KR19980701324A - PESTICIDAL COMPOUNDS - Google Patents

Abstract

The present invention relates to a compound for controlling pests having formula (I) or a salt thereof:

(I)

Where

n represents an integer of 0 to 4;

m represents an integer of 0 or 1;

Each R is individually a halogen atom or nitro, cyano, hydroxyl, alkyl, alkenyl, haloalkyl, haloalkenyl, alkoxy, haloalkoxy, haloalkenoxy, amino, alkylamino, dialkylamino, alkoxycarbonyl, Carboxyl, alkanoyl, alkylthio, alkylsulfinyl, alkylsulfonyl, carbamoyl, alkylamido, cycloalkyl, aryl or aralkyl groups;

R ¹ and R ² each represent individually substituted or unsubstituted alkoxy, or together represent = O, = S or = N-OR ⁹ groups (wherein R ⁹ represents a hydrogen atom or a substituted or unsubstituted alkyl group) );

R ³ represents a group which is converted to a hydroxyl group, a -OL group (where L is a leaving group), or a -OL ¹ group (wherein L ¹ is a leaving group) in the body;

R ⁶ represents a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy or aryloxy group;

R ⁷ and R ⁸ each represent a substituted or unsubstituted alkoxy group, or together form a = O, = S or = N-OR ⁹ group wherein R ⁹ is as defined above;

R ⁴ and R ⁵ each represent a halogen atom or a substituted or unsubstituted alkyl or alkenyl group, or form a substituted or unsubstituted cycloalkyl or cycloalkenyl ring with a carbon atom between them;

A is preferably a straight or branched alkyl or alkenyl group which may be substituted or unsubstituted by halogen, and represents an acyclic carbon chain connecting the 3-position and -CR ⁴ R ⁵ R ⁶ moiety of the illustrated naphthalene ring;

Provided that when R ¹ and R ² , and R ⁷ and R ⁸ are ═O groups, m and n are 0, R ⁴ and R ⁵ are methyl and R ⁶ is ethenyl, R is hydroxyl or It is not ethanooxy.

Description

Pest Control Compounds

The present invention provides novel 1,2,3,4-substituted naphthalene compounds used as pesticides, in particular as insecticides, acaricides and fungicides; Methods of preparing these compounds; Compositions containing these compounds, and methods of using these compounds and compositions to control pests.

US 2,572,946 describes compositions for controlling ticks and aphids, wherein the active ingredient is a compound of formula (P1):

Where

R ₁ is a radical containing 6 to 15 carbon atoms selected from the group consisting of alkyl, cyclohexyl and cyclohexylalkyl; Although n-alkyl, iso-alkyl, alkylcycloalkyl and aralkyl groups are illustrated, no specific tick or aphid control data for these groups are given.

DE 2641343 A1 generally describes compounds of formula (P2):

Where

R ₁ is a straight, branched, or ring C _8-14 alkyl group,

R ₂ is straight or branched C _1-17 alkyl, C _2-17 alkenyl, C _3-6 cycloalkyl, C _1-4 alkoxy, -CH ₂ OCH ₃ , -CH ₂ OCH ₂ CH ₃ or -CH = CH Is a -COOH group,

X and Y are hydrogen, fluorine, chlorine or bromine atoms or methyl or methoxy groups. The compound exhibits acaricide and aphid control activity, but only compounds in which R ₁ is a linear C ₈ or C _11-14 alkyl group have this activity.

US 4,110,473 relates to a method of protecting a plant from ticks, including treating the plant with a compound of formula (P3):

Where

Y is hydrogen, fluorine, chlorine, or bromine;

R ₁ is branched, ring or straight chain C _8-14 alkyl;

R ₂ is branched or straight chain C _1-12 saturated alkyl or C _3-12 unsaturated alkyl, or C _3-6 cycloalkyl, unsubstituted or substituted by one or two chlorine, bromine, methoxy or ethoxy substituents.

DE 3801743 A1 generally describes compounds of the formula (P4):

Where

n is 0 to 12,

R ¹ is hydrogen or substituted or unsubstituted alkyl, aralkyl, alkylcarbonyl, (hetero) arylcarbonyl, alkoxycarbonyl, alkylsulfonyl or arylsulfonyl groups,

R ² is haloalkyl, substituted or unsubstituted (hetero) aryl, or substituted cycloalkyl group. These compounds are known to exhibit acaricide and fungicidal activity.

n is 0, R ¹ is a hydrogen atom, R ² is 4- (t-butyl) cyclohexyl, 4- (trimethylsilyl) cyclohexyl, 4- (cyclohexyl) -cyclohexyl, 2-trifluoromethyl Is a cyclohexyl or 3,5-di (trifluoromethyl) -cyclohexyl group or n is 0, R ¹ is an ethanoyl group, R ² is 4- (t-butyl) cyclohexyl, 4- (cyclohexyl) Ten compounds of formula (P4) which are cyclohexyl, 2- or 3-trifluoromethylcyclohexyl or 3,5-di (trifluoromethyl) -cyclohexyl groups are described in detail. Wherein n is 0, R ¹ is a hydrogen atom and R ² is a 4- (t-butyl) cyclohexyl or 4- (trimethylsilyl) cyclohexyl group with a tick agent for two compounds of formula (P4) The activity is proved.

EP 0077550 describes compounds of the formula (P5):

Where

R is an alkyl group of 1 to 10 carbon atoms and the patent application describes the use of the compounds in veterinary formulations, in particular for the prevention of protozoan infections.

There are no published prior arts for pesticidal or salby naphthoquinone compounds, in which the quaternary carbon atoms are bonded directly to the naphthoquinone ring or attached to the naphthoquinone ring via an n-alkyl group or an iso-alkyl group.

Co-pending International Application No. PCT / GB95 / 00953 relates to naturally-occurring compounds of formula (P6):

Where

R is a hydrogen atom or a hydroxyl or ethanoyloxy group, said patent relates to the use of such compounds as pest control agents, in particular fungicides, insecticides and / or tick control agents. Such compounds are already described in the following literature as plant metabolites: Reference literature-Chamy et al., (1993) Bol. SoC. Chil. Quim. 38 187-190.

Fieser et al., Fieser et al. J.A.C.S. Vol. 70, no. 6 (1948)] describes the preparation of 2-alkyl-3-hydroxynaphthalene-1,4-dione, wherein the alkyl group comprises quaternary carbon but has no pesticidal activity against fungi, insects or mites Is attributed to these quaternary carbons. This document relates to anti-protozoal activity and quaternary compounds have the minimum activity described.

Santisopasri et al., Santisopasri et al. Biotech. Biotech. Biochem. 59 (10) 1999-2000 (1995) and the Annual Meeting of the Pesticide Science Society of Japan, Tokyo, March 1993, p55, describe naturally-occurring anti-fungal naphthalene-1,4-dione, wherein The alkyl group in is a 2,6-dimethyl-2,6-octadienoxy 2,2-dimethylpropyl group and the corresponding 2,2-dimethyl 3-hydroxypropyl group metabolite.

The present inventors have now developed related compounds and synthetic naphthoquinones which have advantageous pesticidal properties as compared to compounds already known in the art, which are particularly applicable to the treatment of certain pests such as fungi, insects and / or mites. Preferred synthetic compounds of the invention, in particular, have excellent pesticidal activity against agaris and / or aphids and / or fungi; Most preferred compounds exhibit useful activity against two or more, preferably all of these pests. Many compounds of the present invention also exhibit anti-feedant activity against some or more insects or ticks.

According to a first aspect of the present invention, there is provided the use of a compound of formula (1) or a salt thereof as a pest control agent against powdery, insect insect and / or fungal pests:

Where

n is an integer from 0 to 4;

m is an integer of 0 or 1;

Each R is individually a halogen atom or nitro, cyano, hydroxyl, alkyl, alkenyl, haloalkyl, haloalkenyl, alkoxy, haloalkoxy, haloalkenoxy, amino, alkylamino, dialkylamino, alkoxycarbonyl , Carboxyl, alkanoyl, alkylthio, alkylsulfinyl, alkylsulfonyl, carbamoyl, alkylamido, cycloalkyl, aryl or aralkyl groups;

R ¹ and R ² are each independently a substituted or unsubstituted alkoxy group or together form = O, = S or = N-OR ⁹ (wherein R ⁹ is a hydrogen atom or a substituted or unsubstituted alkyl group) and ;

R ³ is a hydroxy group or a -OL group (wherein L is a group which is converted in the body to a -OL ¹ group where L ¹ is a leaving group or L ¹ is a leaving group);

R ⁶ is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy or aryloxy group;

R ⁷ and R ⁸ are individually substituted or unsubstituted alkoxy groups or together form = O, = S or = N-OR ⁹ (wherein R ⁹ is as defined above);

R ⁴ and R ⁵ are each independently hydrogen or a halogen atom or a substituted or unsubstituted alkyl or alkenyl group, or a substituted or unsubstituted C _4-8 cycloalkyl or cycloalkenyl ring linked together by a carbon atom therebetween;

A is preferably a straight or branched chain alkyl or alkenyl group which may be substituted or unsubstituted by halogen, and represents an acyclic carbon chain connecting the 3-position and -CR ⁴ R ⁵ R ⁶ moiety of the naphthalene ring;

Provided that when R ² and R ¹ , and R ⁸ and R ⁷ are ═O groups and n is 0, i) R ⁴ and R ⁵ are methyl, m is 0 and R ⁶ is ethenyl, R ³ Is not hydroxyl or ethanoyloxy, (ii) when R ⁴ and R ⁵ are methyl, m is 0 or 1, A is —CH ₂ — or — (CH ₂ ) ₂ — and R ³ is hydroxyl R ⁶ is not methyl, (iii) when R ⁴ and R ⁵ are methyl, m is 1, A is-(CH ₂ ) ₂ -and R ³ is hydroxyl, R ⁶ is not chloro, ( iv) when R ⁴ and R ⁵ together with a carbon atom between them form a cyclohexyl ring, m is 1, A is -CH ₂ -and R ³ is hydroxyl, R ⁶ is not methyl, ( v) when R ⁴ and R ⁵ are methyl, m is 1, A is -CH ₂ -and R ³ is hydroxyl, then R ⁶ is hydroxymethyl or its 2,6-dimethyl-2,6-octa It is not a dienoate ester.

If the compound of formula (I) contains a group defined as alkyl, alkenyl or alkynyl substituent, unless otherwise defined, the compound may be straight or branched and may be 12 or less, preferably 6 or less, and In particular, it may contain up to 4 carbon atoms. Cycloalkyl or cycloalkenyl groups may contain 3 to 10, more preferably 5 to 8 carbon atoms. The aryl group can be all aromatic hydrocarbon groups, in particular phenyl or naphthyl groups. Aralkyl groups may be all alkyl groups defined above, in particular benzyl groups substituted by alkyl groups, substituted by aryl groups as defined above.

Where all such substituents are substituted or unsubstituted, the optionally present substituents may be one or more substituents commonly used in pest control compounds and / or modifications of such compounds to affect activity, persistence, permeability or other properties. Can be. Specific examples of such substituents include, for example, halogen atoms, nitro, cyano, hydroxyl, alkyl, alkenyl, haloalkyl, haloalkenyl, alkoxy, haloalkoxy, amino, alkylamino, dialkylamino, alkoxycarbonyl, Carboxyl, alkanoyl, alkylthio, alkylsulfinyl, alkylsulfonyl, carbamoyl, alkylamido, cycloalkyl, phenyl and benzyl groups. In general, up to three substituents may be present. When all of the above substituents are or contain alkyl substituents, the substituents may be straight or branched and may contain up to 12, preferably up to 6, and most preferably up to 4 carbon atoms. When the substituent is or contains an aryl or cycloalkyl moiety, the aryl or cycloalkyl moiety is itself one or more halogen atoms, nitro, cyano, alkyl, alkenyl, haloalkyl, haloalkenyl, alkoxy or haloalkoxy groups. It may be substituted by. Preferably, the aryl moiety is a phenyl moiety and a cycloalkyl moiety containing 3 to 8, preferably 4 to 7 carbon atoms.

If present, R is a halogen atom or nitro, cyano, hydroxyl, C _1-4 alkyl, C _1-4 haloalkyl, C _2-4 alkenyl, C _2-4 haloalkenyl, C _1-4 alkoxy , C _1-4 haloalkoxy, C _1-4 alkylamino, di-C _1-4 alkylamino, C _1-4 alkoxycarbonyl, C _1-4 alkylthio, C _1-4 alkylsulfinyl or C _1- It is preferable that it is a ₄ alkylsulfonyl group.

If present, R is a halogen atom or C _1-4 alkyl, C _1-4 haloalkyl, C _2-4 alkenyl, C _2-4 haloalkenyl, C _1-4 alkoxy or C _1-4 haloalkoxy More preferred.

Preferably n is 0, 1 or 2, more preferably n is zero.

R ¹ and R ² are each individually C _1-4 alkoxy, in particular a methoxy group or together are = O, = S or = N-OR ⁹ (wherein R ⁹ is a hydrogen atom or a C _1-4 alkyl, in particular a methyl group) It is preferable to form It is particularly preferred that R ¹ and R ² are both methoxy groups or together form a ═O group.

When R ³ is a -OL group, L is a leaving group or a group converted in the body to a -OL ¹ group in which L ¹ is a leaving group, and the leaving group may be any group commonly used as a leaving group. The leaving group is preferably such that the pKa value of the acid LOH or L ¹ OH in water is from 1 to 7, preferably from 1 to 6 and more preferably from 1 to 5.

In the case where R ³ is a group converted in the body to the -OL ¹ group in which L is a leaving group, it is preferable that the conversion should be performed in the plant to be protected or the pest to be removed, preferably by the action of an enzyme in the plant or pest . For example, if R ³ is a β-acid group such as -O-CH ₂ CH ₂ CO-OH, not -CH ₂ CH ₂ CO-OH is a leaving group, this means that -CO-CH ₂ -CO-OH is leaving It can be enzymatically oxidized by the group β-oxidant to give the —O—CO—CH ₂ —CO—OH group.

Preferably, R ³ is —OR ¹⁰ group wherein R ¹⁰ is a hydrogen atom, substituted or unsubstituted alkyl, alkenyl, aryl or aralkyl group or —CO—R ¹¹ , —CO—OR 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 ) group (wherein R ¹¹ is a hydrogen atom, substituted or unsubstituted alkyl, alkenyl, aryl or aralkyl group or —NR ¹² R ¹³ group, R ¹² and R ¹³ are hydrogen atoms) Or a substituted or unsubstituted alkyl group, X is an oxygen or sulfur atom. When R ¹⁰ or R ¹¹ is a substituted or unsubstituted aryl or aralkyl group, it is preferred that the aryl group or moiety is a phenyl group or moiety and the optional substituents are halogen atoms, nitrogen and C _1-4 alkyl groups. Particular preference is given to substitution at the 4-position of the phenyl ring. For R ³ , the term substituted or unsubstituted includes, for example, substitution with a silicone containing group (eg, a trialkylsilyl group such as trimethylsilyl) as a substituent on R ¹⁰ , R ¹¹ or R ¹² . do. Preferably R ³ is a hydroxyl group or -O-CO-R ¹¹ or -O-CO-OR ¹¹ group, wherein R ¹¹ is a hydrogen atom or C _1-12 alkyl, C _1-12 haloalkyl, C _1-12 hydroxyalkyl, C _1-12 carboxyalkyl, phenyl or benzyl group.

Especially preferably, R ³ is a -OH or -O-CO-OR ¹¹ group, wherein R ¹¹ is a hydrogen atom or a C _1-6 alkyl, C _1-6 haloalkyl, phenyl or benzyl group. Most preferably R ¹¹ is a methyl, ethyl, propyl or butyl group.

Preferably R ⁶ is C _1-16 alkyl, C _2-16 alkenyl, C _1-16 haloalkyl, C _2-16 haloalkyl, C _1-16 alkanoylalkyl, C _1-16 alkoxyalkyl, C _{1 -16} alkoxy, C _1-16 haloalkoxy or C _1-16 alkoxyalkoxy group. More preferably these groups have a C _1-6 length or C _2-6 length in the case of alkenyl.

More preferably, R ⁶ is C _1-6 alkyl (particularly methyl or ethyl), C _1-16 haloalkyl (eg, trifluoromethyl, difluoromethyl or monofluoromethyl groups), or C _{2 -16} alkenyl or C _1-6 haloalkenyl.

Preferably, R ⁷ and R ⁸ are individually C _1-4 alkyl groups or together form = O or = N-OR ⁹ where R ⁹ is a hydrogen atom or a C _1-4 alkyl group, but more preferably Preferably, R ⁷ and R ⁸ are both methoxy groups or together form a ═O group.

Compounds wherein R ¹ and R ² and R ⁷ and R ⁸ are each an alkoxy group or together are a = S or NOR ⁹ group include naphthoquinones corresponding to the present invention; It will be appreciated by those skilled in the art that they are potential biological precursors to naphthoquinone, which is the preferred compound of the present invention.

Preferably, R ⁴ and R ⁵ are each independently hydrogen or a C _1-4 alkyl, C _1-4 haloalkyl, C _2-4 alkenyl or C _2-4 haloalkenyl group, or a carbon atom in between Together with a substituted or unsubstituted cycloalkyl or cycloalkenyl ring, which ring is preferably unsubstituted or substituted by halogen, alkyl, haloalkyl, alkenyl or haloalkenyl.

Compounds of formula (I) of the invention may form salts, for example, wherein R ³ is a hydroxyl group. Suitable bases for producing such salts include inorganic bases such as sodium hydroxide, potassium hydroxide or sodium carbonate, and organic bases such as tertiary amines such as triethylamine and cyclic amines such as pyrrolidine.

It will be appreciated by those skilled in the art that many of the compounds for use in the present invention exist as different geometrical isomers and diastereomers. The present invention thus encompasses each of the individual isomers and mixtures thereof.

The inventors have determined that the compounds of the present invention are of particular interest as long as they exhibit pest control activity against the species and lineage of pests that have developed resistance to currently used pest control agents. Thus, the compounds of the present invention will be used specifically for insect, mite and fungal strains that are resistant to other pest control agents on the market. We provide a special activity profile suitable for controlling a particular group of pests by providing a quaternary quaternary carbon atom in which the R ⁴ , R ⁵ and R ⁶ groups are bonded to the A group or to the 3-position of the ring shown in Formula I in three or more arbitrary arrangements It was confirmed that it can provide.

In a first preferred class of compounds of the compounds of the first aspect of the invention, the quaternary carbon atoms are selected from -CR ⁴ R ⁵ R ⁶ groups, wherein R ⁴ and R ⁵ are independently halogen or substituted or unsubstituted And co-pending PCT / GB95 / 00953, which are provided at positions immediately adjacent to the naphthalene ring in the form of an alkyl or alkenyl group, and which are mentioned above in the proviso appended to the definition of formula (I).

In the first preferred distinguishing group, compounds of formula (II) or salts thereof are provided:

Where

R, R ¹ , R ² , R ³ , R ⁶ , R ⁷ and R ⁸ and n are as defined for Formula I, and R ⁴ and R ⁵ represent halogen or substituted or unsubstituted alkyl or alkenyl groups .

More preferred compounds of formula (II) are those wherein R ² and R ¹ and R ⁸ and R ⁷ are both = 0; R ⁴ and R ⁵ are each independently a C _1-4 alkyl or C _1-4 haloalkyl group, R ⁶ is C _1-7 alkyl, C _1-7 haloalkyl, C _1-7 alkoxyalkyl, C _1-7 Alkoxy, C _2-7 alkoxyalkoxy, C _2-7 alkenyl, C _2-7 haloalkenyl or C _2-7 alkoxyalkenyl group. R ³ is preferably OH, —O—CO—R ¹¹ or —O—CO—OR ¹¹ , wherein R ¹¹ is C _1-3 alkyl, most preferably —OH. More preferably R ⁶ is C _1-7 alkyl, C _2-7 alkenyl or C _1-7 haloalkyl or C _2-7 haloalkenyl group, most preferably R ⁶ is C _1-6 alkyl, C _1-6 haloalkyl, C ₂ alkenyl or C ₂ haloalkenyl group. Most preferably R ⁴ and R ⁵ are methyl.

We have found that this first preferred group generally has effective pesticidal activity against insects, ticks and fungi, and in particular ticks and dusty. Especially susceptible flour is Bemisia species.

In a second preferred distinguishing group in the compounds of the first aspect of the invention, the quaternary carbon atoms are provided as part of a cycloalkyl or cycloalkenyl ring, and thus the second group in the preferred compounds of formula (I) Is preferably formula (III).

Where

n, A, R, R ¹ , R ² , R ³ , R ⁶ , R ⁷ and R ⁸ are as defined for Formula (I);

m represents 0 to 1;

R ⁴ and R ⁵ together with the carbon atom in between form a substituted or unsubstituted cycloalkyl or cycloalkenyl group.

More preferably, the compounds of the group are of formula (III), wherein R ² and R ¹ , and R ⁸ and R ⁷ are all = 0; n and m are 0; R ⁴ and R ⁵ together with the carbon atom between them form a substituted or unsubstituted fully saturated cycloalkyl ring; R ⁶ represents a C _1-16 alkyl or C _2-16 alkenyl group unsubstituted or substituted by hydrogen; R ³ is preferably OH, —O—CO—R ¹¹ or —O—CO—OR ¹¹ , wherein R ¹¹ is C _1-3 alkyl, most preferably —OH.

More preferably R ⁴ and R ⁵ together with a carbon atom in between form a C _4-8 saturated cycloalkyl ring, most preferably unsubstituted or substituted by chlorine or fluorine; More preferably a C _5-8 cycloalkyl ring, R ⁶ is C _1-6 alkyl, C _2-6 alkenyl, C _1-6 haloalkyl group, C _2-6 haloalkenyl group or halogen. An exceptionally active compound in the crowd is a compound wherein R ⁴ and R ⁵ together with a carbon atom between the two form a cyclohexyl ring and R ⁶ is C _1-2 alkyl or C ₂ alkenyl.

The second preferred group of compounds of the present invention is particularly effective against specific fungi as well as against ticks and dusty , the most active compounds having exceptional activity against dusty , especially Bemisia species, while retaining activity against ticks. .

In a third distinct group in the compounds of the first aspect of the invention, the quaternary carbon atoms are not in a cycloalkyl or cycloalkenyl group and are from 2 to 16, more preferably from 2 to 10, from the naphthalene ring They are as far apart as carbon atoms. Most preferably, the quaternary carbon is four to eight carbon atoms long from the naphthalene ring.

Thus, in the above distinguishing group, preferred compounds of formula (I) have the following preferred formula (IV):

Where

n, A, R, R ¹ , R ² , R ³ , R ⁶ , R ⁷ and R ⁸ are as defined for Formula (I);

R ⁴ and R ⁵ each independently represent a halogen or a substituted or unsubstituted alkyl or alkenyl group.

In order to save floury, group A preferably has 3 to 7 carbon atom chains between the naphthalene ring and the quaternary carbon atoms, especially when it is an alkylene chain without side chains.

In order to provide high potency to aphids, group A preferably has 4 to 8 carbon atom chains between the naphthalene ring and the quaternary carbon atoms, especially when this is an alkylene chain without side chains.

For these two cases, the presence of one or more side chains on the binding carbon chain of A will allow the peak activity to be obtained using shorter chain lengths between the naphthalene ring and the quaternary carbon.

More preferred compounds of this group have formula (IV), wherein R ² and R ¹ and R ⁸ and R ⁷ are both ═O; m is 1 and A is a C _3-8 alkyl or alkenyl chain which may be substituted by halogen or by halogenated side chains. Preferably R ⁴ , R ⁵ and R ⁶ are C _1-6 alkyl or haloalkyl or C _2-6 alkenyl or haloalkenyl. R ³ is preferably OH, —O—CO—R ¹¹ or —O—CO—OR ¹¹ , wherein R ¹¹ is C _1-3 alkyl, most preferably —OH.

Preferred compounds of this group include those in which A is a-(CH ₂ ) _a -group where a is 1 to 7, or a-(CH ₂ ) _a -CH = CH- (CH ₂ ) _b group, wherein a and b are compounds in which the sum of the two is from 0 to 6, preferably from 0 to 5, most preferably from 0 to 4, and analogs of these compounds, wherein at least one carbon atom of these groups is alkyl, haloalkyl , Alkenyl, haloalkenyl or halogen).

A second aspect of the invention provides a compound of formula (I) as a pest control agent; Particularly as insecticides, aphids and / or fungicides, in particular for use against mites, dusty, aphids and / or fungi. Particularly susceptible flourishes include flourishes of the Bemisia species. Especially susceptible aphids include aphids of the species Myzus and Aphis. Particularly sensitive fungi include fungi of the species Aspergillus, Pyricularia, Rhizoctonia, Erisiphe and Botrytis.

A preferred use of the second aspect is the use of a compound of formula (II) as a pest control against insects, ticks and / or fungi.

A second preferred use of the second aspect is to use a compound of formula (III) as a pest control against mites, aphids and / or dusty.

A third preferred use of the second aspect is the use of compounds of formula (IV) as pest control agents for mites and / or aphids.

In addition to the direct pesticidal activity, ie, direct lethal toxicity, exhibited by the compounds of formulas (I), (II), (III) and (IV), the present inventors have found that these compounds contain many types of insects, in particular Diabrotia species (Western and Eastern Corn Root Worm), as well as species listed above, as well as species such as Spodoptera littoralis and Spodoptera frugiperda, and Padon Cocklet It was confirmed that it also exhibits anti-pendant activity against beetle such as Phaedon cochleaiae Fab. Accordingly, the present invention also provides the use of the compounds of the present invention as pest control agents that act as insect and tick anti-pendant agents.

A fourth aspect of the present invention relates to a method for controlling pests, in particular insects, ticks and fungal pests, at the locus, which process the locus in a compound of formula (I), preferably in formula (II), ( Treatment with a compound of III) or (IV).

Preferably, the locus comprises pests, ie insects, mites and / or fungi themselves or environments that are susceptible to or attacked by pests. More preferably, the locus comprises the pests themselves, stored food ingredients, plants or animals susceptible to or attacked by the pests, seeds of such plants or the environment in which these plants are growing or will be grown. Specifically, the compounds of formula (I) are sprayed in a room to control housekeeping by houseflies or other insects, mites or fungi, in the domestic environment, for the treatment of stored crops, in particular grains, or for growing such as cotton or rice. Medical or veterinary as a spray of livestock, in a horticultural or agricultural environment, for example, to prevent or treat trauma by insects or mites, by spraying on crops in the air to control reversal by pests, in particular powdery and related species. Can be used in the environment.

In a fifth aspect the present invention relates to a process for preparing compounds of formula (I) as defined above and in particular compounds of formula (II), (III) and (IV).

When the compound is a compound of formula (I) wherein m is 0, this method comprises reacting a compound of formula (V) with a compound of formula (VI) to produce a compound of formula (VII):

Where

n, R and R ³ are as defined above and R ³ is especially -OH.

Where

X represents a leaving group, preferably a hydroxyl group or a halogen, in particular a chlorine or bromine atom,

R ¹¹¹ , R ¹²¹ and R ¹³¹ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group,

R ⁴ and R ⁵ are as defined in formula (I).

Where

n, R, R ¹¹¹ , R ¹²¹ , R ¹³¹ , R ⁴ and R ⁵ are as defined above.

In case X represents a hydroxyl group, the reaction can be carried out under Mitsunobu reaction conditions, ie at 0 ° C., for example using diethyl azodicarboxylate and triphenylphosphine in tetrahydrofuran. Can be. If X represents a halogen atom, the reaction can be carried out using alkylating conditions, ie a suitable solvent such as dichloromethane, and a base such as triethylamine.

Thereafter, the compound of compound (VII) may be heated in a suitable solvent, preferably an alcohol such as ethanol, resulting in a Klaisen-type rearrangement, resulting in a compound of formula (VIII):

The alkyl aldehyde is reacted directly with the compound of formula (V) in a polar organic solvent under alkaline conditions (e.g. in the presence of pyrrolidine) and then under acidic conditions (e.g. in a nonpolar solvent such as benzene). It is also possible to obtain 3-alkenyl substituted naphthalene ring compounds by heating the p-toluenesulfonic acid) product to remove moisture.

Compounds of formula (VIII) are consistent with compounds of formulas (I), (II) and (IV) in which R ⁶ represents a substituted or unsubstituted alkenyl group, and other compounds of formula (I) by various induction processes Can be switched to.

For example, a compound of formula (I) wherein R ⁶ represents a substituted or unsubstituted alkyl group is produced by hydrogenating a suitable compound of formula (VIII), for example, using hydrogen gas with palladium on charcoal as a catalyst You can. Most compounds of formula (V) are commercially available, but can be prepared from similar 2-hydroxybenzoquinones, for example, by Diels Alder reaction.

m is 1, i.e. compounds of formulas (I), (II), (III) and (IV), having special applicability in the production of compounds of formula (III) or (IV) In an alternative process for preparing a compound of formula (V), the compound of formula (V) is prepared in the presence of free radical initiators such as ammonium persulfate and silver nitrate in a suitable solvent such as aqueous acetonitrile, carboxylic acid CR ₄ R ₅ R _6- (A) a compound of formula (I), (II), (III) or (IV) by reaction with _m- COOH, wherein A, m, R ⁴ , R ⁵ and R ⁶ are as defined above Produces:

Formula (V)

Where

n, R and R ³ are as defined above.

The compound of formula (I) obtained in this way can then be further reacted using the derivation process described above or a combination thereof to obtain another compound of formula (I) as desired.

Many 1-methylcycloalkylcarboxylic acids and cyclos for use in the above alternative process wherein R ⁴ and R ⁵ together with a carbon atom between the two form a cycloalkyl or cycloalkenyl ring of 3 to 10 carbons. Alkylenecarboxylic acids are commercially available, and the carboxylic acid groups on these 1-methylcycloalkylcarboxylic acids and cycloalkylenecarboxylic acids are extended by known techniques to give longer carbon chain lengths, if necessary. Substitutions can be made using techniques well known to those skilled in the art. For example, the Arnst-Eistert reaction can be used to achieve -CH ₂ -extension (see, for example, Meier and Zeller (1975) Angew. Chem. Int. Ed.Ewgl . , 14 , 32). Alternatively, a compound in which m is 1 may react a similar cycloalkanone with ethyl cyanoacetate and then with Grignard reagent and then hydrolyze to yield (1′-substituted-cycloalkyl) -acetic acid (See, eg, Amsterdamsky et al (1975) Bull. Soc. Chim. Fr. (3-4 Part 2), p635-643 and Muhs MAPhD Thesis, University of Washington, Diss Abst. 14 , 765 (1954). ) Increase the carbon chain length by one.

To prepare a compound containing R ⁴ R ⁵ incorporated into a ring having more carbon atoms, a similar monobromo-substituted cycloalkyl or cycloalkenyl compound was used to produce a Grignard compound using magnesium, followed by CO ₂ (For example in the form of dry ice) and can be converted to carboxylic acids. The carboxylic acids thus formed are alkylated in the presence of butyllithium, for example by using compound R ⁶ -I (eg methyl iodide), wherein R ⁶ is a suitable group as defined above under these conditions. -Alkyl carboxylates.

For the preparation of 1-fluoro-cycloalkyl / cycloalkenyl carboxylic acids, a method of CA 75: 1776lu can be used, in which the buta-1,3-diene in the presence of 4-hydroxy-phenol The reaction is carried out with 1-fluoro-1-carboxy ethene while heating, followed by reduction of cyclounsaturation to convert cycloalkenyl to cycloalkyl compound. Alternatively, a similar 2-keto-cycloalkyl-carboxylate compound can be reacted with sodium ethoxylated and fluorine gas to give 1-fluoro-2-keto-cycloalkyl-carboxylate, followed by a keto group Can be reduced using (i) MeSH (ii) Raney nickel and (iii) potassium hydroxide base (see J. Org . Chem. (1983) 48 , 724-727 and J.Org . Chem. (1982) . 47 , 3242-3247).

Substitution (eg, alkylation) of the cycloalkyl / cycloalkylene ring at a position other than the 1-position to the carboxylate can be accomplished by methods known to those skilled in the art. Starting from the ring 1-unsaturated cycloalkene carboxyl alkyl esters, alkylation can be induced at the 1-position as described above, and then using light as an initiator, compounds R ²⁰ -X wherein R ²⁰ is alkyl Or haloalkyl and X is halogen (e.g. compound CF ₃ X) introduces an alkyl or haloalkyl group (e.g. CF ₃ -group). Subsequently, reduction using palladium-carbon catalysis conditions saturates the unsaturated bonds.

1-trifluoromethyl cycloalkyl / cycloalkenyl carboxylates can be reacted, for example, with cycloalkyl / cycloalkenyl-carboxylate, for example in the presence of LDA, or with 1-keto -Cycloalkyl / cycloalkenyl-carboxylate can be obtained by reacting with fluoromethyl iodide in the presence of triethylamine and then reducing. Alternatively, 2-trifluoromethyl acrylic acid is reacted with substituted or unsubstituted buta-1,3-diene while heating in the presence of 4-hydroxyphenol, thereby substituted or unsubstituted 1-trifluoromethyl cyclo Alkenyl carboxylic acids can be obtained.

Compounds unsaturated for R ⁶ are described in Wood et al. J. Chem. Soc Perkin Trans 1 (1985) 1645-1659, to yield the following compound (IX), wherein R ¹⁴¹ in the following compound (IX) is hydrogen or substituted or unsubstituted alkyl, alkenyl, Alkynyl, aryl, alkoxy, alkenoxy, alkynoxy or aryloxy and the compound is reacted with naphthaquinone under conditions to achieve rearrangement as described above. Reduction of such compounds allows access to iso-alkyl groups.

In a further method of preparing a compound of the present invention, the compound of formula (5) is reacted with formula X- (A) _m -CHR ⁴ R ⁵ , wherein R ⁴ and R ⁵ , A are And X is a leaving group that leaves the compound to give the charged radical ⁺ (A) _m -CHR ⁴ R ⁵ , for example X can be a halogen atom and a tosyl group). This reaction is carried out in the presence of an acid, for example Lewis acid, such as ammonium chloride, under the conditions broadly described in the literature: Fieser and Grates (J. Am. Chem. Soc. (1941) 63 , 2943-2953.

Many other manipulations will be apparent to those skilled in the art in order to access other compounds of formula (I).

R ³ is defined above a compound of formula (I) compounds of formula (I) represents a group of departure is a R ³ represents a hydroxyl group as an organic base, preferably a tertiary amine, or carbonate such as triethylamine and It can be prepared by reacting with compound XL in which X represents a halogen atom in the presence of the same inorganic base. For example, a compound of formula (I) in which R ³ represents an —O—CO—R ¹¹ group, wherein R ¹¹ is as defined above may be, for example, dichloromethane in the presence of a base such as triethylamine. It can be prepared by acylating the hydroxy group in a suitable compound of formula (V) using acyl chloride R ¹¹ -CO-Cl in a suitable solvent such as. Alternatively, the compound of formula (I) wherein R ³ represents a hydroxyl group is added to the acid compound HO-L in the presence of a dehydrating agent such as dicyclohexylcarbodiimide, wherein L is as defined above and acid C = Including the O moiety). Another route to the compounds R ³ is, that R ³ represents a hydroxyl group -OM group (wherein, M is a metal ion Im) represents the compounds as defined above for salts of compounds of formula (I) It is provided by reacting with XL.

Compounds of formula (I) in which R ² and R ¹ and / or R ⁸ and R ⁷ each independently represent a substituted or unsubstituted alkoxy group may be used in basic or acidic conditions, for example, using potassium hydroxide solution in methanol. Can be prepared by ketalizing one or both carbonyls in a suitable compound of formula (V) or a similar compound of formula (I) with a suitable alcohol.

Compounds of formula (I) in which R ² and R ¹ and / or R ⁸ and R ⁷ together form a thiocarbonyl group are suitable compounds of formula (I), wherein R ² and R ¹ and R ⁸ and R ⁷ All represent 0) using a protecting group as necessary to provide Lawesson's Reagent (2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphane- 2,4-disulfide).

Compounds of formula (I) in which R ² and R ¹ and / or R ⁸ and R ⁷ together form an oxime group = N-OR ⁹ , wherein R ⁹ is as defined above, may be selected from the appropriate formula (I) Compounds, wherein R ² and R ¹ and R ⁸ and R ⁷ are all = 0, are represented by the formula R ⁹ O-NH ₂ , wherein R ⁹ is as defined above, in the presence of a base such as pyridine. It can be prepared by treatment with hydroxylamine or alkoxylamine.

The combination process of the above derivation process can be carried out to obtain the desired compound of formula (I).

A sixth aspect of the invention relates to a composition comprising a compound of formula (I) as defined above, preferably a compound of formula (II), (III) or (IV) together with one or more carriers. Such compositions may contain a single compound of the present invention or a mixture of several compounds. It is also observed that the various isomers or mixtures of isomers may have varying levels or spectra of activity, so that the compositions of the present invention may comprise individual isomers or mixtures of isomers.

The composition of the present invention typically contains from 0.001 to 95% by weight of the active ingredient of formula (I). The compositions of the present invention preferably contain from 0.001 to 25% by weight of active ingredient when they are in a form which can be used directly. However, high concentrations (eg, 95% or less) may be present in the composition to be sold as a concentrate diluted prior to use.

The compositions of the present invention can be mixed with various suitable inert carriers such as solvents, diluents and / or surface-active agents to form powders, granular solids, wettable powders, mosquito coils or other solid formulations or emulsions, emulsifying concentrates, sprays. Aerosols or other liquid formulations may be produced. Suitable solvents and diluents include aliphatic and aromatic hydrocarbons such as water, xylene or other petroleum fractions and alcohols such as ethanol. Surface-active agents can be of anionic, cationic or non-ionic type. Antioxidants or other stabilizers may also include flavoring and coloring agents. These inert carriers may be of the type and proportion commonly used in pest control compositions, which are conveniently inert to the physiological function of the plant to be treated.

Examples of carriers known to be suitable for use in compositions incorporating naphthalene-1,4-dione for use as pest control include the specifications of US 2572946, US4110473, US4970328 and JP90 / 152943 (Agro-Kanesho KK), More specifically, the carriers described in the examples are included.

In addition to these inert carriers, the compositions of the present invention may also contain one or more other active ingredients. These other active ingredients may be other compounds that exhibit pest control activity, and these compounds may have a synergistic effect with the compounds of the present invention.

The invention will be described for the purpose of explanation only with reference to the following non-limiting examples and comparative examples. Still other embodiments of the invention will be apparent to those skilled in the art in this respect.

Examples 1 to 23 relate to the preparation and properties of the compounds of formula (II) which form the first part of the first aspect of the invention; Examples 24 to 34 relate to the preparation and properties of the compounds of formula (III) which form the second part of the first aspect of the invention, and Examples 35 to 50 are seen in conjunction with the examples of compounds of formula (II) The preparation and properties of the compound of formula (IV) forming the third part of the first aspect of the invention, Example 46 is for comparison. Examples 51-53 illustrate the preparation of intermediate compounds of formula (V) wherein n is at least one. Table 14 relates comparative data for compounds wherein the 3-substituent is straight alkyl. Starting materials were purchased from Aldrich Chemical Company.

Example 1

Preparation of 2- (1,1-dimethylpropyl) -3-hydroxynaphthalene-1,4-dione

Formula I: n and m = 0; R ¹ + R ² and R ⁷ + R ⁸ both represent = O, R ³ = -OH; -CR ⁴ R ⁵ -=-C (CH ₃ ) _2- ; R ⁶ = -C ₂ H ₅ )

(a) Preparation of 2- (3-methylbut-2-enyloxy) -naphthalene-1,4-dione

To a stirred solution of 2-hydroxynaphthalene-1,4-dione (10.0 g, 57.4 mmol) and triphenylphosphine (15.1 g, 57.4 mmol) in dry tetrahydrofuran (150 ml) was diluted with diethyl azodicarboxylate ( 10.0 g, 57.4 mmol) was added at 0 ° C. under nitrogen atmosphere. After stirring for an additional 5 minutes, a solution of 3-methylbut-2-enol (7.42 g, 86.1 mmol) in dry tetrahydrofuran (10 ml) was added dropwise and stirred for 2 hours. The precipitate was recovered, air-dried and recrystallized from aqueous methanol to give 2- (3-methylbut-2-enyloxy) naphthalene-1,4-dione (8.3 g) as a yellow crystalline solid. m.p .: 138 ° C.

(b) Preparation of 2- (1,1-dimethylprop-2-enyl) -3-hydroxy-naphthalene-1,4-dione

A solution of 2- (3-methylbut-2-enyloxy) naphthalene-1,4-dione (4.27 g, 24.8 mmol) obtained in (a) in dry ethanol (125 ml) was refluxed for 6 hours. The mixture was cooled and the solvent removed in vacuo. The residue was dissolved in diethyl ether and extracted with 1% (w / v) aqueous sodium hydroxide solution (6 × 25 ml). The combined basic fractions were acidified to pH 5 with 2M hydrochloric acid and extracted with diethyl ether (6 × 25 ml). The combined etheric extracts were washed successively with water (2x25 ml), saturated aqueous sodium chloride solution (25 ml) and dried over anhydrous magnesium sulfate. Filtration and evaporation of the solvent under reduced pressure followed by recrystallization from aqueous methanol gave 2 (1,1-dimethylprop-2-enyl) -3-hydroxynaphthalene-1,4-dione (4.27 g) as yellow crystalline. Obtained as a solid. m.p .: 60 ° C.

(c) Preparation of 2 (1,1-dimethylpropyl) -3-hydroxy-naphthalene-1,4-dione

2- (1,1-dimethylprop-2-enyl) -3-hydroxynaphthalene-1,4-dione (2.00 g, 8.3 mmol) obtained in (b) in anhydrous ethanol (30 ml) and 10 on charcoal A mixture of% palladium (50 mg) was stirred at room temperature (about 20 ° C.) for 1 hour under hydrogen (balloon) atmosphere. The mixture was filtered through CELITE® (acid wash, approximately 95% SiO ₂ ) and the solvent was evaporated under reduced pressure. The residue was recrystallized from methanol-gasoline to give 2- (1,1-dimethylpropyl) -3-hydroxynaphthalene-1,4-dione (1.98 g) as a yellow crystalline solid. mp: 52 ° C.

Example 2

Preparation of 2- (1,1-dimethylpropyl) -3-ethanoyloxy-naphthalene-1,4-dione

Formula I: n and m = 0; R ¹ + R ² and R ⁷ + R ⁸ both represent = O; R ³ = -O-CO-CH ₃ ; -CR ⁴ R ^5- = -C ( CH ₃ ) _2- : R ⁶ = -C ₂ H ₅ )

Pyridine (0.5) in a stirred solution of 2- (1,1-dimethylpropyl) -3-hydroxynaphthalene-1,4-dione (2.00 g; 8.2 mmol) obtained in Example 1 above in dry dichloromethane (20 ml). ml) and ethanol chloride (2.59 g) were added sequentially at 0 ° C. Then the mixture was stirred for 30 minutes, diluted with diethyl ether, washed with water, saturated sodium hydrogen carbonate solution and saturated sodium chloride solution and dried over magnesium sulfate. Filtration and evaporation of the solvent under reduced pressure followed by silica gel column chromatography gave 2- (1,1-dimethylpropyl) -3-ethanoyloxynaphthalene-1,4-dione (2.06 g) as a yellow crystalline solid. Obtained. m.p .: 53 ° C.

Example 3

Preparation of 2- (t-butyl) -3-hydroxy-naphthalene-1,4-dione

(Formula I: n and m = 0; R ¹ + R ² and R ⁷ + R ⁸ both represent = O; R ³ = -OH; -CR ⁴ R ^5- = -C (CH ₃ ) _2- : R ⁶ = -CH ₃ )

2-hydroxynaphthalene-1,4-dione (1.00 g, 5.68 mmol), pivalic acid (870 mg, 8.51 mmol) and silver nitrate (568 mg) in a mixture of acetonitrile (20 ml) and water (20 ml) at 60-65 ° C. Heated at. A solution of ammonium persulfate (1.94 g, 8.51 mmol) in water (10 ml) was added dropwise, and the mixture was heated for 1 hour. The mixture was then cooled to room temperature (about 20 ° C.), diluted with diethyl ether and extracted with 1% (w / v) aqueous sodium hydroxide solution (4 × 25 ml). The combined aqueous layers were then acidified with 2M hydrochloric acid and extracted with diethyl ether (3 × 25 ml). Thereafter, the combined ethereal extracts were washed with water and saturated sodium chloride and dried over magnesium sulfate. Filtration and evaporation of the solvent under reduced pressure and purification by silica gel column chromatography gave 2- ( t -butyl) -3-hydroxynaphthalene-1,4-dione (450 mg) as a yellow crystalline solid. mp: 89 ° C.

Examples 4-11 and 13

By a method analogous to that described in Examples 1 and 2 above, another compound according to the invention was prepared as listed in Table 1 below. In the above table, compounds are identified with reference to formula (I).

Example 12

Preparation of 2- (1,1-dimethylprop-2-enyl) -3-methoxy-naphthalene-1,4-dione

Formula I: n and m = 0; R ¹ + R ² and R ⁷ + R ⁸ both represent = O; R ³ = -OCH ₃ ; m is 0; -CR ⁴ R ^5- = -C (CH ₃ ) _2- : R ⁶ = -CH = CH ₂ )

Ether of diazomethane (2 ml) in a stirred solution of 2- (1,1-dimethylprop-2-enyl) -3-hydroxy-naphthalene-1,4-dione (50 mg, 0.21 mmol) in ether (5 ml) The aqueous solution was added at 0 ° C. under reduced pressure. After 2 hours, the solvent was removed under reduced pressure and the residue was purified by silica gel column chromatography to give the title compound (47 mg).

Example 14

Preparation of 1,1-dimethoxy-2- (1,1-dimethylprop-2-enyl) -3-hydroxynaphthalene-1,4-dione

(a) 2- (1,1-dimethylprop-2-enyl) -3-acetyloxy-naphthalene-1,4-dione.

The standard acetylation method of Example 2 was repeated for compound 1 (b) (1.00 g, 4.13 mmol) to afford the title compound.

(b) 1,1-dimethoxy-2-hydroxy-3- (1,1-dimethylprop-2-enyl) -naphthalen-4-one.

To a stirred solution of compound 14 (a) (750 mg, 2.63 mmol) in methanol (30 mL) and THF (5 mL) was added an aqueous solution of potassium hydroxide (1.0 g) in water (10 mL). After the mixture was stirred for 1 hour, the volume was reduced in half, diluted with water (20 ml) and the aqueous mixture was extracted with ether (3x20 ml). The combined ether fractions were washed successively with water (2x20ml), saturated sodium carbonate solution (3x20ml), water (2x20ml), saturated sodium chloride solution (20ml) and dried over magnesium sulfate. Filtration and evaporation of the solvent under reduced pressure and silica gel chromatography gave the title compound (173 mg).

Example 15

Preparation of 2- (1,1-dimethylprop-2-enyl) -2-hydroxy-1-methoxyimino-naphthalen-4-one.

A solution of the product of Example 1 (b) (250 mg, 1.03 mmol) and methoxyamine hydrochloride (95 mg, 1.14 mmol) in pyridine (5 ml) was stirred for 48 hours. The reaction mixture was dissolved in ether (50 ml), washed with water (2 × 10 ml), 2M hydrochloric acid (2 × 10 ml), water (2 × 10 ml), saturated sodium chloride solution (10 ml) and dried over magnesium sulfate. Filtration and evaporation of the solvent under reduced pressure and silica gel chromatography gave the title compound (56 mg).

In all examples below n and m are 0, R ⁴ = R ⁵ = CH ₃ , and R ⁷ and R ⁸ together form ═O Example number R ¹ R ² R ³ R ⁶ m.p. (° C) ^N D 4 = O -O-CO-C ₂ H ₅ -CH = CH ₂ 1.5621 5 〃 -O-CO- ⁿ C ₃ H ₇ 〃 1.5560 6 〃 -O-CO- ⁿ C ₄ H ₉ 〃 1.5436 7 〃 -O-CO- ⁿ C ₅ H ₁₁ 〃 1.6532 8 〃 -O-CO- ⁿ C ₉ H ₁₉ 〃 1.6532 9 〃 -O-CO-CH ₂ F 〃 1.5429 10 〃 -O-CO-CH (CH ₃ ) ₂ 〃 1.5390 11 〃 -O-CO-C ₆ H ₅ 〃 88-90 12 〃 -OCH ₃ 〃 65 1.6042 13 〃 -O-CH ₂ C ₆ H ₅ 〃 14 -OCH ₃ -OCH ₃ -OH 〃 67 15 = N-OCH ₃ 〃 〃 114-115 16 = O 〃 ⁿ C ₃ H ₇ 17 〃 -O-CO-C ₂ H ₅ ⁿ C ₃ H ₇ 18 〃 -OH ⁿ C ₅ H ₁₁ Note ⁿ D means sodium D line.

Example 19

Pest control activity

Pest control activity was carried out using housefly, mustard beetle. Tick and dust were assayed.

Housefly (MD) (Musca domestica)

1 μl drops of test compound dissolved in acetone in female flies were treated on the thorax. Two isotypes of 15 flies were used at each dose ratio and six dose ratios were used per compound under test. After treatment, flies were kept at 20 ° C. ± 1 ° C. and lethality after treatment was measured 24 and 48 hours after treatment. LD ₅₀ values were calculated in several μg of test compound per fly (Sawicki et al., Bulletin of the World Health Organization, 35, 893 (1966) and Sawicki et al., Entomologia and Exp.Appli 10, 253). , (1967)).

Mustard Beetle (PC) (Phaedon cochleariae Fab)

An acetone solution of 1 μl drop of test compound was applied to the abdomen of adult mustard beetle using a micro drop applicator. The mortality was measured after the treated insects were maintained for 48 hours. Two isotypes of 20 to 25 mustard beetles were used at each dose level and five dose levels were treated comparatively. LD ₅₀ values were calculated as in houseflies.

Diamond-back moth (PX) (Plutella xylostella)

The fifth insect larvae were treated with test compounds in 0.5 μl drop of acetone. Three isotypes out of 10 larvae were used at each dose and five dose ratios were used per compound under test. After treatment, the larvae were maintained at about 22 ° C. and lethality was assessed as failure of pupalization after 5 days. LD ₅₀ values were calculated for houseflies.

Tick (TU) (Tetranychus urticae)

Twenty five adult female ticks were soaked in 35 μl of test compound solution in a 1: 4 acetone-water mixture for 30 seconds. The flies were maintained at 21 ° C. ± 2 ° C. and lethality was measured 72 hours after treatment. Ticks were recorded as alive indicating repeat (non-reflux) migration of one or more mobile appendages after the cycle. Each of the three isotypes of 25 ticks was used at each dose ratio and 5 or 6 dose ratios were used per compound under test. LD ₅₀ values were calculated in ppm solution of test compounds per insect. The test was performed using a susceptible tick (GSS) supplied by Schering, AG, Berlin.

BT (Bemisia tabaci)

Acetone solution (0.100 ml) of the test compound was placed in a 10 ml glass bottle and evaporated to rotate to precipitate a membrane of the compound. Thirty adult flours were placed in glass jars, and after 60 minutes, the treated insects were transferred to an untreated cotton leaf disc kept moist on a layer of radish gel. The temperature was maintained at 25 ° C. and lethality was measured 48 hours later. Three isoforms were used at each of 5 to 7 dose levels per compound. LD ₅₀ values were calculated using a computer software package (Polo-PC, available from LeOra Software, Berkeley, Calif.) (MR Cahill and B. Hackett in Proceedings Brighton Crop Protection Conference, 1992). The test was carried out using susceptible strains (SUD-S) collected from cotton in Sudan in 1978.

The results of the test are shown in Tables 3 and 4 below. Values provided are LD ₅₀ (μg / insect) or LC ₅₀ (ppm solution of test compound) unless otherwise stated.

In all tables presented herein, the lack of detectable activity is indicated by 'NA' and no test is indicated by '-'.

Example Compound MD (LD ₅₀ ) PC (LD ₅₀ ) PX (LD ₅₀ ) TU (GSS) (LD ₅₀ ) BT (SUD-S) (LD ₅₀ ) One 10 c.10 - 39 19 2 10 c.6.0 c.10 64 4.8 3 c. 2.5 c.6.0 c.8.0 81 8 4 8.2 3.9 - 18 5.3 5 - 6.9 - 84 13 6 c.2.0- 2.1 - 27 16 7 20 c.6.0 - 53 100 8 - c.8.0 c.0.1 630 - 9 - 0.41 - 140 13.4 10 20 c.6.0 - 15 35 11 - - c.50 - 12 20 c.12.0 - - - 13 20 20 c.8.0 1000 1000 14 c.2.5 c.6.0 - c.800 - 15 - 35% ^* - - 97% ^** 16 8.8 c.10 - 91 10 17 14 NA - c100 - 18 13 c.15 - c100 10 A 20 0.36 - 64 82 ^* % Lethality at 20 μg / insect (LD ₅₀ ) ^** % lethality in 1000 ppm solution of test compound Compound A = DE 2641343 A1 as Example 1 on page 5, 2-n-dodecyl-3-ethanoyl Naphthalene-1,4-dione (Formula I: n = 0; R ¹ + R ² , and R ⁷ + R ⁸ are both = O; R ³ = -O-CO-CH ₃ ; -CR ⁴ R ^5- = -CH-; R ⁶ = ^-n C ₁₁ H ₂₃ )

Example 20

Activity against resistant mites (TU) (Tetranychus urticae)

The test of Example 16 (TU (GUSS)) was repeated using a tick system with a bismuth against bifenthrin (NYR-Bif-1000). The NYR-Bif-1000 strain was provided by Cornell University Entomology Department in New York State.

The results of this test are described in Table 3 below. The given value is LC ₅₀ (ppm solution of test compound).

Example Compound TU (NYR-Bif-1000) (LC ₅₀ ) One 84 ppm 2 83 ppm

Example 21

Activity against resistant flour (BT) (Bemisia tabaci)

The (BT (SUD-S)) test of Garui was repeated using Garuda of Resistance (Ned 7). The Ned 7 strain was collected from Hibiscus in the Netherlands in April 1993 by J.Fransen and shows high resistance to organophosphate and carbamate insecticides and insect growth regulator buprofezin.

The results of the test are listed in Table 4 below. The value provided is LC ₅₀ (ppm solution of test compound).

Compound number BT (Ned 7) (LC ₅₀ ) 5 21 A 470

Further testing with various strains of floury resistance showed that the compounds of Examples 1-15 were highly active against resistant strains.

Example 22

Aphid control activity

Activity against the resistant (R) and susceptible (S) strains of aphids ( Myzus persicae ) was evaluated using the following method.

The capture ring of the pluon was insufficiently painted inside the 4 cm length of the glass tubing (1.5 cm diameter), and square insect repellent was attached to one end of each tube with a rubber band. Subsequently, 15 wild adult adults were carefully transferred into the tube using a sable hairbrush and the tube was sealed with a second square gauze.

The tubes containing aphids were immersed in the pesticide solution for 10 seconds, dried on blotting paper, and lightly knocked over the tubes, so that the treated aphids dropped to the unsoaked ends of each tube. Handling mortality (typically 0 or very low) is recorded after 1 hour, when aphids are placed on a Chinese cabbage leaf-bed (35 mm diameter) on agar layer (25 mm deep) in a disposable plastic container (30 mm high). Was moved in and confined by applying a ring of pluon to the exposed lips of the container. The container was stored upright without ribs in a constant environmental facility maintained at 25 ° C. with continuous illumination of the room. Lethality was assessed at 24, 48 and 72 hours. Two isotypes of 15 aphids each were used at each dose ratio and 5 or 6 dose ratios per compound under test.

Testing was carried out using susceptible aphids (US1L) collected in the fields of East Anglia (UK) and very resistant aphids (794Jz) (R3 esterase, susceptible AChE) collected from greenhouses in the UK. Was performed.

The results of this test are described in Table 5 below. The value given is the% lethality corrected for the control data. Controls included test solutions free of active ingredients.

Further tests using the susceptible strains of Aphis gossipii 81-171B were also performed, with the results showing particularly useful activity for compounds of formula (IV).

Example Compound Concentration of active ingredient Control mortality 250 ppm 100 ppm 40 PPM One SR 2643 1110 03 100 2 SR 2747 317 200 00 3 SR 8787 2713 410 00

Example 23

Fungicidal activity

The bactericidal toxicity of the encoded compounds against isolates of Aspergillus niger, Pycurulari duck (= Magnaprotegrisci) and Rizoktonia sorani were tested in vitro.

Each compound was contained in 0.5 ml of solvent per 250 ml of agar into potato dextrose radish in solvent (50/50 ethanol / acetone) while the radish in the autoclave was kept molten and cooled to 50 ° C. Each compound was tested at a single concentration (100mgl ⁻¹ ).

In general, each test of the two compounds involved three control treatments: I) standard fungicides (carbendazim of 1 or 5mgl ^- 1 or prochloraz of 1mgl- ¹ ); ii) containing only ethanol / acetone; iii) no additives. Fungicides used as standards can be considered as representative commercially available active compounds.

Each bacterium was tested on three a homologous fungal colonies per plate (one colony for R. Solani) on agar in four Petri dishes per treatment. A. Niger and R. Solani were incubated at 20-25 ° C. for 4 days and P. duckwood was incubated for 7 days. Then, the degree of increase in colony diameter was measured and used to determine activity.

The results of the test are presented in Table 6 below. The value provided is the percent inhibition of growth in the colony diameter of the agar plate at the given concentration of reagent.

Example Compound fungi Activity at 100 mg l ^-1 Activity at 5 mg l ^-1 Activity at 1 mg l ^-1 One A.niger 63 2 A.niger 38 3 A.niger 61 One P.oryzae 100 2 P.oryzae 89 3 P.oryzae 100 One R.solani 95 2 R.solani 81 3 R.solani 92 Prochloraz A.niger 97.8 Carbendazim P.oryzae 99.8 14.7 Carbendazim R.solani 82.4 3.3

In addition, tests have shown that compounds of formula (I) exhibit good fungicidal activity over a broad spectrum of fungi causing disease in cereals and broadleaf crops. In particular, good activity is not only in the genus Rhizoctonia , Pyricularia and Aspergillus , but also in Erysiphe (especially Erysiphe graminis ), and Botrytis (as described above). Botrytis ) (in particular Botrytis fabae and Botrytis cinerea ) have been observed.

Example 24

Preparation of 2-hydroxy-3- (1'-methylcyclopentyl) -naphthalene-1,4-dione.

(Formula III: n = 0; m = 0; R ¹ + R ² and R ⁷ + R ⁸ both represent = 0; R ³ = -OH; -CR ⁴ R ^5- = cyclopentyl; R ⁶ = -CH ₃ )

To a stirred solution of diisopropylamine (3.95 g, 39.0 mmol) in dry THF (50 ml) was added n-butyllithium (2.5 M, 11.7 ml, 29.3 mmol) at −78 ° C. under nitrogen atmosphere. After the mixture was stirred for 10 minutes, methyl cyclopentanecarboxylate (Aldrich) (2.5 g, 19.5 mmol) was added dropwise. After stirring was continued for an additional 10 minutes, methyl iodide (8.31 g, 58.5 mmol) was added dropwise. The reaction mixture was stirred at −78 ° C. for an additional hour, then warmed to room temperature and stirred for an additional hour. The reaction mixture was poured onto a mixture of water and ether (1: 1, 100 ml) and acidified with dilute hydrochloric acid (2M). The aqueous solution was separated, further extracted with ether (3 × 25 ml), and the combined ether layers were washed with water (2 × 50 ml), saturated sodium chloride solution (50 ml) and dried over MgSO ₄ . Filtration and removal of the solvent under reduced pressure gave 1-methylcyclopentanecarboxylate as a colorless oil (2.38 g, bp 106 ° C. in 10 mm Hg [Kugelrohr]).

A solution of methyl ester (2.30 g) and potassium hydroxide (5.00 g) in a mixture of ethylene glycol (40 ml) and water (10 ml) was refluxed for 16 hours, then cooled to room temperature, diluted with ether and the aqueous layer was Isolate, acidify with dilute hydrochloric acid (2M) and extract with ether (2 × 25 ml). The combined ether layers were washed with water (2 × 25 ml), then with saturated sodium chloride solution (25 ml) and dried over MgSO ₄ . Filtration and evaporation gave 1-methylcyclopentanecarboxylic acid (1.69 g).

50% excess of the acid was added to a stirred solution of 2-hydroxynaphthalene-1,4-dione (1.00 g, 5.7 mmol) and silver nitrate (600 mg) in a mixture of acetonitrile (20 ml) and water (20 ml) at 65 ° C. And a solution of ammonium persulfate (1.96 g, 8.6 mmol) in water (10 ml) were added slowly to the solution over 15 minutes. The mixture was heated for an additional hour, then cooled to room temperature (about 20 ° C.) and diluted with diethyl ether (50 ml). The organic phase was separated and washed successively with water, dilute aqueous sodium hydrogen carbonate solution, water and saturated sodium chloride solution and then dried over magnesium sulfate as described in Example 3. After filtration and evaporation of the solvent under reduced pressure, silica gel column chromatography using 2: 1 gasoline: diethyl ether as eluent gave 2-hydroxy-3- (1-methylcyclopentyl) naphthalene-1,4-dione (mp 116-118 ° C.) was obtained.

Example 25

Preparation of 2-hydroxy-3- (1'-methylcyclohexyl) -naphthalene-1,4-dione

(Formula III: n = 0; m = 0; R ¹ + R ² and R ⁷ + R ⁸ both represent = 0; R ³ = -OH; -CR ⁴ R ^5- = cyclohexyl; R ⁶ = -CH ₃ )

2-hydroxy-naphthalene-1,4-dione (1.00 g, 5.7 mmol), 1-methylcyclohexanecarboxylic acid (1.22 g, 8.6 in a mixture of acetonitrile (20 ml) and water (20 ml) at 65 ° C. mmol) and silver nitrate (600 mg) were added slowly over 15 minutes with a solution of ammonium persulfate (1.96 g, 8.6 mmol) in water (10 ml). The mixture was heated for an additional hour, then cooled to room temperature (about 20 ° C.) and diluted with diethyl ether (50 ml). The organic phase was separated and washed with water, dilute aqueous sodium hydrogen carbonate solution, water and saturated sodium chloride solution and then dried over magnesium sulfate. After filtration and evaporation of the solvent under reduced pressure, silica gel column chromatography using 2: 1 gasoline: diethyl ether as eluent gave 2-hydroxy-3- (1-methylcyclohexyl) naphthalene-1,4- Dione (296 mg) was obtained as a yellow crystalline compound. m.p .: 79 ° C.

Example 26

Preparation of 2- (1'-ethylcyclohexyl) -3-hydroxy-naphthalene-1,4-dione

The title compound was prepared by hydrogenating the compound of Example 27 provided as described below using a Pd / C catalyst in ethanol (mp 56 ° C.) using the method of Example 1c.

Example 27

Preparation of 2- (1'-ethylenecyclohexyl) -3-hydroxy-naphthalene-1,4-dione

(Formula III: n = 0; m = 0; R ¹ + R ² and R ⁷ + R ⁸ both represent = 0; R ³ = -OH; -CR ⁴ R ^5- = cyclohexyl; R ⁶ = -CH = CH ₂ )

Lithium to a stirred solution of ethylcyclohexylidene acetate (see Wadsvorth and Emmons in Org. Synth.Coll.Vol 5 547) (3.00 g, 17.8 mmol) in dry ether (50 ml) at 0 ° C. under nitrogen atmosphere. Aluminum hydride (407 mg, 10.7 mmol) is added in portions and the mixture is stirred for 2 hours and then quenched with dilute hydrochloric acid (2M; 20 ml). The mixture was filtered, the aqueous layer was separated and further extracted with ether (2x25ml), and the combined ether layers were washed with water (2x25ml) and saturated sodium chloride solution (25ml) and then dried over MgSO ₄ . Filtration and evaporation of the solvent and distillation of the residue gave 2-cyclohexylidene ethanol (2.16 g, bp at 112 mmHg [Kugelrohr]. 112 ° C.).

Diethyl in THF (2 ml) to a stirred solution of 2-hydroxy-naphthalene-1,4-dione (2.50 g, 14.4 mmol) and triphenylphosphine (3.79 g, 14.4 mmol) in dry THF (50 ml) under nitrogen A solution of azodicarboxylate (2.50 g, 14.4 mmol) was added dropwise. After the mixture was stirred for 5 minutes, cyclohexylidene ethanol (2.00 g, 15.8 mmol) in THF (2 ml) was added dropwise. The mixture was stirred for 2 hours to raise the temperature to room temperature, then diluted with ether (100 ml) and washed with 1% sodium hydroxide solution (5x25 ml), water (2x25 ml) and saturated sodium chloride solution (25 ml) and on MgSO ₄ Dried. Filtration and evaporation of the solvent gave a brown residue which was dissolved in ethanol (50 ml) and refluxed for 6 hours. The mixture was cooled down, concentrated to half the volume and diluted with ether (100 ml). The ethereal solution is extracted with 1% sodium hydroxide solution (6x25ml), the combined basic fractions are acidified (2M hydrochloric acid), extracted with ether (6x25ml) and the combined ether layers are water (2x25ml) and saturated sodium chloride solution. (25 ml) and dried over MgSO ₄ . Filtration and evaporation of the solvent and silica gel column chromatography gave the title compound as a yellow crystalline compound (153 mg; mp 112-113 ° C.).

Example 28

Preparation of 2-hydroxy-3- (1'-trifluoromethylcyclohexyl) -naphthalene-1,4-dione

(Formula III: n = 0; m = 0; R ¹ + R ² and R ⁷ + R ⁸ both represent = 0; R ³ = -OH; -CR ⁴ R ^5- = cyclohexyl; R ⁶ = -CF ₃ ).

Trifluoromethylacrylic acid (1.5 g: 10.7 mmol), butadiene sulfone (1.27 g: 10.7 mmol) and hydroxyquinone (15 mg) were placed in a pressure vessel bomb (pressure at completion of approximately 3 bar) at 160 ° C. for 2 hours 30 minutes. Heated. Then the mixture was cooled down, dissolved in diethyl ether and extracted with 2M sodium hydroxide (3 × 25 ml). The combined basic fractions were acidified with 2M HCl and extracted with diethyl ether (5 × 25 ml). The combined ether fractions were washed with water, washed with sodium chloride solution, dried over magnesium sulfate, filtered and the solvent removed to give a brownish solid (1.267 g). The crude product was purified on a silica column using 1: 1 petroleum ether / diethyl ether eluent to afford 927 mg of product 1-trifluoromethylcyclohexyl-3-enecarboxylic acid. The compound was hydrogenated by the method of Example 1 (c) to afford 1-trifluoromethylcyclohexanecarboxylic acid.

2-benzoyloxy-naphthalene-1,4-dione (355 mg: 1.27 mmol), 1-trifluoromethylcyclohexane carboxylic acid (250 mg: 1.27 mmol) and silver nitrate (1.08 mg: 0.64 mmol) were added to acetonitrile (5 ml). ) And water (3 ml) at 65-70 ° C. A solution of ammonium persulfate (436 mg: 1.91 mmol) in water (1 ml) was added dropwise, and the mixture was heated for 1 hour. The reaction mixture was cooled down, diluted with water (20 ml) and extracted with ether (3 × 20 ml). The combined ether layers were dried over magnesium sulfate and evaporated to dryness.

The resulting ester was dissolved in a mixture of THF (20 ml) and 2M aqueous KOH (10 ml) and hydrolyzed by stirring at room temperature for 2 hours. The mixture was diluted with water (20 ml), washed with ether (2 × 20 ml), acidified with 2M HCl and extracted with ether (3 × 20 ml). The combined ether extracts were washed with water, dried over magnesium sulfate and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography to give the product (m. P. 114 ° C).

Example 29

Preparation of 2-hydroxy-3- (1'-methylcycloheptyl) -naphthalene-1,4-dione

Formula III: n = 0; m = 0; R ¹ + R ² and R ⁷ + R ⁸ both represent = 0; R ³ = -OH; -CR ⁴ R ^5- = cycloheptyl; R ⁶ = -CH ₃ )

To a stirred solution of diisopropylamine (7.47 g, 73.8 mmol) in dry THF at −78 ° C. and nitrogen was added n-butyllithium (2.5 M, 29.5 ml, 73.8 mmol). After the mixture was stirred for 10 minutes, cycloheptancarboxylic acid (2.10 g, 14.8 mmol) was added dropwise and the reaction was stirred at −78 ° C. for an additional 10 minutes to reflux for an additional 2 hours. The reaction was cooled to 0 ° C. and methyl iodide (5.76 g, 40.6 ml) was added dropwise, then refluxed for an additional hour and cooled to room temperature. The reaction mixture was poured onto a mixture of water / ether (100 ml / 50 ml), the aqueous layer was separated, acidified with dilute hydrochloric acid (2M) and extracted with ether (5 × 25 ml). The combined ether layers were washed with water (2x50ml) and saturated sodium chloride solution (50ml) and then dried over MgSO ₄ . Filtration and evaporation of the solvent under reduced pressure gave 1-methylcycloheptancarboxylic acid (2.20 g, mp 46 ° C.) which was recrystallized from hexane. The title compound was produced by the method of Example 24 using this acid instead of 1-methylcyclopentanecarboxylic acid.

Examples 30 and 31

Additional compounds of the second group of the first aspect of the invention were synthesized by methods similar to those of Examples 24-29, and Tables 9 and 10 below are shown as Examples 30 and 31, which contain physical data and Activity data is described.

Example 33

Preparation of 2-acetoxy-3-((1'-methylcyclohexyl) -methyl) -naphthalene-1,4-dione.

2-acetoxy-naphthalene-1,4-dione (1.12 g; 5.18 mmol), (1-methylcyclohexyl) acetic acid (Amsterdamsky et al.) In acetonitrile (15 ml) and water (20 ml) heated at 65-70 ° C. Ammonium persulfate (1.77 g, in water (10 ml) in a stirred solution of Bull. Soc. Chim. Fr (1975) 3-4 part 2, 635-643) and silver nitrate (520 mg). 7.77 mmol) in an aqueous solution. After heating for 1 hour, the mixture was cooled, diluted with water (50 ml) and extracted with ether (3 × 40 ml). The combined ether fractions were washed with water (3x25ml), saturated sodium chloride solution (25ml) and dried over magnesium sulfate. Filtration and evaporation of the solvent under reduced pressure and silica gel chromatography gave the title compound as a yellow solid (736 mg).

Examples 32 and 34

2-hydroxy-3-((1'methylcyclohexyl) -methyl) -naphthalene-1,4-dione (Example 32) and 1.1-dimethoxy-2-hydroxy-3-((1'-methyl Preparation of cyclohexyl) -methyl) -naphthalene-1,4-dione (Example 34).

To compound of Example 33 (750 mg; 2.3 mmol) in a mixture of THF / methanol (1: 1, 30 ml) was added to a stirred solution an aqueous solution of potassium hydroxide (6.45 mg; 11.5 mmol) in water (8 ml) at room temperature. And the reaction was stirred for 2 hours. The mixture was diluted with water (100 ml), washed with ether (20 ml), acidified with 2M hydrochloric acid and extracted with ether (3 × 25 ml). The combined ether layers were washed with water (2x20ml), saturated sodium chloride solution (20ml) and dried over magnesium sulfate. Filtration and evaporation of the solvent under reduced pressure and silica gel column chromatography gave the compounds of Examples 32 and 34 in two bands.

Pest control activity was assessed for housefly, mustard beetle, mites, aphids, and flours using the method of Examples 19-22. All lines were susceptible unless otherwise noted; Further testing with resistant strains showed that many of the compounds of formula (III) are highly active against the resistant strain.

The flour activity test for (BT (SUD-S)) was repeated using flour of the resistant strain (Ned 1/2). The Ned 1/2 strain is a complex collection collected in 1992 in the Netherlands from Gerbera and Bouvardia by ICI Netherlands, which includes pyredoid insecticides such as cypermethrin, organic phosphates and High resistance to carbamate insecticide and insect growth regulator buprofezin.

The results of these tests are described in Table 7 below. The given value is LC ₅₀ (ppm solution of test compound).

Example Compound BT (Ned 1/2) (LC ₅₀ ) 25 Compound B 0.110 Compound B = Table 1 of DE3801743 A1 which is Example 1, 2-hydroxy-3- (4-t-butylcyclohexyl) -naphthalene-1,4-dione

The method of Example 22 was repeated using the preferred compound of formula III, the results are shown in Table 8.

Example Compound Aphid lineage Concentration of active ingredient Control mortality 250 ppm 100 ppm 40 PPM 25 SR 6779 2327 710 00

A compound of formula (III), wherein R ² and R ¹ are ═O, R ⁸ and R ⁷ are ═O; n = 0 and m = 1 unless stated otherwise Example Compound R ³ m A R ⁴ R ⁵ R ⁶ Etc m.p. 24 -OH 0 - Cyclopentyl -CH ₃ 117-118 ℃ 25 -OH 0 - Cyclohexyl -CH ₃ 79 ℃ 26 -OH 0 - Cyclohexyl -CH ₂ -CH ₃ 56 ℃ 27 -OH 0 - Cyclohexyl -CH = CH ₂ 112-113 ℃ 28 -OH 0 - Cyclohexyl -CF ₃ 114 ℃ 29 -OH 0 - Cycloheptyl -CH ₃ 68 ℃ 30 -OH 0 - Cyclopentyl -CH = CH ₂ 92-94 ℃ 31 -OH 0 - Cyclohex-2-enyl -CH ₃ 89-90 ℃ 32 -OH One -CH _2- Cyclohexyl -CH ₃ 114 ℃ 33 -OAc One -CH _2- Cyclohexyl -CH ₃ 114 ℃ 34 -OH One -CH _2- Cyclohexyl -CH ₃ R1, R2 = OMe 136-138 ℃

Activity of the compounds of Examples 24 to 33 against insects and tick pests Example Compound PCLD ₅₀ (μg / insect) MDLD ₅₀ (μg / insect) MP% 100% mortality TULD ₅₀ (μg / insect) BTLD ₅₀ (μg / insect) 24 - NA 44 48 33 25 5 1.9 22 28 0.1 26 2.9 13 NA 100 2.9 27 4.7 6.0 NA c80 0.9 28 - 14 5 40 24 30 20 15 NA 6 c50 31 5 6 5 c50 4.7 32 2 3.6 50 2.9 3.6 33 2.8 5.7 30 2.3 5.1

Example 1, Table 1 (2-hydroxy-3- (4- t -butylcyclohexyl) -naphthalene-1,4-dione (Formula II: n = 0) of DE 3801743 A1, which is a conventional compound by comparison; m = 0; R ¹ + R ² and R ⁷ + R ⁸ both represent = O; R ³ = -OH; -CR ⁴ R ^5- = 4- t -butylcyclohexyl; but R ⁶ = H then (Not included in Formula I or II)) were tested against the same pest, and MD LD _{50 of} 15.5, PC LD _{50 of} 0.53, TU (GSS) LC ₅₀ of 44 and BT (SUD-S) LC ₅₀ of 18 Indicated.

Fungal toxicity of the encoded compounds to isolates of Aspergillus niger , Pyricularia oryzae ( = Magnaporthe grisea ) and Rhizoctonia solani was tested in vitro by the method described in Example 23 using the preferred compounds of formula (III).

The results of these tests are described in Table 11 below. The value given is% growth inhibition of colony diameter in agar plate.

Example Compound fungi Activity at 100 mg 1 ^-1 Activity at 5mg 1 ^-1 Activity at 1 mg 1 ^-1 25 A.niger 45 25 P.oryzae 94 25 R.solani 93 Prochloraz A.niger 97.8 Carbendazim P.oryzae 99.8 14.7 Carbendazim R.solani 82.4 3.3

In addition, the test shows good fungicidal activity against a broad spectrum of fungi in which compounds of formula III cause disease in both cereal and broadleaf crops. In particular, good activity has been observed for fungi of the genus Erysiphe , in particular Erysiphe graminis , and Botrytis , in particular Botrytis fabae and Botrytis cinerea , as well as Rhizoctonia, Pyricularia and Aspergillus , as described above.

Example 35

Preparation of 2- (2,2-dimethylpropyl) -3-hydroxy-naphthalene-1,4-dione

The compound was prepared by the method as described in Examples 1-15. Lawson (0.15 g), 3,3-dimethylbutyric acid (0.15 g), and silver nitrate (0.15 g) were heated to 60-65 ° C. in a mixture of acetonitrile (5 ml) and water (5 ml). A solution of ammonium persulfate (0.3 g) in water (5 ml) was added dropwise and the mixture was heated for 1 h and then treated as in Example 3 to afford the title compound. The crude product was purified on silica gel column using 20% diethyl ether eluent in petroleum ether and recrystallized from petroleum ether to afford 38 mg of the title compound.

Example 36

Preparation of 2- (3,3-dimethylbutyl) -3-hydroxy-naphthalene-1,4-dione

Sodium hydroxide solution (1M; 100 ml) was added 2-ethanoyloxy-3- (3,3-dimethylbutyl) -naphthalene-1,4-dione (3.5 g) in THF (100 ml) at room temperature (see Example 44 ) And stirred for 4 hours. THF was removed under vacuum and the resulting solution was washed with diethyl ether (× 3). The aqueous layer was then acidified and extracted with diethyl ether (x3), the combined extracts were extracted with water, dried over magnesium sulfate and evaporated to dryness in vacuo to afford 3 g of the title compound.

Example 37

Preparation of 2- (4,4-dimethylpentyl) -3-hydroxy-naphthalene-1,4-dione

3,3-dimethyl butan-1-ol (1.3 g) was stirred in pyridinium chlorochloromate (5.5 g) and dichloromethane (30 ml) at room temperature for 2 hours, diluted with ether and filtered. Wittich Reagent Ph ₃ P = CH—CO ₂ C ₂ H ₅ (Carboethoxymethylenetriphenylphosphoran) (3.6 g) was added to the filtrate and stirred overnight. The mixture was evaporated in vacuo and the residue was purified by silica gel chromatography to yield 1.25 g of ethyl 5,5-dimethylhex-2-enoate.

The product is dissolved in a mixture of THF (20 ml) and 2M potassium hydroxide (10 ml), stirred at room temperature for 2 hours, diluted with water, washed with ether (2x30 ml), the aqueous layer is acidified and ether (2x30 ml). Extracted. The combined extracts were washed with water, dried over magnesium sulfate and the solvent was evaporated to give 5,5-dimethylhex-2-enoic acid.

This acid is reacted with benzoyloxynaphthalene-1,4-dione and hydrolyzed by the method of Example 28 to give 2- (4,4-dimethylpent-1enyl) -3-hydroxy-naphthalene-1,4 -Dione was obtained. The product thus obtained was hydrogenated by the method of Example 1 (c) to afford the title compound (406 mg).

Example 38

Preparation of 2- (5,5-dimethylhexyl) -3-hydroxy-naphthalene-1,4-dione

2- (5,5-dimethylhex-2-enyl) -3-hydroxynaphthalene-1,4-dione (391 mg) prepared in Example 45 was dissolved in ethyl acetate (15 ml), and hydrogen and 100 mg of Pd / Hydrogenation with C catalyst as in Example 1 (c) afforded 371 mg of the title compound.

Examples 39-41

Preparation of similar 2- (6,6-dimethylheptyl), 2- (7,7-dimethyloctyl) and 2- (8,8-dimethylnonyl) compounds using PtO ₂ in methanol instead of Pd / C The hydrogenation as described in Example 1 (c) was carried out using commercially available starting materials by methods analogous to those of Example 48.

Example 42

Preparation of 2- (3,3-dimethyl-but-1-enyl) -3-hydroxy-naphthalene-1,4-dione

Lawson (2-hydroxynaphthalene-1,4-dione) (1.4 g) and 3,3-dimethyl-butanal (1.0 g) were dissolved in 20 ml THF at room temperature and 795 μl of pyrrolidone was added. Was stirred for an additional 20 minutes. The solvent was removed in vacuo and the residue was dissolved in benzene (40 ml) before p-toluenesulfonic acid (2.3 g) was added. The mixture was refluxed for 1 h, then cooled with ether, then the organic phase was washed with sodium bicarbonate solution, then washed once with dilute HCl, once with water and dried under vacuum. The product was purified by chromatography using 10% EtOAc / petroleum ether eluent and then crystallized from methanol to give 260 mg; m.p. 126-128 ° C.

Example 43

Preparation of 2- (6,6-dimethylhep-4-enyl) -3-hydroxy-naphthalene-1,4-dione

2- (7,7-dimethyloct-5-enyl) -3-hydroxynaphthalene-1,4-dione (0.1 g) in degassed dioxane (1 ml) (see Example 44), 30% hydrogen peroxide ( 60 μl), a solution of aqueous sodium carbonate (36 mg in 1 ml) was heated for 40 minutes under nitrogen until the solution became colorless. 20% aqueous copper sulfate (II) sulfate (30 μl) is added; when bubbling stops, 25% aqueous sodium hydroxide (0.6 ml) and 20% aqueous copper sulfate (II) sulfate (1.5 ml) are added and the mixture is 70 ° C .; Stirred for 30 min. 2 N hydrochloric acid (5 ml) was added during cooling and the product was extracted with diethyl ether (3 ×) and treated as in Example 48.

The crude product was purified by silica gel chromatography using 10% diethyl ether / gasoline as eluent to afford 50 mg of the title compound.

Example 44

Preparation of 2- (7., 7-dimethyloct-5-enyl) -3-hydroxy-naphthalene-1,4-dione

This compound was prepared using the method of Example 36 following a method analogous to the method used in Example 48 below.

Example 45

Preparation of 2- (5,5-dimethylhex-1-enyl) -3-hydroxy-naphthalene-1,4-dione

Ethyl 5,5-dimethylhexanoate (1.87 g) (prepared in Example 34 by esterification) was dissolved in 30 ml THF and lithium aluminum hydride (2 g) was added dropwise. The reaction was stirred at 0 ° C. for 2 hours, then quenched with 2 ml of 15% NaOH and 6 ml water, diluted with dichloromethane, filtered through CELITE (RTM) and the solvent evaporated to give 5,5-dimethylhexanol product (1 , 1 g) was obtained as a weak volatile liquid. The alcohol was dissolved in 30 ml dichloromethane containing pyridinium chlorochromate and stirred at room temperature to convert to the corresponding aldehyde 5,5-dimethylhexan.

Performing the method described in Example 42 using aldehyde (8.46 mmol) with Lawson (1.18 g), THF (20 ml), pyrrolidine (672 μl), benzene (40 ml) and p-toluenesulfonic acid (1.95 g) Coupling to Lawson. 391 mg of the title compound was isolated after purification.

Example 46-47

The ethanoyloxy derivatives of 3- (t-butyl) compound (Example 46; Formula (II)) and Example 36 (Example 47) were prepared by the method of Example 2.

Example 48

Alternative Preparation of 2-Ethanoyloxy-3- (3,3-dimethylbutyl) -naphthalene-1,4-dione (Example 47).

1-chloro-3,3-dimethylbutane (10 g) was added dropwise to magnesium turning (2 g) with the initial amount of iodine crystals in dry diethyl ether (100 ml) and Grignard production proceeded over 1 hour. To complete. The mixture was poured very slowly onto dry ice (50 g) and 0.5N sodium hydroxide was added, giving a basic aqueous layer and extracted with diethyl ether (x2). The basic aqueous layer was acidified, extracted with diethyl ether, dried over magnesium sulfate, filtered and then evaporated in vacuo to yield 7.2 g of 4,4-dimethyl pentanoic acid.

4,4-dimethylpentanoate (0.6 g), 2-benzyloxynaphthalene-1,4-dione (1 g) and silver nitrate (0.8 g) obtained above were stirred with acetonitrile (25 ml) and water (25 ml). Heated at 60-65 ° C. in the resulting mixture. A solution of ammonium peroxide (1.5 g) in water (10 ml) was added dropwise and the mixture was heated for one hour, then cooled to room temperature and treated as in Example 3 to yield 0.37 g of the title compound.

Example 49

Preparation of 2-Ethanoioxy-3- (10,10-dimethylundecane-7-enyl) -naphthalene-1,4-dione

8-triphenylphosphonium octanoic acid bromide salt (2.43 g) was prepared by reacting triphenyl phosphine with 8-bromooctanoic acid in xylene solvent under reflux conditions and removing the solvent. The residue was dissolved in THF (20 ml) / DMSO (2 ml) and butyllithium (2.5 M; 4 ml) in hexane (4 ml) was added dropwise at 0 ° C. After warming to room temperature over 30 minutes, 3,3-dimethylbutanal (0.5 g) in THF (5 ml) was added dropwise and the mixture was stirred at room temperature for 3 hours. Water and diluted hydrochloric acid were added and the mixture was extracted with diethyl ether (x3). Pure product 11,11-dimethyldodecane-8-enoic acid (0.4 g) was obtained after silica gel column chromatography.

This acid (0.34 g) was reacted with 2-ethanoyloxynaphthalene-1,4-dione (0.4 g) using the method of Example 47 to yield 26 mg of the title compound.

Additional compounds in the table below were synthesized using these general methods.

A compound of formula (IV), wherein R ² and R ¹ and R ⁸ and R ⁷ are ═O and n = 0, and a compound of formula II (m is O ^* ) Example Compound R ³ m A R ⁴ R ⁵ R ⁶ mp or nD 35 OH One -CH _2- CH ₃ CH ₃ CH ₃ 115-116 ℃ 36 OH One -(CH ₂ ) _2- CH ₃ CH ₃ CH ₃ 119-120 ℃ 37 OH One -(CH ₂ ) _3- CH ₃ CH ₃ CH ₃ 119 ℃ 38 OH One -(CH ₂ ) _4- CH ₃ CH ₃ CH ₃ 82-84 ℃ 39 OH One -(CH ₂ ) _5- CH ₃ CH ₃ CH ₃ 40 OH One -(CH ₂ ) _6- CH ₃ CH ₃ CH ₃ 62-63 ℃ 41 OH One -(CH ₂ ) _7- CH ₃ CH ₃ CH ₃ 42 OH One -CH = CH- CH ₃ CH ₃ CH ₃ 126-128 ℃ 43 OH One -(CH ₂ ) ₃ CH = CH- CH ₃ CH ₃ CH ₃ 79-80 ℃ 44 OH One -(CH ₂ ) ₄ CH = CH- CH ₃ CH ₃ CH ₃ 69-70 ℃ 45 OH One -CH = CH- (CH ₂ ) _2- CH ₃ CH ₃ CH ₃ 46 ^* OCOCH ₃ 0 - CH ₃ CH ₃ CH ₃ 57-58 ℃ 47 OCOCH ₃ One -(CH ₂ ) _2- CH ₃ CH ₃ CH ₃ 75-76 ℃ 49 OCOCH ₃ One -(CH ₂ ) ₆ -CH = CH-CH _2- CH ₃ CH ₃ CH ₃ 1.5286 50 OH One -(CH ₂ ) _2- CH ₃ CH ₃ CH = CH2

Pest Control Activity of Compounds of Formula (IV) Example Compound PCLD ₅₀ (μg / insect) MDLD ₅₀ (μg / insect) MP% Lethality 100 ppm TULD ₅₀ (ppm / insect) BTLD ₅₀ (ppm / insect) 35 4.6 1.2 - - c12 36 1.3 NA c24 36 c7 37 NA NA c70 2.9 16 38 c8 5.3 c100 3.5 c60 39 - c5 c100 9.6 21 40 - c5 c100 5 13 42 3.6 NA - c100 17 43 - - c100 11.5 c60 44 - c10 c100 4.3 c100 46 c15 2.3 c60 c500 NA 47 c1 2.2 c100 c20 2.1 49 c10 c18 c15 2.3 NA 50 - - - 6.5 16

Comparative Example R ¹ R ² and R ⁷ R ⁸ == 0; R ³ = OH Naphthalene3 position PCLD ₅₀ (μg / insect) MDLD ₅₀ (μg / insect) MP% Lethality 100 ppm TULD ₅₀ (ppm / insect) BTLD ₅₀ (ppm / insect) -H NA NA - NA NA -CH ₃ NA NA - NA NA -CH ₂ CH ₃ NA NA - NA NA -(CH ₂ ) ₂ CH ₃ c10 NA - c1000 80 -(CH ₂ ) ₃ CH ₃ c5 c10 - 65 13 -(CH ₂ ) ₄ CH ₃ c7 NA - 16 17 -(CH ₂ ) ₅ CH ₃ c7 c20 0 170 9.4 -(CH ₂ ) ₇ CH ₃ 0.78 1.9 - c1000 19 -(CH ₂ ) ₉ CH ₃ 1.9 NA - 5.5 100 -(CH ₂ ) ₁₀ CH ₃ c0.4 NA - 1.4 100 -(CH ₂ ) ₁₁ CH ₃ NA NA 0 60 100 -(CH ₂ ) ₁₃ CH ₃ NA NA - 1.3 NA

Examples 51-53

Synthesis of substituted naphthalene-1,4-dione at positions 5-8 on naphthalene ring

Example 51

Of 2- (t-butyl) -3-hydroxy-6-methyl-naphthalene-1,4-dione and 2- (t-butyl) -3-hydroxy-7-methyl-naphthalene-1,4-dione Produce

(a) Preparation of 6-methyl-naphthalene-1,4-dione

A solution of 1,4-benzoquinone (13.9 g, 128 mmol) and isoprene (13.1 ml, 131 mmol) was stirred in glacial acetic acid (44 ml) at room temperature for 68 hours. The mixture was diluted with water (44 ml) and refluxed for 1 hour 30 minutes. The mixture was cooled to room temperature, acetic acid (84 ml) and chromic acid [chromium trioxide in water (30 ml) (29.4 g)] were added sequentially and then refluxed for an additional 1 hour and 30 minutes. After cooling, the mixture was diluted with water (200 ml) and extracted with ether (3 × 50 ml). The combined ether fractions were washed with dilute sodium hydroxide solution (2M; 2x50ml), water (2x50ml), saturated sodium chloride solution (50ml) and dried over magnesium sulfate. Filtration and evaporation of the solvent under reduced pressure and recrystallization from petroleum ether were repeated to give the title compound (7 g).

(b) 2-amino-6 and 7-methyl-1,4-naphthalene-1,4-dione

To a stirred solution of 6-methyl naphthalene-1,4-dione (2.1 g, 12 mmol) in glacial acetic acid (60 ml) at room temperature was added a solution of sodium azide (1.58 g) in water (5 ml). The mixture was stirred for 2 days, then washed with water (200 ml), stirred for 15 minutes and filtered. The filtrate was neutralized with sodium bicarbonate and extracted with chloroform (3 × 25 ml). The combined chloroform extracts were washed with saturated sodium bicarbonate solution, brine and dried (CaSO ₄ ). Filtration and drying of the solvent under reduced pressure and silica gel chromatography gave the title compound (100 mg) as a 3: 2 mixture of isomers.

(c) 2-hydroxy-6- and -7-methyl-naphthalene-1,4-dione

The aminomethyl naphthalene-1,4-dione mixture (200 mg) from (b) was refluxed in water (20 ml) and concentrated sulfuric acid (10 ml) for 20 minutes. The cooled mixture was poured into ice / water (50 g) and extracted with ether (3 × 25 ml). The combined ether extracts were washed with water, saturated NaHCO ₃ , water, saturated NaCl solution and dried (MgSO ₄ ). Filtration and evaporation of the solvent and purification by silica gel column chromatography gave the title compound (68 mg).

(d) Preparation of 2- (t-butyl) -3-hydroxy-6 and 7-methyl-3-hydroxy-naphthalene-1,4-dione

The addition of the silver peroxide / nitrate on aminomethyl compound (64 mg, 0.34 mmol), trimethylacetic acid (52 mg, 0.51 mmol) gave the title compound as a 3: 2 mixture of isomers (12 mg).

Example 52

Preparation of 2- (t-butyl) -6 and 7-dimethyl-3-hydroxy-naphthalene-1,4-dione

Steps (a) to (d) were repeated replacing isoprene with 2,3-dimethyl-1,3-butadiene.

Example 53

Preparation of 2- (t-butyl) -3-hydroxy-5 and 8-methyl-1,4-naphthalene-1,4-dione

Steps (a) to (d) were repeated replacing isoprene with piperylene.

(a) Preparation of 6-methyl-1,4-naphthalene-1,4-dione

A solution of 1,4-benzoquinone (13.9 g, 128 mmol) and isoprene (13.1 ml, 131 mol) was stirred in glacial acetic acid (44 ml) at room temperature for 68 hours. The mixture was diluted with water (44 ml) and refluxed for 1 hour 30 minutes. The mixture was cooled to room temperature, acetic acid (84 ml) and chromic acid [chromium trioxide in water (30 ml) (29.4 g)) were added sequentially and then refluxed for an additional 1 hour and 30 minutes. After cooling, the mixture was diluted with water (200 ml) and extracted with ether (3 × 50 ml). The combined ether fractions were washed with dilute sodium hydroxide solution (2M; 2x50ml), water (2x50ml), saturated sodium chloride solution (50ml) and dried over magnesium sulfate. Filtration and evaporation of the solvent under reduced pressure and recrystallization from petroleum ether were repeated to give the title compound (7 g).

Toxicity data

In addition to the specific pesticidal and acaricide tests described above, the compounds of the present invention have been subjected to further tests on toxicity to mammals and so-called friendly species such as Chrysloperla carnea, Aleochora bilineata and Coccinella septempunctata .

The total body LD ₅₀ in mice for the compound of Example 25 (2-hydroxy-3- (1′-methylcyclohexyl) -naphthalene-1,4-dione) was found to be 2786 mg / Kg body weight, which is currently It is much safer in mammalian toxicity than many standard insecticides on the market.

LD ₅₀ values of 1000 ppm / object or more were found for several compounds tested for Chrysloperla carnea, Aleochora bilineata and Coccinella septempunctata .

Claims (50)

A compound of formula (I) or a salt thereof: (I) Where n represents an integer of 0 to 4; m represents an integer of 0 or 1; Each R is individually a halogen atom or nitro, cyano, hydroxyl, alkyl, alkenyl, haloalkyl, haloalkenyl, alkoxy, haloalkoxy, haloalkenoxy, amino, alkylamino, dialkylamino, alkoxycarbonyl , Carboxyl, alkanoyl, alkylthio, alkylsulfinyl, alkylsulfonyl, carbamoyl, alkylamido, cycloalkyl, aryl or aralkyl groups; R ¹ and R ² each independently represent = O, = S or = N-OR ⁹ , wherein R ⁹ represents a halogen atom or a substituted or unsubstituted alkyl group; R ³ represents a hydroxyl group, or a group which is converted to a -OL group, where L is a leaving group, or a -OL ¹ group in which the body is a leaving group, wherein L ¹ is a leaving group; R ⁶ represents a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy or aryloxy group; R ⁷ and R ⁸ represent individually substituted or unsubstituted alkoxy groups, or together form a = 0, = S or = N-OR ⁹ group, wherein R ⁹ is as defined above; R ⁴ and R ⁵ each independently represent a halogen atom or a substituted or unsubstituted alkyl or alkenyl group, or form a substituted or unsubstituted cycloalkyl or cycloalkenyl ring with a carbon atom between them; A is a substituted or unsubstituted straight or branched alkyl or alkenyl group, which represents an acyclic carbon chain connecting the 3-position and -CR ⁴ R ⁵ R ⁶ moiety of the naphthalene ring shown; Provided that when R ² and R ¹ , and R ⁸ and R ⁷ are = O groups, m and n are 0, R ⁴ and R ⁵ are methyl and R ⁶ is ethenyl, then R ³ is hydroxyl Or ethanoyloxy. The compound of claim 1, wherein R ¹ and R ² , and / or R ⁷ and R ⁸ are each independently a C _1-4 alkoxy group, or R ² and R ¹ and / or R ⁸ and R ⁷ together are a ═O group Forming a compound. ^3. The method according to claim 1, wherein R ³ is a -OL group (where L is a leaving group) or a group converted to a -OL ¹ group in the body, wherein the pK _a value of the acid LOH or L ¹ OH in water Compound 1 to 7, characterized in that. 4. A compound according to claim 3, wherein R ³ is a group which is converted in the body to a -OL group, where L is a leaving group, and the conversion is carried out in the plant to be protected or the pest to be controlled. 5. The compound of claim 1, wherein R ⁶ is C _1-16 alkyl, C _2-16 alkenyl, C _1-16 haloalkyl, C _2-16 haloalkenyl, C _1-16 alkanoyl A alkyl, C _1-16 alkoxyalkyl, C _1-16 alkoxy, C _1-16 haloalkoxy or C _1-16 alkoxyalkoxy group. ^6. A compound according to claim 5, wherein R ⁶ is a group having C _1-6 carbons in length. 7. Compounds according to any of claims 1 to 6, characterized in that they are naphthalene-1,4-dione. 8. The compound of claim 1, wherein R ⁴ and R ⁵ individually represent C _1-4 alkyl, C _1-4 haloalkyl, C _2-4 alkenyl, C _2-4 haloalkenyl Or together with a carbon atom between the two form a cycloalkyl or cycloalkenyl group unsubstituted or substituted by halogen, alkyl, haloalkyl, alkenyl or haloalkenyl. A compound according to any one of claims 1 to 8, having the formula (II) or a salt thereof: (II) Where R, R ¹ , R ² , R ³ , R ⁶ , R ⁷ , R ⁸ and n are as defined for formula (I), and R ⁴ and R ⁵ are halogen or substituted or unsubstituted alkyl or alkenyl groups to be. 10. The compound of claim 9 wherein n is 0; R ² and R ¹ , and R ⁸ and R ⁷ are both = 0; R ⁴ and R ⁵ each independently represent a C _1-4 alkyl or C _1-4 haloalkyl group, R ⁷⁶ represents C _1-7 alkyl, C _1-7 haloalkyl, C _1-7 alkoxyalkyl, C _{1- 7} alkoxy, C _1-7 alkoxyalkoxy, C _2-7 alkenyl, C ₂ -C ₇ haloalkenyl or C ₂ -C ₇ alkoxyalkenyl group. The compound of claim 10, wherein R ⁶ is a C _1-6 alkyl, C _1-6 haloalkyl, C ₂ alkenyl or C ₂ haloalkenyl group. 9. A compound according to claim 1, having the formula (III): (III) Where n, m, A, R, R ¹ , R ² , R ³ , R ⁶ , R ⁷ and R ⁸ are as defined for Formula (I); R ⁴ and R ⁵ together with the carbon atom in between form a substituted or unsubstituted cycloalkyl or cycloalkenyl group. 13. The compound of claim 12, wherein R ² and R ¹ and R ⁸ and R ⁷ both represent = O; n is 0; R ⁴ and R ⁵ together with the carbon atom between them form a substituted or unsubstituted fully saturated cycloalkyl ring; R ⁶ represents a C _1-16 alkyl or C _2-16 alkenyl group substituted by halogen. 14. The method of claim 13, wherein, R ⁴ and R ⁵ is a halogen, alkyl, haloalkyl, optionally substituted with alkenyl or haloalkenyl or unsubstituted C _4-8 saturated cycloalkyl ring together with the carbon atom between the two Forming a compound. 15. The compound of claim 14, wherein R ⁴ and R ⁵ together with the carbon atom between the two form a C _5-8 cycloalkyl ring substituted or unsubstituted by halogen, alkyl, haloalkyl, alkenyl or haloalkenyl; , R ⁶ is C _1-6 alkyl, C _2-6 alkenyl, C _1-6 haloalkyl or C _2-6 haloalkenyl group or halogen, and R ³ is hydroxy or acetoxy. 16. A compound according to claim 14 or 15, wherein R ⁴ and R ⁵ together with a carbon atom between them form a substituted or unsubstituted cyclohexyl ring. The compound of claim 14 or 15, wherein R ⁴ and R ⁵ together with a carbon atom between them form a substituted or unsubstituted cyclohexyl ring, and R ⁶ is halogenated C _1-2 alkyl or C ₂ egg. A compound characterized by representing a kenyl group. 18. The compound of claim 17, wherein m is zero. 18. The compound of claim 17, wherein m is 1 and A is -CH _2- . 9. A compound according to claim 1, having the formula IV. (IV) Where n, A, R, R ¹ , R ² , R ³ , R ⁶ , R ⁷ and R ⁸ are as defined for Formula (I); R ⁴ and R ⁵ each independently represent a halogen or a substituted or unsubstituted alkyl or alkenyl group. The compound of claim 20, wherein R ² and R ¹ , and R ⁸ and R ⁷ are both = 0; A is a C _3-8 alkyl or alkenyl chain which may be substituted by halogen or a side chain which may be halogenated. The compound of claim 20, wherein R ⁴ , R ⁵ and R ⁶ are individually C _1-6 alkyl, C _1-6 haloalkyl, C _2-6 alkenyl or C _2-6 haloalkenyl. 23. The compound of any one of claims 20-22, wherein A is a-(CH ₂ ) _a -group, wherein a is 1 to 7,-(CH ₂ ) _A -CH = CH- (CH ₂ ) _b- (where a and b are the sum of two from 0 to 6) or a group similar to those groups in which at least one carbon atom of these groups is substituted by alkyl, haloalkyl, alkenyl, haloalkenyl or halogen Compound. 24. The compound of claim 23, wherein a and b sum between 0 and 3. A method of using the compound of formula (I) as a pest control agent. A method according to claim 25, which is used as an insecticide, aphids and / or fungicides. 27. The method according to claim 26, which is used for mites, dusty and / or aphids. A method of using the compound of formula III as a pest control against ticks, aphids and / or dusty. A method of using the compound of formula IV as a pest control against ticks and / or aphids. A method of controlling pests in a locus, comprising treating the locus with a compound of formula (I). 31. The method of claim 30, wherein the pests are insects, ticks and / or fungi. 32. The method of claim 30 or 31, wherein the compound has formula (II), (III) or (IV). 33. The method of claim 32, wherein the locus comprises a pest itself or an environment susceptible to or attacked by the pest. The compound of formula (V) is reacted with a compound of formula (VI) to produce a compound of formula (VII), and the compound of formula (VII) is heated in a suitable solvent to achieve the Klaisen-type rearrangement. A process for preparing a compound of formula (I) wherein m is 0, comprising producing a compound of: (V) Where R and R ³ are as defined in formula (I). (VI) Where X represents a leaving group, preferably a hydroxyl group or a halogen, in particular a chlorine or bromine atom, R ¹¹¹ , R ¹²¹ and R ¹³¹ each independently represent a hydrogen atom or a substituted alkyl group, R ⁴ and R ⁵ are as defined in formula (I). (VII) Where n, R, R ¹¹¹ , R ¹²¹ , R ¹³¹ , R ⁴ and R ⁵ are as defined above. (VIII) 35. The method of claim 34, wherein X represents a hydroxyl group and the reaction is carried out under midwestern conditions. 35. The method of claim 34, wherein X represents a halogen atom and the reaction is carried out under alkylation conditions. Aldehyde A-CR ⁴ R ⁵ R ⁶ , wherein A, R ⁴ , R ⁵ and R ⁶ are as defined for Formula (I), where A is the free of the acyclic carbon chain instead of the 3-position of the naphthalene ring Of the compound of formula (I), characterized in that the product is directly reacted with a compound of formula (V) in a polar organic solvent under alkaline conditions, followed by heating the product under acidic conditions in a nonpolar solvent. Manufacturing method. Compounds of formula (V) wherein carboxylic acid CR ⁴ R ⁵ R ^6- (A) _m -COOH in the presence of a free radical initiator, wherein A, m, R ⁴ , R ⁵ and R ⁶ are A process for the preparation of a compound of formula (I) which comprises reacting with (V) Where n, R and R ³ are as defined above. The compound of formula (V) is a compound of formula X- (A) _m- CR ⁴ R ⁵ R ⁶ , wherein A, m, R ⁴ , R ⁵ and R ⁶ are represented by formula (I) and (X) And X is a leaving group which leaves in the presence of an acid to give the radical ⁺ -(A) _m -CR ⁴ R ⁵ R ⁶ ). (V) 40. The method of claim 39, wherein X is a halogen or tosyl group. 41. The method of claim 39 or 40, wherein the acid is a Lewis acid. 42. The method of claim 41, wherein the Lewis acid is aluminum chloride. A composition comprising a compound of formula (I) as defined above together with one or more carriers. 44. A composition according to claim 43, which contains from 0.001 to 95% by weight of active ingredient of formula (I). 44. A composition according to claim 43, containing from 0.001 to 25% by weight of active ingredient. A compound of formula (VII) as defined in claim 34: (VII) A compound of formula A-CR ⁴ R ⁵ R ⁶ , wherein A, m, R ⁴ , R ⁵ and R ⁶ are as defined for formula (I), (II), (III) or (IV), A has an aldehyde group at the free end of the compound). A compound of formula CR ⁴ R ⁵ R ^6- (A) _m -COOH, wherein A, m, R ⁴ , R ⁵ and R ⁶ are as defined for Formula (I). A compound of formula X- (A) _m- CR ⁴ R ⁵ R ⁶ , wherein A, m, R ⁴ , R ⁵ and R ⁶ are as defined for formula (I), and X is leaving in the presence of an acid Thereby leaving the radical ⁺ -(A) _m -CR ⁴ R ⁵ R ⁶ . 50. The compound of any of claims 47-49, wherein A, m, R ⁴ , R ⁵ and R ⁶ are according to any of claims 2-24.