RU2173049C2 - Substituted naphthalene-1,4-dins possessing pesticide properties, method of preparation thereof, utilization thereof as pesticides, pest control method involving these compounds, and pesticide composition including them - Google Patents

Abstract

FIELD: biologically active compounds. SUBSTANCE: invention provides novel substituted naphthalene-1,4-dions, which can be used as insecticides against whitefly. Compounds are depicted by general formula I:

(I), wherein n= 0, m=0, R¹ and R², taken together, form oxo group; R³ denotes hydroxyl group or group -OCOR¹¹, in which R¹¹ is C1-alkyl; R⁷ and R⁸, taken together, form oxo group; R⁴ and R⁵, independently from each other, denote hydrogen atom or methyl or, taken together with carbon atom, to which they are linked, form C4- C8-cycloalkyl ring, 4-tert-butylcyclohexyl ring, full number of carbon atoms in most long carbon chain in position 3 of naphthalene cycle not exceeding 2. EFFECT: enhanced pesticide activity. 37 cl, 6 tbl, 5 ex

Description

 The present invention relates to the use of certain 1,2,3,4-substituted naphthalene derivatives as pesticides having activity against whiteflies and certain fungi; to methods for producing these compounds; to compositions containing these compounds; as well as the use of compounds and compositions for controlling whiteflies, Lepidoptera and pests.

где R обозначает радикал, содержащий от 6 до 15 атомов углерода, и выбранный из алкильных, циклогексильных и циклогексилалкильных групп, например таких как н-алкильная, изоалкильная, алкилциклоалкильная и аралкильная группы. Каких-либо конкретных данных об акарицидной или афицидной активности этих соединений не приводится, а поэтому также отсутствуют какие-либо указания относительно того, которые из множества соединений являются наилучшими, и являются ли они действительно пригодными для борьбы не только с клещами и тлями, но и с другими вредителями.US Pat. No. 2,572,946 discloses a tick and aphid control composition comprising, as an active ingredient, a compound of general formula (P1):

where R is a radical containing from 6 to 15 carbon atoms and selected from alkyl, cyclohexyl and cyclohexylalkyl groups, for example, such as n-alkyl, isoalkyl, alkylcycloalkyl and aralkyl groups. There are no specific data on the acaricidal or aphidic activity of these compounds, and therefore there is also no indication as to which of the many compounds are the best, and whether they are really suitable for combating not only ticks and aphids, but also with other pests.

где R₁ обозначает прямую, разветвленную или циклическую C_8-14-алкильную группу; R₂ обозначает прямую или разветвленную C_1-17-алкильную, C_2-17-алкенильную, C_3-6-циклоалкильную, C_1-4-алкокси-, -CH₂OCH₃-, -CH₂OCH₂CH₃- или -CH=CH-COOH-группу; а X и Y обозначают водород, атом фтора, хлора или брома, либо метильную или метокси-группу. Указывается, что эти соединения обладают акарицидной и афицидной активностью, однако было показано, что такой активностью обладают только соединения, в которых R₁ является линейной C₈- или C_11-14-алкильной группой.In DE 2641343, in General terms, disclosed compounds of General formula (P2):

where R ₁ denotes a straight, branched or cyclic 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 — COOH group; and X and Y are hydrogen, a fluorine, chlorine or bromine atom, or a methyl or methoxy group. It is indicated that these compounds have acaricidal and acidic activity, however, it has been shown that only compounds in which R ₁ is a linear C ₈ or C _11-14 alkyl group have such activity.

где Y обозначает водород, фтор, хлор или бром; R₁₂ обозначает C_8-14-алкил с разветвленной, циклической или прямой цепью; R₂ обозначает прямой или разветвленный насыщенный C_1-12-алкил или ненасыщенный C_3-12-алкил, необязательно замещенный одним или двумя заместителями, такими как атом хлора, атом брома метокси- или этокси-группа; или C_3-6-циклоалкил.US Pat. No. 4,110,473 discloses a method of protecting plants from ticks (acarides) by treating a plant with a compound of general formula (P3):

where Y is hydrogen, fluoro, chloro or bromo; R ₁₂ is branched, cyclic or straight chain C _8-14 alkyl; R ₂ is straight or branched saturated C _1-12 alkyl or unsaturated C _3-12 alkyl optionally substituted with one or two substituents, such as a chlorine atom, a bromine atom, a methoxy or ethoxy group; or C _3-6 cycloalkyl.

GB 1553424 discloses a compound of general formula (P3), where R ₂ is H and R ₁ is optionally substituted cyclohexyl, which is intended to be used as an active agent for treating infections in cattle infected with theileriosis, and in EP 0123238 and EP 0123230 discloses similar compounds used as agents against infection with simple microorganisms and coccidiosis.

где n = 0-12; R¹ обозначает водород или необязательно замещенную алкильную, аралкильную, алкилкарбонильную, (гетеро)арилкарбонильную, алкоксикарбонильную, алкилсульфонильную или арилсульфонильную группу; a R² обозначает галогеналкильную, необязательно замещенную (гетеро)арильную или замещенную циклоалкильную группу. Указывается, что эти соединения обладают акарицидной и фунгицидной активностью.DE 3801743 A1 generally discloses compounds of general formula (P4):

where n = 0-12; R ¹ is hydrogen or an optionally substituted alkyl, aralkyl, alkylcarbonyl, (hetero) arylcarbonyl, alkoxycarbonyl, alkylsulfonyl or arylsulfonyl group; a R ² is a haloalkyl, optionally substituted (hetero) aryl or substituted cycloalkyl group. It is indicated that these compounds have acaricidal and fungicidal activity.

More specifically, 10 compounds of formula (P4) in which n = 0; R ¹ represents a hydrogen atom; a R ² is a 4- (tert-butyl) cyclohexyl, 4- (trimethylsilyl) cyclohexyl, 4- (cyclohexyl) cyclohexyl, 2-trifluoromethyl cyclohexyl or 3,5-di (trifluoromethyl) cyclohexyl group; or n = 0, R ¹ is an ethanoyl group, and R ² is a 4- (tert-butyl) cyclohexyl, 4- (cyclohexyl) cyclohexyl, 2- or 3-trifluoromethylcyclohexyl, or 3,5-di (trifluoromethyl) cyclohexyl group. Of these compounds, acaricidal activity was demonstrated for two compounds of formula (P4), where n = 0, R ¹ is a hydrogen atom, and R ² is a 4- (tert-butyl) cyclohexyl or 4- (trimethylsilyl) cyclohexyl group.

где R обозначает алкильную группу, имеющую от 1 до 10 атомов углерода; и описывается их использование в ветеринарных препаратах, в частности, для профилактики инфекций, вызываемых протозойными микроорганизмами.EP 0077550 discloses compounds of general formula (P5)

where R is an alkyl group having from 1 to 10 carbon atoms; and describes their use in veterinary drugs, in particular for the prevention of infections caused by protozoan microorganisms.

где R обозначает атом водорода или гидроксильную или этаноилокси-группу, а также описано их использование в качестве пестицидов, а в частности, в качестве фунгицидов, инсектицидов и/или акарицидов. Ранее эти соединения были описаны как растительные метаболиты (см., Chamy et al., (1993) Bol. Soc. Chil. Quim. 38, 187-190).In the simultaneously pending international application N PCT / GB 95/00953 natural compounds of the general formula (P6) are described:

where R denotes a hydrogen atom or a hydroxyl or ethanoyloxy group, and their use as pesticides, and in particular as fungicides, insecticides and / or acaricides, is also described. Previously, these compounds have been described as plant metabolites (see, Chamy et al., (1993) Bol. Soc. Chil. Quim. 38, 187-190).

где R₁ обозначает прямую, разветвленную или циклическую C_8-14алкильную группу, a R₂ обозначает прямую или разветвленную C_1-6-алкильную группу или C_3-6-циклоалкильную группу. Было показано, что эти соединения обладают акарицидной и афицидной активностью, однако, при этом, было показано, что такой активностью обладают лишь соединения, где R₁ является линейной C₁₁ или C₁₂-алкильной группой.DE 2520793 A1 generally describes compounds of the general formula (P7):

wherein R ₁ is a straight, branched or cyclic C _8-14 alkyl group, and R ₂ is a straight or branched C _1-6 alkyl group or a C _3-6 cycloalkyl group. It was shown that these compounds have acaricidal and acidic activity, however, it was shown that only compounds where R ₁ is a linear C ₁₁ or C ₁₂ alkyl group have such activity.

где R¹ обозначает замещенную или незамещенную C_3-12 циклоалкильную группу. Указывается, что эти соединения обладают активностью против Theileria у крупного рогатого скота и овец, однако было показано, что такой активностью обладает лишь соединение, в котором R¹ является циклогептилом.EP 0002228 generally discloses compounds of general formula (P8):

where R ¹ denotes a substituted or unsubstituted C _3-12 cycloalkyl group. These compounds are indicated to be active against Theileria in cattle and sheep, however, it has been shown that only the compound in which R ¹ is cycloheptyl has been shown to have such activity.

 Fieser et al., As well as other collaborators, have disclosed various 2-hydroxy or 2-alkoxy-3-substituted naphthalene-1,4-dione compounds that can be used to treat malaria (see, for example, US 2553647, US 3578685 and JACS (1948) Vol. 70, pp. 3156-3165), or as antitumor agents (see, FP 2085660). These compounds include a number of 3-isoalkyl-substituted compounds. US Pat. No. 2,398,418 (Fieser) describes a process for preparing 2,3-disubstituted naphthalene-1,4-dione compounds from the corresponding 2-substituted compound.

 The authors of the present invention found that many of the previously disclosed naphthoquinones do not have high activity against whiteflies, and in particular, it was found that most of the acidic and acaricidal compounds specifically disclosed in previous studies did not show the expected effectiveness when tested against resistant and susceptible types of whiteflies.

 It has now been found by the present inventors that some synthetic naphthoquinones and related 1,4-derivatized compounds have higher pesticidal activity than previously disclosed compounds for use as pesticides, and especially for controlling whiteflies. Preferred compounds of the present invention have excellent pesticidal activity against, inter alia, whiteflies and / or fungi, and most preferred compounds also have good activity against ticks and / or aphids. The compounds described in the present invention can, in particular, be used against strains of whitefly and fungi that have developed resistance to one or more commercially available pesticides, currently widely used.

или его соли в качестве пестицида против белокрылки, Lepidoptera и/или грибков-вредителей,
где n представляет целое число от 0 до 4;
m представляет целое число 0 или 1;
каждый из R независимо представляет атом галогена или нитро-, циано-, гидроксильную, алкильную, алкенильную, галогеналкильную, галогеналкенильную, алкокси-, галогеналкокси-, галогеналкенокси-, амино-, алкиламино-диалкиламино-, алкоксикарбонильную, карбоксильную, алканоильную, алкилтио-, алкилсульфинильную, алкилсульфонильную, карбамоильную, алкиламидо-, циклоалкильную, арильную или аралкильную группу,
каждый из R¹ и R² независимо представляет необязательно замещенную алкокси-группу, либо взятые вместе R₁ и R₂ представляют группу =O, =S или = N-OR⁹, где R⁹ обозначает атом водорода или необязательно замещенную алкильную группу;
R³ представляет гидроксильную группу или группу -OL, где L обозначает уходящую группу, или группу, которая in vivo трансформируется в группу -OL¹, где L¹ обозначает уходящую группу;
R⁷ и R⁸ независимо представляют необязательно замещенную алкокси-группу, либо взятые вместе, они представляют группу =O, =S или =N-OR⁹, где R⁹ является таким, как он был определен выше;
R⁴ и R⁵ независимо представляют атом водорода или галогена; необязательно замещенную алкильную или алкенильную группу; либо взятые вместе с атомом углерода, находящимся между ними, R⁴ и R⁵ образуют необязательно замещенное C_4-8-циклоалкильное или циклоалкенильное кольцо; а A представляет прямую или разветвленную алкильную или алкенильную группу, которая является необязательно замещенной, предпочтительно, галогеном, и ациклическая углеродная цепь которой связана с нафталиновым кольцом в 3-положении и с группой -CHR⁴R⁵; причем в этой цепи A не является четвертичным атомом углерода, а общее число атомов углерода в самой длинной углеродной цепи, идущей от 3-положения указанного нафталинового кольца составляет не более 8.In a first aspect, the present invention relates to the use of a compound of general formula (I):

or its salt as a pesticide against whiteflies, Lepidoptera and / or pests,
where n represents an integer from 0 to 4;
m represents an integer of 0 or 1;
each of R independently represents a halogen atom or nitro, cyano, hydroxyl, alkyl, alkenyl, haloalkyl, haloalkenyl, alkoxy, haloalkoxy, haloalkeno, amino, alkylamino dialkylamino, alkoxycarbonyl, carboxyl, alkanoyl, alkylsulfinyl, alkylsulfonyl, carbamoyl, alkylamido, cycloalkyl, aryl or aralkyl groups,
each of R ¹ and R ² independently represents an optionally substituted alkoxy group, or taken together R ₁ and R ₂ represent a group = O, = S or = N-OR ⁹ , where R ⁹ represents a hydrogen atom or an optionally substituted alkyl group;
R ³ represents a hydroxyl group or an -OL group, where L is a leaving group, or a group that is transformed in vivo into an -OL ¹ group, where L ¹ is a leaving group;
R ⁷ and R ⁸ independently represent an optionally substituted alkoxy group, or taken together, they represent a group = O, = S or = N-OR ⁹ , where R ⁹ is as defined above;
R ⁴ and R ⁵ independently represent a hydrogen or halogen atom; an optionally substituted alkyl or alkenyl group; or taken together with the carbon atom between them, R ⁴ and R ⁵ form an optionally substituted C _4-8 cycloalkyl or cycloalkenyl ring; and A represents a straight or branched alkyl or alkenyl group which is optionally substituted, preferably by halogen, and whose acyclic carbon chain is attached to the naphthalene ring at the 3-position and to the —CHR ⁴ R ⁵ group; moreover, in this chain A is not a Quaternary carbon atom, and the total number of carbon atoms in the longest carbon chain extending from the 3-position of said naphthalene ring is not more than 8.

It is preferable that the total number of carbon atoms in the longest chain from the 3-position of the naphthalene ring is from 4 to 8, and more preferably from 5 to 7. If the number of carbon atoms is limited to 1 or 2, then such a compound loses its activity against whiteflies, however, its fungicidal activity remains quite high. If -CHR ⁴ R ⁵ forms a carbocyclic ring, it is preferable that this group be directly attached to naphthalene at the 3-position, since an increase in the number of carbon atoms between the naphthalene ring and the carboxyl ring leads to a decrease in anti-whitefly activity.

 The compounds described above are preferably used against whiteflies, especially against the species Bemisia, and / or against fungi, especially against the species Rhizoctonia, Aspergillus and Pyricularia, for example, R. solani, P.oryzae and A. niger, which have developed resistance to one or several commercial preparations not related to naphthoquinone pesticides, and it is most preferable to use these compounds against whiteflies of the species Bemisia tabaci strains such as Ned 1/2, Ned 7, and Pak, and the authors of the present invention it was found that these types of whiteflies especially in susceptible to the pesticidal action of the compounds described in this application, compared, for example, with compounds specifically tested in US 2572946, US 4110473 and DE 2641343. Although DE 38001743 mentions some of the compounds used per se in the present invention, and indicates that these compounds can be used against many species of insects and fungi, however, the above work does not provide any indications regarding the predominant use of these compounds for controlling whiteflies.

 If the compound of formula I contains a group defined as an alkyl, alkenyl or alkynyl substituent group (unless otherwise specified), this group may be linear or branched, and may contain up to 12, preferably up to 4, and more preferably up to 4 carbon atoms . A cycloalkyl or cycloalkenyl group may contain from 3 to 10, and most preferably from 5 to 8 carbon atoms. The aryl group may be any aromatic hydrocarbon group, and especially a phenyl or naphthyl group. An aralkyl group may be any alkyl group as defined above that is substituted by an aryl group as defined above, in particular a benzyl group; or an aryl group substituted with an alkyl group.

 If the above substituents are defined as optionally substituted, then their optionally present substituent groups may be any one or more standard groups commonly used in the development of pesticidal compounds and / or in the modification of such compounds in order to increase their activity, endurance, permeability or improvement other properties. Specific examples of such substituents are halogen atoms, nitro, cyano, hydroxyl, alkyl, alkenyl, haloalkyl, haloalkenyl, alkoxy, haloalkoxy, amino, alkylamino, dialkylamino, alkoxycarbonyl, carboxyl, alkanoyl, alkylthio, alkylsulfonyl , carbamoyl, alkylamido, cycloalkyl, phenyl and benzyl groups. Basically, 0-3 substituents may be present. If any of the above substituents represents or contains an alkyl substituent group, then such a group may be linear or branched and may contain up to 12, preferably up to 6, and most preferably up to 4 carbon atoms. If any of the above substituents represents or contains an aryl or cycloalkyl group, then such an aryl or cycloalkyl group may itself be substituted by one or more halogen atoms, or one or more nitro, cyano, alkyl, alkenyl, haloalkyl, halogenalkenyl alkoxy or haloalkoxy groups. It is preferred that the aryl group is a phenyl group and the cycloalkyl group contains from 3 to 8, and preferably from 4 to 7 carbon atoms.

Preferably, if present, R represents a halogen atom or a nitro, cyano, hydroxyl, C _1-4 alkyl, C _2-4 halogenated, C _2-4 alkenyl, C _2-4 halogenated, 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 _1-4 alkylsulfonyl group.

More preferably, if present, R represents 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 group.

 It is also preferred that n = 0, 1 or 2, and it is particularly preferred that n = 0.

In addition, it is preferable that R ¹ and R ² independently represent a C _1-4 alkoxy group, in particular a methoxy group, or it is preferred that R ¹ and R ² taken together represent a group = O or = N-OR ⁹ , where R ⁹ represents a hydrogen atom or a C _1-4 alkyl group, and in particular a methyl group. It is preferable that both R ¹ and R ² represent a methoxy group, or, taken together, they represent a group = O.

If R ³ is an —OL group, where L is a leaving group, or a group that is converted in vivo to a group —OL ¹ , where L ¹ is a leaving group, then said leaving group may be any group that is commonly used in as a leaving group. Moreover, such a leaving group is preferred in which the pK _a value of the acid LOH or L ¹ OH in water is from 1 to 7, more preferably from 1 to 6, and particularly preferably from 1 to 5.

In case R ³ represents a group which is converted in vivo to the group —OL ¹ , where L is a leaving group, then it is preferable that such a conversion takes place in a protected plant or in a pest against which protection is carried out, preferably under the action of enzymes present in a plant or in a pest. So, for example, if R ³ represents a β-acid group such as —O — CH ₂ CH ₂ CO — OH, where —CH ₂ CH ₂ CO — OH is not a leaving group, then this group can be subjected to enzymatic oxidation in vivo for example, under the action of β-oxidase, to form the group —O — CO — CH ₂ —CO — OH, where —CO — CH ₂ —CO — OH is a leaving group.

Preferably, R ³ represents an —OR ¹⁰ group, where R ¹⁰ represents a hydrogen atom, an optionally substituted alkyl, alkenyl, aryl or aralkyl group; or a group -CO-R ¹¹ , -CO-OR ¹¹ , -SOR ¹¹ , -SO-R ¹¹ , -P (X) (OR ¹² ) (OR ¹³ ), -R (X) (R ¹² ) (OR ¹³ ), -P (OR ¹² ) (OR ¹³ ) or -P (R ¹² ) (OR ¹³ ), where R ¹¹ represents a hydrogen atom, an optionally substituted alkyl, alkenyl, aryl or aralkyl group, or a group —NR ¹² R ¹³ , where R ¹² and R ¹³ independently represent a hydrogen atom or an optionally substituted alkyl group, and X represents an oxygen or sulfur atom. If R ¹⁰ or R ¹¹ represents an optionally substituted aryl or aralkyl group, then it is preferable that the aryl group or part be a phenyl group or part, and optionally substituents are halogen atoms, a nitro group and a C _1-4 alkyl group. Particularly preferred is substitution at the 4-position of the phenyl ring. The term “optionally substituted” as used in relation to R ³ means, for example, substitution with silicon-containing groups, for example trialkylsilyl groups, such as trimethylsilyl, used as a substituent on R ¹⁰ , R ¹¹ or R ¹² .

Preferably R ³ represents a hydroxyl group or a group —O — CO — R ¹¹ or —O — CO — OR ¹¹ , where R ¹¹ represents a hydrogen atom or C _1-12 alkyl, C _1-12 haloalkyl, C _1-12 hydroxyalkyl, C _1-12 carboxyalkyl, phenyl or benzyl group.

It is particularly preferred that R ³ represents a —OH or —O — CO — R ¹¹ group, where R ¹¹ represents a hydrogen atom or a C _1-6 alkyl, C _1-6 haloalkyl, phenyl or benzyl group. It is most preferred that R ¹¹ represents a methyl, ethyl, propyl or butyl group.

Preferably, if R ⁷ and R ⁸ independently represent a C _1-4 alkoxy group, or, taken together, they represent a group = O or = N-OR ⁹ , where R ⁹ is a hydrogen atom or a C _1-4 alkyl group, and it is particularly preferred that each of R ⁷ and R ⁸ is a methoxy group, or taken together they form a group = O.

It should be noted that the compounds where each of R ¹ and R ² , and R ⁷ and R ⁸ are an alkoxy group, or each of the pairs taken together R ¹ and R ² , and R ⁷ and R ⁸ form = S or the NOR ⁹ group, are potential biological precursors of the corresponding naphthoquinones, which are preferred compounds of the present invention.

Preferably, each of R ⁴ and R ⁵ independently represents hydrogen, or a C _1-7 alkyl, C _1-7 haloalkyl, C _2-7 alkenyl or C _2-7 haloalkenyl group, or R ⁴ and R ⁵ taken together with the adjacent and a carbon atom between them, form a C _4-8 cycloalkyl or cycloalkenyl ring, which is optionally substituted with substituents selected from halogen and methyl, ethyl, ethenyl, halogenmethyl, haloethyl and haloethenyl groups. More preferably, if R ⁴ and R ^{5 are} independently selected from C _1-4 alkyl, C _1-4 haloalkyl, C _2-4 alkenyl and C _2-4 haloalkenyl groups, or if R ⁴ and R ⁵ taken together form ring.

The compounds of formula I can form salts if, for example, R ³ is a hydroxyl group. Suitable bases for the formation of such salts are inorganic bases such as sodium hydroxide, potassium hydroxide or sodium carbonate; and organic bases, for example, tertiary amines, such as triethylamine, and cyclic amines, such as pyrrolidine.

 It should be noted that many compounds used for the purposes of the present invention can exist in the form of various geometric isomers and diastereomers. Thus, the scope of the present invention encompasses both individual isomers and mixtures thereof.

In a first preferred group of compounds used in accordance with the first aspect of the present invention, the —CHR ⁴ R ⁵ moiety is directly adjacent to the naphthalene ring, where R ⁴ and R ⁵ independently represent hydrogen, halogen, or an optionally halogen-substituted alkyl or alkenyl group.

или его соль, где R, R¹, R², R³, R⁷ и R⁸ и n являются такими, как они были определены выше для формулы (I), а R⁴ и R⁵ независимо представляют водород или галоген, либо алкильную или алкенильную группу, которая является галогензамещенной, при этом длина ее углеродной цепи остается в пределах, установленных выше для формулы (I).The specified first preferred group of compounds used for the purposes of the present invention includes compounds of General formula (II):

or its salt, where R, R ¹ , R ² , R ³ , R ⁷ and R ⁸ and n are as defined above for formula (I), and R ⁴ and R ⁵ independently represent hydrogen or halogen, or an alkyl or alkenyl group, which is halogen-substituted, while the length of its carbon chain remains within the limits established above for formula (I).

More preferred are compounds of formula (II), where n = 0; R ¹ with R ² and R ⁷ with R ⁸ form = O; and where one of R ⁴ and R ⁵ represents a hydrogen atom, either a C _1-7 alkyl, C _1-7 haloalkyl, C _2-7 alkenyl or C _2-7 haloalkenyl group, and the other is independently selected from C _1-7 alkyl, C _1-7 haloalkyl, C _2-7 alkenyl and C _2-7 haloalkenyl groups. R ³ is preferably —OH, —O — CO — R ^11, or —O — CO — OR ¹¹ , wherein R ¹¹ is C _1-3 alkyl; and most preferably —OH. The most preferred portion of —CHR ⁴ R ⁵ contains from 2 to 5 carbon atoms.

 The inventors of the present invention have found that this first preferred group of compounds has mainly good activity against whiteflies, and if the longest chain at the 3-position consists of 7 carbon atoms or less, then this group of compounds also has good activity against fungi, such as R. solani, P. oryzae and A. niger, and retains activity against ticks.

где n, A, R, R¹, R², R³, R⁷ и R⁸ являются такими, как они были определены выше для общей формулы (I); m обозначает целое число 0 или 1; a R⁴ и R⁵, взятые вместе со смежным и расположенным между ними атомом углерода, образуют необязательно замещенное C_5-7 циклоалкильное или циклоалкенильное кольцо.In a second preferred particular group of compounds used in the first aspect of the present invention, the —CHR ⁴ R ⁵ group is part of a cycloalkyl or cycloalkenyl ring, and therefore this second group of preferred compounds of formula (I) preferably has formula (III):

where n, A, R, R ¹ , R ² , R ³ , R ⁷ and R ⁸ are as defined above for the general formula (I); m is an integer of 0 or 1; a R ⁴ and R ⁵ taken together with an adjacent and adjacent carbon atom form an optionally substituted C _5-7 cycloalkyl or cycloalkenyl ring.

More preferably, compounds of this group are compounds of formula (III), wherein R ¹ with R ² and R ⁷ with R ⁸ form = 0; n and m are 0; a R ⁴ and R ⁵ taken together with an adjacent carbon atom form a fully saturated C _5-7 cycloalkyl ring, which is optionally substituted.

Even more preferably, if R ⁴ and R ⁵ , taken together with an adjacent and adjacent carbon atom, form a saturated C _5-7 cycloalkyl ring substituted with a halogen, preferably chlorine or fluorine, or C _1-4 alkyl, halogenated, C _{2 -4} alkenyl or halogenoalkenyl group R ²⁰ . Most preferably, if R ⁴ and R ⁵ taken together with an adjacent carbon atom form a cyclopentyl or cyclohexyl ring substituted at one or more of the 2-3 or 4 positions with an R ²⁰ group.

 Preferred compounds of this second preferred group of the present invention are extremely effective against whiteflies, especially against the species B. tabaci, if in these compounds the cycloalkyl or cycloalkenyl ring is directly linked to the naphthalene ring, i.e. m = 0.

In a third separate group of compounds of the first aspect of the present invention, the -CHR ⁴ R ⁵ portion does not form a cycloalkyl or cycloalkenyl ring, and is 1-6 carbon atoms away from the naphthalene ring, most preferably 2-4 carbon atoms long.

где n, A, R, R¹, R², R³, R⁷ и R⁸ являются такими, как они были определены выше для общей формулы (I); a R⁴ и R⁵, каждый независимо представляет атом галогена или необязательно замещенную алкильную или алкенильную группу.Thus, the compounds of formula (I) related to this third group of compounds used for the purposes of the present invention preferably have the formula (IV):

where n, A, R, R ¹ , R ² , R ³ , R ⁷ and R ⁸ are as defined above for the general formula (I); a R ⁴ and R ⁵ each independently represents a halogen atom or an optionally substituted alkyl or alkenyl group.

More preferred compounds of this group are compounds of formula (IV), where n = 0; R ¹ with R ² and R ⁷ with R ⁸ form = 0; and A represents a C _1-6 alkyl, C _1-6 haloalkyl, C _2-6 alkenyl or C _2-6 haloalkenyl chain which may be substituted with halogen; or branched chain, which can be halogenated. R ⁴ and R ⁵ are preferably C _2-6 alkyl, C _2-6 haloalkyl, C _2-6 alkenyl, or C _2-6 haloalkenyl. R ³ is preferably —OH, —O — CO — R ^11, or —O — CO — OR ¹¹ , where R ¹¹ is C _1-3 alkyl, and most preferably OH.

Preferred compounds of this group are compounds where A is a group - (CH ₂ ) _a , where a is an integer from 1 to 6, and more preferably from 1 to 4; or - (CH ₂ ) _a —CH = CH— (CH ₂ ) _b where a and b are integers that add up to from 0 to 4; as well as analogues of these compounds, where one or more carbon atoms are substituted by alkyl, haloalkyl, alkenyl, haloalkenyl or halogen.

Particularly effective for use in the present invention are compounds of formula (III) in which one or more of A, R ⁴ and R ⁵ represent a haloalkyl or haloalkenyl group, and especially a trifluoromethyl group. Compounds in which —A-CHR ⁴ R ⁵ represents an isofluoroalkyl group, for example, such as 2-trifluoromethylpropyl or 2,2-di-trifluoromethylethyl, are preferred. In this case, both unsubstituted and halogenated compounds have good activity against the above fungi, if the longest chain in the 3-position is up to 7 carbon atoms.

In a second aspect, the present invention relates to new compounds of formula (I) in which —CHR ⁴ R ⁵ forms a 2-substituted cycloalkyl ring, preferably 2-substituted with C _1-4 alkyl or C _1-4 haloalkyl; or - (A) _m CHR ⁴ R ⁵ is an isohaloalkyl group.

 Preferred 2-substituted cycloalkyl compounds, such as 2-hydroxy-3- (2-methyl-cyclohexyl) -naphthalene-1,4-dione, are not only new compounds, but also have compared to 3- and 4-substituted cycloalkyl compounds unexpectedly high degree of activity against whiteflies.

где n, m, A, R, R¹, R², R³, R⁷ и R⁸ являются такими, как они были определены выше для общей формулы (I), a R²⁰ выбирают из C_1-4 алкила, C_1-4 галогеналкила, C_2-4 алкила и C_2-4 галогеналкила.Thus, in this aspect, the present invention relates to a compound of formula (VI):

where n, m, A, R, R ¹ , R ² , R ³ , R ⁷ and R ⁸ are as defined above for the general formula (I), and R ^{20 is} selected from C _1-4 alkyl, C _1-4 haloalkyl; C _2-4 alkyl; and C _2-4 haloalkyl.

где n, m, A, R, R¹, R², R³, R⁷ и R⁸ являются такими, как они были определены выше для общей формулы (I), а один или более из A, R⁴ и R⁵ представляет или включает галогеналкильную группу. В предпочтительных соединениях A представляет C_1-4 алкиленовую группу, а один из R⁴ и R⁵ представляет трифторметил.In particular, in this aspect, the present invention relates to a compound of formula (VII)

where n, m, A, R, R ¹ , R ² , R ³ , R ⁷ and R ⁸ are as defined above for the general formula (I), and one or more of A, R ⁴ and R ⁵ represents or includes a haloalkyl group. In preferred compounds, A represents a C _1-4 alkylene group, and one of R ⁴ and R ⁵ represents trifluoromethyl.

 Preferred isohaloalkyl compounds of the formula (VI), such as 2-hydroxy-3- (2-trifluoromethylpropyl) -naphthalene-1,4-dione, are not only new, but also have a high degree of activity against both ticks and whiteflies.

Other new compounds of the present invention are compounds of formula (I) in which R ¹ with R ² and / or R ⁷ with R ⁸ do not form both = O.

 In a third aspect, the present invention relates to a method for controlling a whitefly, Lepidoptera and / or pest fungi in foci of their spread, comprising treating these foci with a compound of general formula (I), and preferably a compound of general formula (II), (III) or (Iv).

 Preferred foci are habitats of pests, i.e. whiteflies, Lepidoptera and / or fungi, as such, or an environment exposed or affected by pests. Foci of pests as such, stored food products, plants or animals exposed to or which may be affected by pests, seeds of said plants, or the environment in which these plants grow or are grown, are more preferred. In particular, the compounds of formula I can be used at home for the treatment of living rooms in order to combat indoor flies or other insects, ticks or fungi parasites; on garden or agricultural land for processing cultivated crops, such as cotton or rice, or stored crops, especially cereals, in order to protect them from pests, especially whiteflies and related species, as well as in medical or veterinary practice, for example for the treatment of cattle in order to protect it or to treat it from pests.

 In its fourth aspect, the present invention also relates to a method for producing compounds of formula (I), and in particular, compounds of formulas (II), (III) and (IV) as defined above.

где n, R и R³ определены выше, подвергают реакции с карбоновой кислотой CHR⁴R⁵-(A)m-COOH, где R⁴ и R⁵ определены выше, в присутствии инициатора свободнорадикальной реакции, такого как пероксисульфат аммония или нитрат серебра в подходящем растворителе, таком как водный ацетонитрил, в результате чего получают соединение общей формулы (I), (II), (III) или (IV). Соединения формулы (V) являются коммерчески доступными, но в любом случае они могут быть получены из соответствующих доступных бензохинонов и замещенных алканов, например, с помощью реакции Дильса-Альдера.In a preferred method for preparing compounds of formula (I), (II), (III) and (IV), a compound of general formula (V):

where n, R and R ^{3 are as} defined above, are reacted with a carboxylic acid CHR ⁴ R ⁵ - (A) m-COOH, where R ⁴ and R ^{5 are as} defined above, in the presence of a free radical initiator such as ammonium peroxysulfate or silver nitrate in a suitable solvent, such as aqueous acetonitrile, whereby a compound of the general formula (I), (II), (III) or (IV) is obtained. The compounds of formula (V) are commercially available, but in any case they can be obtained from the corresponding available benzoquinones and substituted alkanes, for example, using the Diels-Alder reaction.

In yet another method for preparing compounds of the present invention, a compound of formula (V) is reacted with a compound of formula X- (A) _m CHR ⁴ R ⁵ where R ⁴ , R ⁵ A and m are as defined above for formula (I) ), and X is a leaving group, which may be, for example, a halogen atom or a tosyl group, and which then cleaves from the compound to form a charged radical ⁺ (A) _m —CHR ⁴ R ⁵ . This reaction is carried out in the presence of an acid, for example Lewis acid, such as aluminum chloride, under conditions widely described by Fieser and Gates (J. Am. Chem. Soc. (1941) 63, 2943-2953).

 The compounds of formula (I) obtained by these methods can then be subjected to the derivatization reactions described above, their combinations, to obtain, if necessary, other compounds of formula (I).

In this alternative method, when R ⁴ and R ⁵ taken together with an adjacent carbon atom form a cycloalkyl or cycloalkenyl ring of 3-10 carbon atoms, many commercially available cycloalkyl and cycloalkylene carboxylic acids can be used, and those present on them carboxylic acid groups can be extended using standard techniques to form longer carbon chains, and then protected, if necessary, using techniques well known to those skilled in the art. So, for example, to obtain the -CH ₂ extension, the Arnst-Elstert reaction can be carried out (see, for example, Meier and Zeller (1975), Anqew. Chem. Int. Ed. Ewgl., 14, 32). Alternatively, compounds in which m = 1 can be prepared by reacting the corresponding cycloalkanone with ethyl cyanoacetate, and then reacting with the Grignard reagent and subsequent hydrolysis to form cycloalkylacetic acid (see, for example, Amsterdamsky et al. (1975) Bull. Soc. Chim. Fr. (3-4 Part 2), p. 635-643; and Muhs MA PhD Thesis. University of Washington. Diss Abst., 14, 765 (1954), resulting in a chain length increase of 1.

To obtain compounds containing R ⁴ R ⁵ - rings having a greater number of carbon atoms, the corresponding monobromosubstituted cycloalkyl or cycloalkenyl compounds can be converted to carboxylates by preparing the Grignard compound using magnesium and then treating it with carbon dioxide (CO ₂ ) taken for example, in the form of dry ice. The carboxylic acid thus formed can be converted to an alkyl carboxylate by alkylation using, for example, R ⁶ -1, such as methyl iodide, in the presence of butyllithium, where R ⁶ is a group as defined above which is stable under these conditions.

The substitution reaction, for example, alkylation, of a cycloalkyl / cycloalkylene ring at non-1-position, to form a carboxylate, can be carried out by known methods. Using alkyl esters of a monounsaturated ring of cycloalkylene carboxylic acid as starting compounds, the alkylation can be carried out in the desired position as described previously, and then using light radiation as an initiator, a reaction can be carried out, for example, with CF ₃ X, which proceeds under reducing conditions in the presence of a palladium-on-carbon catalyst, and which allows the introduction of CF ₃ groups, resulting in the saturation of the unsaturated bond. To obtain other compounds of formula (I) can be used many other operations known to everyone skilled in the art.

Compounds of formula (I) in which R ³ is a leaving group as defined above can be prepared by reacting a compound of formula (I) in which R ³ is a hydroxyl group with compound XL, where X is a halogen atom, in the presence of an organic base preferably a tertiary amine, such as triethylamine, or an inorganic base, such as sodium carbonate. So, for example, compounds of formula (I) in which R ³ represents a group —O — CO — R ¹¹ , where R ¹¹ is as defined above, can be obtained by acylating a hydroxy group in the corresponding compound of formula I, for example using R ¹¹ -CO-Cl acyl chloride in a suitable solvent such as dichloromethane in the presence of a base such as triethylamine. Alternatively, compounds of formula (I) in which R ³ represents a hydroxyl group may be reacted with compound HO-L, where L is as defined above and includes an acid group C = O, in the presence of a dehydrating agent such as dicyclohexylcarbodiimide. Another way to obtain such compounds involves the reaction of a metal salt of a compound of formula (I) in which R ³ represents a hydroxyl group, that is, R ³ represents a group —OM, where M is a metal ion, with
XL compound as defined above.

Compounds of formula (I) in which R ¹ with R ² and / or R ⁷ with R ⁸ independently represent an optionally substituted alkoxy group can be prepared by ketalization of one or both carbonyl groups in the corresponding compound of formula (I) or (V) for example, by using a suitable alcohol under basic or acidic conditions, for example, by using a solution of potassium hydroxide in methanol.

Compounds of formula (I) in which R ¹ and R ² taken together and / or R ⁷ and R ⁸ taken together form a thiocarbonyl group = S can be obtained by treating the corresponding compound of formula (I), where both pairs R ¹ with R ² and / or R ⁷ with R ⁸ form = O, a thiating agent, such as Lawesson's reagent (2,4-bis (4-methoxyphenyl) -1,3-dithia-2, 4-diphosphetan-2, 4-disulfide), using protective groups, where necessary.

The compounds of formula (I) in which R ¹ and R ² taken together and / or R ⁷ with R ⁸ taken together form an oxime group = N-OR ⁹ , where R ^{9 is} defined above, can be obtained by processing the corresponding the compounds of formula (I), where both R ¹ and R ² , and R ⁷ and R ⁸ form = O, hydroxylamine or alkoxylamine of the formula R ⁹ O-NH ₂ where R ^{9 is} defined above, in the presence of a base such as pyridine.

 To obtain the desired compound of formula (I), a combination of the above derivatization methods may be carried out.

 In a fifth aspect, the present invention relates to an insecticidal and / or fungicidal composition comprising a compound of formula (I), and preferably a compound of formula (II), (III) or (IV) as defined above, in combination with at least one carrier. The specified composition may contain one compound or a mixture of several compounds of the present compounds. It was also found that different isomers or mixtures of isomers can have different levels or spectra of activity, and therefore the compositions may contain individual isomers or mixtures of isomers.

 The compositions of the present invention may contain, in general, from 0.001 to 95% by weight of the active ingredient of formula (I). Preferred compositions contain from 0.001 to 25% by weight of the active ingredient if these compositions are present in a form ready for use. However, compositions made in the form of concentrates diluted immediately prior to use may contain higher concentrations of the active ingredient, for example up to 95%.

 The compositions of the present invention can be mixed with various inert carriers such as solvents, diluents and / or surfactants to form dusts, granular solid preparations, wettable powders, mosquito coils or other solid preparations; or emulsions, emulsifiable concentrates, spray solutions, aerosols or other liquid preparations. Suitable solvents and diluents are water, aliphatic and aromatic hydrocarbons, such as xylene or other petroleum fractions, and alcohols, such as ethanol. Surfactants can be anionic, cationogenic or nonionic. In addition, the compositions may also contain antioxidants or other stabilizers, as well as flavoring and coloring agents. The types of these inert carriers and their ratios can be used in accordance with standard practice commonly used in the manufacture of pesticidal compositions, and therefore these carriers are mainly inert with respect to the physiology of the treated plant.

 Examples of carriers that are known to be suitable for use in pesticidal compositions containing naphthalene-1,4-dione are given in the descriptions, and in particular in the examples of US patents 2572946, 4110473, 4970328 and Japanese patent 90/152943 (the latter Agro-Kanesho KK patent).

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

 In more detail, the present invention is described in the following examples and comparative examples, which are provided for illustrative purposes only and should not be construed as limiting the present invention. Based on these examples, other embodiments of the invention may be practiced.

 Tables 1-6 explain the invention.

EXAMPLES
Example 1
Preparation of 2-cyclohexyl-3-hydroxy-naphthalene-1,4-dione
To a mixed solution of 2-hydroxynaphthalene-1,4-dione (1.00 g, 5.74 mmol), cyclohexanecarboxylic acid (1.10 g, 8.61 mmol), silver nitrate (520 mg) in acetonitrile (15 ml) and water (20 ml) heated at 65-70 ^° C., an aqueous solution of ammonium persulfate (1.77 g, 7.77 mmol) in water (10 ml) was added. After heating for 1 hour, the mixture was cooled, diluted with water (50 ml) and extracted with ether (3 x 40 ml). The combined ether fractions were washed with water (3 x 25 ml), saturated sodium chloride solution (25 ml) and dried over magnesium sulfate. After filtration, evaporation of the solvents under reduced pressure, and chromatography on silica gel, the title compound was obtained (354 mg, mp 133 ^° C). This compound is indicated in the table as compound 12.

Example 2
Preparation of 2-hydroxy-3- (4-methylcyclohexyl) naphthalene-1,4-dione
By the method described in example 1 and using lauson (i.e., 2-hydroxy-naphthalene-1,4-dione) (1.00 g) and 4-methylcyclohexanecarboxylic acid (1.23 g), the desired compound (100 mg, mp 101 ^° C). This compound is indicated in the table as compound 19.

Example 3
Preparation of 2-hydroxy-3- (1-methylbutyl) naphthalene-1,4-dione
By the method described in example 1, using 2-acetyloxinaphthalene-1,4-dione (1.24 g, 5.74 mmol) and 2-methylpentanoic acid (1.00 g), the desired compound (608 mg) was obtained after hydrolysis in 30 ml of THF using potassium hydroxide (in a 5-fold excess) in water (8 ml) (mp 82-83 ^° C). This compound is indicated in the table below as compound 3.

Example 4
Preparation of 2-hydroxy-3- (2-trifluoromethylpropyl) -1,4-naphthoquinone
2-acetyloxinaphthalene-1,4-dione (1.24 g) and 3-trifluoromethylbutanoic acid (1.08 g) were subjected to the reaction as described in Example 3, whereby the target compound (353 mg) was obtained (mp. 168 ^o C). This compound is indicated in the table below as compound 11.

Other compounds shown in the tables were obtained by the above General methods. Compound 20 corresponds to example 1 in table 1 (DE 3801743 A1) and is 2-hydroxy-3- (4-tert-butylcyclohexyl) naphthalene-1,4-dione (Formula I: n = 0; m = 0; R ¹ and R ² taken together and R ⁷ + R ⁸ taken together represent = O; R ³ = —OH; and —CHR ⁴ R ⁵ - = 4-tert-butylcyclohexyl).

Pesticidal activity
Using the methods described below, pesticidal activity was evaluated against houseflies, mustard fleas, ticks and whiteflies.

Indoor Flies (MD) (Musca domestica)
Female houseflies were treated in the thorax region with one microliter drop of the test compound dissolved in acetone. To test each dose, 15 flies were used in two duplicates, with 6 doses of varying powers for each test compound being used. After treatment, the flies were kept at a temperature of 20 ± 1 ^o C and after 24 and 48 hours after treatment, the number of dead flies was estimated. LD ₅₀ values were calculated in micrograms of the test compound per fly (see, Sawicki et al., Bulletin of the World Health Organization, 35, 893 (1966) and Sawicki et al., Entomologia and Exp. Appli. 10, 253 ( 1967)).

Mustard Flea (PC) (Phaedon cochleariae Fab)
One microliter drop of the acetone solution of the test compound was applied to the abdomen of adult mustard fleas using a microdrop applicator. The treated insects were kept for 48 hours, after which the number of dead insects was estimated. To test each dose level, 20–25 mustard fleas in two duplicates were used, with five dose levels being compared. LD ₅₀ values were calculated in the same manner as in the case of house flies.

Ticks (TU) (Tetranychus urticae)
25 adult female ticks were immersed for 30 sec in 35 μl of a solution of the test compound in a mixture of acetone and water (1: 4). The treated insects were kept at 21 ± 2 ^° C. and 72 hours after the treatment, the number of dead insects was counted. Ticks with a convulsive (non-reflex) movement of more than one motor limb, detected after a specified period of time, were considered alive. Three duplicates of 25 ticks were used for each test dose, with each test compound being used in 5 or 6 different doses. LD ₅₀ values are expressed in ppm. a solution of the test compound per insect. Tests were performed using a susceptible strain of ticks (GSS) supplied by Schering, AG, Berlin.

Whitefly (BT) (Bemisia tabaci)
Acetone solutions (0.100 ml) of the test compounds were placed in 10 ml glass vessels and evaporated by rotation to form a film of the precipitated compound. After this, 30 adult whiteflies were placed inside the vessels, and then, after 60 minutes, the treated insects were transferred to the untreated disks of cotton leaves, which were kept moist on an agar gel layer. The temperature was maintained at 25 ^o C. After 48 hours, the degree of insect death was assessed. Three duplicates were used for each of 5-7 dose levels of each test compound. LC ₅₀ values were calculated on a computer using the appropriate software system ("Polo-PC", supplied by LeOra Software, Berkeley, California). (See, MP Cahill and W. Hackett in the "Proceedings Brighton Crop Protection Conference", 1992). Tests were performed using a susceptible whitefly strain (SUD-S), which was harvested from cotton in Sudan in 1978.

The results of these tests are presented below in tables 3 and 4. Unless otherwise specified, the data in the tables are presented as LD ₅₀ (μg / insect) or as LC ₅₀ (ppm solution of the test compound).

Activity against resistant whitefly (BT) (Bemisia tabaci)
The experiment described above with whiteflies (BT) (Ned-s) was repeated, except that in this case, a resistant strain of whitefly Ned 1/2 was used. Strain Ned 1/2 is a mixed collection collected from gerbera (Gerbera) and bouvardia (Bouvardia) in the Netherlands (ICI, Netherlands) in 1991, and exhibits a high degree of resistance to pyrethroid insecticides such as cypermethrin, organophosphate and carbamate insecticides as well as to the insect growth regulator buprofecin.

The results of these tests are given below. Data are presented as LC ₅₀ values (ppm solution of test compound).

Connection - BT (Ned 1/2) LC ₅₀
12 - 6.4
20 - 100
In addition, it was found that in addition to activity against whiteflies, the studied compounds also had activity against Diabrotica (long-barked flea) and Lepidoptera, for example Spodoptera, for example S. littoralis and S. frugiperda. So, for example, compound 4 in local processing has an LC ₅₀ (ppm) of the order of 5, 10, and 20 for these three species, and compound 13 has an LC _{50 of} approximately 20, 12, and 20 for Diabrotica, S. littoralis and S. frugiperda, respectively. In relation to specific species of insects, anti-feeding activity was also observed.

Fungicidal activity
In vitro tests were carried out on the fungicidal toxicity of the compounds in relation to isolates of Aspergillus niger, Pyricularia oryzae (= Magnaporthe grisea) and Rhizoctonia solani.

Each compound was introduced into potato agar with dextrose in a solvent (ethanol / acetone = 50/50) in a ratio of 0.5 ml of solvent per 250 ml of agar; while the autoclaved agar was melted and cooled to 50 ^o C. Each compound was tested in only one concentration (100 mg / l).

 Each test, usually of two compounds, included three control treatments: standard fungicide (carbendazim at a concentration of 1 or 5 mg / l, or prochlorase at a concentration of 1 mg / l); only one ethanol / acetone mixture, and no additives. Fungicides used as standards can be considered representative of active commercial compounds.

Each fungus was tested on agar in four Petri dishes for each treatment; while three fungal colonies are replicas per one cup (one colony for R. solani). A. niger and R. solani were incubated for 4 days at 20-25 ^° C, while P. oryzae was incubated for 7 days. Then the increase in the diameter of the colonies was measured and the obtained data was used to determine activity.

 The results of these tests are presented below in table 5. These results are given as% inhibition of colony growth (ie, increase in their diameter) at a given concentration of the agent.

 In addition to the compounds described above, data are also provided for compound 21 (2-methyl-3-hydroxy-naphthalene-1,4-dione) and for compound 22 (2-ethyl-3-hydroxy-naphthalene-1,4-dione). For comparison, table 5 presents the inhibition data by standard agents.

 In addition, tests have shown that the compounds of formula I have good fungicidal activity against a wide range of fungi that cause diseases in both cereals and leafy crops. For example, good activity was observed against fungi of the genus Erysiphe, in particular Erysiphe graminis, and the genus Botrytis, in particular Botrytis fabae and Botrytis cinerea, as well as the genus Rhizoctonia, Pyricularia and Aspergillus, as was demonstrated above.

Example 5
Obtaining 2-hydroxy-naphthalene-1,4-diones used as starting material for the preparation of compounds in which n = 1 or more
As a result of the Diels-Alder reaction carried out using the corresponding quinone compounds, the corresponding 2-hydroxy-naphthalene-1,4-diones were obtained, used as starting compounds for the preparation of compounds where n = 1 or more. The following are specific examples.

(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) for 68 hours at room temperature. The resulting mixture was diluted with water (44 ml) and heated under reflux for one and a half hours. The mixture was then cooled to room temperature and acetic acid (84 ml) and chromic acid (chromium trioxide (29.4 g) in water (30 ml)) were added sequentially, after which the mixture was heated under reflux for another 1.5 hours. After cooling, the mixture was diluted with water (200 ml) and extracted with ether (3 x 50 ml). The combined ether fractions were washed with dilute sodium hydroxide solution (2M; 2 x 50 ml), water (2 x 50 ml), saturated sodium chloride solution (50 ml) and dried over magnesium sulfate. After filtration, evaporation of the solvent under reduced pressure and recrystallization from petroleum ether, the target compound (7 g) was obtained.

(b) 2-amino-6- and 7-methyl-1,4-naphthalene-1,4-dione
To a stirred solution of 6-methylnaphthalene-1,4-dione (2.1 g, 12 mmol) in glacial acetic acid (60 ml) was added a solution of sodium azide (1.58 g) in water (5 ml) at room temperature. The resulting mixture was stirred for 2 days, and then diluted with water (200 ml) and after stirring for another 15 minutes, the mixture was filtered. The filtrate was neutralized with sodium bicarbonate and extracted with chloroform (3 x 25 ml). The combined chloroform extracts were washed with saturated sodium bicarbonate and brine, and then dried (CaSO ₄ ). After filtration, evaporation of the solvent under reduced pressure and chromatography on silica gel, the target compound (100 mg) was obtained as a mixture of (3: 2) isomers.

(c) 2-Hydroxy-6- and 7-methylnaphthalene-1,4-dione
The mixture of aminomethylnaphthalene-1,4-dione isomers (200 mg) obtained as described in part (b) was heated under reflux 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 x 25 ml). The combined ether extracts were washed with water, saturated sodium bicarbonate (NaHCO ₃ ), water and saturated NaCl, and then dried over magnesium sulfate (MgSO ₄ ). After filtration, evaporation of the solvent and purification by silica gel column chromatography, the target compound (68 mg) was obtained.

Claims (37)

1. The use of the compounds of General formula (I) as an insecticide against whiteflies, Lepidoptera:

where n = 0; m is 0;
R ¹ and R ² taken together represent a group = O,
R ³ represents a hydroxyl group or an —OCOR ¹¹ group, where R ¹¹ is C ₁ -alkyl (methyl);
R ⁷ and R ⁸ taken together represent a group = O;
R ⁴ and R ⁵ independently represent a hydrogen atom or methyl, or taken together with the adjacent carbon atom to which they are attached, represent a C _4-8 cycloalkyl ring, a 4-tert-butylcyclohexyl ring, with the total number of carbon atoms in the longest the carbon chain coming from the mothballs cycle in the indicated position 3 is not more than 2.  2. The use according to claim 1 against Bemisia whitefly.  3. The use according to claim 2 against the whitefly Bemisia tabaci. 4. The use according to any one of the preceding paragraphs, where R ⁴ and R ⁵ independently represent methyl or, taken together with the adjacent carbon atom to which they are attached, represent a C _4-8 cycloalkyl ring, a 4-tert-butylcyclohexyl ring. 5. The use of compounds according to any one of the preceding paragraphs, where R ⁴ and R ⁵ represent a methyl group. 6. The use of a compound according to claim 1, wherein the group —CHR ⁴ R ⁵ represents a methyl or ethyl group. 7. The use of a compound according to any one of claims 1 to 4, characterized in that said compound is a compound of formula (III)

where n, m, R ¹ , R ² , R ³ , R ⁷ and R ^{8 are} defined for the general formula (I); a R ⁴ and R ⁵ together with the adjacent carbon atom to which they are attached represent a C _4-8 cycloalkyl ring, a 4-tert-butylcyclohexyl ring. 8. Substituted naphthalene-1,4-dione of the formula (VI)

where n = 0; m is an integer of 0 or 1;
R ³ represents a hydroxyl group or an —OCOR ¹¹ group, where R ¹¹ is C _1-6 alkyl;
R ²⁰ represents C _1-4 alkyl;
A represents an unbranched or branched alkyl group that binds the naphthalene ring at the indicated position 3 with the group

where A does not contain a Quaternary carbon atom in the chain, while the total number of carbon atoms in the longest carbon chain coming from the mothballs in the indicated position 3 is not more than 8. 9. Substituted naphthalene-1,4-dione of the formula (VII)

where n = 0; m is an integer of 0 or 1;
R ³ represents a hydroxyl group or an —OCOR ¹¹ group, where R ¹¹ is C _1-6 alkyl;
R ⁴ and R ⁵ independently represent a C _1-7 alkyl or C _1-7 haloalkyl group in which at least one of R ⁴ and R ⁵ represents a C _1-7 haloalkyl group;
A represents an unbranched or branched alkyl group that binds the naphthalene ring at the indicated position 3 to the group —CHR ⁴ R ⁵ , where A does not contain a quaternary carbon atom in the chain, while the total number of carbon atoms in the longest carbon chain extending from the naphthalene ring in the indicated position 3, is not more than 8. 10. The compound according to claim 9, where A represents a C _1-4 alkylene group, and one of R ⁴ and R ⁵ represents trifluoromethyl. 11. A method of combating Lepidoptera whitefly in a foci of infection, comprising treating said foci of infection with a compound of general formula (I)

where n = 0; m is an integer of 0 or 1;
R ¹ and R ² taken together represent a group = O,
R ³ represents a hydroxyl group or an —OCOR ¹¹ group, where R ¹¹ is C _1-6 alkyl;
R ⁷ and R ⁸ taken together represent a group = O;
R ⁴ and R ⁵ independently represent a hydrogen atom or a C _1-7 alkyl group optionally substituted with a halogen atom, a cyano group, a C _1-4 alkoxy group, a di- (C _1-4 ) alkylamino group, phenyl; A C _2-7 alkenyl group; or R ⁴ and R ⁵ together with an adjacent carbon atom represent a C _4-8 cycloalkyl ring optionally substituted with a C _1-4 alkyl or cycloalkenyl ring; and A represents an unbranched or branched alkyl or alkenyl group, optionally substituted by a halogen atom, which binds the naphthalene ring at the indicated position 3 with the group —CHR ⁴ R ⁵ , where A does not contain a quaternary carbon atom in the chain, with the total number of carbon atoms in the most long carbon chain coming from the naphthalene cycle in the specified position 3 is not more than 8.  12. The method according to claim 11, characterized in that said parasites are Bemisia and / or Spodoptera. 13. The method according to claim 11 or 12, characterized in that said compound is a compound of general formula (II)

where R, R ¹ , R ² , R ³ , R ⁷ and R ⁸ and n are as defined in claim 11, and R ⁴ and R ⁵ independently represents an optionally substituted C _1-7 alkyl or C _2-7 alkenyl a group. 14. The method according to claim 11 or 12, characterized in that said compound is a compound of general formula (III)

where R, R ¹ , R ² , R ³ , R ⁷ and R ⁸ , A, m and n are defined as described in clause 11, and R ⁴ and R ⁵ together with an adjacent carbon atom represent a C _4-8 cycloalkyl ring, optionally substituted C _1-4 alkyl, or a cycloalkenyl ring. 15. The method according to claim 11 or 12, characterized in that said compound is a compound of general formula (IV)

where R, R ¹ , R ² , R ³ , R ⁷ , R ⁸ , A and n are defined as indicated in claim 11, and R ⁴ and R ⁵ independently represent an optionally substituted C _1-7 alkyl or C _{2- 7-} alkenyl group.  16. The method according to any one of paragraphs.13 to 15, where the specified focus of the lesion includes pests as such or the environment, which is exposed or subjected to damage by pests. 17. A method of obtaining compounds of formula (VI) according to claim 8 and compounds of formula (VII) according to claim 9, comprising reacting a compound of formula (V)

where n, R and R ^{3 are} defined as described in paragraphs 8 and 9, with a carboxylic acid of the formula CHR ⁴ R ⁵ - (A) _m -COOH, where R ⁴ , R ⁵ , m and A are defined as indicated in paragraph 9 or R ⁴ and R ⁵ together form a group

as defined in clause 8. 18. Insecticidal composition containing a compound of formula (I)

where n = 0; m is an integer of 0 or 1;
R ¹ and R ² taken together represent a group = O,
R ³ represents a hydroxyl group or an —OCOR ¹¹ group, where R ¹¹ is C _1-6 alkyl;
R ⁷ and R ⁸ taken together represent a group = O;
R ⁴ and R ⁵ independently represent a hydrogen atom or a C _1-7 alkyl group optionally substituted with a halogen atom, a cyano group, a C _1-4 alkoxy group, a di- (C _1-4 ) alkylamino group, phenyl; A C _2-7 alkenyl group; or R ⁴ and R ⁵ together with an adjacent carbon atom represent a C _4-8 cycloalkyl ring optionally substituted with a C _1-4 alkyl or cycloalkenyl ring;
A represents an unbranched or branched alkyl or alkenyl group optionally substituted by a halogen atom that binds the naphthalene ring at the indicated position 3 to the group —CHR ⁴ R ⁵ , and where A does not contain a quaternary carbon atom in the chain, with the total number of carbon atoms in the most the long carbon chain extending from the naphthalene cycle at said position 3 is not more than 8, in combination with at least one carrier.  19. The insecticidal composition according to p. 18, characterized in that it contains 0.001 to 95 wt.% The active ingredient of the formula (I).  20. The insecticidal composition according to claim 19, characterized in that it contains 0.001 to 25 wt.% Of the active ingredient.  21. The composition according to claim 19 or 20, obtained in a form suitable for use against whiteflies or Lepidoptera. 22. The use of the compounds of General formula (I) as a fungicide against pest fungi:

where n = 0; m is 0;
R ¹ and R ² taken together represent a group = O,
R ³ represents a hydroxyl group;
R ⁷ and R ⁸ taken together represent a group = O;
R ⁴ and R ⁵ independently represent a hydrogen atom or methyl.  23. The use according to claim 22 against fungi of Rhizoctonia, Pyricularia and / or Aspergillus.  24. The use according to claim 23 against R.solani, P.orysae or A.niger. 25. The use according to any one of paragraphs.22-24, where R ⁴ and R ⁵ represent a methyl group. 26. The use of the compound according to item 22, where the group-CHR ⁴ R ⁵ represents a methyl or ethyl group. 27. A method for controlling pest fungi in a foci of infection, comprising treating said foci of infection with a compound of the general formula (I)

where n = 0; m is 0;
R ¹ and R ² taken together represent a group = O,
R ³ represents a hydroxyl group or an —OCOR ¹¹ group, where R ¹¹ is C _1-6 alkyl;
R ⁷ and R ⁸ taken together represent a group = O;
R ⁴ and R ⁵ independently represent a hydrogen atom or a C _1-7 alkyl or C _1-7 haloalkyl group; or R ⁴ and R ⁵ together with an adjacent carbon atom represent a C _4-8 cycloalkyl ring optionally substituted with C _1-4 alkyl.  28. The method according to item 27, wherein said pest fungi are Rhizoctonia, Pyricularia and / or Aspergillus. 29. The method according to item 27 or 28, characterized in that said compound is a compound of general formula (II)

where R, R ¹ , R ² , R ³ , R ⁷ and R ⁸ and n are as defined in claim 27, and R ⁴ and R ⁵ independently represent a C _1-7 alkyl or C _1-7 haloalkyl group. 30. The method according to item 27 or 28, characterized in that said compound is a compound of general formula (III)

where n, m, R, R ¹ , R ² , R ³ , R ⁷ and R ^{8 are} defined as indicated in paragraph 27,
R ⁴ and R ⁵ together with an adjacent carbon atom represent a C _4-8 cycloalkyl ring optionally substituted with a C _1-4 alkyl group.  31. The method according to any one of paragraphs.29 and 30, where the specified lesion includes pests as such or the environment, which is exposed or subjected to damage by pests. 32. The method according to item 27, wherein the compound is a compound of general formula (I), in which CHR ⁴ R ⁵ represents a C _1-2 alkyl or halogenated group. 33. A fungicidal composition containing a compound of formula (I)

where n = 0; m is 0;
R ¹ and R ² taken together represent a group = O,
R ³ represents a hydroxyl group or an —OCOR ¹¹ group, where R ¹¹ is C _1-6 alkyl;
R ⁷ and R ⁸ taken together represent a group = O;
R ⁴ and R ⁵ independently represent a hydrogen atom or a C _1-7 alkyl or C _1-7 haloalkyl group; or R ⁴ and R ⁵ together with an adjacent carbon atom represent a C _4-8 cycloalkyl ring optionally substituted with C _1-4 alkyl,
in combination with at least one carrier.  34. The fungicidal composition according to p. 33, characterized in that it contains 0.001 to 95 wt.% The active ingredient of the formula (I).  35. The fungicidal composition according to claim 34, characterized in that it contains 0.001 to 25 wt.% Of the active ingredient.  36. A compound according to any one of claims 8 or 9, suitable as an insecticide against whitefly and Lepidoptera insect pests.  37. The compound of any one of claims 8 or 9, suitable as a fungicide against pest fungi. Priority on points:
01/10/95 - according to claims 1 - 3, 5, 11, 12, 19 - 21;
07/04/95 - according to paragraphs 22 - 24, 27, 28, 33, 34, 35;
01/10/96 - according to paragraphs 4, 6 - 10, 13, 14 - 18, 25, 26, 29 - 32, 36, 37.

Images