CN101735210B - N-substituted oxadiazine compounds with insecticidal and bactericidal activities, preparation method thereof and use thereof - Google Patents

N-substituted oxadiazine compounds with insecticidal and bactericidal activities, preparation method thereof and use thereof Download PDF

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CN101735210B
CN101735210B CN 200910227085 CN200910227085A CN101735210B CN 101735210 B CN101735210 B CN 101735210B CN 200910227085 CN200910227085 CN 200910227085 CN 200910227085 A CN200910227085 A CN 200910227085A CN 101735210 B CN101735210 B CN 101735210B
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methyl
benzo
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oxadiazine
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CN101735210A (en
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黄明智
胡志彬
王晓光
任叶果
尹笃林
裴晖
何莲
柳爱平
余淑英
罗裴贤
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Hunan Research Institute of Chemical Industry
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Abstract

The invention discloses N-substituted oxadiazine compounds with insecticidal and bactericidal activities represented by a chemical formula (I) and a preparation method thereof and use thereof. The N-substitute oxadiazine compounds are represented by the chemical formula (I), wherein in the general formula (I), R1 may be a benzene ring, a benzoxazinone or benzoxazolone; R2 may be hydrogen or halogenated linear or branched C2 to C6 alky alkenyl, or C3 to C6 cycloalkyl. The method for preparation the compounds of the general formula (I) comprises the following two reaction steps and the reaction formula is shown below. In the reaction formula, R1 and R2 are the same as R1 and R2 in the general formula (I). The biological activity assay shows that the compounds of the general formula (I) of the invention have a 90 percent insecticidal activity on Mythimnaseparata at a concentration of 1,000 mg/L, and a 70 to 100 percent bactericidal activity on Erysiphegraminis at a concentration of 500 mg/L.

Description

Has N substituted dioxazine compound of desinsection, fungicidal activity and its production and use
Technical field
The present invention relates to have desinsection, the N substituted dioxazine compound of fungicidal activity and preparation method thereof.
Background technology
Oxadiazine class (Oxadiazine) sterilant indoxacarb (WO92/11249) is the exploitation in 1992 of Dupont (DuPont) company and the novel sodium channel blocking-up type sterilant of registering listing in calendar year 2001.It has ultra-high efficiency, highly selective, low residue and the mankind, environment, crop and non-target organism is waited safely characteristics, is for the integrated control of insect and the desirable medicament of resistance management.
The initiative of indoxacarb (1) originates from the kobus Wellinga of Philips-Duphar company in 1972 and the Compound P H 60-41 (2) of Rudolph Mulder report, it has the active compound of blocking-up sodium-ion channel, lepidopteran, coleopteran pest is had active preferably.Replace based on discovery compound R H-3421 (3) in 1985 by changing on this basis, it has good insecticidal activity to lepidopterans and coleopterous insect, lower to mammalian toxicity, degradation in soil is also very fast, but this compounds accumulation in vivo and problems such as toxicity of non-target organism are failed to solve always.Based on above characteristics, investigators use the optimum theories such as bioisostere, side chain closed loop, the structure of pyrazoline has been carried out progressively optimizing, through indazole (4), semicarbazone (5), pyridazine (6), finally find oxadiazine (7) structure, obtained sterilant indoxacarb (1) through the prodrug design theory again.The structural formula of above-mentioned 1-7 is as follows:
In order to find new Gao Huo oxadiazine compounds, compound shown in the formula (I) and analogue thereof have been done a large amount of research both at home and abroad, but
Figure G2009102270856D00011
Mainly concentrate on the research of insecticidal activity aspect.In WO9211249, announced the Arthropodicidal De oxadiazine compounds of a large amount of formulas (I), wherein R 2Mostly be-H ,-CH 3Or-COOR, R 1Be phenyl ring system; The chlorine that WO9220682 has announced formula (I) changes CF into 3, R 2For-Et, R 1Gao Huo oxadiazine compounds for p-trifluoromethyl phenyl; The chlorine that WO9516676 has announced formula (I) changes CF into 3, R 2For-H, R 1Be the active compound to the pentafluoride-sulfanyl phenyl; CN1663384 has announced R 2For-COOCH 3, R 1High-activity compound for phenyl or p-trifluoromethyl phenyl.To R 1For the compound of condensed ring system has no report.
For finding new Gao Huo oxadiazine compounds, the inventor constantly carries out Study on Structure Optimizing to general structure (I), the compound that finally works out N substituted dioxazine general structure (I) has bactericidal and insecticidal activity, and is optimized transformation on this basis.
Summary of the invention
The purpose of this invention is to provide and have N substituted dioxazine compound of bactericidal and insecticidal activity and preparation method thereof with chemical structure of general formula (I) expression.
The present invention represents with chemical structure of general formula (I):
Figure G2009102270856D00021
R in the general formula (I) 1Be phenyl ring system, benzoxazinone-based or benzoxazolone system;
R 2Be the halo straight or branched alkane thiazolinyl of hydrogen or 2-6 carbon, the cycloalkyl of a 3-6 carbon.
The preparation method of general formula of the present invention (I) compound comprises following two reactions steps, and reaction formula is as follows:
Figure G2009102270856D00022
R in the reaction formula 1, R 2With R in the general formula (I) 1, R 2Identical.
The first step reaction is as raw material take (A) and hydrogen, take ethyl acetate or methyl acetate, methyl alcohol, ethanol/water as solvent, take palladium or activated carbon loaded palladium as catalyzer, the charge capacity of palladium is 5%～10% (weight percentage), take acetic acid, sodium acetate, SODIUM PHOSPHATE, MONOBASIC as catalyst, the catalyst dosage is 0.1～1.0 times of raw material (A) weight, reaction pressure is normal pressure, temperature of reaction is room temperature to 50 ℃, 20～200 hours reaction times, react complete, obtain intermediate (B) after elimination catalyzer, the water washing.
The second step reaction is as raw material take gained intermediate (B), compound (C), trichloromethylchloroformate (D), take ethyl acetate or methyl acetate, acetone, methylene dichloride, ethylene dichloride, chloroform, benzene, toluene as solvent, take triethylamine or pyridine as depolymerizing agent, the trichloromethylchloroformate dosage is 1～3 times of raw material (B) molar weight, temperature of reaction is-10 ℃ and extremely refluxes, 1～20 hour time, after finishing, reaction gets rid of excessive phosgene with nitrogen, namely get general formula of the present invention (I) compound.
The separating-purifying of general formula (I) compound adopts the method for recrystallization, solvent is one or more the mixture in methyl alcohol, ethanol, propyl alcohol, ethyl acetate, methyl acetate, sherwood oil, benzene,toluene,xylene, chloroform, the methylene dichloride, or the method that adopts column chromatography to separate.
Raw material (A) is according to the synthetic and initiative research (Dalian University of Technology, 2005) of Dingning's Master's thesis “ oxadiazine insecticides " synthetic the obtaining of method of describing, raw material (C), (D) directly buy.
The general formula of partial synthesis of the present invention (I) compound is as follows:
7-chloro-2-{[(7-fluoro-2-methyl-3-oxygen-4-(Propargyl)-3, and 4-dihydro-2H-benzo [Isosorbide-5-Nitrae] oxazine-6-yl) amino] formyl radical }-2; 3,4a, 5-tetrahydrochysene indeno [1; 2-e] [1,3,4] oxadiazine-4a-methyl-formiates (following represent with code name I-01)
7-chloro-2-{[(7-fluoro-3-oxygen-4-(2-oxyethyl group-2-oxygen ethyl)-3, and 4-dihydro-2H-benzo [Isosorbide-5-Nitrae] oxazine-6-yl) amino] formyl radical }-2; 3,4a, 5-tetrahydrochysene indeno [1; 2-e] [1,3,4] oxadiazine-4a-methyl-formiates (following represent with code name I-02)
7-chloro-2-{[(7-fluoro-2-methyl-3-oxygen-4-methyl-3,4-dihydro-2H-benzo [Isosorbide-5-Nitrae] oxazine-6-yl) amino] formyl radical }-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate (following represent with code name I-03)
7-chloro-2-{[(7-fluoro-3-oxygen-3,4-dihydro-2H-benzo [Isosorbide-5-Nitrae] oxazine-6-yl) amino] formyl radical }-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate (following represent with code name I-04)
7-chloro-2-{[(7-fluoro-2-methyl-3-oxygen-4-ethyl-3,4-dihydro-2H-benzo [Isosorbide-5-Nitrae] oxazine-6-yl) amino] formyl radical }-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate (following represent with code name I-05)
7-chloro-2-{[(7-fluoro-3-oxygen-4-(Propargyl)-3, and 4-dihydro-2H-benzo [Isosorbide-5-Nitrae] oxazine-6-yl) amino] formyl radical }-2; 3,4a, 5-tetrahydrochysene indeno [1; 2-e] [1,3,4] oxadiazine-4a-methyl-formiates (following represent with code name I-06)
7-chloro-2-{[(7-fluoro-3-oxygen-4-methyl-3,4-dihydro-2H-benzo [Isosorbide-5-Nitrae] oxazine-6-yl) amino] formyl radical }-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate (following represent with code name I-07)
7-chloro-2-{[(6-fluoro-3-oxygen-3,4-dihydro-2H-benzo [Isosorbide-5-Nitrae] oxazine-7-yl) amino] formyl radical }-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate (following represent with code name I-08)
7-chloro-2-{[(3-oxygen-3,4-dihydro-2H-benzo [Isosorbide-5-Nitrae] oxazine-6-yl) amino] formyl radical }-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate (following represent with code name I-09)
7-chloro-2-(2-oxygen-3-propyl group-2,3-dihydrobenzo [d] oxazole-6-formamyl)-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate (following represent with code name I-10)
7-chloro-2-(2-oxygen-3-ethyl-2,3-dihydrobenzo [d] oxazole-6-formamyl)-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate (following represent with code name I-11)
7-chloro-2-(2-oxygen-2,3-dihydrobenzo [d] oxazole-6-formamyl)-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate (following represent with code name I-12)
7-chloro-2-(2-oxygen-5-methyl-2,3-dihydrobenzo [d] oxazole-6-formamyl)-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate (following represent with code name I-13)
7-chloro-2-(2-oxygen-3-methyl-5-fluoro-2,3-dihydrobenzo [d] oxazole-6-formamyl)-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate (following represent with code name I-14)
7-chloro-2-(2-oxygen-3-methyl-5-chloro-2,3-dihydrobenzo [d] oxazole-6-formamyl)-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate (following represent with code name I-15)
7-chloro-2-[(3-chlorallyl) (4-Trifluoromethoxyphen-l) formamyl]-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate (following represent with code name I-16)
7-chloro-2-[(cyclopropyl methyl) (4-Trifluoromethoxyphen-l) formamyl]-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate (following represent with code name I-17)
The general formula of partial synthesis of the present invention (I) compound (I-01～I-17) materialization data see Table 1, IR and 1H NMR data see Table 2.
Table 1: the general formula of partial synthesis of the present invention (I) compound (chemical structure and the fusing point of I-01～I-17)
Figure G2009102270856D00041
Table 2: the general formula of partial synthesis of the present invention (I) compound (IR of I-01～I-17) and 1H NMR
Figure G2009102270856D00051
Figure G2009102270856D00061
Biological activity test shows, general formula of the present invention (I) compound has deadly activity more than 90% to mythimna separata (Mythimna separata) when 1000mg/L; When 500mg/L, wheat powdery mildew (Erysiphe graminis) there is 70%～100% bacteriostatic activity.
Embodiment
Embodiment 1:7-chloro-2,3,4a, the preparation of 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate (taking off the benzyl intermediate B).
Add 1.6g NaH at 250mL in three mouthfuls of reaction flasks of airway thermometer 2PO 4With 20mL H 2O after the dissolving, adds 0.08g 10%Pd/C, adds simultaneously the 20mL ethyl acetate, passes into N 2, magnetic agitation is heated to 35 ℃.Other gets the 100mL there-necked flask, adds 4.0g (10mmol) 2-benzyl-4a-methyl-7-chloro-4a, 5-dihydro indeno [1,2-e] [1,3,4] oxadiazine-2,4a (3H)-dicarboxylic acid esters and 40mL ethyl acetate and 20mL methyl acetate.Heated and stirred passes into N 2, after the dissolving, about 30min, solution join in the reaction flask that Pd/C is housed, and about cooling temperature to 5 ℃, pass into hydrogen, magnetic agitation reaction 3h.Filter, reclaim Pd/C, filtrate is poured the separating funnel layering into, gets organic phase, and water 15mL ethyl acetate extraction merges organic phase, and saturated aqueous common salt (15mL) is washed anhydrous Na 2SO 4Drying, precipitation gets light yellow viscous liquid, and sealing is preserved, and is directly used in next step reaction.
Embodiment 2:7-chloro-2-{[(7-fluoro-2-methyl-3-oxygen-4-(Propargyl)-3, and 4-dihydro-2H-benzo [Isosorbide-5-Nitrae] oxazine-6-yl) amino] formyl radical }-2; 3,4a, 5-tetrahydrochysene indeno [1; 2-e] [the preparation of 1,3,4] oxadiazine-4a-methyl-formiates (Compound I-01).
To taking off the mixing solutions of benzyl intermediate B with adding 30mL methylene dichloride and 2.67g (10mmol) in the 100mL there-necked flask of thermometer, drip 2.02g (0.02mol) triethylamine, cryosel is bathed, magnetic agitation, when waiting to be cooled to-5 ℃, drip 1.00g (7.1mmol) trichloromethylchloroformate, rapid stirring behind the reaction 15min, passes into nitrogen and gets rid of excessive phosgene, add 1.40g (6mmol) intermediate 6-amino-7-fluoro-2-methyl-4-propargyl-2H-benzo [b] [1,4] oxazine-3 (4H)-ketone, room temperature reaction 1h, reaction solution pour in the 30mL frozen water, the separating funnel layering, get organic phase, water with methylene dichloride (15mL) extraction once merges organic phase, saturated aqueous common salt (20mL) washs once, anhydrous Na 2SO 4Drying, precipitation, column chromatography (use ethyl acetate: the mixed solution of sherwood oil=1: 4 (V/V) is made moving phase).Get white powder 1.83g, be target compound, purity 96%, yield 58%.
Embodiment 3:7-chloro-2-{[(7-fluoro-3-oxygen-3,4-dihydro-2H-benzo [Isosorbide-5-Nitrae] oxazine-6-yl) amino] formyl radical }-2,3,4a, the preparation of 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate (Compound I-04).
100mL there-necked flask with thermometer, add methylene dichloride 30mL and 2.67g (10mmol) and take off the mixing solutions of benzyl intermediate B, drip 2.02g (0.02mol) triethylamine, cryosel is bathed, magnetic agitation, when waiting to be cooled to-5 ℃ of left and right sides, drip 1.00g (7.1mmol) trichloromethylchloroformate, rapid stirring, behind the reaction 15min, pass into nitrogen and get rid of excessive phosgene, add 1.09g (6mmol) intermediate 6-amino-7-fluoro-2H-benzo [b] [Isosorbide-5-Nitrae] oxazine-3 (4H)-ketone, room temperature reaction 1h, reaction solution is poured in the 30mL frozen water, and organic phase is got in the separating funnel layering, water with methylene dichloride (15mL) extraction once, merge organic phase, saturated aqueous common salt (20mL) washs once, anhydrous Na 2SO 4Drying, precipitation, column chromatography (use ethyl acetate: the mixed solution of sherwood oil=1: 4 (V/V) is made moving phase) gets white powder 1.82g, is target compound, purity 95%, yield 64%.
Embodiment 4:7-chloro-2-{[(7-fluoro-2-methyl-3-oxygen-4-ethyl-3, and 4-dihydro-2H-benzo [Isosorbide-5-Nitrae] oxazine-6-yl) amino] formyl radical }-2; 3,4a, 5-tetrahydrochysene indeno [1; 2-e] [the preparation of 1,3,4] oxadiazine-4a-methyl-formiates (Compound I-05).
To taking off the mixing solutions of benzyl intermediate B with adding 30mL methylene dichloride and 2.67g (10mmol) in the 100mL there-necked flask of thermometer, drip 2.02g (0.02mol) triethylamine, cryosel is bathed, magnetic agitation, when waiting to be cooled to-5 ℃ of left and right sides, drip 1.00g (7.1mmol) trichloromethylchloroformate, rapid stirring behind the reaction 15min, passes into nitrogen and gets rid of excessive phosgene, add 1.34g (6mmol) intermediate 6-amino-7-fluoro-2-methyl-4-ethyl-2H-benzo [b] [1,4] oxazine-3 (4H)-ketone, room temperature reaction 1h, reaction solution pour in the 30mL frozen water, the separating funnel layering, get organic phase, water with methylene dichloride (15mL) extraction once merges organic phase, saturated aqueous common salt (20mL) washs once, anhydrous Na 2SO 4Drying, precipitation, column chromatography (use ethyl acetate: the mixed solution of sherwood oil=1: 4 (V/V) is made moving phase) gets white powder 1.89g, is target compound, purity 96%, yield 61%.
Embodiment 5:7-chloro-2-(2-oxygen-3-methyl-5-chloro-2,3-dihydrobenzo [d] oxazole-6-formamyl)-2,3,4a, the preparation of 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate (Compound I-15).
To taking off the mixing solutions of benzyl intermediate B with adding 30mL methylene dichloride and 2.67g (10mmol) in the 100mL there-necked flask of thermometer, drip 2.02g (0.02mol) triethylamine, cryosel is bathed, magnetic agitation when waiting to be cooled to-5 ℃ of left and right sides, drips 1.00g (7.1mmol) trichloromethylchloroformate, rapid stirring, behind the reaction 15min, pass into nitrogen and get rid of excessive phosgene, add 1.18g (6mmol) intermediate 6-amino-3-methyl-5-chloro-benzo [d] oxazole-2 (3H)-ketone.Room temperature reaction 1h.Reaction solution is poured in the 30mL frozen water, and organic phase is got in the separating funnel layering, and water with methylene dichloride (15mL) extraction once merges organic phase, and saturated aqueous common salt (20mL) washs once, anhydrous Na 2SO 4Drying, precipitation, column chromatography (use ethyl acetate: the mixed solution of sherwood oil=1: 4 (V/V) is made moving phase), precipitation gets white powder 1.56g, is target compound, purity 97%, yield 53%.
Embodiment 6:7-chloro-2-[(3-chlorallyl) (4-Trifluoromethoxyphen-l) formamyl]-2,3,4a, the preparation of 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate (Compound I-16).
To taking off the mixing solutions of benzyl intermediate B with adding 30mL methylene dichloride and 2.67g (10mmol) in the 100mL there-necked flask of thermometer, drip 2.02g (0.02mol) triethylamine, cryosel is bathed, magnetic agitation when waiting to be cooled to-5 ℃ of left and right sides, drips 1.00g (7.1mmol) trichloromethylchloroformate, rapid stirring, behind the reaction 15min, pass into nitrogen and get rid of excessive phosgene, add 1.51g (6mmol) intermediate N (3-chlorallyl)-4-trifluoromethoxy phenylamino.Room temperature reaction 1h.Reaction solution is poured in the 30mL frozen water, and organic phase is got in the separating funnel layering, and water with methylene dichloride (15mL) extraction once merges organic phase, and saturated aqueous common salt (20mL) washs once, anhydrous Na 2SO 4Drying, precipitation, column chromatography (use ethyl acetate: the mixed solution of sherwood oil=1: 9 (V/V) is made moving phase), precipitation gets white powder 1.82g, is target compound, purity 96%, yield 56%.
Embodiment 7:7-chloro-2-[(cyclopropyl methyl) (4-Trifluoromethoxyphen-l) formamyl]-2,3,4a, the preparation of 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate (Compound I-17).
To taking off the mixing solutions of benzyl intermediate B with adding 30mL methylene dichloride and 2.67g (10mmol) in the 100mL there-necked flask of thermometer, drip 2.02g (0.02mol) triethylamine, cryosel is bathed, magnetic agitation when waiting to be cooled to-5 ℃ of left and right sides, drips 1.00g (7.1mmol) trichloromethylchloroformate, rapid stirring, behind the reaction 15min, pass into nitrogen and get rid of excessive phosgene, add 1.39g (6mmol) intermediate N cyclopropyl methyl-4-trifluoromethoxy phenylamino.Room temperature reaction 1h.Reaction solution is poured in the 30mL frozen water, and organic phase is got in the separating funnel layering, and water with methylene dichloride (15mL) extraction once merges organic phase, and saturated aqueous common salt (20mL) washs once, anhydrous Na 2SO 4Drying, precipitation, column chromatography (use ethyl acetate: the mixed solution of sherwood oil=1: 9 (V/V) is made moving phase), precipitation gets white powder 1.88g, is target compound, purity 97%, yield 52%.
Application Example 1: desinsection, fungicidal activity test
The concentrated floating agent of preparation: water, tensio-active agent, antifreezing agent, defoamer, thickening material and the sanitas with certain proportioning mixes composition homogeneous water first, and then (I) De oxadiazine compounds, suitable solvent and emulsifying agent, co-emulsifier mix makes it become even oil phase with formula provided by the invention.At last under high-speed stirring with the even oil phase emulsifiable concentrates that namely can be made into mixed with water.Be diluted with water to required any concentration during use.
Insecticidal Activity to mythimna separata (Mythimna separata)
Method is as follows: will be by the former medicine of Ti Gong De oxadiazine compounds of the present invention of above-mentioned Agrotechnical formulation embodiment method preparation, dissolve with a small amount of organic solvent such as DMF, add again an amount of Tween80 emulsifying agent, stir, adding clear water, to be made into the pesticidal solutions of predetermined concentration for subsequent use, in being lined with the culture dish of filter paper (Ф 90mm), puts into 4 of the basically identical maize leafs of size, access again 10 of mythimna separata third-instar larvaes, be put under the Potter spray tower and spray with liquid to be measured.Spray amount 1ml/10 head, 3 repetitions.Be disposed, be put into the recovery indoor cultivation.Regularly observe.Check behind the 48h and the record death condition, calculate mortality ratio.Activity in per-cent, is divided into A, B, C, D level Four with respect to blank, and mortality ratio 100%-90% is the A level, and mortality ratio 90%-70% is the B level, and mortality ratio 70%-50% is the C level, and mortality ratio 50%-0% is the D level.Partial test the results are shown in Table 3.
Table 3: the compounds of this invention of part shown in general formula (I) is to the activity of mythimna separata (Mythimna separata)
Compound I-01 I-04 I-05 I-15 I-16
Active rank * A A A A A
*: test concentrations is 1000mg/L.
Fungicidal activity evaluation to wheat powdery mildew (Erysiphe graminis)
Method is as follows: testing compound is dissolved in suitable solvent such as the acetone, add again an amount of Tween80 emulsifying agent, stir, adding clear water, to be made into the pesticidal solutions of predetermined concentration for subsequent use, the liquid for preparing is evenly sprayed on stem and leaf of Wheat for subsequent use, behind the liquid natural air drying, 24h after chemicals treatment evenly shakes off to be inoculated on the stem and leaf of Wheat of processing with the fresh spore of wheat powdery mildew that produces in the 24h on the morbidity wheat leaf blade.Every processing is no less than 3 basins, every basin 10 strains.Inoculation is rear in 10-15 days " Invest, Then Investigate " results of artificial climate greenhouse placement.Partial test the results are shown in Table 4.
Table 4: the compounds of this invention of part shown in general formula (I) is to the activity of wheat powdery mildew (Erysiphe graminis)
Compound I-15 I-16 I-17
Active rank * A B B
*: test concentrations is 500mg/L.

Claims (3)

1.N substituted dioxazine compound is characterized in that (I) is as follows for chemical structure of general formula with chemical structure of general formula (I) expression:
Figure FDA00002183679800011
Wherein:
Work as R 1Be 7-fluoro-2-methyl-4-(Propargyl)-2H-benzo [b] [Isosorbide-5-Nitrae] oxazine-3 (4H)-ketone-6-base, R 2During for hydrogen, general formula (I) is 7-chloro-2-{[(7-fluoro-2-methyl-3-oxygen-4-(Propargyl)-3, and 4-dihydro-2H-benzo [Isosorbide-5-Nitrae] oxazine-6-yl) amino] formyl radical }-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiates;
Work as R 1Be 7-fluoro-4-(2-oxyethyl group-2-oxygen ethyl)-2H-benzo [b] [Isosorbide-5-Nitrae] oxazine-3 (4H)-ketone-6-base, R 2During for hydrogen, general formula (I) is 7-chloro-2-{[(7-fluoro-3-oxygen-4-(2-oxyethyl group-2-oxygen ethyl)-3, and 4-dihydro-2H-benzo [Isosorbide-5-Nitrae] oxazine-6-yl) amino] formyl radical }-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiates;
Work as R 1Be 7-fluoro-2,4-dimethyl-2H-benzo [b] [Isosorbide-5-Nitrae] oxazine-3 (4H)-ketone-6-base, R 2During for hydrogen, general formula (I) is 7-chloro-2-{[(7-fluoro-2-methyl-3-oxygen-4-methyl-3,4-dihydro-2H-benzo [Isosorbide-5-Nitrae] oxazine-6-yl) amino] formyl radical }-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate;
Work as R 1Be 7-fluoro-2H-benzo [b] [Isosorbide-5-Nitrae] oxazine-3 (4H)-ketone-6-base, R 2During for hydrogen, general formula (I) is 7-chloro-2-{[(7-fluoro-3-oxygen-3,4-dihydro-2H-benzo [Isosorbide-5-Nitrae] oxazine-6-yl) amino] formyl radical }-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate;
Work as R 1Be 7-fluoro-2-methyl-4-ethyl-2H-benzo [b] [Isosorbide-5-Nitrae] oxazine-3 (4H)-ketone-6-base, R 2During for hydrogen, general formula (I) is 7-chloro-2-{[(7-fluoro-2-methyl-3-oxygen-4-ethyl-3,4-dihydro-2H-benzo [Isosorbide-5-Nitrae] oxazine-6-yl) amino] formyl radical }-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate;
Work as R 1Be 7-fluoro-4-(Propargyl)-2H-benzo [b] [Isosorbide-5-Nitrae] oxazine-3 (4H)-ketone-6-base, R 2During for hydrogen, general formula (I) is 7-chloro-2-{[(7-fluoro-3-oxygen-4-(Propargyl)-3,4-dihydro-2H-benzo [Isosorbide-5-Nitrae] oxazine-6-yl) amino] formyl radical }-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate;
Work as R 1Be 7-fluoro-4-methyl-2H-benzo [b] [Isosorbide-5-Nitrae] oxazine-3 (4H)-ketone-6-base, R 2During for hydrogen, general formula (I) is 7-chloro-2-{[(7-fluoro-3-oxygen-4-methyl-3,4-dihydro-2H-benzo [Isosorbide-5-Nitrae] oxazine-6-yl) amino] formyl radical }-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate;
Work as R 1Be 6-fluoro-2H-benzo [b] [Isosorbide-5-Nitrae] oxazine-3 (4H)-ketone-7-base, R 2During for hydrogen, general formula (I) is 7-chloro-2-{[(6-fluoro-3-oxygen-3,4-dihydro-2H-benzo [Isosorbide-5-Nitrae] oxazine-7-yl) amino] formyl radical }-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate;
Work as R 1Be 2H-benzo [b] [Isosorbide-5-Nitrae] oxazine-3 (4H)-ketone-6-base, R 2During for hydrogen, general formula (I) is 7-chloro-2-{[(3-oxygen-3,4-dihydro-2H-benzo [Isosorbide-5-Nitrae] oxazine-6-yl) amino] formyl radical }-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate;
Work as R 1Be 3-propyl group benzo [d] oxazole-2 (3H)-ketone-6-base, R 2During for hydrogen, general formula (I) is 7-chloro-2-(2-oxygen-3-propyl group-2,3-dihydrobenzo [d] oxazole-6-formamyl)-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate;
Work as R 1Be 3-ethyl benzo [d] oxazole-2 (3H)-ketone-6-base, R 2During for hydrogen, general formula (I) is 7-chloro-2-(2-oxygen-3-ethyl-2,3-dihydrobenzo [d] oxazole-6-formamyl)-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate;
Work as R 1Be benzo [d] oxazole-2 (3H)-ketone-6-base, R 2During for hydrogen, general formula (I) is 7-chloro-2-(2-oxygen-2,3-dihydrobenzo [d] oxazole-6-formamyl)-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate;
Work as R 1Be 5-methyl benzo [d] oxazole-2 (3H)-ketone-6-base, R 2During for hydrogen, general formula (I) is 7-chloro-2-(2-oxygen-5-methyl-2,3-dihydrobenzo [d] oxazole-6-formamyl)-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate;
Work as R 1Be 5-fluoro-3-methyl benzo [d] oxazole-2 (3H)-ketone-6-base, R 2During for hydrogen, general formula (I) is 7-chloro-2-(2-oxygen-3-methyl-5-fluoro-2,3-dihydrobenzo [d] oxazole-6-formamyl)-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate;
Work as R 1Be 5-chloro-3-methyl benzo [d] oxazole-2 (3H)-ketone-6-base, R 2During for hydrogen, general formula (I) is 7-chloro-2-(2-oxygen-3-methyl-5-chloro-2,3-dihydrobenzo [d] oxazole-6-formamyl)-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate;
Work as R 1Be 4-Trifluoromethoxyphen-l, R 2During for the 3-chlorallyl, general formula (I) is 7-chloro-2-[(3-chlorallyl) (4-Trifluoromethoxyphen-l) formamyl]-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate;
Work as R 1Be 4-Trifluoromethoxyphen-l, R 2During for the cyclopropyl methyl, general formula (I) is 7-chloro-2-[(cyclopropyl methyl) (4-Trifluoromethoxyphen-l) formamyl]-2,3,4a, 5-tetrahydrochysene indeno [1,2-e] [1,3,4] oxadiazine-4a-methyl-formiate.
2. the preparation method of N substituted dioxazine compound according to claim 1 is characterized in that comprising following two reactions steps, and reaction formula is as follows:
Figure FDA00002183679800021
R in the reaction formula 1, R 2With R in the general formula (I) 1, R 2Identical;
The first step reaction is as raw material take (A) and hydrogen, take ethyl acetate or methyl acetate, methyl alcohol, ethanol/water as solvent, take palladium or activated carbon loaded palladium as catalyzer, the charge capacity of palladium is 5%～10%(weight percentage), take acetic acid, sodium acetate, SODIUM PHOSPHATE, MONOBASIC as catalyst, the catalyst dosage is 0.1～1.0 times of raw material (A) weight, reaction pressure is normal pressure, temperature of reaction is room temperature to 50 ℃, 20～200 hours reaction times, react complete, obtain intermediate (B) after elimination catalyzer, the water washing;
The second step reaction is as raw material take gained intermediate (B), compound (C), trichloromethylchloroformate (D), take ethyl acetate or methyl acetate, acetone, methylene dichloride, ethylene dichloride, chloroform, benzene, toluene as solvent, take triethylamine or pyridine as depolymerizing agent, the trichloromethylchloroformate dosage is 1～3 times of raw material (B) molar weight, temperature of reaction is-10 ℃ and extremely refluxes, 1～20 hour time, after finishing, reaction gets rid of excessive phosgene with nitrogen, namely get general formula of the present invention (I) compound; The separating-purifying of gained general formula (I) compound adopts the method for recrystallization, solvent is one or more the mixture in methyl alcohol, ethanol, propyl alcohol, ethyl acetate, methyl acetate, sherwood oil, benzene,toluene,xylene, chloroform, the methylene dichloride, or the method that adopts column chromatography to separate.
3. the purposes of N substituted dioxazine compound according to claim 1 is characterized in that mythimna separata (Mythimna separata) and wheat powdery mildew (Erysiphe graminis) are had prevention effect.
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