CA2203998A1 - Heterocyclyl-amino-and heterocyclyl-oxy-cycloalkenyl derivatives, their use as pest control agents and fungicides - Google Patents

Abstract

The invention concerns heterocyclylamino and heterocyclyloxy-cycloalkenyl derivatives of the formula (a) in which Ar is optionally substituted 4-pyridyl or 4-pyrimidyl; X is NH, O, S, SO or SO2; E is a bond or alkanediyl; a and b may each be 0 to 3, but not 0 at the same time; R4 is halogen, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy or optionally substituted phenyl; v may be 0 to 2; U is a bond, O, S, SO, SO2 or optionally substituted imino; V
is a bond, CO, -CQ-T- or -CT'=N- where Q, T and T' are as defined in the description and R5 is alkyl, alkenyl, alkinyl, optionally substituted aryl or heteroaryl, cyano, NO2, alkyloximino or a silyl group. The invention also concerns methods for the preparation of such compounds and their use as pest-control agents and fungicides.

Description

; _ CA 02203998 1997-04-29 r1 E, ~
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WO 96/13487 ~ ~ 'S'LArr~ PCT/~P95/04088 Heterocyclyl-amino- and heterocyclyl-oxy-cyclo~lk~nyl derivatives, their u~e as pest control agents and fungicides The invention relates to heterocyclyl-amino- and hetero-cyclyl-oxy-cyclo~lkenyl derivatives, processes for their preparation and their use as pest control agents and fungicides.

It is already known that certain 4--cycloalkoxy-substi-tuted nitrogen-contA;n;ng heterocycl:ic compounds have an insecticidal, acaricidal, ixodicidal and fungicidal action (cf. WO 9300536).

Novel 4-amino- and 4-alkoxy-substituted nitrogen-contain-ing heterocyclic compounds of the formula I
( R ~ ) v ~E ~U-V-R5 (1) X
R3~A
R 2~N'J~ R 1 in which R1 is hydrogen, halogen, (C1-C4)-alkyl, (C1-C4)-halo-alkyl, (C3-C5)-cycloalkyl or (C3-C5)-halocycloalkyl;
R2 and R3 are identical or different and independently of one another are each hydrogen, halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C3-C8)-cycloalkyl, (C3-C8)-halocycloalkyl, (C1-C4)-alkoxy, (C1-C4)-halo-alkoxy, (C1-C4)-alkoxy-(C1-C4)-~lkyl, (C1-C4)-halo-alkoxy-(C1-C4)-alkyl, (C1~c4)~alk~xY-(cl-c4)-halo-alkyl, (C1-C4)-haloalkoxy-(C1-C4'~-haloalkyl, (C1-C4)-alkylamino,(C1-C4)-alkylthio,(C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C1-C4)-haloalkylthio, (Cl-C4)-haloalkylsulfinyl, (Cl-C,,~)-haloalkylsulfonyl, -(C1-C4)-alkylthio-(C1-C4)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C1-C4)-alko~,ycarbonyl, cyano, (C1-C4)-cyanoalkyl or thiocyano r or R2 and R3, together with the carbon atoms to which they are bonded, form an unsaturated 5- or 6-membered i~ocyclic ring which, if it is a 5-membered ring, can contain an oxygen or sulfur atom instead of CH2, or, if it is a 6-membered ring, can contain one or two nitrogen atoms instead of one or two CH unit~, and is optionally substituted by~1, 2 or 3 identical or different radicals, these radicals being (C1-C4)-alkyl, (C1-C4)-haloalkyl, pre!ferably trifluoro-methyl, halogen, (C1-C4)-alkoxy or (C1-C4)-halo-alkoxy, or R2 and R3, together with the carbon atoms to which they are bonded, form a saturated 5-, 6- or 7-membered isocyclic ring which can contain oxyye~ and/or sulfur instead of one or two CH2 groups and is optionally ~ubstituted by 1, 2 or 3 (C1-C4)-alkyl groups;
A is CH or N;
X is NH, oxyye~ or S(O)q, where q = 0, 1 or 2;
E is a direct bond or a straight-chain or branched (C1-C4)-alkanediyl group, prefexably a direct bond;
a and b are identical or different and independently of one another are the numbers 0, 1, 2 or 3, where a and b are not 3imultaneously 0;
R4 is halogen, (C1-C4)-alkyl, (C3-C7)-cycloalkyl, (C1-C4)-haloalkyl, (C1-C4)-alkox~, (C1-C4)-halo~lkoxy or optionally substituted phenyl;
v is 0, 1 or 2;
U is a direct single bond, oxygen, a group S(O)y~
where y = 0, 1 or 2, or a group NR6, in which R6 is hydrogen, (C1- C4)- alkyl or (C1-C4)-alkoxy;
V i~ a direct single bond, carborlyl or a grouping of the formula -C-T- -C-N-~
or Q ~' .
in which Q is oxygen, sulfur or (C1--C4)-alkylimino, T is oxygen, sulfur or a group NR6 and T' is (C1-C4)-alkoxy, (C1-C4)-alkylthio or NR6 R6 , and in which R6 and R6 are identical or different and have the meAn;ngs given above for R6; and R5 is a radical from the series consisting of alkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted heterocyclyl, cyano, halogen, nitro, alkyloY;~;no or a group SiR7R8R9, in which R7 and R8 are (C1-C4)-alkyl and R9 i.8 alkyl, cycloalkyl, aryl or arylalkyl;
and the alkyl, alkenyl, alkynyl or alkyloY; m; no radicals mentioned for R5, R7, R8 and R9 have, where appropriate, at least one of the following features:
i. one or more, preferably up to three, non-adjac-ent CH2 groups are replaced by C0 and/or hetero atom units, such as 0, S(O)y~ where y = 0, 1 or 2, NR6 or SiR7 R8 , in which R6 has the me~n;ngs given above for R6 and in which R7 and R8 have the mean-ings given above for R7 and R8;
ii. 3 to 12 atoms of these raclicals form an up to 12-membered ring;
iii. the radicals are optionally substituted by one or more, preferably up to three, in the case of halogen up to the m~Y;ml~m number of, identical or different radicals from the series consisting of halogen, alkyl, cycloalkyl, aryl, aryloxy, arylthio, heterocyclyl, heterocyclyloxy, heterocyclylthio, haloalkyl, arylalkyl, cycloalkylalkyl, A 1 ,koYy~
haloalkoxy, alkylthio, cycloalkoxy, Al k~nOylOXy, halo~lkAnoyloxy, cyclo~lkAnoyloxy, cycloalkyl-~lk~noyloxy, aroyloxy, arylAlk~noyloxy, alkylsul-fonyloxy, arylsulfonyloxy, heterocyclylcarbonyloxy, hydroxyl, cyano and nitro, where the cycloaliphatic, aromatic or heterocyclic ring systems among those substituents just mentioned can be unsubstituted or provided with up to three - in the case of halogen, preferably fluorine, also up to the mAY;m--m number ~ of - identical or different substituents;

and salts thereof, preferably acid addition salts, . have been found.

~ Preferred compounds of the formula ~: are those in which R4 is halogen, preferably fluorine, chlorine and bromine, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloAlkoxy or (C1-C4)-alkylthio; and R5 can be (Cl-C20)-alkYl~ (c2-c2o)-alkenyl~ (C2-C20)_ alkynyl, optionally substituted aryl, optionally substituted heterocyclyl, cyano, halogen, hydroxyl, carboxyl, nitro, (C1-C20)-alky:Lox;m;nQ or a group SiR7R8R9, in which R7 and R8 are (C1-C4)-alkyl and R9 is (C1-C20)-alkyl or optionally substituted aryl;
and the alkyl, alkenyl, alkynyl or alkylo~;m;no radicals mentioned for R5, R7, R8 and R9 have, where appropriate, at least one of the following features:
i. one or more, preferably up to three, non-adja-cent CH2 groups are replaced by CO and/or hetero atom units, such as O, S(O)y~ ~rhere y = O, 1 or 2, NR6 or SiR7 R8 , in which R6 has the me~n;ng8 given above for R6 and in which R7 and R8 have the m~n;ng8 given above for R7 and R8;
ii. 3 to 8 atoms of these rad.icals form an up to 8-membered ring;
iii. the radicals are optionally substituted by one or more, preferably up to three, in the case of halogen up to the maximum number of, identical or different radicals from the series consisting of halogen, (C1-C12)-alkyl, (C3-C~)-cycloalkyl, aryl, aryloxy, arylthio, heterocyclyl, heterocyclyloxy, heterocyclylthio, (Cl-C12)-haloalkyl, aryl-(C1-C4)-alkyl, (C3-C8)-cycloalkyl-(C1-C4)-alkyl, (Cl-Cl2)-alkoxy, (C1-C12)-halo~lk~Yy, (C1-C12)-alkylthio, (C3-C8)-cycloalkoxy, (C1-C12)-~lk~noyloxy, (C1-C12)-halo~lk~noyloxy, (C3-C8)-cyclo~lkAnoyloxy, (C3-C8)-cycloalkyl-(C1-C12)-~lk~noyloxy~ aroyloxy, aryl-(Cl-C4)-alkanoyloxy, (Cl-C12)-alkylsulfonyloxy, arylsulfonyloxy, heterocyclylcarbonyloxy, hydroxyl, cyano and nitro, where the cycloaliphatic, aromatic CA 02203998 l997-04-29 t ~ .

.~
or heterocyclic ring systems among the substituents just mentioned can be unsubstituted or provided with up to three - in the case of halogen, preferably fluorine, also up to the maximum number of identical or different substituents and the other radicals and variables are as defined above;
and salts thereof, preferably acid addition salts.

Compounds of the formula I which are more preferred are those in which R1 is hydrogen or fluorine;
R2 is (C1-C4)-alkyl, cyclopropyl, halocyclopropyl, halo(C1-C2)-alkyl, methoxymethyl or cyano;
R3 is hydrogen, halogen, methyl, ethyl, methoxy, ethoxy, cyano or (C1-C4)-alkoxycarbonyl; or R2 and R3, together with the carbon atoms to which they are bonded, form an optionally substituted unsatu-rated 5- or 6-membered ring whi.ch, in the case of the 5-membered ring, can cont.ain a sulfur atom instead of a CH2 unit, or R2 and R3, together with the carbon atoms to which they are bonded, form a saturated 5- or 6-membered ring which can contain a sulfur or an oxygen atom instead of a CH2 unit;
A is CH or N;
X is NH or oxygen;
E is a direct bond;
a i 8 the number 1 and b is the number 2;
R4 is hydrogen, (C1-C4)-alkyl, trifluoromethyl or (C1-C4)-alkoxy;
and the other radicals and variables are defined as above;
and salts thereof;
in particular those compounds in which R1 is hydrogen;
R2 is methyl, ethyl, propyl, isoprc)pyl, 1-fluoroethyl, trifluoromethyl, cyclopropyl or methoxymethyl;
R3 is halogen, methyl, ethyl, methoxy, ethoxy, cyano or (Cl-C4)- alkoxycarbonyl, or t R2 and R3, together with the ring system to which they are bonded, form the c~uinazolin.e or quinoline sys-tem, which can be substituted by fluorine in the carbocyclic part, or R2 and R3, together with the carbon atoms to which they are bonded, form a saturated 6-membered ring which can contain an oxy~el~ or sulfur atom instead of a CH2 group;
r is 0;
U is a direct bond or oxygen; and V is a direct bond;
and salts thereof.

Particularly preferred compounds of the formula I are those in which R1 is hydrogen;
R2 is ethyl, propyl, isopropyl, l-fluoroethyl, tri-fluoromethyl or methoxymethyl;
R3 is fluorine, chlorine, bromine or methoxy;
or in the case where A is nitroc3en, R2 and R3, together with the ring system to which they are bonded, form the c~inazoline system, which can be substituted by a fluorine atom, or R2 and R3, together with the ring system to which they are bonded, form the 5,6,7,8-tetrahydro~uinazoline system;
A is CH or N;
X is NH or oxygen;
E is a direct bond;
a is the number 1 and b is the number 2;
v is 0;
U is a direct bond or oxygen and V is a direct bond;
and salts thereof.

Compounds of the formula I which are most preferred are those in which R1 is hydrogen;

., 7 R2 is ethyl or methoxymethyl;
R3 is fluorine, chlorine, bromine or methoxy, or R2 and R3, where A = N, together with the ring system to which they are bonded, form the quinazoline or the 5,6,7,8-tetrahydroquinazoline system;
R5 i8 (Cl-C20)-alkYl~ (C2-C20)-alkenyl or (C2-C20)-alkynyl, where 3 - 6 carbon atoms of these hydro-carbon radicals can form a ring and/or these hydro-carbon radicals can optionally be substituted by a phenyl radical, which can be unsubstituted or pro-vided with up to three, in the case of fluorine also up to the m~;ml number of, identical or different substituents;
A is CH or N;
X is NH or oxygen;
E is a direct bond;
U and V together are a direct bond;
v is 0 and the other radicals and variables are defined as above;
and salts thereof;
in particular those in which R2 i8 methoxymethyl and R3 is methoxy, or R2 is ethyl and R3 is chlorine or bromine, X is NH;
R5 is (C1-C20)-alkyl or (C2-C20)-a:Lkenyl, where 3 - 6 carbon atoms of this radical can form a ring and/or this radical can optionally be substituted by a phenyl radical, which can be unsubstituted or pro-vided with up to three, in the case of fluorine also up to the ~-Y;m~m number of, identical or different substituents; and the other radicals and variables are defined as above;
and salts thereof.

In the above formula I, "halogen" is to be understood as a fluorine, chlorine, bromine or iodine atom, preferably a fluorine, chlorine or bromine atom;
the term "(C1-C4)-alkyl" is to be ~mderstood as an un-branched or branched hydrocarbon radical having 1 - 4 ~5 ~

carbon atoms, such as, for example, the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methyl~l~yl or tert-butyl radical;
the term "(Cl-C20)-alkyl" is to be understood as the abovementioned alkyl radicals, as well as, for example, the pentyl, 2-methylbutyl or l,1-dim,ethylpropyl radical and the hexyl, heptyl, octyl, 1,1,3,3-tetramethylbutyl, nonyl, l-decyl, 2-decyl, undecyl, doc~ecyl, pentadecyl or eicosyl radical;
the term "(C1-C4)-haloalkyl" is to be understood as an alkyl group mentioned under the term "(C1-C4)-alkyl", in which one or more hydrogen atoms are replaced by the abovementioned halogen atoms, preferably chlorine or fluorine, such as, for example, t:he trifluoromethyl group, the 1-fluoroethyl group, the 2,2,2-trifluoroethyl group, the chloromethyl or fluoromethyl group, the difluoromethyl group or the 1,1,2,2-tetrafluoroethyl group;
the term "(C3-C5)-cycloalkyl" is preferably to be under-stood as the cyclopropyl, cyclobul;yl or cyclopentylgroup;
the term "(C3-C8)-cycloalkyl" is preferably to be under-stood as the cyclopropyl, cyclobutyl, cyclopentyl, cyclo-hexyl, cycloheptyl or cyclooctyl group, and also bicyclic systems, such as, for example, the norbornyl group;
the term "(C3-C8)-halocycloalkyl" is to be understood as a group mentioned under the term "(C3-C8)-cycloalkyl" in which one or more hydrogen atoms are replaced by the abovementioned halogen atoms, preferably chlorine or fluorine;
the term "(C1-C4)-alkoxy" is under~tood as an alkoxy group, the hydrocarbon radical of whi.ch haO the m~n;ngs given under the term "(C1-C4)-alkyl";
the term "(C1-C4)-haloalkoxy" is to be understood as a haloalkoxy group, the halo-hydrocarbon radical of which has the ~A-n;ngs given under the term "(Cl-C4)-halo-alkyl";
the term "(Cl-C4)-alkoxy-(Cl-C4)-alkyl" is to be under-stood as, for example, a 1-methox~ethyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a methoxy-methyl or ethoxymethyl group, a 3-methoxypropyl group or a 4-butoxybutyl group;
the term "(C1-C4)-alkylthio" is to be understood as an alkylthio group, the hydrocarbon radical of which has the meAn;ngs given under the term "(C1-C~)-alkyl";
the term "(C1-C4)-alkylthio-(Cl-C4)-alkyl" i8 to be understood as, for example, methylthi.omethyl, ethylthio-methyl, propylthiomethyl, 2-methylthioethyl, 2-ethylthio-ethyl or 3-methylthiopropyl;
the term "(C2-C4)-alkenyl" is to be understood as, for example, the vinyl, allyl, 2-methy1-2-propenyl or 2-butenyl group;
the term "(C2-C20)-alkenyl" i8 to be understood as the abovementioned radicals, as well as, for example, the 2-pentenyl, 2-decenyl or the 2-eicosen~l group;
the term "(C2-C4)-alkynyl" is to be understood as, for example, the ethynyl, propargyl, 2-methyl-2-propyne or 2-butynyl group;
the term "(C2-C20)-alkynyl" is to be understood as the abovementioned radicals, as well as, for example, the 2-pentynyl or the 2-decynyl group;
the term "(C1-C4)-alkoxycarbonyl" is to be understood as, for example, the methoxycarbonyl, ethoxycarbonyl, pro-poxycarbonyl, butoxycarbonyl or tert-butoxycarbonyl group;
the term "(C1-C12)-alkoxycarbonyl" is to be understood as the abovementioned radicals, as well as, for example, the hexyloxycarbonyl, 2-methylhexyloxycarbonyl, decyloxy-carbonyl or dodecyloxycarbonyl group;the term "cyano-(C1-C4)-alkyl" is to be understood as a cyanoalkyl group, the hydrocarbon radical of which has the me~n;ngs given under the term "(C1-C4)-alkyl";
the term "(C1-C20)-alkylidene" is to be understood as, for example, the exo-methylene, ethylidene, propylidene, 1-methyl-propylidene, butylidene, octylidene or dodecyli-dene group;
the term "(C1-C20)-alkylox;~;no" is to be understood as an o~;m;no group which is etherified on the oxygen by one of ~; I

the alkyl groups mentioned under the term "(C1-C20)-alkyl n;
the term "aryl" is to be understood as an isocyclic aromatic radical having preferably 6 to 14, in particular 6 to 12, carbon atoms, such as, ~or exz~mple, phenyl, naphthyl or biphenylyl, preferably phenyl;
the term "heterocyclyl" is to be unflerstood as a hetero-aromatic or heteroaliphatic ring sy~tem, "heteroaromatic ring system" being understood as an aryl radical in which at least one CH group i8 replaced by N and/or at least two adjacent CH groups are replaced by S, NH or 0, for example a radical of thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, :isoxazole, pyrazole, 1,3,4-oxadiazole, 1~3~4-th;zl~;azole~ 1,3,4-triazole, 1,2,4-oxadiazole, 1,2,4-thiadiazole, 1,2,4-triazole, 1,2,3-triazole, 1,2,3,4-tetrazole, benzo~b]thiophene, benzo~b]furan, indole, benzo~c]thiophene, benzo[c]furan, isoindole, benzoxazole, benzothiazole, benzimidazole, benzisoxazole, benzisothiazole, benzopyrazole, benzo-thiadiazole, benzotriazole, dibenzofuran, dibenzothio-phene, carbazole, pyridine, pyrazine, pyrimidine, pyrida-zine, 1,3,5-triazine, 1,2,4-triazine, 1,2,4,5-triazine, quinoline, isoquinoline, ~l;noYz~line, quinazoline, cinnoline, l,8-naphthyridine, 1,5--naphthyridine, 1,6-naphthyridine, 1,7-naphthyridine, phthalazine, pyrido-pyrimidine, purine, pteridine or 4H-quinolizine;
and the term "heteroaliphatic ring system" being under-stood as a (C3-C8)-cycloalkyl radical in which at least one carbon unit, preferably up to three carbon units, are replaced by 0, S or a group NR1l, and R11 is hydrogen, (Cl-C4)- alkyl, (C1- C4)- alkoxy or aryl;
the term "substituted aryl" is to be understood as an aryl radical which can be provided with one or more, preferably up to three, in the case of fluorine up to the -Y;m-.m number of, identical or dif.ferent radicals from the series consisting of halogen, (C'1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkoxy-(C1-C4)-alkyl, (C1-C4)-alkylthio, (C1-C4)-alkoxy-alkyl, phenyl ~ rh ~n oYy, haloph ~n o~y ~ ( Cl - C4 ) -alkylphenoxy, (Cl-C4)-haloA~koYyph~noyy~ (Cl-C4)-halo-alkylphenoxy, phenylthio, heterocycl.yl, heterocyclylthio or heterocyclyloxy;
the term "substituted heterocyclyl" is to be understood as a heteroaromatic or heteroaliphat.ic ring system, which can be provided with one or more, preferably up to three, in the case of fluorine also up to the mA~;mnm number of, identical or different radicals from the substituents listed above under the term "substit:uted aryl";
"cycloaliphatic, aromatic and het.erocyclic radicals"
optionally provided with substituents are to be under-stood as radicals such as, for example, aryloxy, aryl-thio, heterocyclyloxy, heterocyclylthio, aroyl, aroyloxy, cycloalkyl or cycloA~kAnoyl~ which can be provided with one or more, preferably up to three, in the case of fluorine also up to the maximum nu~ber of identical or different substituents of those listed for "substituted aryl";
the term "aryl-(Cl-C4)-alkyl" is to be understood as an alkyl group mentioned under the term "(C1-C4)-alkyl"
which is substituted by an aryl radi.cal;
the term "aryloxy" is to be understood as, for example, the phPnoYy or 1- or 2-naphthyloxy group;
the term "arylthio" is to be understood as, for example, the phenylthio or the 1- or 2-napht~lylthio group;
the term "heterocyclyloxy" or "heterocyclylthio" is to be understood as one of the abovementioned heterocyclic radicals which are linked via an oxygen or sulfur atom.

The substituents with which the various aliphatic, aromatic and heterocyclic ring syst:ems can be provided include, for example, halogen, (Cl-C'4)-alkyl, trimethyl-silyl, (Cl-C4)-haloalkyl, (Cl-C4)-alkoxy, (C1-C4)-halo-alkoxy, (C1-C4)-alkoxy-(C1-C4)-alkyl, (C1-C4)-alkylthio, alkylsulfinyl, alkylsulfonyl, phenyl, ph ~noYy~ halo-ph~noYy~ (Cl- C4)-alkylphenoxy, (C1- C4)- alkoxyphenoxy, (cl-c4)-haloalkoxyphenoxy~ (C1-C4)-haloalkylphenoxy, phenylthio, heterocyclyl, heterocyclylthio or hetero-cyclyloxy, where one or more hydrogen atoms, in the case CA 02203998 l997-04-29 of fluorine also up to the ~ m number, in the alkyl radicals and the radicals derived therefrom can be replaced by halogen, preferably chlorine or fluorine.

Fur~herrore, the definition that "the alkyl, alkenyl, alkynyl or alkyloy;m;no radicals men~ioned for R5, R7, R8 and R9 have, where appropriate, at: least one of the following features:
i. one or more, preferably up to three, non-adjacent CH2 groups are replaced by C0 and/or hetero atom units, such as 0, S(O)yl where y = 0, 1 or 2, NR6 or SiR7 R8 in which R6 has the m~n;ngs given above for R6 and in which R7 and R8 have the me~n;ngs given above for R7 and R8;
ii. 3 to 12 atoms of these radicals form an up to 12-m~mhered ring;iii. the radicals are optionally substituted by one or more, preferably up to three, in the case of halogen up to the maY;mllm number of, identical or different radicals from the series consisting of halogen, alkyl, cycloalkyl, aryl, aryloxy, arylthio, heterocyclyl, heterocyclyloxy, heterocyclylthio, haloalkyl, arylalkyl, cycloalkylalkyl, alkoxy, haloalkoxy, alkylthio, cycloalkoxy, ~lk~noyloxy, halo~lk~noyloxy,cyclo~lk~noyloxy,cyc:loalkylAlk~noyloxy, aroyloxy, arylalkanoyloxy, alkylsulfonyloxy, arylsulfonyloxy, heterocyclylcarbony].oxy, hydroxyl, cyano and nitro, where the cycloaliphatic, aromatic or heterocyclic ring systems among thole substituents just mentioned can be unsubstituted or provided with up to three, in the case of halogen, preferably fluorine, also up to the ~-Y;m-lm n~mher of, identical or different substituents embraces, for example, alkoxyalkyl radicals, such as, for example, the methoxymethyl, methoxyethyl or ethoxyethyl group; or alkoxy-alkoxy-alkyl radicals, such as, for example, the methoxy- or ethoxyethoxyethyl group; or alkylthioalkyl radicals, such as, for example, the methyl- or the ethylthioethyl group; or alkylsulfinyl-alkyl radicals, such as, for exam~)le, the methyl- or ethylsulfinylethyl group; or alkylsulfonyl-alkyl rad-icals, such as, for example, the methyl- or ethylsul-fonylethyl group; or alkyl-dialkylsilyl-alkyl radicals, such as, for example, the trimethylsilylmethyl or the ethyldimethylsilylethyl group; or alkyl-cycloalkyl radicals, such as, for example, the ~-methyl-cyclohexyl, 3-ethyl-cyclopentyl or the 4-tert-butyl-cyclohexyl group;
or cycloalkyl-alkyl radicals, such a~s, for example, the cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl or 1-cyclohexyl-1-methylethyl group or aryl-alkyl radicals, such as, for example, the benzyl, the 2-phenylethyl, the 1-phenylethyl or the 1-methyl-1-phenylethyl group, the 3-phenylprop~l or the 4-phenyl-butyl group, the 2-methyl-2-phenyl-ethyl group or the 1-methyl or 2-methylnaphthyl group; or heterocyclylalkyl radicals, such as, for example, the thienylmethyl, pyridylmethyl, furfuryl, tetrahydrofurfuryl, tetrahydro-pyranylmethyl or the 1,3-dioxolan-2-ylethyl group; or aryloxyalkyl radicals, such as, for example, the phenoYy-methyl or naphthoxymethyl group; or cycloalkyl radicalswhich are monocyclic, as listed above under the term "(C3-C8)-cycloalkyl", bicyclic, such a8, for example, the norbornyl radical or the bicyclo[2.2.2]octane radical, or fused, such as the decahydronaphthyl radical; or else haloalkyl derivatives of the correspo~;ng groups, such as, for example, haloalkyl, haloalkoxyalkyl, alkoxy-haloalkyl, haloalkyl-cycloalkyl or halocycloalkyl radicals.

The explanation given above appl:ies accordingly to homologues and radicals derived therefrom.

The explanation given above appl:ies accordingly to radicals where no concrete number of carbon atoms is stated, and to homologues or radical~ derived therefrom.

The present invention relates to the compounds of the formula I in the form of the free b~se or an acid addi-tion salt. Acids which can be used for salt formation are CA 02203998 l997-04-29 ~, inorganic acids, such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid or phosphoric acid, or organic acids, such as formic acid, acetic acid, propionic acid, oxalic acid, fumaric acid, adipic acid, stearic acid, oleic acid, methanesulfonic acid, benzene-sulfonic acid or toluenesulfonic acid.

The compounds of the formula I sometimes have one or more chirality elements. Racemates or diastereomers can therefore occur. The invention relates both to the pure isomers and to mixtures thereof. The mixtures of dia-stereomers can be separated into the components by customary methods, for example by selective crystalliza-tion from suitable solvents or by chromatography. Race-mates can be separated into the enantiomers by customary methods, thus, for example, by salt formation with an optically active acid, separation of the diastereomeric salts and liberation of the pure enantiomers by meAn~ of a base.

The invention furthermore relates to a process for the preparation of compounds of the formula I, which com-prises reacting a compound of the formula II

R XN~1~R 1 in which A, R1, R2 and R3 have the meAn;ngs given under formula I and L is a leaving group, such as, for example, halogen, alkylthio, ~lk~ne~ulfonyloxy or arylsulfonyloxy, alkylsulfonyl or arylsulfonyl, with a nucleophile of the formula III

CA 02203998 l997-04-29 ( R ~ ) HX-E~U-V-Rs ( I I I ) in which X, E, a, b, v, U, V, R4 and ~5 ha~e the m~An;n~S
given under formula I, and, if R3 is hydrogen, if appro-priate halogenating, preferably chlorinating or brominat-ing, the compounds of the formula ~: thus obtained, or obtA; ne~ in another manner, in po~iti.on 5 of the hetero-cyclic radical, or further derivatizing R5 in the side chain.

The substitution reaction described abo~e i~ known in principle. The lea~ing group L can be varied within wide limits and can be, for example, a halogen atom, such as fluorine, chlorine, bromine or iodine, or alkylthio, such as methyl- or ethylthio; or alkanesulfonyloxy, such as methane-, trifluoromethane- or ethanesulfonyloxy, or arylsulfonyloxy, such aa benzenesulfonyloxy or toluene-sulfonyloxy, or alkylsulfonyl, such as methyl- or ethyl-sulfonyl, or arylsulfonyl, such as phenyl- or toluene-sulfonyl.

The abovementioned reaction is carried out in a tempera-ture range of 20 - 150~C, expediently in the presence of a base and if appropriate in an inert organic solvent, such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidin-2-one, dioxane, tetrahydro f uran, 4-methyl-2-pentanone, methanol, ethanol, butanol, ethylene glycol, ethylene glycol dimethyl ether, toluene, chlorobenzene or xylene. Mixtures of the 801-~ents mentioned can also be used. Suitable bases are, for example, alkali metal or alkaline earth metal carbonates, bicarbonates, amides or hydrides, such as sodium carbon-ate, sodium bicarbonate, potassium carbonate, sodium amide or sodium hydride, or organolithium compounds, such as n-butyllithium.

Suitable bases in the case where X is oxygen are, for example, alkali metal or alkaline earth metal carbonates, bicarbonates, amides or hydrides, such as sodium carbon-ate, sodium bicarbonate, potassium carbonate, sodium amide or sodium hydride, and in the case where X is NH, these are, for example, alkali metal or alkaline earth metal carbonates, bicarbonates, hyclroxides, amides or hydrides, such as sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide, sodium amide or sodium hydride, or organic bases, such as triethylamine or pyridine. A second equivalent of an amine of the formula III can also be employed as an auxiliary base.

The starting compounds of the formula II are either known or they can be prepared by processe~ analogous to known processes; cf., for example:

Quinolines: Org. Synth., Coll. Vol. 3, 272 (1955) 1,5-Naphthyridines: J. Amer. Chem. Soc. 68, 1317 (1946) and British Patent 1,6-Naphthyridines: J. Chem. Soc. 1960, 1790 1,7-Naphthyridines: J. Org. Chem. 19, 2008 (1954) 1,8-Naphthyridines: Synthesis 1974, 809 Pyridopyrimidines: EP-A-414 386 Pteridines: J. Chem. Soc. 1951, 474 Starting substances which are used in the case where A is a nitrogen atom are acetoacetic e~ter derivatives, which are converted into the halopyrimidines via the corres-pon~; ng hydroxypyrimidines:

HO HO

( H2N ) C~ XN~J~ SH N2 ~ J

/ (Ba~) /

C~O

NH
COOR R I //
--Y\NH2 ( a a ~
HO

X~N P 3 ~ I I ( L ~ C I ) The starting compounds of the formula II can furthermore be obtained by processes analogous to known processes from malonic ester derivati~es:
Ho N N2 ~ ~N ~~C I ~ ( 112 . L ~ C I ) ItOOC ( ~) Ho Nll The compounds of the formula II in lqhich R3 is halogen can be obt~; neA by halogenation by ~lown processes.
~.
The nucleophiles of the formula III required as starting substances can be prepared by known. processes, in the case where X is oxygen, for exampler by reduction of a carbonyl group with a suitable reducing agent, for example a complex metal hydride, or in the case of an aldehyde or ketone also with hydrogen and a hydrogenation catalyst. To prepare the cis-cycloh~YAnols, the precur-sors for the particularly preferred cis-cyclohexyloxy derivatives, catalytic hydrogenation of suitably substi-tuted phenols or reduction of suitably substitutedcycloh~YAnone derivatives with comI~lex hydrides which carry very bulky sub~tituents, such as, for example, L-Selectride , is particularly suitable.

In the case where ~lacuna] is NH, the nucleophiles of the formula III recluired as starting substances can be prepared by known processes, for example by reduction of an oxime or of a nitrile with a suitable reducing agent, for example a complex metal hydride or hydrogen, in the presence of a hydrogenation catalyst, reductive amination or Leuckart-Wallach reaction of an aldehyde or ketone or Gabriel reaction of an alkyl halide or tosylate. To prepare the cyclohexylamines, the precursors for the particularly preferred cyclohexylamino derivatives, reductive Am;nAtion of suitably substituted cycloh~YAnones with ammonium ~alts and sodium cyanoborohydride or with ~m~on;a and hydrogen in the presence of metal catalysts, such as nickel, ruthenium, rhodium or palladium, is particularly suitable, the content of desired cis-amine by this method being particularly high. Another method :is hydrogenation of amines in the pre~ence of hydrogenation catalysts.

To prepare the precursors for the particularly preferred cyclohexanyl derivatives, the following reactions are suitable in particular:
~0 1.) Alkyl, alkenyl or aryl derivatives (a = 1, b = 2, U and V = direct bond) " t OH

X ~ X R S
R ~9 X

X ~RS

B o ~ B

2.) Alkyl, alkenyl or aryl derivatives (a = 1, 2 or 3, b = 1, 2 or 3, U and V = direct bond) R ) ~ B ) r ~R~) O ~

~,~ UO

RS ~ (R4 NH40~ H2N- ~

RS

3.) Cyclohex-3-enyl-amino and -alkoxy derivati~es (R4) (R4)~

~ ~ Bu 1- ~t9 ~ U-V-R5 / 2. RS-V-U-X

(R4) o ~ U _ V _ R S
EtOH, NH3 (R4)~ j R4)~
O ~ U-V-R5 ~ HO ~ U-V-R5 NaCNBH3 NH40Ac~
(R4)~

H2N--{~ U-V-R5 Preparation of 1-methoxy-1,4-cyclohexadienes or cyclohex-3-enones: J. Chem. Soc. Perkin Trans 1, 7 (1983); J. Org.
Chem. 29, 2351 (1964); J. Org. Chem. 41, 531 (1976).

While having a good plant tolerance and favorable toxi-city towards warm-blooded animals, the acti~re compounds are suitable for controlling ~n;m~l pests, in particular insects, arachnids, helminths and molluscs, very particu-5 larly preferably for control of in~ects and arachnids,which occur in agriculture, in animal breeding, in forestry, in the protection of stored products and materials and in the hygiene sectc)r. They are acti~re against normally sensitive and resistant species and all 10 or individual stages of development. The abovementioned pests include:
From the order of the Acarina, for example, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta olei~rora, Boophilus 8pp., 15 Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosaL, Panonychus spp., Tetranychus spp., Eotetranychus spp., Oligonychus spp.
and Eutetranychus spp..
20 From the order of the Isopoda, for example, Oniscus asselus, Armadium ~rulgar and Porcellio scaber.
From the order of the Diplopoda, fox example, Blaniulus guttulatus.
From the order of the Chilopoda, for example, Geophilus 25 carpophagus and Scutigera spp..
From the order of the Symphyla, for example, Scutigerella immaculata.
From the order of the Thysanura, for example, Lepisma saccharina.
30 From the order of the Collembola, for example, Onychiurus armatus.
From the order of the Orthoptera, for example, Blatta orientalis, Periplaneta americana, l~Jeucophaea madeirae, Blatella g~ n;ca, Acheta domesticus, Gryllotalpa spp., 35 Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria.
From the order of the Isoptera, for example, Reticulitermes spp..
From the order of the Anoplura, fox example, Phylloera ~ .

vastatrix, Pemphigus spp., Pediculus hum~anus corporis, Haematopinus spp. and T;nogn:~thu8 spp..
From the order of the Mallophaga, for example, Trichodectes pp. and Damalinea spp..
From the order of the Thysanopt:era, for example, Hercinothrips femoralis and Thrips tabaci.
From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp..
From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus ar~n~;n;s, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelus bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp..
From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Eyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Buccu].atrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammecl, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona ma~n~n;~- and Tortrix viridana.
From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha ~nm;n;ca, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylloides chrysocephala, Epilachan varivestis, Atomaria spp., Oryzaephilus sur;n~m~n~is, Anthonl~m~l~ spp., Sitophilus spp., Otiorrhynchus sulcatus, ~, ~

Cosmopolites sordidus, Ceuthorrynchus assimilis, Hypera postica, Dermestes spp., Trogoder~a, Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium p~ylloides, Tribolium spp., Tenebrio molitor, Atriotes spp., Co~o~rus spp., Melolontha melolontha, Amrh;m-llon solstitialis and Costelytra zealandica.
From the order of the Hymenoptera, ior example, Diprion spp., Hoplocampa spp., Lasius spp., r~onnmorium pharaonis and Cespa spp..
From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, MU8Ca 8pp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hypobosca 8pp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Peyo~l~ia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa.
From the order of the SiphonAptera, for example, Xenopsylla cheopsis and Ceratophyllus spp..
From the order of the Arachnida, for example, Scorpio maurus and Latrodectus mactans.
From the class of helm;nths, for example, Haemo~ch~
Trichostrongulus, Ostertagia, Cooperia, Chabertia, Strongyloides, Oesophagostomum, Hyostrongulus, Ancylostoma, Ascaris and Heterakis, as well as Fasciola and phytotoxic nematodes, for example those from the genera Meloidogyne, Heterodera, Ditylenchus, Aphelenchoides, Radopholus, Globodera, Pratyl~nch Longidorus and Xiphinema.
From the class of Gastropoda, for example, Deroceras spp., Arion spp., Lymnaea spp., Galba spp., Succinea spp., Bi~rh~laria spp., Bulinus spp. and Oncomelania spp..
From the class of Bivalva, for example, Dreissena spp..

The phytoparasitic nematodes which can be controlled according to the invention include, for example, the root-parasitic 80il nematodes, such as, for example, those of the genera Meloidogyne (root gall nematodes, such as Meloidogyne incognita, Me].oidogyne hapla and Meloidogyne javanica), Heterodera and Globodera (cyst-forming nematodes, such as Globodera rostochiensis, Globodera pallida and Heterodera trifolii), and of the genera Radopholus, such as Radopholus similis, Pratylenchll~, such as Pratylenchl~ neglectus, Pratyl~nchll~ penetrans and Praty].~nch-l~ curvitatus;
Tylenchlllus such as Tyl~nchlllus semipenetrans, Tylenchorhynchus, such as Tylenchorhynchus dubius and Tylenchorhynchus claytoni, Roty:Lenchll~ such as Rotylen~hll~ robustus, Haliocoty:L~nchllR such as Haliocotyl~nchll~ multicinctus, Be:Lonoaimus such as Belonoaimus longicaudatus, Longidoru3 such as Longidorus elongatus, Trichodorus such as Trichodorus primitivus and Xiphinema such as Xiphinema index.

The nematode genera Ditylenchll~ (stem parasites, such as Dityl~nchll~ dipsaci and Dityl~nchll~ destructor), Aphelenchoides (leaf nematodes, such as Aphelenchoides ritzemabosi) and Anguina (flower nematodes, such as Anguina tritici) can furthermore be controlled with the compounds according to the invention.

The invention also relates to compositions, in particular insecticidal and acaricidal composit:;ons, which comprise the compounds of the formula I, in addition to suitable formulating auxiliaries.

The compositions according to the invention in general comprise the active compounds of the formula I to the extent of 1 to 95% by weight.

They can be formulated in various ways, as determined by the biological and/or chemico-physical parameters.
Appropriate formulation possibilities are therefore:
wettable powders (WP), emulsifiable concentrates (EC), aqueous solutions (SL), emulsions, ~prayable solutions, oil- or water-based dispersions (SC), suspoemulsions (SE), dusting powders (DP), seed-dressing compositions, granules in the form of micro, spray, ab~orption and adsorption granules, water-dispersib].e granules (WG), ULV
formulations, microcapsules, waxes or baits.

These individual types of formulation are known in principle and are described, for exa~ple, in:
Winnacker-~uchler, "Chemische Technologie (Chemical Technology)", Volume 7, C. Hauser Verlag Munich, 4th Edition 1986; van Falkenberg, "Pesticides Formula-tions", Marcel Dekker N.Y., 2nd Edition 1972 - 73;
K. Martens, "Spray Drying Handbook", 3rd Edition 1979, G. Goodwin Ltd., T~n~Qn.

The necessary formulating auxiliar.ies, such as inert materials, surfactants, solvents and further additives, are likewise known and are described, for example, in:
Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Edition, Darland Books, Caldwell N.J.;
H. v. Olphen, "Introduction to Clay Colloid Chemistry", 2nd Edition, J. Wiley & Sons, N.Y.; Marschen, "Solvents Guide", 2nd Edition, InterscieDce, N.Y. 1950;
McCutcheon's, "Detergents and Emul~ifiers ~nn~ , MC
Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclo-pedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt, "Grenzflach~r~ktive Athylenoxid-addukte" (Surface-active Ethylene Oxide Adducts)", Wiss.
Verlagsgesell., Stuttgart 1967; Winnacker-Kuchler, "Chemische Technologie (Chemical Technology)", Volume 7, C. Hauser Verlag Munich, 4th Edition 1986.

Combinations with other pesticidally active substances, fertilizers and/or growth regulators can also be prepared on the basis of these formulations, for example in the form of a ready-to-use formulation or as a tank mix.
Wettable powders are preparations which are uniformly dispersible in water and al~o comprise, in addition to the active compound and as well as a diluent or inert substance, wetting agents, for examl?le polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols or alkyl-or alkylphenol-sulfonates, and dis]?ersing agents, for example sodium ligninsulfonate or sodium 2~2~-~;n~phthyl-methane-6,6'-disulfonate. Emulsifiable concentrates are prepared by dissolving the active co~pound in an organic solvent, for example butanol, cycloh~Y~none~ dimethyl-formamide or xylene, or else higher-boiling aromatics or hydrocarbons, with the addition of one or more emul-sifiers. Emulsifiers which can be used are, for example:alkylarylsulfonic acid calcium salts, such as Ca dodecyl-benzene-sulfonate, or nonionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensation products, alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or polyoxyethylene sorbitol esters.

Dusting powders are obtained by gr;n~;ng the active compound with finely divided solid substances, for example talc or naturally occurring clays, such as kaolin, bentonite, pyrophillite or diatomaceous earth.
Granules can be prepared either by spraying the active compound onto adsorbent, grAn~ r inert material or by applying active compound concentrates to the surface of carrier substances, such as sand, ka41inites or granular inert material, by means of a&esive~, for example poly-vinyl alcohol, sodium polyacrylate or else mineral oils.
Suitable active compounds can also be granulated in the m~nner customary for the preparation of fertilizer granules - if desired as a mixture with fertilizers.

In wettable powders, the active compound concentration is, for example, about 10 to 90% by weight, the r~m~;n~er to 100% by weight comprising customary formulating constituents. In emul~ifiable concentrates, the active compound concentration can be about 5 to 80% by weight.
Dust-like formulations usually co~lprise 5 to 20% by weight of active compound, and sprayable solutions about '1 ;

2 to 20% by weight. In granules, the active compound content depends partly on whether the active compound is present in liquid or solid form, and on which granulating auxiliaries, fillers and the like are used.

In addition, the active compound formulations mentioned comprise, if appropriate, the particular customary tackifying agents, wetting agents, dispersing agent~, emulsifiers, penetration agents, solvents, fillers or carrier substances.

For use, the concentrates in the commercially available form are diluted in the customary marmer, if appropriate, for example by means of water in the case of wettable powders, emulsifiable concentrates, dispersions and in some cases also microgranules. Dust-like and grAnlllAr formulations and sprayable solutions are usually not diluted further with additional inert substances before use .

The application amount re~uired varies with the external conditions, such as temperature, humidity and the like.
It can vary within wide limits, for example between 0.0005 and 10.0 kg/ha or more of active substance, but is preferably between 0.001 and 5 kg/ha.

In their commercially available for~nulations and in the use forms prepared from these formlllations, the active compounds according to the invention can be present as mixtures with other active compounds, such as insecti-cides, attractants, sterilizing agents, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.

The pest control agents include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, formami-dines, tin compounds, substances prepared by microorgan-isms and the like. Preferred partners in the mixture are 1. from the group of phosphorus compounds acephate, azamethiphos, azinphos-eth.yl, azinphosmethyl, bromophos, bromophos-ethyl, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, demeton, demeton-S-methyl, demeton-S-methylsulphon, dialifos, diazinon, dichlorvos, dicrotophos, 0,0-1,2,2,2-tetrachloroethyl-phosphorothioate (SD 208 304), dimethoate, disulfoton, EPN, ethion, ethoprophos, etrimfos, f~rh-.~, fenamiphos, fenitriothion, fensulfothion, fenthion, fonofos, formo-thion, heptenophos, isozophos, isothioate, isoxathion,malathion, methacrifos, methamidophos, methidathion, salithion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parat:hion-methyl, phen-thoate, phorate, phosalone, phosfolan, phosmet, pho~pham-idon, p~ny;m, pirimiphos, pirimiphos-ethyl, pirimiphos-methyl, profenofos, propaphos, proet~mr~os, prothiofos, pyraclofos, pyridapenthion, quinalphos, sulprofos, temephos, terbufos, tetrachlorvinphos, thiometon, triazo-phos, trichlorphon, vamidothion;

2. from the group of carbamates aldicarb, 2-sec-butylphenylmethyl~arbamate (BPMC), carbaryl, carbofuran, carbosulfan, cloethocarb, benfura-carb, ethiofencarb, furathiocarb, isoprocarb, methomyl, 5-methyl-m-cumenylbutyryl(methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, ethyl 4,6,9-triaza-4-benzyl-6, 10-dimethyl-8-oxa-7-oxo-5,11-dithia-9-dodecenoate (OR 135), 1-methylthio(ethyliden~m;no)-N-methyl-N-(morpholinothio)carbamate (IJC 51717);

3. from the group of carboxylic acid esters allethrin, alphametrin, 5-benzyl-3-furylmethyl (E)-(lR)-cis,2,2-di-methyl3-(2-oxothiolan-3-ylidenemethyl)cyclo-propanecarboxylate, bioallethrin, bioallethrin ((S)-cyclopentyl isomer), bioresmethrin, biphenate, (RS)-1-cyano-1-(6-phenoxy-2-pyridyl)methyl (lRS)-trans-3-(4-tert-butylphenyl)-2,2-dimethylcyclopropanecarboxylate (NCI 85193), cycloprothrin, cyhalothrin, cythithrin, cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate (D isomer), permethrin, pheothrin ((R) isomer), d-pralethrin, pyrethrins (naturally occurring products), resmethrin, tefluthrin, tetramethrin, tralometh:rin;

4. from the group of amidines amitraz, chlordimeform;

5. from the group of tin compound~
cyhexatin, fenbutatin oxide;

6. others abamectin, Bacillus thuringiensis, bensultap, binapacryl, bromopropylate, buprofezin, camphec~-lor, cartap, chloro-benzilate, chlorfluazuron, 2-(4-chlorophenyl)-4,5-di-phenylthiophene (UBI-T 930), chlorfentezine, 2-naphthyl-methyl cyclopropanecarboxylate (Ro 12-0470), cyromazin, ethyl N-(3,5-dichloro-4-(1,1,2,3,3,3-hexafluoro-1-propyl-oxy)phenyl)carbamoyl)-2-chlorobenzocarboximate, DDT, dicofol, N-(N-(3,5-di-chloro-4-~1,1,2,2-tetrafluoro-ethoxy)phenylamino)carbonyl)-2,6-difluorobenzamide (XRD 473), diflubenzuron, N-(2,3-dihydro-3-methyl-1,3-thiazol-2-ylidene)-2,4-xylidine, dinobuton, dinocap, endosulfan,ethofenprox, (4-ethoxyphenyl)(dimethyl)(3-(3-phenoxyphenyl)propyl)silane, (4-ethoxyphenyl)(3-(4-fluoro-3-ph~nnYyphenyl)propyl)dimethylsilane, fenoxycarb, 2-fluoro-5-(4-(4-ethoxyphenyl)-4-methyl-1-pentyl)diphenyl ether (MTI 800), granulosis and nuclear polyhedrosis ~iruses, fenthiocarb, flubenzimi.ne, flucycloxuron, fluf~nox-l~on, gamma-HCH, hexythiazox, hydramethylnon (AC 217300), ivermectin, 2-nitromethyl-4,5-dihydro-6H-thiazine (DS 52618), 2-nitromethy].-3,4-dihydrothiazole (SD 35651), 2-nitromethylene-1,2-thiazinan-3-cylc~h~
dehyde (WL 108477), propargite, teflubenzuron, tetra-difon, tetrasul, thiocyclam, trifumuron, imidacloprid.

The active compound content of the use forms prepared from the commercially a~ailable formulations can be from 0.00000001 to 95% by weight of active compound, prefer-ably between 0.00001 and 1% by weight.

The formulations are used in a customary manner appropri-ate for the use forms.

The active compounds according to the invention are also suitable for controlling endo- and ectoparasites in the veterinary medicines sector and in t:he ~n;m~l h~lch~n~y sector.

The active compounds according to the invention are used here in a known manner, such as by oral use in the form of, for example, tablets, capsules, drinks or granules, by dermal use in the form of, for example, dipping, spraying, pouring on (pour-on and spot-on formulations) and dusting, and by parenteral use in the form of, for example, an injection.

The novel compounds of the formula I according to the invention can accordingly also be particularly advantage-ously employed in livestock husbandry (for example cattle, sheep, pigs and poultry, SUC]l as chickens, geese and the like). In a preferred embo~;~~nt of the inven-tion, the novel compounds are admini~tered orally to the ~n;m~l 8, if appropriate in suitable formulations (cf.
above) and if appropriate with the dr; nk; ng water or feed. Since they are excreted i~ the feces in an effective manner, the development of insects in the feces of the animals can be prevented very easily in this way.
The particular suitable dosages and formulations depend in particular on the species and the stage of development of the stock ~n;m~18 and also on the severity of infestation, and can easily be determined and specified by the customary methods. In the case of cattle, the novel compounds can be used, for ex~mple, in dosages of 0.01 to 1 mg/kg of body weight.

The compounds of the formula I according to the invention are also distinguished by an out~t~n~; ng fungicidal action. Fungal pathogens which have already penetrated into the plant tissue can successiully be controlled curatively. This is particularly important and advantage-ous in the case of those fungal di~eases which can nolonger be controlled effectively with the otherwise customary fungicides after infection has occurred. The action spectrum of the compounds claimed includes various economically important phytopathogenic fungi, such as, for example, Plasmopara viticola, Erysiphe graminis, Phytophthora infestaus, Pyricularia oryzae, Pyrenophora teres, Leptosphaera notorum, Pelliscularia sasatrii and Puccinia recondita.

In addition, the compounds according to the invention are also suitable for use in industrial ~ectors, for example as wood preservatives, as preservatives in paints, in cooling lubricants for metalworking or as preservatives in drilling and cutting oils.

The active compounds according to the invention can be used in their commercially available formulations either by themselves or in combination with other fungicides known from the literature.

The following products may be mentioned, for example, as fungicides which are known from the literature and can be combined according to the invention with the compounds of the formula I: aldimorph, andoprim, anilazine, BAS 480F, BAS 450F, b~n~l~yl, benodanil, benomyl, binapacryl, bitertanol, bromuconazole, buthiobate, captafol, captan, carbendazim, carboxin, CGA 173506, cyprofuram, dichlo-fluanid, dichlomezin, diclobutrazol, diethofencarb,difenconazole (CGA 169374), difluconazole, dimethirimol, dimethomorph, diniconazole, dinocap, dithianon, dode-morph, dodine, edifenfos, ethirmol, etridiazole, fenari-mol, fenfuram, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferimzone (TF 164), fluazinam, fluobenzimine, flu~uinconazole, fluorimide, flusilazole, flutolanil, flutriafol, folpet, fosetyl-aluminium, fuberidazole, fulsulfamide (MT-F 651), fura-laxyl, furconazole, furmecylclox, guazatine, hexacon-azole, ICI A5504, imazalil, imibenconazole, iprobenfos, iprodione, isoprothiolane, RNF 317, copper compounds, such as Cu oxychloride, oxine-Cu and Cu oxides, mancozeb, maneb, mepanipyrim (KIF 3535), metconazol, mepronil, metalaxyl, methasulfocarb, methfuroxam, MON 24000, myclobutanil, nabam, nitrothalidopropyl, nuarimol, ofurace, ox~ yl, oxycarboxin, penconazol, pencycuron, PP 969, probenazole, propineb, prochloraz, procymidon, propamocarb, propiconazol, prothiocarb, pyracarbolid, pyrazophos, pyrifenox, pyroquilon, rabenzazole, RH7592, sulfur, tebuconazole, TF 167, thiabendazole, thicyofen, thiophanate-methyl, thiram, tolclofos-methyl, tolyl-fluanid, triadimefon, triadimenol, tricyclazole, tridemorph, triflumizol, triforine, validamycin, vinchlo-zolin, XRD 563, zineb, sodium dodecylsulfonate, sodium dodecyl sulfate, sodium C13/C15-alcollol ether-sulfonate, sodium cetostearylphosphate ester, dioctyl sodium sulfo-succinate, sodium isopropyl-naphthalenesulfonate, sodium methylenebisnaphthalene-sulfonate, cetyl-trimethyl-ammonium chloride, salts of long-chain primary, secondary or tertiary amines, alkyl-propyleneamines, lauryl-pyrimidinium bromide, ethoxylated quaternized fatty ;ne~, alkyl-dimethyl-benzylammonium chloride and 1-hydroxyethyl-2-alkyl-imidazoline.

The abovementioned combination partners are known active c~ _o~ ds, most of which are described in Ch. R. Worthing, S.B. Walker, The Pesticide M~n~ , 7th Edition (1983), British Crop Protection Council. The active compound content of the use forms prepared from the commercially available formulations can vary within wide limits, and the active compound concentration of the use forms can be from 0.0001 up to 95% by weight of active compound, preferably between 0.0001 and 1% by weight. The formula-tions are used in a customary manner appropriate for the use forms.

-The following examples serve to illu~;trate the invention without this being limited by these.

A. Formulation examples a) A dusting powder is ob~A;ne~ by mixing 10 parts by weight of active compound and 90 parts by weight of talc, as an inert substance, zmd cn~ninl~ting the mixture in a h-- ne~ mill.

b) A wettable powder which is rea~ily dispersible in water is obt~;n~ by mixing 25 parts by weight of active compound, 65 parts by weight of kaolin-con-t~;n;ng c~uartz, as an inert substance, 10 parts by weight of potassium ligninsulfonate and 1 part by weight of sodium oleoyl methyl tauride, as wetting and dispersing agents, and gr;n~;ng the mixture in a pinned disk mill.

c) A dispersion concentrate which is readily dispers-ible in water is prepared by mixing 40 parts by weight of active compound with 7 parts by weight of a sulfosuccinic acid half-ester, 2 parts by weight of a ligninsulfonic acid sodium ~alt and 51 parts by weight of water and gr;n~; ng the! mixture to a fine-ness of less than 5 microns in a gr;n~;ng bead mill.

d) An emulsifiable concentrate can be prepared from 15 parts by weight of active compound, 75 parts by weight of cyclohexane, as a solvent, and 10 parts by weight of oxyethylated nonylphenol (10 ethylene oxide units), as an emulsifier.

e) Granules can be prepared from 2 to 15 parts by weight of active compound and an inert granule carrier material, such as attapulgite, pumice gran-ules and/or c~uartz sand. A suspension of the wettable powder from Example b) with a solids con-tent of 30% is expediently used, and this is sprayed r,, onto the surface of attapulgite granules and the material is dried and m; ~e~ intimately. The weight content of the wettable powder here is about 5% and that of the inert carrier material is about g5% of the finished granules.

B. Biological examples Insecticidal and acaricidal action Example l: Action on the brown p:Lant hopper Young rice plants (Oryza sativa) were dipped in aqueous dilutions of a wettable powder concentrate having a concentration of 250 ppm (based on the active compound), and after the concentrate had drained off, the plants were infested with L4 larval stages of the nice brown plant hopper Nilaparvata lugens.
After being placed in a test cage, these were observed at 28~C and a high atmospheric humidity for 3 days and the mortality of the test ~n;m~l 8 was det:ermined.

The co ~o~ds according to Examples B and C produced a 100% mortality in the test ~n;m~l 8 at; 250 ppm.

Example 2: Action on diabrotica lmdecimpunctata Larvae (L3) of the southern corn rootworm (Diabrotica undecimpunctata) were placed on disks of filter paper impregnated with in each case 1 ml of an acetone dilution of a wettable powder in a concentration of 250 ppm, based on the active compound. After the acetone had evaporated off, the dishes were closed and kept at 28~C for 3 days and the mortality of the larvae was then determined.
100% mortality was found with the co~lpounds according to Examples B and C.

Example 3: Action on the eggs of the American cotton st~;ner Disks of filter paper on which eggs (egg age: 2 days) of the American cotton st~;n~ (Oncopeltus fasciatus) lie were treated with in each case 1 ml of an aqueous formu-lation comprising 250 ppm of the particular active compound. After the deposit had dried on, the disks of filter paper were kept in Petri dishes at room tempera-ture and ~-Y;m~m atmospheric humidit:y. After 7 days, the ovicidal action was determ;ne~. 100% ovicidal action (mortality of the eggs) was found with Examples B and C.

Example 4: Action on the black bean aphid Broad bean plants (Vicia faba) heavily infested with black bean aphids (Aphis fabae, adult population) were sprayed with an aqueous formulation comprising 250 ppm of the particular active compound until the formulation started to drip. After the plants had been grown in a greenhouse for 3 days, the mortality of the aphids (adult population) was investigated. 100% mortality was found with Examples A, B, C and D.

Example 5: Action on the common red spider mite Bean plants (Phaseolus vulgaris ssp. vulgaris var. nanus) heavily infested with common red spider mites (Tetranychus urticae, adult population) were sprayed with an aqueous formulation comprising 250 ppm of the particu-lar active compound until the formulation started to drip. After the plants had been gro~ in a greenhouse for 7 days, the mortality of the spider mites (adult popula-tion) was investigated. 100% mortality was found with Examples A, B, C and D.

Example 6: Action on the fruit-tree red spider mite Apple plants (Malus domestica) heavily infested with .~ .

fruit-tree red spider mites (Panonychus ulmi, adult population) were ~prayed with an aqueous formulation comprising 250 ppm of the particular active compound until the formulation started to drip. After the plants had been grown in a greenhouse for 'i days, the mortality of the fruit-tree red spider mites (adult population) was investigated. 100% mortality was found with Examples A, B, C and D.

Example 7: Citrus mealy-bug Bean plants (Phaseolus w lgaris ssp. vulgaris var. nanus) heavily infested with citrus mealy-bugs (Planococcus citri, larvae of the 2nd development: stage) were sprayed with an aqueous formulation comprising 250 ppm of the particular active compound until the~ formulation started to drip. After the plants had been grown in a greenhouse for 7 days, the mortality of the citrus mealy-bugs (adult population) was investigated. 100% mortality was found with Examples B and C.

Example 8: Action on the housefly The base and lid of a Petri dish were coated on the inside with in each case 3 ml of an aqueous dilution of a wettable powder concentrate comprising 250 ppm of the particular active compound. After the deposit had dried on, houseflies (Musca domestica) 24 hours old were placed in the Petri dishes and these were closed with the treated lid. After 3 hours at a room temperature of 20~C, the mortality of the flies was investigated. 100%
destruction was achieved with compo~ds B and C.

Example 9: Ovicidal action (M~n~3llc~ sexta) Petri dishes were covered with Jaan filter paper on the inside of the base and 20 1 day old e~ggs of M~n-3llca sexta were in each case placed on the paper. About 1 ml of a synthetic insect feed diet was then placed in the center CA 02203998 l997-04-29 i, .

of the Petri dish and the inside of the base with the eggs and feed diet were sprayed with an acaueous wettable powder suspension of the test products correspon~; ng to 600 l/ha. After the Petri dishes had been closed and kept at room temperature for 5 days, the mortality of the eggs was determined. Compound B produced an action of 100%.

Example 10:

Larvae (~4) of the cockroach Blaberus craniifer were injected with active compounds dissolved in methanol.
After application of the compounds according to Examples B and C (2 x 10-4 g of active ingredient/
animal), 100% mortality was to be found after 48 hours.

Example 11:

Larvae (L4) of the tobacco hawk-moth MAn~c~ sexta were injected with active compounds dissolved in acetone.
After application of the compound acc:ording to Examples B
and C (2 x 10-4 g of active ingredient/:~n;~Ql), 100%
mortality was to be found after 48 hours.

Use as an antiparasitic Example 12:

In vitro test on tropical cattle ticks (Boophilus microplus) The activity of the compounds according to the invention against ticks was to be detected in the following test design:

To prepare a suitable formulation of the active compound, the active compounds were dissolved i.n a concentration of 10% (w/v) in a mixture comprising dimethylformamide (85 g), nonylphenol polyglycol ether (3 g) and oxyethyl-ated castor oil (7 g), and the emulsion concentrates thus obtained were diluted with water to a test concentration of 500 ppm.

In each case ten fully satiated females of the tropical tick Boophilus microplus were immersed in these active compound dilutions for five minutes. The ticks were then dried on filter paper and fixed on their back to an adhesive film for the purpose of laying eggs. The tick~
were stored in a heated cabinet at 28~C and an atmos-pheric humidity of 90%.

As a control, tick females were dipped only in water. The inhibition of oviposition two weeks after the treatment was used to evaluate the activity.

In this test, the compounds according to Example C cause in each case 100% inhibition of oviposition in an active compound concentration of 500 ppm.

C. Preparation examples Example A

4-~4-(1,1,3,3-Tetramethylbutyl)-cyclohex-3-enoxy]-5,6,7,8-tetrahydroquinazoline 0.46 g (15.3 mmol) of sodium hydride (80% strength dispersion in mineral oil) was added to a solution of 2.3 g (11.2 mmol) of 4-[(1,1,3,3-tetramethyl)butyl]-cyclohex-3-enol in 20 ml of tetrahydrofuran and the mixture was heated under reflux for 3 hours. After cooling to room temperature, 1.7 g (10.2 mmol) of 4-chloro-5,6,7,8-tetrahydroquinazoline, dissolved in 5 ml of tetrahydrofuran, were added and the mixture was heated under reflux for a further 2 hours. A.fter cooling to room temperature, isopropanol was added to the reaction solu-tion and the mixture was subsequerltly stirred for 15 minutes and then extracted with metllylene chloride. The organic phase was dried and concentrated. For purification, the residue was chromatographed over silica gel with petroleum ether/ethyl acetate 1 : 1. This gave 2.3 g (66%
of theory) of yellow oil, which gradually solidified.

Preparation examples for4-(4-alkylcyclohex-3-enylamino)-pyrimidines Example B

4-t4-(1,1,3,3-Tetramethylbutyl)-cyclohex-3-enylamino]-5-chloro-6-ethylpyrimidine 1.2 g (13.5 mmol) of R2CO3 were initially introduced into 10 ml of dimethylformamide, 1.6 g (9 mmol) of 4-[(1,1,3,3-tetramethyl)-butyl]-cyclohex-3-enylamine were added and the mixture was stirred at 80~C for 4 hours.
For working up, the cooled reaction solution was taken up in water. The mixture was extracted with ether and the combined organic phases were washed with water, dried and concentrated. For purification, the residue was chromato-graphed over silica gel with petroleum ether/ethyl acetate 5 : 1. This gave 1.3 g (43.3% of theory) of colorless oil.

Preparation of 4-[(1,1,3,3-tetrameth~l)-butyl~-cyclohex-3-enylamine 7 g (33 mmol) of 4-[(1,1,3,3-tetramethyl)-butyl]-cyclo-hex-3-enone were stirred in 100 g of isopropanol with 2.1 g (33 mmol) of sodium cyanoborohydride and 25.9 g (0.33 mol) of ammonium acetate in the presence of 7 g of molecular sieve (3 A) at room tempe ature for 72 hours.
The reaction solution was filtered and the filtrate was concentrated. The residue was taken up in 15% strength NaOH and the mixture was extracted with CH2Cl2. The combined methylene chloride phases were extracted by stirring twice with dilute hydrochloric acid and the combined hydrochloric acid phases were rendered basic with 30% strength sodium hydroxide solution. The mixture r was extracted with methylene chloride and the organic phase was dried and concentrated. 4.6 g (70% of theory) of yellow oil remained.

Preparation of 4-[(1,1,3,3-tetramethyl)-butyl]-cyclohex-3-enol 10.0 g (48 mmol) of 4-[(1,1,3,3-tetramethyl)-butyl]-cyclohex-3-enone were initially introduced into 60 ml of ethanol, 2.7 g (0.07 mol) of sodium borohydride, dis-solved in 20 ml of water, were added dropwise and the mixture was stirred at room temperature for 3 hours. The reaction solution was concentrated to dryness, the residue was taken up in water and t:he mixture was ren-dered weakly acidic with 2N HCl at 0~C. It was extracted with ether and the combined ether phases were washed with saturated NaCl solution and dried. Concentration gave 7.1 g (70% of theory) of product as a colorless solid which was reacted without further purification.

Preparation of 4-~(1,1,3,3-tetrameth~l)-butyl]-cyclohex-3-enone 40 g (0.17 mol) of 1-methoxy-4-[(1,1,3,3-tetramethyl)-butyl]-cyclohexa-1,4-diene were initi.ally introduced into 500 ml of methanol, 600 ml of 10% strength H2S04 were added dropwise at room temperature and the mixture was subsequently stirred for 2 hours. The reaction solution was poured onto water and extracted with ether. The combined ether phases were washed with H20 and saturated NaCl solution and dried. Concentration gave 37 g (99% of theory) of colorless liquid, which was reacted without further purification.

Preparationofl-methoxy-4-~(1,1,3,3-tetramethyl)-butyl]-cyclohexa-1,4-diene 105 g (0.48 mol) of 4-[(1,1,3,3-tetramethyl)-butyl]-anisole were initially introduced into a mixture of CA 02203998 l997-04-29 i. , 180 ml of tert-butanol and 120 ml of tetrahydrofuran, and 1600 ml of ~mm~;a were con~n~ed in at -78~C. 13.3 g (1.9 mol) of lithium were added in portions and the mixture was then refluxed for 1 hour. Methanol and water were 81Owly added to the reaction solution. After the ammonia had been evaporated off, the residue was extracted with ether. The organic phase was washed with water, dried over MgS04 and concentrated. Thi~ gave 95.8 g (90% of theory) of a colorle~s liquid, which was reacted without further purification.

Preparation of 4-~(1,1,3,3-tetramethyl)-butyl]-anisole 100 g (0.48 mol) of 4-~(1,1,3,3-tetramethyl)-butyl]-phenol and 93.8 g (0.68 mol) of R2CO3 were initially introduced into 260 ml of acetone. 67 g (0.53 mol) of dimethyl sulfate were added dropwise to the reaction solution. When the evolution of heat had subsided, the mixture was heated under reflux for 4 hours, while stirring. 130 ml of acetone were disl-illed off, 40 ml of NH40H were added and the mixture was ~3ubsequently stirred for 10 minutes. Water was then added to the reaction solution, the mixture was extracted with ether and the combined organic phases were washed with water, 2N NaOH
and then with saturated NaCl solution and dried over MgSO4. Concentration gave 105 g (98% of theory) of solid product, which was reacted without f~lrther purification.

Preparation examples for 4-(1-aryl-1-cyclohexen-4-yl-amino)-pyrimidine Example C

5-Chloro-6-ethyl-4-[1-(3-fluoro-4-methoxy-phenyl)-cyclo-hexen-4-ylamino]-pyrimidine 1.6 g (7 mmol) of 4-amino-1-(3-fluoro-4-methoxy-phenyl)-cyclohexene, 1.2 g (7 mmol) of 4,5-dichloro-6-ethyl-pyrimidine and 1.4 g (14 mmol) of triethylamine were r ~
~ 42 ~
heated under reflux in 5 ml of toluene for 10 hours. For working up, the mixture was diluted with toluene and extracted by stirring with water. The organic phase was dried and concentrated. For purificat:ion, the residue was chromatographed o~er silica gel with pe~roleum ether/
ethyl acetate 7 : 3. This gave 0.6 g (27.6% of theory) of colorless oil which gradually crystallized. Melting point 86 - 87~C.

Preparation of the educt amine 4-Amino-1-(3-fluoro-4-methoxy-phenyl)-cycloh eYen e 10.1 g (46 mmol) of 1-(3-fluoro-4-methoxy-phenyl)-cyclo-hexen-4-one, 35.5 g (0.46 mol) of ammonium acetate and 17 g of 3 A molecular sie~e were initially introduced into 250 ml of isopropanol, and 2.9 g (46 mmol) of sodium cyanoborohydride were introduced in portions at 0~C, while stirring. The mixture was stirred at room tempera-ture for 72 hours, the solvent was ~~tripped off and the residue was extracted by stirring several times with methylene chloride/2N sodium hydroxide solution. The combined methylene chloride phases were extracted by stirring twice with dilute hydrochloric acid and the combined hydrochloric acid phases were rendered strongly basic with 30% strength ~odium hydroxide solution. The mixture was extracted with methylene chloride and the organic phase was dried and concentrated. 3.3 g (32.4% of theory) of product r~m~; neA as a yellow oil which gradually solidified.

Preparation of 1-(3-fluoro-4-methoxy-phenyl)-cycloh~Yen-4-one 101.0 g (0.36 mol) of 4-hydroxy-4-(3-fluoro-4-methoxy-phenyl)-cycloh~Y~no~e ethylene keta:L were stirred in a mixture of 500 ml of formic acid and 30 ml of water at room temperature for 24 hours. After the formic acid had been stripped off, the residue was taken up in methylene chloride and the mixture was washed with sodium bicarbon-ate solution and water, dried and concentrated. This gave 71 g (89.5% of theory) of colorless solid, which was reacted without further purification.
Melting point 68 - 70~C.

Preparation of 4-hydroxy-4-(3-fluoro-4-methoxy-phenyl)-cycloh~no~e ethylene ketal A Grignard solution was prepared from 100 g (0.49 mol) of 4-bromo-2-fluoroanisole and 13 g (0.53 mol) of magnesium filings in 350 ml of tetrahydrofuran. A solution of 64.0 g (0.41 mol) of cycloh~y~ne-l~4-dione monoethylene ketal in 150 ml of tetrahydrofuran was added dropwise to this at 20 - 30~C. The mixture wa8 stirred at room temperature for 2 hours and under ref.lux for 2 hours. It was poured onto ice, solid ammonium chloride was added, the mixture was diluted with 500 ml of toluene and the organic phase was separated off, dried and concentrated.
This gave 101 g (88% of theory) of solid product, which was reacted without further purification.
Melting point 126 - 128~C.

Example D

0.36 g (12 mmol) of sodium hydride (80% strength disper-sion in mineral oil) was added to a solution of 2.5 g (11 mmol) of 1-(3-fluoro-4-methoxy-phenyl)-4-hydroxy-cyclohexene in 30 ml of tetrahydrofuran and the mixturewas heated under reflux for 2 hours until the evolution of hydrogen had ended. After cooling l-o room temperature, 2.0 g (11 mmol) of 4,5-dichloro-6-ethyl-pyrimidine were added and the mixture was heated under reflux for a further 6 hours. After the solvent had been stripped off, the residue was taken up in water/met:hylene chloride and the organic phase was dried and concentrated. For purifi-cation, the residue was chromatographed over silica gel with petroleum ether/ethyl acetate 4 : 1. This gave 3.0 g (75.3% of theory) of yellow solid.

~ . , Melting point 63 - 64~C.

Preparation of the educt 1-(3-fluoro-4-methoxy-phenyl)-4-hydroxy-cyclohexene 10.0 g (45 mmol) of 1-(3-fluoro-4-methoxy-phenyl)-cyclo-h~Y~n-4-one were dissolved in 100 ml of methanol, and 0.9 g (23 mmol) of sodium borohydride was added in portions at 0~C. After the mixture had been stirred at room temperature for 1 hour, 5 ml of acetone were added, the solvent was stripped off and the residue was taken up in 2N sodium hydroxide solution and methylene chloride.
The organic phase was dried and concentrated. 7.4 g (74.0% of theory) of yellow solid remained, which was reacted without further purification.

The following were obtained analogou~ly:

Example E

4-(cis-4-tert-Butyl-cyclohex-3-enyloxy)-quinazoline;
melting point 56 - 57~C.

Example F

5-Chloro-6-ethyl-4-(cis-4-tert-butyl-cyclohex-3-enyl-amino)-pyrimidine; colorless oil.

Example G

5-Bromo-6-ethyl-4-(cis-4-tert-butyl-cyclohex-3-enyl-amino)-pyrimidine; colorless oil.

Example H

5-Chloro-6-ethyl-4-[4-(3,4-dimethylphenyl)-cyclohex-3-enylamino]-pyrimidine; colorless oil.

Example I

4-[4-(3-Fluoro-4-methoxy)-phenyl-cyclohex-3-enyloxy]-quinazoline; melting point 82 - 83~C.

Claims (21)

claims:

1. A compound of the formula I

( I ) in which R1 is hydrogen, halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C3-C5)-cycloalkyl or (C3-C5)-halo-cycloalkyl;
R~ and R3 are identical or different and independently of one another are each hydrogen, halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C3-C8)-cyclo-alkyl, (C3-C8)-halocycloalkyl, (Cl-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkoxy-(C1-C4)-alkyl, (C1-C4)-haloalkoxy-(C1-C4)-alkyl, (C1-C4)-alkoxy-(C1-C4)-haloalkyl, (C1-C4)-haloalkoxy-(C1-C4)-haloalkyl, (C1-C4)-alkylamino, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C1-C4)-haloalkylthio, (C1-C4)-haloalkylsulfinyl, (C1-C4)-haloalkylsulfonyl, (C1-C4)-alkylthio-(C1-C4)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C1-C4)-alkoxycarbonyl, cyano, (C1-C4)-cyanoalkyl or thiocyano; or R~ and R3, together with the carbon atoms to which they are bonded, form an unsaturated 5- or 6-membered isocyclic ring which, if it is a 5-membered ring, can contain an oxygen or sulfur atom instead of CH2, or, if it is a 6-membered ring, can contain one or two nitrogen atoms instead of one or two CH units, and is optionally substituted by 1, 2 or 3 identical or different radicals, these radicals being (C1-C4)-alkyl, (C1-C4)-haloalkyl, preferably trifluoro-methyl, halogen, (C1-C4)-alkoxy or (C1-C4)-haloalkoxy, or R2 and R3, together with the carbon atoms to which they are bonded, form a saturated 5-, 6- or 7-membered isocyclic ring which can contain oxygen and/or sulfur instead of one or two CH2 groups and is optionally substituted by 1, 2 or 3 (C1-C4)-alkyl groups;
A is CH or N;
X is NH, oxygen or S(O)q, where q = 0, 1 or 2;
E is a direct bond or a straight-chain or branched (C1-C4)-alkanediyl group, preferably a direct bond;
a and b are identical or different and independently of one another are the numbers 0, 1, 2 or 3, where a and b are not simultaneously 0;
R4 is halogen, (C1-C4)-alkyl, (C3-C7)-cycloalkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-halo-alkoxy or optionally substituted phenyl;
v is 0, 1 or 2;
U is a direct single bond, oxygen, a group S(O)y, where y = 0, 1 or 2, or a group NR6, in which R6 is hydrogen, (C1-C4)-alkyl or (C1-C4)-alkoxy;
V is a direct single bond, carbonyl or a grouping of the formula or , in which Q is oxygen, sulfur or (C1-C4)-alkyl-imino, T is oxygen, sulfur or a group NR6' and T' is (C1-C4)-alkoxy, (C1-C4)-alkylthio or NR6'-R6" , and in which R6' and R6" are identical or different and have the meanings given above for R6; and R5 is a radical from the series consisting of alkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted heterocyclyl, cyano, halogen, nitro, alkyloximino or a group SiR7R8R9, in which R7 and R8 are (C1-C4)-alkyl and R9 is alkyl, cycloalkyl, aryl or arylalkyl;
and the alkyl, alkenyl, alkynyl or alkyloximino radicals mentioned for R5, R7, R8 and R9 have, where appropriate, at least one of the following features:
i. one or more, preferably up to three, non-adjacent CH2 groups are replaced by CO and/or hetero atom units, such as O, S(O)y, where y = 0, 1 or 2, NR6"' or SiR7'R8' , in which R6"' has the meanings given above for R6 and in which R7' and R8' have the meanings given above for R7 and R8;
ii. 3 to 12 atoms of these radicals form an up to 12-membered ring;
iii. the radicals are optionally substituted by one or more, preferably up to three, in the case of halogen up to the maximum number of, identical or different radicals from the series consisting of halogen, alkyl, cycloalkyl, aryl, aryloxy, arylthio, heterocyclyl, heterocyclyloxy, hetero-cyclylthio, haloalkyl, aryalkyl, cycloalkyl-alkyl, alkoxy, haloalkoxy, alkylthio, cyclo-alkoxy, alkanoyloxy, haloalkanoyloxy, cyclo-alkanoyloxy, cycloalkylalkanoyloxy, aroyloxy, arylalkanoyloxy, alkylsulfonyloxy, arylsulfonyloxy, heterocyclylcarbonyloxy, hydroxyl, cyano and nitro, where the cycloaliphatic, aromatic or heterocyclic ring systems among those substituents just mentioned can be unsubstituted or provided with up to three - in the case of halogen, preferably fluorine, also up to the maximum number of - identical or different substituents;
or a salt thereof.

2. A compound of the formula I as claimed in claim 1, in which R4 is halogen, preferably fluorine, chlorine and bromine, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy or (C1-C4)-alkylthio; and R5 can be (C1-C20)-alkyl, (C2-C20)-alkenyl, (C2-C20)-alkynyl, optionally substituted aryl, optionally substituted heterocyclyl, cyano, halogen, hydroxyl, carboxyl, nitro, (C1-C20)-alkyloximino or a group SiR7R3R9, in which R7 and R3 are (C1-C4)-alkyl and R9 is (C1-C20)-alkyl or optionally substituted aryl; and the alkyl, alkenyl, alkynyl or alkyloximino radicals mentioned for R5, R7, R8 and R9 have, where appropriate, at least one of the following features:
i. one or more, preferably up to three, non-adjacent CH2 groups are replaced by CO and/or hetero atom units, such as O, S(O)y, where y = 0, 1 or 2, NR6"' or SiR7'R8' , in which R6"' has the meanings given above for R6 and in which R7 and R8 have the meanings given above for R7 and R8;
ii. 3 to 8 atoms of these radicals form an up to 8-membered ring;
iii. the radicals are optionally substituted by one or more, preferably up to three, in the case of halogen up to the maximum number of, identical or different radicals from the series consisting of halogen, (C1-C12)-alkyl, (C3-C8)-cycloalkyl, aryl, aryloxy, arylthio, heterocyclyl, heterocyclyloxy, heterocyclylthio, (C1-C12)-haloalkyl, aryl-(C1-C4)-alkyl, (C3-C8)-cycloalkyl-(C1-C4)-alkyl, (C1-C12)-alkoxy, (C1-C12)-haloalkoxy, (C1-C12)-alkylthio, (C3-C8)-cycloalkoxy, (C1-C12)-alkanoyloxy, (C1-C12)-haloalkanoyloxy, (C3-C8)-cycloalkanoyloxy, (C3-C8)-cycloalkyl-(C1-C12)-alkanoyloxy, aroyloxy, aryl-(C1-C4)-alkanoyloxy, (C1-C12)-alkylsulfonyloxy, arylsulfonyloxy, heterocyclylcarbonyloxy, hydroxyl, cyano and nitro, where the cycloaliphatic, aromatic or heterocyclic ring systems among the substituents just mentioned can be unsubstituted or provided with up to three - in the case of halogen, preferably fluorine, also up to the substituents number of - identical or different substituents and the other radicals and variables are as defined above;
or a salt thereof.

3. A compound of the formula I as claimed in claim 1 or 2, in which R1 is hydrogen or fluorine;
R~ is (C1-C4)-alkyl, cyclopropyl, halocyclopropyl, halo(Cl-C2)-alkyl, methoxymethyl or cyano;
R3 is hydrogen, halogen, methyl, ethyl, methoxy, ethoxy, cyano or (C1-C4)-alkoxycarbonyl; or R~ and R3, together with the carbon atoms to which they are bonded, form an optionally substituted unsaturated 5- or 6-membered ring which, in the case of the 5-membered ring, can contain a sulfur atom instead of a CH2 unit, or R~ and R3, together with the carbon atoms to which they are bonded, form a saturated 5- or 6-mem-bered ring which can contain a sulfur or an oxygen atom instead of a CH2 unit;
A is CH or N;
X is NH or oxygen;
E is a direct bond;
a is the number 1 and b is the number 2;
R4 is hydrogen, (C1-C4)-alkyl, trifluoromethyl or (C1-C4)-alkoxy;
and the other radicals and variables are defined as above;
or a salt thereof.

4. A compound of the formula I as claimed in one of claims 1 to 3, in which R1 is hydrogen;
R2 is methyl, ethyl, propyl, isopropyl, 1-fluoro-ethyl, trifluoromethyl, cyclopropyl or methoxy-methyl;
R3 is halogen, methyl, ethyl, methoxy, ethoxy, cyano or (C1-C4)-alkoxycarbonyl, or R~ and R3, together with the ring system to which they are bonded, form the quinazoline or quinoline system, which can be substituted by fluorine in the carbocyclic part, or R~ and R3, together with the carbon atoms to which they are bonded, form a saturated 6-membered ring which can contain an oxygen or sulfur atom instead of a CH2 group;
r is 0;
U is a direct bond or oxygen; and V is a direct bond;
or a salt thereof.

5. A compound of the formula I as claimed in one of claims 1 to 4, in which R1 is hydrogen;
R~ is ethyl, propyl, isopropyl, 1-fluoroethyl, trifluoromethyl or methoxymethyl;
R3 is fluorine, chlorine, bromine or methoxy;
or in the case where A is nitrogen, R~ and R3, together with the ring system to which they are bonded, form the quinazoline system, which can be substituted by a fluorine atom, or R~ and R3, together with the ring system to which they are bonded, form the 5,6,7,8-tetrahydroquinazoline system;
A -is CH or N;
X is NH or oxygen;
E is a direct bond;
a is the number 1 and b is the number 2;

v is 0;
U is a direct bond or oxygen and V is a direct bond;
or a salt thereof.

6. A compound of the formula I as claimed in one of claims 1 to 5, in which R1 is hydrogen;
R2 is ethyl or methoxymethyl;
R3 is fluorine, chlorine, bromine or methoxy, or R2 and R3, where A = N, together with the ring system to which they are bonded, form the quinazoline or the 5,6,7,8-tetrahydroquinazoline system;
R5 is (C1-C20)-alkyl, (C2-C20)-alkenyl or (C2-C20)-alkynyl, where 3 - 6 carbon atoms of these hydrocarbon radicals can form a ring and/or these hydrocarbon radicals can optionally be substituted by a phenyl radical, which can be unsubstituted or provided with up to three, in the case of fluorine also up to the maximum number of, identical or different substituents;
A is CH or N;
X is NH or oxygen;
E is a direct bond;
U and V together are a direct bond;
v is 0 and the other radicals and variables are defined as above;
or a salt thereof.

7. A compound of the formula I as claimed in one of claims 1 to 6, in which R2 is methoxymethyl and R3 is methoxy, or R2 is ethyl and R3 is chlorine or bromine, R5 is (C1-C20)-alkyl or (C2-C20)-alkenyl, where 3 -6 carbon atoms of this radical can form a ring and/or this radical can optionally be substituted by a phenyl radical, which can be unsubstituted or provided with up to three, in the case of fluorine also up to the maximum number of, identical or different substituents;
X is NH; and the other radicals and variables are defined as above;
or a salt thereof.

8. A process for the preparation of a compound of the formula I as claimed in one of claims 1 to 7, which comprises reacting a compound of the formula II

( I I ) in which A, R1, R~ and R3 have the meanings given under formula I and L is a leaving group, with a compound of the formula III

(III) in which X, E, a, b, v, U, V, R4 and R5 have the meanings given in claim 1 under formula I, and, if R3 is hydrogen, if appropriate halogenating, the compound of the formula I thus obtained, or obtained in another manner, in position 5 of the heterocyclic radical, or further derivatizing R5 in the side chain, and if appropriate converting the compound thus obtained into its salt.

9. A composition comprising at least one compound as claimed in one of claims 1 to 7 and at least one formulating agent.

10. A fungicidal composition as claimed in claim 9 comprising a fungicidally active amount of at least one compound as claimed in one of claims 1 to 7 together with the additives or auxiliaries customary for this use.

11. An insecticidal, acaricidal, ixodicidal or nematicidal composition as claimed in claim 9, comprising an active amount of at least one compound as claimed in one of claims 1 to 7 together with the additives or auxiliaries customary for this use.

12. A plant protection composition comprising a fungicidally, insecticidally, acaricidally, ixodicidally or nematicidally active amount of at least one compound as claimed in one of claims 1 to 7 and at least one further active compound, preferably from the series consisting of fungicides, insecticides, attractants, sterilizing agents, acaricides, nematicides and herbicides, together with the auxiliaries and additives customary for this use.

13. A composition for use in wood preservation or as a preservative in sealing compositions, in paints, in cooling lubricants for metalworking or in drilling and cutting oils, comprising an active amount of at least one compound as claimed in one of claims 1 to 7 together with the auxiliaries and additives customary for these uses.

14. A compound as claimed in one of claims 1 to 7 or a composition as claimed in claim 9 for use as an animal medicament, preferably in controlling endo or ectoparasites.

15. A process for the preparation of a composition as claimed in one of claims 9 to 14, which comprises bringing the active compound and the other additives together and converting them into a suitable use form.

16. The use of a compound as claimed in one of claims 1 to 7 or of a composition as claimed in one of claims 9, 10, 12 and 13 as a fungicide.

17. The use of a compound as claimed in one of claims 1 to 7 or of a composition as claimed in one of claims 9, 10 and 13 as a wood preservative or as a preservative in sealing compositions, in paints, in cooling lubricants for metalworking or in drilling and cutting oils.

18. A method of controlling phytopathogenic fungi, which comprises applying a fungicidally active amount of a compound as claimed in one of claims 1 to 7 or of a composition as claimed in one of claims 9, 10 and 11 to these or to the plants, areas or substrates infested by them or to seed.

19. A method of controlling harmful insects, Acarina, molluscs and nematodes, in which an active amount of a compound as claimed in one of claims 1 to 7 or of a composition as claimed in one of claims 9, 10 and 12 is applied to these or to the plants, areas or substrates infested by them.

20. The use of a compound as claimed in one of claims 1 to 7 or of a composition as claimed in one of claims 9, 10 and 12 for controlling harmful insects, Acarina, molluscs and nematodes.

21. Seed treated or coated with an active amount of a compound as claimed in one of claims 1 to 7 or of a composition as claimed in one of claims 9, 10 and 12.