CN114644574B - Dioxime ether compound and preparation method and application thereof - Google Patents
Dioxime ether compound and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a dioxime ether compound shown as a structural formula I or II, a preparation method thereof and application thereof as a bactericide or insecticide.
Wherein R is 1 ～R 5 Selected from the group consisting of: C1-C2 alkyl, C3-C4 linear alkyl or C3-C5 allyl; y is selected from: o or NH.
Description
Technical Field
The invention relates to a preparation method and application of a new compound, in particular to a dioxime ether compound and application thereof in preparing bactericides and insecticides.
Background
The commercially available dioximes are trifloxystrobin (trifloxystrobin, trade name Flint, 1), the chemical name: (2Z) -2-methoxyimino-2- [2- [ [1- [3- (trifluoromethyl) phenyl ] ethylideneamino ] oxymethyl ] phenyl ] acetic acid methyl ester.
The activity test of the Strobilurin compounds containing phenyl side chains synthesized by Li and the like [ Chemical Research in Chinese university, 2006,22 (1): 45-50] shows that the compounds have broad-spectrum antifungal activity and good bactericidal activity on cotton wilt pathogen, cucumber gray mold pathogen, wheat gibberellic disease pathogen, apple ring rot pathogen, maize microspain pathogen and rice sheath blight pathogen, wherein the compound 2 is a dioxime ether compound.
A series of Strobilurin compounds with benzene rings in side chains are synthesized by ginger, billows and the like [ organic chemistry, 2014,34 (4): 774-782], wherein the compounds 3-5 have good inhibition activity on wheat scab germs, the inhibition rates are respectively 60.0%, 50.0% and 56.3%, and the inhibition activities are equivalent to that of positive control trifloxystrobin (53.3%).
The invention aims to develop a dioxime ether compound bactericide or pesticide.
Disclosure of Invention
The invention aims to provide a class of dioxime ether compounds, a preparation method thereof and application of the compounds as bactericides or insecticides.
In order to solve the technical problem, the invention provides the following technical scheme:
the first aspect of the technical scheme of the invention provides a class of dioxime ether compounds shown as structural formula I or II:
wherein R is 1 ～R 5 Selected from: C1-C2 alkyl, C3-C4 linear alkyl or C3-C5 allyl; y is selected from: o or NH.
In the first aspect of the technical scheme, the dioxime ether compound shown in the formula I is selected from compounds shown in formulas IA and IB:
wherein R is 1 ～R 4 Selected from: C1-C2 alkyl, C3-C4 straight-chain alkyl or C3-C5 allyl.
In the first aspect of the technical scheme of the invention, the dioxime ether compound shown in the formula II is selected from compounds shown in formulas II A and II B:
wherein R is 1 ～R 5 Selected from the group consisting of: C1-C2 alkyl, C3-C4 straight-chain alkyl or C3-C5 allyl.
In the first aspect of the technical scheme of the invention, a class of dioxime ether compounds is selected from the following compounds:
in a second aspect of the present invention, there is provided a process for the preparation of a dioxime ether compound, wherein the compounds of formulae ia and ib are prepared as follows:
wherein R is 1 ～R 4 Selected from: C1-C2 alkyl, C3-C4 straight-chain alkyl or C3-C5 allyl; x is selected from: chlorine, bromine or iodine.
The second aspect of the technical scheme of the invention provides a preparation method of a dioxime ether compound, wherein the preparation reactions of the compounds shown in the formulas II A and II B are as follows:
wherein R is 1 ～R 5 Selected from the group consisting of: C1-C2 alkyl, C3-C4 straight-chain alkyl or C3-C5 allyl; x is selected from: chlorine, bromine or iodine.
The third aspect of the technical scheme of the invention provides a monoxime ether compound shown as a structural formula III:
the fourth aspect of the technical scheme of the invention provides a preparation method of a monoxime ether compound, which is characterized in that the preparation reaction is as follows:
wherein R is 3 ～R 5 Selected from: C1-C2 alkyl, C3-C4 straight-chain alkyl or C3-C5 allyl.
The fifth aspect of the technical scheme of the invention provides an application of the monoxime ether compound in preparing a dioxime ether compound shown as a formula IIA; the preparation reaction is as follows:
wherein R is 1 ～R 5 Selected from the group consisting of: C1-C2 alkyl, C3-C4 linear alkyl or C3-C5 allyl; x is selected from: chlorine, bromine or iodine.
The sixth aspect of the technical scheme of the invention provides application of the dioxime ether compound in preparing bactericides or insecticides.
The beneficial technical effects are as follows:
the dioxime ether compound of the invention is a compound with bactericidal activity or insecticidal activity.
Detailed Description
The following examples are intended to illustrate the invention without further limiting it.
Example 1
(E) Preparation of methyl (Ia) -2- (methoxyimino) -2- (2- ((3- ((E) -1- (methoxyimino) ethyl) phenoxy) methyl) phenyl) acetate
1.0mmol of (E) -1- (3-hydroxyphenyl) ethanone oxime methyl ether, 1.1mmol of potassium carbonate, 5mL of acetonitrile and 0.6mmol of potassium iodide are added in batches under stirring at room temperature, 1.05mmol of (E) -2-bromomethyl-alpha-methoxyimino methyl phenylacetate is heated to reflux and reacted for 3 hours, the mixture is decompressed and desolventized, extracted by ethyl acetate, washed by water, dried by anhydrous sodium sulfate, desolventized and separated by column chromatography (V) Petroleum ether ∶V Ethyl acetate = 8: 1) to obtain (E) -methyl 2- (methoxyimino) -2- (2- ((3- ((E) -1- (methoxyimino) ethyl) phenoxy) methyl) phenyl) acetate (ia), viscous liquid with yield of 82.6%; 1 H NMR(400MHz，CDCl 3 ) δ: 7.56-6.82 (m, 8H, aromatic hydrogen), 4.98 (s, 2H, OCH) 2 )，4.04(s，3H，NOCH 3 )，4.00(s，3H，NOCH 3 )，3.85(s，3H，OCH 3 )，2.20(s，3H，CH 3 )。
Example 2
(E) Preparation of (E) -2- (methoxyimino) -2- (2- ((3- ((E) -1- (methoxyimino) ethyl) phenoxy) methyl) phenyl) acethylamine (Ib)
0.5mmol of compound Ia, 5mmol of methylamine water solution and 5mL of methanol react for 6h under reflux, and (E) -2- (methoxyimino) -2- (2- ((3- ((E) -1- (methoxyimino) ethyl) phenoxy) methyl) phenyl) acetyl methylamine (Ib) is obtained by exsolution and column chromatography separation, and viscous liquid is obtained with the yield of 91.5%. 1 H NMR(400MHz，CDCl 3 ) δ: 7.56-6.82 (m, 8H, aromatic hydrogen), 4.96 (s, 2H, OCH) 2 )，3.99(s，3H，NOCH 3 )，3.93(s，3H，NOCH 3 )，2.89(d，J＝4.9Hz，2H，NCH 3 )，2.20(s，3H，CH 3 )； 13 C NMR(101MHz，CDCl 3 )δ：162.89，158.63，154.45，151.17，138.04，135.23，129.44，129.36，129.26，128.90，128.01，127.74，118.86，115.28，112.57，68.62，63.31，61.93，26.20，12.70。
Example 3
Preparation of 5-acetyl-7-hydroxy-2, 2-dimethyl-2, 3-dihydrobenzofuran
3.75mmol of anhydrous zinc chloride and 5mL of dichloromethane are stirred under the condition of ice-water bath (below 10 ℃), 2.5mmol of 2, 2-dimethyl-2, 3-dihydrobenzofuran-7-acetate is added into a three-necked bottle, and then 3.5mmol of acetyl chloride is slowly dropped into the three-necked bottle for reaction for 1 hour under ice bath. Then adding 20% sodium bicarbonate solution to adjust the pH value to be neutral, washing with water, desolventizing, and carrying out column chromatography separation to obtain 5-acetyl-2, 2-dimethyl-2, 3-dihydrobenzofuran-7-acetate which is directly used in the next step.
5mmol of 5-acetyl-2, 2-dimethyl-2, 3-dihydrobenzofuran-7-acetate and 10mL of methanol, then 5.4mL of 20% sodium hydroxide is added, the mixture is stirred at room temperature for 0.5h, concentrated in vacuum, cooled to 0 ℃, adjusted to pH 3-4 with 10% hydrochloric acid, filtered, washed and dried to obtain 5-acetyl-7-hydroxy-2, 2-dimethyl-2, 3-dihydrobenzofuran, 1 H NMR(400MHz,CDCl 3 ) Δ 7.44 (s, 1H, benzen), 7.41 (s, 1H, benzen), 5.42 (s, 1H, OH), 3.07 (s, 2H, CH) 2 )，2.52(s，3H，CH 3 )，1.52(s，6H，2×CH 3 ). Used in example 4 to prepare (E) -1- (7-hydroxy-2, 2-dimethyl-2, 3-dihydrobenzofuran-5-yl) ethanone oxime methyl ether.
Example 4
(E) Preparation of (E) -1- (7-hydroxy-2, 2-dimethyl-2, 3-dihydrobenzofuran-5-yl) ethanone oxime methyl ether (IIIa)
0.412g (2.0 mmol) of 5-acetyl-7-hydroxy-2, 2-dimethyl-2, 3-dihydrobenzofuran (example 3), 0.334g (4.0 mmol) of methoxyamino hydrochloride, 0.328g (4.0 mmol) of anhydrous sodium acetate, 10mL of ethanol, are heated to reflux for 2 hoursIn the preparation process, desolventizing, adding 30mL ethyl acetate to dilute, extracting, separating by column chromatography to obtain (E) -1- (7-hydroxy-2, 2-dimethyl-2, 3-dihydrobenzofuran-5-yl) ethanone oxime methyl ether, 1 H NMR(400MHz，CDCl 3 ) Δ 7.06 (s, 1H, benzen), 7.03 (s, 1H, benzen), 3.96 (s, 3H, NOCH) 3 )，3.03(s，2H，CH 2 )，2.16(s，3H，CH 3 )，1.49(s，6H，2×CH 3 )； 13 C NMR(101MHz，CDCl 3 ) δ 154.75, 146.88, 139.94, 129.86, 128.04, 115.11, 113.15, 88.90, 61.74, 43.34, 28.19, 12.87. The procedure used in example 5 to prepare methyl (2E) -2- (methoxyimino) -2- (2- (((5- (1- (methoxyimino) ethyl) -2, 2-dimethyl-2, 3-dihydrobenzofuran-7-yl) oxy) methyl) phenyl) acetate.
Example 5
(2E) Preparation of methyl (IIa) -2- (methoxyimino) -2- (2- (((5- (1- (methoxyimino) ethyl) -2, 2-dimethyl-2, 3-dihydrobenzofuran-7-yl) oxy) methyl) phenyl) acetate
The compound iiia obtained in example 4 was selected as a starting material and prepared according to the method of example 1 to give methyl (2E) -2- (methoxyimino) -2- (2- (((5- (1- (methoxyimino) ethyl) -2, 2-dimethyl-2, 3-dihydrobenzofuran-7-yl) oxy) methyl) phenyl) acetate (iia) as a white solid in 85.9% yield; m.p.79-81 ℃; 1 H NMR(400MHz，CDCl 3 )δ：7.60～7.15(m，4H，C 6 H 4 )，7.09(s，1H，C 6 H 2 )，6.94(s，1H，C 6 H 2 )，5.04(s，2H，CH 2 O)，4.04(s，3H，NOCH 3 )，3.94(s，3H，NOCH 3 )，3.85(s，3H，OCH 3 )，3.01(s，2H，CH 2 )，2.10(s，3H，CH 3 )，1.50(s，6H，2×CH 3 )； 13 C NMR(101MHz，CDCl 3 )δ：163.23，154.72，149.29，149.08，142.88，135.55，129.50，129.39，129.15，128.73，128.28，127.81，127.53，116.28，112.74，88.20，69.40，63.79，61.70，52.95，43.10，28.20，12.84。
example 6
(2E) Preparation of (E) -2- (methoxyimino) -2- (2- (((5- (1- (methoxyimino) ethyl) -2, 2-dimethyl-2, 3-dihydrobenzofuran-7-yl) oxy) methyl) phenyl) aceylmethylamine (IIb)
The compound iia obtained in example 5 was selected as a starting material and prepared according to the method of example 2 to give (2E) -2- (methoxyimino) -2- (2- (((5- (1- (methoxyimino) ethyl) -2, 2-dimethyl-2, 3-dihydrobenzofuran-7-yl) oxy) methyl) phenyl) aceylmethylamine (iib) in a viscous liquid with a yield of 94.8%; 1 H NMR(400MHz，CDCl 3 )δ：7.54～7.21(m，4H，C 6 H 4 )，7.09(s，1H，C 6 H 2 )，6.97(s，1H，C 6 H 2 )，6.79(d，J＝2.8Hz，1H，NH)，5.05(s，2H，CH 2 O)，3.95(s，3H，NOCH 3 )，3.94(s，3H，NOCH 3 )，3.01(s，2H，CH 2 )，2.87(d，J＝4.9Hz，3H，NCH 3 )，2.11(s，3H，CH 3 )，1.50(s，6H，2×CH 3 )； 13 C NMR(101MHz，CDCl 3 )δ：163.10，154.88，151.26，148.97，142.90，135.46，129.48，129.40，129.05，128.87，128.59，127.99，127.59，116.22，112.64，88.20，69.83，63.19，61.74，43.11，28.24，26.30，12.91。
example 7
Preparation of 5-propionyl-7-hydroxy-2, 2-dimethyl-2, 3-dihydrobenzofuran
3.75mmol of anhydrous zinc chloride and 5mL of dichloromethane are stirred under the condition of ice-water bath (below 10 ℃), 2.5mmol of 2, 2-dimethyl-2, 3-dihydrobenzofuran-7-acetate is added into a three-necked bottle, and then 3.5mmol of propionyl chloride is slowly dropped into the three-necked bottle for reaction for 1 hour under ice bath. Then adding 20% sodium bicarbonate solution to adjust the pH value to be neutral, washing with water, desolventizing, and carrying out column chromatography separation to obtain 5-propionyl-2, 2-dimethyl-2, 3-dihydrobenzofuran-7-acetic ester which is directly used in the next step.
5mmol of 5-propionyl-2, 2-dimethyl-2, 3-dihydrobenzofuran-7-acetate and 10mL of methanol, then 5.4mL of 20% sodium hydroxide is added, the mixture is stirred for 0.5h at room temperature, concentrated in vacuum, cooled to 0 ℃, and the pH is adjusted to 3-4 by 10% hydrochloric acid, filtered, washed and dried to obtain the 5-propionyl-7-hydroxy-2, 2-dimethyl-2, 3-dihydrobenzofuran. Used in example 8 to prepare (E) -1- (7-hydroxy-2, 2-dimethyl-2, 3-dihydrobenzofuran-5-yl) acetoxime methyl ether.
Example 8
(E) Preparation of (E) -1- (7-hydroxy-2, 2-dimethyl-2, 3-dihydrobenzofuran-5-yl) acetoxime methyl ether (IIIb)
0.440g (2.0 mmol) of 5-propionyl-7-hydroxy-2, 2-dimethyl-2, 3-dihydrobenzofuran (example 7), 0.334g (4.0 mmol) of methoxyamino hydrochloride, 0.328g (4.0 mmol) of anhydrous sodium acetate, 10mL of ethanol, heating to reflux for 2 hours, desolventizing, diluting with 30mL of ethyl acetate, extracting, and separating by column chromatography to obtain (E) -1- (7-hydroxy-2, 2-dimethyl-2, 3-dihydrobenzofuran-5-yl) acetoxime methyl ether (IIIb). Used in example 9 to prepare methyl (E) -2- (methoxyimino) -2- (2- (((5- ((E) -1- (methoxyimino) propyl) -2, 2-dimethyl-2, 3-dihydrobenzofuran-7-yl) oxy) methyl) phenyl) acetate.
Example 9
(E) Preparation of methyl (IIc) -2- (methoxyimino) -2- (2- (((5- ((E) -1- (methoxyimino) propyl) -2, 2-dimethyl-2, 3-dihydrobenzofuran-7-yl) oxy) methyl) phenyl) acetate
The compound iiib obtained in example 8 was selected as a starting material and prepared according to the method of example 1 to give methyl (E) -2- (methoxyimino) -2- (2- (((5- ((E) -1- (methoxyimino) propyl) -2, 2-dimethyl-2, 3-dihydrobenzofuran-7-yl) oxy) methyl) phenyl) acetate (iic) as a viscous liquid in 86.4% yield; 1 H NMR(400MHz，CDCl 3 )δ：7.60～7.15(m，4H，C 6 H 4 )，7.09(s，1H，C 6 H 2 )，6.93(s，1H，C 6 H 2 )，5.04(s，2H，OCH 2 )，4.03(s，3H，NOCH 3 )，3.92(s，3H，NOCH 3 )，3.84(s，3H，OCH 3 )，3.02(s，2H，CH 2 )，2.61(q，J＝7.7Hz，2H，CH 3 CH 2 )，1.51(s，6H，2×CH 3 )，1.02(t，J＝7.5Hz，3H，CH 3 )； 13 C NMR(101MHz，CDCl 3 )δ：163.22，158.77，149.29，149.01，142.83，135.57，129.45，129.15，128.77，128.53，128.29，127.78，127.50，116.55，113.11，88.16，76.73，69.46，63.77，61.60，52.94，43.12，28.61，28.23，20.04，14.20。
example 10
(E) Preparation of (E) -2- (methoxyimino) -2- (2- (((5- ((E) -1- (methoxyimino) propyl) -2, 2-dimethyl-2, 3-dihydrobenzofuran-7-yl) oxy) methyl) phenyl) aceylmethylamine (IId)
The compound iic obtained in example 9 was selected as a starting material and prepared according to the method of example 2 to give (E) -2- (methoxyimino) -2- (2- (((5- ((E) -1- (methoxyimino) propyl) -2, 2-dimethyl-2, 3-dihydrobenzofuran-7-yl) oxy) methyl) phenyl) acethylamine (iid) in a viscous liquid with a yield of 93.5%; 1 H NMR(400MHz，CDCl 3 )δ：7.53～7.22(m，4H，C 6 H 4 )，7.08(s，1H，C 6 H 2 )，6.95(s，1H，C 6 H 2 )，6.79(d，J＝4.1Hz，1H，NH)，5.05(s，2H，OCH 2 )，3.94(s，3H，NOCH 3 )，3.93(s，3H，NOCH 3 )，3.02(s，2H，CH 2 )，2.88(d，J＝4.9Hz，3H，NCH 3 )，2.63(q，J＝7.5Hz，2H，CH 3 CH 2 )，1.50(s，6H，2×CH 3 )，1.01(t，J＝7.5Hz，3H，CH 3 )； 13 C NMR(101MHz，CDCl 3 )δ：163.11，159.99，151.30，148.96，142.92，135.46，129.37，129.09，128.89，128.66，128.26，128.02，127.57，116.47，112.91，88.16，69.92，63.15，61.68，43.12，28.25，26.27，20.13，11.24。
example 11
Preparation of 5-butyryl-7-hydroxy-2, 2-dimethyl-2, 3-dihydrobenzofuran
3.75mmol of anhydrous zinc chloride and 5mL of dichloromethane are stirred under the condition of ice-water bath (below 10 ℃), 2.5mmol of 2, 2-dimethyl-2, 3-dihydrobenzofuran-7-acetate is added into a three-necked bottle, and then 3.5mmol of butyryl chloride is slowly added dropwise for reaction for 1 hour under ice bath. Then adding 20% sodium bicarbonate solution to adjust the pH value to be neutral, washing with water, removing the solvent, and carrying out column chromatography separation to obtain 5-butyryl-2, 2-dimethyl-2, 3-dihydrobenzofuran-7-acetate which is directly used in the next step. 5mmol of 5-butyryl-2, 2-dimethyl-2, 3-dihydrobenzofuran-7-acetate and 10mL of methanol, followed by addition of 5.4mL of 20% sodium hydroxide, stirring at room temperature for 0.5h, concentration in vacuo, and cooling to 0 ℃ with 10% hydrochloric acid to pH = 3-4, filtration, washing, and drying to give 5-butyryl-7-hydroxy-2, 2-dimethyl-2, 3-dihydrobenzofuran. Used in example 12 to prepare (E) -1- (7-hydroxy-2, 2-dimethyl-2, 3-dihydrobenzofuran-5-yl) butanone oxime methyl ether.
Example 12
(E) Preparation of (E) -1- (7-hydroxy-2, 2-dimethyl-2, 3-dihydrobenzofuran-5-yl) butanone oxime methyl ether (IIIc)
0.468g (2.0 mmol) of 5-butyryl-7-hydroxy-2, 2-dimethyl-2, 3-dihydrobenzofuran (example 11), 0.334g (4.0 mmol) of methoxyamino hydrochloride, 0.328g (4.0 mmol) of anhydrous sodium acetate and 10mL of ethanol are heated to reflux for 2 hours, desolventized, diluted with 30mL of ethyl acetate, extracted and separated by column chromatography to obtain (E) -1- (7-hydroxy-2, 2-dimethyl-2, 3-dihydrobenzofuran-5-yl) butanone oxime methyl ether (IIIc). Used in example 13 to prepare methyl (E) -2- (methoxyimino) -2- (2- (((5- ((E) -1- (methoxyimino) butyl) -2, 2-dimethyl-2, 3-dihydrobenzofuran-7-yl) oxy) methyl) phenyl) acetate.
Example 13
(E) Preparation of methyl (IIe) -2- (methoxyimino) -2- (2- (((5- ((E) -1- (methoxyimino) butyl) -2, 2-dimethyl-2, 3-dihydrobenzofuran-7-yl) oxy) methyl) phenyl) acetate
The compound iiic obtained in example 12 was selected as a starting material and prepared according to the method of example 1 to give methyl (E) -2- (methoxyimino) -2- (2- (((5- ((E) -1- (methoxyimino) butyl) -2, 2-dimethyl-2, 3-dihydrobenzofuran-7-yl) oxy) methyl) phenyl) acetate (ie) as a white solid in 83.2% yield; m.p.102-104 ℃; 1 H NMR(400MHz，CDCl 3 )δ：7.58～7.15(m，4H，C 6 H 4 )，7.07(s，1H，C 6 H 2 )，6.90(s，1H，C 6 H 2 )，5.04(s，2H，OCH 2 )，4.03(s，3H，NOCH 3 )，3.90(s，3H，NOCH 3 )，3.85(s，3H，OCH 3 )，3.01(s，2H，CH 2 )，2.57(t，J＝7.7Hz，2H，CH 2 )，1.51(s，6H，2×CH 3 )，1.40(m，2H，CH 3 CH 2 )，0.87(t，J＝7.3Hz，3H，CH 3 )； 13 C NMR(101MHz，CDCl 3 )δ：163.22，158.77，149.29，149.01，142.83，135.57，129.45，129.15，128.77，128.53，128.29，127.78，127.50，116.55，113.11，88.16，76.73，69.46，63.77，61.60，52.94，43.12，28.61，28.23，20.04，14.20。
example 14
(2E) Preparation of (E) -2- (methoxyimino) -2- (2- (((5- (1- (methoxyimino) butyl) -2, 2-dimethyl-2, 3-dihydrobenzofuran-7-yl) oxy) methyl) phenyl) aceylmethylamine (IIf)
The compound ie obtained in example 13 was selected as a starting material and prepared according to the method of example 2 to give (2E) -2- (methoxyimino) -2- (2- (((5- (1- (methoxyimino) butyl) -2, 2-dimethyl-2, 3-dihydrobenzofuran-7-yl) oxy) methyl) phenyl) aceylmethylamine (if) as a viscous liquid in a yield of 94.7%; 1 H NMR(400MHz，CDCl 3 )δ：7.52～7.22(m，4H，C 6 H 4 )，7.07(s，1H，C 6 H 2 )，6.93(s，1H，C 6 H 2 )，6.79(s，1H，NH)，5.05(s，2H，OCH 2 )，3.93(s，3H，NOCH 3 )，3.91(s，3H，NOCH 3 )，3.02(s，2H，CH 2 )，2.88(d，J＝4.9Hz，3H，NCH 3 )，2.59(t，J＝7.7Hz，2H，CH 2 )，1.50(s，6H，2×CH 3 )，1.41(dd，J＝15.1，7.5Hz，2H，CH 3 CH 2 )，0.87(t，J＝7.3Hz，3H，CH 3 )； 13 C NMR(101MHz，CDCl 3 )δ：163.10，158.90，151.32，148.90，142.85，135.46，129.35，129.09，128.89，128.63，127.98，127.55，116.49，113.04，88.14，76.72，69.92，63.15，61.61，43.13，28.60，28.26，26.28，20.05，14.21。
example 15
Determination of bactericidal activity of dioxime ether compound
Purpose of the test
The toxicity of the new compound to various pathogenic bacteria under the test concentration is measured indoors, and the bactericidal activity of the new compound is preliminarily evaluated.
2 test conditions
2.1 test targets
Cucumber Botrytis cinerea (Botrytis cinerea), alternaria tabaci (Alternaria alternata), wheat gibberellic disease (Gibberella zeae), sclerotinia sclerotiorum (Sclerotinia sclerotiorum) and Phytophthora capsici (Phytophthora capsicii), all of which are stored in a refrigerator (4-8 ℃), inoculated into a culture dish from a test tube slant for 2-3 days before the test, and cultured at a proper temperature for the test. The culture medium for experiments is potato agar (PDA).
2.2 culture conditions
The culture conditions of the test target and the tested target are that the temperature is 25 +/-5 ℃ and the relative humidity is 65 +/-5 percent
2.3 instrumentation
A beaker, a pipette, a measuring cylinder, a culture dish, an autoclave, a constant temperature biochemical incubator and the like.
Design of the experiment
3.1 test agents: the compounds of the examples.
3.2 test concentrations
The concentration of the in vitro medicament is set to be 25mg/L; the concentration of the corn rust disease germ and wheat powdery mildew disease medicament is set to be 500mg/L.
3.3 preparation of the medicament
Raw materials: weighing required amount by using a ten-thousandth electronic balance; solvent: n, N-Dimethylformamide (DMF), 0.2%; emulsifier: 80,0.1 percent of Tween;
and (3) ordinary sieve determination: accurately weighing 0.0500g of sample, dissolving with 0.20mL of LDMF, adding 98.8mL of sterile water containing 0.1% Tween80 emulsifier, stirring well, and making into 500mg/L solution.
4 test method
Refer to "evaluation of biological Activity of pesticides SOP".
Botrytis cinerea, alternaria alternata, fusarium graminearum, sclerotinia sclerotiorum and phytophthora capsici: according to a biological measurement standard method NY/T1156.2-2006, a medicine-containing culture medium method is adopted: 2mL of each 500mg/L compound solution was added to 38mL of PDA cooled to 45 ℃ to prepare a drug-containing medium plate with a final concentration of 25 mg/L. Then, 6.5mm diameter hypha blocks are taken from the edge of the cultured test germ colony and transferred to a culture medium containing the medicine, and the treatment is repeated for 4 times. After the treatment, the culture medium is placed in a constant-temperature biochemical incubator at 28 ℃ for culture, the diameter of a bacterial colony is measured after 4 days, and the growth inhibition rate is calculated.
5 evaluation of Fungicide Activity
After treatment, the morbidity and the hypha growth of the leaves and the plants are regularly observed and recorded, and the control effect and the inhibition rate are calculated according to the disease index and the hypha diameter.
The in vitro bactericidal activity and the in vivo bactericidal activity of the hydroxamic ether compounds are shown in the following table:
"-": not testing
The dioxime ether compound has good bactericidal activity and can be used for preparing bactericides to be applied in agriculture.
Example 16
Determination of insecticidal activity of dioxime ether compounds
1 test target
Broad bean aphid (Aphis fabae) is a sensitive strain which is bred for years indoors by broad bean seedlings, and the test insect is 3-day-old Aphis fabarum. Armyworm (Mythimna sepatara) line was raised with fresh corn leaves for years of sensitive lines; the test insects were 3-instar larvae.
2 culture conditions
The culture conditions of the test target and the post-test target are 25 +/-5 ℃, the relative humidity is 65 +/-5%, and the illumination period is 12/12h (L/D).
3 test agents (technical): a dioxime ether compound.
4, preparing a raw medicine by using the medicine: weighing the required amount by using a ten-thousandth electronic balance; solvent: n, N-Dimethylformamide (DMF), 0.2%; emulsifier: 80.2 percent of Tween; adding clear water to dilute to the required concentration. The insecticidal activity of the new compound is general sieve: the test concentration was 500mg/L.
The 5 test method refers to "evaluation of pesticide biological Activity SOP".
The broad bean aphid general sieve adopts an impregnation method: cutting off broad bean seedlings with 3-day-old broad bean aphids, soaking in the prepared liquid medicine for 10 seconds, taking out, inserting into a sponge full of water, covering with a horse lamp shade, and repeating for 2 times each treatment. After the treatment, the culture medium is placed in an observation chamber for culture, the culture medium is observed regularly, the death condition is checked and recorded after 72 hours, and the death rate is calculated.
The armyworm comprehensive toxicity test method adopts a Potter spraying method, fresh and tender corn leaves are cut into fragments with basically consistent sizes, and the fragments are placed into a culture dish (phi 90 mm) which is previously padded with filter paper. Then 10 heads of mythimna separata larvae of 3 years old are inoculated into the dish, the dish is put under a Potter spray tower for quantitative spraying, the amount of the spraying liquid is 1mL, and the spraying is repeated for 3 times per concentration. And after the treatment is finished, covering a dish cover, placing the dish cover in an observation chamber for culture, periodically observing, and checking and recording the death condition of the test insects after 72 hours.
6 poisoning Activity
The poisoning activity of preferred compounds: when the concentration of the effective component is 500mg/L, after treatment for 72 hours, the death rate of the compounds Ia and Ib to aphids is 100.00 percent; the mortality rates of the compounds IIa and IIb to armyworm are both 100.00%.
The dioxime ether compound has good insecticidal activity and can be used for preparing insecticides for agricultural application.
Claims (5)
1. A class of dioxime ether compounds represented by the structural formula II:
wherein R is 1 ～R 5 Selected from the group consisting of: C1-C2 alkaneA base or C3-C4 linear alkyl; y is selected from: o or NH.
2. The hydroxamic ether compound according to claim 1, selected from the group consisting of compounds represented by formulae ia and ib:
wherein R is 1 ～R 5 Is as defined in claim 1.
3. The dioxime ether compound of claim 1, which is selected from the group consisting of:
4. the process for preparing a dioxime ether compound according to claim 2, wherein the compound of formula IIA is prepared by the following reaction:
the preparation reaction of the monoxime ether compound shown in the formula III is as follows:
wherein R is 1 ～R 5 As defined in claim 1; x is selected from: chlorine, bromine or iodine.
5. Use of a dioxime ether compound as claimed in any of claims 1 to 3 for the preparation of a pesticidal composition against armyworm.
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| DE59309100D1 (en) * | 1992-07-15 | 1998-12-03 | Basf Ag | Substituted oxime ethers and their use to control pests |
| JP3229023B2 (en) * | 1992-07-29 | 2001-11-12 | マツダ株式会社 | Hydrogen gas supply system for hydrogen engine |
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| CN1850819A (en) * | 2006-05-24 | 2006-10-25 | 中山市凯达精细化工股份有限公司 | Method for preparing dihydro safrole |
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| Synthesis and biological evaluation of kresoxim-methyl analogues as novel inhibitors of hypoxia-inducible factor (HIF)-1 accumulation in cancer cells;Sanghyuck Lee 等;《Bioorganic & medicinal chemistry letters》;20170509;第27卷(第13期);第3026-3029页 * |
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