CN1177906A - Pesticidal compounds - Google Patents

Abstract

Pesticidal compounds having general formula (I) or a salt thereof is provided, in which n represents an integer from 0 to 4; m represents an integer 0 or 1; each R independently represents a halogen atom or a nitro, cyano, hydroxyl, alkyl, alkenyl, haloalkyl, haloalkenyl, alkoxy, haloalkoxy, haloalkenoxy, amino, alkylamino, dialkylamino, alkoxycarbonyl, carboxyl, alkanoyl, alkylthio, alkylsulphinyl, alkylsulphonyl, carbamoyl, alkylamido, cycloalkyl, aryl or aralkyl group; R<1> and R<2> each independently represent an optionally substituted alkoxy group or together represent a group =O, =S or =N-OR<9>, where R<9> represents a hydrogen atom or an optionally substituted alkyl group; R<3> represents a hydroxyl group, or a group -OL where L is a leaving group, or a group which in vivo is transformed into a group -OL<1> where L<1> is a leaving group; R<6> represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy or aryloxy group; R<7> and R<8> independently represent an optionally substituted alkoxy group or together represent a group =O, =S or =N-OR<9>, where R<9> is as previously defined; wherein R4 and R5 independently represent a halogen atom or an optionally substituted alkyl or alkenyl group, or together with the interjacent carbon atom represent an optionally substituted cylcoalkyl or cycloalkenyl ring; and A represents a straight or branched chain alkyl or alkenyl group, which may be optionally substituted, preferably with halogen, an acyclic carbon chain of which links the 3 position of the naphthalene ring shown and the moiety -CR<4>R<5>R<6>; with the proviso that when R<1> and R<2>, and R<7> and R<8> are groups =0, m and n =0; R<4> and R<5> are methyl and R<6> is ethenyl; R<3> is not hydroxyl or ethnoyloxy.

Description

Agricultural chemical compound

The present invention relates to new with used as pesticides, in particular as 1,2,3 of insecticide, miticide and fungicide, the 4-substituted naphthalene compounds; The preparation method of these compounds; The purposes that contains these compound compositions and these compounds and composition control pest.

US2,572,946 disclose the composition of control acarian and aphid, but do not provide their concrete killing mite or kill the aphid data, and wherein active component is that general formula is the compound of (P1)

Wherein R is the group that contains 6-15 carbon atom, is selected from alkyl, cyclohexyl and cyclohexyl alkyl; For example positive alkyl, isoalkyl, alkyl-cycloalkyl and aralkyl.

DE2641343A1 discloses general formula (P2) compound prevailingly

R wherein ₁Be straight chain, side chain or ring C _8-14Alkyl, R ₂Be straight or branched C _1-17Alkyl, C _2-17Alkenyl, C _3-6Cycloalkyl, C _1-4Alkoxyl ,-CH ₂OCH ₃,-CH ₂OCH ₂CH ₃Or-CH=CH-COOH, and X and Y represent hydrogen, fluorine, chlorine or bromine atom or methyl or methoxy.It is said that these compounds have extremely mite and kill the aphid activity, but R wherein only ₁It is straight chain C ₈Or C _11-14Alkyl shows to have described activity.

US4,110,473 have related to the method that prevents that plant is encroached on by acarian (mite), and this method comprises with general formula (P3) compound treatment plant

Wherein Y is hydrogen, fluorine, chlorine or bromine; R ₁Be side chain, ring or straight chain C _8-14Alkyl, R ₂Be side chain or straight chain C _1-12Saturated alkyl or the C that is at random replaced by one or two chlorine, bromine, methoxy or ethoxy substituting group _3-12Unsaturated alkyl, or C _3-6Cycloalkyl.

DE3801743A1 discloses general formula (P4) compound prevailingly

Wherein n is 0-12, R ¹Expression hydrogen or the alkyl, aralkyl, alkyl-carbonyl, (mixing) aryl carbonyl, alkoxy carbonyl group, alkyl sulphonyl or the aryl sulfonyl that replace arbitrarily, and R ²Expression haloalkyl, (mixing) aryl that replaces arbitrarily or the cycloalkyl of replacement.It is said that these compounds have the mite and the Fungicidally active of killing.

Specifically disclose ten formulas (P4) compound, wherein n is 0, R ¹Be hydrogen atom, and R ²Be 4-(tert-butyl group) cyclohexyl, 4-(trifluoromethyl silicyl) cyclohexyl, 4-(cyclohexyl) cyclohexyl, 2-trifluoromethyl cyclohexyl or 3,5-two (trifluoromethyl) cyclohexyl, perhaps n is 0, R ¹Be acetyl group and R ²Be 4-(tert-butyl group) cyclohexyl, 4-(cyclohexyl) cyclohexyl, 2-or 3-trifluoromethyl cyclohexyl or 3,5-two (trifluoromethyl) cyclohexyl.In these compounds, confirmed that two kinds of formulas (P4) compound has acaricidal activity, wherein n be 0, R ¹Be hydrogen atom and R ²It is 4-(tert-butyl group) cyclohexyl or 4-(trifluoromethyl silicyl) cyclohexyl.

EP0077550 discloses general formula (P5) compound

Wherein R is the alkyl of 1-10 carbon atom, and has described it at veterinary formulations, particularly prevent purposes in the protozoal infections preparation.

Do not relate to antifungal, desinsection in the prior art or kill the mite naphthoquinone compound, wherein quaternary carbon atom directly is connected with the naphthoquinones ring, is perhaps just passing through or isoalkyl is connected with the naphthoquinones ring.

Common unsettled International Application PCT/GB 95/00953 relates to the natural products compound of general formula (P6)

Wherein R represents hydrogen atom or hydroxyl or acetoxyl group, also relates to these compounds as agricultural chemicals, particularly fungicide, insecticide and/or acaricidal purposes.These compounds before disclosed (Bol.Soc.Chil.Quim.38187-190) by (1993) such as Chamy as plant metabolites.

The inventor has now developed synthetic naphthoquinone compound and has compared the compound with favourable agricultural chemicals character with known in the art those, and these compounds are especially for handling specific fungi, insect and/or mite class pest.The preferred synthetic compound of the present invention has fabulous pesticide activity, particularly kills aleyrodid (whitefly) and/or acarian and/or aphid and/or fungi activity; Most preferred demonstrate have anti-at least two kinds, preferably to the activity that has of all above-mentioned insects.Chemical compound lot of the present invention also has the antifeedant activity at least some insects or mite.

One aspect of the present invention provides general formula (I) compound or its salt

Wherein

N represents the integer of 0-4; M represents 0 or 1 integer;

Each R represents halogen atom or nitro, cyano group, hydroxyl, alkyl, alkenyl, haloalkyl, haloalkenyl group, alkoxyl, halogenated alkoxy, haloalkene oxygen base, amino, alkylamino, dialkylamino, alkoxy carbonyl group, carboxyl, alkanoyl, alkylthio group, alkyl sulphinyl, alkyl sulphonyl, carbamoyl, alkyl amido, cycloalkyl, aryl or aralkyl independently;

R ¹And R ²The alkoxyl that expression independently of one another replaces arbitrarily, perhaps they represent together=O ,=S or=N-OR ⁹, R wherein ⁹Expression hydrogen atom or the alkyl that replaces arbitrarily;

R ³The expression hydroxyl or-OL group (wherein L is a leaving group) or the expression be converted in vivo-OL ¹The group of group (L wherein ¹Be leaving group);

R ⁶Alkyl, alkenyl, alkynyl group, cycloalkyl, cycloalkenyl group, aryl, alkoxyl, alkenyloxy, chain oxy-acetylene, cycloalkyloxy, cyclenes oxygen base or aryloxy group that expression replaces arbitrarily;

R ⁷And R ⁸The alkoxyl that expression independently of one another replaces arbitrarily, perhaps they represent together=O ,=S or=N-OR ⁹, R wherein ⁹As defined above; And

R wherein ⁴And R ⁵Represent halogen atom or the alkyl or the alkenyl that replace arbitrarily independently of one another, perhaps they represent any cycloalkyl or cyclenes basic ring that replaces with the carbon atom that is in wherein; And

A represents straight or branched alkyl or alkenyl, and they can at random be substituted, preferably replaced by halogen, A be with shown in 3 of naphthalene nucleus and-CR ⁴R ⁵R ⁶The acyclic carbochain that group links to each other; Condition is to work as R ¹With R ²And R ⁷With R ⁸During for=O, m and n=0, R ⁴And R ⁵Be methyl, and R ⁶When being vinyl, R ³Not hydroxyl or acetoxyl group.

When formula I compound contain clearly regulation but not clearly when the alkyl of regulation, alkenyl or alkynyl group substituting group, they can be straight or brancheds, and can contain maximum 12 carbon atoms, preferably contain maximum 6 carbon atoms, especially contain 4 carbon atoms.Cycloalkyl or cycloalkenyl group can contain 3-10,5-8 carbon atom most preferably.Aryl can be any aromatic hydrocarbyl, particularly phenyl or naphthyl.Aralkyl can be any alkyl, the particularly benzyl that is at random replaced by alkyl that are replaced by the aryl of above-mentioned definition of above-mentioned definition.

When any aforementioned substituting group is meant arbitrarily when substituted, the substituting group that exists can be the exploitation agricultural chemical compound and/or modify these compounds to influence in those substituting groups commonly used in its activity, lasting effect, penetrability or other character one or more arbitrarily.These substituent instantiations comprise, for example halogen atom, nitro, cyano group, hydroxyl, alkyl, alkenyl, haloalkyl, haloalkenyl group, alkoxyl, halogenated alkoxy, amino, alkylamino, dialkylamino, alkoxy carbonyl group, carboxyl, alkanoyl, alkylthio group, alkyl sulphinyl, alkyl sulphonyl, carbamoyl, alkyl amido, cycloalkyl, phenyl and benzyl.Usually, can there be 0-3 substituting group.When any aforementioned substituting group was represented or contained alkyl substituent, described alkyl substituent can be a straight or branched, and can contain maximum 12 carbon atoms, preferably contains 6 carbon atoms at most, most preferably contains maximum 4 carbon atoms.When any aforementioned substituting group was represented or contained aryl or cycloalkyl, aryl or cycloalkyl itself can be replaced by one or more halogen atoms, nitro, cyano group, alkyl, alkenyl, haloalkyl, haloalkenyl group, alkoxyl or halogenated alkoxy.Preferably, aryl is a phenyl, and cycloalkyl contains 3-8 carbon atom, preferably contains 4-7 carbon atom.

If there is R, then R preferably represents halogen atom or nitro, cyano group, hydroxyl, C _1-4Alkyl, C _1-4Haloalkyl, C _2-4Alkenyl, C _2-4Haloalkenyl group, C _1-4Alkoxyl, C _1-4Halogenated alkoxy, C _1-4Alkylamino, two-C _1-4Alkylamino, C _1-4Alkoxy carbonyl group, C _1-4Alkylthio group, C _1-4Alkyl sulphinyl or C _1-4Alkyl sulphonyl.

If there is R, then R more preferably represents halogen atom or C _1-4Alkyl, C _1-4Haloalkyl, C _2-4Alkenyl, C _2-4Haloalkenyl group, C _1-4Alkoxyl or C _1-4Halogenated alkoxy.

Preferably n is 0,1 or 2, and the especially preferred n of being is 0.

Also preferred R ¹And R ²Represent C independently of one another _1-4Alkoxyl, particularly methoxyl group, perhaps the two combine expression=O or=N-OR ⁹, R wherein ⁹Expression hydrogen atom or C _1-4Alkyl, particularly methyl.Especially preferred is R ¹And R ²Be methoxyl group or the two expression that combines=O group.

Work as R ³Be-the OL group (wherein L is a leaving group) or can in vivo be converted into-OL ¹Group the time, leaving group can be any group of often making leaving group.Preferred leaving group is the pK of sour LOH in water _aValue is 1-7, those leaving groups of 1-6, especially 1-5 more preferably.

Work as R ³Expression can in vivo be converted into-OL ¹(L wherein ¹Be leaving group) group the time, carry out this conversion in the pest body that preferably in protected plant, maybe will prevent and treat, particularly by in the plant or the effect of the enzyme in the pest body.For example, if R ³The expression β-acidic group for example-O-CH ₂CH ₂CO-OH (wherein-CH ₂CH ₂CO-OH is not a leaving group), then can pass through for example oxidation formation-O-CO-CH of tryptophan side-chain alpha of enzyme in vivo ₂-CO-OH group, wherein-CO-CH ₂-CO-OH is a leaving group.

R preferably ³Expression-OR ¹⁰(R wherein ¹⁰Expression hydrogen atom, the alkyl, alkenyl, the aryl or aralkyl that replace arbitrarily), perhaps R ³Expression-CO-R ¹¹,-CO-O-R ¹¹,-SOR ¹¹,-SO ₂-R ¹¹,-P (X) (OR ¹²) (OR ¹³) ,-P (X) (R ¹²) (OR ¹³) ,-P (OR ¹²) (OR ¹³) or-P (R ¹²) (OR ¹³), R wherein ¹¹Expression hydrogen atom, the alkyl that replaces arbitrarily, alkenyl, aryl or aralkyl or-NR ¹²R ¹³Group; R ¹²And R ¹³Independently represent hydrogen atom or the alkyl that replaces arbitrarily, and X represents oxygen or sulphur atom.Work as R ¹⁰Or R ¹¹When representing the aryl or aralkyl of replacement arbitrarily, preferred aryl groups is a phenyl, and substituting group is selected from halogen atom, nitro and C arbitrarily _1-4Alkyl.It is particularly preferred replacing in the 4-position of benzyl ring.With at R ¹⁰, R ¹¹Or R ¹²On substituting group the same, for R ³Described term replaces arbitrarily comprises that for example trialkylsilkl such as trimethyl silyl replace the group that is for example contained silicon atom.

Preferably, R ³The expression hydroxyl or-O-CO-R ¹¹,-O-CO-OR ¹¹, R wherein ¹¹Expression hydrogen atom or C _1-12Alkyl, C _1-12Haloalkyl, C _1-12Hydroxyalkyl, C _1-12Carboxyalkyl, phenyl or benzyl.

Particularly preferably be R ³Expression-OH or-O-CO-R ¹¹, R wherein ¹¹Expression hydrogen atom or C _1-6Alkyl, C _1-6Haloalkyl, phenyl or benzyl.Most preferably, R ¹¹Be methyl, ethyl, propyl group or butyl.

Preferred R ⁶Expression C _1-16Alkyl, C _2-16Alkenyl, C _1-16Haloalkyl, C _2-16Haloalkenyl group, C _1-16Alkane acyl alkyl, C _1-16Alkoxyalkyl, C _1-16Alkoxyl, C _1-16Halogenated alkoxy or C _1-16The alkoxyl alkoxyl.Preferred these groups are C _1-6Chain length, perhaps chain length is C when for thiazolinyl _2-6

R further preferably ⁶Expression C _1-6Alkyl, particularly methyl or ethyl, C _1-6Haloalkyl, for example trifluoromethyl, difluoromethyl or a methyl fluoride, perhaps C _2-6Alkenyl or C _2-6Haloalkenyl group.

Preferably, R ⁷And R ⁸Represent C independently _1-4Alkoxyl, perhaps they combine expression=O or=N-OR ⁹, R wherein ⁹Expression hydrogen atom or C _1-4Alkyl, but particularly preferably be R ⁷And R ⁸The expression methoxyl group that combines, expression=O perhaps combines.

Concerning the professional of this area, it is evident that, wherein R ¹And R ²And R ⁷And R ⁸Be together alkoxyl or together for=S or NOR ⁹Compound will be the possible biology precursor of corresponding naphthoquinone compound, naphthoquinones is the preferred compound of the present invention.

Preferably, R ⁴And R ⁵Represent C independently of one another _1-4Alkyl, C _1-4Haloalkyl, C _2-4Alkenyl or C _2-4Haloalkenyl group, perhaps they and be in carbon atom between them cycloalkyl or the cyclenes basic ring that expression replaces arbitrarily that combine, this ring is preferably at random replaced by halogen, alkyl, haloalkyl, alkenyl or haloalkenyl group.

Formula I compound can form salt, for example works as R ³During the expression hydroxyl.The suitable alkali that forms these salt comprises inorganic base for example sodium hydroxide, potassium hydroxide or sodium carbonate, and organic base for example tertiary amine such as triethylamine and cyclammonium such as pyrrolidines.

This area professional should be appreciated that The compounds of this invention exists different geometric isomers and diastereomer.Comprise each isomer and composition thereof in the scope of the present invention.

The inventor determines that The compounds of this invention has produced the pest kind of resistance to those agricultural chemicals that current sale is used and has been that the pesticide activity that demonstrates is to make us interested especially.Therefore, The compounds of this invention is specially adapted to prevent and treat those produce resistance to other commercially available agricultural chemicals insect, mite strain and fungi strain system.The inventor proves conclusively, with R ⁴, R ⁵And R ⁶Group can provide at least three kinds of optically-active configurations with 3 feature quaternary carbon atoms that are connected that encircle shown in group A or the formula I, thereby the given activity that is applicable to the specific insect of control is provided.

In the compound of first group of preferred unique first aspect present invention, quaternary carbon atom is with group-CR ⁴R ⁵R ⁶Form directly and naphthalene nucleus adjoin R wherein ⁴And R ⁵Represent halogen or the alkyl or the alkenyl that replace arbitrarily independently, wherein do not comprise those compounds among the aforementioned common pending application PCT/GB95/00953 and belong to those compounds in the additional conditions in the formula I definition.

The compound or its salt of general formula (II) is provided in the compound of first group of preferred uniqueness

Wherein R, R ¹, R ², R ³, R ⁶, R ⁷And R ⁸And n is as defining formula I, and R ⁴And R ⁵Expression halogen or the alkyl or the alkenyl that replace arbitrarily.

Preferred general formula (II) compound is following compound, and wherein n is 0, R ¹With R ²And R ⁷With R ⁸Be together=O; R wherein ⁴And R ⁵Represent C independently of one another _1-4Alkyl or C _1-4Haloalkyl, and R ⁶Expression C _1-7Alkyl, C _1-7Haloalkyl, C _1-7Alkoxyalkyl, C _1-7Alkoxyl, C _1-7Alkoxyl alkoxyl, C _2-7Alkenyl, C _2-7Haloalkenyl group or C _2-7The alkoxyl thiazolinyl.R ³Be preferably hydroxyl or-O-CO-R ¹¹Or-O-CO-OR ¹¹, R wherein ¹¹Be C _1-3Alkyl, most preferably R ³Be hydroxyl.Further preferred R ⁶Expression C _1-7Alkyl, C _2-7Alkenyl or C _1-7Haloalkyl or C _2-7Haloalkenyl group, most preferably R ⁶Expression C _1-6Alkyl, C _1-6Haloalkyl, C ₂Alkenyl or C ₂Haloalkenyl group.R most preferably ⁴And R ⁵Be methyl.

The inventor finds that first group of preferred compound particularly has insecticidal activity to mite and aleyrodid generally speaking to insect, acarian and fungi.Min Gan aleyrodid is the kind of Aleyrodes (Bemisia) especially.

In the compound of second group of preferred unique first aspect present invention, quaternary carbon atom exists as the part of cycloalkyl or cyclenes basic ring, and therefore, second group of preferred formula (I) compound is preferred formula (III) compound

Wherein

N, A, R, R ¹, R ², R ³, R ⁶, R ⁷And R ⁸Such as mutual-through type (I) definition,

M represents the integer of 0-1;

And R ⁴And R ⁵Represent any cycloalkyl or cycloalkenyl group that replaces with the carbon atom that is between them.

Preferred formula (III) compound is following compound, wherein R ¹With R ²And R ⁷With R ⁸Be together=O; N and m are 0; R ⁴And R ⁵Represent saturated, any substituted cycloalkyl ring fully with the carbon atom that is between them; And R ⁶The C that expression is at random replaced by halogen _1-16Alkyl or C _2-16Alkenyl.R ³Be preferably hydroxyl ,-O-CO-R ¹¹Or-O-CO-OR ¹¹, R wherein ¹¹Be C _1-3Alkyl, most preferably R ³Be hydroxyl.

Further preferably, R ⁴And R ⁵Represent saturated, any substituted C with the carbon atom that is between them _4-8Cycloalkyl ring is most preferably replaced by chlorine or fluorine; Further preferably be C _5-8Cycloalkyl ring, and R ⁶Be C _1-6Alkyl, C _2-6Alkenyl, C _1-6Haloalkyl, C _2-6Haloalkenyl group or halogen.Superior reactive compound is those following compounds, wherein R in this group compound ⁴And R ⁵Represent cyclohexyl ring with the carbon atom that is between them, and R ⁶Be C _1-2Alkyl or C ₂Alkenyl.

Preferred second group of preferred compound of the present invention be to acarian and aleyrodid and effective especially to some fungi, and the most activated compound has kept the activity to acarian simultaneously to aleyrodid, particularly Aleyrodes (Bemisia) kind is had superior activity.

In the compound of the first aspect present invention of the 3rd group of uniqueness, quaternary carbon atom and is positioned at apart from naphthalene nucleus 2-16 carbon atom chain strong point not on cycloalkyl or cycloalkenyl group, more preferably apart from naphthalene nucleus 2-10 carbon atom chain length.Most preferably quaternary carbon atom is apart from naphthalene nucleus 4-8 carbon atom chain length.

Therefore, in the unique compound of this group, preferred formula (I) compound is preferred formula (IV) compound

Wherein

N, A, R, R ¹, R ², R ³, R ⁶, R ⁷And R ⁸Such as mutual-through type (I) definition,

And R ⁴And R ⁵Represent halogen or the alkyl or the alkenyl that replace arbitrarily independently of one another.

In order to prevent and treat aleyrodid, group A preferably has 3-7 carbon atom between naphthalene nucleus and quaternary carbon atom, particularly when it is the straight-chain alkyl-sub-chain.

For the compound of high-efficiency prevention and control aphid is provided, group A preferably has 4-8 carbon atom between naphthalene nucleus and quaternary carbon atom, particularly when it is the straight-chain alkyl-sub-chain.

For above-mentioned two kinds of situations, connecting the peak activity that exists one or more side chains will reach use short chain length acquisition between naphthalene nucleus and quaternary carbon atom on the carbochain A.

Preferred this group compound is following formula (IV) compound, wherein R ¹With R ²And R ⁷With R ⁸Be together=O; M is 1; A is C _3-8The alkyl or alkenyl chain, it can be replaced by halogen or straight chain that can halo.Preferably, R ⁴, R ⁵And R ⁶Be C _1-6Alkyl or haloalkyl or C _2-6Alkenyl or haloalkenyl group.R ³Be preferably hydroxyl ,-O-CO-R ¹¹Or-O-CO-OR ¹¹, R wherein ¹¹Be C _1-3Alkyl, most preferably R ³Be hydroxyl.

Preferably following compound in this group compound, wherein A is-(CH ₂) _a-group (wherein a is the integer of 1-7) or-(CH ₂) _a-CH=CH-(CH ₂) _b-group (wherein a and b are that summation is the integer of 0-6, and more preferably its summation is 0-5, and most preferably its summation is 0-4), and wherein one or more carbon atoms are by the analog of these groups of alkyl, haloalkyl, alkenyl, haloalkenyl group or halogen replacement.

Second aspect present invention provides formula (I) compound as agricultural chemicals, particularly as the purposes of insecticide, miticide and/or fungicide, in particular for the purposes of control acarian, aleyrodid, aphid and/or fungi.Min Gan aleyrodid comprises Aleyrodes (Bemisia) kind especially.Min Gan aphid comprises knurl volume Aphis and Aphis kind especially.Min Gan fungi comprises aspergillus, Pyricularia Sacc., Rhizoctonia, Erysiphe and Botrytis kind especially.

The preferable use of this second aspect is the purposes of formula (II) compound as the agricultural chemicals of control insect, acarian and/or fungi.

Second preferable use of this second aspect is the purposes of formula (III) compound as the agricultural chemicals of control acarian, aphid and/or aleyrodid.

The 3rd preferable use of this second aspect is the purposes of formula (IV) compound as the agricultural chemicals of anti-acarian and/or aphid.

Except formula (I), (II), (III) and (IV) the direct pesticide activity of compound, it is direct lethal toxicity activity, the inventor determines, these compounds also to the insect of many types (particularly to the chrysomelid genus of bar (Diabrotica) kind (the chrysomelid and Eastern Corn RootWorm of corn young shoot root), Lepidoptera (Lepidoptera) is as the greedy noctuid (Spodoptera frugiperda) in prodenia litura (Spodoptera littoralis) and meadow and beetle such as horseradish daikon leaf beetle Fab (Phaedon cochleaiae Fab)) and those species of specifically noting above have antifeedant activity.

A fourth aspect of the present invention provides the method at a certain place antagonism insect, particularly insect, mite and fungi pest, and this method comprises with general formula (I) compound, preferably use general formula (II), (III) or (IV) the described place of compound treatment.

Preferably, there is pest in described place, i.e. insect, mite and/or fungi, and this place itself maybe can be subjected to or be subjected to the surrounding environment of pest invasion and attack.More preferably, this place itself exists pest, storage that food is arranged, is subjected to plant or animal, the seed of these plants or the environment that described plant is rely and grows that pest is attacked.Specifically, formula I compound can be used for sparging in the home environment indoor in case the invasion of manage a household fly or other insects, mite or fungi, be used for gardening or agricultural environment to handle the grain storage such as grain, perhaps sparge growing crop for example on cotton or the rice with the invasion of antagonism insect, the particularly aleyrodid and the insect of relevant kind, and place medicine or veterinary drug, for example as ox with spray to prevent or to treat the invasion of insect or mite.

A fifth aspect of the present invention also provides and has prepared as defined above formula (I) compound, particularly preparation formula (II), (III) and (IV) method of compound.

If the m in described formula (I) compound is 0, then described method can comprise with general formula (VI) compound treatment general formula (V) compound

Wherein n, R and R ³As defined above, R ³Be preferably-OH,

Wherein X represents leaving group, preferred hydroxyl or halogen, preferred especially chlorine or bromine atom; R ¹¹¹, R ¹²¹And R ¹³¹Represent hydrogen atom or the alkyl that replaces arbitrarily independently of one another, and R ⁴And R ⁵Such as in formula (I) definition,

Produce general formula (VII) compound

Wherein n, R, R ¹¹¹, R ¹²¹, R ¹³¹, R ⁴And R ⁵As defined above.When X represented hydroxyl, this reaction can be carried out under the Mitsunobu reaction condition, that is, and and at 0 ℃ and for example use diethyl azodiformate and triphenyl phasphine in oxolane.When X represented halogen atom, this was reflected under the alkylation conditions, promptly used suitable solvent such as carrene and alkali such as triethylamine to carry out.

Then, can be in suitable solvent, preferred alcohols such as ethanol heated type (VII) compound, carry out Claisen rearangement, obtain general formula (VIII) compound

Can also be in polar organic solvent, under alkali condition, for example in pyrrolidines, direct and formula (V) the compound reaction with alkyl aldehydes, then non-polar solven for example in the benzene, under acid condition, for example in p-methyl benzenesulfonic acid, heat products therefrom, dewatering obtains the naphthalene cycle compound of 3-alkenyl substituted.

Formula (VIII) compound and R wherein ⁶The formula (I) of the thiazolinyl that expression replaces arbitrarily, (II) and (IV) compound is corresponding, and can change into other formulas (I) compound by various deriving methods.

For example,, use hydrogen, can produce wherein R suitable formula (VIII) hydrogenation of compounds by making catalyzer with palladium on carbon ⁶The formula I compound of the alkyl that expression replaces arbitrarily.Numerical expression (V) compound can buy mostly, also can be prepared by for example DielsAlder reaction by corresponding 2-hydroxyl benzoquinones.

In another kind of preparation formula (I), (II), (III) and (IV) in the method for compound (it is 1 formula (I) compound that this method is particularly useful for making m wherein, be formula (III) or (IV) compound), radical initiator for example in the presence of ammonium persulfate and the silver nitrate, at suitable solvent for example in the acetonitrile solution, with general formula (V) compound and carboxylic acid CR ₄R ₅R ₆-(A) _m-COOH (wherein A, m, R ⁴, R ⁵And R ⁶Reaction as defined above) forms general formula (I), (II), (III) or (IV) compound

Wherein n, R and R ³As defined above.

Formula (I) compound that is obtained by this method can also adopt the method for above-mentioned derivatization method or its combination further to react, and obtains above-mentioned other formulas (I) compound.

For using this method that substitutes, if R wherein ⁴And R ⁵Form the cycloalkyl or the cyclenes basic ring of 3-10 carbon with the carbon atom between them, many 1-methyl cycloalkyl and cycloalkenyl group carboxylic acid can buy, and the hydroxy-acid group on it can adopt the known technology expansion to obtain longer carbon chain lengths, then if desired, can adopt the known technology of this area professional to replace.For example can use Arnst-Eistert reaction acquisition-CH ₂-expansion (referring to for example, Meier and Zeller (1975) Angew.Chem.Int.Ed.Ewgl., 14,32).By corresponding cyclanone and cyan-acetic ester reaction, can to obtain m wherein be 1 another kind of compound to the Yu Geshi reagent reacting then, after hydrolysis, obtain (1 '-cycloalkyl that replaces)-acetate (referring to for example, Amsterdamsky etc. (1975) Bull.Soc.Chim.Fr. (3-4Part2), p635-643 and Muhs M.A.PhD Thesis, University of Washington.Diss Abst.14,765 (1954)), increased by 1 carbon chain lengths.

Contain R in order to prepare in ring with big carbon number ⁴R ⁵Compound, can use magnesium, then with carbonic acid gas for example the carbonic acid gas of dry ice form handle, by forming the grignard compound, cycloalkyl or cycloalkenyl group compound that corresponding monobromo is replaced are converted into carboxylic acid.In the presence of butyl lithium, adopt compound R ⁶-I (for example iodomethane) carries out alkylated reaction, formed carboxylic acid can be converted into carboxylic acid 1-Arrcostab, wherein R ⁶Be as defined above, be suitable for the group of these conditions.

In order to prepare 1-fluorine cycloalkyl/cycloalkenyl group carboxylic acid, can adopt the method for CA75:17761u, fourth-1 wherein, 3-diene and 1-fluoro-1-carboxyl ethene react under heating condition in the presence of the 4-hydroxyl phenol, make the unsaturated partial reduction of ring then, the cycloalkenyl group compound is converted into compound cycloalkyl.Perhaps, can be with corresponding 2-ketone-cycloalkyl-carbonate and caustic alcohol and fluorine gas reaction, obtain 1-fluoro-2-ketone-cycloalkyl-carboxylate, use then (i) MeSH (ii) Raney nickel and (iii) potassium hydroxide base with ketone group reduction (referring to " organic chemistry magazine " (J.Org.Chem.) (1983) 48,724-727 and " organic chemistry magazine " (J.Org.Chem.) (1982) 47.3242-3247).

Can adopt the known method of this area professional, on other positions except carboxylic acid group 1-position, cycloalkyl/cyclenes basic ring be replaced for example alkylation.Begin by single unsaturated cyclenes alkyl carboxylates, can directly carry out alkylating as previously mentioned in the 1-position, use up then and make initator and compound R ₂₀-X (R wherein ²⁰Be alkyl or haloalkyl, and X is a halogen) Compound C F for example ₃The X reaction can be introduced for example CF of alkyl or haloalkyl ₃-group.Use the palladium on carbon catalytic condition to reduce then, can unsaturated bond is saturated.

For example, react in the presence of LDA by cycloalkyl/cycloalkenyl group carboxylate methyl ester and for example trifluoromethyl iodine, perhaps in the presence of triethylamine, react by 1-ketone group cycloalkyl/cycloalkenyl group carboxylate and trifluoromethyl iodine, reduce afterwards, can obtain cycloalkyl/cycloalkenyl group carboxylic acid 1-methyl ester trifluoroacetate.Perhaps, can be in the presence of the 4-hydroxyl phenol, with 2-trifluoromethyl acrylate and the fourth-1 that replaces arbitrarily, the 3-diene adds thermal response, the 1-trifluoromethyl cycloalkenyl group carboxylic acid that is replaced arbitrarily.

Employing Wood etc. can obtain wherein R in the method described in J.Chem.Soc Perkin Trans 1 (1985) 1645-1659 ⁶Undersaturated compound, thus compound (IX), wherein R produced ¹⁴¹Be alkyl, alkenyl, alkynyl group, aryl, alkoxyl, alkene oxygen base, alkynyloxy group or the aryloxy group of hydrogen or replacement arbitrarily, this compound reacts with naphthoquinones under above-mentioned condition of resetting.This compound reduction can be obtained isoalkyl.

In another preparation method of The compounds of this invention, with formula (V) compound and formula X-(A) _m-CR ⁴R ⁵R ⁶(R wherein ⁴, R ⁵, R ⁶, A and m be as defining formula I, and X will break away from compound to produce charged group ⁺(A) _m-CR ⁴R ⁵R ⁶Leaving group; For example X can be halogen atom or tosyl) reaction.Acid for example Lewis acid as aluminium chloride in the presence of, use Fieser and the described condition widely of Gates carry out this reaction (J.Am.Chem.Soc. (1941) 63,2943-2953).

For this area professional, also have many other and prepare the method for other general formulas (I) compound.

In the presence of organic base (preferred tertiary amine such as triethylamine) or inorganic base (for example sodium carbonate), by R wherein ³Formula (I) compound of expression hydroxyl and X wherein represent compounds X-L reaction of halogen atom, can prepare wherein R ³Represent the formula of leaving group (I) compound as defined above.For example, in the presence of alkali such as triethylamine, use at the suitable solvent acyl chlorides R in the carrene for example ¹¹-CO-Cl can prepare wherein R with the acylated hydroxy in the suitable formula V compound ³Expression-O-CO-R ¹¹The formula I compound of group, wherein R ¹¹As defined above.Perhaps, can be for example in the presence of the dicyclohexyl carbodiimide at dehydrating agent, R wherein ³Formula I compound and the acid compounds HO-L of expression hydroxyl react, and wherein L as defined above and comprise sour C=O group.Another approach is by R wherein ³The expression hydroxyl (is R ³Expression-OM group, wherein M is a metal ion) the slaine and compounds X-L reaction as defined above of formula (I) compound, prepare described compound.

For example, under alkalescence or acid condition, use suitable alcohol, for example use the methanol solution of potassium hydroxide, one or two carbonyl ketonization with in suitable formula (V) compound or corresponding formula (I) compound can prepare wherein R ¹With R ²And/or R ⁷With R ⁸Formula (I) compound of the alkoxyl that independent separately expression replaces arbitrarily.

By with thiation reagent for example Lawesson reagent (2,4-two (4-methoxyphenyl)-1,3-dithia-2,4-diphosphane-2,4-disulphide) handle suitable formula (I) compound (R wherein ¹With R ²Together and/or R ⁷With R ⁸Be together=O), can prepare wherein R ¹With R ²Together and/or R ⁷With R ⁸Represent formula (I) compound of thiocarbonyl group=S together, if desired, can use protecting group.

At alkali for example in the presence of the pyridine, by using formula R ⁹O-NH ₂Azanol or alkoxyamine (R wherein ⁹As defined above) handle wherein R ¹With R ²Together and/or R ⁷With R ⁸Be together=formula (I) compound of O, can prepare wherein R ¹With R ²Together and/or R ⁷With R ⁸Represent oximido=N-OR together ⁹Formula (I) compound (R wherein ⁹As defined above).

With above-mentioned deriving method combination carrying out to prepare required formula (I) compound.

A sixth aspect of the present invention provides composition, wherein contains formula (I) compound, preferably formula (II), (III) or (IV) compound and at least a carrier as defined above.Described composition can contain the single The compounds of this invention or the mixture of several The compounds of this invention.What also should face is that different isomer or mixture of isomers can have different activity levels or activity profile, so said composition can contain single isomer or mixture of isomers.

Composition of the present invention contains the formula I active component of 0.001-95% (weight) usually.When occurring with direct available form, preferred compositions contains the active component of 0.001-25% (weight).Yet, in composition, can contain higher concentration active component up to 95%, said composition is sold with the form of concentrate, before use dilution.

The present composition can for example solvent, thinner and/or surfactant mix formation pulvis, granular solids, wetting powder, coiled mosquito-repellent incense or other solid pharmaceutical preparations or emulsion, missible oil, spray, aerosol or other liquid preparations with various suitable inert carriers.Suitable solvent and thinner comprise water, aliphatic series and aromatic hydrocarbon for example dimethylbenzene or other petroleum distillates and pure as ethanol.Surfactant can be anionic, cationic or nonionic.Liquid can comprise antioxidant or other stabilizing agents and spices and colouring agent.These inert carriers can be typically and balancedly to use, for example these carriers conventional use such in composition pesticide, so they are inertia to handled plant usually.

Be suitable for being mixed with the naphthalene-1 that desinsection is used, the example of the known carrier that uses in the composition of 4-diketone comprises US2572946, US4110473, US4970328 and JP90/152943 specification, especially those described in the embodiment of (latter belongs to Agro-Kanesho KK).

Except these inert carriers, the present composition can also contain one or more other active component.These other active component can be other compounds that have other compounds of insecticidal activity and can have synergistic effect with The compounds of this invention.

The present invention further describes with reference to following non-limiting examples and comparative example, and this description only is illustrative.Also there is other and these similar embodiment of embodiment for those skilled in the art.

Embodiment

Embodiment 1-23 relates to the preparation and the character of formula (II) compound that constitutes first aspect present invention first; Embodiment 24-34 relates to the preparation and the character of formula (III) compound that constitutes the first aspect present invention second portion; And embodiment 35-50 relates to formula (IV) compound of formation first aspect present invention third part and the preparation and the character of formula (II) examples of compounds; Embodiment 46 is used for comparison.It is 1 or greater than the preparation of 1 formula (IV) midbody compound that embodiment 51-53 has described n wherein.It is the relevant comparing data of compound of straight chained alkyl that table 14 provides with 3-substituting group wherein.Raw material is available from Aldrich chemical company.

Embodiment 1

Preparation 2-(1, the 1-dimethyl propyl)-3-hydroxyl naphthalene-1, the 4-diketone

(formula I:n and m=0; R ¹+ R ²Together and R ⁷+ R ⁸Equal expression=O together, R ³=-OH;-CR ⁴R ⁵C (the CH of-=- ₃) ₂-; R ⁶=-C ₂H ₅)

(a) preparation 2-(3-methyl but-2-ene oxygen) naphthalene-1, the 4-diketone

Under 0 ℃ and blanket of nitrogen, to the 2 hydroxy naphthalene that is stirring-1,4-diketone (10.0 grams, 57.4 mMs) and triphenyl phasphine (15.1 grams, 57.4 mM) add diethylazodicarboxylate's (10.0 grams, 57.4 mMs) in the solution in anhydrous tetrahydro furan (150 milliliters).After stirring 5 minutes again, drip the solution of 3-methyl but-2-ene alcohol (7.42 grams, 86.1 mMs) in anhydrous tetrahydro furan (10 milliliters), and continue to stir 2 hours.Collecting precipitation, the air drying, and from methanol aqueous solution, be recrystallized, obtaining 2-(3-methyl but-2-ene oxygen) naphthalene-1,4-diketone (8.3 gram) is the yellow crystal solid, fusing point: 138 ℃.

(b) preparation 2-(1,1-dimethyl propylene-2-thiazolinyl)-3-hydroxyl-naphthalene-1, the 4-diketone

With 2-(the 3-methyl but-2-ene oxygen) naphthalene-1 that above-mentioned steps (a) obtains, the solution of 4-diketone (4.27 grams, 24.8 mMs) in absolute ethyl alcohol (125 milliliters) refluxed 6 hours.With this mixture cooling and solvent removed in vacuo.Residue is dissolved in the ether, and extracts with 1% (w/V) sodium hydrate aqueous solution (6 * 25 milliliters).The alkaline cut that merges uses the 2M hcl acidifying to pH5, and extracts with ether (6 * 25 milliliters).The ether extracted liquid that merges is water (2 * 25 milliliters), saturated sodium-chloride water solution (25 milliliters) washing successively, uses anhydrous magnesium sulfate drying.Filter and solvent evaporated under reduced pressure, be recrystallized from methanol aqueous solution then, obtain 2-(1,1-dimethyl propylene-2-thiazolinyl)-3-hydroxyl-naphthalene-1,4-diketone (4.27 gram) is the yellow crystal solid, fusing point: 60 ℃.

(c) preparation 2-(1, the 1-dimethyl propyl)-3-hydroxyl naphthalene-1, the 4-diketone

The 2-(1 that above-mentioned steps (b) is obtained, 1-dimethyl propylene-2-thiazolinyl)-3-hydroxyl-naphthalene-1,4-diketone (2.00 grams, 8.3 mMs) and the mixture of 10% palladium on carbon (50 milligrams) in absolute ethyl alcohol (30 milliliters) stirred 1 hour down in room temperature (about 20 ℃) and nitrogen atmosphere (aryballos).This mixture filters through diatomite (" CELITE ", registration mark) (pickling, about 95% silica), and solvent evaporated under reduced pressure.Residue is recrystallized from methyl alcohol-gasoline, obtains 2-(1, the 1-dimethyl propyl)-3-hydroxyl naphthalene-1, and 4-diketone (1.98 gram) is the yellow crystal solid.Fusing point: 52 ℃.

Embodiment 2

Preparation 2-(1, the 1-dimethyl propyl)-3-acetyl oxygen-naphthalene-1, the 4-diketone

(formula I:n and m=0; R ¹+ R ²Together and R ⁷+ R ⁸Equal expression=O together, R ³=-CO-CH ₃-CR ⁴R ⁵C (the CH of-=- ₃) ₂-; R ⁶=-C ₂H ₅)

At 0 ℃, to the 2-that in the foregoing description 1, obtains (1 that is stirring, the 1-dimethyl propyl)-and 3-hydroxyl naphthalene-1, add pyridine (0.5 milliliter) and chloroacetic chloride (2.59 gram) in the solution of 4-diketone (2.00 grams, 8.2 mMs) in anhydrous methylene chloride (20 milliliters) successively.Stirred this mixture then 30 minutes, afterwards with the ether dilution, water, saturated sodium bicarbonate solution and saturated nacl aqueous solution washing, and use dried over mgso.Filter and solvent evaporated under reduced pressure, then through silica gel chromatography, obtain 2-(1, the 1-dimethyl propyl)-3-acetyl chomene-1,4-diketone (2.06 gram) is the yellow crystal solid, fusing point: 53 ℃.

Embodiment 3

Preparation 2-(tert-butyl group)-3-hydroxyl-naphthalene-1, the 4-diketone

(formula I:n and m=0; R ¹+ R ²Together and R ⁷+ R ⁸Equal expression=O together, R ³=-OH;-CR ⁴R ⁵C (the CH of-=- ₃) ₂-; R ⁶=-CH ₃)

At 60-65 ℃, with 2 hydroxy naphthalene-1,4-diketone (1.00 grams, 5.68 mMs), neopentanoic acid (870 milligrams, 8.51 mMs) and silver nitrate (568 milligrams) heat in the mixture of acetonitrile (20 milliliters) and water (20 milliliters).Drip the solution of ammonium persulfate (1.94 grams, 8.51 mMs) in water (10 milliliters), heated this mixture then 1 hour.This mixture is cooled to room temperature (about 20 ℃),, uses the aqueous solution (4 * 25 milliliters) extraction of 1% (w/v) sodium hydroxide then with the ether dilution.The water 2M hcl acidifying that merges, and extract with ether (3 * 25 milliliters).Ether extracted liquid water that merges and saturated nacl aqueous solution washing, and use dried over mgso.Filter and solvent evaporated under reduced pressure, then through silica gel chromatography, obtain 2-(tert-butyl group)-3-hydroxyl naphthalene-1,4-diketone (450 milligrams) is the yellow crystal solid, fusing point: 89 ℃.

Embodiment 4-11 and 13

Adopt and the foregoing description 1 and 2 described similar methods, prepare other compound of the present invention described in the following Table I.In this table, determine each compound with reference to formula I.

Embodiment 12

Preparation 2-(1,1-dimethyl propylene-2-thiazolinyl)-3-methoxyl group-naphthalene-1, the 4-diketone

(formula I:n and m=0; R ¹+ R ²Together and R ⁷+ R ⁸Equal expression=O together, R ³=-OCH ₃M is 0;-CR ⁴R ⁵C (the CH of-=- ₃) ₂-; R ⁶=-CH=CH ₂)

Under 0 ℃ and blanket of nitrogen,, add the diethyl ether solution (2 milliliters) of diazomethane in the solution of 4-diketone (50 milligrams, 0.21 mM) in ether (5 milliliters) to the 2-that is stirring (1,1-dimethyl propylene-2-thiazolinyl)-3-hydroxyl-naphthalene-1.After 2 hours, removal of solvent under reduced pressure, residue obtains title compound (47 milligrams) through silica gel chromatography.

Embodiment 14

Preparation 1,1-dimethoxy-2-(1,1-dimethyl propylene-2-thiazolinyl)-3-hydroxyl naphthalene-1,4-diketone

(a) 2-(1,1-dimethyl propylene-2-thiazolinyl)-3-acetyl oxygen-naphthalene-1, the 4-diketone

Standard acetylization method to compound 1 (b) (1.00 grams, 4.13 mMs) repetition embodiment 2 obtains title compound.

(b) 1,1-dimethoxy-2-hydroxyl-3-(1,1-dimethyl propylene-2-thiazolinyl)-naphthalene-4-ketone

In the solution of the compound 14 (a) that is stirring (750 milligrams, 2.63 mMs) in methyl alcohol (30 milliliters) and THF (5 milliliters), add the solution of potassium hydroxide (1.0 gram) in water (10 milliliters).Stirred this mixture 1 hour, and then its volume was reduced to half, ether (3 * 20 milliliters) extraction aqueous mixture is used in water (20 milliliters) dilution then.The ether cut that merges is water (2 * 20 milliliters), saturated sodium carbonate solution (3 * 20 milliliters), water (2 * 20 milliliters), saturated nacl aqueous solution (20 milliliters) washing successively, and uses dried over mgso.Filter and solvent evaporated under reduced pressure,, obtain title compound (173 milligrams) then through silica gel chromatography.

Embodiment 15

Preparation 2-(1,1-dimethyl propylene-2-thiazolinyl)-2-hydroxyl-1-methoxyimino-naphthalene-4-ketone

Solution stirring in pyridine (5 milliliters) is 48 hours with embodiment 1 (b) product (250 milligrams, 1.03 mMs) and methoxy amine hydrochlorate (95 milligrams, 1.14 mMs).Reactant mixture is dissolved in the ether (50 milliliters), water (2 * 10 milliliters), 2M hydrochloric acid (2 * 10 milliliters), water (2 * 10 milliliters), saturated nacl aqueous solution (10 milliliters) washing, and use dried over mgso.Filter and solvent evaporated under reduced pressure,, obtain title compound (56 milligrams) then through silica gel chromatography.

Table 1 in following all embodiment, n and m=O, R ⁴=R ⁵=CH ₃And R ⁷With R ⁸Expression=O together

The embodiment numbering	????R 1	????R 2	????R 3	????R 6	Fusing point (℃)	????n D
							????4 ????5 ????6 ????7 ????8 ????9 ????10 ????11	＝O ″ ″ ″ ″ ″ ″ ″		????-O-CO-C 2H 5????-O-CO- nC 3H 7????-O-CO- nC 4H 9????-O-CO- nC 5H 11????-O-CO- nC 9H 19????-O-CO-CH 2F ????-O-CO-CH(CH 3) 2????-O-CO-C 6H 5	-CH＝CH 2?″ ?″ ?″ ?″ ?″ ?″ ?″	????88-90	????1.5621 ????1.5560 ????1.5436 ????1.6532 ????1.6532 ????1.5429 ????1.5390

NB n _DBe meant refractive index at sodium D-line

Table 1 (continuing) in following all embodiment, n and m=O, R ⁴=R ⁵=CH ₃And R ⁷With R ⁸Expression=O together

The embodiment numbering	????R 1	????R 2	????R 3	????R 6	Fusing point (℃)	????n D
							????12 ????13 ????14 ????15 ????16 ????17 ????18	＝O ″ -OCH 3??????-OCH 3＝N-CH 3-O ″??? ″		-OCH 3-O-CH 2C 6H 5-OH ″ ″ -O-CO-C 2H 5-OH	-CH＝CH 2″ ″ ″ - nC 3H 7- nC 3H 7- nC 5H 11	????65 ????67 ????114-115	????1.6042

NB n _DBe meant refractive index at sodium D-line

Embodiment 19

Insecticidal activity

Adopt the insecticidal activity of following method evaluation to housefly, horseradish daikon leaf beetle, diamond-back moth (larva), mite and aleyrodid.

Housefly (MD) (Musca domestica)

Handle the chest of female housefly with the experimental compound that 1 microlitre is dissolved in the acetone.Each dose ratio is used two groups of houseflies, and 15 every group, each experimental compound uses 6 dose ratio.After the processing, housefly placed under 20 ℃ ± 1 ℃ the temperature, and in back 24 hours of processing and 48 hours definite lethality.Calculate LD ₅₀Value is represented (referring to Sawicki etc., World Health Organization's communique, 35,893 (1966) and Sawicki etc., Entomologia and Exp.Appli10,253. (1967)) with microgram experimental compound/housefly.

Horseradish daikon leaf beetle (PC) (Phaedon cochleariae Fab)

Use the droplet applicator, the acetone soln of 1 microlitre experimental compound is coated in the belly of the chrysomelid adult of horseradish ape.The insect of handling is supported and determines lethality after 48 hours.Each dosage level uses two groups of horseradish apes chrysomelid, and every group 20-25,5 dosage levels of comparison process.As the housefly experiment, calculate LD ₅₀Value.

Diamond-back moth (PX) (Plutella xylostella)

Handle 5 instar larvaes with the experimental compound of 0.5 microlitre in acetone.Each dose ratio is used three groups of larvas, and 10 every group, each experimental compound uses 5 dose ratio.After the processing, larva is placed under about 22 ℃ of conditions, failing to pupate after 5 days is death, determines lethality.As the housefly experiment, calculate LD ₅₀Value.

Mite (TU) (T.urticae Koch (Tetranychus urticae))

25 female mite adults are immersed 35 microlitre experimental compounds in the solution in 1: 4 acetone-water mixture 30 seconds.The insect of accepting experiment placed under 21 ℃ ± 2 ℃ the condition, and in back 72 hours definite lethality of processing.Writing down (non-the turning back) repeatedly of the above motion appendage of mite during this period moves to show its survival.Each dosage level uses two groups of mites, and 25 every group, each experimental compound uses 5 or 6 dose ratio.Calculate LD ₅₀Value is represented with the ppm/ insect of experimental compound solution.Use Schering, the sensitive strain of the mite that AG, Berling provide (GSS) carries out this experiment.

Aleyrodid (BT) (sweet potato whitefly (Bemisia tabaci))

The acetone soln (0.100 milliliter) of experimental compound is placed 10 milliliters of vials, and rotary evaporation deposits the film of compound.30 adult whiteflies are put into bottle, after 60 minutes, the insect of accepting experiment is relayed on untreated, the cotton leaf dish of preserving moisture on the agaropectin.Keep 25 ℃ temperature, determine lethality after 48 hours.Each dosage level uses three groups of aleyrodids, and each experimental compound uses 5-7 dosage level.The software kit (available from LeOra Software, Berkeley, the ＂ Polo-PC of California) (referring to the Proceedings Brighton Crop Protection Conference of M.R.Cahill and B.Hackett, 1992) that uses a computer calculates LD ₅₀Value (ppm solution).The cotton aleyrodid sensitive strain (SUD-S) that uses Sudan to collect in 1978 carries out this experiment.

These result of experiment row in the following Table 2.Except as otherwise noted, given numerical value is LD ₅₀(microgram/insect) and LC ₅₀(ppm of experimental compound).

In all tables of listing in this manual, do not have detectable activity, represent not experimentize with ＇-＇ with ' NA ' expression.

Table 2

Compound embodiment numbering	????MD ??(LD 50)	????PC ????(LD 50)	????PX ????(LD 50)	????TU(GSS) ????(LC 50)	BT(SUD-S) ????(LC 50)
						????1 ????2 ????3 ????4 ????5 ????6 ????7 ????8 ????9 ????10 ????11 ????12 ????13 ????14 ????15 ????16 ????17 ????18 ????A	????＜10 ????＜10 ????c.2.5 ????8.2 ?????- ????c.2.0 ????＞20 ?????- ?????- ????＞20 ?????- ????＞20 ????＞20 ????c.2.5 ?????- ????8.8 ????14 ????13 ??＞＞20	????c.10 ????c.6.0 ????c.6.0 ????3.9 ????6.9 ????2.1 ????c.6.0 ????c.8.0 ????0.41 ????c.6.0 ?????- ????c.12.0 ????＞20 ????c.6.0 ????35％ *????c.10 ????NA ????c.15 ????0.36	?????- ????c.10 ????c.8.0 ?????- ?????- ?????- ?????- ????c.0.1 ?????- ?????- ?????- ?????- ????c.8.0 ?????- ?????- ?????- ?????- ?????- ?????-	????39 ????64 ????81 ????18 ????84 ????27 ????53 ????630 ????140 ????15 ????c.50 ????- ??＞1000 ????c.800 ????- ????91 ????50 ????c100 ????64	????19 ????4.8 ????8 ????5.3 ????13 ????16 ????＜100 ?????- ????13.4 ????35 ?????- ?????- ??＞1000 ?????- ????97％ **????10 ?????- ????10 ????82

^*Kill % (LD in the concentration of 20 μ g/ insects ₅₀) ^*The 1000ppm test compound solution kill %

Compd A=embodiment 1, the 5th page of DE 2641343A1, and this compound is

The positive decyl of 2--3-acetoxyl group naphthalene-1, the 4-diketone

(formula I:n and m=0; R ¹+ R ²Together and R ⁷+ R ⁸Equal together

For=O:R ³=-O-CO-CH ₃: R ⁴=R ⁵=H; R ⁶= ⁿC ₁₁H ₂₃)

Embodiment 20

The activity of antagonism mite (TU) (T.urticae Koch (Tetranychus urticae))

Use the experiment (TU (GSS)) of mite strain (NYR-Bif-1000) the repetition embodiment 16 of anti-bifenthrin.NYR-Bif-1000 mite strain is provided by New York, United States Cornell University department of entomology.

This experimental result is listed in the following table 3.Given numerical value is LC ₅₀(ppm of experimental compound).

Table 3

The compound of embodiment numbering	????TU(NYR-Bif-1000) ????(LC 50)
		????1	????84ppm
????2	????83ppm

Embodiment 21

The activity of antagonism aleyrodid (BT) (sweet potato whitefly (Bemisia tabaci))

Use resistance aleyrodid strain (Ned7) to repeat the experiment (BT (SUD-S)) of embodiment 16.Ned7 aleyrodid strain is gathered from the Hibiscus plant in Holland in April, 1993 by J.Fransen, and organophosphorus compounds and carbamate insecticide and insect growth regulator, IGR Buprofezin are had the height resistance.

This experimental result is listed in the following table 4.Given numerical value is LC ₅₀(ppm of experimental compound).

Table 4

The compound of embodiment numbering	????BT(Ned7) ????(LC 50)
		????5	????21
????A	????470

Other experiments of carrying out with various resistance aleyrodid strains have shown that also the compound antagonism strain of embodiment 1-15 has high activity.

Embodiment 22

Kill the aphid activity

Adopt following method to estimate the activity of antagonism (R) and susceptibility (S) black peach aphid (Myzus persicae) strain.

Encircle in the above brushing polytetrafluoroethylene (PTFE) trapping of the half at the inboard place of 4 centimetres of glass tubes of diameter 1.5 centimeter length, and fasten the square tulle that the energy shelves are lived insect at an end of every test tube with elastic cord.With the sable hairbrush 15 aptery adults are changed in the glass tube gently then, seal test tube with the 2nd side's tulle.

The test tube that aphid is housed is immersed 10 seconds in the insecticide solution, blot, reverse then and pat, make the aphid of processing drop on a not end of submergence of every test tube with blotting paper.After 1 hour, recording processing lethality (being generally 0 or very low), then aphid is changed over to placing on the Chinese cabbage leaf dish (35 millimeters of diameters) on the agar bed (25 millimeters deep) in disposable use plastic containers (30 millimeters high), and seal the mouth that container exposes with polytetrafluoroethylene ring.Vessel port is placed up, do not add a cover, place constant environmental facility, make it keep 25 ℃ and lasting room light photograph.Measured lethality at 24,48 and 72 hours.Each dose ratio is used two groups of aphids, and 15 every group, each experimental compound uses 5 or 6 dose ratio.

Be used in responsive aphid strain (US1L) that the big Tanaka of East Anglia (UK) collects and the aphid strain (794jz) that has resistance (R3 esterase, responsive AChE) that from the Britain greenhouse, collects and carry out this experiment.

This result of experiment is listed in the following table 5.Be % lethality to numerical value with respect to contrasting data.The employed experimental solutions of control group does not contain active component.

Also use responsive cotten aphid strain 81-171B further to test, the result shows to have activity, and especially formula (IV) compound has activity.

Table 5

The compound of embodiment numbering		The concentration of active component			The contrast lethality
						????250PPM	????100PPM	????40PPM
		????1	????S ????R	????26 ????43					????11 ????10	????00 ????03	????10 ????00
????2	????S ????R				????27 ????47	????03 ????17	????20 ????00	????00 ????00
		????3	????S ????R	????87 ????87					????27 ????13	????04 ????10	????00 ????00

Embodiment 23

Fungicidally active

External test numbering compound to black aspergillus, Magnaporthe grisea (=Magnaporthegrisea) and the fungitoxicity of the separator of Solanum rhizoctonia.

Each compound is incorporated in the potato agar glucose in the solvent (50/50 ethanol/acetone), and 0.5 milliliter of solvent of per 250 milliliters of agar makes and presses hot agar fusion, and is cooled to 50 ℃.Each compound is carried out (100 milligram 1 of single concentration ^-1) experiment.

Two kinds of compounds are used in each experiment usually, comprise three kinds of control treatment: (i) conventional fungicide (carbendazim, 1 or 5 milligram 1 ^-1Or prochloraz, 1 milligram 1 ^-1); (ii) only use ethanol/acetone; (iii) there is not adding ingredient.Fungicide as standard is considered to typical compound activated, that can buy.

On agar every kind of fungi is experimentized in four Petri wares for each processing, every block of plate uses 3 fungus colonies (the Solanum rhizoctonia is only used a bacterium colony).At 20-25 ℃ black aspergillus and Solanum rhizoctonia were cultivated 4 days, Magnaporthe grisea was cultivated 7 days.Measure the increase of colony diameter then, and be used for measuring active.

These result of experiment are listed in the following table 6.Given numerical value is the % inhibiting rate of colony diameter growth on agar plate.

Table 6

The compound of embodiment numbering	Fungi	??100mgl -1Activity	??5mgl -1Activity	??1mgl -1Activity
					????1	Black aspergillus	????63
????2	Black aspergillus	????38
					????3	Black aspergillus	????61
????1	Magnaporthe grisea	???100
					????2	Magnaporthe grisea	????89
????3	Rice pears bag	???100
					????1	The Solanum rhizoctonia	????95
????2	The Solanum rhizoctonia	????81
					????3	The Solanum rhizoctonia	????92
Prochloraz	Black aspergillus			????97.8
					Carbendazim	Magnaporthe grisea		????99.8	????14.7
Carbendazim	The Solanum rhizoctonia		????82.4	????3.3

In addition, experiment shows that formula I compound has good Fungicidally active to the broad spectrum fungus that causes cereal and broad leaf crop disease.Especially have been found that formula I compound to Erysiphe particularly standing grain powdery mildew and Botrytis particularly broad bean grape spore and gray botrytis and above-mentioned Rhizoctonia, Pyricularia Sacc. and aspergillus have good activity.

Embodiment 24

Preparation 2-hydroxyl-3-(1 '-methylcyclopentyl)-naphthalene-1, the 4-diketone

(formula III: n=0; M=0; R ¹+ R ²Together and R ⁷+ R ⁸Equal expression=O together, R ³=-OH;-CR ⁴R ⁵-=cyclopenta; R ⁶=-CH ₃)

Under-78 ℃ and blanket of nitrogen, in the solution of the diisopropylamine that is stirring (3.95 grams, 39.0 mMs) in anhydrous THF (50 milliliters), add n-BuLi (2.5M, 11.7 milliliters, 29.3 mMs).Stir this mixture 10 minutes, and dripped cyclopentane-carboxylic acid methyl esters (Aldrich) (2.5 grams, 19.5 mMs) then.Continue to stir 10 minutes, drip methyl iodide (8.31 grams, 58.5 mMs) then.Reactant mixture was stirred 1 hour at-78 ℃ again, make it be warmed to room temperature then, and stirred again 1 hour in room temperature.Reactant mixture is poured in the mixture (1: 1,100 milliliters) of water and ether, with watery hydrochloric acid (2M) acidifying.Fractionate aqueous solutions, and with ether (3 * 25 milliliters) extraction, the ether layer water of merging (2 * 50 milliliters), saturated nacl aqueous solution (50 milliliters) washing, and use dried over mgso.Filter and solvent evaporated under reduced pressure, obtain 1-methyl cyclopentane methyl formate, be colorless oil (2.38 grams, the boiling point under 10mmHg is 106 ℃ [Kugelrohr]).

Solution in the mixture of ethylene glycol (40 milliliters) and water (10 milliliters) refluxed 16 hours with above-mentioned methyl esters (2.30 gram) and potassium hydroxide (5.00 gram), be cooled to room temperature then, with the ether dilution, separate water layer afterwards, with watery hydrochloric acid (2M) acidifying, and extract with ether (2 * 25 milliliters).Saturated nacl aqueous solution (25 milliliters) washing is used in ether layer water (2 * 25 milliliters) washing that merges then, uses dried over mgso.Filter and evaporation, obtain 1-methyl cyclopentane formic acid (1.69 gram).

At 65 ℃, to the 2 hydroxy naphthalene that is stirring-1,4-diketone (1.00 grams, 5.7 add 50% excessive above-mentioned acid mM) and in the solution of silver nitrate (600 milligrams) in acetonitrile (20 milliliters) and water (20 milliliters), and wherein slowly add the solution of ammonium persulfate (1.96 grams, 8.6 mMs) in water (10 milliliters) with 15 fens clockwise.This mixture was heated 1 hour again, be cooled to room temperature (about 20 ℃) then, and dilute with ether (50 milliliters).Separate organic facies, water, dilute aqueous solution of sodium bicarbonate, water and saturated nacl aqueous solution washing are used dried over mgso as described in embodiment 3 successively.Filter and solvent evaporated under reduced pressure, adopt 2: 1 benzinums then: ether is made the silica gel chromatography of eluant, eluent, obtains 2 hydroxyls-3-(1-methylcyclopentyl) naphthalene-1,4-diketone (fusing point 116-118 ℃).

Embodiment 25

Preparation 2-hydroxyl-3-(1 '-methylcyclohexyl)-naphthalene-1, the 4-diketone

(formula III: n=0; M=0; R ¹+ R ²Together and R ⁷+ R ⁸Equal expression=O together, R ³=-OH;-CR ⁴R ⁵-=cyclohexyl; R ⁶=-CH ₃)

At 65 ℃, with 15 minutes, to the 2 hydroxy naphthalene that is stirring-1,4-diketone (1.00 grams, 5.7 1-hexahydrotoluene formic acid (1.22 grams mM),, 8.6 mM) and slowly add the solution of ammonium persulfate (1.96 gram, 8.6 mMs) in water (10 milliliters) in the solution of silver nitrate (600 milligrams) in the mixture of acetonitrile (20 milliliters) and water (20 milliliters).This mixture was heated 1 hour again, be cooled to room temperature (about 20 ℃) then, and dilute with ether (50 milliliters).Separate organic facies, dried over mgso is used in water, dilute aqueous solution of sodium bicarbonate, water and saturated nacl aqueous solution washing then successively.Filter and solvent evaporated under reduced pressure, adopt 2: 1 benzinums then: ether is made the silica gel chromatography of eluant, eluent, obtains 2 hydroxyls-3-(1-methylcyclohexyl) naphthalene-1, and 4-diketone (296 milligrams) is the yellow crystal compound, fusing point: 79 ℃.

Embodiment 26

Preparation 2-(1 '-the ethyl cyclohexyl)-3-hydroxyl-naphthalene-1, the 4-diketone

By under the condition that provides hereinafter, be used in the Pd/C catalyzer (56 ℃ of fusing points) in the ethanol, adopt the hydrogenation of compounds of the method for embodiment 1c, the preparation title compound with embodiment 27.

Embodiment 27

Preparation 2-(1 '-the vinyl cyclohexyl)-3-hydroxyl-naphthalene-1, the 4-diketone

(formula III: n=0; M=0; R ¹+ R ²Together and R ⁷+ R ⁸Equal expression=O together, R ³=-OH;-CR ⁴R ⁵-=cyclohexyl; R ⁶=-CH=CH ₂)

Under 0 ℃ and blanket of nitrogen, to the cyclohexylidene ethyl acetate that is stirring (referring to wadsworth and Emmons at Org.Synth.Coll.Vol5, approach described in 547) (3.00 grams, 17.8 mM) add (407 milligrams of lithium aluminium hydride in the solution in absolute ether (50 milliliters) in batches, 10.7 mM), and stirred this mixture 2 hours, use watery hydrochloric acid (2M then; 20 milliliters) cessation reaction.Reactant mixture is filtered, separate water layer, with ether (2 * 25 milliliters) extraction, ether layer water of merging (2 * 25 milliliters) and saturated nacl aqueous solution (25 milliliters) washing, and use dried over mgso.Filter and evaporating solvent, evaporation residue obtains 2-cyclohexylidene ethanol (2.16 grams are 112 ℃ [Kugelrohr] at the boiling point of 10mmHg).

Under blanket of nitrogen, to the 2-hydroxyl-naphthalene-1 that is stirring, 4-diketone (2.50 grams, 14.4 mMs) and triphenyl phasphine (3.79 grams, 14.4 mM) drip the solution of diethylazodicarboxylate's (2.50 grams, 14.4 mMs) in THF (2 milliliters) in the solution in anhydrous THF (50 milliliters).Stirred this mixture 5 minutes, drip then cyclohexylidene ethanol in THF (2ml) (2.00g, 15.8mmol).Stirred this mixture 2 hours, and made temperature rise to room temperature, use ether (100 milliliters) dilution then, and, use dried over mgso with 1% sodium hydroxide solution (5 * 25 milliliters), water (2 * 25 milliliters) and saturated nacl aqueous solution (25 milliliters) washing.Filter and evaporating solvent, obtain brown residue, be dissolved in this residue in the ethanol (50 milliliters) and refluxed 6 hours.With this mixture cooling, be concentrated into the volume of half, and dilute with ether (100 milliliters).Diethyl ether solution extracts with 1% sodium hydroxide solution (6 * 25 milliliters), with the alkaline cut acidifying (2M hydrochloric acid) that merges, with ether (6 * 25 milliliters) extraction, dried over mgso is used in ether layer water of merging (2 * 25 milliliters) and saturated nacl aqueous solution (25 milliliters) washing.Filter and evaporating solvent,, obtain title compound, be (153 milligrams of yellow crystal compounds through silica gel chromatography; Fusing point 112-113 ℃).

Embodiment 28

Preparation 2-hydroxyl-3-(1 '-the trifluoromethyl cyclohexyl)-naphthalene-1, the 4-diketone

(formula III: n=0; M=0; R ¹+ R ²Together and R ⁷+ R ⁸Equal expression=O together, R ³=-OH;-CR ⁴R ⁵-=cyclohexyl; R ⁶=-CF ₃)

In pressure pan (pressure when finishing is about 3 crust), trifluoromethyl acrylate (1.5 grams, 10.7 mMs), butadiene sulfone (1.27 grams, 10.7 mMs) and hydroxyquinone (15 milligrams) were heated 2.5 hours at 160 ℃.Then this mixture is cooled off, and be dissolved in the ether, with 2M sodium hydroxide (3 * 25 milliliters) extraction.The alkaline cut 2M hcl acidifying that merges, and extract with ether (5 * 25 milliliters).The ether cut that merges washes with water, with the saturated nacl aqueous solution washing, uses dried over mgso afterwards then, filters and evaporating solvent, obtains light brown solid (1.267 gram).Adopt 1: 1 petroleum ether/ethyl ether to make eluant, eluent, crude product is carried out purifying on silicagel column, obtain 927 milligrams of product 1-trifluoromethyl hexamethylene-3-zinecarboxylic acids.The method that adopts embodiment 1 (c) obtains 1-trifluoromethyl hexahydrobenzoid acid with this hydrogenation of compounds.

At 65-70 ℃, with 2-benzoyloxy-naphthalene-1, (250 milligrams of 4-diketone (355 milligrams, 1.27 mMs), 1-trifluoromethyl naphthenic acids, 1.27 mM) and silver nitrate (108 milligrams, 0.64 mM) in acetonitrile (5 milliliters) and water (3 milliliters), heat.Drip the solution of ammonium persulfate (436 milligrams, 1.91 mMs) in water (1 milliliter), and with this mixture heating 1 hour.With the reactant mixture cooling, water (20 milliliters) dilutes, and extracts with ether (3 * 20 milliliters).The ether layer that merges is with dried over mgso and be evaporated to dried.

Be dissolved in THF (20 milliliters) and the 2M potassium hydroxide aqueous solution (10 milliliters) its hydrolysis by ester gained, and stirring at room 2 hours.This mixture water (20 milliliters) dilution with ether (2 * 20 milliliters) washing, is used the 2M hcl acidifying, and is extracted with ether (3 * 20 milliliters).The ether extracted liquid that merges washes with water, with dried over mgso and solvent evaporated under reduced pressure.Residue obtains required product (114 ℃ of fusing points) through silica gel chromatography.

Embodiment 29

Preparation 2-hydroxyl-3-(1 '-the methyl suberyl)-naphthalene-1, the 4-diketone

(formula III: n=0; M=0; R ¹+ R ²Together and R ⁷+ R ⁸Equal expression=O together, R ³=-OH;-CR ⁴R ⁵-=suberyl; R ⁶=-CH ₃)

Under-78 ℃ and blanket of nitrogen, in the solution of the diisopropylamine that is stirring (7.47 grams, 73.8 mMs) in anhydrous THF, add n-BuLi (2.5M, 29.5 milliliters, 73.8 mMs).Stirred this mixture 10 minutes, and dripped suberyl formic acid (2.10 grams, 14.8 mMs) then, and stirred this reactant again 10 minutes, refluxed then 2 hours at-78 ℃.Reactant is cooled to 0 ℃, drips iodomethane (5.76 grams, 40.6 milliliters), and then refluxed 1 hour, afterwards it is cooled to room temperature.Reactant mixture is poured in the mixture of water/ether (100 milliliters/50 milliliters), separated water layer, use watery hydrochloric acid (2M) acidifying, and extract with ether (5 * 25 milliliters).Ether layer water (2 * 50 milliliters) washing that merges, and, use dried over mgso then with saturated nacl aqueous solution (50 milliliters) washing.Filter and solvent evaporated under reduced pressure, obtain 1-methyl cycloheptane formic acid, this product is recrystallization from hexane (2.20 grams, 46 ℃ of fusing points).With this acid substitution 1-methyl cyclopentane formic acid, adopt the method for embodiment 24 to prepare title compound.

Embodiment 30 and 31

Adopt and the similar method of the foregoing description 24-29, other compound that synthetic first aspect present invention is second group, described compound has provided physical data and activity data referring to the embodiment 30 and 31 compounds of tabulating down in 9 and 10 in this table.

Embodiment 33

Preparation 2-acetoxy-3-((1 '-methylcyclohexyl)-methyl)-naphthalene-1, the 4-diketone

At 65-70 ℃, to the 2-acetoxyl group-naphthalene-1 that is stirring, 4-diketone (1.12 grams, 5.18 mM), (employing Amsterdamsky etc. are in Bull.Soc.Chim.Fr (1975) 3-4 part 2 for (1-methylcyclohexyl) acetate, the described method preparation of 635-643) (850 milligram, 5.44 mM) and add the solution of ammonium persulfate (1.77 gram, 7.77 mMs) in water (10 milliliters) in the solution of silver nitrate (520 milligrams) in acetonitrile (15 milliliters) and water (20 milliliters).With this mixture heating cooling after 1 hour, water (50 milliliters) dilution is with ether (3 * 40 milliliters) extraction.Dried over mgso is used in ether cut water (3 * 25 milliliters) that merges and saturated nacl aqueous solution (25 milliliters) washing.Filter and solvent evaporated under reduced pressure, and carry out the silica gel chromatograph purifying, obtain title compound, be yellow solid (736 milligrams).

Embodiment 32 and 34

Preparation 2-hydroxyl-3-((1 '-methylcyclohexyl)-methyl)-naphthalene-1,4-diketone (embodiment 32) and 1,1-dimethoxy-2-hydroxyl-3-((1 '-methylcyclohexyl)-methyl)-naphthalene-1,4-diketone (embodiment 34)

At room temperature, to the compound (750 milligrams, 2.3 mMs) of embodiment 33 THF/ methyl alcohol (1: 1; 30 milliliters) in solution in add (6.45 milligrams in potassium hydroxide; 11.5 the solution in water (8 milliliters) mM), and stirred reaction mixture 2 hours.This mixture water (100 milliliters) washing with ether (20 milliliters) washing, is used the 2M hcl acidifying, and is extracted with ether (3 * 25 milliliters).The ether layer water (2 * 20 milliliters) that merges, saturated nacl aqueous solution (20 milliliters) washing, and use dried over mgso.Filtering and solvent evaporated under reduced pressure, through silica gel chromatography, obtain the compound of embodiment 32 and 34, is two bands of a spectrum.

Adopt the method for embodiment 19-22, estimate insecticidal activity housefly, horseradish daikon leaf beetle, mite, aphid and aleyrodid.All strains all are sensitive strains, unless otherwise; With the further evidence of the resistant strain of aleyrodid, many formula III compound antagonism strains all have high activity.

Repeat aleyrodid activity experiment (BT (SUD-S)) with resistance aleyrodid strain (Ned1/2).The strain of Ned1/2 aleyrodid is to gather thing by the complexity that ICI Netherlands gathered from Gerbera and Bouvardia at Netherland in 1992, and for example cypermethrin, organophosphorus compounds and carbamate insecticide and insect growth regulator, IGR Buprofezin have the height resistance to pyrethroid insecticides.

These experimental results are listed in the following table 7.Given numerical value is LC ₅₀(the ppm solution of experimental compound).

Table 7

The compound of embodiment numbering	????BT(Ned1/2) ????(LC 50)
		????25	????0.1
????B	????100

Compd B=embodiment 1, and the table 1 of DE 3801743A1 is 2-hydroxyl-3-(4-tert-butylcyclohexyl)-naphthalene-1,4-diketone.

Method with preferred formula III compound repetition embodiment 22 the results are shown in the table 8.

Table 8

The compound of embodiment numbering	The aphid strain	The concentration of active component			The contrast lethality
						??250PPM	??100PPM	??40PPM
		????25	????S ????R	????67 ????79					????23 ????27	????07 ????10	????0 ????0

Fig. 9

Compound is formula III compound, wherein R ¹With R ²Be=O R ⁷With R ⁸Be=O is except as otherwise noted; N=0 and m=1.

The compound of embodiment numbering	?????R 3	??m	????A	????R 4	????R 5	????R 6	Other	Fusing point
									????24 ????25 ????26 ????27 ????28 ????29 ????30 ????31 ????32 ????33 ????34	????-OH ????-OH ????-OH ????-OH ????-OH ????-OH ????-OH ????-OH ????-OH ????-OAc ????-OH	????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????1 ????1 ????1	????- ????- ????- ????- ????- ????- ????- ????- ????-CH 2- ????-CH 2- ????-CH 2-	Cyclopenta cyclohexyl ring hexyl cyclohexyl ring hexyl suberyl cyclopenta hexamethylene-2-thiazolinyl cyclohexyl ring hexyl cyclohexyl		????-CH 3????-CH 3??-CH 2-CH 3??-CH＝CH 2????-CF 3????-CH 3??-CH＝CH 2????-CH 3????-CH 3????-CH 3????-CH 3	?R1，R2＝OMe	??117-118℃ ??79℃ ??56℃ ??112-113℃ ??114℃ ??68℃ ??92-94℃ ??89-90℃ ??114℃ ??114℃ ??136-138℃

Table 10

Embodiment 24-33 compound is to the activity of insect and mite

The compound of embodiment numbering	????PC LD 50(μ g/ insect)	????MD LD 50(μ g/ insect)	MP kills %100PPm	????TU ?LC 50(ppm/ insect)	????BT ?LC 50(PPm/ insect)
						????24 ????25 ????26 ????27 ????28 ????30 ????31 ????32 ????33	????- ????5 ????2.9 ????4.7 ????- ????＜20 ????5 ????＜2 ????2.8	????NA ????1.9 ????1.3 ????60 ????14 ????15 ????6 ????3.6 ????5.7	????44 ????22 ????NA ????NA ????5 ????NA ????5 ????50 ????30	????48 ????28 ????＞100 ????c80 ????40 ????6 ????c50 ????2.9 ????2.3	????33 ????0.1 ????2.9 ????0.9 ????24 ????c50 ????4.7 ????3.6 ????5.1

For the compound with prior art compares, to embodiment 1, be compound 2-hydroxyl-3-(4-the tert-butylcyclohexyl)-naphthalene-1 in the table 1 of DE3801743A1,4-diketone (formula II:n=0; M=0; R ¹+ R ²Together and R ⁷+ R ⁸Equal expression=O together, R ³=-OH;-CR ⁴R ⁵-=4-tert-butylcyclohexyl; And R ⁶=H, therefore included for formula I or II) resist the experiment of same insect, the MDLD that obtains ₅₀Value is 15.5, PCLD ₅₀Value is 0.53, TU (GSS) LC ₅₀Value is 44 and BT (SUD-S) LC ₅₀Value is 18.

According to embodiment 23 described methods, use the fungitoxicity of preferred formula (III) compound external test numbering compound to the separator of black aspergillus, Magnaporthe grisea (=Magnaporthe grisea) and Solanum rhizoctonia.

These result of experiment are listed as in the following Table 11, and given numerical value is the % inhibiting rate of colony diameter growth on agar plate.

Table 11

The compound of embodiment numbering	Fungi	??100mgl -1Activity	??5mgl -1Activity	??1mgl -1Activity
					????25	Black aspergillus	????45
????25	Magnaporthe grisea	????94
					????25	The Solanum rhizoctonia	????93
Prochloraz	Black aspergillus			????97.8
					Carbendazim	Magnaporthe grisea		????99.8	????14.7
Carbendazim	The Solanum rhizoctonia		????82.4	????3.3

In addition, experiment shows that formula (III) compound has good Fungicidally active to the broad spectrum fungus that causes cereal and broad leaf crop disease.Especially have been found that to Erysiphe particularly standing grain powdery mildew and Botrytis particularly broad bean grape spore and gray botrytis and above-mentioned Rhizoctonia, Pyricularia Sacc. and aspergillus have good activity.

Embodiment 35

Preparation 2-(2, the 2-dimethyl propyl)-3-hydroxyl-naphthalene-1, the 4-diketone

Prepare this compound according to the described conventional method of embodiment 1-15.At 60-65 ℃, with Lawsone (0.15 gram), 3,3-acid dimethyl (0.15 gram) and silver nitrate (0.15 gram) heat in the mixture of acetonitrile (5 milliliters) and water (5 milliliters).Drip the solution of ammonium persulfate (0.3 gram) in water (5 milliliters), and heated this mixture 1 hour, handle according to embodiment 3 described methods then, obtain title compound.20% ether of employing in benzinum made eluant, eluent, crude product carried out purifying on silicagel column, and be recrystallized from benzinum, obtains 38 milligrams of title compounds.

Embodiment 36

Preparation 2-(3, the 3-dimethylbutyl)-3-hydroxyl-naphthalene-1, the 4-diketone

In room temperature,, add sodium hydroxide solution (1M in 4-diketone (3.5 gram) (referring to embodiment 44) solution in THF (100 milliliters) to 2-acetoxy-3-(3, the 3-dimethylbutyl)-naphthalene-1; 100 milliliters), and stirred 4 hours.Vacuum is removed THF, and gained solution washs with ether (3 *).With the water layer acidifying, use ether (3 *) extraction then, the extract of merging washes with water, uses dried over mgso, and vacuum evaporation obtains 3 gram title compounds to doing then.

Embodiment 37

Preparation 2-(4,4-dimethyl amyl group)-3-hydroxyl-naphthalene-1, the 4-diketone

In room temperature, with 3,3-dimethyl butyrate-1-alcohol (1.3 gram) stirs with pyridinium chlorochromate (5.5 gram) in carrene (30 milliliters), with ether dilution and filtration.In filtrate, add Wittig reagent Ph ₃P=CH-CO ₂C ₂H ₅(ethoxycarbonyl methylene tri phenyl phosphine) (3.6 gram) also stirs and spends the night.This mixture of vacuum evaporation, residue be through the silica gel chromatograph purifying, obtains 1.25 grams 5, the 5-dimethyl oneself-2-olefin(e) acid ethyl ester.

This product is dissolved in the mixture of THF (20 milliliters) and 2M potassium hydroxide (10 milliliters), and stirring at room 2 hours, dilute with water with ether (2 * 30 milliliters) washing, acidifying water layer, was used ether (2 * 30 milliliters) extraction then.The extract that merges washes with water, use dried over mgso, and evaporating solvent, obtains 5, and the 5-dimethyl is own-the 2-olefin(e) acid.

This acid and benzoyloxy naphthalene-1,4-two reactive ketones adopt the method hydrolysis of embodiment 28, obtain 2-(4,4-dimethyl-penten-1-thiazolinyl)-3-hydroxyl-naphthalene-1, the 4-diketone.The method that adopts embodiment 1 (c) obtains title compound (406 milligrams) with products therefrom hydrogenation.

Embodiment 38

Preparation 2-(5,5-dimethyl hexyl)-3-hydroxyl-naphthalene-1, the 4-diketone

2-(5 with preparation among the embodiment 45, the 5-dimethyl oneself-the 2-thiazolinyl)-3-hydroxyl naphthalene-1,4-diketone (391 milligrams) is dissolved in the ethyl acetate (15 milliliters), and according to the described method of embodiment 1 (c), carry out hydrogenation with hydrogen and 100 milligrams of Pd/C catalyzer, obtain 371 milligrams of title compounds.

Embodiment 39-41

According to embodiment 48 similar methods and as being used in the PtO in the methyl alcohol as described in the embodiment 1 (c) ₂Replace Pd/C to carry out hydrogenation, with the corresponding 2-of feedstock production (6,6-dimethyl heptyl), 2-(7,7-dimethyl octyl group) and 2-(8, the 8-dimethyl nonyl) compound that can buy.

Embodiment 42

Preparation 2-(3,3-dimethyl butyrate-1-thiazolinyl)-3-hydroxyl-naphthalene-1, the 4-diketone

At room temperature, with Lawsone (2 hydroxy naphthalene-1,4-diketone) (1.4 gram) and 3,3-dimethyl butyraldehyde (1.0 gram) is dissolved among 20 milliliters of THF, and adds 795 microlitre pyrrolidines, and reaction stirred is 20 minutes then.Solvent removed in vacuo is dissolved in residue in the benzene (40 milliliters), adds p-methyl benzenesulfonic acid (2.3 gram) then.This mixture was refluxed 1 hour, cooling, with the ether dilution, organic facies is washed with sodium bicarbonate solution then, then with the watery hydrochloric acid washing once and wash once vacuum drying afterwards with water.Product is made eluant, eluent through chromatogram purification with 10% ethyl acetate/petroleum ether, and crystallization from methyl alcohol, obtains 260 milligrams of title compounds; Fusing point 126-128 ℃.

Embodiment 43

Preparation 2-(6,6-dimethyl-g-4-thiazolinyl)-3-hydroxyl-naphthalene-1, the 4-diketone

Under 70 ℃ and blanket of nitrogen, with 2-(7,7-dimethyl-octa-5-thiazolinyl)-3-hydroxyl naphthalene-1, (36 milligrams of 4-diketone (0.1 gram) (referring to embodiment 44), 30% hydrogen peroxide (60 microlitre), aqueous sodium carbonates, in 1 ml water) solution heating in degassing diox (1 milliliter) 40 minutes, become colorless until solution.Add 20% copper sulphate (II) aqueous solution (30 microlitre), when stopping to foam, add 25% sodium hydrate aqueous solution (0.6 milliliter) and 20% copper sulphate (II) aqueous solution (1.5 milliliters), and stirred this mixture 30 minutes at 70 ℃.After the cooling, add 2N hydrochloric acid (5 milliliters), product extracts with ether (3 *), and handles according to embodiment 48 described methods.

Make eluant, eluent with 10% ether/gasoline, crude product through the silica gel chromatography purifying, is obtained 50 milligrams of title compounds.

Embodiment 44

Preparation 2-(7,7-dimethyl-octa-5-thiazolinyl)-3-hydroxyl-naphthalene-1, the 4-diketone

Adopt with embodiment 48 in used similar method, adopt embodiment 36 described methods to prepare title compound then.

Embodiment 45

The preparation 2-(5, the 5-dimethyl oneself-the 1-thiazolinyl)-3-hydroxyl-naphthalene-1, the 4-diketone

With 5,5-dimethyl ethyl hexanoate (1.87 gram) (preparing by esterification in embodiment 34) is dissolved among 30 milliliters of THF, adds lithium aluminium hydride (2 gram) in batches.0 ℃ of reaction stirred 2 hours, use 2 milliliter of 15% sodium hydroxide and 6 ml water cessation reactions then, with the carrene dilution, filter, and evaporating solvent through diatomite (RTM), obtain 5,5-dimethyl hexanol product (1.1 gram) is the liquid of volatilization slightly.This alcohol is dissolved in 30 milliliters of carrene that contain the chloro-chromic acid pyridine, and, is translated into corresponding aldehyde in stirring at room, promptly 5,5-dimethyl hexanal.

According to the method described in the embodiment 42, use Lawwone (1.18 gram), THF (20 milliliters), pyrrolidines (672 microlitre), benzene (40 milliliters) and p-methyl benzenesulfonic acid (1.95 gram) with gained aldehyde (8.46 mM) and Lawsone coupling.Isolate 391 milligrams of title compounds behind the purifying.

Embodiment 46-47

(embodiment 46 to adopt the method for embodiment 2 to prepare the ethoxycarbonyl derivative of 3-(tert-butyl group) compound; Formula (II) compound) and the ethoxycarbonyl derivative (embodiment 47) of embodiment 36 compounds.

Embodiment 48

2-ethoxycarbonyl-3-(3,3 ,-dimethylbutyl)-naphthalene-1, the another kind of preparation method of 4-diketone (embodiment 47)

In the iodine catalyst of magnesium rod in absolute ether (100 milliliters) (2 gram) and initiation amount, drip 1-chloro-3,3-dimethylbutane (10 gram), and with Grignard reagent was formed in 1 hour to react carry out complete.This mixture is poured in the dry ice (50 gram) very lentamente, and added 0.5N sodium hydroxide, gained alkalescence water layer extracts with ether (* 2).With the alkaline water layer acidifying of alkalescence, and use extracted with diethyl ether, use dried over mgso, filter and vacuum evaporation, obtain 7.2 grams 4,4-dimethyl valeric acid.

With above-mentioned obtain 4,4-dimethyl valeric acid (0.6 gram), 2-benzyloxy naphthalene-1,4-diketone (1 gram) and silver nitrate (0.8 restrains) in the mixture of acetonitrile (25 milliliters) and water (25 milliliters) 60-65 ℃ of heating.Drip the solution of ammonium persulfate (1.5 gram) in water (10 milliliters), and heated this mixture 1 hour, be cooled to room temperature then, handle, obtain 0.37 gram title compound according to the method for embodiment 3.

Embodiment 49

Preparation 2-ethoxycarbonyl-3-(10,10-dimethyl 11-7-thiazolinyl)-naphthalene-1, the 4-diketone

By the sad prepared in reaction bromination 8-triphenyl phosphonium caprylate (2.43 gram) in xylene solvent and under the counterflow condition of triphenyl phasphine and 8-bromine, and remove and desolvate.Residue is dissolved among THF (20 milliliters)/DMSO (2 milliliters), and at the butyl lithium (2.5M of 0 ℃ of dropping in hexane (4 milliliters); 4 milliliters).After being warmed to room temperature, with dripped in 30 minutes in THF (5 milliliters) 3,3-dimethyl butyraldehyde (0.5 gram), and in this mixture of stirring at room 3 hours.Add entry and watery hydrochloric acid, extract this mixture with ether (* 3).After silica gel chromatography, obtain pure products 11,11-dimethyl 12-8-olefin(e) acid (0.4 gram).

This acid (0.34 gram) is according to method and the 2-ethoxycarbonyl naphthalene-1 of embodiment 47, and 4-diketone (0.4 gram) reaction obtains 26 gram title compounds.

Adopt other compounds in the synthetic following table of these conventional methods.

Table 12 formula (IV) compound is R wherein ¹With R ², and R ⁷With R ⁸Be=O and=O ,+formula (II) compound, wherein m is 0 ^*

The compound of embodiment numbering	????R 3	????m	????A	????R 4	????R 5	????R 6	Fusing point is nD
								????35 ????36 ????37 ????38 ????39 ????40 ????41 ????42 ????43 ????44 ????45 ????46 *????47 ????49 ????50	????OH ????OH ????OH ????OH ????OH ????OH ????OH ????OH ????OH ????OH ????OH ????OCOCH 3????OCOCH 3????OCOCH 3????OH	????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????0 ????1 ????1 ????1	????-CH 2- ????-(CH 2) 2- ????-(CH 2) 3- ????-(CH 2) 4- ????-(CH 2) 5- ????-(CH 2) 6- ????-(CH 2) 7- ????-CH＝CH- ????-(CH 2) 3CH＝CH- ????-(CH 2) 4CH＝CH- ????-CH＝CH-(CH 2) 2- ????-(CH 2) 2- ????-(CH 2) 6-CH＝CH-CH 2- ????-(CH 2) 2-	????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3	????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3	????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3?CH＝CH 2	????115-116℃ ????119-120℃ ????119℃ ????82-84℃ ????62-63℃ ????126-128℃ ????79-80℃ ????69-70℃ ????57-58℃ ????75-76℃ ????1.5286

Table 13 formula (IV) is for the insecticidal activity of compound

The compound of embodiment numbering	????PC ?LD 50(μ g/ insect)	????MD LD 50(μ g/ insect)	M P kills %100ppm	????TU ?LC 50(ppm/ insect)	????BT ?LC 50(PPm/ insect)
						????35 ????36 ????37 ????38 ????39 ????40 ????42 ????43 ????44 ????46 ????47 ????49 ????50	????4.6 ????1.3 ????NA ????c8 ????- ????- ????3.6 ????- ????- ????c15 ????c1 ????c10 ????-	????1.2 ????NA ????NA ????5.3 ????c5 ????c5 ????NA ????- ????c10 ????2.3 ????2.2 ????c18 ????-	????- ????c24 ????c70 ????c100 ????c100 ????c100 ????- ????c100 ????c100 ????c60 ????c100 ????c15 ????-	????- ????36 ????2.9 ????3.5 ????9.6 ????5 ????c100 ????11.5 ????4.3 ????c500 ????c20 ????2.3 ????6.5	????c12 ????c7 ????16 ????c60 ????21 ????13 ????17 ????c60 ????c100 ????NA ????2.1 ????NA ????16

Table 14 comparing embodiment R ¹R ²And R ⁷R ⁸==O; R ³=OH

3 of naphthalenes	????PC ?LD 50(μ g/ insect)	????MD LD 50(μ g/ insect)	MP kills %100PPm	????TU ?LC 50(ppn/ insect)	????BT ?LC 50(PPm/ insect)
						????-H ????-CH 3??-CH 2CH 3??-(CH 2) 2CH 3??-(CH 2) 3CH 3??-(CH 2) 4CH 3??-(CH 2) 5CH 3??-(CH 2) 7CH 3??-(CH 2) 9CH 3??-(CH 2) 10CH 3??-(CH 2) 11CH 3??-(CH 2) 13CH 3	????NA ????NA ????NA ????c10 ????c5 ????c7 ????c7 ????0.78 ????1.9 ????c0.4 ????NA ????NA	????NA ????NA ????NA ????NA ????c10 ????NA ????c20 ????1.9 ????NA ????NA ????NA ????NA	????- ????- ????- ????- ????- ????- ????0 ????- ????- ????- ????0 ????-	????NA ????NA ????NA ????c1000 ????65 ????16 ????170 ????c1000 ????5.5 ????1.4 ????＜60 ????1.3	????NA ????NA ????NA ????80 ????13 ????17 ????9.4 ????19 ????＞100 ????＞100 ????＞100 ????NA

Embodiment 51-53

Synthesize the naphthalene-1 that replaces in naphthalene nucleus 5-8 position, the 4-diketone

Embodiment 51

Preparation 2-(tert-butyl group)-3-hydroxyl-6-methyl-naphthalene-1,4-diketone and 2-(tert-butyl group)-3-hydroxyl-7-methyl-naphthalene-1,4-diketone

(a) preparation 6-methyl-naphthalene-1, the 4-diketone

At room temperature, with 1, the 4-benzoquinones (13.9 grams, 128 mMs) and the solution of isoprene (13.1 milliliters, 131 mMs) stirred 68 hours in glacial acetic acid (44 milliliters).This mixture water (44 milliliters) dilution, and refluxed 1.5 hours.This mixture is cooled to room temperature, adds acetate (84 milliliters) and chromic acid [chromium trioxide (29.4 gram) is in water (30 milliliters)] successively, refluxed again 1.5 hours.After the cooling, this mixture water (200 milliliters) dilution is with ether (3 * 50 milliliters) extraction.The ether cut that merges diluted sodium hydroxide solution (2M; 2 * 50 milliliters), the washing of water (2 * 50 milliliters), saturated nacl aqueous solution (50 milliliters), and use dried over mgso.Filter and solvent evaporated under reduced pressure, from benzinum, be recrystallized repeatedly, obtain title compound (7 gram).

(b) 2-amino-6 and 7-methyl isophthalic acid, 4-naphthalene-1,4-diketone

At room temperature, to the 6-methyl naphthalene-1 that is stirring, add the solution of sodium azide (1.58 gram) in water (5 milliliters) in the solution of 4-diketone (2.1 grams, 12 mMs) in glacial acetic acid (60 milliliters).Stirred this mixture 2 days, water (200 milliliters) dilution then, and stirred again 15 minutes, filter afterwards.Filtrate neutralizes with sodium bicarbonate solution, with chloroform (3 * 25 milliliters) extraction.The chloroform extraction liquid that merges is used the calcium sulphate drying with saturated sodium bicarbonate solution and salt water washing.Filter and solvent evaporated under reduced pressure,, obtain title compound (100 milligrams), be 3: 2 mixtures of isomer through the silica gel chromatograph purifying.

(c) 2-hydroxyl-6-and-7-methyl-naphthalene-1, the 4-diketone

With the amino methyl naphthalene-1 that above-mentioned (b) obtains, 4-two alcohol/ketone mixtures (200 milligrams) refluxed 20 minutes in the water (20 milliliters) and the concentrated sulfuric acid (10 milliliters).The mixture of cooling is poured in the mixture of ice/water (50 gram), and extracted with ether (3 * 25 milliliters).The ether extracted liquid water that merges, saturated sodium bicarbonate, water, saturated nacl aqueous solution washing, and use dried over mgso.Filter and evaporating solvent,, obtain title compound (68 milligrams) through silica gel chromatography.

(d) preparation 2-(tert-butyl group)-3-hydroxyl-6 and 7-methyl-3-hydroxyl-naphthalene-1, the 4-diketone

With the persulfate/silver nitrate group of standard and amino methyl compound (64 milligrams, 0.34 mM), trimethylace tonitric (52 milligrams, 0.51 mM) adduction, obtain title compound, be 3: 2 mixtures (12 milligrams) of isomer.

Embodiment 52

Preparation 2-(tert-butyl group)-6 and 7-dimethyl-3-hydroxyl-naphthalene-1, the 4-diketone

Repeat above-mentioned steps (a) to (d), just with 2,3-dimethyl-1,3-butadiene replaces isoprene.

Embodiment 53

Preparation 2-(tert-butyl group)-3-hydroxyl-5 and 8-methyl isophthalic acid, 4-naphthalene-1,4-diketone

Repeat above-mentioned steps (a) to (d), just replace isoprene with piperylene.

(a) preparation 6-methyl isophthalic acid, 4-naphthalene-1,4-diketone

At room temperature, with 1, the 4-benzoquinones (13.9 grams, 128 mMs) and the solution of isoprene (13.1 milliliters, 131 mMs) stirred 68 hours in glacial acetic acid (44 milliliters).This mixture water (44 milliliters) dilution, and refluxed 1.5 hours.This mixture is cooled to room temperature, adds acetate (84 milliliters) and chromic acid [chromium trioxide (29.4 gram) is in water (30 milliliters)] successively, refluxed again 1.5 hours.After the cooling, this mixture water (200 milliliters) dilution is with ether (3 * 50 milliliters) extraction.The ether cut that merges diluted sodium hydroxide solution (2M; 2 * 50 milliliters), the washing of water (2 * 50 milliliters), saturated nacl aqueous solution (50 milliliters), and use dried over mgso.Filter and solvent evaporated under reduced pressure, from benzinum, be recrystallized repeatedly, obtain title compound (7 gram).

Toxicity data

Except above-mentioned concrete desinsection and acaricidic experiment, also provide the present invention about further experiment to mammal and so-called useful species such as Chrysloperla carnea, Aleochora bilineata and coccinella septempunctata (Coccinella septempunctata).

After measured, embodiment 25 compounds, i.e. 2-hydroxyl-3-(1 '-methylcyclohexyl)-naphthalene-1, the 4-diketone is to the whole LD of rat ₅₀Be 2786 milligrams/kg body weight, this shows that it is significantly higher than the safety of at present commercially available many conventional pesticides to mammiferous toxicity aspect.

After measured, several experimental compounds are to the LD of Chrysloperla carnea, Aleochorabilineata and coccinella septempunctata (Coccinella septempunctata) ₅₀Value is greater than the 1000ppm/ individuality.

Claims (50)

1. general formula (I) compound or its salt

Wherein

N represents the integer of 0-4; M represents 0 or 1 integer;

Each R represents halogen atom or nitro, cyano group, hydroxyl, alkyl, alkenyl, haloalkyl, haloalkenyl group, alkoxyl, halogenated alkoxy, haloalkene oxygen base, amino, alkylamino, dialkylamino, alkoxy carbonyl group, carboxyl, alkanoyl, alkylthio group, alkyl sulphinyl, alkyl sulphonyl, carbamoyl, alkyl amido, cycloalkyl, aryl or aralkyl independently;

R ¹And R ²The alkoxyl that expression independently of one another replaces arbitrarily, perhaps they represent together=O ,=S or=N-OR ⁹, R wherein ⁹Expression hydrogen atom or the alkyl that replaces arbitrarily;

R ³The expression hydroxyl or-OL group (wherein L is a leaving group) or the expression be converted in vivo-OL ¹The group of group (L wherein ¹Be leaving group);

R ⁶Alkyl, alkenyl, alkynyl group, cycloalkyl, cycloalkenyl group, aryl, alkoxyl, alkenyloxy, chain oxy-acetylene, cycloalkyloxy, cyclenes oxygen base or aryloxy group that expression replaces arbitrarily;

R ⁷And R ⁸The alkoxyl that expression independently of one another replaces arbitrarily, perhaps they represent together=O ,=S or=N-OR ⁹, R wherein ⁹As defined above; And

R wherein ₄And R ₅Represent halogen atom or the alkyl or the alkenyl that replace arbitrarily independently of one another, perhaps their carbon atoms in the middle of being in them are represented the cycloalkyl or the cyclenes basic ring of replacement arbitrarily; And

A represents straight or branched alkyl or alkenyl, and they can at random be substituted, A be with shown in 3 of naphthalene nucleus and-CR ⁴R ⁵R ⁶The acyclic carbochain that group links to each other; Condition is to work as R ¹With R ²And R ⁷With R ⁸During for=O, m and n=0, R ⁴And R ⁵Be methyl, and R ⁶When being vinyl, R ³Not hydroxyl or acetoxyl group.

2. the compound of claim 1, wherein R ¹With R ²And/or R ⁷With R ⁸Represent C together independently of one another _1-4Alkoxyl or R ¹With R ²And/or R ⁷With R ⁸All represent group=O together.

3. claim 1 or 2 compound, wherein R ³Be-the OL group, wherein L is a leaving group, perhaps R ³Be in vivo to be converted into-OL ¹Group, wherein sour LOH or L ¹The pK of OH in water _aValue is 1-7.

4. the compound of claim 3, wherein R ³Be can in vivo be converted into-group of OL, wherein L is a leaving group, and described conversion is to carry out in the pest body that maybe will prevent and treat in protected plant.

5. the compound of any one, wherein R among the claim 1-4 ⁶Expression C _1-16Alkyl, C _2-16Alkenyl, C _1-16Haloalkyl, C _2-16Haloalkenyl group, C _1-16Alkane acyl alkyl, C _1-16Alkoxyalkyl, C _1-16Alkoxyl, C _1-16Halogenated alkoxy or C _1-16The alkoxyl alkoxyl.

6. the compound of claim 5, wherein R ⁶Expression C _1-6The group of chain length.

7. the compound of any one in the aforementioned claim is characterized in that described compound is a naphthalene-1, the 4-diketone.

8. the compound of any one, wherein R in the aforementioned claim ⁴And R ⁵Represent C independently of one another _1-4Alkyl, C _1-4Haloalkyl, C _2-4Alkenyl or C _2-4Haloalkenyl group, perhaps they and be in carbon atom between them cycloalkyl or the cycloalkenyl group that expression at random replaces by halogen, alkyl, haloalkyl, alkenyl or haloalkenyl group that combine.

9. the compound of any one among the claim 1-8 is characterized in that described compound is the compound or its salt of general formula (II)

Wherein R, R ¹, R ², R ³, R ⁶, R ⁷And R ⁸And n is as defining formula I, and R ⁴And R ⁵Expression halogen or the alkyl or the alkenyl that replace arbitrarily.

10. the compound of claim 9, wherein n is 0, R ¹With R ²And R ⁷With R ⁸Be together=O; R wherein ⁴And R ⁵Represent C independently of one another _1-4Alkyl or C _1-4Haloalkyl, and R ⁶Expression C _1-7Alkyl, C _1-7Haloalkyl, C _1-7Alkoxyalkyl, C _1-7Alkoxyl, C _1-7Alkoxyl alkoxyl, C _2-7Alkenyl, C _2-7Haloalkenyl group or C _2-7The alkoxyl thiazolinyl.

11. the compound of claim 10, wherein R ⁶Expression C _1-6Alkyl, C _1-6Haloalkyl, C ₂Alkenyl or C ₂Haloalkenyl group.

12. the compound of any one among the claim 1-8 is characterized in that described compound is formula (III) compound

Wherein

N, m, A, R, R ¹, R ², R ³, R ⁶, R ⁷And R ⁸Such as mutual-through type (I) definition;

And R ⁴And R ⁵Represent any cycloalkyl or cycloalkenyl group that replaces with the carbon atom that is between them.

13. the compound of claim 12, wherein R ¹With R ²And R ⁷With R ⁸Be together=O; N is 0; R ⁴And R ⁵Represent saturated, any substituted cycloalkyl ring fully with the carbon atom that is between them; And R ⁶The C that expression is at random replaced by halogen _1-16Alkyl or C _2-16Alkenyl.

14. the compound of claim 13, wherein R ⁴And R ⁵Represent C with the carbon atom that is between them _4-8Cycloalkyl ring saturated, that replaced by halogen, alkyl, haloalkyl, alkenyl or haloalkenyl group arbitrarily.

15. the compound of claim 14, wherein R ⁴And R ⁵Represent arbitrarily by the C of halogen, alkyl, haloalkyl, alkenyl or haloalkenyl group replacement with the carbon atom that is between them _5-8Cycloalkyl ring, and R ⁶Be C _1-6Alkyl, C _2-6Alkenyl, C _1-6Haloalkyl or C _2-6Haloalkenyl group or halogen, and R ³Be hydroxyl or acetoxyl group.

16. the compound of claim 14 or 15, wherein R ⁴And R ⁵Represent any substituted cyclohexyl ring with the carbon atom that is between them.

17. the compound of claim 14 or 15, wherein R ⁴And R ⁵Represent any substituted cyclohexyl ring with the carbon atom that is between them, and R ⁶Expression is arbitrarily by the C of halogenation _1-2Alkyl or C ₂Alkenyl.

18. the compound of claim 17, wherein m is 0.

19. the compound of claim 17, wherein m is 1, and A is-CH ₂-.

20. the compound of any one among the claim 1-8 is characterized in that described compound is formula (IV) compound

Wherein

N, A, R, R ¹, R ², R ³, R ⁶, R ⁷And R ⁸Such as mutual-through type (I) definition,

And R ⁴And R ⁵Represent halogen or the alkyl or the alkenyl that replace arbitrarily independently of one another.

21. the compound of claim 20, wherein R ¹With R ²And R ⁷With R ⁸Be together=O; And A is C _3-8The alkyl or alkenyl chain, it can be replaced by halogen or straight chain that can halo.

22. the compound of claim 20, wherein R ⁴, R ⁵And R ⁶Be independently selected from C _1-6Alkyl, C _1-6Haloalkyl, C _2-6Alkenyl or C _2-6Haloalkenyl group.

23. claim 20,21 or 22 compound is characterized in that A is-(CH ₂) _a-group, wherein a is the integer of 1-7, perhaps A is-(CH ₂) _a-CH=CH-(CH ₂) _b-group, wherein a and b are that summation is the integer of 0-6, perhaps A is that wherein one or more carbon atoms are by the analog of these groups of alkyl, haloalkyl, alkenyl, haloalkenyl group or halogen replacement.

24. the compound of claim 23, wherein the summation of a and b is 0-3.

25. formula (I) compound is as the purposes of agricultural chemicals.

26. the purposes of claim 25, purposes wherein are as insecticide, miticide and/or fungicide.

27. the purposes of claim 26, purposes wherein are control acarian, aleyrodid, aphid and/or fungi.

28. formula (III) compound is as the purposes of the agricultural chemicals of control acarian, aphid and/or aleyrodid.

29. formula (IV) compound is as the purposes of the agricultural chemicals of control acarian and/or aphid.

30. in the method for a certain place control pest, this method comprises with the described place of general formula (I) compound treatment.

31. the method for claim 30 is characterized in that described pest is insect, mite and/or fungi.

32. the method for claim 30 or 31 is characterized in that compound used therefor is general formula (II), (III) or (IV) compound.

33. the method for claim 32, wherein said place comprise the surrounding environment that insect itself maybe can be subjected to or be subjected to the insect invasion and attack.

34. prepare m wherein and be the method for 0 formula (I) compound, described method comprises with general formula (VI) compound treatment general formula (V) compound

Wherein n, R and R ³Such as in formula (I) definition,

Wherein X represents leaving group, preferred hydroxyl or halogen, preferred especially chlorine or bromine atom; R ¹¹¹, R ¹²¹And R ¹³¹Represent hydrogen atom or the alkyl that replaces arbitrarily independently of one another, and R ⁴And R ⁵Such as in formula (I) definition, produce general formula (VII) compound

Wherein n, R, R ¹¹¹, R ¹²¹, R ¹³¹, R ⁴And R ⁵As defined above;

And heated type in suitable solvent (VII) compound carries out Claisen rearangement, obtains general formula (VIII) compound

35. the method for claim 34, wherein X represents hydroxyl, and is reflected under the Mitsunobu condition and carries out.

36. the method for claim 34, wherein X represents halogen atom, and is reflected under the alkylating condition and carries out.

37. the method for preparation formula (I) compound is characterized in that: in polar organic solvent, under alkali condition, with aldehyde A-CR ⁴R ⁵R ⁶(wherein A, R ⁴, R ⁵And R ⁶Such as in formula I definition, and A has aldehyde radical at the free-end of acyclic carbochain rather than in the 3-position of naphthalene nucleus) directly with the reaction of formula (V) compound, then in non-polar solven, under acid condition the heating products therefrom with elimination water.

38. being included in radical initiator, the method for preparation formula (I) compound, this method exist down, with general formula (V) compound and carboxylic acid CR ⁴R ⁵R ⁶-(A) _m-COOH (wherein A, m, R ⁴, R ⁵And R ⁶As formula I is defined) reaction,

Wherein n, R and R ³As defined above.

39. the method for preparation formula (I) compound, this method comprise general formula (V) compound and general formula X-(A) _m-CR ⁴R ⁵R ⁶(wherein A, m, R ⁴, R ⁵And R ⁶As formula I is defined, and X breaks away from compound to produce in the presence of acid ⁺(A) _m-CR ⁴R ⁵R ⁶The leaving group of group) reaction

40. the method for claim 39, wherein X is halogen or tosyl.

41. the method for claim 39 or 40, wherein said acid is lewis acid.

42. the method for claim 41, wherein lewis acid is an aluminium chloride.

43. composition wherein contains formula (I) compound and at least a carrier as defined above.

44. the composition of claim 43 is characterized in that wherein containing the formula I active component of 0.001-95% (weight).

45. the composition of claim 43 is characterized in that wherein containing the active component of 0.001-25% (weight).

46. the defined formula of claim 34 (VII) compound

47. formula A-CR ⁴R ⁵R ⁶Compound, wherein A, m, R ⁴, R ⁵And R ⁶Such as to formula (I), (II), (III) or (IV) definition, and A is the aldehyde radical that is positioned at its free-end.

48. formula CR ⁴R ⁵R ⁶-(A) _m-COOH compound, wherein A, m, R ⁴, R ⁵And R ⁶Such as to formula (I) definition.

49. formula X-(A) _m-CR ⁴R ⁵R ⁶Compound, wherein A, m, R ⁴, R ⁵And R ⁶As formula I is defined, and X breaks away from compound to produce in the presence of acid ⁺(A) _m-CR ⁴R ⁵R ⁶The leaving group of group.

50. the compound of any one among the claim 47-49, wherein A, m, R ⁴, R ⁵And R ⁶Such as claim 2-24 in any one definition.