AU2008361735B2 - Hydrocarbylidene nitrohydrozinecarboximidamides and a method for making the same, as well as their uses as an insecticide - Google Patents
Hydrocarbylidene nitrohydrozinecarboximidamides and a method for making the same, as well as their uses as an insecticide Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/72—Nitrogen atoms
- C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
- A01N47/44—Guanidine; Derivatives thereof
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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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- C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C281/16—Compounds containing any of the groups, e.g. aminoguanidine
- C07C281/18—Compounds containing any of the groups, e.g. aminoguanidine the other nitrogen atom being further doubly-bound to a carbon atom, e.g. guanylhydrazones
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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- C07—ORGANIC CHEMISTRY
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- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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Abstract
Abstract The present invention discloses hydrocarbylidene nitrohydrozinecarboximidamides and the use thereof as well as a method for making the same. T he structural general 5 formula of the compounds are shown in formula I, wherein, RI is Cl - CIO saturated and/or unsaturated aliphatic hydrocarbonyl, benzyl, substituted benzyl, halogenated picolyl, halogenated thiazolyl methyl, tetrahydrofuryl methyl or oxazolyl methyl; R2 is hydrogen, Cl - C5 saturated and/or unsaturated aliphatic hydrocarbonyl, phenyl, substituted phenyl, pyridyl or substituted pyridyl; R3 is hydrogen, C1 - CIO saturated 10 and/or unsaturated aliphatic hydrocarbonyl, furyl, phenyl, substituted phenyl, benzyl or substituted benzyl. T he tests of insecticidal activity show that the hydrocarbylidene nitrohydrozinecarboximidamides shown by formula (1) have high preventive efficiency against insect pests of plants, such as aphid, plant hopper, cotton bollworm, asparagus caterpillar, and the like, and can be used as plant insecticides. R1 NHW"NH' N R2 (formula I)
Description
C-\NRPortbl\DCC\KXG\373340)0 1 DOC-5/07/2011 Hydrocarbylidene nitrohydrozinecarboximidamides and a method for making the same, as well as their uses as an insecticide Field of the Invention 5 The present invention relates to hydrocarbylidene nitrohydrozinecarboximidamides and a method for making the same, as well as their uses as an insecticide. Background of the Invention 10 Nicotine is a natural alkaloid, which has been used as an insecticide as early as the nineteen century, and the target which acts on is the postsynaptic nicotinic acetylcholine receptor (nAchRs). However, the insecticidal activity of Nicotine is low, and it is highly toxic to human beings. With the Nicotine being as a leading compound, such insecticides 15 have been fully developed and successive several generations of products have been commercially developed, since Bayer AG successfully developed the neonicotinoid insecticides, Imidacloprid, in 1980s. Neonicotine insecticides have high insecticidal activities and broad insecticidal spectrum, and are safe to mammalian and other environmental lives. The above insecticides have structural general formula as shown in 20 formula A. In contrast, the use of semicarbazone compounds as insecticides is developed a little late, however, the development of such insecticides has become a new hotspot since Dupont Corporation successfully developed indoxacarb in 1992. The action target of such 25 insecticides is sodium ion channel, and they specially effect on nearly all of Lepidoptera pest, but they are safe to each of mammalian, avian and aquatic animal. Such insecticides have the structural general formula as shown in Formula B.
C:\NRPortb \DCC\KXG373340)_1 DOC-5A/2011 -2 R1 X R1 R 2
R
3 I I R N ) Z R N " R4
R
2
R
3 0 Formula A Formula B As to the biocompatibility, insecticides acting on a single target generally quickly result in resistance, and insecticides acting on multiple targets do slowly. 5 Summary of the Invention In one or more aspects the present invention may advantageously provide hydrocarbylidene nitrohydrozinecarboximidamides and a method for making the same. 10 -3 The present invention provides hydrocarbylidene nitrohydrozinecarboximidamides which has structural general formula as shown in formula I: N JIN2 ( RNH NH'N R2 R3 (Formula I) 5 Wherein: RI is C1 - C10 saturated and/or unsaturated aliphatic hydrocarbonyl, benzyl, substituted benzyl, halogenated picolyl, halogenated thiazolyl methyl, tetrahydrofuryl methyl or oxazolyl methyl, wherein the substituent of said substituted benzyl can be halogen 10 (specificially F, Cl, Br, and I), amino, hydroxy, Cl - C5 alkyl or Cl - C5 alkoxyl , and the like; R2 is hydrogen, C1 - C5 saturated and/or unsaturated aliphatic hydrocarbonyl, phenyl, substituted phenyl, pyridyl or substituted pyridyl, wherein the substituent of said 15 substituted phenyl can be halogen, hydroxy, amino, Cl - C5 alkyl, CI - C5 alkoxyl, aryl (such as phenyl, pyridyl, imidazolyl, oxazolyl, and thiazyl), aryloxy (such as phenoxy, and pyridinyloxy) and the like, and the substituent of said substituted pyridyl can be halogen, Cl - C5 alkyl, Cl - C5 alkoxyl, aryloxy (such as phenoxy, and pyridinyloxy) and the like; 20 R3 is hydrogen, Cl - CI0 saturated and/or unsaturated aliphatic hydrocarbonyl, furyl, phenyl, substituted phenyl, benzyl or substituted benzyl, wherein the substituent of said substituted phenyl can be halogen, hydroxy, amino, substituted amino (such as methylamino, and dimethylamino), nitro, Cl - C5 alkyl, Cl - C5 alkoxyl, aryl (such as 25 phenyl, pyridyl, imidazolyl, oxazolyl, thiazyl), aryloxy (such as phenoxy and pyridinyloxy) and the like, and the substituent of said substituted benzyl can be halogen, hydroxy, amino, Cl - C5 alkyl, Cl - C5 alkoxyl, aryl (such as phenyl, pyridyl, imidazolyl, oxazolyl, and thiazyl), aryloxy (such as phenoxy and pyridinyloxy), and the like; 30 Preferred RI is Cl - CIO unsaturated aliphatic hydrocarbonyl, halogenated picolyl, halogenated thiazolyl methyl or tetrahydrofuryl methyl; preferred R2 is hydrogen or Cl - C5 saturated and/or unsaturated aliphatic hydrocarbonyl; and preferred R3 is substituted phenyl or C I - C10 saturated and/or unsaturated aliphatic hydrocarbonyl; 35 More preferred RI is allyl, propargyl or chloro-picolyl; more preferred R2 is hydrogen; and more preferred R3 is substituted phenyl or C3 - C7 saturated and/or unsaturated aliphatic hydrocarbonyl.
C:\NRPortbK\DCC\KXG17340. I DOC-5M7/2011 -4 The saturated and/or unsaturated aliphatic hydrocarbonyl of the present invention can be linear or branched. The present invention provides a method for making the hydrocarbylidene 5 nitrohydrozinecarboximidamides shown in structural general formula I, including the following steps: 1) Reacting nitroguanidine with hydrazine hydrate to form N' nitrohydrazinecarboximidamide shown by formula II; NO2
H
2 N NHNH 2 10 (Formula 11) 2) Reacting N'-nitrohydrazinecarboximidamide shown by formula II with carbonyl compounds shown by the structural general formula III under acid catalysis, to form hydrocarbylidene nitrohydrozinecarboximidamides shown by the structural general 15 formula IV; NNO O " N R2 H2N 0 R2 R 3 R3 (Formula III) (Formula IV) 3) Reacting the compounds shown by the structural general formula IV with compounds shown by the structural general formula V (haloh ydrocarbons or sulfonic 20 esters) under alkali catalysis, to form compounds shown by the structural general formula I; R1-X (Formula V) CWRPotbN\DCC\KXG\373340_..I DOC-5S7/20l -5 Wherein, R2 of formula II and formula III are hydrogen, Cl - C5 saturated and/or unsaturated aliphatic hydrocarbonyl, phenyl, substituted phenyl, pyridyl or substituted pyridyl, wherein the substituent of said substituted phenyl can be halogen, hydroxy, amino, CI - C5 alkyl, Cl - C5 alkoxyl, aryl (such as phenyl, pyridyl, imidazolyl, oxazolyl, and 5 thiazyl), aryloxy (such as phenoxy, and pyridinyloxy) and the like, and the substituent of said substituted pyridyl can be halogen, Cl - C5 alkyl, CI - C5 alkoxyl, aryloxy (such as phenoxy, and pyridinyloxy), and the like; R3 is hydrogen, Cl - CIO saturated and/or unsaturated aliphatic hydrocarbonyl, furyl, 10 phenyl, substituted phenyl, benzyl or substituted benzyl, wherein the substituent of said substituted phenyl can be halogen, hydroxy, amino, substituted amino (such as methylamino, and dimethylamino), Cl - C5 alkyl, Cl - C5 alkoxyl, aryl (such as phenyl, pyridyl, imidazolyl, oxazolyl, and thiazyl), aryloxy (such as phenoxy, and pyridinyloxy) and the like, and the substituent of said substituted benzyl can be halogen, hydroxy, amino, 15 Cl - C5 alkyl, Cl - C5 alkoxyl, aryl (such as phenyl, pyridyl, imidazolyl, oxazolyl, and thiazyl), aryloxy (such as phenoxy, and pyridinyloxy), and the like; RI of formula V is Cl - C10 saturated and/or unsaturated aliphatic hydrocarbonyl, benzyl, substituted benzyl, halogenated picolyl, halogenated thiazolyl methyl, tetrahydrofuryl 20 methyl or oxazolyl methyl, wherein the substituent of said substituted benzyl can be halogen, amino, hydroxy, CI - C5 alkyl or Cl - C5 alkoxyl and the like, and X of formula V is Cl, Br, I, OTos (p-tosyloxy) or OTf (trifluoromethane sulfonyl);
CH
3 -0 S0 2 0- F 3
CS
2 0 25 p-tosyloxy trifluoromethane sulfonyl Preferred RI is Cl - CIO unsaturated aliphatic hydrocarbonyl, halogenated picolyl, halogenated thiazolyl methyl or tetrahydrofuryl methyl, preferred R2 is hydrogen or Cl C5 saturated and/or unsaturated aliphatic hydrocarbonyl; preferred R3 is substituted phenyl 30 or CI - C 10 saturated and/or unsaturated aliphatic hydrocarbonyl; C:\N4RPortbl\DCC\KXG\37334).I DOC.5A)7/01 1 -6 More preferred RI is allyl, propargyl or chloro-picolyl, more preferred R2 is hydrogen, more preferred R3 is substituted phenyl or C3-C7 saturated and/or unsaturated aliphatic hydrocarbonyl. 5 The reaction in step 1) is conducted in a solvent, and said solvent can be water; and the reaction temperature of said reaction is 45-70'C. The molar ratio of nitroguanidine to hydrazine hydrate in step 1) is 1:1-1:1.5. The reaction in step 2) is conducted in a solvent, and said solvent can be anhydrous ethanol 10 or methanol; the reaction temperature of said reaction can be 50-80'C; and the acids used in said reaction can be acetic acid or p-toluenesulfonic acid. The molar ratio of N'-nitrohydrazinecarboximidamide shown by formula II to carbonyl compounds shown by the structural general formula III in step 2) is 1:1-1:2. 15 The reaction in step 3) is conducted in a solvent, and said solvent can be DMF (dimethylformamide) or DME (dimethylacetamide); the reaction temperature of said reaction can be 0-50*C; and the alkalies used in said reaction can be sodium hydride, sodium ethoxide, sodium methoxide or sodium amide. The molar ratio of the compounds shown by the structural general formula IV to the compounds shown by the -7 structural general formula V in step 3) is (1:1.2)-(1:2.5). Another object of the present invention is to provide the use of hydrocarbylidene nitrohydrozinecarboximidamides shown by the structural general formula I. 5 The present invention provides the use of hydrocarbylidene nitrohydrozinecar boximidamides shown by the structural general formula I , wherein the compounds shown by the structural general formula I or pharmaceutically acceptable salts thereof or pharmaceutical compositions containing any of them can be used to prepare plant 10 insecticides. A further object of the present invention is to provide a plant insecticidal drug or formulation. 15 The active ingredient of plant insecticidal drugs or formulations provided by the present invention is hydrocarbylidene nitrohydrozinecarboximidamides shown by the structural general formula I or pharmaceutically acceptable salts thereof. The mass percent content of the active ingredient of said insecticidal drugs or 20 formulations is 0.01%-99.99%. Said insecticides can be processed into any acceptable dosage form as required. For example, the dosage form can be suspension, emulsion, aerosol, wettable powder, emulsifiable concentrate, and granule. 25 The preparation methods of dosage form are exemplified as follows: The preparation of the suspension: the content of active ingredient in the conventional formulation is 5% - 35%. With the water being media, active pharmaceutical 30 ingredients, water dispersant, suspending agent and antifreeze agent and the like, are added into the sander and are ground, to prepare suspension. The preparation of the wettable powder: according to the requirement of formulation, active pharmaceutical ingredients, a variety of surfactants and solid diluents, and the 35 like, are fully mixed, and after ultrafinly grinding, the wettable powder product of predetermined content can be obtained. In order to prepare the wettable powder suitable for spraying, active pharmaceutical ingredients and comminuted solid powder such as clay, inorganic silicate, carbonate and wetting agent, adhesive and/or dispersant can also constitute a mixture. 40 The preparation of the emulsifiable concentrate: according to the requirement of -8 formulation, the active ingredients are dissolved into organic solvents, and emulsifying agents and other adjuvants are added and processed to form the formulation. Solvents can be toluene, xylene, methanol, and the like, and a cosolvent if necessary; and the other adjuvants including stabilizer, permeate agent and erosion inhibitor, and the like. 5 The compounds shown by the structural general formula I provided by the present invention and the insecticidal drugs or formulations with said compounds being active ingredient can control and kill a broad range of pests, which includes sucking insects , biting insects and other plant pests, pests of grain storage, and sanitary pests causing 10 health hazard, and the like. The pests are exemplified as follows: Homoptera pests include aphididae, aleyrodidae, delphacidae, psyllidae, jassidae and 15 coccidae pests. Aphididae pests can specifically be aphis gossypii, bean aphid, myzus persicae, hyalopterus pruni, turnip aphid or cabbage aphid; delphacidae pests can specifically be nilaparvata lugens or rice planthopper; aleyrodidae pests can specifically be bemisia tabaci gennadius; jassidae pests can specifically be rice leajhopper(Nephotettix bipunctatus ); and coccidae pests can specifically be arrowhead 20 scale(Unaspis yanonensis). Lepidoptera pests include noctuidae and plutellidae pests. Noctuidae pests can specifically be asparagus caterpillar, Spodoptera litura Fab or Helicoverpa armigera; plutellidae pests can specifically be Plutella xylostella. 25 The plant insecticidal drugs or formulations provided by the present invention can be used to prevent insect pests of plants. Especially, the plant insecticidal drugs or formulations have special efficiency against piercing-sucking type pests, scratching type mouthparts pests, such as various aphid, plant hopper, leafhoppei, mealworm and Thrips palmi, and have high efficiency against Helicoverpa armigera and asparagus 30 caterpillar. A further object of the present invention is to provide a method for preventing insect pests of plants. 35 The method for preventing from insect pests of plants provided by the present invention is to apply the plant insecticidal drugs or formulations provided by the present invention to plant leaves and/or plant fruits and/or plant seeds, and the places where the plant leaves and/or plant fruits and/or plant seeds are growing or are expected to be grown. The active ingredient of the plant insecticidal drugs or formulations is administrated at 40 the concentration of 1-600mg/L, and preferably, at the concentration of 3-50 mg/L.
C\NRPorbhIDCC\KXG\373340(_ I DOC-5A)7/2011 -9 The best modes of carrying out the invention Hydrocarbylidene nitrohydrozinecarboximidamides of the present invention can be synthesized by following steps: 0
HNH
2
NH
2 N /NO 2 R2 ) R3 N"N2
H
2 0 HOAc H2 NHN R
H
2 N NHNO 2
H
2 N NHNH 2
H
2 N
R
3 R3- X R N R2 Base HN NH 5
R
3 The present invention is further illustrated in combination with the following specific examples. It should be understood that these examples are used only to illustrate the present invention, but not to limit the scope of the present invention. In the following examples, experimental methods which do not indicate particular conditions usually are 10 carried out under normal conditions or under the conditions proposed by the manufacturer. Unless otherwise specified, percentage and parts are calculated based on the mass. In the following, using 2-isobutylidene-N'-nitrohydrozinecarboximidamide and 2-(2' nitrophenyl methylene)-N-nitrohydrozinecarboximidamide as examples, the preparation 15 method of hydrocarbylidene nitrohydrozinecarboximidamides provided by formula (I) of the present invention is illustrated. Example 1 20 The synthesis of 2-isobutylidene-N'-nitrohydrozinecarboximidamide (the compound 1 of formula I, wherein RI is methyl, R2 is hydrogen, and R3 is isopropyl): (1) the synthesis of N'-nitrohydrozinecarboximidamide C:\NRPonb\DCC\KXG373340xIDOC-S017/211 -10 N H 2 0 NNO 2 + NH 3 || + N 2 H4 ||
H
2
N-C-NHNO
2
H
2 N-C-NHNH 2 To 250mL three-necked flask, 5.Og (0.048mol) nitroguanidine and 70mL water were sequentially added. It was heated to 55'C under magnetic stirring, and the aqueous 5 solution of 85% by mass of hydrazine hydrates (wherein, the mass of the hydrazine hydrates added was 3.5g (0.059mol)) was slowly added dropwise through a drop funnel. The reaction was continued for 20 minutes, while the temperature of materials was kept between 55 and 60'C. When the materials turned into an orange clear liquid, it was cooled quickly with an ice water bath, and about 6mL concentrated HCI (the mass 10 percent is 37%) was slowly added dropwise to adjust pH as 5 - 6; the materials were continued to be cooled to 2 - 3*C and lasted for 1 hour. The resulting product was filtered under reduced pressure, and washed with a little ice water, and air-dried in a fume hood. The resulting product was recrystallized with hot water, and 2.74g light yellow powder (N'-nitro amino guanidine) was obtained in 48% yield, and the melting point of 15 which is 191 - 192'C. Structural characteristic data are provided as follows: 'H NMR(DMSO-d,, 6ppm) : 4.69 (s, 2H, -NHNH 2 ), 7.56 (s, 1H,-NHNH 2 ), 8.27 (s, 1 H,-NHN0 2 ), 9.33 (s, I H, C=NH). 20 (2) The synthesis of 2-isobutylidene-N'-nitrohydrozinecarboximidamide To 250mL three-necked flask, 24g (0.2mol) N'-nitrohydrozinecarboximidamide, IOOmL anhydrous ethanol, and 2.4mL glacial acetic acid were sequentially added. It was heated to 25 65*C under magnetic stirring, and 19.Og (0.24mol) isobutylaldehyde (the compounds in formula III, wherein R2 is hydrogen, and R3 is isopropyl) was slowly added dropwise through a drop funnel. After the addition was complete, the mixture was heated to reflux, and the reaction was refluxed for 3 hours. The temperature was lowered, and the solvent was removed under the reduced pressure. The resulting crude product was recrystallized C \NRPorlb\DCC\KXG\373140_ I DOC-5A7/20 I - 11 with ethanol-petroleum ether (3:1 by volume) to obtain 20g light yellow powder (2-isobutylidene-N'-nitrohydrozinecarboximidamide) in 52% yield, and the melting point of which is 76-78'C. 5 (3) The synthesis of 2-isobutylidene-N-methyl-N'-nitrohydrozinecarboximidamide (compound 1) To 50mL three-necked flask, 7.Og (0.04 mol) 2-isobutylidene-N'-nitrohydrozine carboximidamides and 30mL anhydrous DMF were sequentially added. A drying tube was 10 installed, magnetically stirring was run, and ice water bath was used to lower the temperature. The temperature was lowered to below I 0 0 C, the solution of 70% by mass of sodium hydride in DMF was added in three times (wherein, the mass of added sodium hydride is 2.4g (0.07mol)), and the mixture was reacted for 1 hour. The solution of 11.5g (0.08mol) iodomethane and 30mL anhydrous DMF was slowly added dropwise through a 15 drop funnel. After the addition was complete, the ice water bath was removed, and the temperature was raised to room temperature naturally. After the mixture was reacted for 2 hours at room temperature, 150mL water was added, and solids were precipitated. The resulting product was seted, filtered, washed with water, and dried to obtain 2.9g colorless plate-like crystal (2-isobutylidene-N-methyl-N'-nitrohydrozinecarboximidamides) in 45% 20 yield, which was recrystallized with ethanol-petroleum ether (1:2 by volume), and its melting point is 60-61*C. Structural characteristic data are provided as follows: 'IHNMR(CDCl 3 , 6ppm): 1.18-1.16(q, 6H), 2.62-2.73(m, 1H), 3.36(d, 3H), 7.15-7.16(t, 1H), 25 7.45(s, 1 H), 9.05(s, I H) elemental analysis C% H% N% theoretical value: 38.50 7.00 37.41 measured value: 38.53 6.89 37.35 30 Example 2 C:\NRPonbl\DCC\KXG 3340_ IDOC-5A7/201 I - 12 The synthesis of 2-(2'-nitrobenzylidene)-N-propyl-N'-nitrohydrozinecarboximidamides (the compound ZNQ-103 in formula I, wherein RI is propyl, R2 is hydrogen, and R3 is o-nitrophenyl) 5 (1) The synthesis of 2-(2'-nitrobenzylidene)-N'-nitrohydrozinecarboximidamides
NO
2 NO 2
NNO
2
NNO
2 - HOAc CHO C~---NNHCNH 2 + H 2 0
NH
2
NHCNH
2 + / H To 250mL three-necked flask, 2.Og (0.017mol) N'-nitrohydrozinecarboximidamide, IOOmL anhydrous ethanol and 0.2mL glacial acetic acid were sequentially added. It was 10 heated to 65'C under magnetic stirring, and the solution of 3.02g (0.020mol) o-nitrobenzaldehyde (the compounds in formula III, wherein R2 is hydrogen, and R3 is o-nitrophenyl) and 10mL anhydrous ethanol was slowly added dropwise through a drop funnel. After the addition was complete, the mixture was heated to reflux, and refluxed for 3 hours. The temperature was lowered, the solvent was removed under the reduced 15 pressure, and solids were precipitated. The resulting crude product was recrystallized with chloroform to obtain 3.21g orange powder (2-(2'-nitrobenzylidene)-N' nitrohydrozinecarboximidamide) in 75% yield, and the melting point is 225 -226'C. (2) The synthesis of 2-(2'-nitrobenzyl idene)-N-propyl-N'-nitrohydrozinecarboximid 20 amides (ZNQ-103)
NO
2
NO
2
NNO
2 NH NaH 11 =N-NH--NHNO 2 + CH 3
CH
2
CH
2 1 D - C=N-NH-C-NH-CH 2
CH
2
CH
3 To 250mL three-necked flask, 2.Og (0.008mol) 2-(2'-nitrobenzylidene)-N'-nitro hydrozinecarboximidamides and 50mL anhydrous DMF were sequentially added. A 25 drying tube was installed, magnetical stirring was run, and ice water bath was used to lower the temperature. The temperature was lowered to below 10'C, the solution of C :NRPortb\DCC\XG\37334N IDOC-5)7/2011 - 13 70% by mass of sodium hydride in DMF was added in three times (wherein, the mass of added sodium hydride is 0.48g (0.014mol)), and the mixture was reacted for I hour. The solution of 2.72g (0.016mol) iodopropane and lOmL anhydrous DMF was slowly added dropwise through a drop funnel. After the addition was complete, the ice water 5 bath was removed, and the temperature was raised to room temperature naturally. After the mixture was reacted for 2 hours at room temperature, 150mL water was added, and solids were precipitated. The resulting product was seted, filtered, washed with water, and dried to obtain 1.34g yellow powder (2-(2'-nitrobenzylidene)-N-propyl-N' 10 nitrohydrozinecarboximidamides) in 57% yield, which was recrystallized with ethyl acetate with 158'C melting point. Structural characteristic data are provided as follows: 'H NMR (DMSO-d 6 , 6ppm): 3.89 (s, 3H, -CH 3 ), 4.79-4.82 (m, 2H, -CH 2 -), 5.12-5.29 (m, 15 2H, -NCH2), 6.94-7.04 (m, 2H, -ArH), 7.39-7.45 (m, I H, -ArH), 7.80-7.83 (m, I H, -ArH), 8.29 (s, I H, -CH=N-), 9.16 (s, 2H, -NH-x2). elemental analysis C% H% N% 20 theoretical value: 44.90 4.80 28.56 measured value: 44.90 4.73 28.51 Example 3 Test on the insecticidal activity of compounds of the present invention 25 Aphis, which belongs to Homoptera and has a piercing-sucking mouthpart, is a common pest for agricultural plant. The test subjects are myzus persicae, hyalopterus pruni, and aphis gossypii, and the test is performed by the way of immersing. Myzus persicae were derived from cabbage fields in Hai Dian district, Beijing, hyalopterus pruni were derived 30 from peach tree in Dian district, Beijing, and aphis gossypii were derived from hibiscus trees in Hai Dian district, Beijing. Each test was carried out using 3 day-old nymphae.
C:\NRPonb\DCC\KXG\37314(X.I DOC-5ffi7/201l -14 Operational precedure: 20 mg compounds provided by the present invention (calculated based on 100% content) was exactly weighed and formulated into 0.5% by mass of stock solution with 4mL acetone. Then, the stock solution was formulated into a series of liquid medicine to be determined using aqueous solution containing 0.1% by mass of Triton X 5 100. The leaves with aphides were chosen, and 3-day-old nymphae were left. After the leaves with aphides were immersed into the liquid medicine for 5 seconds and air-dried, the amount of aphides was recorded, and aphides were put into the culture dishes with moistened filter paper, then the culture dishes were capped and put into light incubator at (25±1)'C. Each of medicament treated 30 or more aphides, while the - 15 blank controls being set up. After 5 - 48 hours, the results were examined. The criteria for death judgment is: slightly touching the bodies of the pest, the one which can not normally creep is considered as dead individual. 5 Corrected mortality (%)=(mortality of samples-mortality of blank controls)/(1-mortality of blank controls)x 100%. Aleyrodids belong to homoptera pests and has a piercing-sucking mouthpart. Bemisia 10 tabaci Gennadius was tested by the way of spraying. Operational precedure: firstly, the samples were dissolved with dimethyl sulfoxide, then were formulated into a solution at concentration of 500mg/L using distilled water solution containing 0.01% by mass of Triton, and clean water was used as a blank 15 control. The leaf of cotton was drilled using a punch to generate a leaf discs with a diameter of 18mm, and the drilled leaf disc was immersed into liquid medicine for 5 seconds, then air-dired at room temperature. Following about 2 hours, the leaf disc was placed back upwards on the bottom of digitiform tube plated with agar (the concentration is 1.4%). The treated digitiform tube was inversely placed on top of 20 bemisia tabaci gennadius (eclosion was carried out for 24 hours), and then leaf was flicked, bemisia tabaci gennadius can automatically fly into the tube. Each tube can collect 25 bemisia tabaci gennadius. The tube orifice was packed (wrapped) with gauze, and then the tube was inversely placed in an insectarium for normal breeding. The breeding conditions are: L/D (photoperiod) is 14:10, T (temperature) is 26±20, RH 25 (relative humidity) is 75±5%. After 1 hour, the condition of the test-insect was examined. If a test-insect was dead, then the test insect was not counted. After 48 hours, the results were collected. Helicoverpa armigera belongs to noctuidae of Lepidoptera and has a chewing 30 mouthpart. The compound sample was weighted using a balance with 0.0001 accuracy, and was formulated into a stock solution with Dimethylformamide (DMF). Then, the stock solution was formulated into a liquid medicine to be determined using aqueous solution containing 0.1% by mass of Triton X-100. 35 Operational precedure: the cotton leaves were rinsed, and clean amaranth leaves were drilled using a punch to generate a leaf disc of 2 cm diameter, then the leaf disc was immersed into the liquid medicine for 10 seconds. After air-dried, the leaf disc was placed into ten-well test box. 2-day-old larvae of asparagus caterpillar were inoculated, one larva for each well, and the plastic wrap was covered. After being capped, the test 40 box was placed into a light incubator at the temperature of (27±1) 0C. After 48 hours, -16 the results were examined. The individuals which body response abnormally or irresponsively to slightly touching with a hand setting (dial needle) were deemed as dead. 5 Asparagus caterpillar belongs to noctuidae of Lepidoptera and has a chewing mouthpart. T he liquid medicine was formulated using medicament: the compound sample was weighted using a balance with 0.0001 accuracy, and formulated into stock solution with dimethylformamide (DMF). Then, the stock solution was formulated into the liquid medicine to be determined using aqueous solution containing 0.1% by mass 10 of Triton X-100. Operational precedure: the amaranth leaves were rinsed, and clean amaranth leaves were drilled using a punch to generate a leaf disc of 2 cm diameter, then the leaf disc was immersed into the liquid medicine for 10 seconds. After air-dried, the leaf disc was 15 placed into ten-well test box. 2-day-old larvae of asparagus caterpillar were inoculated; one larva for each well, and the plastic wrap was covered. A fter being capped, the test box was placed into a light incubator at the temperature of (27±1) *C. After 48 hours, the results were examined. The individuals which body response abnormally or irresponsively to slightly touching with a hand setting (dial needle) were deemed as 20 dead. The results were shown in Table 1-4 below. RN IN R _NH NH' R2 R3 (formula I) 25 Table 1. The r esults of mortality of compounds of formula I to various pests. mortality(%) bemisia Helicove tabaci asparagus myzus gennadi
.
caterpillar No. R,
R
2
R
3 persicae us armigera (500pg/mL (600ptg/mL) (500pg/ (500 ig/ ) _ ML) 'mL) I CH 3 H CH(CH 3
)
2 4.7 40 40 2 CH 2
CH
3 H CH(CH 3
)
2 53.6 60 [50 -17 3 CH 2
CH
2
CH
3 H CH(CH 3
)
2 14.4 30 20 4 (CH 2
)
3
CH
3 H CH(CH 3
)
2 31.6 10 20 5 CH 2
CH=CH
2 H CH(CH 3
)
2 27.8 90 30 6 CH 2 CECH H CH(CH 3
)
2 37.9 100 60 7 CH 2 Ph H CH(CH 3
)
2 18.4 40 50 8 C"2 ' / H CH(CH 3
)
2 87.0 60 40 9 CH 2
CH
3 H CH 2
CH
3 54.2 60 20 10 CH 2
CH
2
CH
3 H CH 2
CH
3 78.3 80 20 11 (CH 2
)
3
CH
3 H CH 2
CH
3 1.5 50 50 12 CH 2
CH=CH
2 H CH 2
CH
3 30 40 13 CH 2 CECH H CH 2
CH
3 5.0 50 0 14 CH 2 Ph H CH 2
CH
3 18.8 40 30 15 c' H CH 2
CH
3 / 10 20 16 CH 3 H 31.4 30 70 17 CH 2
CH
3 H 19.8 40 40 18 CH 2
CH
2
CH
3 H / 50 60 19 (CH 2
)
3
CH
3 H 67.5 40 60 20 CI- 2
CH=CH
2 H 5.2 0 50 21 CH 2 C=CH H 12.8 20 30 22 CH 2 Ph H 7.1 20 20 23 CH Cl H 1 9.8 30 40
CH
2
CH
2 C 24 CH 2
CH
3 H 4.7 40 0
H
3 25 CH 2
CH
2
CH
3 H CH2CH2C 50 10
H
3 _ _ _ _ 26 (CH 2
)
3
CH
3 H CH2CH2C 65.3 1 20 60
H
3 _ _ _ _ 27 CH 2
CH=CH
2 H CH 2
CH
2 C 65.1 30 40
H
3 28 CH 2 CECH H CH2CH2C 11.4 60 70
H
3 -18
CH
2
CH
2 C 29 CH 2 Ph H / 60 50
H
3 30 CH2 C H CH2CH2C 80.7 40 40
H
3 31 CH 3 H CH=CHCH 3 42.6 60 10 32 CH 2
CH
3 H CII=CHCH 3 48.0 0 0 33 CH 2
CH
2
CH
3 H CH=CHCH 3 19.5 70 70 34 (CH 2
)
3
CH
3 H CH=CHCH 3 / 40 60 35 CH 2
CH=CH
2 H CH=CHCH 3 56.7 20 60 36 CH 2 CECH H CH=CHCH 3 35.0 30 50 37 CH 2 Ph H CH=CICI 3 / 70 20 38 CH2 ci H CH=CHCH 3 1.2 30 0 39 CH 2
CH
3 H CH=CI1 2 / 20 40 40 CH 2
CH
2
CH
3 H CH=CH 2 8.3 30 20 41 (CH 2
)
3
CH
3 H CH=CH 2 74.7 20 10 42 CH 2
CH=CH
2 H CH=CH 2 37.1 20 0 43 CH 2 CECH H CI-=CH 2 / 40 20 44 CH 2 Ph H CH=CH 2 45.8 30 0 45 CH 2
CH
2
CH
3 H (CH 2
)
5
CH
3 16.9 20 20 46 (CH2)3CH3 H (CH 2
)
5
CH
3 / 20 30 47 CH 2 CH=CiH 2 H (CH 2
)
5
CH
3 23.7 0 0 48 CH 2 CECH H (CH 2
)
5
CH
3 13.0 30 0 49 CH 2 Ph H (CH 2
)
5
CH
3 28.6 50 0 50 CH2 \ C' H (CH 2
)
5
CH
3 100 20 0 51 CH 2
CH
2
CH
3 H (CH 2
)
3
CH
3 13.3 30 10 52 (CH 2
)
3
CH
3 H (CH 2
)
3
CH
3 81.0 20 60 53 CH 2
CH=CH
2 H (CH 2
)
3
CH
3 81.0 40 80 54 CH 2 CECH H (CH 2
)
3
CH
3 47.6 40 10 55 CH 2 Ph H (CH 2
)
3
CH
3 49.2 10 30 56 CH c I H (CH 2
)
3
CH
3 100 70 20 57 CH 3 H C 43 20 20 58 CH 2
CH
3 H CH3 86.0 30 30 59 CH 2
CH
2
CH
3 H CH / 50 0 60 (CH 2
)
3
CH
3 H -- &CH, 93.2 0 0 61 CH 2
CH=CH
2 H CH, 82.4 80 80 62 CH 2 CCH H - / CH, 8.1 60 60 -19 63 CH 2
CH
3 H C' / 10 100 64 CH 2
CH
2
CH
3 H ci 35.6 50 50 65 (CH 2
)
3
CH
3 H /c' 1.5 0 60 66 CH 2 Ph H C' 33.2 10 70 67 CH 2
C-I=CH
2 H c' / 10 50 68 CH 2 CECH H - / cl 37.4 0 70 w CHI 69 CH 2
CH
3 H 90.6 30 80 wCHI 70 CH 2
CH
2
CH
3 H 40 80 71 CH 2 Ph H 30 90 cII' 72 CII 2
CH=CH
2 H -- &N 23.6 50 50 C1I, CH30 73 CH 2
CH
2
CH
3 H 20.2 50 70 CH,O 74 (CH 2
)
3
CH
3 H 40.4 0 30 75 CH 2 Ph H 92.8 30 90 CH ,O 76 CH 2 C-=CI-1 2 H 3.4 40 80 CH O 77 CH 2 CECH H - 4.2 30 50 OCH, 78 CH 3 H 48.3 80 60 OCH' 79 CH 2
CH
3 H 17.3 0 60 80 CH 2
CH
2
CH
3 H / 50 70 ocil' 81 (CH 2
)
3
CH
3 H 65.2 40 60 82 CH 2 Ph H _/ 60 50 OCHI 83 CI- 2
CH=CH
2 H - / 20 50 ociI' 84 CH 2 CECH H O 35.0 10 70 85 CH 2
CH
3 H 51.5 20 40 -20 86 CH 2
CH
2
CH
3 H 14.8 30 80 87 (CH 2
)
3
CH
3 H 96.4 10 50 88 CH 2 Ph H 20.9 10 30 89 CH 2
CH=CH
2 H 30.6 10 80 cI 90 CH 2
CH
2
CH
3 H _ 41.2 10 50 CI 91 (CH 2
)
3
CH
3 H - 1.2 0 80 CI 92 CH 2 Ph H _ 45.8 50 70 CI 93 CH 2 CH=CI-1 2 H - 96.0 40 70 CI 94 CH 2 C=CH H - 31.2 50 60 OCH, 95 CH 3 H /OC2H 58.0 40 80
OCH
1 96 CH 2
CH
2
CH
3 H - /QC2H5 73.4 20 50 OCH, 97 (CH 2
)
3
CH
3 H -6 OC2HS 35.8 40 70 98 CH 2 Ph H H./..... 5 13.3 40 10 OCH, 99 CH 2
CH=CH
2 H -6 0^ 45.8 50 30 100 CH 2
CH
2
CH
3 H F 20.3 20 90 101 CH 2
CH=CH
2 H F 17.7 40 30 102 CH 2 C=CH H F 31.6 50 50 02N 103 CH 2
CH
2
CH
3 H 31.5 20 60 0 2 N 104 CH 2 CH=CI1 2 H -/ 40 50 CHCIICli2O 105 CH 2
CH
2
CH
3 H 2.2 50 50 -21 CHCIHCH 2 O 106 (CH 2
)
3
CH
3 H 23.8 30 30 107 CH1- ci H CH37 10 20 108 CH2 C H C / 50 50
CH
3 0 109 C1"2 /0 ' H / 40 90 10 C- H 92.8 6.67 0 30 cI S CH Cl H - 22.0 13.89 0 40 112 CM, C' H - /OCH, 54.4 3.77 10 90 02N 113 Cf c1 H 100 10.00 50 70 114 c ' H F 72.3 2.04 40 70 115 c H 86.0 9.30 10 80 0 116 CH 3 H 10.29 CI 117 CH 3 H _ 17.78 OPh 118 CH 3 H 14.81 CHIO 119 CH 3 H 72.00 N 120 CH 3 H 82.76 121 CH 3 H -& CH, 16.95 OIN 122 CH 3 H 21.82 123 CH 3 H 4.69 124 CH 3 H 88.68 0 CI 125 CH 2
CH
3 H - 53.06 OCH13 126 CH 2
CH
3 H - / OC2I: 6.67 -22 127 CH 2
CH
3 H C 24.56 0 2 N 128 CH 2
CH
3 H 19.05 129 CH 2
CH
3 H F 8.62 130 CH 2
CH
2
CH
3 H /OCH 18.46 131 CH 2 Ph H & 1.89 0 2 N 132 CH 2 Ph H 9.68 133 CH 2 Ph H F 3,77 OCH, 134 CH 2 Cl H - / OC 2 H 1.82 Table 2. The insecticidal activity of the compounds of formula I to myzus persicae(24h). Compound Item 400ig/mL 200 tg/mL IOOpg/mL 50 tg/mL 25pg/mL 50 numbers of 96/96 103/107 87/87 91/92 78/78 death/total numbers mortality(%) 100 96.3 100 98.9 100 56 numbers of 77/77 81/81 149/149 96/99 104/104 death/total numbers mortality(%) 100 100 100 97.0 100 87 numbers of 74/74 77/77 77/78 79/81 56/84 death/total numbers mortality(%) 100 100 98.7 97.5 66.7 93 numbers of 93/93 114/114 104/104 94/98 112/112 death/total numbers mortality(%) 100 100 100 95.9 100 113 numbers of 84/88 92/92 85/85 66/68 48/80 death/total numbers mortality(%) 95.5 100 100 97.1 60.0 -23 CK numbers of death/total 6/129 numbers mortality(%) 4.7 Table 3. The insecticidal activity of the compounds of formula I to hyalopterus pruni (24h). Compound Item 400ptg/mL 200 g/mL 100pig/mL 50[tg/mL 25ig/mL 50 numbers of 102/102 110/110 101/101 98/102 104/108 death/total numbers mortality(%) 100 100 100 96.1 96.3 56 numbers of 103/103 101/101 121/121 96/101 100/104 death/total numbers mortality(%) 100 100 100 95.0 96.2 87 numbers of 99/99 107/107 110/114 94/101 90/114 death/total numbers mortality(%) 100 100 96.5 93.1 78.9 93 numbers of 103/103 110/110 103/103 104/108 102/112 death/total numbers mortality(%) 100 100 100 96.3 91.1 113 numbers of 114/114 102/102 105/107 106/110 88/118 death/total numbers mortality(%) 100 100 98.1 96.4 74.6 CK numbers of 11/226 death/total numbers mortality(%) 4.9 5 Table 4. The insecticidal activity of the compounds of formula I to aphis gossypii (24h). compound item 50ig/mL 12.5pjg/mL 3.13pig/mL 50 numbers of 245/245 150/150 156/157 death/total numbers mortality(%) 100 100 99.4 C:\NRPorbl\DCC\KXG\373340_ I.DOC-5A172011 - 24 56 numbers of 166/178 136/164 121/157 death/total numbers mortality(%) 93.3 82.9 77.1 87 numbers of 99/104 99/114 141/185 death/total numbers mortality(%) 95.2 86.8 76.2 93 numbers of 138/138 124/124 178/186 death/total numbers mortality(%) 100 100 95.7 113 numbers of 176/176 132/132 104/121 death/total numbers mortality(%) 100 100 86.0 CK numbers of 1/85 death/total numbers mortality(%) 1.2 Industrial application The present invention provides hydrocarbylidene nitrohydrozinecarboximidamides of 5 structural general formula shown as formula 1, and the use thereof as well as the method for making the same. These compounds were prepared by the inventors of the present invention through broadly investigation and rationally designing, as well as screening lots of compounds. Screened compounds have high insecticidal activity, and are prepared easily and conveniently. In addition, the present invention provides a preferred processing 10 route, which has high safety and low cost, thus making practical value of these compounds be greatly improved.
C \NRPorbl\DCC\KXG\373340 1. DOC-5A0/2101 -25 The experiments of insecticidal activity show that the hydrocarbylidene nitrohydrozine carboximidamides shown by formula (I) have high preventive efficiency against insect pests of plants, such as aphid, plant hopper, Helicoverpa armigera, asparagus caterpillar, and the like, so these compounds can be used as plant insecticides. 5 N N2 Rl,,11 N R2 H HY
R
3 (Formula I) The reference in this specification to any prior publication (or information derived from it), or to any matter which is known, is not, and should not be taken as an acknowledgment or 10 admission or any form of suggestion that that prior publication (or information derived from it) or known matter forms part of the common general knowledge in the field of endeavour to which this specification relates. Throughout this specification and the claims which follow, unless the context requires 15 otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.
Claims (28)
1. Compounds shown by formula I or pharmaceutically acceptable salts thereof: 5 R o"N R2 R 3 (formula I) wherein: RI is Cl - CIO saturated and/or unsaturated aliphatic hydrocarbonyl, benzyl, 10 substituted benzyl, halogenated picolyl, halogenated thiazolyl methyl, tetrahydrofuryl methyl or oxazolyl methyl; R2 is hydrogen, Cl - C5 saturated and/or unsaturated aliphatic hydrocarbonyl, phenyl, substituted phenyl, pyridyl or substituted pyridyl; R3 is hydrogen, Cl - CI0 saturated and/or unsaturated aliphatic hydrocarbonyl, 15 furyl, phenyl, substituted phenyl, benzyl or substituted benzyl.
2. The compounds according to claim 1, wherein RI is CI - CIO unsaturated aliphatic hydrocarbonyl, halogenated picolyl, halogenated thiazolyl methyl or tetrahydrofuryl methyl. 20
3. The compounds according to claim 2, wherein RI is allyl, propargyl or chloro-picolyl.
4. The compounds according to claim 1, wherein R2 is hydrogen or CI - C5 25 saturated and/or unsaturated aliphatic hydrocarbonyl.
5. The compounds according to claim 2, wherein R2 is hydrogen. C\NRPobl\DCCKXG0733400_1.DOC-5A)72011 -27
6. The compounds according to any one of claims 1-5, wherein R3 is substituted phenyl or C1 - C10 saturated and/or unsaturated aliphatic hydrocarbonyl.
7. The compounds according to claim 6, wherein R3 is substituted phenyl or 5 C3-C7 saturated and/or unsaturated aliphatic hydrocarbonyl.
8. A method for making the compounds of claim 1, the method comprising the following steps: 1) Reacting nitroguanidine with hydrazine hydrate to form the compounds 10 shown by the structural general formula II; NNO 2 H 2 N NHNH 2 (formula 11) 2) Reacting the compounds shown by the structural general formula II with the compounds shown by the structural general formula III under acid catalysis s, to form the compounds shown by the structural general formula IV; 15 N. NO 2 20 H2N R2 R3 R3 (formula III) (formula IV) 3) Reacting the compounds shown by the structural general formula IV with compounds shown by the structural general formula V under alkalis catalysis, to form the compounds shown by the structural general formula I; 20 R1-X (formula V) C-\NRPortbl\DCC\KXG\373340_( DOC-5A)7/2ol1 - 28 wherein, R2s of formula II and formula II1 are hydrogen, Cl - C5 saturated and/or unsaturated aliphatic hydrocarbonyl, phenyl, substituted phenyl, pyridyl or substituted pyridyl, R3 is hydrogen, CI - CIO saturated and/or unsaturated aliphatic hydrocarbonyl, 5 furyl, phenyl, substituted phenyl, benzyl or substituted benzyl, RI of formula V is Cl - CIO saturated and/or unsaturated aliphatic hydrocarbonyl, benzyl, substituted benzyl, halogenated picolyl, halogenated thiazolyl methyl, tetrahydrofuryl methyl or oxazolyl methyl, X of formula V is Cl, Br, I, CH 3 -0 S0 2 0- or F 3 CSO 2 0 10
9. The method according to claim 8, wherein RI is CI - CIO saturated and/or unsaturated aliphatic hydrocarbonyl, halogenated picolyl, halogenated thiazolyl methyl or tetrahydrofuryl methyl. 15
10. The method according to claim 9, wherein RI is allyl, propargyl or chloro picolyl.
11. The method according to claim 8, wherein R2 is hydrogen or Cl - C5 saturated and/or unsaturated aliphatic hydrocarbonyl. 20
12. The method according to claim 11, wherein R2 is hydrogen.
13. The method according to any one of claims 8-12, wherein R3 is substituted phenyl or CI - C10 saturated and/or unsaturated aliphatic hydrocarbonyl. 25
14. The method according to claim 13, wherein R3 is substituted phenyl or C3-C7 saturated and/or unsaturated aliphatic hydrocarbonyl.
15. The method according to any one of claims 8-14, wherein the reaction in 30 step 1) is conducted in a solvent, and said solvent is water; and the reaction temperature of C:\NRPo.blDCC\KXC\3733400_1 DOC-S7/2011 - 29 said reaction is 45-70'C; the molar ratio of nitroguanidine to hydrazine hydrate in step 1) is
16. The method according to any one of claims 8-15, wherein the reaction in 5 step 2) is conducted in a solvent, and said solvent is anhydrous ethanol or methanol; the reaction temperature of said reaction is 50-80'C; the acids used in said reaction is acetic acid or p-toluenesulfonic acid; and the molar ratio of compunds shown by the structural general formula If to compounds shown by the structural general formula III in step 2) is (1:1)-(1:2). 10
17. The method according to any one of claims 8-16, wherein reaction in step 3) is conducted in a solvent, and said solvent is dimethylformamide or dimethylacetamide; the reaction temperature of said reaction is 0-50'C; the alkais used in said reaction is sodium hydride, sodium ethoxide, sodium methoxide or sodium amide; and the molar ratio 15 of the compounds shown by the structural general formula IV to the compounds shown by the structural general formula V in step 3) is (1:1.2)-(1:2.5).
18. The use of the compounds according to any one of claims 1-7 or pharmaceutically acceptable salts thereof or pharmaceutical compositions containing any 20 one of them for manufacturing plant insecticides.
19. The use according to claim 18, wherein the plant insecticides are insecticides that kill homoptera pests and/or lepidoptera pests. 25
20. The use according to claim 19, wherein the homoptera pests are at least one family of the following six families: aphididae, aleyrodidae, delphacidae, psyllidae, jassidae and coccidae pests; and the lepidoptera pests are noctuidae and/or plutellidae.
21. A plant insecticidal drug or formulation whose active ingredient is the 30 compound according to any one of claims 1-7 or pharmaceutically acceptable salts thereof. C \NRPotnbl)CC\KXG\37334X) I DOC.5)7/2011I - 30
22. The plant insecticidal drug or formulation according to claim 21, wherein the active ingredient of the plant insecticidal drug or formulation is 0.01%-99.99% by mass. 5
23. The plant insecticidal drug or formulation according to claim 21 or claim 22, wherein the plant insecticidal drugs or formulations is the drug or formulation that kills homoptera pests and/or lepidoptera pests.
24. The plant insecticidal drug or formulation according to any one of claims 10 21-23, wherein the homoptera pests are at least one family of the following six families: aphididae, aleyrodidae, delphacidae, psyllidae, jassidae and coccidae pests; and the lepidoptera pests are noctuidae and/or plutellidae.
25. The use of the plant insecticidal drug or formulation according to any one of 15 claims 21-24 in preventing insect pests of plants.
26. A method for preventing insect pests of plants by applying the plant insecticidal drug or formulation according to any one of claims 21-24 to plant leaves and/or plant fruits and/or plant seeds, and the places where the plant leaves and/or plant 20 fruits and/or plant seeds are growing or are expected to be grown; the active ingredient of the plant insecticidal drug or formulation is administrated at the concentration of 1-600mg/L.
27. The method according to claim 26, wherein the active ingredient of the 25 plant insecticidal drug or formulation is administrated at the concentration of 3-50 mg/L.
28. A compound according to claim 1 substantially as hereinbefore described with reference to any one of the Examples.
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| PCT/CN2008/001919 WO2010060231A1 (en) | 2008-11-25 | 2008-11-25 | Condensed amino nitroguanidine compounds, synthesis and use as botanical insecticides thereof |
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| CN110031623A (en) * | 2019-05-10 | 2019-07-19 | 南京农业大学 | Utilize the method for BA-ELISA detection Bemisia tabaci drug resistance |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993004032A1 (en) * | 1991-08-22 | 1993-03-04 | Nippon Soda Co., Ltd. | Novel amine derivative, production thereof, and insecticide |
| EP0974579B1 (en) * | 1998-07-24 | 2001-10-17 | Mitsui Chemicals, Inc. | Nitroisourea derivatives |
-
2008
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993004032A1 (en) * | 1991-08-22 | 1993-03-04 | Nippon Soda Co., Ltd. | Novel amine derivative, production thereof, and insecticide |
| EP0974579B1 (en) * | 1998-07-24 | 2001-10-17 | Mitsui Chemicals, Inc. | Nitroisourea derivatives |
Non-Patent Citations (12)
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|---|
| RN339096-17-2 * |
| RN383168-51-2 * |
| RN575496-66-1 * |
| RN90122-11-3 * |
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| RN904247-33-2 * |
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| RN904249-52-1 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110031623A (en) * | 2019-05-10 | 2019-07-19 | 南京农业大学 | Utilize the method for BA-ELISA detection Bemisia tabaci drug resistance |
| CN110031623B (en) * | 2019-05-10 | 2021-10-15 | 南京农业大学 | A method for detecting drug resistance of Bemisia tabaci by BA-ELISA |
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| AU2008361735A1 (en) | 2010-06-10 |
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