WO2013003977A1 - 2,5-二取代-3-硝亚胺基-1,2,4-三唑啉类化合物及其制备方法与其作为杀虫剂的应用 - Google Patents
2,5-二取代-3-硝亚胺基-1,2,4-三唑啉类化合物及其制备方法与其作为杀虫剂的应用 Download PDFInfo
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- WO2013003977A1 WO2013003977A1 PCT/CN2011/001096 CN2011001096W WO2013003977A1 WO 2013003977 A1 WO2013003977 A1 WO 2013003977A1 CN 2011001096 W CN2011001096 W CN 2011001096W WO 2013003977 A1 WO2013003977 A1 WO 2013003977A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/14—Nitrogen atoms
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
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- the present invention relates to 2,5-disubstituted-3-niminoimido-1,2,4-triazoline compounds and precursors thereof, nitroaminoamino compounds, processes for their preparation, and their use as insecticides Application of the agent.
- the imidacloprid developed by Bayer in the 1980s is an outstanding representative of neonicotinoid insecticides. It has excellent control effects on sucking pests, certain chewable pests, soil pests and pet fleas. A wide range of applications. Subsequently, it was found that dehydropyridinium, a metabolite of imidacloprid in the soil, has stronger insecticidal activity than it, which has caused great interest. However, the synthesis of dehydropyrimidin is not easy, and it has not been able to be industrialized on a large scale.
- the object of the present invention is to provide an insecticidal active compound 2,5-disubstituted-3-niminoimido-1,2,4-triazoline having a structure similar to dehydropyrimidin, and a precursor compound nitro group for preparing the same Aminoguanidine compounds.
- ⁇ is a C1 ⁇ C10 saturated or unsaturated aliphatic hydrocarbon group, a C1 ⁇ C10 saturated or unsaturated fluoroaliphatic hydrocarbon group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted thiazolyl group, a substituted or Unsubstituted pyrazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted isoxazolyl, or tetrahydrofuranyl; wherein, substituted phenyl, substituted pyridyl, substituted thiazolyl, substituted
- the substituents in the pyrazolyl, substituted oxazolyl and substituted isoxazolyl groups may be independently selected from any one or more of the following groups: halogen (specifically F, Cl, Br, I), amino group, hydroxyl
- the substituent in the phenyl group may be halogen, hydroxy, amino, C1 to C5 alkyl, C1 to C5 alkoxy, C1 to C5 fluoroalkyl or C1 to C5 fluoroalkoxy, aryl (e.g., phenyl, pyridyl, imidazolyl, oxazolyl, thiazolyl), aryloxy (e.g., phenoxy, pyridyloxy), etc.
- the substituent in the substituted pyridyl group may be halogen, C1 a C5 al
- the substituent in the substituted furyl group may be a halogen, a trifluoromethyl group or the like, and the substituent in the substituted naphthyl group may be a C1 to C5 alkyl group, a hydroxyl group, a nitro group, a halogen group, an amino group or the like.
- Preferred is (: 1 to (: 10 unsaturated aliphatic hydrocarbon group, halopy pyridyl group, halothiazolyl group, or tetrahydrofuranyl group; preferably R 2 is hydrogen, substituted phenyl group, or C1 to C7 saturated or unsaturated aliphatic hydrocarbon group) .
- ⁇ is vinyl, ethynyl, chloropyridyl, chlorothiazolyl, tetrahydrofuran-3-yl; more preferably R 2 is hydrogen, halophenyl or C3 to C7 saturated or unsaturated aliphatic hydrocarbon.
- the saturated or unsaturated aliphatic hydrocarbon group in the present invention may be a straight chain or a branched chain.
- a method for preparing a 2,5-disubstituted-3-niminoimido-1,2,4-triazoline of the formula I and a nitroamino hydrazine compound of the formula VI includes the following steps:
- nitroguanidine reacts with hydrazine hydrate to form nitroaminoguanidine of formula II;
- ⁇ is the same as in the formula I, X is Cl, Br, I, OTos (p-toluenesulfonyloxy) or OTf (trifluoromethanesulfonyloxy);
- reaction in the step 1) is carried out in a solvent
- the solvent may be water
- reaction temperature of the reaction is 45-70 ° C
- the molar ratio of nitroguanidine to hydrazine hydrate can be 1: (1-1.5).
- the reaction in the step 2) is carried out in a solvent, and the solvent may be anhydrous ethanol or methanol; the reaction temperature of the reaction may be 50-80 ° C; the acid used in the reaction may specifically be acetic acid or Toluenesulfonic acid.
- Step 2) The molar ratio of the nitroaminopurine to the carbonyl compound of the formula III in the reaction may be 1: (1-2).
- the reaction in the step 3) is carried out in a solvent, which may be DMF (; dimethylformamide) or DME (; dimethylacetamide;); the reaction temperature may be 0-50 ° C; The base used in the reaction may specifically be sodium hydride, sodium ethoxide, sodium methoxide or sodium amide.
- Step 3) The molar ratio of the compound of the formula IV to the compound of the formula V may be 1: (1.2-2.5).
- the reaction in the step 4) is carried out in a solvent, which may be water, methanol, ethanol, acetonitrile; the temperature of the reaction is 0-100 ° C; the weakly acidic medium may be dilute hydrochloric acid, dilute sulfuric acid, Phosphoric acid or acetic acid; the weakly basic medium may be an aqueous solution of sodium carbonate, an aqueous solution of sodium acetate, dilute sodium hydroxide, pyridine, or triethylamine.
- a solvent which may be water, methanol, ethanol, acetonitrile
- the temperature of the reaction is 0-100 ° C
- the weakly acidic medium may be dilute hydrochloric acid, dilute sulfuric acid, Phosphoric acid or acetic acid
- the weakly basic medium may be an aqueous solution of sodium carbonate, an aqueous solution of sodium acetate, dilute sodium hydroxide, pyridine, or triethylamine.
- Another object of the present invention is to provide a 2,5-disubstituted-1,2,4-triazoline-3-nitroimine compound of the formula I and a nitroamino hydrazine compound of the formula VI the use of.
- the 2,5-disubstituted-1,2,4-triazoline-3-niminoimine compound represented by the structural formula of the formula I provided by the present invention and the nitroaminoamino compound represented by the formula VI The use of the compound of formula I and VI or a pharmaceutically acceptable salt thereof or a pharmaceutical composition containing any of them Application in plant pesticides.
- Still another object of the present invention is to provide two plant insecticides and their formulations.
- the plant insecticidal drug or preparation provided by the invention wherein the active ingredient is a 2,5-disubstituted-1,2,4-triazoline-3-niminoimine compound represented by the formula I; A nitroaminoguanidine compound of the formula VI or a pharmaceutically acceptable salt thereof.
- the mass percentage of the active ingredient in the plant insecticide or preparation is from 0.01% to 99.99%.
- the insecticidal formulation can be processed into any acceptable dosage form as desired.
- it may be a suspending agent, an emulsion, an aerosol, a wettable powder, an emulsifiable concentrate, a granule, or the like.
- suspending agent The active ingredient content in the commonly used formula is 5%-35%.
- the water, the main drug, the water dispersing agent, the suspending agent and the antifreezing agent are added to the sander and ground to prepare a suspending agent.
- Preparation of wettable powder According to the formulation requirements, the original drug, various surfactants and solid diluents are thoroughly mixed, and after superfine pulverization, a predetermined content of the wettable powder product is obtained. In order to prepare a wettable powder suitable for spraying, a mixture of the original drug and a finely divided solid powder such as a clay, an inorganic silicate, a carbonate, and a wetting agent, a binder and/or a dispersing agent may also be used.
- a finely divided solid powder such as a clay, an inorganic silicate, a carbonate, and a wetting agent, a binder and/or a dispersing agent may also be used.
- emulsifiable concentrate It is prepared by dissolving the active ingredient in an organic solvent according to the formulation requirements, adding emulsifier and other auxiliary agents.
- the solvent may be toluene, xylene, methanol, etc., and if necessary, a cosolvent; other additives, including stabilizers, penetrants, and corrosion inhibitors.
- the compounds of formula I and formula VI provided by the present invention and insecticidal drugs or preparations using the same as active ingredients can control and eliminate a wide range of pests, including sucking insects (Sucking insects), mites (; Biting insects) ) and other plant pests, storage of cereal pests and health pests that cause health hazards.
- Homopteran pests include pests of the family Polygonaceae, Fanicidae, Polygonaceae, Hibiscus, Aphididae and Polygonaceae.
- the pests of the genus Polygonaceae may be cotton aphid, soybean meal, peach aphid, peach meal, radish or cabbage aphid; the pests of the plant may be brown planthopper or rice planthopper; the pests of the whitefly may be beech white;
- the pests of the genus Polygonaceae can be black-tailed spider mites; the pests of the genus Polygonaceae can be genus.
- Lepidopteran pests include the Noctuidae and the Plutella xylostella pests.
- the pest of the Noctuidae can be Beet armyworm, Spodoptera litura or Helicoverpa armigera; the pest of the genus Hydrangea can be Plutella xylostella.
- the true eyeworm includes the leafhopper pest.
- the leaf worm can specifically be cinnabar leafhopper.
- the plant insecticidal drugs or preparations provided by the present invention can be used for controlling plant pests. Especially for sucking pests, scraping mouthparts pests, such as various types of aphids, flying locusts, leaf mites, leaf mites, white mites, scorpion horses have special effects, and are highly effective against cotton bollworm and beet armyworm.
- the method for controlling plant pests provided by the present invention is to apply the plant insecticidal drug or preparation provided by the present invention to plant leaves and/or fruits and/or seeds, and the leaves and/or fruits and/or seeds of the plants are being In an environment in which growth or anticipation is to be grown; the active ingredient of the plant insecticide or formulation is applied at a concentration of from 1 to 600 mg/L, preferably at a concentration of from 3 to 50 mg/L.
- the structure characterization data is as follows: 1H NMR (CDCl 3 , 5 ppm): 0.93 (t, 3H), 1.28-1.38 (m, 2H) ; 1.48-1.58 (m, 2H), 2.36-2.42 (m, 2H), 5.25 ( s, 2H), 7.39 (t, lH), 7.42 (s, lH), 7.42 (brs, lH), 8.99 (brs, lH)
- Example 3 the insecticidal activity test of the compound of formula I and formula VI provided by the present invention
- Aphids belong to Homoptera pests and have a sucking mouth device, which is a common pest of common crops.
- ⁇ ⁇ ⁇ (radish ⁇ ) (z ⁇ op s er /m/) is the test object, tested by dipping method.
- the peach aphid was collected from the cabbage field in Haidian District, Beijing.
- the peach aphid was collected from Taoshu, Haidian District, Beijing.
- the cotton aphid was collected from Mudu Tree, Haidian District, Beijing.
- the vegetable tube was collected from the cabbage field in Haidian District, Beijing.
- the 3 day old nymph was measured.
- Triton X-100 The mass percentage of 0.5% mother liquor is used to make a mass percentage of 0.5% mother liquor, and the mass content is 0.1% Triton X-100.
- the aqueous solution is formulated into a measuring solution having a concentration of 0.06% (i.e., 600 ppm) (the solution can be diluted to the desired concentration when the concentration is low;).
- the criteria for death judgment are: Lightly touching the worm, and the individual who cannot crawl normally is regarded as a dead individual.
- Corrected mortality (%) (sample mortality - blank control mortality) I (1-blank control mortality) ⁇ 100%.
- the cinnabar is a female cockroach i Tetranychus cinnabarinus Boisduva, taken from the singular beta cotton field.
- the insecticidal activity is determined by the dipping method.
- the bean leaves transferred to the cinnabar leafhopper are immersed in the liquid for 5 s. After drying, the number of insects is recorded in a petri dish with moisturizing filter paper, and the petiole is moisturized.
- the criteria for death are: Light-touched worms, individuals who cannot crawl normally are considered dead individuals.
- Helicoverpa armigera is a pest of Lepidoptera, and has a chewing mouth.
- the sample of the compound is weighed in a one-tenth of a 10,000-week volume, and the mother liquor is prepared with dimethylformamide (DMF), and then 0.1% Triton
- Operation process Clean the cotton leaf, use a puncher to cut the clean leek leaf into a 2cm diameter leaf dish, soak it in the liquid for 10s, dry it, put the leaf dish into the 10-hole test box, and connect the cotton bollworm 2nd instar larvae, 1 per hole, add plastic wrap, cover and put in (27 ⁇ 1) °C light incubator. Check the results after 48 hours. Death occurs when the needle touches the insect body and the reaction is abnormal or non-responsive.
- DMF dimethylformamide
- Operation process Wash the leek leaves and use a puncher to cut the clean leek leaves into diameters.
- WP wettable powder
- SC suspending agent
- the present invention provides a 2,5-disubstituted-3-niminoimido-1,2,4-triazoline compound of the formula I and a precursor compound thereof, and a nitro group of the formula VI.
- Preparation methods and applications of terpenoids The above compounds are extensively investigated and rationally designed by the inventors of the present invention, and The screening of the quantitative compound has a high insecticidal activity, and the preparation method is simple, and provides a preferred process route, which has good safety and low cost, and the practical application value of the compound is greatly improved.
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Abstract
本发明公开了2,5-二取代-3-硝亚胺基-1,2,4-三唑啉类化合物及其前体硝基缩氨基胍类化合物的制备方法与应用。它们的结构式如式(I)和式(VI)所示,其中,R1为C1〜C10饱和或不饱和脂肪烃基、C1〜C10饱和或不饱和氟代脂肪烃基、取代或未取代的苯基、取代或未取代的吡啶基、取代或未取代的噻唑基、取代或未取代的吡唑基、取代或未取代的恶唑基、取代或未取代的异恶唑基、或四氢呋喃基;R2为氢、C1〜C10饱和或不饱和脂肪烃基、取代或未取代的苯基、取代或未取代的吡啶基、取代或未取代的呋喃基、取代或未取代的萘基。杀虫活性实验表明,式(I)所示的及式(VI)所示的化合物对蚜虫、飞虱、叶螨、棉铃虫、甜菜夜蛾等农作物害虫具有很高的防效,可用作植物杀虫剂使用。
Description
2,5-二取代 -3-硝亚胺基 -1,2,4-三唑啉类化合物及其制备方法与其作为 杀虫剂的应用 技术领域
本发明涉及 2,5-二取代 -3-硝亚胺基 -1,2,4-三唑啉类化合物及其前体硝基 缩氨基胍类化合物与它们的制备方法, 以及其作为杀虫剂的应用。
背景技术
拜耳公司于 20世纪 80年代开发的吡虫啉是新烟碱类杀虫剂的杰出代 表, 对吮吸式害虫、 某些咀嚼性害虫、 土壤害虫及宠物跳蚤等具有优异的 防效, 在农业生产中取得了广泛的应用。 随后人们发现吡虫啉在土壤中的 代谢产物脱氢吡虫啉具有比其更强的杀虫活性, 从而引起了人们极大的兴 趣, 但脱氢吡虫啉合成不易, 目前尚无法大规模工业化生产。
发明公开
本发明的目的是提供结构与脱氢吡虫啉类似的杀虫活性化合物 2,5-二取 代 -3-硝亚胺基 -1,2,4-三唑啉, 以及制备它们的前体化合物硝基缩氨基胍类 化合物。
本发明所提供的 2,5-二取代 -3-硝亚胺基 -1,2,4-三唑啉类化合物的结构 通式如式 I所示, 其前体化合物硝基缩氨基胍类化合物的结构通式如式 VI 所示:
N'N02
NN02
NH X R
N Η2Ν « 2
Ri H
(;式 I) (;式 VI)
式 I和式 VI中:
!^为 C1〜C10饱和或不饱和脂肪烃基、 C1〜C10饱和或不饱和氟代脂 肪烃基、 取代或未取代的苯基、 取代或未取代的吡啶基、 取代或未取代的 噻唑基、 取代或未取代的吡唑基、 取代或未取代的恶唑基、 取代或未取代 的异恶唑基、 或四氢呋喃基; 其中, 所述取代的苯基、 取代的吡啶基、 取 代的噻唑基、 取代的吡唑基、 取代的恶唑基和取代的异恶唑基中的取代基 可独立的选自下述基团中的任意一种或几种: 卤素 (具体可为 F、 Cl、 Br、 I) 、 氨基、 羟基、 C1〜C5的烷基、 C1〜C5的烷氧基、 C1〜C5的氟
代烷基和 C1〜C5的氟代烷氧基等;
为氢、 C1〜C10饱和或不饱和脂肪烃基、 取代或未取代的苯基、 取 代或未取代的吡啶基、 取代或未取代的呋喃基、 取代或未取代的萘基; 其 中, 所述取代苯基中的取代基可为卤素、 羟基、 氨基、 C1〜C5的烷基、 C1〜C5的烷氧基、 C1〜C5的氟代烷基或 C1〜C5的氟代烷氧基、 芳基 (如: 苯基、 吡啶基、 咪唑基、 恶唑基、 噻唑基) 、 芳氧基 (如: 苯氧 基、 吡啶氧基) 等, 所述取代吡啶基中的取代基可为卤素、 C1〜C5的烷 基、 C1〜C5的烷氧基、 C1〜C5的氟代烷基或 C1〜C5的氟代烷氧基、 芳 氧基 (如: 苯氧基、 吡啶氧基) 等, 所述取代呋喃基中的取代基可为卤 素、 三氟甲基等, 所述取代的萘基中的取代基可为 C1〜C5烷基、 羟基、 硝 基、 卤素、 氨基等。
优选的 为(:1〜(:10不饱和脂肪烃基、 卤代吡啶基、 卤代噻唑基、 或四氢呋喃基; 优选的 R2为氢、 取代苯基、 或 C1〜C7饱和或不饱和脂肪 烃基。
更优选的!^为乙烯基、 乙炔基、 氯代吡啶基、 氯代噻唑基、 四氢呋 喃 -3-基; 更优选的 R2为氢、 卤代苯基或 C3〜C7饱和或不饱和脂肪烃基。
本发明中所述饱和或不饱和脂肪烃基可为直链或支链。
本发明所提供的制备式 I所示的 2,5-二取代 -3-硝亚胺基 -1,2,4-三唑啉 和式 VI所示的硝基缩氨基胍类化合物的方法, 包括以下步骤:
(式 II )
2 ) 将式 II所示的硝基氨基胍与式 III所示的羰基化合物在酸催化作用下 反应, 生成式 IV所示的硝基缩氨基胍;
0 NN02
人 H2N人 N'N丫
H R2 Η ΐ
(式 III) (式 IV)
3)将式 IV所示的化合物与式 V所示的化合物 代烃或磺酸酯;)在碱催 化作用下反应, 生成式 VI所示的化合物;
NN02
H2N人 «2
R X ^ H
(式 V) (式 VI)
4)将式 VI所示的化合物在弱酸性或弱碱性介质中反应关环, 生成式 I 结构通式所示的化合物;
其中, 式 III和式 VI中 R2的定义与式 VI、 式 I中的 R2相同;
式 中!^的定义与式 I中相同, X为 Cl、 Br、 I、 OTos (对甲苯磺酰 氧基) 或 OTf (三氟甲磺酰氧基) ;
CH3~^G^S02°_ F3CS020—
对甲苯磺酰氧基 三氟甲磺酸基 其中, 步骤 1) 中所述反应在溶剂中进行, 所述溶剂可为水; 所述反 应的反应温度为 45-70°C, 所述反应中硝基胍与水合肼的摩尔比可为 1: (1-1.5) 。
步骤 2) 中所述反应在溶剂中进行, 所述溶剂可为无水乙醇或甲醇; 所述反应的反应温度可为 50-80°C; 所述反应中所用的酸具体可为醋酸或对 甲苯磺酸。 步骤 2) 所述反应中硝基氨基胍与式 III所示的羰基化合物的摩 尔比可为 1: (1-2) 。
步骤 3) 中所述反应在溶剂中进行, 所述溶剂可为 DMF (;二甲基甲酰胺) 或 DME (;二甲基乙酰胺;); 所述反应的反应温度可为 0-50°C; 所述反应中所 用的碱具体可为氢化钠、 乙醇钠、 甲醇钠或氨基钠。 步骤 3) 中式 IV所示 化合物与式 V所示化合物的摩尔比可为 1: (1.2-2.5) 。
步骤 4) 中所述反应在溶剂中进行, 所述溶剂可为水、 甲醇、 乙醇、 乙腈; 所述反应的温度为 0-100°C; 所述弱酸性介质可以为稀盐酸、 稀硫 酸、 磷酸或乙酸; 所述弱碱性介质可以为碳酸钠水溶液、 乙酸钠水溶液、 稀氢氧化钠、 吡啶、 三乙胺。
本发明的另一个目的是提供式 I所示的 2,5-二取代 -1,2,4-三唑啉 -3-硝 亚胺类化合物以及式 VI所示的硝基缩氨基胍类化合物的用途。
本发明所提供的式 I结构通式所示的 2,5-二取代 -1,2,4-三唑啉 -3-硝亚 胺类化合物及式 VI所示的硝基缩氨基胍类化合物的用途是式 I及 VI所示 的化合物或其药学上可接受的盐或含有它们中任何一种的药物组合物在制
备植物杀虫剂中的应用。
本发明的再一个目的是提供两种植物杀虫药物以及它们的制剂。
本发明所提供的植物杀虫药物或制剂, 它的活性成分为式 I结构通式 所示的 2,5-二取代 - 1,2,4-三唑啉 -3-硝亚胺类化合物及式 VI所示的硝基缩氨 基胍类化合物或其药学上可接受的盐。
所述植物杀虫药物或制剂中活性成分的质量百分含量为 0.01%- 99.99%。
所述杀虫制剂可以按需要加工成任何可接受的剂型。 例如可以是悬浮 剂、 乳剂、 气雾剂、 可湿性粉剂、 乳油、 颗粒剂等。
剂型的配制方法举例如下:
悬浮剂的配制: 常用配方中活性组分含量为 5%-35%。 以水为介质, 将原药、 水分散剂、 助悬剂和抗冻剂等加入磨砂机中, 进行研磨, 制成悬 浮剂。
可湿性粉剂的配制: 按配方要求, 将原药、 各种表面活性剂及固体稀 释剂等充分混合, 经超细粉碎后, 即得到预定含量的可湿性粉剂产品。 为 制备适于喷洒用的可湿性粉剂, 也可将原药和研细的固体粉末如粘土、 无 机硅酸盐、 碳酸盐以及润湿剂、 粘合剂和 /或分散剂组成混合物。
乳油的配制: 按配方要求将有效成分溶于有机溶剂中, 并添加乳化剂 和其它助剂加工制成。 溶剂可采用甲苯、 二甲苯、 甲醇等, 在需要时也含 有共溶剂; 其它助剂, 包括稳定剂、 渗透剂和腐蚀抑制剂等。
本发明所提供的式 I及式 VI所示化合物以及以它们为活性成分的杀虫 药物或制剂能控制和消灭广泛的害虫, 包括吸式虫 (; Sucking insects) , 剌式 虫 (; Biting insects)和其他植物害虫, 储藏谷类的害虫和引起健康危害的卫生 害虫等。
所述害虫举例如下:
同翅目害虫包括蚜科、 粉虱科、 飞虱科、 木虱科、 叶蝉科和蚧科的害 虫。 蚜科害虫具体可为棉蚜、 豆蚜、 桃蚜、 桃粉蚜、 萝卜蚜或甘蓝蚜虫; 飞虱科害虫具体可为褐飞虱或稻飞虱; 粉虱科害虫具体可为烟粉虱; 叶蝉 科害虫具体可为黑尾叶蝉; 蚧科害虫具体可为矢尖蚧。
鳞翅目害虫包括夜蛾科和菜蛾科害虫。 夜蛾科害虫具体可为甜菜夜 蛾、 斜纹夜蛾或棉铃虫; 菜蛾科害虫具体可为小菜蛾。
真螨目害虫包括叶螨科害虫。 叶螨科害虫具体可为朱砂叶螨。
本发明所提供的植物杀虫药物或制剂可用于防治植物害虫。 尤其对剌 吸式害虫、 刮吸式口器害虫, 如各类蚜虫、 飞虱、 叶蝉、 叶螨、 粉虱、 蓟 马有特效, 对棉铃虫、 甜菜夜蛾高效。
本发明再一个目的是提供一种防治植物害虫的方法。
本发明所提供的防治植物害虫的方法, 是将本发明所提供的植物杀虫 药物或制剂施用在植物叶子和 /或果实和 /或种子上, 以及植物叶子和 /或果 实和 /或种子正在生长或预期要生长的环境中; 所述植物杀虫药物或制剂的 活性成分的施用浓度为 l-600mg/L, 优选施用浓度为 3-50 mg/L。
实施发明的最佳方式
本发明 2,5-二取代 -3-硝亚胺基 -1,2,4-三唑啉类化合物和硝基缩氨基胍 类化合物可通过如下的反应步骤合成:
下面结合具体实施例, 进一步阐述本发明。 应理解, 这些实施例仅用 于说明本发明而不用于限制本发明的范围。 下列实施例中未注明具体实施 条件的实验方法, 通常按照常规条件, 或按照制造厂商所建议的条件。 除 非另外说明, 否则百分比和份数按质量计算。
下面以 2-(2-氯吡啶 -5-甲基) -3-硝亚胺基 -1,2,4-三唑啉和 2-(2-氯噻唑 -5- 甲基) -5-丁基 -3-硝亚胺基 -1,2,4-三唑啉为例, 阐明本发明所提供的式 ( I ) 所示 2,5-二取代 -3-硝亚胺基 -1,2,4-三唑啉类化合物的制备方法。
实施例 1、 2-(2-氯吡啶 -5-甲基) -3-硝亚胺基 -1,2,4-三唑啉 (式 I中 R1为 2-氯吡啶 -5-基, R2为氢)的合成:
(l) N'-硝基氨基胍的合成
于 250mL三口瓶中, 依次投入硝基胍 5.0g (0.048mol)和水 70mL。 磁 搅拌下加热至 55 °C时, 从滴液漏斗中缓慢滴加质量百分含量为 85%的水合 肼的水溶液 (其中, 加入水合肼的质量为 3.5g (0.059mol) ) 。 保持物料温 度在 55〜60°C之间继续反应 20分钟。 当物料变为橙黄色澄清液时, 用冰
水浴快速冷却, 并缓慢滴加浓盐酸 (质量百分含量为 37%) 约 6mL至 pH 值为 5〜6; 继续冷却至 2〜3 °C并保持 1小时。 减压抽滤, 用少量冰水洗 涤, 用热水重结晶, 得浅黄色粉未 (Ν'-硝基氨基胍) 2.74g, 收率 48%, 熔点 191〜192°C。
结构表征数据如下:
1H NMR(DMSO-d6, 5ppm): 4.69(s,2H,-NHNH2),7.56(s, lH,-NHNH2), 8.27(s, lH,-NHNO2),9.33(s, lH,C=Ng)。
(2) Ν'-硝基甲醛缩氨基胍的合成
于 250ml三口瓶中, 依次投入 N,-硝基氨基胍 2.0g(0.017mol), 无水甲 醇 30mL和冰醋酸 0.25mL, 磁力搅拌下加热至 50°C, 从恒压滴液漏斗中缓 慢滴加 40%甲醛 1.6g ( 0.02mol) , 滴加完毕, 加热至回流, 并回流 1.0小 时。 降温, 冷却, 有大量白色晶体析出, 得 2.1g, 收率 95%, 直接用于下 一步反应。
(3) Ν'-硝基 -N-(2-氯吡啶 -5-甲基)甲醛缩氨基胍的合成
于 250mL 三口瓶中, 依次投入 N,-硝基甲醛缩氨基胍 2.6g (0.02 mol) , 无水 DMF 40mL和少量 KI, 安装干燥管, 开动磁搅拌, 并用冰水 浴降温。 降温至 10°C以下, 分 3 批加入质量含量为 70%的氢化钠 1.37 g (0.04mol), 并反应 1小时。 从滴液漏斗中缓慢滴加 2-氯 -5-氯甲基吡啶 4.8g (0.03mol)和无水 DMF 20mL的溶液。 滴加完毕, 撤去冰水浴, 自然升温至 室温。 在室温下反应 16小时后, 缓慢加入 200mL水中, 有深红色粘稠状 化合物出现, 柱层析 (石油醚: 乙酸乙酯 =2:3, v/v) , 得白色固体 (Ν'-硝 基 _Ν- ( 2-氯 -吡啶 -5-甲基) 甲醛缩氨基胍) l. lg, 收率 21%, 熔点 124〜 126 °C。
结构表征数据如下:
1HNMR(DMSO-d6,5ppm):6.88(d, 1H),7.13(d, lH),8.41(brs, lH),8.74(brs,
1H), 11.67(S, 1H)
(4) 2-(2-氯吡啶 -5-甲基) -3-硝亚胺基 -1,2,4-三唑啉的合成
于 250mL三口瓶中, 依次投入 3.0gN,-硝基 -N- (2-氯吡啶 -5-甲基) 甲 醛缩氨基胍和 80mL 5mol/L的醋酸水溶液, 加热至回流, 并保持 5小时。 冷却, 有红色油状物析出, 柱层析 (石油醚: 乙酸乙酯 =1 : 1, v/v) , 得白
色晶体 (2- ( 2-氯吡啶 -5-甲基) -3-硝亚胺基 -1,2,4-三唑啉) 1.2g, 收率 40%, 熔点: 113〜115°C。
结构表征数据如下:
1H NMR(DMSO-d6,5ppm):5.27(s,2H),7.53(d, lH),7.79(q, lH),8.41(d, 1H), 8.53(s, lH), 14.05(brs, lH) 实施例 2、 2-(2-氯噻唑 -5-甲基) -5-丁基 -3-硝亚胺基 -1,2,4-三唑啉 (式 I 中 R1为 2-氯噻唑 -5-基, R2为丁基)的合成
(1) Ν'-硝基正戊醛缩氨基胍的合成
于 250ml三口瓶中, 依次投入 N,-硝基氨基胍 2.0g(0.017mol), 无水甲 醇 30mL和冰醋酸 0.25mL, 磁力搅拌下加热至 50°C, 从恒压滴液漏斗中缓 慢滴加正戊醛 1.7g (0.02mol) , 滴加完毕, 加热至回流反应 1.0小时。 降 温, 减压脱去溶剂, 将所得粗品用乙醇-石油醚 (体积比为 3 : 1 ) 重结晶, 得淡黄色粉末 (Ν'-硝基正戊醛缩氨基胍) 2.6g, 收率 83%, 熔点 94〜 95°C。
(2) Ν'-硝基 -N-(2-氯噻唑 -5-甲基)正戊醛缩氨基胍的合成
于 250mL三口瓶中, 依次投入 N,-硝基正戊醛缩氨基胍 3.7g (0.02 mol) , 无水 DMF 40mL和少量 KI, 安装干燥管, 开动磁搅拌, 并用冰水 浴降温。 降温至 10°C以下, 分 3 批加入质量含量为 70%的氢化钠 1.37 g (0.04mol), 并反应 1小时。 从滴液漏斗中缓慢滴加 2-氯 -5氯甲基噻唑 5.1g (0.03mol)和无水 DMF 20mL的溶液。 滴加完毕, 撤去冰水浴, 自然升温至 室温。 在室温下反应 16 小时后, 缓慢加入 200mL水中, 析出固体。 静 置, 过滤, 水洗涤, 干燥, 得无色针状晶体 (Ν'-硝基 -N-2- (2-氯噻唑 -5- 甲基) 正戊醛缩氨基胍) 3.2g, 收率 51%。 用乙醇-石油醚 (体积比为 1 : 2) 重结晶, 熔点 60〜61 °C。
结构表征数据如下: 1H NMR(CDCl3,5ppm):0.93(t,3H), 1.28-1.38(m,2H); 1.48-1.58(m,2H),2.36-2.42(m,2H),5.25(s,2H),7.39(t, lH),7.42(s, lH),7.42(brs, lH),8.99(brs, lH)
(3) 2-(2-氯噻唑 -5-甲基) -5-丁基 -3-硝亚胺基 -1,2,4-三唑啉的合成
于 250mL三口瓶中, 依次投入 3.0g N,-硝基 -N-2- (2-氯噻唑 -5-甲基)
正戊醛缩氨基胍和 80mL 5mol/L的醋酸水溶液, 加热至回流, 并保持 5小 时。 冷却, 有红色油状物析出, 柱层析 (石油醚: 乙酸乙酯 =2:3 , v/v) , 得白色晶体 (2- ( 2-氯吡啶 -5-甲基) -3-硝亚胺基 -1,2,4-三唑啉) 1.2g, 收 率 40%,熔点: 88~90°C o
结构表征数据如下: 1H NMR (DMSO-d6,5ppm):0.89(t,3H), 1.26-
1.36(m,2H), 1.58-1.67(m,2H),2.66-2.71(m,2H),5.39(s,2H),7.75(s, lH), 13.85
(brs, lH)
合成化合物结构见表 1和表 2。
表 1.化合物 I的结构和分析数据
N N02
NN02 H
(式 VI)
gossypii), 菜缢管蚜 (萝卜蚜) ( z^op s er /m/)为测试对象, 采用浸渍法 测试。 其中桃蚜采自北京市海淀区甘蓝田, 桃粉蚜采自北京市海淀区桃 树, 棉蚜采自北京市海淀区木槿树, 菜缢管蚜采自北京市海淀区甘蓝田, 均使用 3日龄若虫进行测定。
操作过程: 准确称取本发明所提供的化合物 20mg (;按 100%含量计 算;), 用 4mL丙酮配制成质量百分含量为 0.5%母液, 再用含有质量含量 0. 1%Triton X- 100的水溶液配制成浓度为 0.06% (即 600ppm) 的测定药液 (低浓度测定时以此溶液稀释至所需浓度即可;)。 选择带蚜叶片, 留下 3日龄 若蚜, 将带蚜叶片在药液中浸渍 5s, 晾干后记录虫数, 放入加有保湿滤纸 的培养皿中, 加盖后放入 (25±1)°C光照培养箱中, 每个药剂处理 30头以
上, 同时设空白对照。 5-48小时后检査结果。
死亡判断标准为: 轻触虫体, 不能正常爬行的害虫个体视为死亡个 体。
校正死亡率 (%) = (样品死亡率 -空白对照死亡率) I ( 1-空白对照死 亡率) χ 100%。
朱砂叶螨雌成螨 i Tetranychus cinnabarinus Boisduva , 采自甘单 β棉 田。 用万分之一天平于 20 mL称量瓶称取 12 mg化合物样品, 再用 1〜5 mL 移液枪取 2 mL丙酮 /甲醇 (1 : 1)混合溶剂加入称量瓶, 待其充分溶解后, 加 入 18 ml含有 0. 1%吐温 -80 的水溶液, 充分混匀, 得 600 igl h 的测定 液。
操作过程: 采用浸渍法进行杀虫活性测定, 将转接好朱砂叶螨的豆叶在药 液中浸渍 5 s, 晾干后记录虫数放入加有保湿滤纸的培养皿中, 叶柄用保湿 棉保湿, 加盖后放入 (25±1)°C光照培养箱中。 每个药剂处理 20头以上。 48 小时后检査结果。 死亡判断标准为: 轻触虫体, 不能正常爬行的害虫个体 视为死亡个体。
棉铃虫属鳞翅目夜蛾科害虫, 具有咀嚼口器。 用万分之一天平量瓶称 取化合物样品, 用二甲基甲酰胺 (DMF ) 配制成母液, 再用含 0. 1%曲拉通
X- 100的水溶液配制测定药液。
操作过程: 将棉叶清洗干净, 用打孔器器将干净苋菜叶打成直径 2cm叶 碟, 在药液中浸渍 10s, 晾干后将叶碟放入 10孔试验盒中, 接入棉铃虫 2 龄幼虫, 每孔 1头, 加保鲜膜、 加盖后放入 (27±1)°C光照培养箱中。 48小 时后检査结果。 以拨针轻触虫体反应不正常或无反应者为死亡。
甜菜夜蛾属鳞翅目夜蛾科害虫, 具有咀嚼口器, 采用药剂配制: 用万 分之一天平量瓶称取化合物样品, 用二甲基甲酰胺 (DMF ) 配制成母液, 再用含 0. 1%曲拉通 X- 100的水溶液配制测定药液。
操作过程: 将苋菜叶清洗干净, 用打孔器器将干净苋菜叶打成直径
2cm叶碟, 在药液中浸渍 10s, 晾干后将叶碟放入 10孔试验盒中, 接入甜 菜夜蛾 2龄幼虫, 每孔 1头, 加保鲜膜、 加盖后放入 (27±1)°C光照培养箱 中。 48小时后检査结果。 以拨针轻触虫体反应不正常或无反应者为死亡。 杀虫活性结果见表 3和表 4。 表 3.化合物 I对蚜虫杀灭活性 (^OOppm)
化合物 校正死亡率(%)
桃蚜 (48hrs) 瓜 (棉)蚜 (24hrs) 桃粉蚜(24hrs) 菜缢管蚜 (24hrs;i
1-01 42.6 55.8 33.2 75.0
1-02 32.0 45.5 40.1 44.4
1-03 75.3 50.9 25.2 100
1-04 32.3 41.7 27.6 60.3
1-05 55.5 50.0 46.3 62.3
1-06 26.7 54.3 15.3 51.8
1-07 30.0 47.5 43.2 75.2
1-08 100 32.6 94.7 100
1-09 72.2 41.7 55.5 81.6
I -10 78.0 57.7 60.2 85.8
1-11 52.3 14.3 40.2 77.3
1-12 46.9 34.4 23.8 63.8
1-13 85.2 60.4 79.6 88.2
1-14 93.5 100 97.8 100
1-15 76.4 55.6 65.6 93.0
1-16 77.8 46.2 60.3 90.8
1-17 56.0 30.0 25.9 77.3
1-18 66.0 67.4 32.3 69.7
1-19 76.2 88.9 78.6 7.0
1-20 16.8 59.4 20.6 50.1
1-21 87.5 100 100 100
1-22 13.2 55.0 25.2 7.3
1-23 56.6 57.1 75.3 62.3
1-24 60.8 27.7 26.1 36.2
1-25 89.9 46.7 90.5 100
1-26 91.7 55.9 89.3 100
1-27 100 100 98.0 100
1-28 68.2 73.0 69.8 48.9
1-29 60.5 20.0 56.9 67.4
1-30 72.0 44.7 68.6 73.6
1-31 59.2 68.1 63.5 21.0
1-32 88.0 44.1 80.2 94.6
1-33 54.6 40.0 65.3 32.0
1-34 100 96.7 94.4 99.2
I 35 42.2 30.6 36.4 24.4
1-36 68.5 56.0 59.0 46.8
1-37 88.7 60.6 92.2 86.5
1-38 56.4 65.1 64.3 32.6
1-39 90.3 73.8 88.8 95.7
1-40 83.3 40.3 86.4 78.9
1-41 100 96.9 66.7 95.4
1-42 86.5 31.3 78.8 100
1-43 95.6 61.5 87.6 96.7
1-44 32.3 25.7 55.5 45.2
1-45 78.9 78.1 65.2 77.3
1-46 76.2 63.3 55.8 31.4
1-47 89.5 85.4 82.5 72.3
1-48 68.8 45.0 75.6 94.9
1-49 76.9 54.8 52.0 96.7
1-50 65.2 54.8 46.5 71.1
1-51 58.5 47.7 75.3 40.4
1-52 69.6 40.3 50.0 49.2
1-53 95.8 100 97.0 100 吡虫啉 100 62.3 100 62.3 表 4.化合物 VI的杀虫活性
表 5.部分化合物 I和 VI对蚜虫的杀虫活性
校正死亡率(%)
化合物 桃蚜 瓜!;棉;!蚜 菜缢管蚜
lOppm 3ppm lOppm 3ppm lOppm 3ppm
< 1 -08 98.3 92.5 45.5 13.2 88.7 65.4
1 -14 Ο 99.4 94.6 99.4 95.6 100 98.8
1 -21 96.5 93.4 98.3 95.1 99.8 96.7
1 -25 88.6 80.7 75.2 60.3 95.7 88.3
1 -26 81.4 82.3 65.5 50.2 88.9 86.4
1 -27 100 98.6 98.7 96.3 100 99.4
1 -34 98.2 90.3 92.6 89.6 90.5 90.2
1 -37 78.6 65.8 69.7 63.5 88.2 79.1
1 -39 82.4 78.2 69.5 60.8 86.9 70.2
1 -41 98.4 90.4 88.3 89.0 90.5 86.4
1 -42 66.6 56.8 50.4 51.7 87.6 80.5
1 -43 79.4 60.3 69.8 42.0 88.4 80.2
1 -53 100 95.6 95.4 92.6 100 98.7
VI -07 75.5 60.6 45.3 26.8 65.2 50.2
61.2 46.9 79.8 72.5 59.4 46.3
VI -26 52.4 50.5 23.7 22.0 53.5 21.4
VI -33 66.8 61.5 77.3 54.6 44.1 23.5
59.8 47.6 42.5 15.9 66.4 36.8
VI -41 100 99.8 92.3 90.6 100 99.6
VI -46 45.2 30.0 65.4 48.3 23.2 4.0
76.6 62.5 78.5 62.0 80.4 75.1
VI -53 100 94.3 90.2 91.0 100 99.8 表 6.化合物 VI-41和 VI-53对蚜虫的田间小区防效
"WP"代表可湿性粉剂; " SC"代表悬浮剂。
表 7.化合物 VI-41和 VI-53对稻飞虱的田间小区防效
表中, "WP"代表可湿性粉剂; " SC"代表悬浮剂。 工业应用
本发明提供了结构通式如式 I所示 2,5-二取代 -3-硝亚胺基 -1,2,4-三唑 啉类化合物及其前体化合物式 VI所示硝基缩氨基胍类化合物的制备方法与 应用。 上述化合物是本发明的发明人经过广泛调研和合理设计, 通过对大
量化合物的筛选, 优选出的一类的杀虫活性高, 且制备方法简便, 并提供 了一条优选的工艺路线, 安全性好, 成本低廉, 使得该化合物的实际应用 价值大大提高。
杀虫活性实验表明, 式 ( I ) 所示 2,5-二取代 -3-硝亚胺基 - 1,2,4-三唑 啉类化合物和式 (VI ) 所示硝基缩氨基胍类化合物对蚜虫、 飞虱、 叶螨、 棉铃虫、 甜菜夜蛾等农作物害虫具有很高的防效, 可用作植物杀虫剂使 用。 2
(式 I) (式 VI)
Claims
1、 式 I所示化合物或其药学上可接受的盐:
N'N02
R2
(式 I)
其中: 为 C1〜C10饱和或不饱和脂肪烃基、 C1〜C10饱和或不饱和 氟代脂肪烃基、 取代或未取代的苯基、 取代或未取代的吡啶基、 取代或未 取代的噻唑基、 取代或未取代的吡唑基、 取代或未取代的恶唑基、 取代或 未取代的异恶唑基、 或四氢呋喃基;
为氢、 C1〜C10饱和或不饱和脂肪烃基、 取代或未取代的苯基、 取 代或未取代的吡啶基、 取代或未取代的呋喃基、 取代或未取代的萘基。
2、 根据权利要求 1所述的化合物或其药学上可接受的盐, 其特征在 于: 所述 中, 所述取代的苯基、 取代的吡啶基、 取代的噻唑基、 取代的 吡唑基、 取代的恶唑基和取代的异恶唑基中的取代基独立的选自下述基团 中的任意一种: 卤素、 氨基、 羟基、 C1〜C5的烷基、 C1〜C5的烷氧基、 C1〜C5的氟代烷基和 C1〜C5的氟代烷氧基。
3、 根据权利要求 1或 2所述的化合物或其药学上可接受的盐, 其特征 在于: 所述 为(:1〜(:10不饱和脂肪烃基、 卤代吡啶基、 卤代噻唑基、 或四氢呋喃基; 优选为乙烯基、 乙炔基、 氯代吡啶基、 氯代噻唑基或四氢 呋喃 -3-基。
4、 根据权利要求 1所述的化合物或其药学上可接受的盐, 其特征在 于: 所述 中, 所述取代苯基中的取代基为卤素、 羟基、 氨基、 C1〜C5 的烷基、 C1〜C5的烷氧基、 C1〜C5的氟代烷基、 C1〜C5的氟代烷氧 基、 芳基、 或芳氧基; 所述取代吡啶基中的取代基为卤素、 C1〜C5的烷 基、 C1〜C5的烷氧基、 C1〜C5的氟代烷基、 C1〜C5的氟代烷氧基、 或 芳氧基; 所述取代呋喃基中的取代基为 ¾素或 C1〜C5的烷基; 所述取代的 萘基中的取代基为卤素、 羟基、 氨基、 硝基、 羧基或氰基。
5、 根据权利要求 1或 4所述的化合物或其药学上可接受的盐, 其特征 在于: 所述 为氢、 取代苯基、 或 C1〜C7 饱和或不饱和脂肪烃基; 优选 为氢、 卤代苯基、 或 C3〜C7饱和或不饱和脂肪烃基。
6、 式 VI所示化合物或其药学上可接受的盐:
NN02
F?! H
(式 VI)
其中: !^为 C1〜C10饱和或不饱和脂肪烃基、 C1〜C10饱和或不饱和 氟代脂肪烃基、 取代或未取代的苯基、 取代或未取代的吡啶基、 取代或未 取代的噻唑基、 取代或未取代的吡唑基、 取代或未取代的恶唑基、 取代或 未取代的异恶唑基、 或四氢呋喃基;
为氢、 C1〜C10饱和或不饱和脂肪烃基、 取代或未取代的苯基、 取 代或未取代的吡啶基、 取代或未取代的呋喃基、 取代或未取代的萘基。
7、 根据权利要求 6所述的化合物或其药学上可接受的盐, 其特征在 于: 所述 中, 所述取代的苯基、 取代的吡啶基、 取代的噻唑基、 取代的 吡唑基、 取代的恶唑基和取代的异恶唑基中的取代基独立的选自下述基团 中的任意一种: 卤素、 氨基、 羟基、 C1〜C5的烷基、 C1〜C5的烷氧基、 C1〜C5的氟代烷基和 C1〜C5的氟代烷氧基。
8、 根据权利要求 6或 7所述的化合物或其药学上可接受的盐, 其特征 在于: 所述 为(:1〜(:10不饱和脂肪烃基、 卤代吡啶基、 卤代噻唑基、 或四氢呋喃基; 优选为乙烯基、 乙炔基、 氯代吡啶基、 氯代噻唑基或四氢 呋喃 -3-基。
9、 根据权利要求 6所述的化合物或其药学上可接受的盐, 其特征在 于: 所述 R2中, 所述取代苯基中的取代基为卤素、 羟基、 氨基、 C1〜C5 的烷基、 C1〜C5的烷氧基、 C1〜C5的氟代烷基、 C1〜C5的氟代烷氧 基、 芳基、 或芳氧基; 所述取代吡啶基中的取代基为卤素、 C1〜C5的烷 基、 C1〜C5的烷氧基、 C1〜C5的氟代烷基、 C1〜C5的氟代烷氧基、 或 芳氧基; 所述取代呋喃基中的取代基为 ¾素或 C1〜C5的烷基; 所述取代的 萘基中的取代基为卤素、 羟基、 氨基、 硝基、 羧基或氰基。
10、 根据权利要求 6或 9所述的化合物或其药学上可接受的盐, 其特征在 于: 所述 为氢、 取代苯基、 或 C1〜C7饱和或不饱和脂肪烃基; 优选为 氢、 卤代苯基、 或 C3〜C7饱和或不饱和脂肪烃基。
(式 II)
(式 III) (式 IV)
3)将式 IV所示的化合物与式 V所示的化合物在碱催化作用下反应, 生 成式 VI所示的化合物;
NN02
R X Ri H
(式 V) (式 VI)
其中, 式 III和式 VI中 R2的定义与式 VI相同;
式 中!^的定义与式 VI相同,
式 V中的 X为 Cl、 Br, ^"O 或 P3eSG2G—。
12、 根据权利要求 11所述的方法, 其特征在于: 步骤 1) 中所述反应 在溶剂中进行, 所述溶剂为水; 所述反应的反应温度为 45-70°C; 所述反应 中硝基胍与水合肼的摩尔比为 1: (1-1.5) 。
13、 根据权利要求 11所述的方法, 其特征在于: 步骤 2) 中所述反应 在溶剂中进行, 所述溶剂为无水乙醇或甲醇; 所述反应的反应温度为 50- 80°C; 所述反应中所用的酸为醋酸或对甲苯磺酸; 所述反应中硝基氨基胍 与式 III所示的羰基化合物的摩尔比为 1: (1-2) 。
14、 根据权利要求 11所述的方法, 其特征在于: 步骤 3) 中所述反应 在溶剂中进行, 所述溶剂为二甲基甲酰胺或二甲基乙酰胺; 所述反应的反 应温度为 0-50°C; 所述反应中所用的碱为氢化钠、 乙醇钠、 甲醇钠或氨基 钠; 所述反应中式 IV所示化合物与式 V所示化合物的摩尔比可为 1: (1.2- 2.5) 。
15、 制备权利要求 1-5 中任一项所述式 I所示化合物的方法, 包括下 述步骤: 将式 VI所示的化合物进行关环反应, 生成式 I所示的化合物。
16、 根据权利要求 15所述的方法, 其特征在于: 所述关环反应在弱酸 性或弱碱性介质存在下进行, 所述弱酸性介质为稀盐酸、 稀硫酸、 磷酸或 乙酸; 所述弱碱性介质为碳酸钠水溶液、 乙酸钠水溶液、 稀氢氧化钠、 吡 啶或三乙胺;
所述关环反应的反应溶剂为水、 甲醇或乙醇; 所述反应的温度为 0-
100°C。
17、 权利要求 1- 10中任一所述的化合物或其药学上可接受的盐或含有 它们中任何一种的药物组合物在制备植物杀虫剂中的应用。
18、 根据权利要求 17所述的应用, 其特征在于: 所述植物杀虫剂用于 杀灭下述至少一目害虫: 同翅目害虫、 鳞翅目害虫和真螨目害虫。
19、 根据权利要求 18所述的应用, 其特征在于: 所述同翅目害虫为下 述六个科中的至少一科: 蚜科、 粉虱科、 飞虱科、 木虱科、 叶蝉科和蚧 科; 所述鳞翅目害虫为夜蛾科和 /或菜蛾科; 所述真螨目害虫为叶螨科害 虫。
20、 一种植物杀虫药物或制剂, 它的活性成分为权利要求 1- 10中任一 所述的化合物或其药学上可接受的盐。
21、 根据权利要求 20所述的植物杀虫药物或制剂, 其特征在于: 所述 植物杀虫药物或制剂中活性成分的质量百分含量为 0.01%-99.99%。
22、 根据权利要求 20或 21所述的植物杀虫药物或制剂, 其特征在 于: 所述植物杀虫药物或制剂用于杀灭同翅目害虫和 /或鳞翅目害虫和 /或真 螨目害虫。
23、 根据权利要求 22所述的植物杀虫药物或制剂, 其特征在于: 所述 同翅目害虫为下述六个科中的至少一科: 蚜科、 粉虱科、 飞虱科、 木虱 科、 叶蝉科和蚧科; 所述鳞翅目害虫为夜蛾科和 /或菜蛾科; 所述真螨目害 虫为叶螨科害虫。
24、 权利要求 20-23 中任一项所述的植物杀虫药物或制剂在防治植物 害虫中的应用。
25、 一种防治植物害虫的方法, 是将权利要求 20-23中任一所述的植 物杀虫药物或制剂施用在植物叶子和 /或果实和 /或种子上, 以及植物叶子和 /或果实和 /或种子正在生长或预期要生长的环境中; 所述植物杀虫药物或制 剂的活性成分的施用浓度为 l-600mg/L, 优选施用浓度为 3-50 mg/L。
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