CN1077451A - The nitroethylene class and the nitrofuanidine of Arthropodicidal - Google Patents

Abstract

The agricultural composition that the invention discloses methyl substituted ring-type nitroethylene class and nitrofuanidine compound (formula I) and contain them, they can effectively control the arthropods in agricultural and the non-agricultural environment.

Description

The nitroethylene class and the nitrofuanidine of Arthropodicidal

The present invention relates to methyl substituted ring-type nitroethylene class and nitrofuanidine compound as arthropodicide (particularly controlling lantern fly and leafhopper).

Go up from classifying, GB patent 1,483,633 discloses the type compound of the present invention as sterilant.Go up from classifying, WO patent 91/17659 discloses the method with type compound control lantern fly of the present invention and leafhopper.Go up from classifying, United States Patent (USP) 4,880,933 disclose the intermediate of type compound of the present invention as sterilant.But there is not concrete open The compounds of this invention in the above referred-to references.

The present invention relates to all how much and the formula I compound and the agricultural thereof of steric isomer go up the salt that is suitable for, the agricultural composition that contains them, and they agricultural and non-agricultural on conduct control the application of arthropods (particularly lantern fly and leafhopper).The structural formula of formula I compound is as follows:

R wherein ¹Be H, CH ₂CN, C ₁-C ₄Alkyl, C ₁-C ₄Haloalkyl, formyl radical, C ₂-C ₄Alkyl-carbonyl, C ₂-C ₃Alkoxy carbonyl, C ₂-C ₄Alkoxyalkyl, C ₃-C ₆Dialkoxy alkyl, C ₁-C ₃Alkoxyl group, C ₁-C ₃Alkyl sulphonyl, C ₂-C ₄Alkenyl, C ₂-C ₄Alkynyl, C ₁-C ₄Alkylamino, C ₂-C ₄Dialkylamino or by R ²Any benzyl that replaces;

R ²Be halogen, C ₁-C ₂Alkyl, C ₁-C ₂Haloalkyl, C ₁-C ₂Alkoxyl group, C ₁-C ₂Alkylthio, C ₁-C ₂Halogenated alkylthio, C ₁-C ₂Halogenated alkoxy, NO ₂Or CN;

Z is CHNO ₂Or NNO ₂

Compd A is following formula I compound, wherein R preferably ¹Be H, C ₁-C ₄Alkyl, formyl radical, CH ₂S(O) ₂Or CH ₃C(O).Compd B is that wherein Z is CHNO preferably ₂Compd A.Compound C is that wherein Z is NNO preferably ₂Compd A.

By feature, for biological activity and synthetic easily, the compound of preferentially selecting for use is respectively compd B and Compound C preferably preferably, and they are

The 5-methyl isophthalic acid-[the 2-(methylthio group) ethyl]-2-(nitro methylene)-imidazolidine; And

The 5-methyl isophthalic acid-[the 2-(methylthio group) ethyl]-N-nitro-2-alkyl imidazole imine.

The present invention preferably composition all contain above shown in compound preferably, control occupy the arthropods of leaf and soil and nematode pests preferably method be use above-mentioned shown in compound and composition.

In above-mentioned definition, term " alkyl " independent or that use in compound word (as alkylthio or haloalkyl) means the alkyl of straight or branched, as methyl, ethyl, n-propyl, sec.-propyl or different butyl isomer.Alkoxyl group is meant methoxyl group, oxyethyl group, positive propoxy and isopropoxy.Alkenyl means the alkene of straight or branched, as vinyl, 1-propenyl, 2-propenyl and different butenyl isomer.Alkynyl means the alkynes of straight or branched, as ethynyl, 1-proyl, 2-propynyl and different butynyl isomer.Alkylthio is meant methylthio group and ethylmercapto group.Alkyl sulphonyl and alkylamino and above example have similar definition.

Independent or the halogen in compound word (as haloalkyl) is meant fluorine, chlorine, bromine or iodine.In addition, if be used for compound word (as haloalkyl), this alkyl can partially or even wholly be replaced by identical or different halogen atom.The example of haloalkyl comprises CH ₂CHF ₂, CF ₂CF ₃And CH ₂CHFCl.

The sum of carbon atom is with " C in substituting group _i-C _j" prefix represents that i and j are the numerals from 1-6 here.C for example ₁-C ₃Alkyl sulphonyl is meant that methyl sulphonyl is up to the sulfonyl propyl base; C ₂Alkoxyl group is meant OCH ₂CH ₃, C ₃Alkoxyl group is meant OCH ₂CH ₂CH ₃And OCH(CH ₃) ₂; C ₂Alkyl-carbonyl is meant C(O) CH ₃, C ₄Alkyl-carbonyl is meant C(O) CH ₂CH ₂CH ₃And C(O) CH(CH ₃) ₂; Last example C ₃Alkoxy carbonyl is meant C(O) OCH ₂CH ₃, C ₄Alkoxy carbonyl is meant C(O) CH ₂CH ₂CH ₃And C(O) CH(CH ₃) ₂

R wherein ¹The formula I compound that is a group rather than hydrogen can be by R wherein ¹For method preparation like the formula I compounds of hydrogen, see reaction formula 1.

Wherein II is alkylating reagent, acylating reagent or sulfonylation agent.

Typical condition comprises formula I compound (R ¹=H) with alkylating agent, acylating reagent or the sulfonylation agent represented with II in suitable solvent, under proton acceptor exists, carry out chemical combination.Formula II compound is used equimolar amount usually, or stoichiometric calculation is excessive, and formula II compound comprises alkylating reagent such as alkylogen and sulphonate, acylating reagent such as carboxylic acid halides and acid anhydrides, sulfonylation agent such as sulfonic acid halide and acid anhydrides.The amount that proton acceptor is usually used is a 1-20 mole a great deal of, and comprises metal hydride such as NaH and KH, amide (as the diisopropylaminoethyl lithium), amine (as pyridine and triethylamine), inorganic carbonate (as Quilonum Retard, yellow soda ash, salt of wormwood and cesium carbonate), metal alkoxide (as sodium methylate and potassium tert.-butoxide) and oxyhydroxide (as NaOH and KOH).Solvent commonly used comprises polar aprotic solvent such as dimethyl formamide, N-Methyl pyrrolidone and acetonitrile, ether (as ether and tetrahydrofuran (THF)), and the active solvent of proton such as methyl alcohol, ethanol, third alcohol and water.Common temperature of reaction be 0 ° to the solvent refluxing temperature, the reaction times be 5 minutes to a couple of days.

R wherein ¹For the formula I compound of H can be prepared by laxative remedy by shown in the reaction formula 2: formula III compound and 2-chloroethyl methyl thioether (IV) are reacted in the presence of proton acceptor.

Z=CHNO wherein ₂Or NNO ₂

The alkali (as NaH) that reaction shown in the reaction formula 2 is usually included in 1 a great deal of exists down, in polar aprotic solvent (as DMF), and 150 ℃ in the room temperature chamber, be preferably in 100 ℃, the III of equimolar amount is mixed with IV.Usually by laxative remedy product is separated: to remove and desolvate, then on silicagel column, carry out chromatography, with suitable solvent or solvent liquid wash-out, described solvent includes, but is not limited to the mixed solution of chlorine part, methylene dichloride, methyl alcohol, ethanol, ethyl acetate, triethylamine, saturated ammonium hydroxide aqueous solution or these solvents.

In addition, R wherein ¹Be hydrogen, Z is CHNO ₂Formula I compound can see reaction formula 3 by diamines (V) and formula VI compound prepared in reaction.

Wherein X is leavings group such as SCH ₂, OC ₆H ₅Or halogen.

Reaction formula 3 is usually included in polar solvent such as methyl alcohol, ethanol, acetonitrile, tetrahydrofuran (THF) or water (but being not limited to these) exist down, equimolar amount V and IV (being generally 1, two (the methylthio group)-2-nitroethylenes of 1-) are mixed.Can use proton acceptor such as NaOH, yellow soda ash or triethylamine (but being not limited to these).

In addition, R wherein ¹Be H, Z is CHNO ₂Formula I compound can press method preparation: with being similar to above reaction formula 3 described reaction conditionss, make diamines (V) and 2,2,2-three halo nitroethanes (formula VII) react, and see reaction formula 4.The reaction of reaction formula 4 generally includes the alkali of using the 1-10 molar equivalent such as amine (for example triethylamine and pyridine), carbonate (as Na ₂CO ₃, K ₂CO ₃And NaHCO ₃) or oxyhydroxide (as LiOH, NaOH or KOH) (but being not limited to these).

X wherein ¹, X ²And X ³Be halogen.

R wherein ¹Be H, Z is NNO ₂Formula I compound can use the reaction formula 3 described methods that are quite analogous to, (wherein Y is NH by diamines V and nitroguanidine VIII ₂) or the S-methyl-(wherein Y is SCH to N-nitro isothiourea VIII ₂) reaction make.R wherein ¹Be H, Z is NNO ₂Formula I compound in reaction formula 5.

Y=NH wherein ₂Or SCH ₃

Wherein Z is CHNO ₂Formula III compound can pass through 1 (IX) and formula VI compound prepared in reaction, see reaction formula 6.It is described that the conditionally complete that carries out above-mentioned reaction is similar to reaction formula 3.

Reaction formula 6

Wherein X is leavings group such as SCH ₃Or OC ₆H ₅

Wherein Z is NNO ₂Formula III compound can press method preparation: to be quite analogous to preparation (R in the reaction formula 5 ¹=H, Z=NNO ₂) described mode, by 1 (IX) and the reaction of formula VIII compound.

Diamines (V) can make with the two step method described in the reaction formula 7.

Reaction formula 7

In the step ⅰ of reaction formula 7, making the 2-(methylthio group) ethylamine (X) and potassium cyanide and acetaldehyde exists down in the acid of 1-2 a great deal of, reacts in solvent, generates the amino-nitrile XI.Other cyanide salt and HCN also can be used for this method.The hydrohalogen of X and other acid salt also can be used for this method.Suitable solvent includes, but is not limited to methyl alcohol, ethanol, Virahol and water, and the mixed solution of these solvents.In document (Synth.Commun. for example, 1985,15,157; Synthesis, 1979,127) can find the many other method of preparation amino-nitrile (as XI) in.

In the step ⅱ of reaction formula 7, the amino-nitrile XI generates the diamines V through reduction.Use lithium aluminum hydride, its amount is 0.75-3 mole a great deal of, in solvent such as ether or THF ,-10 ℃ to the solvent refluxing temperature, can very easily finish above-mentioned reduction reaction.In addition, applications catalyst (as palladium/carbon) carries out hydrogenation, also can finish the reduction reaction of XI, and the result generates V.

Following example is further narrated the present invention.

Example 1

Steps A: the ethylamino 2-(2-(methylthio group)] propionitrile

With 24.4 gram (0.27 mole) 2-(methylthio groups) solution of ethamine and 100ml methyl alcohol places ice bath to be cooled to 5-10 ℃, and in 15 minutes to wherein dripping 294ml 1M aqueous hydrochloric acid.The solution of gained adds 13 gram (0.29 mole) acetaldehyde in 5-10 ℃ subsequently again in the 5-10 ℃ of solution-treated with 17.4 gram (0.27 mole) potassium cyanide and 150ml water.The solution of gained is poured 1L saturated sodium bicarbonate aqueous solution and 300ml CH into then in stirring at room 6 hours ₂Cl ₂Mixed solution in, water layer is with two parts of other 200ml CH ₂Cl ₂Extraction, the organic layer of the merging saturated NaHCO of 500ml ₃Solution washing is through anhydrous MgSO ₄Drying is filtered and is concentrated, and obtains 37.6 gram (97%) faint yellow oily things.

¹HNMR（200MHz，CDCl ₃）δ3.78-3.60（m，1H），3.17-2.97（m，1H），2.94-2.74（m，1H），2.71-2.62（m，2H），2.12（s，3H），1.67（br s，1H），1.52（d，J＝7Hz，3H）.

Step B:N ²-[the 2-(methylthio group) ethyl]-1, the 2-propylene diamine

In 0 ℃ of lithium aluminum hydride (84ml 1M(CH to vigorous stirring (mechanical stirrer) ₃CH ₂) 20 solution, 0.084 mole) and (CH ₃CH ₂) ₂O(163ml) drip the product and the 82ml(CH of 6.04 gram (0.042 mole) steps A in the solution ₃CH ₂) ₂The solution of O.The white uneven mixture of gained is cooled to 0 ℃ then in 0 ℃ of stirring 1 hour, adds solution, 3.1ml15%NaOH solution and the 9.3ml water of 3.1ml water in the 10ml tetrahydrofuran (THF) carefully successively in 0 ℃.The mixture 155ml(CH that generates ₃CH ₂) ₂The O dilution, and in stirred overnight at room temperature.The mixture that obtains is filtered, and concentrating filter liquor obtains 6.4 gram deep yellow oily things.

¹HNMR（200MHz，CDCl ₃）δ2.97-2.45（m，7H），2.11（s，3H），1.75（br s，3H），1.05（d，J＝6Hz，3H）.

Step C:5-(methyl isophthalic acid-[the 2-(methylthio group) ethyl]-the 2-(Nitromethylene)-imidazolidine (compound 1)

With product, 2.9 gram (0.018 moles) 2 of 2.6 gram (0.018 mole) step B, the vlil of 2-pair-(methylthio group)-1-nitroethylene and 18ml dehydrated alcohol 5 hours, cool to room temperature, and concentrate, obtain 4.8 gram brown oil.This oily matter is through flash chromatography on silica gel, with 40: 1: 0.1 CH ₂Cl ₂: CH ₃CH ₂OH: 48%NH ₄The OH wash-out obtains 1.8 gram yellow oil, solidifies m.p.60-62 ℃ during this oily matter is placed.Solid grinds with 1-chlorobutane, obtains in 66-68 ℃ of fused beige solid.

¹HNMR（200MHz，CDCl ₃）δ8.63（br s，1H），6.53（s，1H），4.21-4.03（m，1H），3.90（t，1H），3.40-3.28（m，3H），2.78-2.58（m，2H），2.16（s，3H），1.36（d，3H）.

The 5-methyl isophthalic acid-[the 2-(methylthio group) ethyl]-N-nitro-2-alkyl imidazole imine (compound 2)

With the vlil of products, 2.4 gram S-methyl-N-nitro isothioureas and the 18ml dehydrated alcohol of 2.6 gram (0.018 mole) examples 1 step B 18 hours.The mixture cool to room temperature of gained, and concentrate, 3.5 gram brown oil obtained.This oily matter is through flash chromatography on silica gel, with 40: 1: 0.1 CH ₂Cl ₂: CH ₃CH ₂OH: 48%NH ₄The OH wash-out obtains the faint yellow oily thing of 1.25 grams.

¹HNMR（200MHz，CDCl ₃）δ8.08（br s，1H），4.18 4.00（m，1H），3.92（t，1H），3.78（dd，1H），3.42-3.24（m，2H），2.84-2.60（m，2H），2.17（s，3H），1.37（d，3H）.

With the general method of narration here, or it significantly improves one's methods and can make table 1, and 2 and the compound of key A.

At table 1,2 and key A in use following symbol:

Me＝CH ₃n-Bu＝（CH ₂） ₃CH ₃

Et＝CH ₂CH ₃i-Bu＝CH ₂CH（CH ₃） ₂

n-Pr＝（CH ₂） ₂CH ₃s-Bu＝CH（CH ₃）CH ₂CH ₃

i-Pr＝CH（CH ₃） ₂t-Bu＝C（CH ₃） ₃

Table 1

Table 2

Composition/purposes

Compound of the present invention is gone up the carrier (comprising liquid or solid thinner or organic solvent) that is suitable for agricultural usually and is used from the composition.Therefore, Arthropodicidal dompositions of the present invention comprises the formula I compound and at least a following composition of significant quantity: (a) tensio-active agent, (b) organic solvent and (c) at least a solid or liquid diluent.Preparation commonly used can be by general method preparation.They comprise pulvis, granule, poison bait, pill, solution, suspension agent, emulsion, wettable powder, missible oil, flowable pulvis etc.Sprayable composition is added in the suitable medium, and sprays with the sprayed volume of the hundreds of liters of about 1-/hectare.The composition of high density is mainly as the intermediate of further preparation.Above-mentioned each preparation generally contains the consumption of effective constituent, thinner and the tensio-active agent of significant quantity and composition in following about scope, and effective constituent adds tensio-active agent and/or thinner equals 100%(weight here).

% (weight)

Effective constituent thinner tensio-active agent

Wettable powder 25-90 0-74 1-10

Oil-suspending agent, emulsion, 5-50 40-95 0-15

Solution (comprising missible oil)

Pulvis 1-25 70-99 0-5

Granule, poison bait and pill 0.01-99 5-99.99 0-15

High concentration composition 90-99 0-10 0-2

General solid diluent is at Watkins etc., Handbook of InsecticideDust Diluents and Carriers, and second edition, Dorland Books, Caldwell narrates among the New Jersey..To wettable powder, preferably select absorptivity thinner preferably for use, to pulvis, preferentially select fine and close thinner for use.General liquid diluent and solvent be at Marsden, Solvents Guide, second edition, Interscience, New York, narration in 1950..Suspension concentrates is preferably 0.1% o'clock solvability; The strong solution agent is more stable for being separated in the time of 0 ℃.Mclutcheon ' s Detergents and Emusifiers Annual, Allured Publ.Corp., Ridgewood, New Jersey, and Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ.Co., Inc., New York has incorporated tensio-active agent into own forces and has introduced purposes in 1964.In order to reduce foam, caking, burn into bacterial growth etc., all preparations can contain than minor amounts of additives.In order to use, used each composition is preferably through USEPA or similarly government organs' approval of this country.

The method of preparation above-mentioned composition is known.By simply each composition being mixed with solution.Thin solids composition makes by mixing and pulverizing (pulverizing with beater grinder or jet mill usually).The agent of water dispersible granules can make by making the agglomeration of finely powdered composition; Example is seen Cross etc., Pesticide formulations, Washington, D.C., 1988, pp.251-259.Suspension agent makes by wet crushing mill; Example is seen, U.S. patent 3,060,084.Granule and pill can be sprayed to active substance on the ready-formed particulate vector or by agglomeration technique and make.See Browning, " Agglomeration ", Chemical Engineering, December 4,1967, P.147 and below, Perry ' s Chemical Engineer ' s Handbook, the 4th edition, McGraw-Hill, New York, 1963, P.8-57 and below, and WO patent 91/13546.Pill can be by 4,172, the 714 described preparations of U.S. patent.Water-dispersible and water dissolvable granule can be by DE patent 3,246,493 described being prepared.

See U.S. patent 3,235 about the other data of preparation technique, 361:6 row 16 row-7 row 19 row and example 10-41; U.S. patent 3,309,192:5 row 43 row-7 row 62 row and example 8,12,15,39,41,52,53,58,132,138-140,162-164,166,167 and 169-182; U.S. patent 2,891,855:3 row 66 row-5 row 17 row and example 1-4; Klingman, Weed Control as Science, John Wiley and Sons, Inc., New York, 1961, pp.81-96; And Hance etc., Weed Control Handbook, the 8th edition, Blackwell Scientific Publications, Oxford, 1989.

Parts all in the following example all are weight percentage.Compound number reference retrieval Table A.

Example A

Missible oil

Compound 1 20%

The sulphonate and 10% that oil is molten

The mixture of Soxylat A 25-7

Isophorone 70%

Each composition is mixed, stirring with accelerate dissolution under the heating at leisure.In packaging operation, comprise through the fie screen strainer and filtering, to guarantee in the product without any external insolubles.

Example B

Wettable powder

Compound 1 30%

Sodium alkyl naphthalene sulfonate 2%

Sodium lignosulfonate 2%

Synthetic soft silica 3%

Kaolin 63%

Effective constituent is mixed in mixing machine with inert substance.After pulverizing in beater grinder, material mixes once more, and sieves by 50 mesh sieves.

Embodiment C

Pulvis

The wettable powder 10% of example B

Pyrophyllite (powdery) 90%

With wettable powder and pyrophyllite thinner thorough mixing, pack then.This product is suitable to be used as pulvis.

Example D

Granule

Compound 1 2%

Montmorillonite particle (low sample volatile material, 98%

0.71/0.30 millimeter; USS 25-50 number sieve)

Effective constituent is dissolved in volatile solvent such as the acetone, in biconical nozzle mixing machine it is sprayed on the montmorillonite particle.Add heat extraction acetone then.Make particle cooling and packing again.

Example E

Granule

The wettable powder 15% of example B

Gypsum 69%

Vitriolate of tartar 16%

Each composition mixes in rotary mixing machine, and spray water is until finishing granulation.When most of material reached desired 0.1-0.42 millimeter (USS, 18-40 number sieve) scope, taking-up particle, drying also sieved.Excessive particle is pulverized so that make the material of the other scope that meets the requirements.Above-mentioned particle contains 4.5% effective constituent.

Example F

Solution

Compound 1 25%

N-methyl-pyrrolidone 75%

Each composition is mixed and stirring, so that preparation is fit to the solution of directly a small amount of dispenser.

Example G

Water suspending agent

Compound 2 40.0%

Polyacrylate thickeners 0.3%

4-dodecylphenol polyglycol ether 0.5%

Sodium phosphate dibasic 1.0%

SODIUM PHOSPHATE, MONOBASIC 0.5%

Polyvinyl alcohol 1.0%

Water 56.7%

Mixed being incorporated in the sand mill of each composition pulverized together, make the particle of making in fact all below 5 microns big.

Example H

Prefabricated particle

Talcum 85%

Calcium lignin sulphonate 12%

Sodium lignosulfonate 3%

Each composition mixed and with about 20% water-wet.Make mixture extruding become fragment, length is generally the 1-10 millimeter, diameter is about 1 millimeter garden column form object, makes it dry and use by the described method of example I.

The example I

Granule

Compound 1 2%

Example H ready-formed particle 98%

Compound 1 is dissolved in the acetone, and in mixing machine, is sprayed on the ready-formed particle.Add heat extraction acetone.Make particle cooling and packing then.

Example J

The particle poison bait

Compound 1 3.0%

The nonyl phenol of polyethoxylated and 9.0%

The mixture of Sodium dodecylbenzene sulfonate

Ground corn cob 88.0%

Effective constituent and surfactant mixtures are dissolved in the suitable solvent such as acetone, and are sprayed on the ground corn cob.Make particle drying and packing then.

The compounds of this invention is supported leaf, that fruit is supported, seed is supported, arthropods aquatic and that occupy soil has (comprising insect, mite and nematode) effect of wide spectrum, these arthropodss are insects of the grain of growth and the farm crop that store, forestry, chamber crop, ornamental crops, nursery crop, storage and fiber product, domestic animal, family and the public place and animal health.The professional who knows the present technique field understands that not every compound all has same effect to all insects.But all compounds of the present invention all demonstrate activity to following insect; Lepidopterous ovum, larva and adult; That ovum of Coleoptera and leaf are supported, that fruit is supported, that root is supported, that seed is supported larva and adult; The ovum of Hemiptera and Homoptera, larva and adult; Flour mite purpose ovum, larva, nymph and adult; The adult and the larva of total wing order, Orthoptera and Dermaptera; Dipterous ovum, larva and adult; And the adult of nematoda and larva.Compound of the present invention also to Hymenoptera, Isoptera, Anoplura, Siphonaptera, The insect that Lian order, Thysanoptera and psocid are ended; The insect of spider shape guiding principle; And worm also has activity.These compounds are effective especially to following insect: cucumber 11 asterophyllite first food root subspecies (Diabrotica undecimpunctata howardi), two leafhoppers (Mascrosteles fascifrons), cotton boll resembles (Anthonomus grandis), T.urticae Koch (Tetranychus urticae), autumn mythimna separata (Spodoptera frugiperda), black bean aphid (Aphis fabae), Heliothis virescens (Heliothis virescens), Lissorhoptrus oryzophilus Kuschel (Lissorhoptrus oryzophilus), rice leaf beetles (OulemaOxyzae), white back of the body rice lice (Sogatella furcifera), rice green leafhopper (Nephotettix cincticeps), Nilaparvata lugen (brown planthopper) (Nilaparvata lugens), small brown-back rice plant-hopper (Laodelphax striatellus), striped rice borer (Chilo suppressalis), Cnaphalocrocis medinali(rice leaf roller) (Cnaphalocrocis medinalis), scotinophora lurida (Scotinophora lurida), niphe elongata (Lagynotomus elongatus), China Nezara viridula smaragdula Fabricius. (Leptocorisa chinensis), green stinkbug of rice sour jujube (Cletus puntiger) and Nezara viridula smaragdula Fabricius. (Nezara viridula).Narrate in more detail for insect, see WO patent 90/10623 and WO patent 92/00673.

The compounds of this invention also can be learned and goes up compounds effective and mix with one or more other sterilants, mycocide, nematocides, bactericide, miticide, semiochemicals, repellent, attractive substance, pheromone, feeding yield stimulant or other biological, obtains having the multicomponent sterilant of the more wide spectrum of agricultural protection effect.Can have with the example of other agricultural protection agent of The compounds of this invention prescription: sterilant such as monocrotophos, the furans pellet, tetrachlorvinphos, the Malathion, methyl 1, Insecticide 1179, the desinsection amidino groups, diazinon, Deltamethrin, grass oxime prestige, nitrile chlorobenzene phenothrin, esfenvalerate, Permanone, bromine chlorine phosphorus, the worm mite disappears, triflumuron, diflubenzuron, it is plain that methoxy is protected the children, Buprofezin, Suo Shuan goes out, acephate, the methyl R-1582, Chlorpyrifos, Rogor, fonofos, isofenphos, first thiophene sulphur phosphorus, acephatemet, R-1504, phosphamidon, Phosalone, go out and decide prestige, phorate, special fourth phorate, Trichlorphon, methoxychlor, bifenthrin, biphenate, cyfloxylate, kill mite chrysanthemum ester, the first Flumethrin, bifenthrin, tralomethrin, Halizan and fish Teng ketone; Mycocide such as derosal, thiuram, dodine, maneb, chloroneb, F-1991, frost urea cyanogen, fenpropidin, powder rust quinoline, triadimefon, Vancide 89, thiophanate methyl, thiabendazole, fosetylaluminium, m-tetrachlorophthalodinitrile, dicloran, going out, it is clean, Difolatan, RP-26019, dislike acid amides, Vinclozoline, kasugamycin, nitrile bacterium azoles, tebuconazole, difenoconazole, alkene azoles alcohol, fluquinconazole, Pencomazole, Wocosin 50TK, uniconzole, flutriafol, pounce on the bacterium azoles, pyrifenox, the phonetic alcohol of two chlorobenzenes, plant place's alcohol, the powder rust is clear, COPPER OXYCHLORIDE 37,5, the antibacterial third ammonia ester, Phaltan and fluzilazol; Nematocides is as the line oxime that goes out, Nemacur and fourth epithio phosphorus; Bactericide such as terramycin, Streptomycin sulphate and Basic Chrome Sulphate, miticide such as Niagara 9044, quinomethionate, G-23922, kelthane, Hooker HRS 16, cyhexatin, hexythiazox, amine three nitrogen mites, propargite and mite are finished tin; And biological pesticide such as Bacillus thuringiensis and bacculovirus.

In some example, will have the similar control scope but different other arthropodicide and the usefulness of the mode of action is particularly advantageous for delaying drug resistance.

The present invention comprises that also control occupy the method for the arthropods of leaf and soil and nematode pests and protection farm crop, animal and human's body health; this method comprises the formula I compound of using one or more; perhaps contain at least a significant quantity above-claimed cpd composition to comprise agricultural and/or non-agriculturally be subjected to the environment of insect infringement, to shielded zone, perhaps directly insect is controlled.Best application method is the apparatus spraying, and it is distributed in the insect environment in leaf, animal, people or house compound, is distributed in soil or the animal, is distributed to the plant part of being encroached on or needing protection.In addition, the granule composite of above-claimed cpd can impose on leaf or impose on soil or paddy or mix with soil or paddy.Can also use other application method, they comprise directed and residual spray, arosol spray, interior absorption, poison bait, ear tag, bolus, sprays, fumigant, aerosol agent and many other application methods.The compounds of this invention can be sneaked in the poison bait and by arthropods and search for food, perhaps be placed on and lure that they ingest or make with another kind of method in device (as trap etc.) of its contact The compounds of this invention into.

The compounds of this invention can be used by its pure state, but usually great majority are compound and compositions of forming of suitable carriers, thinner and tensio-active agent of using by one or more, and can form composition with grain, this will decide according to the enduse of expection.Application method comprises the water dispersant or the refining oil solution of the The compounds of this invention of spraying preferably.Mix the effect that usually can improve compound mutually with spray oils, spray oils concentrated solution, spreader-sticker, tackiness agent, auxiliary and synergistic agent and other solvents such as piperonyl butoxide.

For effective control, required dispenser ratio depends on following factor: such as life cycle of the arthropodan kind of required control, insect, life stage, its size, place, season, host crop or animal, feeding behavior, mating behavior, ambient moisture, the temperature in a year etc.In general, the ratio of dispenser is about 0.01-2 kilogram effective constituent/hectare, the insect pest that is enough under normal conditions agroecosystem provides extensive effectively control, but 0.001 kilogram/hectare may be enough, perhaps may need 8 kilograms/hectare like that many.For non-agricultural dispenser, effectively ratio is about 1.0-50 milligram/rice ², but 0.1 milligram/meter ²May be enough, maybe may need 150 milligrams/meter ²Like that many.

Below test formula I compound is to the control effect of specific insect; Key A is seen in the description of compound.But the provide protection of the Pest Control that The compounds of this invention provided never is limited to mentioned kind.The compound that does not comprise or without screening, the mortality ratio that perhaps provides is less than 80%.

Key A

Compound Z R ¹M.p. ℃

1 CHNO ₂H 66-68

2 NNO ₂H oil

3 CHNO ₂CH ₂CHCH ₂oil

4 NNO ₂C(O)CH ₃oil

Compound number ¹H NMR data 1

32 6.41(s,1H),5.94-5.75(m,1H),

5.35-5.18(m,2H),4.08-3.78(m,5H),

3.43(dt,1H),3.12(dd,1H),2.83-2.58

(m,2H),2.14(s,3H),1.35(d,3H).

43 4.01(dd,1H),3.84-3.78(m,1H),

3.74-3.65(m,1H),3.38(dd,1H),3.27

(ddd,1H),2.78-2.60(m,2H),2.51

(s,3H),2.17(s,3H),1.29(d,3H).

¹Except as otherwise noted, in CDCl ₃The middle nuclear magnetic resonance spectrum that obtains.

S=is unimodal, d=doublet, t=triplet, m=multiplet

²The spectrum that obtains in 200MHz

³The spectrum that obtains in 400MHz

Test A

Autumn mythimna separata

Testing apparatus is the impact-resistant vinylbenzene dish that has 12 apertures.These apertures contain the filter paper of water-wet and about 8 centimetres ²Horn shape leaf (lima leaf).Autumn mythimna separata (Spodoptera frugiperda) larva of 15-20 3 worms order is placed the plastic cup of 8 ounces (230ml).The solution (with acetone: distilled water (75: 25) is solvent) of each test compound is sprayed on this dish and the cup.Make the dish that transmits on the conveying belt and cup directly be in flat fan-shaped hydraulic efficiency pressure nozzle below and spray, this hydraulic efficiency pressure nozzle is at 30 pounds/inch ²(207KPa) spray with the ratio of 0.5 pound of effective constituent/acre (about 0.55 kilogram/hectare) under the pressure.Then with (1 larva of per 1 aperture) in the insect immigration dish.Cover dish and under 27 ℃ and 50% relative humidity, kept 48 hours, write down larva death toll in 12 apertures of horn shape leaf (lima leaves) then.In the test-compound, the mortality ratio that compound 1 obtains is more than 80% or 80%.

Test B

Cucumber 11 asterophyllite first food root subspecies

The device that preparation is made up of 8 ounces of (230ml) plastic cups, each plastic cup include 1 inch ²Soybean-malt extract food.Testing apparatus is sprayed by the described method of test A with each solution of test-compound.Cup spraying back drying is eaten root subspecies (Diabrotic undecimpunctata howardi) larva with the cucumber 11 asterophyllite first of 52 worm orders and is placed each cup.Cover cup then, and under 27 ℃ and 50% relative humidity, kept 48 hours.Then, record death toll.After 48 hours, in the test-compound, the mortality ratio that compound 1,2,3,4 obtains is more than 80% or 80%.

Test C

Two leafhoppers

Testing apparatus is the cup of a series of 12 ounces (350ml), contains oat (Avena sativa) seedling in 1 inch (2.5 centimetres) sterile soil layer of each cup and 1/2 inch sand bed.Testing apparatus is sprayed by the described method of test A in order to each solution of listing compound down.After the oat drying of spraying, 10-15 two leafhoppers (Macrosteles fascifrons) adult is sucked in each cup that covers with porose cover.Cup kept 48 hours under 27 ℃ and 50% relative humidity, write down death toll then.In the test-compound, the mortality ratio that compound 1,2,4 obtains is more than 80% or 80%.

Test D

Cotton boll resembles

5 cotton bolls are resembled (Anthonomus grandis) adult to be put in each cup of a series of 9 ounces (260ml).Testing apparatus is sprayed by the described method of test A in order to each solution of listing compound down.Each cup covers with porose cover then, and keeps 48 hours under 27 ℃ and 50% relative humidity, writes down death toll then.In the test-compound, the mortality ratio that compound 1,2 obtains is more than 80% or 80%.

Test E

Black bean aphid

Each nasturtium leaf is encroached on 10-15 aphid (black bean aphid in each stage), and sprays by the described method of test A above its downside.Then blade is placed on the diameter that contains the 4ml sugar aqueous solution and is in 3/8 inch the bottle, and cover, climb away from the aphid that blade falls preventing with 1 ounce of volumetrical cleaning plastic cup.Testing apparatus kept 48 hours under 27 ℃ and 50% relative humidity, write down death toll then.In the test-compound, the mortality ratio that compound 1,2,3 obtains is more than 80% or 80%.

Test F

Solution system is to the activity of rice green leafhopper nymph

Directly be added to reagent in the 10ml distilled water and make fully and dissolve.This reagent solution is poured in the taper testing apparatus.Make 3 strain paddy rice seedlings place device then by the spongy dish of perforation.Spongy dish is immersed in the reagent solution seedling root system system fully, and partly is isolated in the top of solution in the atmosphere of plant.Spongy dish also can prevent to test nymph contact test solution by accident.Reagent solution surface and spongy tray bottom be spaced apart the 7-10 millimeter, can prevent the spongy plate of reagent accidental contamination like this.The concentration of reagent in test solution is 100ppm.Make the paddy rice bacterium absorption reagent 24 hours in the calm liquid in keeping the growth cell of 27 ℃ and 65% relative humidity of growing directly from seeds.Rice green leafhopper (Nephotettix Cineticeps) nymph of 8-10 3 worms order is moved in the testing apparatus with aspirator pump.The device of being encroached on remains under the above-mentioned identical temperature and humidity condition.Survival in 24-48 hour of record infringement back and dead nymph shallow lake overgrown with wild plants order.The insect that can not creep is classified death as.In the test-compound, in infringement back 48 hours, the mortality ratio that compound 1,2 obtains was more than 80% or 80%.

Test G

Solution system is to the activity of rice brown planthopper nymph

Except that the test kind is that this test carry out to the same procedure of rice green leafhopper nymph activity test in the applying soln system the Nilaparvata lugen (brown planthopper) (Nilaparvata lugens).In the test-compound, in infringement back 48 hours, the mortality ratio that compound 1,2 obtains was more than 80% or 80%.

Test H

Contact toxicity to the rice green leafhopper nymph

3 strains, 1.5 blade stages and about 10 centimetres of high paddy rice (Oryza sativa) seedling moved into contain in 1/2 ounce of plastic cup of Kumiai Brown artificial soil.In cup, add 7ml distilled water then.Prepare reagent by laxative remedy: at first medicine is dissolved in the acetone, adds water then, making final trial concentration is 75: 25(acetone: water).Then 4 plastic cups (each cup is made revision test) are placed on the rotating spraying cell.In 2.0 kilograms per centimeter ²Under the pressure, with air atomization nozzle with cup with 45 seconds of 50ml reagent solution spray.Between the spray phase in 45 seconds, finish 7.5 rotations.After the dispenser, treated cup remains on about 2 hours of the case inner drying of ventilating pit.After the drying, cup is put into the taper testing apparatus, and soil surface covers with 2-3 millimeter quartz sand.Rice green leafhopper (Nephotettix cincticeps) nymph of 8-10 3 worms order is moved in the testing apparatus with aspirator pump.Testing apparatus remains under 27 ℃ and 65% relative humidity.Record is invaded and is cut back survival in 24 and 48 hours and dead nymph number.The insect that can not creep is classified death as.In the test-compound, compound 1,2,4 is more than 80% or 80% in the mortality ratio that obtained in 48 hours under the 100ppm concentration.

The test I

Contact toxicity to the brown suspicion of rice lice nymph

3 strains, 1.5 blade stages and about 10 centimetres of high paddy rice (Oryza sativa) seedling moved into contain in 1/2 ounce of (14ml) plastic cup of Kumiai Brown artificial soil.In cup, add 7ml distilled water then.Prepare reagent by laxative remedy: at first medicine is dissolved in the acetone, adds water then, making final trial concentration is 75: 25(acetone: water).Then 4 plastic cups (each cup is made revision test) are placed on the rotating spraying cell.Under 2.0 kilograms per centimeter, 2 pressure, with air atomization nozzle with cup with 45 seconds of 50ml reagent solution spray.Between the spray phase in 45 seconds, finish 7.5 rotations.After the dispenser, treated cup remains on about 2 hours of the case inner drying of ventilating pit.After the drying, cup is put into the taper testing apparatus, and soil surface covers with 2-3 millimeter quartz sand.Nilaparvata lugen (brown planthopper) (Nilaparvarta lugens) nymph of 8-10 3 worms order is moved in the testing apparatus with aspirator pump.Testing apparatus remains under 27 ℃ and 65% relative humidity.Survival in 24 and 48 hours of record infringement back and dead nymph number.The mixed worm that can not creep is classified death as.In the test-compound, compound 1,2 is more than 80% or 80% in the mortality ratio that obtained at 48 o'clock under the 100ppm concentration.

The test fourth be with compound 1 and demethyl derivative (say that on kind this derivative is open in GB patent 1,483,633, and particularly in WO patent 91/17649 as compound 14(p.96) open) compare.Each compound is tested independently under the same conditions, but does not directly compare.

Test J

Table 3 has compared The compounds of this invention 1 and the viewed activity of demethyl derivative (compd A).Each compound is tested independently in top test H and the described condition of I (but the dispenser ratio is 2.5ppm), but does not directly compare.

Table 3

(observed mortality ratio, %)

Species compound 1 compd A

To rice green leafhopper nymph 100 59

Contact toxicity

To rice brown planthopper nymph 90 24

Contact toxicity

Claims (8)

1, formula I compound and agricultural thereof go up the salt that is suitable for,

R wherein ¹Be H, CH ₂CN, C ₁-C ₄Alkyl, C ₁-C ₄Haloalkyl, formyl radical, C ₂-C ₄Alkyl-carbonyl, C ₂-C ₃Alkoxy carbonyl, C ₂-C ₄Alkoxyalkyl, C ₃-C ₆Dialkoxy alkyl, C ₁-C ₃Alkoxyl group, C ₁-C ₃Alkyl sulphonyl, C ₂-C ₄Alkenyl, C ₂-C ₄Alkynyl, C ₁-C ₄Alkylamino, C ₂-C ₄Dialkylamino or by R ²Any benzyl that replaces,

R ²Be halogen, C ₁-C ₂Alkyl, C ₁-C ₂Haloalkyl, C ₁-C ₂Alkoxyl group, C ₁-C ₂Alkylthio, C ₁-C ₂Halogenated alkylthio, C ₁-C ₂Halogenated alkoxy, NO ₂Or CN;

Z is CHNO ₂Or NNO ₂

2, the described compound of claim 1, wherein R ¹Be H, C ₁-C ₄Alkyl, formyl radical, CH ₃S(O) ₂Or CH ₃C(O).

3, the described compound of claim 2, wherein Z is CHNO ₂

4, the described compound of claim 2, wherein Z is NNO ₂

5, the described compound of claim 3, this compound are 5-methyl isophthalic acid-[2-(methylthio group) ethyl]-2-(Nitromethylenes)-imidazolidine.

6, the described compound of claim 4, this compound are 5-methyl isophthalic acid-[2-(methylthio group) ethyl]-N-nitro-2-alkyl imidazole imines.

7, the composition of Arthropodicidal, said composition comprise formula I compound and at least a (a) tensio-active agent of significant quantity, (b) organic solvent, and (c) at least a solid or solution dilution agent,

R wherein ¹Be H, CH ₂CN, C ₁-C ₄Alkyl, C ₁-C ₄Haloalkyl, formyl radical, C ₂-C ₄Alkyl-carbonyl, C ₂-C ₃Alkoxy carbonyl, C ₂-C ₄Alkoxyalkyl, C ₃-C ₆Dialkoxy alkyl, C ₁-C ₃Alkoxyl group, C ₁-C ₃Alkyl sulphonyl, C ₂-C ₄Alkenyl, C ₂-C ₄Alkynyl, C ₁-C ₄Alkylamino, C ₂-C ₄Dialkylamino or by R ²Any benzyl that replaces;

R ²Be halogen, C ₁-C ₂Alkyl, C ₁-C ₂Haloalkyl, C ₁-C ₂Alkoxyl group, C ₁-C ₂Alkylthio, C ₁-C ₂Halogenated alkylthio, C ₁-C ₂Halogenated alkoxy, NO ₂Or CN;

Z is CHNO ₂Or NNO ₂

8, control occupy the arthropods of leaf and soil and the method for nematode pests; this method comprise will the formula I compound of significant quantity and agricultural go up place, the zone that needs protection that the salt that is suitable for or Arthropodicidal dompositions impose on infringement or directly impose on above-mentioned insect; described Arthropodicidal dompositions comprises formula I compound and at least a (a) tensio-active agent of significant quantity; (b) organic solvent; and (c) at least a solid or liquid diluent, formula I compound is here

R wherein ¹Be H, CH ₂CN, C ₁-C ₄Alkyl, C ₁-C ₄Haloalkyl, formyl radical, C ₂-C ₄Alkyl-carbonyl, C ₂-C ₃Alkoxy carbonyl, C ₂-C ₄Alkoxyalkyl, C ₃-C ₆Dialkoxy alkyl, C ₁-C ₃Alkoxyl group, C ₁-C ₃Alkyl sulphonyl, C ₂-C ₄Alkenyl, C ₂-C ₄Alkynyl, C ₁-C ₄Alkylamino, C ₂-C ₄Dialkylamino or by R ²Any benzyl that replaces;

R ²Be halogen, C ₁-C ₂Alkyl, C ₁-C ₂Haloalkyl, C ₁-C ₂Alkoxyl group, C ₁-C ₂Alkylthio, C ₁-C ₂Halogenated alkylthio, C ₁-C ₂Halogenated alkoxy, NO ₂Or CN;

Z is CHNO ₂Or NNO ₂