，3H，OCH 3)，4.23(d，J＝12.0Hz，1H，6-H)，4.49(s，1H，12a-H)，4.58(d，J＝12.0Hz，1H，6H)，4.74(s，1H，6a-H)，4.90(s，1H，7’-H)，5.05(s，1H，7’-H)，5.15(t，J＝8.8Hz，1H，5’-H)，5.26(s，2H，OCH 2)，6.39(s，1H，4-H)，6.41(s，1H，1-H)，6.44(d，J＝8.8Hz，1H，10-H)，7.37(d，J＝8.0Hz，1H，C 5H 3N5-H)，7.72(d，J＝8.8Hz，1H，11-H)，7.82(d，J＝8.0Hz，1H，C 5H 3N4-H)，8.52(s，1H，C 5H 3N2-H)。
Embodiment 15 rotenone oximes are synthetic to chloromethyl benzyl oxide (15)
Figure A20081003144100111
Rotenone oxime 1.5g, DMF 25ml, sodium hydroxide 0.2g, stir 20min, add chloromethyl Benzyl Chloride 1.26g, room temperature reaction 8.5h, slowly add saturated aqueous common salt to reaction solution, standing demix filters, dry cake, ethyl alcohol recrystallization, column chromatography, ethyl acetate: sherwood oil=1: 3 wash-out, obtain white solid 1.2g, 165～168 ℃ of fusing points, yield 57.1%. 1H-NMR(CDCl 3，400MHz)δ：1.75(s，3H，8’-CH 3)，2.91(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.27(dd，J＝9.6Hz，J＝16Hz，1H，4’-H)，3.52(s，3H，OCH 3)，3.78(s，3H，OCH 3)，4.22(d，J＝12.0Hz，1H，6-H)，4.49(d，J＝2.4Hz，1H，12a-H)，4.58(m，3H，6-H，-CH 2Cl)，4.78(d，J＝3.6Hz，1H，6a-H)，4.90(s，1H，7’-H)，5.06(s，1H，7’-H)，5.15(t，J＝8.8Hz，1H，5’-H)，5.23(d，J＝12.0Hz，1H，OCH 2)，5.32(d，J＝12.0Hz，1H，OCH 2)，6.40(s，1H，4-H)，6.45(s，1H，1-H)，6.45(d，J＝8.4Hz，1H，10-H)，7.39(d，J＝8.0Hz，2H，C 6H 42-H，C 6H 46-H)，7.48(d，J＝8.0Hz，2H，C 6H 43-H，C 6H 45-H)，7.79(d，J＝8.4Hz，1H，11-H)。
Embodiment 16 rotenone oximes are synthetic to chloromethyl biphenyl methyl ether (16)
Figure A20081003144100112
Rotenone oxime 1.5g, DMF 25ml, sodium hydroxide 0.2g, stir 20min, add 4,4 '-dichloromethyl biphenyl 1.3g, room temperature reaction 8.5h slowly adds saturated aqueous common salt, standing demix to reaction solution, filter dry cake, ethyl alcohol recrystallization, column chromatography, ethyl acetate: sherwood oil=1: 3 wash-out obtains white solid 1.0g, fusing point＞255 ℃, yield 41.2%. 1H-NMR(CDCl 3，400MHz)δ：1.75(s，3H，8’-CH 3)，2.92(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.28(dd，J＝9.6Hz，J＝16Hz，1H，4’-H)，3.52(s，3H，OCH 3)，3.78(s，3H，OCH 3)，4.23(d，J＝12.0Hz，1H，6-H)，4.50(d，J＝2.8Hz，1H，12a-H)，4.58(dd，1H，J＝2.4Hz，J＝12.4Hz，-CH 2Cl)，4.64(s，2H，6H，-CH 2Cl)，4.81(d，J＝3.2Hz，1H，6a-H)，4.90(s，1H，7’-H)，5.06(s，1H，7’-H)，5.15(t，J＝8.8Hz，1H，5’-H)，5.23(d，J＝12.4Hz，1H，OCH 2)，5.32(d，J＝12.4Hz，1H，OCH 2)，6.40(s，1H，4-H)，6.45(d，J＝8.8Hz，1H，10-H)，6.48(s，1H，1-H)，7.46～7.58(m，8H，C 6H 4-C 6H 4)，7.80(d，J＝8.8Hz，1H，11-H)。
Synthesizing of embodiment 17 2 rotenone oxime terephthaldehyde ethers (17)
Figure A20081003144100121
Rotenone oxime 1.5g, DMF 25ml, sodium hydroxide 0.2g, stir 20min, add chloromethyl Benzyl Chloride 0.32g, room temperature reaction 15.5h, slowly add saturated aqueous common salt to reaction solution, standing demix filters, dry cake, ethyl alcohol recrystallization, column chromatography, ethyl acetate: sherwood oil=1: 3 wash-out, obtain white solid 1.0g, fusing point＞255 ℃, yield 55.6%. 1H-NMR(CDCl 3，400MHz)δ：1.75(s，3H，8’-CH 3)，2.91(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.27(dd，J＝9.6Hz，J＝16Hz，1H，4’-H)，3.57(s，3H，OCH 3)，3.78(s，3H，OCH 3)，4.22(d，J＝12.0Hz，1H，6-H)，4.49(d，J＝2.4Hz，1H，12a-H)，4.57(dd，J＝2.4Hz，J＝12.0Hz，1H，6-H)，4.78(d，J＝3.2Hz，1H，6a-H)，4.90(s，1H，7’-H)，5.05(s，1H，7’-H)，5.15(t，J＝8.8Hz，1H，5’-H)，5.25(d，J＝12.0Hz，1H，OCH 2)，5.30(d，J＝12.0Hz，1H，OCH 2)，6.40(s，1H，4-H)，6.45(d，J＝8.4Hz，1H，10-H)，6.50(s，1H，1-H)，7.45(s，2H，C 6H 4-H)，7.78(d，J＝8.4Hz，1H，11-H)。
Synthesizing of embodiment 18 2 rotenone oxime distich phenylene dimethyl ethers (18)
Figure A20081003144100122
Rotenone oxime 1.5g, DMF 25ml, stirring at room, add sodium hydroxide 0.4g, stir 20min, add 4,4 '-dichloromethyl biphenyl 0.33g, 50 ℃ of reaction 12h slowly add saturated aqueous common salt to reaction solution, standing demix filters dry cake, ethyl alcohol recrystallization, column chromatography, ethyl acetate: sherwood oil=1: 3 wash-out, obtain white solid 1.0g, fusing point＞255 ℃, yield 44.5%. 1H-NMR(CDCl 3，400MHz)δ：1.76(s，6H，2×8’-CH 3)，2.92(dd，J＝8.0Hz，J＝16Hz，2H，2×4’-H)，3.24(dd，J＝9.6Hz，J＝16Hz，2H，2×4’-H)，3.52(s，6H，2×OCH 3)，3.78(s，6H，2×OCH 3)，4.22(d，J＝12.0Hz，2H，2×6-H)，4.51(s，2H，2×12a-H)，4.58(dd，2H，J＝2.4Hz，J＝12.0Hz，2×6-H)，4.82(d，J＝2.8Hz，2H，2×6a-H)，4.90(s，2H，2×7’-H)，5.06(s，2H，2×7’-H)，5.13(t，J＝8.8Hz，2H，2×5’-H)，5.28(d，J＝12.0Hz，2H，OCH 2)，5.36(d，J＝12.0Hz，2H，OCH 2)，6.40(s，2H，2×4-H)，6.45(d，J＝8.4Hz，2H，2×10-H)，6.49(s，2H，2×1-H)，7.58(m，2×C 6H 48H)，7.81(d，J＝8.4Hz，2H，11-H)。
Synthesizing of embodiment 19 rotenone oximes-3-amyl ether (19)
Rotenone oxime 1.5g, DMF 15ml, sodium hydroxide 0.2g, stir 20min, drip the DMF solution 10ml that contains 3-bromo pentane silane 1.1g, room temperature reaction 8.5h, slowly add saturated aqueous common salt to reaction solution, standing demix filters dry cake, ethyl alcohol recrystallization, obtain white solid 1.3g, 193～195 ℃ of fusing points, yield 70.3%. 1H-NMR(CDCl 3，400MHz)δ：0.95(t，J＝7.6Hz，3H，CH 3)，1.02(t，J＝7.6Hz，3H，CH 3)，1.60～1.83(m，7H，8’-CH 3，2×CH 2)，2.92(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.28(dd，J＝9.6Hz，J＝16Hz，1H，4’-H)，3.73(s，3H，OCH 3)，3.80(s，3H，OCH 3)，4.15(quin，J＝6.0Hz，1H，-OCH)，4.27(d，J＝11.6Hz，1H，6-H)，4.51(d，J＝2.4Hz，1H，12a-H)，4.59(dd，J＝2.4Hz，J＝12.0Hz，1H，6-H)，4.79(d，J＝3.2Hz，1H，6a-H)，4.90(s，1H，7’-H)，5.05(s，1H，7’-H)，5.15(t，J＝8.8Hz，1H，5’-H)，6.42(s，1H，4-H)，6.43(d，J＝8.4Hz，1H，10-H)，6.56(s，1H，1-H)，7.77(d，J＝8.4Hz，1H，11-H)。
Synthesizing of embodiment 20 rotenone oxime ether (20)
Rotenone oxime 1.5g, DMF 15ml, sodium hydroxide 0.2g, stir 20min, drip the DMF solution 10ml that contains iodoethane 1.1g, room temperature reaction 3.5h, slowly add saturated aqueous common salt to reaction solution, standing demix filters dry cake, ethyl alcohol recrystallization, obtain white solid 1.2g, 168～171 ℃ of fusing points, yield 69.5%. 1H-NMR(CDCl 3，400MHz)δ：1.39(t，J＝7.2Hz，3H，CH 3)，1.76(s，3H，8’-CH 3)，2.92(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.28(dd，J＝10Hz，J＝16Hz，1H，4’-H)，3.74(s，3H，OCH 3)，3.80(s，3H，OCH 3)，4.24(d，J＝12.0Hz，1H，6-H)，4.22～4.36(m，2H，-OCH 2)4.50(d，J＝2.4Hz，1H，12a-H)，4.59(dd，J＝2.4Hz，J＝12.0Hz，1H，6-H)，4.78(d，J＝3.2Hz，1H，6a-H)，4.90(s，1H，7’-H)，5.06(s，1H，7’-H)，5.15(t，J＝8.4Hz，1H，5’-H)，6.42(s，1H，4-H)，6.43(d，J＝8.4Hz，1H，10-H)，6.56(s，1H，1-H)，7.78(d，J＝8.4Hz，1H，11-H)。
Synthesizing of embodiment 21 rotenone oxime 2-bromine ether (21)
Rotenone oxime 1.5g, DMF 15ml, sodium hydroxide 0.2g, the potassiumiodide of catalytic amount stirs 20min, drips to contain 1, the DMF solution 10ml of 2-ethylene dibromide 1.36g, room temperature reaction 36.5h slowly adds saturated aqueous common salt to reaction solution, standing demix filters dry cake, ethyl alcohol recrystallization, column chromatography, ethyl acetate: sherwood oil=1: 3 wash-out, obtain white solid 0.8g, fusing point＞255 ℃, yield 40%. 1H-NMR(CDCl 3，400MHz)δ：1.75(s，3H，8’-CH 3)，2.92(dd，J＝8.0Hz，J＝16Hz，1H，4’-H)，3.28(dd，J＝10.0Hz，J＝16Hz，1H，4’-H)，3.71(m，2H，-CH 2Br)，3.76(s，3H，OCH 3)，3.80(s，3H，OCH 3)，4.26(d，J＝12.0Hz，1H，6-H)，4.53(m，3H，12a-H，-OCH 2)，4.59(dd，J＝2.4Hz，J＝12.0Hz，1H，6-H)，4.83(d，J＝3.2Hz，1H，6a-H)，4.90(s，1H，7’-H)，5.06(s，1H，7’-H)，5.16(t，J＝8.8Hz，1H，5’-H)，6.42(s，1H，4-H)，6.44(d，J＝8.8Hz，1H，10-H)，6.54(s，1H，1-H)，7.74(d，J＝8.8Hz，1H，11-H)。
Embodiment 22 rotenone oximes 2,4-dimethyl-5-chloromethyl benzyl oxide (22) synthetic
Figure A20081003144100141
Rotenone oxime 1.5g, DMF 15ml, sodium hydroxide 0.2g, stir 20min, add 5-chloromethyl-2,4-dimethyl chloride methylbenzene 0.73g, room temperature reaction 10h slowly adds saturated aqueous common salt, standing demix to reaction solution, filter dry cake, ethyl alcohol recrystallization, column chromatography, ethyl acetate: sherwood oil=1: 3 wash-out obtains white solid 1.1g, 186～188 ℃ of fusing points, yield 54.5%. 1H-NMR(CDCl 3，400MHz)δ：1.75(s，3H，8’-CH 3)，2.39(s，3H，-CH 3)，2.41(s，3H，-CH 3)，2.91(dd，J＝8.4Hz，J＝16Hz，1H，4’-H)，3.27(dd，J＝10.0Hz，J＝16Hz，1H，4’-H)，3.57(s，3H，OCH 3)，3.78(s，3H，OCH 3)，4.22(d，J＝12.4Hz，1H，6-H)，4.49(d，J＝2.4Hz，1H，12a-H)，4.58(m，3H，6-H，-CH 2Cl)，4.76(d，J＝3.2Hz，1H，6a-H)，4.90(s，1H，7’-H)，5.05(s，1H，7’-H)，5.15(t，J＝8.8Hz，1H，5’-H)，5.23(d，J＝12.0Hz，1H，OCH 2)，5.30(d，J＝12.0Hz，1H，OCH 2)，6.40(s，1H，4-H)，6.45(s，1H，1-H)，6.45(d，J＝8.8Hz，1H，10-H)，7.04(s，3H，C 6H 43-H)，7.34(s，1H，C 6H 46-H)，7.79(d，J＝8.8Hz，1H，11-H)。
Embodiment 23 2 rotenone oximes 4,6-dimethyl-1,3-phenylene dimethyl ether (23) synthetic
Figure A20081003144100142
Rotenone oxime 1.5g, DMF 15ml, sodium hydroxide 0.4g, stir 20min, add 5-chloromethyl-2,4-dimethyl chloride methylbenzene 0.36g, room temperature reaction 15h slowly adds saturated aqueous common salt, standing demix to reaction solution, filter dry cake, ethyl alcohol recrystallization, column chromatography, ethyl acetate: sherwood oil=1: 3 wash-out obtains white solid 0.8g, fusing point＞255 ℃, yield 44.4%. 1H-NMR(CDCl 3，400MHz)δ：1.75(s，6H，2×8’-CH 3)，2.41(s，6H，-CH 3)，2.90(dd，J＝8.4Hz，J＝16Hz，2H，2×4’-H)，3.25(dd，J＝9.6Hz，J＝16Hz，2H，2×4’-H)，3.58(s，6H，2×OCH 3)，3.78(s，6H，2×OCH 3)，4.22(d，J＝12.0Hz，2H，2×6-H)，4.46(s，2H，2×12a-H)，4.52(dd，2H，J＝2.0Hz，J＝12.0Hz，2×6-H)，4.70(d，J＝2.4Hz，2H，2×6a-H)，4.90(s，2H，2×7’-H)，5.05(s，2H，2×7’-H)，5.14(t，J＝8.8Hz，2H，2×5’-H)，5.23(d，J＝10.8Hz，2H，OCH 2)，5.32(d，J＝10.8Hz，2H，OCH 2)，6.36(s，2H，2×4-H)，6.44(s，2H，2×1-H)，6.38(d，J＝8.8Hz，2H，2×10-H)，7.03(s，1H，C 6H 4?5″-H)，7.43(s，1H，C 6H 4?2″-H)，7.79(d，J＝8.8Hz，1H，11-H)。
Embodiment 24 rotenone oximes 2,5-dimethyl-4-chloromethyl benzyl oxide (24) synthetic
Figure A20081003144100151
Rotenone oxime 3.6mmol, DMF 15ml, sodium hydroxide 5mmol, stir 20min, add 4-chloromethyl-2,5-dimethyl chloride methylbenzene 0.73g, room temperature reaction 10h slowly adds saturated aqueous common salt, standing demix to reaction solution, filter dry cake, ethyl alcohol recrystallization, column chromatography, ethyl acetate: sherwood oil=1: 3 wash-out obtains white solid 1.2g, fusing point＞255 ℃, yield 54.6%. 1H-NMR(CDCl 3，400MHz)δ：1.75(s，3H，8’-CH 3)，2.25(s，6H，2×CH 3)，2.41(s，3H，-CH 3)，2.91(dd，J＝8.4Hz，J＝16Hz，1H，4’-H)，3.27(dd，J＝10.0Hz，J＝16Hz，1H，4’-H)，3.55(s，3H，OCH 3)，3.78(s，3H，OCH 3)，4.20(d，J＝12.0Hz，1H，6-H)，4.48(t，J＝2.4Hz，1H，12a-H)，4.56(dd，1H，6-H，J＝2.0Hz，J＝12.0Hz)4.78(m，3H，6a-H，-CH 2Cl)，4.90(s，1H，7’-H)，5.05(s，1H，7’-H)，5.14(t，J＝8.8Hz，1H，5’-H)，5.33(d，J＝11.6Hz，1H，OCH 2)，5.40(d，J＝11.6Hz，1H，OCH 2)，6.39(s，1H，4-H)，6.42(s，1H，1-H)，6.45(d，J＝8.8Hz，1H，10-H)，7.18(s，3H，C 6H 43-H)，7.25(d，J＝10.8Hz，1H，C 6H 4?6-H)，7.75(d，J＝8.8Hz，1H，11-H).
Embodiment 25 rotenone oxime ethers are measured the poisoning of mythimna separata, aphid, leafhopper, red spider
Mythimna separata is adopted the Potter spray method, and concentration is 1000mg/L; Green rice leafhopper is adopted pickling process, and concentration is 500mg/L; Black bean aphid adopts pickling process, and concentration is 500mg/L; Two-spotted spider mite is adopted pickling process, and concentration is 500mg/L.
Rotenone oxime ethoxy carbonyl methyl ether (10) is when 1000mg/L, and processing 48h reaches 90% to the lethality rate of mythimna separata; Rotenone oxime propenyl ether (6) is when 500mg/L, and processing 48h is 52.43% to the lethality rate of red spider.
Embodiment 26 fungicidal activities are measured
1. for the examination bacterial classification
Pyricularia oryzae (Pyricularia oryzae), Rhizoctonia solani Kuhn (Rhizoctonia solani), botrytis cinerea pers (Botrytis cinerea), Sclerotinia sclerotiorum (Sclerotonia sclerotiorum), fusarium graminearum (Gibberella zeae), Phytophthora capsici germ (phytophythoracapsici).Above bacterial classification all is kept in the refrigerator (4～8 ℃), tests to be inoculated in the culture dish from the test tube slant in preceding 2～3 days, cultivates to be for experiment under optimal temperature.Experiment is potato agar substratum (PDA) with substratum.Wheat powdery mildew is preserved spore with stem and leaf of Wheat and is for experiment.
2. measuring method
Accurately take by weighing an amount of new compound to be measured, with suitable solvent dissolving and adding small amounts of emulsifiers, be diluted to finite concentration earlier with clear water.Concrete grammar is as follows:
Pyricularia oryzae, fusarium graminearum, Phytophthora capsici germ, botrytis cinerea pers and Sclerotinia sclerotiorum: adopt toxic medium therapy, general sieve concentration is 25mg/L.
Rhizoctonia solani Kuhn: adopt the excised leaf culture method, general sieve concentration is 500mg/L.
Wheat powdery mildew: adopt pot-culture method, general sieve concentration is 500mg/L.
3. fungicidal activity
Handle incidence and the mycelial growth situation of back routine observation record blade, plant,, calculate preventive effect and inhibiting rate according to disease index and hyphal diameter.
Growth inhibition ratio (%)=(contrast colony diameter-processing colony diameter) * 100/ (contrast colony diameter-bacterium cake diameter).
The general sieve result of rotenone oxime ether fungicidal activity is that compound 15,16,17,18,19,20 and 23 (500mg/L) are respectively 60%, 60%, 80%, 95%, 90%, 90% and 95% to the sheath blight fungus inhibiting rate; Compound 12 and 13 (25mg/L) is respectively 63% and 55.1% to Phytophthora capsici germ inhibiting rate.

Claims (9)

1, a rotenoid oxime ether is characterized in that described compound has chemical structural formula shown in formula I or the formula II:
Figure A20081003144100021
Wherein, R is selected from: C 1～C 18Alkyl; XCH 2CH 2, X=Cl, Br, I, F, OH, CN; C 3～C 18Alkylidene group; ArCH 2, Ar=phenyl ring, substituted benzene ring, cyclohexyl biphenyl, substituted biphenyl ring, heterocycle, substituted heterocycle; CH 2YCH 2, Y=phenyl ring, substituted benzene ring, cyclohexyl biphenyl, substituted biphenyl ring, heterocycle, substituted heterocycle; EtCHCO 2Et, CH 2CO 2Pr-i, EtCHCO 2Et, EtCHCO 2H, EtCHCO 2H or
Figure A20081003144100022
2, rotenone oxime ether according to claim 1 is characterized in that, described heterocycle is selected from pyridine, piperidines, piperazine, morpholine, imidazoles, 1,2,4-triazole or furans; Substituted heterocycle is selected from picoline or Methylimidazole; The substituted biphenyl ring is selected from methyl diphenyl or dimethyl diphenyl.
3, the preparation method of the described rotenone oxime ether of claim 1, it is characterized in that the preparation method with compound of structural formula shown in formula I or the formula II is that rotenone oxime, catalyzer, alkali and alkylating agent react in appropriate solvent, reaction finishes, filter washing, the dry rotenone oxime ether that gets.
According to the preparation method of the described rotenone oxime ether of claim 3, it is characterized in that 4, catalyzer is potassiumiodide, sodium iodide or phase-transfer catalyst.Phase-transfer catalyst is one or more in tetramethyl ammonium chloride, tetraethylammonium bromide, Tetrabutyl amonium bromide, 4-butyl ammonium hydrogen sulfate, four fourth Neutral ammonium fluorides, 4-phenyl phosphonium bromide, tri-phenyl-ethyl phosphonium bromide, hexaoxacyclooctadecane-6-6, Tetrabutyl amonium bromide, benzyltriethylammoinium chloride, the tetrabutylammonium iodide.
5, according to the preparation method of the described rotenone oxime ether of claim 3, it is characterized in that described alkali is one or more in sodium hydroxide, potassium hydroxide, lithium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, triethylamine, piperidines and the pyridine.
According to the preparation method of the described rotenone oxime ether of claim 3, it is characterized in that 6, alkylating agent is a kind of in sulfuric ester, sulphonate, phosphoric acid ester, hydrochloric ether, hydrobromic ether, idohydrocarbon, dichloromethane, two hydrobromic ethers, two idohydrocarbons.
According to the preparation method of the described rotenone oxime ether of claim 3, it is characterized in that 7, temperature of reaction is-20 ℃～150 ℃.
According to the preparation method of the described rotenone oxime ether of claim 3, it is characterized in that 8, reaction solvent is alcohol, acetone, ethyl acetate, chloroform, tetrahydrofuran (THF), N, one or more in dinethylformamide, the methyl-sulphoxide.
9, the application of the described rotenone oxime ether of claim 1 is characterized in that, the compound of structural formula shown in formula I or the formula II be used to prepare desinsection, sterilant.
CN2008100314412A 2008-06-05 2008-06-05 Rotenone oxime ether, preparation method and applications thereof Expired - Fee Related CN101284836B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN103304356A (en) * 2012-03-12 2013-09-18 北京乐威泰克医药技术有限公司 Hydroxylamine synthesis method
CN104262333A (en) * 2014-09-18 2015-01-07 长沙理工大学 2- (propylene-2-yl) -2, 3-dihydrobenzofuran-4-phenol derivative and preparation method and application thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102295650A (en) * 2011-06-30 2011-12-28 湖南大学 Rotenone oxime allyl / propargyl ether and application of the same as insecticide
CN103304356A (en) * 2012-03-12 2013-09-18 北京乐威泰克医药技术有限公司 Hydroxylamine synthesis method
CN103304356B (en) * 2012-03-12 2016-01-20 北京乐威泰克医药技术有限公司 The synthetic method of azanol
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
CN104262333A (en) * 2014-09-18 2015-01-07 长沙理工大学 2- (propylene-2-yl) -2, 3-dihydrobenzofuran-4-phenol derivative and preparation method and application thereof
CN104262333B (en) * 2014-09-18 2016-07-13 长沙理工大学 2- (propylene-2-yl) -2, 3-dihydrobenzofuran-4-phenol derivative and preparation method and application thereof

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