Pesticides compositions.

The present invention relates to the use of bicyclic compounds as pesticides.

It is already known that bicyclic compounds are chlorinated have insecticidal activity (Patent of the United States of America N.^I 2,546 174).

It is known further that the 5-nitrate 6 a-trichloromethylnorbornene has insecticidal activity (Abstracts, 60 MECT, quoting 5360e).

However, the activity of these compounds is not always entirely satisfactory, mainly when used at low concentrations.

The applicant has now been discovered that can be used as pesticides the bicyclic compounds known partially derivatives of general formulae (I-):

in which

R¹ denotes hydrogen, cyano, halogen, optionally substituted alkyl, optionally substituted aryl, carboxyl, optionally substituted alkoxycarbonyl, optionally substituted aryloxycarbonyl, optionally substituted aminocarbonyl,

R is a cyano group, a nitro, a halogen, a haloalkyl group, R is CN, a

halogen or haloalkyl group when R ^

4

or R is a CCI,,

3⁰

R is hydrogen, optionally substituted alkyl, optionally substituted aryl, nitro group, halogen, hydroxy, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted alkylthio, optionally substituted arylthio, acyloxy group, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl, a cyano, alkoxycarbonyl optionally substituted, aralkoxycarbonyle, optionally substituted aryloxycarbonyl,

is hydrogen, optionally substituted alkyl, optionally substituted aryl, nitro group, a halogen, an alkoxy group optionally substituted, optionally substituted aryloxy, optionally substituted alkylthio, optionally substituted arylthio, acyloxy group, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl, optionally substituted alkoxycarbonyl, optionally substituted aryloxycarbonyl, the R ^ and may together form a

optionally substituted methylene group,

6, 7 8

The R -, wherein R, R are equal or different and represent, independently of one another, hydrogen, optionally substituted alkyl, optionally substituted aryl, halogen, cyano, optionally substituted alkoxycarbonyl, optionally substituted aryloxycarbonyl, an alkoxy, an aryloxy, optionally substituted alkylthio, arylthio group optionally

6, 7

substituted, R and R may together form

a double bond or an oxygen atom, or

5 ε 7 sec.

alternatively R and R and/or R and R may together form a methylene group optionally substituted, "

10

R are identical or different and represent, independently of one another, hydrogen, optionally substituted alkyl, an optionally substituted aryl group, cyano group, optionally substituted alkoxycarbonyl, optionally substituted aryloxycarbonyl, an alkoxy, an aryloxy, optionally substituted alkylthio, optionally substituted arylthio or fluorine,

11, 12

The R, R represent hydrogen, optionally substituted alkyl, optionally substituted aryl, halogen, cyano, optionally substituted alkoxycarbonyl, optionally substituted aryloxycarbonyl, an alkoxy, an aryloxy, optionally substituted alkylthio,

11, 12 optionally substituted arylthio, R and R may together form oxygen, sulfur, an imino group, alkylimino, triazoles or a methylene group optionally substituted.

The formula (I-) covers the stereoisomers and optical isomers possible in each case.

Surprisingly that the substituted bicyclic compounds of formula I exhibit improved insecticidal activity that the compounds previously known. They additionally act as rodenticide. The active substances according to the invention are defined by formula (I-).

In formula I, the variables preferably have the following values:

R¹ is hydrogen, halogen, alkyl to c4, halo to c ^, phenyl,

a cyano, aminocarbonyl,

2

R is a cyano group, a nitro, a halogen, a

2

to c ^ halo group, R being a

cN, halogen or a group - halogén

3, 4

alkyl when R or R is a CCI,,

3^

R is hydrogen, alkyl group of C₁ to c₄ , phenyl optionally substituted with halogen, an alkyl radical or a group n0₂ , halogen, haloalkyl group in to c ^, acetoxy, (alkoxy-c ^) carbonyl, aralkoxycarbonyle, phenyloxycarbonyl, a cyano, a nitro, hydroxyl, alkoxy-c ^, phenyloxy, R is CN, halogen or haloalkyl group when R ^ or R * is a group CCL is ^,

is hydrogen, alkyl|to c_F. a phenyl group optionally substituted by a halogen or a radical ^ nanograms, halogen, haloalkyl group c-a-j-c ^, (alkoxy-c ^) carbonyl or R³ and R ^ form

dihalogenomethylene together,

The R ' R represent, independently of one another, hydrogen, alkyl group of C|to c₄ , phenyl, halogen, haloalkyl group in to c ^, alkylthio to c₄ , phenylthio, phenoxy, alkoxy-c ^, R.³ and R ^ forming

set a double bond or oxygen,

R and r10 represent, independently of one another,

hydrogen, an alkyl group in the Cj to c ^, R.¹¹ and r12 halo to c₄ or fluorine, represent, independently I ' HFU each other,

hydrogen, alkyl to, haloalkyl C<j to C.₄ , halogen or together form an ethylidene group or isopropylidene.

In formula I, the variables have very advantageously the following values ii

R is cyano, 1 * hydrogène, a group 1 methyl, ethyl, fluorine, trifluoromethyl,

is cyano, fluorine, trifluoromethyl, nitro group, trichloromethyl, r2 representing NC, w, MC₃ or CCI4 when R³ or R ^ represent. CClj,

represents

hydrogen, methyl, ethyl, bromine, chlorine, fluorine, cyano, trifluoromethyl, trichloromethyl, acetoxy, hydroxyl, dichlorofluorométhylè, chlorodifluoromethyl, bromodichlorométhyle, phenyl, O-chlorophenyl, nitrophenyl, methoxycarbonyl, ethoxycarbonyl, . pentafluorobenzyloxycarbonyle, phenoxycarbonyl,

hydrogen, . a methyl group # ethyl, the

. ; ' bromine, chlorine, fluorine the ^, trifluoromethyl, trichloromethyl, dichlorefluorométhyle, chlorodifluororaéthyle, bromodichlororaéthyle, phenyl, O chlorophénÿle, nitrophenyl,

: methoxycarbonyl, ethoxycarbonyl,

The R ^ ^ and R together form the group dichloromethylene,

e β•7 has

The R, the R, the R, R represent, independently of one another, hydrogen, methyl, bromine, chlorine, fluorine, a methylthio group or - phenyl

haloalkylthio,

6, 7

R and R together form a double bond or

of 1' oxygen,

R and R represent, independently of one another, hydrogen, methyl or trifluoromethyl -

methyl or fluorine,

11, 12

R and R represent, independently of one another, hydrogen, methyl, fluorine, bromine, chlorine, a group 1 a-brométhyle, 1-chloroethyl, 1 a-brorao~1-to-methylethyl, 1 -

platinic 1 a-methylethyl,

11, 12

R and R together form an ethylidene group or isopropylidene.

Action include in particular the following compounds:

3.3 - ""/ dichloro substituted bicyclo 2.2.1 _7hept-to-5-en-2.2-to-dicarbonitrile 3.3 / - dichloro-bicyclo "2.2.1 _7heptane and 2.2 to-dicarbonitrile 3-chloro-bicyclo/" 2.2.1 _7hept-to-5-en-2.2-to-dicarbonitrile 3-chloro-bicyclo /" 2.2, 1 __7heptane and 2.2 to-dicarbonitrile

5.6 - dibromo 3.3-dichloro-bicyclo /" _Theptane 2.2.1 above 2.2-to-dicarbonitrile

3.3.5.6 - tee trachloro bicyclo 2.2/"". t__7heptane and 2.2 to-dicarbonitrile

5 - bromo 3.3-dichloro-bicyclo/"" 2.2.1 _7hept-to-5-en-2.2-to-dicarbonitrile

6 - bromo 3.3-dichloro bicycio /" ^ 2.2.1-hept-to-5-en-2.2-to-dicarbonitrile

3.3 - dichloro 5,6-epoxy cyclo /" 2.2.1 _7heptane-a 2,2 a-dicarbonitrile

2.2_/ 3 trifluoro-3 a-IFFT luorométhyl bicyclo /" 2.2. 1 VBE1 j7hept-to-5-ene

3.3 bis - (trifluoromethyl) - bicyclo-__7kept 2.2. 1 ""/ " - 5-en-2.2-to-dicarbonitrile

the bis - 3.3 - the bicyclo - (trifluoromethyl)/~__7heptane 2.2.1 above 2.2-to-dicarbonitrile 3-chloro 3-trifluoromethyl bicyclo/"" 2.2.1 _7hept-to-5-en-2.2-to-dicarbonitrile bicydo /" 2.2.1 _7hept-a 5 a-ene 2_F. 2 a-dicarbonitrile

3.3 - dichloro 5.6 epoxy cross-bicyclo/"2.2.1 _7heptane and 2.2 to-dicarbonitrile 3-acetoxy bicyclo /~" 2.2.1 _7hept-to-5-en-2.2-to-dicarbonitrile 3 chloro-méthy L-bicyclo 2.2.1 /~_- 7hept-to-5-en-2.2-to-dicarbonitrile

the bicyclo/^- 2.2.1 _7heptane-a 2,the bicyclo/2 a-dicarbonitrile^- 2.2.1 _7hept-to-5-en-2 a-carbonitrile derivatives

2 chloro-bicy C./ loLINEAGE~2.2.1 _7hept-to-5-en-2 a-cabonitrile roethylic acid ester in 3.3 above dichIoro-to-2-cyano substituted bicyclo /" 2.2.1 _7hept-to-5-en-2~carboxylique

amide¹ acid 3-chloro 2-cyano substituted bicyclo /" 2.2.1 _7hept-to-5-en-2-carboxylic

2.3 - dichloro-bicyclo of £2.2. l/7hspt-to-5-en-2|3 a-dicarbonitrile 5.6-dibromo 3-chloro-bicyclo /~"2.2.1 J7heptane" 2.2-to-dicarbodicarbo.nitrile.

The compounds of general formula 9.ï are partly known and can be prepared by generally known methods.

The compounds of general formula (LAs) are novel;

in this formula

3

R represents chlorine, bromine, fluorine, alkyl group of C₁ to c₄ , trifluoromethyl,

acetoxy,

4

R represents hydrogen, bromine, fluorine, a

methyl or optionally substituted phênyle, the R ^, the R®, the R®, the R ^, the R ^, the R ^ represent, independently of one another, hydrogen, methyl, ethyl, hydroxymethyl, halomethyl, trifluoromethyl or fluorine,

1112

R and R further together a substituted methylene group or atom ' oxygen.

Compounds of the formula (LPNs) by reacting a cyclopentadiene of general formula (III):

wherein R ^, the R®, R-®', the R ^®, the R ^, ^ the R have the meaning indicated above,

with an alkene of general formula (II):

wherein R

top.

³ and R⁴

THE III

have the meaning thereof -

The olefin of formula (II) is then mixed, optionally in a solvent, with the cyclopentadiene of formula (III) or both components are poured dropwise assembly optionally in a solvent.

It is considered as solvents: alkanes such as, for example, pentane, 1' normal hexane, petroleum ether, ligroin; cycloalkanes such as, for example, the 07229 of cyclohexane; aromatic hydrocarbons such as, for example, benzene, toluene, xylene, chlorobenzene; cyclic ethers such as, for example, tetrahydrofuran, dioxane; halogenated hydrocarbons such as, for example, dichloromethane, trichloromethane, tetrachloromethane.

The reaction can be carried out at temperatures of 250 °c to -20, preferably 20 to-10q °C.

The cyclopentadiene II is preferably used as a monomer in a mole ratio with olefin (lll) of 1:1 to 1:10, preferably 1:1 to 1:3. For a reaction temperature of more than 120 °c, preferably from 150 °c, may use a cyclopentadiene dimer (ll).

The new compounds of general formula (I b):

The R ^ denotes chlorine, bromine, fluorine ', alkyl to c₄ , trifluoromethyl, acetoxy, or optionally substituted phenyl

a cyano,

4

R is hydrogen, chlorine, bromine, fluorine, alkyl group of C₁ to c₄ , trifluoromethyl, optionally substituted phenyl, and

5, 8 9, 10 11, 12

The R, the R, the R, the R, the R, R represent, independently of one another, hydrogen or methyl, ethyl, hydroxymethyl, halomethyl, trifluoromethyl or fluorine,

11, 12

R and R are additionally together a substituted methylene group or an oxygen atom, are obtained by reaction with bromine, optionally in a solvent, a compound of the general formula:

R is designated chlorine, bromine, fluorine, an alkyl group of 3 to c₄ , tnp luorométhyle, acétoxv, optionally substituted phenyl, cyano group,

R4 is hydrogen, chlorine, bromine, fluorine, alkyl to c₄ , tnfluorométhyle, optionally substituted phenyl, and

The bromine is added dropwise in a molar ratio of 1:1 to 1:10, preferably 1:1 to 1:3 relative to compound (the), optionally in the same solvent. It is considered as solvents: chlorinated hydrocarbons such as, for example, dichloromethane, trichloromethane, tetrachloromethane; of alcanas such as, for example, pentane, 1' normal hexane; acetic acid.

The reaction is conducted at a temperature of 0 to 100 °c, preferably from 20 to 80 °c. When the reaction has been completed, the solvent and, optionally, the excess bromine are distilled off and the residue is distilled or recrystallized.

R² denotes chlorine, bromine, fluorine, alkyl-c ^, trifluoromethyl, acetoxy, optionally substituted phenyl,

a cyano,

4

R is hydrogen, chlorine, bromine, fluorine, alkyl to c₄ , trifluoromethyl, optionally substituted phenyl, and

R⁵ , R.®, R.⁹ , R.¹⁰ , THE R ^¹ , R.¹² represent, independently of one another, hydrogen, methyl, ethyl, hydroxymethyl, halomethyl or trifluoromethyl or fluorine,

11, 12

R and R may further represent together a substituted methylene group or an oxygen atom,

are obtained by reaction with chlorine compound ' formula (the):

in which

R² denotes chlorine, bromine, fluorine, alkyl-c ^, trifluoromethyl, acetoxy, optionally substituted phenyl, cyano group,

The R ^ is hydrogen, chlorine, bromine, fluorine, alkyl group of C₁ to c₄ , trifluoromethyl, optionally substituted phenyl, and

THE R ^, R.³ , THE R ^ DEGREES, THE R ^, R.¹² are as defined above.

The reaction is advantageously carried out in a chlorinated hydrocarbon such as, for example, dichloromethane, trichloromethane, tetrachloromethane, and at a temperature of 0 to 100 °c, preferably from 20 to 80 °c. Then whatever a chlorine in the mixture until the compound of formula the has fully reacted. If desired, the reaction may be maintained by illumination with a UV lamp or a solar lamp. The solvent is distilled off and the residue is distilled or recrystallized.

The novel compounds of the general formula

R² denotes chlorine, bromine, fluorine, alkyl-c ^, trifluoromethyl, acetoxy, * phenyl optionally substituted, cyano group,

R is hydrogen, chlorine, bromine, fluorine, alkyl-c ^, trifluoromethyl,

optionally substituted phenyl, and

5, 8 8, 1 n it said I?

THE R, THE R, R-, R. , The R, R represent, independently of one another, hydrogen, methyl, ethyl, hydroxymethyl, halomethyl, trifluoromethyl or fluorine,

1112

R and R may further represent a substituted methylene group or assembly H - oxy

gene, *

5, 8

one of the radicals R and R and the other bromine

the I

having the meaning,

are obtained by dehydrobromination of a compound of formula IB, with a base, optionally in a solvent,

O-C.

at least one of the radicals R and R must thus représen -

tert hydrogen.

It is considered as solvents chlorinated hydrocarbons such as, for example, dichloromethane, trichloromethane, tetrachloromethane; aromatic hydrocarbons such as, for example, benzene, toluene, xylene, chlorobenzene; alkanes such as, for example, pentane, 1' normal hexane; cyclic ethers such as, for example, tetrahydrofuran, dioxane.

It is considered as bases preferably tertiary amines such as, for example, triethylamine, diazabicycloundecene, diazabicyclononene, diisopropylethylamine, pyridine, quinoline.

The reaction is carried out at a temperature of

0 to 120^I C., preferably at 20 and 80°.

The molar ratio of compound (lb) to the amine has a 1:10 to 1:1 value, preferably 1:1 to 1:3.

Ammonium bromide formed is separated, for example with aqueous hydrochloric acid and the product is isolated from the organic phase.

The novel compounds of formula (the):

in which

■>

R represents chlorine, bromine, fluorine, a

alkyl-c ^, trifluoromethyl, acetoxy, optionally substituted phenyl or cyano,

The R ^ is hydrogen, chlorine, bromine, fluorine alkyl to c ^, trifluoromethyl, optionally substituted phenyl, and

R⁵ , R.⁹ , The R, the R, R represent, independently of each other 10, 11 12, hydrogen, methyl, ethyl, hydroxymethyl, halomethyl, trifluoromethyl or fluorine,

, 11 and r12 additionally together represent a group

substituted methylene or an oxygen atom, one of the radicals R and R represents chlorine and the other 5, 8 having the definition indicated,

are obtained by reacting and dehydrochlorination of a compound of formula (the), at least one of the radicals and R® to represent hydrogen, by analogy with the procedure followed for (id.).

The novel compounds of formula (yew):

R represents chlorine, bromine, fluorine, a

alkyl-c ^, trifluoromethyl, acetoxy, optionally substituted phenyl, cyano group,

R⁴ is hydrogen, chlorine, bromine, fluorine alkyl group of C₁ to c ^, trifluoromethyl, optionally substituted phenyl, and

R⁸ , R.⁸ , R.⁹ , R.¹⁰ , THE R ^¹ , The R ^ represent, independently EMD ' another, hydrogen, methyl, ethyl, hydroxymethyl, halomethyl, trifluôrométhyle or fluorine,

11, 12

R and R together are further

substituted methylene or an oxygen atom, are obtained by reacting a compound of formula (the) with a peracid.

The reaction is carried out advantageously in a chlorinated hydrocarbon such as, for example, dichloromethane, trichloromethane or in an aromatic hydrocarbon such as, for example, benzene, toluene, the chloroben2ene. Added dropwise in a ratio of 1:1 to 1:2 online solution is, for example, m-acid - at a temperature of 0 to 130 °c. The treatment is' carried out in a conventional manner with a solution of sodium hydrogen carbonate/hydrogénosul ite-GBP. sodium to separate the peracid in excess and m-chlorobenzoic formed. The product (yew). is in the organic phase. The epoxidation can also be performed with other agents such as, for example, peracetic acid or perpropionic acid.

The novel compounds of formula (lg):

R⁸ represents chlorine, -. bromine, fluorine, alkyl-c ^, trifluoromethyl, acetoxy, optionally substituted phenyl, cyano group,

R⁴ is hydrogen, chlorine, bromine, fluorine, alkyl-c ^, trifluoromethyl, optionally substituted phenyl, and

The R ^, the R ^, the R ^, the R ^ degrees, the R ^, represent, independently

one of, the L'another, hydrogen, methyl, ethyl, hydroxymethyl, halomethyl, trifluoromethyl or fluorine,

11, 12

R and R are additionally together a group

substituted methylene or an oxygen atom, are obtained by catalytic hydrogenation of a compound of formula (the) in a solvent.

It is considered as solvents, for example, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane.

Catalysts used are noble metals secured on supports, for example, platinum on carbon attached or foam-palladium.

The reaction is carried out at a temperature of

20 to 100 °c at a pressure of 0.1 and 1.0 mpa to.

We obtain the novel compounds of formula (IH-):

3

R denotes chlorine, bromine, fluorine, alkyl to c₄ , trifluoromethyl, acetoxy, or optionally substituted phenyl

a cyano,

R⁴ is 1' hydrogen, chlorine, bromine, fluorine, alkyl-c ^, trifluoromethyl, optionally substituted phenyl, and

R⁵ , THE R **, R.⁹ , R.¹⁰ , R.^- *¹ , R.¹² represent, independently of one another, hydrogen, methyl, ethyl, hydroxymethyl, halomethyl, trifluoromethyl or fluorine,

11, 12..

R and R are additionally together

a substituted methylene group or an oxygen atom,

by saponifying partially by known methods of the compounds of the formula.

The active substances are suitable, beside their good compatibility with plants and their low toxicity in warm-blooded animals, control of animal pests, in particular insects, mites, encountered in agriculture, in forests, in the protection and commodities stored as well as in the hygiene sector.

They act against species of normal sensitivity and resistant, as well as against all development stages or only some. To the pests mentioned above belong the following:

In the order of the Isopoda, for example Oniscus, Armadillidiumvulgsre, Porcelliqscaber;

in the order of the Diplopoda, for example Blaniulusguttulatus;

in the order of the Chilopoda, for example Geophiluscarpophagus, willwill scutigera specs. ;

in the order of the Symphyla e.g. Scutigerellaimmaculata;

in the order of the Thysanura, for example Lepismasaccnarina;

in the order of the Collembola, for example Qnychiurusarmatus;

in Orthoptera, for example Blattaorientails, Periplaneta americana was, geographica maderae, insects and arachnids, purchased dooesticus, Gryllotalpaspp., Valerianella locusta mlgratoriamigrâtorioides, either Melanoplus differentials, Schistocerca,

in the order of the Dermaptera, for example Forficula Radix auricularia;

in order isoptera, e.g. Reticulitermesspp.,

in the order of the Anoplura, for example grape phylloxera stoma, phemphigus spp., Pediculus corporis be;

Haematopinusspp., SPPs Linognathus.

in order Mallophaga, for example ïrichodectesspp., Damalineaspp.,

in the order Thysanoptera, for example Hercinothripsfemoralis, as thrips tabaci;

in the order of the Heteroptera, for example Eurygasterspp., Dysdercusintermedius, Piesma lorica, Cimexlectularius, Rhodnius prolixus that, triatoma genus SPPs.

in the order Homoptera, for example brassicas whitefly, Bemisia, orTrialeurodes vaporariorum, USDA APHIS gossypii, Brevicoryne brassicas, Cryptomyausribis, Doralisfabae, Doralis Shoene, Eriosonalanigerum, Hyalopterusarundinis, Macrosiphumavenae, Myzusspp., Phorodonhumuli, padi, Empoascaspp., Euscelisbilobatus, Nephotettixcincticeps, Lecàniumcorni, Saissetia Dacus, Laodelphaxstriâtellus, îliiaparvatalugens, Aonidiella immatri, Aspidiotushederae, Pseudococcus SPPs, Psylla sppspp.î ·

üans * 1 * ordre Lepidoptera e.g. toxin receptor bt, Bupaluspiniarius, - Cheimatobia Operpthera brumata, Lithocolletisblancardella, Hyponomeutapadeila, Plutellamaculipennis "; felacosomaneustrta, ^ îhroctischrysorrhoea, iymantriaspp., Bucculatrixthurbériella, Phyllocnistiscitrella, anAgrotis SPPs.., Euxoaspp., Feltiaspp., gears insulana, Keliothisspp., Baphygmaexigua, Mamestra species brassicas, Panolisflammea, Prodenia willwill litura, Spodoptera littoralis' spp., ïriohoplusia nor, Carpocapsapomonella, bilin spp., Chilo SPPs,, Pyrausta ECB mutates, polymorphic Ephestia kühniella, toward Galleria mellonella" Càcoeciapodana, Capuareticulana, Choristoneura fumiferana were, Clysiaaabiguella, Homonamagnanima, j. ïortrixviridana

in 1 * ordre Coleoptera, for example anobiida punctatum, Rhizoperthadominica, Bruchidius=Acanthoscelidesobtectus, Hylotrupesbajulus, Agelastica RFLPs, Beptinotarsadecemlineata, Phaedoncochleariae, aDiabrotica spp., Psylliodeschrysocephala, Epilachna frontalis, Atomariaspp., Oryzaephilussurinamensis, Anthonomusspp., weevil Sitophilus SPPs,, Otiorrhynchus Otiorhynchus sulcatus, cosmopolitan sordidus, Ceuthorrhynchusassimilis * willwill hypera postica, Dermestesspp., Trogodrma spp., Anthrenusspp., Attagenusspp., Lyctus AnorMED, Meligethesaeneus, Ptinusspp., Piptushololeucus, willwill gibbiura psylloides, îriboliumspp., from Tenebrio wort gold, Agriotes SPPs,, Conoderusspp., the Melolontha the Melolontha, Amphimallonsolstitialis, Costelytra zealandica grub }

•: ** 1 in order Hymenoptera, for example. Biprionspp., Hoploeampa SPPs ", j. tasiusspp. Konomoriumpharaonis, Vespa SPPs. the j'

in L¹ the order diptera, for example Aèdes SPPs, of Anopheles spp. ', Culex quinquefaxciatus spp., Brosophila the melanogaster, Muècà sppspp.y Eaimia SPPs .,, / willwill càlliphora erythrocephala, lùcilia. sPPs,, Chrysoayîa SPPs,, fly Cuterebra spp., Gastrophilusspp., HippoboscasppSiomoxysspp., estrus spp., Hypoderma. spp., fabanus SPPs ", Tanniaspp., Bibiohbrtulanus, fried Oscinella, Phorbiaspp., Pegosyiahyoscyami, medflies, olsae oleae, Tipula entire facility.

In order siphonaptères, for example Xenopsylla trispinis cheopis, Ceratophyllus SPPs.

In the order of the Arachnida, for example Scorpiomaurus, Latrodectusmactans.

In the order Acarina, for example Acarus Siro stadium, Argasspp., Ornithodorosspp., Dermanyssusgallinae, by Eriophyes ribis, Phyllocoptruta willwill oleivora, Boophilusspp., Rhipicephalusspp., Amblyommaspp., Hyalomma spp spp., remover spp., Psoroptesspp., Chorioptesspp., scabies spp., Tarsonemusspp., Bryobiapraetiosa, Panonychusspp., SPPs Tetranychus..

²⁰ 0, 7 2, 29 The substances according to the invention are endowed with properties and suitable rodenticide

in combating leporidae (Lagomorpha) and rodents (grouprodentia), such as squirrels (Sciuroidae), rats to pockets of America (Geomyoidae) and in murine (Muroidae), among which there are mainly the muscardins (Muscardinidae) and the mouse (Cricetomyinae).

To lepori belong essentially the leporid such as wild rabbit (Oryctolagus) *, to sciuroidés belong, for example, the European souslik (Citellus parryii Citellus parryii)* and ground squirrels (Citellus parryii luciferase)* or rats to pockets of America belong for example the "Mountain and naine Gopher:" (Thomomys Thomomys talpoides) *.

The number of muscardins, include, for example, dormouse (Glis glis Glis glis) *.

The mouse primarily include, in

the group consisting of mouse long-tail (Murinae), field mice (husband and spec.); rats (antagonize rattus spec.), such as the black rat (antagonize rattus antagonize rattus)* and the brown rat (antagonize Rattus norvegicus)* J mouse domestic (driven spec.), such as Mus *; the group hamsters (Cricetinae), counted hamster (Cricetus cricetus Cricetus cricetus) Europe * and the group consisting of mouse tail (investigated microtines), include, for example, the bank (of Microtus arvalis) *, the voles (of Microtus agrestis) *, the large bank (cinetics terrestris are)* and the muskrat (muskrat zibethica).

{* species particularly important).

The active substances can be incorporated into conventional formulations such as solution, emulsions, slurries, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active compound, very fine encapsulations of polymers and polymer in coating materials for the seed, furthermore in formulations summed charge cells such as cartridges, cans, coils smoke, like, as well as in formulations with very low volume for the nebulization of hot and cold.

These preparations are prepared in a known manner, for example by mixing the active substances with extenders, it is to say liquid solvents, pressurized liquefied gasses and/or solid carriers, optionally using surface-active agents, it is to say emulsifiers and/or dispersants and/or foam-producing agents. In the case of using water as a diluent, can be, for example, can be used as organic solvents as solvents auxiliary.

As liquid solvents, it is considered mainly aromatic hydrocarbons such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic hydrocarbons or chlorinated aliphatic hydrocarbons such as chlorobenzenes, of chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, highly polar solvents such as dimethylformamide and dimethylsuifoxyde, as well as water, * is meant to designate by liquefied gaseous diluents or carriers, liquids which are gaseous at normal temperature and pressure, for example an aerosol propellant such as hydrocarbons halogens as well as butane, propane, nitrogen and carbon dioxide? as solid supports, it is considered: e.g. natural mineral powders such as kaolin, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic mineral powders such as silica, aluminum oxide and silicates highly dispersed;

as solid carriers for granules, it is considered;

for example crushed and fractionated natural rocks such as calcite-, marble, pumice, sepiolite, dolomite particles, as well as synthetic granules of inorganic powders formed organic and granules of organic material such as sawdust, coconut shells, corn cobs and stalks of tobacco, as emulsifiers and/or * agents produces a foam, is, considers; for example emulsifiers not ioncgenes such as esters and anionic fatty dracides polyoxyethylenic, ethers of fatty alcohols yethylenic polyo&, by-example of polyglyGols alkylarylic ethers, alkyl sulfonates "; of alkylëülfates *, sulfonates as well as the d ^ îbumine hydrolysates; as dispersants, considered: for example waste liquors and the méthyicellulose lignosulfitic.

Can be used in the formulations adhesives such as carboxymethylcellulose, natural and synthetic polymers and powdered, granular or latex form, as gum arabic, polyvinyl alcohol, polyvinyl acetate.

One can use dyes such as inorganic pigments, for example iron oxide, titanium oxide, Prussian blue and organic colorants such as dyes of the subclass of 1' alizarin, azo dyes and metal phthalocyanines and nutrients to trace, such as salts of iron, manganese, boron, copper, cobalt alloy, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.

The active substances according to the invention may be present in commercial formulations thereof as well as in the application forms prepared from these formulations, as a mixture with other active substances such as insecticides, attractants sexual, sterilants, acaricides, nematicides, fungicides, growth regulator and herbicides. Among the insecticidal, include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances prepared by microorganisms, andc.

The active substances according to 1' invention may further be present in commercial formulations thereof as well as in the application forms prepared from these formulations, as a mixture with synergists. Synergists are compounds by which the action of the active compounds is increased without the synergist added must itself be recoverable activity.

The active substance content application forms prepared from the commercially available formulations can vary within wide limits. The active substance concentration application forms may be of 0.0000001 to 100% by weight of active compound, preferably from 0.0001 to 1% in ' weight.

The application is carried out in a conventional manner adapted to shapes that is applied.

In the case of applying pests hygiene and stored products, the active substances are characterized by a remarkable residual on wood and clay, as well as by a good stability to the bases on substrates treated lime.

The active substances according to the invention can also be used as rodenticide.

Example 1

100 grams of cyclopentadiene (1.52 mol) are dissolved in 300 ml of monomefic tetrahydrofuran and 220 grams (1.50 moles) of 2.2-dichloro 1-cyano acrylonitrile in 1 liter of tetrahydrofuran are added dropwise.

Allowed to stand still for 10 hours at 25 °c and the solvent is removed by distillation. Can be recrystallize the residue in ethanol is obtained. 255 grams (83%) of 3.3-dichloro-bicyclo/^- 2.2.1 _7hept-to-5-en-2.2-to-dicarbonitrile,

100 Grams is dissolved (0.47 moles) of the compound (VI) prepared in 1' example 1 in 500 ml of trichlorôméthane and added dropwise to 75 grams (0.47 moles) of bromine in 100 ml of trichlorôméthane. Is heated at reflux until the color of the bromine has subsided. The solvent is removed by distillation and remains 175 grams (100%) of 5.6-dibromo 3.3-dichloro-bicyclo /" _7heptane 2.2.1 above 2.2-to-dicarbonitrile, melts at 133 °c.

VII.

There can be obtained the compound vïiib pure (melting point (131 - 133^I C) by fractional crystallization in ethanol.

100 grams (0.47 moles) of the compound (VI) prepared in the example 1 are dissolved in 500 ml of chloroform and the solution is heated to boiling. Chlorine gas is passed through the solution until the starting compound has completely reacted, and based on the analysis by gas chromatography. Is obtained (98%) of 130 g of 3, 3, 5, 6 a-tetrachloro bicyclo /~__7heptane 2.2.1 above 2.2-to-dicarbonitrile, melts at 126 * c (after recrystallization from 1' ethanol).

Example 5

mV

50 grams (0.44 moles) of 2 chloro-1-cyano acrylonitrile and 30 grams (0.45 moles) of cyclopentadiene monomer are dissolved in 500 ml of tetrahydrofuran and the solution is maintained for 15 hours at 25 °c. Vacuum is knocked the volatile components and allowed to recrystallize the residue in ethanol. Is obtained (71%) of 56 grams 3-chloro-bicyclo /" 2.2.1 _7hept-to-2-en-2.2-to-dicarbonitrile. The product is formed of a mixture of compound (a villa) an exo or endo and compound (vïiib).

Example 6

30 grams (0.17 moles) of the compound (VIII-) prepared according to 1' example 5 are dissolved in 170 ml of ethyl acetate, the solution is charged into an autoclave, supplemented with 1% to 3 g of platinum on carbon attached, heated to 50 °c and the pressure is increased to 1.5 mpa with hydrogen. After one hour, is expanded the pressure in the autoclave, the catalyst is separated by filtration and concentrated confectioneries the rotary evaporator. It remains 30 grams (99%) of 3-chloro-bicyclo/"2.2, 1 _7heptane and 2.2 to-dicarbonitriie, melts at 131®C."

Example 7

(0.28 Moles) OS grams of 2 a-chloro~1-cyano 2-trifluoromethyl-acrylonitrile and 18.5 grams (0.28 moles) in 200 ml of monomeric cyclopentadiene dioxane are kept on for 15 hours at 25 °c. The solvent is removed and is 65 grams (95%) of 3-chloro 3 a-trifiuorométhylbicyclo /~2.2.1 _7hept-to-5-en-2.2-to-dicarbonitrile, melts at 173 °c (after recrystallization from ethanol).

Example 8

20 grams|0.15 moles) of 2-acetoxy-1 - - Cyanoindole acrylonitrile and 15 grams {0.23 moles) of cyclopentadiene monomer are kept at 25®C. for 16 hours in 150 ml of tétrahydrofuraraie "bone vacuum flushing all volatile components and 26 grams obtained (e? %) of 3-acetoxy bicyclo/7"~~5 - ene 2.2.1 j7hept * 2, 2 ±fcriledicarbon~, melts at 133 * 0 (after recrystallization from tetrahydrofuran).

Example 9

20 grams (0.11 moles) of the compound (binding of!) prepared in 1' example 5 are dissolved in 300 © 1 laundry éthanoligue 2% potash and heated to reflux for 2 hours. Is treated in the usual manner with a mixture of water and ether and obtained (78%) of 19 g of 3 a-chloro~2-to-eyana~bicyclo/"" 2.2.1 j7hep t~5 - ene - 2 - carboxamide derivatives, 141 and 143 degrees Celsius melts (after recrystallization from ethanol).

Example 10

10 grams (0,036 moles) of 3.3 to-bis~trifluorométhylbicyclo /* " 2.2. the L ^ yhept s-ene-Z group, 2 a-dicarbonitrile (W-. THE J.

Middleton's, 3u 92. Hoary 30, 1402 (1965)) are dissolved in 150 ml of ethyl acetate and the solution is charged into an autoclave. Added 2 g of 5% platinum on carbon attached, is heated to 27 °c and raises the pressure at 0.7 mpa with hydrogen. After 15 min, is expanded to the pressure in the autoclave, which the catalyst is removed by filtration and is concentrated to the person operating the rotary evaporated - *. It remains 10 grams (99%) of 3.3 bis trifluoro-methyl-bicyolo /" 2 .2é1_7heptane and 2.2 to-dicarbonitrile, melts at 178 °c.

50 grams (0.13 moles) of the compound (VII) prepared in the example 3 are dissolved in 300 ml of toluene and 30.4 grams (0.20 moles) of diazabicycloundecene (DBü) in 200 ml of toluene are added dropwise. 1 Hour mask is heated to boiling, is cooled and extracted by shaking with hydrochloric acid 1n. The organic phase is dehydrated with magnesium sulfate and

the concentrate to 1¹ rotary evaporator. It remains 30.5 grams

(78%) of a mixture of 5 a-bromo 3.3-dichloro-bicyclo /~2.2.1 _ 7-a-hept-to-5-en-2.2-to-dicarbonitrile (XlVa) and 6 a-bromo 3.3-dichloro-bicyclo /" 2.2.1 _7hept-to-5-en-2.2-to-dicarbonitrile (XlVb), of melting point in the range of 105

to 107 °c.

XV FRAMES

80 grams (0.54 moles) of 1.2-dichloro 2 a-cyanoacrylonitrile and 44 grams (0.67 mole-) cyclopentadiene monomer are heated at reflux for 9 hours in 1 liter of tetrahydrofuran. The volatile components are expelled and vacuum is achieved (50%) of 58 g of 2.3 to-dichlorobicyclo/^- 2.2.1 _7hept-to-5-en-2.3-to-dicarbonitrlie, melts at 159 °c (after recrystallization from ethanol).

Example 13 07229 m.

21 grams (0.1 moles) of the compound (VI) prepared in 1' example 1 are dissolved in 100 ml of chlorobenzene and 20 grams (0.12 moles) of m-chloroperbenzoic acid in 200 ml of chlorobenzene are added dropwise. Is heated during 4 hours at reflux and treated conventionally with a solution of sodium hydrogen sulfide to destroy the excess peracid and with a solution of sodium hydrogencarbonate to separate acid mchlorobenzolgue. The organic phase is isolated 17 grams (75%) of 3.3-dichloro 5.6-epoxy cyclo/"" _7heptane 2.2.1 above 2.2-to-dicarbonitrile, melts at 229 °c.

Example 14

Added 11.5 gm (0,072 moles) of bromine in 50 ml of trichloromethane to 20 grams (0,072 moles) of 3.3 bis trifluoromethyl bicyclo/™ 2.2.1 _7hept-to-5-en-2.2-to-dicarbonitrile in 150 ml of trichloromethane. The mixture is heated at reflux until the color of the bromine has subsided. Is flush then distilling off the solvent.

It remains 31 grams (93%) of 5.6-dibromo 3.3 bis trifluoro-methyl cyclo /" 2.2. the I ^ THeptane and 2.2 to-dicarbonitrile (melting point 116 °c).

In the following examples, compounds are indicated formulas without giving accuracy on steric relationships.

Example has 07229 TB test₁₀₀ for dipterans

Test animals: parasitizing Musca domestica

Solvent: acetone

2 parts by weight of active substance is resumed in 1000 parts by volume of solvent. The resulting solution is diluted to low * desired concentrations with additional solvent.

2.5 ml of active ingredient solution are introduced to the pipette in a petri dish. At the bottom of the box there is a disk of filter paper of about 9.5 cm in diameter. Allowed the petri dish discovery until the solvent is completely evaporated. The amount of active substance by m² filter paper is increased or decreased depending on the concentration of the active ingredient solution. Then inserted about 25 test animals in the petri dish that is covered with a cover glass.

Observed continuously the status of the test animals. Determining the time required for obtaining an effect of paralysis to 100%.

their concentration and the necessary times louse of £? toto qbtenir test animals, the substances the ACteein ES, an effect of paralysis of 100% emerge from the table " according 9.ï

TB test₁₀₀ the PC>^{starting motor} dipterans (parasitizing Musca domestica)

Concentration

Active substances active substance · ΐ∩ ^ 0 in the solution, 1

Known substance

Toxaphene 0.2 4=^ 0%

nimii (result)

Test 1 Τ ·ΐ 00 for dipterans (parasitizing Musca domestica)

Concentration

Active substances active substance

in the solution,

%

0.02 0.02 min at 0.0002 minutes 0,002 min.

0.02 minutes TABLE (Result)

TB test₁₀ q (parasitizing Musca domestics) dipterans

Concentration

Active substances active substance ^ ΐ θ θ in the solution, %

0.02 65 min at the RF: ν■NC ï4 0.02 90 min.

07229 Such as B

T-test ^ iqo percent dipterans

Test animals: Aëdes aegypti fly

Solvent: acetone

2 parts by weight of active substance is resumed in 1000 parts by volume of solvent. There solution thus obtained is diluted to low desired concentrations with additional solvent.

2.5 ml of active ingredient solution are introduced to the pipette in a petri dish. At the bottom of the box there is a disk of filter paper of about 9.5 cm in diameter. Allowed the petri dish discovery until the solvent is completely evaporated. The amount of active substance by m * of filter paper is increased or decreased depending on the concentration of the active ingredient solution. Then inserted about 25 test animals in the petri dish that is covered with a cover glass.

Observed continuously the status of the test animals. Determining the time required for obtaining an effect of paralysis to 100%.

The test animals, the active compounds, their concentration and the times needed for effect of paralysis of 100% emerge from the following table:

Test of Ti " ORIs p°^{uRs of} dipterans (Aëdes aegypti fly)

Concentration of active substances active substance in the solution, %

Known substance:

Toxaphene

Substances

the invention 9.ï

0.02

0,002

0,002

0,002

60 min at 180 min at 100^AIs 120 kl * 120" TABLE (Following}

TB test_1O 0 for dipterans (Aëdes aegypti fly)

Concentrating, in

Active substances - Tl of active substance_0Ô in the solution,¹⁰⁰

Test 33 * i corrector for dipterans (Aëdes

Concentration

Active substances active substance

in the solution,

0.02 minutes TABLE (Result)

TB test₁₀₀ for dipterans (Aëdes aegypti fly) active substance concentration

tl of active substance_1QQ in the solution, %

60 min. 0.02 60 min.

0.02 120 minutes of Cl

60 minutes E.g. C

Drosophila test

Solvent! 3 parts by weight of dimethylformamide emulsifier: 1 part by weight of ether alkylarylic

of pôlyglycol

To obtain a suitable preparation of active substance/mixture is 1 part by weight of this substance with the indicated amount of solvent and the amount used of emulsifier and the concentrate is diluted to the desired concentration with water.

Is applied to the pipette 1 cm * die the preparation of active substance in a disk of filter paper (7 cm diameter}. placing the wet filter on the opening of a glass container wherein there are 50 Drosophila {Drosophila) and is coated with a glass plate.

After the time indicated/determined the degree of destruction which is expressed even a percentage. 100% means that all flies have then been destroyed;

0% indicates that none of them have been.

In this test/for example, the following compounds of the preparation examples exhibit superior activity, compared to that of the technique:

ïiBL ESCs

(Plant parasitic insects)

Drosophila test

Active substances active substance concentration in the solution,

%

Degree of destruction, %, at the end of

1 day

Toxaphene 0.1 0 (known)

0.1

100

1

LC

The exo/endo-NC

0.1

100■

WITH

NC

- NC

0.1

100

WITH

NC

- NC

the I

H

0.1

100 TABLE (Result) (plant parasitic insects) test on a Drosophila

Concentration of active substances active substance in the solution,

"

the O, 1

0.1

0.1

0.1

0.1

0.1

Degree of truetion *, %, after 1 day

100

100

100

100

100

never TABLE (Result) (parasitic insects âes plants)

Drosophila test

active

Active substance concentration in the solution, %

Degree of destruction, %, at the end of

1 day

Drosophila test

Concentration of active substances active substance in the solution,

%

Degree of destruction, %, at the end of

1 day

Test on a Dora.! ls (systemic action!

Solvent :. 3. parts by weight of dimethylformamide 1. part by weight emulsifier 9.ï alkylarylic polyglycol ether

To obtain a suitable preparation of active substance, is mixed 1 part by weight of this substance with the indicated amount of solvent and the amount mentioned under d * emulsifier and the concentrate is diluted to the desired concentration with water.

Bean plants (is Vicia faba) that are strongly attacked by the black bean aphid (Doralisfabae) are dressed with, each, 20 ml of preparation of active compound of the desired concentration, so that the preparation of active substance penetrates the ground without wetting the growth. The active ingredient is absorbed by the roots and is transmitted to the growth.

After 1 ℮ desired time, determined the degree expressed by a percentage. 100% means that all aphids have then been destroyed, 0% indicates that none of them have been.

In this test, for example, the following compounds of the preparation examples show activity as compared to the state of the technique:

(Plant parasitic insects) test on Doralisfabae (systemic action)

Active substances

Active substance concentration in the solution,

%

Degree of destruction, %, at the end of

4 days

*

Toxaphene 0.1 0 (known)

0

100,100 85 Example I

Test on Tetranychus (resistant form)

Solvent! 3 parts by weight of dimethylformamide emulsifier: 1 part by weight of polyglycol ether alkylarylic

To obtain a suitable preparation of active substance, is mixed 1 part by weight of this substance with the indicated amount of solvent and the amount used of emulsifier and the concentrate is diluted to the desired concentration with water.

Of bean plants (Phaseolus vulgaris extract), which are strongly attacked by the common spider mite (Tetranychus urticae was sought) at all stages of its development, are processed by immersion in. the preparation of active compound of the desired concentration.

After the desired time, determined the degree expressed by a percentage. 100% means that all spider mites have then been destroyed 0% indicates that none of them have been.

In this test, for example, the following compounds of the preparation examples exhibit superior activity, compared to that of the technique:

(Parasitic mites of plants)

Test on Tetranychus

Concentration

active substance

Active substances in the solution #

%

Degree of destruction, %, at the end of

2 days

Toxaphene 0.1 98 (known) 0.01 0

Test of 0.1 100, 0.01 35; limiting concentration/soil insects insect ' test; larvae Phorbia Antigua and in soil solvent: 3 parts by weight of acetone

1 Part by weight emulsifier 9.ï alkylaryligue polyglycol ether

To obtain a suitable preparation of active substance, 1 part is mixed. weight of this substance with the indicated amount of solvent, add the amount of emulsifier is diluted and mentioned the concentrate to the desired concentration with water.

The preparation of active compound is mixed intimately with soil. The concentration of the active substance in the preparation cannot then acts substantially affect, the only determining factor being the amount of active substance fear unit volume of soil, which is expressed in testing laboratory (* mg/1). Introduced the soil in pots is aged at room temperature.

After 24 hours, introduced test animals in the treated soil and 2 to 7 days later, it is determined the degree of activity of the active substance, expressed by a percentage, by counting the dead and live test insects. The degree of activity is 100% if all test insects have been destroyed, it is 0% when it still remains exactly as many test insects living in that in the case of the untreated control.

The active substances, the applied amounts and results emerge from the following table:

Soil insecticides

Active substance

(formula)

Degree of destruction, %, for an active substance concentration of

10 ppm

Toxaphene % of O

(known)

100%

100%

100%

100%

ΐ has Β χ ε Λ ρ. (result)

Soil insecticides

Active substance degree of destruction, %, (formula) for an active substance concentration of 10 ppm

Limit concentration test/soil insects

Test insect larvae of Tenebrio ii raolitor in soil solvent: 3 parts by weight of acetone

Emulsifier: 1 part by weight of polyglycol ether alkylarylic

To obtain a suitable preparation of active substance, is mixed 1 part by weight of this substance with the indicated amount of solvent, add the amount of emulsifier is diluted and mentioned the concentrate to the desired concentration with water.

The preparation of active compound is mixed intimately with soil. The concentration of the substance in the preparation cannot then acts substantially affect, the only determining factor being the amount by weight of active compound per unit volume of earth which is expressed in ppm (=mg/1). Introduced the soil in pots is aged at room temperature.

After 24 hours, introduced test animals in the treated soil and 7 days later, it is determined the degree, expressed by a percentage, by counting the dead and live test insects. The degree of activity is 100% if all test insects have been destroyed, it is 0% when it still remains exactly as many test insects living in that in the case of the untreated control.

The active substances, the applied amounts and results emerge from the following table:

52

07229

Soil insecticides

Larvae molitor larvae in the soil

Active substance

(formula)

Degree of destruction, c/o, for an active substance concentration of 10 ppm

Toxaphene % of O

(known)

100%

100%