CA2094010A1

CA2094010A1 - Benzophenone derivatives

Info

Publication number: CA2094010A1
Application number: CA002094010A
Authority: CA
Inventors: Dieter Durr; Roger Graham Hall; Josef Ehrenfreund; Alfons Pascual
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1992-04-16
Filing date: 1993-04-14
Publication date: 1993-10-17
Also published as: MX9302176A; IL105310A0; HUT64299A; KR940005562A; AU3694393A; EP0566534A1; HU9301105D0; ZA932640B; JPH0625134A; BR9301545A

Abstract

Abstract Benzophenone derivatives Compounds of the formula (I), in which o and p independently of one another are 0,1, 2, 3, 4 or 5, where, if o is greater than 1, the radicals R1 are identical or different and where, if p is greater than 1, the radicals R2 are identical or different;
R1 and R2 independently of one another are C1-C4alkyl, halo-C1-C4alkyl, Cl-C4alkoxy, halo-C1-C4alkoxy, C1-C4alkylthio, halo-C1-C4alkylthio, halogen, -OH, nitro, cyano, phenoxy, -O-S(=O)-R8 or -O-S(=O)2-R8, C2-C4alkynyl, or C2-C4alkynyl which is substituted by phenyl or halogen, or are C2-C4alkenyl, halo-C2-C4alkenyl, and/or two substituents R1 which are bonded to adjacent C atoms of the phenyl ring and/or two substituents R2 which are bonded to adjacent C atoms of the phenyl ring independently of one another together are -Y1-Z-Y2-;
R3 is hydrogen, halogen, -OH, -SH, C1-C4alkyl, C3-C6cycloalkyl, halo-C1-C4alkyl,C1-C4alkoxy, C1-C4alkoxy-C1-C4alkyl, C1-C4alkoxy-C1-C4alkoxy, C1-C4alkylthio or -N(R4)R5;
R4 and R5 independently of one another are hydrogen, C1-C4alkyl or -OH;
R6 is -OR9, -S(O)nR10, -P(O)R11R12 or -NR13R14;
R7 is hydrogen, C1-C4alkyl, C3-C6cycloalkyl, halo-C1-C4alkyl, C1-C4alkoxy-C1-C4alkyl, allyl, C1-C3alkylallyl, haloallyl or propargyl;
R8 is C1-C8alkyl or halo-C1-C8alkyl;

R9 is hydrogen, C1-C4alkyl, halo-C1-C4alkyl, C1-C4alkoxy-C1-C4alkyl, C3-C6cycloalkyl, C2-C6alkenyl, halo-C2-C6alkenyl or propargyl, R10 is hydrogen, C1-C4alkyl, halo-C1-C4alkyl, phenyl or -NR13R14;
R11 and R12 independently of one another are C1-C4alkoxy;
R13 and R14 independently of one another are hydrogen, C1-C4alkyl, halo-C1-C4alkyl, phenyl, C1-C4alkylamido, C1-C4dialkylamido or-NH2;
n is 0, 1 or 2;
Y1 and Y2 independently of one another are O or S; and Z is methylene, eth-1,2-ylene; halomethylene or haloeth-1,2-ylene, and, where applicable, tautomers thereof as well as salts thereof can be used asagrochemical active ingredients and can be prepared in a manner known per se.

FD 4.5/FF

Description

2 ~

Benzo~henone derivatives The invention relates to compolmds of the -formula - -.

(Rl~(R2)p N~N (1), R3J~N~

in which o and p independently of one another are 0, 1, 2, 3, 4 or 5, where, if o is greater than 1, the radicals Rl are identical or different and where, if p is greater than 1, the radicals R2 are identical or different;
Rl and R2 independently of one another are Cl-C4alkyl, halo-CI-C4alkyl, Cl-C4alkoxy, halo-Cl-C4aLkoxy, Cl-C4aLkylthio, halo-Cl-C4aLkylthio, h~ogen, -OH, nitro, cyano, phenoxy, -O-S(=O)-R8 or -O-S(=0)2-R8, C2-C4aLIcynyl, or C2-C4alkynyl which is substib~ted by phenyl or halogen, or are C2-C4alkenyl, halo-C2-C4a~enyl, andlor two substituents Rl which are bonded to adjacent C atoms of the phenyl ring andlor two substituents R2 which are bonded to adjacent C atoms of the phenyl ring independently of one another together are -Yl-Z-Y2-;
R3 is hydrogen, halogen, -OH, -SH, Cl-C4aL~yl, C3-C6cycloaLkyl, halo-Cl-C4aL~cyl, Cl-C4aLkoxy, Cl-C4alkoxy-Cl-C4aLkyl, Cl-C4alkoxy-Cl-C4alkoxy, Cl-C4aL~cylthio or -N(R4)Rs;
R4 and R5 independently of one another are hydrogen, Cl-C4aL~yl or -OH;
R6 is -ORg, -S(O),,RIo, -P(O)RllRl2 or -NRl3Rl4;
R7 is hydrogen, Cl-C4aLt~yl, C3-C6cycloaLt~yl, halo-Cl~C4aLl~yl, Cl-C4aL1~0xy-Cl-C4aL~cyl, allyl, Cl-C3aLI~ylallyl, haloallyl or propargyl;
R8 iS Cl-C8alkyl or halo-Cl-C8aLkyl;
Rg is hydrogen, Cl-C4aLI~yl, halo-Cl-C4aLI~yl, Cl-C4aLkoxy-Cl-C4alkyl, C3-C6cycloalkyl, C2-C6aLtcenyl, halo-C2-C6aL~enyl or propargyl;

Rlo is hydrogen, Cl-C4aLt~yl, halo-Cl-C4aLkyl, phenyl or -NRl3Rl4;
Rll and Rl2 independently of one another are Cl-C4alkoxy;
Rl3 and Rl4 independently of one another are hydrogen, Cl-C4aL~yl, halo-Cl-C4aL~cyl, phenyl, C~-C4aLkylamido, Cl-C4diaLkylamido or -NH2;
nisO, 1 or2;
Yl and Y2 independently of one another are O or S; and Z is methylene, eth-1,2-ylene; halomethylene or haloeth-1,2-ylene, to tautomers of the compounds of the formula I, and to salts of the various tautomers, to a process for the preparation and to the use of these compounds and tautomers, to pesticides comprising a compound of the formula I or of a tautomer or an agrochemically utilisable salt thereof, and to a process for the preparation of the compositions and to the use of these compositions.

In some cases, the compolmds of the formula I can exist as tautomers. If, for example, the radical R~ is hydroxyl or the radical R7 is hydrogen, then the corresponding compounds of the formula I can exist as an equilibrium mixture of tautomers. Accordingly, thecornpounds of the formula l are aLso to be understood as me,aning corresponding tautomers or salts thereof, even when they are not mentioned specific~ly in each case.

The compounds of the ~ormula I and, where appropriate, the tautomers thereof cnn exist in the form of salts. Compounds of the formula I which have at least one basic centre can form, for example, acid addition salts. These are formed, for example, with strong inorganic acids such as mineral acids, for example sulfuric acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids such as unsubstituted Cl-C4aLkanecarboxylic acids or C~-C4alkanecarboxylic acids which are substituted by, for example, halogen, for example acetic acid, saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, maleic acid, fumaric acid or phthalic acid, hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, ~ic acid or citric acid, or benzoic acid, or with organic sulfonic acids such as unsubsdtuted Cl-C4aLIcanesulfonic aclds or arylsulfonic acids, or Cl-C4alkanesulfonic or arylsulfonic acids which are substituted, for example by halogen, such as methane- or p-toluenesulfonic acid. Compounds of the formula I which have at least one acidic group can form salts with bases. Suitable salts with bases are, for example, metal salts such as aLkali metal salts or aLkaline earth metal salts, for example sodium salts, potassium salts or rnagnesium salts, or sal~s wi~ ammonia or an organic amine, such as morpholin, piperidine, pyrrolidine, a mono- di- or tri-lower-alkylamine~ for example ethyl-, diethyl-, 2 ~

triethyl- or dimethylpropylamine, or a mono- di- or trihydroxy-lower-aLI~ylamine, for example mono-, di- or triethanolamine. Corresponding internal salt~s can furthermore be formed, where appropri~te. Preferred within the scope of the invention are agrochemically advantageous salts; however, the invention also embraces salts which are disadvantageous for agrochemical use, for example salts which are toxic to honeybees or fish and which are used, for example, for isolating or purifying free compounds of the formula I oragrochemically utilisable salts thereof. The term "compound of the formula I" therefore also embraces the tautomers of these compounds, their salts, and the salts of the tautomers.

Halogen - per se or as a structural element of groups and compounds such as haloalkyl and haloallyl - is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine, especially fluorine or chlorine.

Unless otherwise de~med, carbon-containing groups and compounds contain in each case 1 up to and including 8, preferably 1 to 4, in particular 1 or 2, carbon atoms.

C3-C6cycloaIkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

AL~cyl - as a group per se and as structural element of other groups and compounds such as haloalkyl, alkoxy, alkoxyalkyl, alkylthio and alkylallyl - is, in each case with due consideration of the specific number of carbon atoms in the corresponding group or compound, either straight-chain, i.e. methyl, ethyl, propyl or butyl, or branched, i.e.
isopropyl, isobutyl, sec-butyl or tert-butyl, pPntyl, hexyl, heptyl or octyl, or their isomers.

HaloaLkyl, haloaL~enyl and haloallyl can be partially halogenated or perhalogenated.
Example of haloaLkyl are methyl which is mono- to trisubstituted by fluorine, chlorine andVor bromine, such as CHF2, CHCl2, CH2Cl or CF3; ethyl which is mono- to pentasubstituted by fluorine, chlorine andlor bromine, such as CH2CF3, CF2CF3, CF2CC13, CF2CHC12, CF2CHF2, CF2CFC12, CF2CHBr2, CF2CHClF, CF2CHBrF or CClFCHClF; propyl or isopropyl, each of which is mono- to heptasubstituted by fluorine, chlorine and/or bromine, such as CE12CHBrCH2Br, CF2CHFCF3, CH2CF2CF3 or CH(CF3)2; and butyl or one of its isomers, each of which is mono- to nonasubstitllted by fluorine, chlorine and/or bromine, such as CF(CF3)CHFCF3 or CH2(CF2)2CF3.
Examples of haloallyl are 3-chloroprop-2-en-1-yl, 3,3-difluoroprop-2-en-1-yl and1,1 ,2,3,3-pentafluoroprop-2-en- 1 -yl.

2 ~

Cl-C4alkoxy-CI-C4alkyl ansl Cl-C4aL1coxy-CI-C4alkoxy are alkyl or aLkoxy groups which are monosubstituted by aLkoxy, it heing possible for both carbon chains independently of one another $o be straight-chain or branched; examples are methoxymethyl, 2-methoxye~yl, ethoxymethyl, 2-isopropoxyethyl, 2-propoxypropyl or 4-methoxybut-2-yl, 2-methoxyethoxy, ethoxymethoxy or 2-isopropoxyethoxy.

C2-C6alkenyl groups are straight-chain or branched aL~cene groups, i.e., for example hex-3-en-1-yl, pent-4-en-1-yl or 2-methyl-but-3-en-1-yl.

Cl-C3aLkylallyl groups are allyl groups which are monosubstituted by straight-chain or branched aLkyl, for exarnple but-2-en-1-yl, pent-2-en-1-yl, 2-methylallyl or 4-methyl-pent-2-en- l-yl.

Preferred embodiments within the scope of the invention are 1) a compound of the formula I in which Rl is -O-S(=0)2-Cl C4aLkyl or -O-S(=0)2-halo-Cl-C4alkyl, each of which is bonded in the 4-position;
R2 is halogen or CF3, each of which is bonded in the 4-position;
R3 is hydrogen, halogen, -OH, -SE~, Cl-C4aLIcyl, C3-C6cycloalkyl, halo-Cl-C4aL~cyl, Cl-C4aL~oxy, Cl-C4alkylthio or-N(R4)R5;
R4 and Rs independently of one another are hydrogen or Cl-C4aL~cyl;
R6 is ORg;
R7 is hydrogen, Cl-C4allyl, halo-CI-C4aLkyl, Cl-C4aLkoxy-CI-C4-aL~yl, allyl, haloallyl, Cl-C3aLtcylallyl or propargyl;
R9 is hydrogen, Cl-C4aLkyl, halo-CI-C~aLkyl, Cl-C4aLI~oxy-Cl-C4alkyl, allyl, Cl-C3aLlcylallyl or propargyl; and o and p are 1, and, where appropriate, tautomers thereof;

2~ a compound of the formula I in which the radicals Rl independently of one another are Cl-C4alkyl, halo-Cl-C4alkyl, Cl-C4aL~coxy, halo-Cl-C4alkoxy, halogen, -O-S(=0)2-Cl-C4aL~yl or -O-S(=0)2-halo-Cl-C4aL~cyl, phenoxy or two radicals Rl together are -OCF2-O-;
in particular halo-Cl-C4aLl~yl, halo-Cl-C4alkoxy, halogen, -O-S(=0)2-Cl-C2alkyl or -O-S(=0)2-halo-Cl-C2aLkyl;

very particularly -O-S(=0)2-C~-C2aL~cyl, -O-S(=0)2-halo-Cl-C2alkyl or Cl-C3-fluoroaLkoxy;
particularly preferably -O-S(=0)2-CH3, -O-S(=0)2-CF3 or -OCF2CHFCF3, and o is 1 or 2, Rl is, in particular,-O-S(=0)2-CF3 which is bonded in the 3- or 4-position and o is 1, or, where appropriate, tautomers thereof;

3) a compound of the formula I in which the radicals R2 independently of one another are Cl-C4alkyl, halo-Cl-C4aLkyl, Cl-C4aLkoxy, halo-Cl-C4aLkoxy, halogen, -O-S(=0)2-Cl-C2aLkyl or -O-S(=0)2-halo-Cl-C2alkyl;
in par~icular fluorine, chlorine, bromine or -CF3; and pislor2;
very particularly those in ~which R2 is chlorine which is bonded in the 4-position and p is l;
or, where appropAate, tautomers thereof;

4) a compolmd of the formula I in which R3 is hydrogen, halogen, -OH, -SH, Cl-C4alkyl, C3-C6cycloalkyl, halo-Cl-C4alkyl, Cl-C4alkoxy, Cl-C4aLkoxy-Cl-C4alkoxy, Cl-C4alkylthio, -I~I2, -NH(Cl-C2alkyl), -N(Cl-C2a~yl)2 or-NHOH;
in par~icular hydrogen -OH, -SH, Cl-C2aLkyl, cyclopropyl, Cl-C2aL~oxy, Cl C2alkoxy-Cl-C2all~oxy, Cl-C2alkylthio, -NH~, -NH(C~3), -N(CH3)2 or -N~lOH;
particularly preferably hydrogen, -OH, -SH, methyl, cyclopropyl, methoxy, methylthio, -NH2, -NH(CH3), -N(CH3)2 or-NHOH;
or, where appropriate, t~utomers thereo~;

5) a compound of the forrnula I in which R6 is -OR9 and Rg is hydrogen, Cl-C4aLkyl, C2-C6aLtcenyl or halo-C2-C6aL~cenyl;
Rg is, in par~cular, hydrogen, Cl-C2alkyl, C2-C3alkenyl or halo-C2-C3aLkenyl;
very particularly in which Rg is methyl or ethyl, or, where appropriate, tautomers thereof;

6) a compound of the formula I in which ~6 iS -S02-Cl-C4alkyl, -S02NH(CH3), -P(O)(OC2~Is)2, -NH2, -N(CH3)NH2 or -NHCON(CH3)2~

2 ~

or, where appropriate, tautomers thereof;

7) a compound of the formula I in which R7 is hydrogen, Cl-C2aLkyl, Cl-C2alkoxy-CI-C2aLkyl, allyl, 2-methylallyl, haloallyl or propargyl;
in par~cular hydrogen, methyl or ethyl, very particularly methyl, or, where appropriate, tautomers thereof;

8) a compound of the formula I in which Rl is -O-S(=0)2-Cl-C2alkyl, -O-S(=0)2-halogen-Cl-C2aL~yl or Cl-C3fluoroalkoxy;
R2 is fluorine or chlorine;
R3 is hydrogen, -OH, -SH, Cl-C2alkyl, cyclopropyl, Cl-C2aL~coxy, Cl-C2aLkoxy-Cl-C2aLkoxy, Cl-C~alkylthio, -NH2, -NH(CH3), -N(CH3)2 or -NHOH;
R6 is -ORg, -SO2-Cl-C4al1cyl~ -SO2MH(CH3), -P()(C2Hs)2~ -NH2, -N(C~3)NH2 or -NHCON(CH3)2;
R7 is hydrogen, methyl or ethyl; and Rg is hydrogen, Cl-C2alkyl, C2-C3alkenyl or halo-C2-C3aLkenyl and o andp are 1 or2, or, where appropriate, tautomers thereof;

9) a compound of the formula I in which Rl is-O-S(-0)2-CH3~ -O-S(=0)2-CF3 or-OCF2CElFCF3;
R2 is chlorine;
R3 is hydrogen, -OH, -SH, Cl-C2alkyl, cyclopropyl, Cl-C2aLkoxy, Cl-C2allcoxy-Cl-C2alkoxy, Cl-C2allcylthio, -NH2, -NH(CH3), -N(CH3)2 or -NHOH;
R6 iS -0~9, -so2-cl-c4alkyl~ -S02NH(CH3). -P()(~2HS)2~ 2~ -N(CH3)N~2 or -NHcoNtcH3)2;
R7 is hydrogen, methyl or edlyl; and Rg is hydrogen, Cl-C2alkyl, C2-C3aLkenyl or halogen-C2-C3aLkenyl und o and p are 1 or2, or, where appropriate, tautorners ~ereof; and 10) A compound of ~e formula I in which Rl is O-S(=O)rCF3 which is bonded in the 4-position;
R2 is chlorine which is bonded in the 4-position;
R3 is hydrogen, -OH, -SH, Cl-C2aLkyl, cyclopropyl, Cl-C2alkoxy, 2 ~

Cl-C2aLkoxy-Cl-C2aL~coxy, Cl-C2alkyltbio, -NH2, -NH(CH3), -N(CH3)2 or -NHOH;
P~6 is -ORg, -SO2-Cl-C4aLkyl, -SO2NH(CH3), -P(0)(0~2Hs)2~ -NH2, -N(CH3)NH2 or -NHCON(CH3)2;
R7 is hydrogen, methyl or ethyl; and Rg is hydrogen, Cl-C2alkyl, C2-C3alkenyl or halo-C2-C3aL~cenyl, and o and p are 1, or, where appropriate, ~automers thereof.

Particularly preferred within the scope of the invention are the compounds of the formula I
which are mentioned in Examples Hl to H6 and, where appropriate, tautomers thereof.

Spcci~lcally preferred within the scope of the invention are (a) 1-(4-chlorophenyl)-4-hydroxy-5-methyl-6-oxa-2,3,5-triaza-1-(4-trifluoromethane-sulfonyloxyphenyl)hepta-1,3-diene, or 1-(4-chlorophenyl)-5-methyl-6-oxa-4-oxo-2,3,5-triaza-1-(4-tritluoromethanesulfonyl-oxyphenyl)hept- l-ene;
(b) 1-(4-chlorophenyl)-4,5-dimethyl-6-oxa-2,3,5-triaza-1-(4-trifluoromethanesulfonyl oxyphenyl)hepta- 1 ,3-diene;
(c) 1-(4-chlorophenyl)-4-hydroxy-5-methyl-6-oxa-2,3,5-triaza-1-(4-methanesulfonyl-oxyphenyl)hepta-l ,3-diene, or 1 (4-chlorophenyl)-5-methyl-6-oxa-4-oxo-2,3,5-triaza-1-(4-methanesulfonyl-oxyphenyl)hept-l-ene;
(d) 1-(4-fluorophenyl)4-hydroxy-5-methyl-6-oxa-2,3,5-triaza-1-(4-trifluoromethane-sulfonyloxyphenyl)hepta- 1,3-diene, or 1-(4-fluorophenyl)-5-methyl-6-oxa-4-oxo-2,3,5-triaza-1-(4-trifluoromethane-sulfonyloxyphenyl)hept-l-ene;
(e) 1-(4-chlorophenyl)-4,5-dimethyl-6-oxa-2,3,5-triaza-1-(4-methanesulfonyloxyphenyl)-hepta-1,3-diene;
(f) 1-(4-chlorophenyl) 4-cyclopropyl-5-methyl-6-oxa-2,3,5-triaza-1-(4-~ifluoromethane-sulfonyloxyphenyl)hepta-1,3-diene;
(g) 1-(4-fiuorophenyl)-4,5-dimethyl-6-oxa-2,3,5-triaza-1-(4-trifluoromethanesul~onyl-oxyphenyl)hepta- 1 ,3-diene;
(h) 1-(4-chlorophenyl)-4-cyclopropyl-5-ethyl-6-oxa-2,3,5-triaza-1-(4-trifluoromethane-sul~onyloxyphenyl)hepta-1,3-diene;
(i) 1-(4-chlorophenyl)-4,5-dimethyl-6-oxa-2,3,5-triaza-1-(4-trifluoromethanesulfonyl-oxyphenyl30cta- 1 ,3-diene;

2 ~

(j) 1^(4-chlorophenyl)-5-ethyl-4-methyl-6-oxa-2,3,5-triaza-1-(4-~ifluoromethanesulfonyl-oxyphenyl)hepta-1,3-diene, and (k) 1-(4-chlorphenyl)-~hydroxy-5-methyl-6-oxa-2,3,5-triaza-1-(4-trifluoromethane-sulfonyloxyphenyl)nona-1,3,8-triene, or 1-~4-chlorophenyl)-5-methyl-6-oxa-4-oxo-2,3,5-triaza-1-(4-trifluoromethanesulfonyl-oxyphenyl)nona- 1 ,8-diene.

The invention also provides a process for the preparation of the compounds of the formula I and, where appropria~e, the tautomers thereof or a salt thereof, which comprises, for example, a) to prepare a compound of the formula I in which R3 is -OH, -SH, -NHR~ or -NHRs, reacting, preferably in the presence of a base, a compound of the formula (Rl)o~3 R2 p (II) N~NH2 or a salt thereof with a compound of the formula z R6 ,~ N' (III), in which Y is O, S, -NR4 or -NRs and Z is halogen, C~-C8aLkoxy, Cl-C8alkylthio, Cl-C8aLkanoyloxy, Cl-C8alkanesulfonyloxy, halo-(:~l-C8aLkanesulfonyloxy, benzenesulfonyloxy or toluenesulfonyloxy, or with a salt and/or, where appropriate, a tautomer thereof, or b) reacting, preferably in the presence of an acid, a compound of the formula (RI)o~~,~(R2 P (IV), with a compound of the formula R (V) or with a salt and/or, where appropria~e, a tautomer thereof, or c) to prepare a compound of the formula I in which 3~3 is -OH, -SH, Cl-C4aL~coxy, C~ 4alkylthio or -N(R4)R5, reacting, preferably in the presence of a base, a compound of the formula (~l~(R2)p `N (Vl), X JJ~ N

in which X is halogen, or a salt andlor, where appropriate, a tautomer thereof, with water, H2S, a C~ 4alkanol, a Cl-C4aLkoxy-Cl-C~alcohol, a mercapto-CI-C4aLkane or a compound of ~e formula HM(~R4)Rs or a salt thereof, or d) to prepare a compound of the formula I in which R3 is hydrogen, Cl-C4aLkyl, halo-Cl-C4alkyl or C3-C6cycloallyl, reacting, prcferably in the presence of a base, a compound of the formula o~ rJ~(R2)p N ~ ~VII), N

in which X is halogen, or a salt thereof, with a compound of the formula HN(R6)R7 or a salt $hereof, or e) to prepare a compolmd of the formula I in which R3 is halogen, preferably chlo~ine or bromine, reacting a compound of the formula I in which R3 is -C)H or -SH, or a salt an(Vor, where appropriate, a tautomer thereof, wi~ a halogenating agent such as PCl3, PCl5, POCl3, PBr3, SOCl2, SOBr2 or COCl2, preferably in ~e presence of a base, and in each case, if desired, converting a compound of the formula I or a tautomer thereof - -which can be obtained by the process or by a different route, in each case in free form or in salt form, into a different compound of the formula I or a tautomer thereof, resolving an isomer mixture which can be obtained according to the process, isolating the desired isomer, and/or converting a free compound of the forrnula I or a tautomer thereof, which can be obtained according to ~he process, into a salt, or converting a salt of a compound of the formula I or of a tautomer thereof, which can be obtained according to the process, into the free compound of the formula I or a tautomer thereof or into a different salt.

What has been said above for tautomers or salts of compounds of the formula I applies analogously, with regard to the tautomers or salts, to startin'g materials mentioned hereinbefore and hereinafter.

The reactions described hereinbefore and hereinafter are carried out in a manner known per se, for example in the absence or, conventionally, in the presence of a suitable solvent or diluent or a mixture of these, the process being carried out as required, with cooling, at room temperature or with heating, f~r example in a temperature range of approximately -80C to the boiling point of tne reaction medium, preferably approximately -20C to approximately +150C, and, if requ~ed, in a sealed container, under pressure, under an inert gas atmosphere and/or under anhydrous conditions. Particularly advantageous reaction conditions can be found in the Examples.

The starting materials rnentioned hereinbefore and hereinafter which are used for the preparation of the compounds of the formula I and, where appropriate, of the tautomers or a salt thereof, are known or can be prepared by methods known per se, for example following the information given below.

Variant a):
Suitable bases for faeilita~ing the elimination of HZ are, for example, hydroxides, hydrides, amides, aLkanolates, carbonates, dialkylamides or aLkylsilylamides of alkali metals or aL~caline earth metals, or aLkylamines, alkylenediamines, free or N-aLkylated, saturated or unsaturated cycloaLkylamines, basic heterocycles, ammonium hydroxides as well as carbocyclic amines. Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methanolate, sodium carbonate, potassium tert-butanolate, potassium carbonate, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-die~hylaniline, wridine, 4-(N,N-dimethylamino)pyAdine, N-methylmorpholinet benzyltrimethylammonium hydroxide as well as 1,5-diazabicyclo[5.4.0]undec-5-ene (DBU).

The reactants can be reacted with each other as such, i.e. without an addition of a solvent or diluent, ~o~ example in the melt. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. Examples of such solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halohydrocarbons such as benzene, toluene, xylene, chlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichlorome~hane, trichloromethane, dichloroethane or trichloroethene; esters such as ethyl acetate; ethers such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, tert-butyl methyl ether, tetrahydrofuran or dioxane; ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone; alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol or glycerol; arnides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or hexamet]hylphosphoric triamide; nitriles such as acetoiutrile; and sulfoxides such as dimethyl sulfo~tide. Bases employed in excess, such as triethylarnine, pyridine, N-methylmorpholine or N,N-diethylaniline, can also act as solvents or diluents.

The reaction is carried out advantageously in a temperature range of approximately -80C
to approximately ~120C, preferably approximately -20C to approximately +50C.

In a preferred embodiment of variant a~, a compound of the formula II is reacted, in an ether, preferably in tehahydrofuran, with a compound of the formula III in which Z is halogen, preferably chlorine, at approximately 0C to approximately 20C in the presence of an alkylamine, preferably in the presence of hiethylamine.

The compounds of ~e formula II or one of the salts thereof and the compounds of the formula m and, where appropriale, the tautomers thereof, or salts thereof, are known or can be prepared analogously to lcnown compounds.

Variant b~-.
Suitable acids for facilitating the condensation are, i~or example, those which have been mentioned above as being suitable for the formation of acid addition salts with compounds of the formula I.

Ihe reactants can be reacted wi~ each other as such, i.e. without an addition of a solvent or diluent, for e~arnple in the melt. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. Examples of such solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halohydrocarbons such as benzene, toluene, xylene, chlorobenzene, bromobenzene, petroleum ether, hexane, cyclohe~ane, dichloromethane, trichloromethane, dichloroethane or trichloroethene; esters such as ethyl acetate; ethers such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, tert-bu~yl methyl ether, tetrahydrofuran or dioxane, ketones such as ace~one, methyl ethyl ketone or methyl isobutyl ketone; alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol or glycerol; amides such a~ N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles such as acetonitrile; and sulfoxides such as dimethyl sulfoxide; and acids, preferably strong organic carboxylic acids such as unsubstituted Cl-C4aLIcanecarboxylic acids or Cl-C4nlkanecarboxylic acids which are substituted, for example by halogen, such as formic acid, acetic acid or propionic acid.

The reacdorl is advantageously carried out in a temperature range of approximately 0C to approximately ~180C, preferably apploximately ~20C to approximately +130C, inmany cases at the reflux temperature of the solvent used.

The compounds of the formula IV and the compounds of the formula V and, where appropriate, the tautomers thereof, as well as the salts thereof, are known or can be prepared analogously to known compounds.

Variant c):
Suitable bases for facilitating elimination of HX are, for example, the bases mentioned in Variant a).

The reactants can be reacted with each other as such, i.e. without an addition of a solvent i 2 ~

or diluent, for example in the melt. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. Examples of such solvents or diluents which may be mentioned are the solvents or diluents mentioned under Variant a). Alternatively, reactants of the ~ormula VI [water, H2S, Cl-C4alkanols, mercapto-Cl-C4aLIcanes, compounds of the formula EIN(R6)R7 or compounds of the formula HN(R4)Rs] which are employed in excess can be used as solvents or diluents.

The reaction is carried out advantageously in a temperature range of approximately -80C
to approximately +120, preferably approximately -10C to approximately +80C.

Thc compounds of ~e folmula VI and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be prepared in a manner known per se, for exampie as described under Process Variant e).

The Cl-C4alkanols, mercapto-CI-C4alkanes and compounds of the formula HN(R~)Rs and salts thereof, all of which are employed as reactants of the compounds of tne formula VI, are known or can be prepared in analogy to known compounds.

Variant d):
Suitable bases for facilitating the elimination of HX are, for example, the bases mentioned under Variant a).

The reactants can be reacted with each other as such, i.e. without an addition of a solvent or diluent, for example in the mel~ In most cases, however, an addition of an inert solvent or diluent or a mixture of these is advantageous. Examples which may be mentioned of such solvents or diluents are the solvents or diluents listed under Variant a). Altematively, reactants of the compounds of the formula VIl [compounds of the formula HN(R6)R7]
which are employed in excess can act as solvents or diluents.

The reaction talces place advantageously in a temperature range of approximately -80C to approximately +150, preferably approximately 0C to approximately +100C.

In a preferred embodiment of Variant d), a compound of the forrnula VII is reacted, in an ester, preferably in ethyl acetate, with a compound of the formula HN(R6)R7 at approximately 0C to approximately +80(: in the presence of an alkylamine, pre~erably in the presence of triethylamine.

2 ~

The compounds of ~e formula HN(R6)R7 as well as the salts thereof, all of which are employed as reactants of the compounds of the formula VII, and the compounds of the formula VII as well as the salts thereof, are known or can be prepared in analogy to known compounds.

Variant e):
Suitable bases for neutralising the hydrohalic acid which forms are, for example, the bases mentioned under Variant a).

The reactant~s can be reacted with each other as such, i.e. without an addition of a solvent or diluent, for example in the melt. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixb~re OI ~hese. Examples which may be mentioned of such solvents or diluents are the solvents or diluents listed under Variant a).

The reaction is carried out advantageously in a temperature range of approximately -80C
to approximately -~180, preferably approximately 0C to approximately tlOOC.

The compounds of the formula I in which R3 is -OH or -SH and the ~automers thereof as well as the salts thereof can be prepared in a manner known per se, for exarnple as described under Process Variant a).

A compound of the formula I or, where appropriate, a tautomer thereof, which can be obtained by the process or by o~her rou~es can be converted into a different compound of the formula I in a manner known per se, by replacing one or more substituents of the s$arting compound of the formula I in a customary manner by a different substituent according to the invention, or by different substituents according to the invention.

It is possible, for example, - to aLkylate hydroxyl groups R3 to give ~l-C4alkoxy groups R3;
- to allylate mercapto groups R3 to give Cl-C4aL~ylthio groups R3; or - to alkylate amino groups R3 to give mono- or dialkylated amino groups R3.

Depending on $he choice of the reaction conditions and starting materials which are suitable in each case, it is possible to replace only one substituent by a different substi$uent according to the invention in one reaction step, or more than one substituent , % ~

can be replaced by different substituents according to the invention in the same reaction step.

Salts of compounds of the formula I can be prepared in a manner known per se. For example, acid addition salts of compo~mds of the formula I are obtained by treating the latter with a suitable acid or with a suitable ion exchanger reagent, and salts with bases are obtained by treating the compounds of the formula I with a suitable base or with a suitable ion exchanger reagent.

Salts of compounds of the formula I can be converted in the customary manner to give the free compounds of the formula I, acid addition salts for example by being treated with a suitable basic agent or with a suitable ion exchanger reagent, and salts with bases for exarnple by being treated with a suitable acid or a suitable ion exchanger reagent.

Salts of compounds of the formula I can be converted in a manner known per se to give different salts of compounds of the formula 1, for example acid addition salts can be converted into different acid addition salts, for example by lleating a salt of an inorganic acid, such as a hydrochloride, with a suitable metal salt, such as a sodium, barium or silver salt of an acid, for example using silver acetate, in a suitable solvent in which an inorganic salt which forms, for example, silver chloride, is insoluble and therefore precipitates from the reaction mixture.

Depending on the procedure or ~e reaction conditions, tha compounds of the forrnula I
which have salt-forming properties can be obtained in free form or in the form of salts.

The compounds of the formula I and, where appropria~e, the tautomers thereof, in each case in free form or in salt f~rm, can exist in the form of one of the isomers which are possible or as a mixture of these, for example, depending on the number and the absolute and relative con~lguration of asymmetric carbon atoms which exist in the molecule, and/or, depending on the configuration of non-aromatic double bonds which exist in the molecule, in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixturcs, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures; in particular, they are also to 5~e understood as meaning syn and anti isomers which can result from the existing C=N double bonds, it being possible for mixtures of syn/anti isomer pairs to be obtained, according to the number of these double bonds. The invention relates to the pure isomers as well as to all isomer .
.

2 ~

mixtures which are possible and is to be understood accordingly in each case hereinbefore and hereinafter, even when stereochemical details are not mentioned specifically in each case.

Diastereomer mixtures and racemate mixtures of compounds of the forrnula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, which can be obtained according to the process - depending on the choice of starting materials and procedures - or via other routes, can be separated in a known manner on the basis of the physico-chemical differences of the components to give the pure diastereomers orracemates, for example by fractional crystallisation, distillation and/or chromatography.

Enantiomer mixtures which can be obtained accordingly, such as racemates, can beresolved by known methods to give the optical antipodes, for example by recrystallisation from an optically active solvent, by chromatography on chiral adsorbents, for example highpressure liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage using specific, immobilised enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-substance racemate witb an optically active acid such as carboxylic acid, for example camphor acid, tar~aric acid or malic acid, or sulfonic acid, for example camphorsulfonic acid, and resolution of the diastereomer mixture obtained in this manner, for example by fractional crystallisation on the basis of their differing soiulbility properties, to give the diastereomers from which the desired enantiomer can be liberated by the action of sui$able agents, for example basic agents.

Pure diastereomers or enantiomers can be obtained according to the invention not only by resolution of suitable isomer mixtures but also by the generally known methods of diastereoselective, or enantioselective, synthesis, for example by carrying out the process according to the invention with stereochemically suitable edducts.

If the individual components differ in their biological activity, it is advantageous to isolate, or synthesise, in each case the biologically more active isomer, for example enantiomer or diastereomer, or isomer mixture, for example enantiomer mixture ordiastereomer mixture.

The compounds of the formula I and, where appropriate, their tautomers, in each case in , , .,.,,, ~ ~ .

. .

2 ~

free form or in sal~ form, can also be obtained in the form of their hydrates and/or include other solvents, for example solvents which may be used for crystallising compounds which exist in solid form.

The invention relates to all those embodirnents of the process by which, starting from a compound which can be obtained in any step of the process as starting material or intermediate, all or some of the missing steps are carried out or a starting material in the forrn of a derivative or salt and/or racemates or antipodes thereof is used or, in particular, formed under the reaction conditions.

It is preferred to use those starting materials and intermediates as well as salts theçeof in the process of the present invention which lead to the compounds of the formula I or salts thereof which have been described at the outset as being particularly valuable.

In particular, the invention relates to the preparation processes described in Examples Hl to~3.

The invention also çelates to the novel stalting materials and intermediates as well as salts thereof which are used according to the invention for the pçeparation of the compounds of the formula I or the salts thereof, to their use and to processes for their preparation.

T~e compounds of ~e formula I according to the invention are valuable active ingredients in ~he ~leld of pest control and they are well tolerated by w~ blooded species, fish and plants. The active ingredients according to the invention act, in particular, against insects and arachmids which can be found in useful plants and ornamentals in agriculture and horticulture, in particular in crops of cotton, vegetables and fruit, and in forests. Other fields of application for the active ingredients according to the invention are the protection of stored products and materials, and in the hygiene sector, in particular the protection of domestic animals and productive livestock. The compounds of the formula I are effective against all or individual development stages of normally sensitive, but also resistant, species of pests. Their activity may become apparent, for example, through mortality of the pests~ either immediately or only after some time has elapsed, for example during moulting, or through reduced oviposition and/or hatching rate.

The abovementioned pests include:
from the order Lepidoptera, for exarnple 2 ~

Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp.,Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sex~a, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., ~podoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni und Yponomeuta spp.;
from the order Coleoptera, for example Agriotes spp., Anthonomus spp., Atomalia linearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp., Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. und Trogoderma spp.;
from the order Orthoptera, for example Blat~ spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. und Schistocerca spp.;
from the order Isoptera, for example Reticuliterrnes spp.;
from the order Psocoptera, for example Liposcelis spp.;
from the order Anoplura, for example Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. und Phylloxera spp.;
from the order Mallophaga, for exarnple Damalinea spp. und Trichodectes spp.;
from the order Thysanoptera, for example Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tabaci und Scirtothrips aurantii;

2 ~

from the order Heteroptera, for example Cimex spp., Distandella theobroma, Dysdercus spp., Euchistus spp. Eurygaster spp.
Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp. und Triatoma spp.;
from lhe order Homoptera, for example Aleurothrixus floGcosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidhlm, Chrysomphalus dictyospenni, Coccus hesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp., Pulvinaria ae~iopica, Quadraspidiotus spp., Rhopalosiphum spp., Saisseda spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae und Unaspis citri;
from the order Hymenoptera, for example Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp.
und Vespa spp.;
from the order Diptera, for example Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp.~ Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoleds pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. und Tipula spp.;
from the order Siphonaptera, for example Ceratophyllus spp. und Xenopsylla cheopis and from the order Thysanura, for example Lepisma saccharina.

The compounds of ~e formula I are particularly suitable for controlling plant-injurious insects from the genera Spodoptera, Heliothis, Plutella and Diabrotica.

The good pesticidal activity of the compounds of the formula I according to the invention corresponds to a mortali~y rate of at least 50-60% of the abovemcntioned pests.

, The activity of the compounds according to the invention and the compositions comprising them can be broadened considerably and adapted to prevailing circumstances by adding other insecticides. Examples of additives which are suitable are representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenols and derivatives, formamidines, oreas, carbamates, pyrethroids, chlorinated hydrocarbons and Bacillus thuringiensis preparations.

The compounds of the formula I are employed as pure active ingredients or, prefelably together with the auxiliaries conventionally used in the art of formulation, and they can therefore be processed in a known manner to give emulsion concentrates, directlysprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules and other encapsulations in polymeric substances. The methods ofapplication such as spraying, atomising, dusting, scattering or pouring, as well as the compositions, are selected to suit the intended aims and prevailing circumstances.

The formulation, i.e. the compositions, preparations or combinations which comprise the active ingredient of the formula I, or combinations of these active ingredients with other insecticides and, if desired, a solid or liquid additive, are prepared in the known manner, for example by intimately mixing and/or grinding the active ingredients with extenders, for example with solvents, solid carriers and, if desired, surface-active compounds (surfactants).

The following are possible as solvents: aromatic hydrocarbons, preferably the fractions C8 to C~2, such as xylene mixtures or substituted napb~alenes, phthalic esters such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane, paraf~ms, alcohols and glycols as well as their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl~ormamide, as well as epoxidised or unepoxidised vegetable oils, such as epoxldised coconut oil or soya oil, or water.

Solid carriers which are used for example ~or dusts and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmorillonite or atapulgite. To improve the physical properties, it is also possible to add highly-disperse silicas or highly-disperse absorptive polymers. Possible particulate, adsorptive carriers for granules are either porous types such as pummice, brick grit, sepioloite or bentonite, or non-sorptive carrier materials such as calcite or sand. Moreover, a large number of granulated materials of hlorganic or organic nature such as, in particular, dolomite or comminuted plant residues, can be used.

Suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants which have good emulsifying, dispersing and wetting properties, depending on the nature of the active ingredient of the formula I to be formulated, or of the combinations of these active ingredients with other insecticides or acaricides. Surfactants are also to be understood as meaning mixtures of surfactants.

Anionic surfactants which can be suitable can be either so-called water-soluble soaps or water-soluble synthetic surface-acti~e compounds.

~oaps which are suitable are the aLkali metal salts, alkaline ear~h metal salts or substituted or unsubstituted ammoniurn salts of higher fatty acids (C10-C22) such as the sodium salts or potassium salts of oleic acid or stearic acid, or of natural fatty acid rnixtures which can be obtained, for example, from coconut oil or tallow oil. Mention must also be made of the fatty acid methyl taurates as well as modified and unmodi~led phospholipids as surfac~ants.

However, so-called synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates.

The fatty sulfonates or fatty sulfates are generally in the folm of aLkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts and, as a rule, have an aL~cyl radlcal having 8 to 22 C atoms, alkyl also including the allyl moiety of acyl radicals, for example the sodium salt or calcium salt of ligninsulfonic acid, of the dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared with ratural fatty acids. This group also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohoVethylene oxide adducts. Tlle sulfonated benzimidazole derivatives preferably contain two sulfonic acid groups and a fatty acid radical having approximately 8-22 C atoms. ALkylaryl sulfonates are, for exarnple, the sodium salts, calcium salts or triethanolamine salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesul~onic acid or of a naph~alenesulfonic acid/formaldehyde condensation product. Other possible substances are suitable phospha~es, for exarnple salts of the phosphoric ester of a p-nonylphenol-(4-14)-ethylene oxide adduct.

2 ~

Possible non-ionic surfactants are mainly polyglycol et'ner derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsa~urated fatty acids and aLkylphenols which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic3 hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the aLtcylphenols.
Other suitable non-ionic surfactants are the water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopolypropylene glycol and alkyl polypropylene glycol which contain 20 to 250 et'nylene glycol ether groups and 10 to 100 propylene glycol ether groups and which have 1 to 10 carbon atoms in the aLkyl chain. As a rule, the compounds mentioned contain 1 to 5 ethylene glycol units per propylene glycol unit.

Examples which may be mentioned of non-ionic surfactants are nonylphenolpolyethoxyet'nanols, castor oil polyglycol ethers, castor oil thioxylate, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Other substances which are possible are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are mainly quateMary ammonium salts which contain, as Nsubstituents, at least one alkyl radical having 8 to 22 C atoms and, as further substituents, lower, free or halogenated alkyl, benzyl, or lower hydroxyaLkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, for example stearyltrimethylammonium cnloride or benzyldi~2-chloroe~hyl)ethylammonium bromide.

As a rule, the pesticidal compositions comprise 0.1 to 99%, in particular 0.1 to 95%, of active ingredient of the formula I or combinations of this active ingredient with o~er insecticides, 1 to 99.9% of a solid or liquid additive and 0 to 25%, in particular 0.1 to 20%, of a surfactant. While concentrated compositions are more preferred as commercially available goods, ~e end consumer uses, as a rule, dilute preparations whose active ingredient concentrations are much lower. Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm. The application rates per hectare are generally 1 to 1000 g of active ingredient per hectare, preferably 25 to 500 g/ha.

Preferred formulations have, in particular, the following composition ~% = per cent by weight):

2 ~

Emulsifiable concentrates:
Active ingredient: 1 to 20 %, preferably 5 to 10 %
Sur~actant: 5 to 30 ~O, preferably 10 to 20 %
Liquid carrier: 50 to 94 %, preferably 70 to 85 ~o Dusts:
Active ingredient: 0.1 to 10 %, preferably 0.1 to 1 %
Solid carrier: 99.9 to 90 %, preferably g9,9 to 99 %

Suspe_on concentrates:
Active ingredient: 5 to 75 %, preferably 10 to 50 %
Water: 94 to 24 %, pre~erably 88 to 30 %
Surfactant: 1 to 40 %, pseferably 2 to 30 %

Wettable powders:
Active ingredient: 0.5 to 90 %, preferably 1 to 80 %
Surfactant: 0.5 to 20 %, preferably 1 to 15 %
Solid carrier: S to 95 %, preferably 15 to 90 %

~}ranules:
Active ingredient: 0.5 to 30 %, preferably 3 to 15 %
Solid carrier: 99.5 to 70 %, preferably 97 to 85 %

The compositions can also comprise fur~er additives such as stabilisers, antifoams, preservatives, viscosity regulators, binders, tackifiers, fertilisers or other active ingrcdients for achieving specific effects.

The examples which follow are intended to illusb ate the invention. They are not to be understood as meaning a restriction of the invention.

Preparation Examples ExampleHl: 1-(4-chlorophenyl)-4-hydroxy-5-methyl-6-oxa-2,3,5-triaza-1-(4-trifluoro-methanesulfonyloxyphenyl)hepta- 1 ,3-diene % ~

Cl F3Cs(=0~2o ~

or 1-(4-chlorophenyl)-5-methyl-6-oxa-4-oxo-2,3,5-triaza-1-(4-trifluoromethanesulfonyl-oxyphenyl)hept-1-ene F3CS(=0)20--~

~ \CH

1.8 g of N-methoxy-N-methylcarbamoyl chloride are added dropwise with stirring at 0 to 10C to a solution of 5 g of 4-chloro-4'-trifluoromethanesulfonyloxybenzophenonehydrazone ~n 40 ml of tetrahydrofuran and 2 ml of triethyh~nine. The precipi~te which has forrned is lE~ltered off, the filtrate is evaporated in vacuo on a rotary evaporator9 and the residue is recrystallised from hexane. This gives ~e ti:~e cornpound in ~e forrn of an isomer mixture which melts at 102 to 114C (Compoulld No. 1).

Example H2: 1-(4-chlorophenyl)-4,5-dimethyl-6-oxa-2,3,5-triaza-1-(4-lrifluoromethanesulfonyloxyphenyl)hepta-1,3-diene F3CS(=0)20 ~

H3C ~CH3 - ' :i.
, 30.7 g of 4-chloro-1-(4-chlorophenyl)-2,3-diaza-1-(4-trifluoromethanesulfonyl-oxyphenyl)penta-1,3-diene are added dropwise at room temperature with stirring to a mi~ture of 32.3 ml of triethylamine, 14.1 g of 0,N-dimethylhydroxylamine and 50 ml of ethyl acetate. The reaction mixture is stirred for 3 hours at 50C and filtered, the filtrate is evaporated in vacuo on a rotary evaporator, and the residue is purified by column chromatography ~silica gel; ethyl acetate/hexane (5:95)]. This gives the title compound in the form of a pale yellow oil having a refractive index nD2l of 1.5741 (Compound No. 25).

Example H3: 4-chloro-1-(4-chlorophenyl) 5-methyl-6-oxa-2,3,5-triaza- 1-(4-trifluoro-methanesulfonyloxyphenyl)hepta- 1 ,3-diene F3CS~=0)20 ~b Cl CH3 23.3 g of 1-~4-chlorophenyl)-4-hydroxy-5-methyl-6-oxa-2,3,5-triaza-1-(4-trifluoro-methanesulfonyloxyphenyl)hepta-1,3-diene are stirred for 30 minutes with 11.5 g of phosphorus pentachloride in 200 ml of toluene with the exclusion of moisture. The mixture is heated to 50C, and stirring is continued for one hour. The solvent is evaporated in vacuo, 100 ml o-f toluene are added, and the mixture is re-evaporated. The oily residue is mixed with 150 ml of hexane, and the precipitate which has formed is removed by filtration. After ~e iiltrate has been evapora~ed, the ~dtle compound is obtained as an oil (Compound 13).

ExampleH4: 1-(4-chlorophenyl)-4-rnercapto-5-methyl-6-oxa-2,3,5-triaza-1-~4-trifluoro-methanesulfonyloxyphenyl)hepta- 1 ,3-diene F3CS(=0)20 ~

\>_ N

or 1-(4-chlorophenyl)-5-methyl-6-oxa-2,3,5-triaza~-thioxo-1-(4-trifluoromethane-sulfonyloxypherlyl)hept-l-ene F3CS(=0)20 ~\

~N
S \CH3 7 g of 4-chloro-1-(4-chlorophellyl)-5-methyl-6-oxa-2i3,5-triaza-1-~4-trifluoromethane-sulfonyloxyphenyl)hepta-1,3-diene are mixed with 50 rnl of tetrahydrofurane, l.S g trietllylamine and 0.5 g of hydrogen sulfide, and the mixture is sti~ed for 5 hours at reflux ~emperature. The reaction solution is evaporated, ~e residue is t~en up in 100 ml of a hexane/ethyl acetate mi~ture (10:1), the mixture is filtered, and the filtrate is concentrated.
This gives ~e crystalline title compound, which has a mel ing point of 136-137C(Compound No. 17).

ExampleH5: 1-(4-chlorophenyl)-5-methyl-4-methylthio-6-oxa-2,3,5-triaza-1-(4-trifluoro-methanesulfonylo~yphenyl)hepta-1,3-diene . ..

2 ~

~1 g~
F3CS(~0)20 ~\

\>_ N
~CH3 5.8 g of 4-chloro-1-(4-chlorophenyl)-5-methyl-6-oxa-2,3,5-tria~a-1-(4-trifluoromethane-sulfonyloxyphenyl)hepta-1,3-diene toge~her with 50 ml of tetrahydrofuran and 1.2 g of sodium thiomethylate are stirred for 24 hours at reflux temperature. The mixture is evaporated, the residue is taken up in hexanelethyl acetate (5:1), and the ~nixture is chromatographed on silica gel. ~his gives the title compound as an oil ~Compound No.
18).

Example H6 the other compounds which are listed in Tables 1 to 5 or, where appropriate, the tautomers thereof can be obtained analogously to the method of preparation described in Examples Hl to H5. They are, as a rule, mixtures of syn and and isomers. The compounds designated * have been isolated as pure syn or and isomers, or pairs of isomers.

.

2 ~ Q

Table 1 Compounds of the formula ~S~.O ~
R~
N--N /O-Rg \\~ N
R/3 ~R7 Comp- R8 R2 R3 ~9 R7 Physical No. data -_ CE~3 Cl OH CH3 CH3 m.p.102-114C
2 CF3 Cl OH c~3 H
3 CF3 Cl OH H CH3 4 CF3 Cl OH CH3 C2EIs m.p.l28-148C
S CF3 (:1 OH C2Hs CH3 m.p.115-123C
6 CF3 Cl OH CH3 CH2CH=CH2 m.p. 97-102C
7 CF3 Cl OH CH3 H m.p. 50-62C
8 CF3 Cl OH CH2CH=C~Cl H m.p. 44-47C
9 CF3 Cl NH2 ~H3 (~H3 c~3 Cl N(CH3)2 CH3 CH3 11 CF3 Cl NHOH CH3 C~I3 12 CF3 Cl NHCH3 CH2CH=CHCH3 CH3 13 CF3 Cl Cl CH3 CH3 oil 14 CF3 Cl OCH3 ~H3 CH3 oil CF3 Cl OCH3 CH3 C2Hs 16 ~F3 Cl OC2Hs CH3 C~3 17 CF3 C1 SH CH3 CH3 m.p.136-137C
18 CF3 Cl ~CH3 CH3 ~H3 oil 1~ CH3 Cl OH CH3 CH3 m.p.134-146 CH3 Cl OH H CH3 21 CH3 Cl OH CE~3 2 ~

Table 1 (continuation) Comp- R8 R2 R3 Rg R7 Physical No. data 22 CH3 F OH C~I3 CH3 m.p.l22-138 23 r~F3 F OH CH3 C~3 m.p.l04 110 24 CF3 Br OH CH3 CH3 CF3 (:1 CH3 C~I3 CH3 nD2l: 1.5741 26 CF3 Cl H CH3 CH3 nD25: 1.5750 27 CF3 Cl CH3 H CH3 28 CF3 Cl CH3 CH3 H m.p.l21-123 29 ~F3 Cl CH3 CH3 C2H5 oil CF3 Cl CH3 C~I3 C3H7 31 c~3 Cl C~I3 CH3 CH2CH=CH2 32 CF3 Cl CH3 H C2~s 33 CF3 Cl CH3 H CH2CH=CHCl 34 CF3 Cl H CH3 H
CF3 Cl H C2H5 CH3 36 CF3 Cl H H E~
37 CF3 Cl CH3 H H
38 CF3 Cl H CH2CH=CH2 H
39 CF3 Cl H CH3 H
CF3 Cl H CH2CH=CH2 H
41 CF3 Cl c-C3Hs CH3 CH3 resin 42 CF3 Cl C2Hs CH3 CH3 43 ~F3 Cl C-c3Hs CH3 C2Hs 44 CF3 Cl C3H7 C~3 CH3 CF3 Cl i-C3H7 CH3 C~3 46 CF3 Cl CH3 t-c4~ H
47 CF3 Cl ~H3 H t-C4Hg 48 CF3 Cl ~4H9 CH3 CH3 2 ~

Table 1 (Continuation) Comp- R8 R2 R3 Rg R7 Physical No. data 49 CF3 Cl CH~Cl CH3 CH3 ~0 CE~3 Cl CH2Br CH3 CH3 51 CF3 F C~3 CH3 CH3 honey 52 CF3 Br CH3 CH3 CH3 54 CH3 Cl CH3 CH3 CH3 m.p. 64-82C
CH2Cl Cl CH3 CH3 CH3 oil 56 CH3 F ICH3 CH3 CH3 resin ~7 CH2CF3 Cl CH3 CH3 CH3 58 CH3 Cl CH3 H CH3 59 CH3 Cl c-C3Hs CH3 CH ~
CF3 Cl CH3 CHS H m.p. 88-102C
61 CF3 Cl CH3 CH2CH=CH2 H m.p. 86-92C
62 CF3 Cl OH C2Hs C2~ls m.p. 130-135C
63 CF3 Cl CH3 CH2CH=CHCl H oil 64 CF3 F CH3 C2H5 C~3 resin CF3 Cl CH3 C2~Is H oil 66 CF3 Cl CH3 C2Hs C~3 oil 67* CF3 F ~H3 CH3 C2Hs m.p. 84-86C
68 CF3 F c-C3Hs CH3 CH3 resin 69 CH3 Cl C~3 C2Hs CH3 m.p. 72-75C
CF3 Cl ~H3 C2Hs C2Hs oil 71 CF3 ~ CH3 CH2CH=CH2 H m.p. 56-60C
72 C~3 F CH3 CH2CH=CHCl H resin 73 CF3 Cl OH CH~CH=CH2 H m.p. 86-92C
74 CF3 Cl ~H C2Hs H m.p. 80-l20C
CF3 Br OH CH3 CH3 76 CF3 Br CH3 ~H3 CH3 oil Table 1 (Continuacion) .
Comp- R8 R2 R3 Rg R7 Physical No. data 77 CF3 Br CH3 CH2CH=CH2 CH3 78 CF3 Br C~3 H CH3 79 CF3 Br CH3 CH3 H

Table 2: Compounds of the formula o O ~ (R2)p CF3 ~o ~
N--N Z

R3_ Comp- R2 R3 Z R7 Physical No. data 3-Cl OH OCH3 C~H3 81 3-Cl CH3 OCH3 CH3 honey 82 3-Cl CH3 OCH2CH=CH2 CH3 83 3-Cl CH3 OH CH3 84 3-Cl CH3 OCH3 2-Cl OH OCH3 CH3 86 2-Cl C~H3 OCH3 CH3 87 2-Cl CH3 OCH2CH=CH2 CH3 88 2-Cl CEl3 OEI CH3 89 2-Cl CH3 OCH3 3,4-Cl2 OH OCH3 CH3 91 3,4-Cl2 CH3 OCH3 ~3 wax 92 3,4-Cl2 CH3 OCH2CH=CH2 CH3 93 3.4-Cl2 CH3 OH CH3 94 3,4-Cl2 ~H3 OCH3 H
2,4-Cl2 OH OCH3 CH3 .. :. ' , ~: -, ,-~ ..

2 ~

Table 2 (Continuation) -Comp. R2 R3 Z R7 Physical No. data _ _ . _ _ _ _ 96 2,4-Cl2 CH3 OCH3 ~H3 97 2,~C12 CH3 OcH2cH=c~2 c~3 98 2,4-Ck CH3 OH CH3 99 2,4-Cl2 CH3 OCH3 H
100 4-Cl C~3 P()(C2Hs)2 CH3 resin 101 4-F CH3 P(O){OC2Hs)2 i-C3H7 resin 102 4-Cl CH3 SO2CH3 CH3 m.p. 76-78C
103 4-Cl c~3 SO2N(CH3~2 CH3 oil 104 4-Cl OH NHCON(CH3)2 H m.p.l26-133C
105 4-Cl SCH3 NH2 H
106 4-Cl CH3 NH2 H
107 4-Cl CH3 N(CH3)NEI2 CEI3 108 3,4-Cl2 SH OCH3 CH3 109 4-Cl SH NE~2 H wax 110 2,4-Cl2 OCH2CH2OCH3 Z = OCH3 CH3 111 3-Cl,4-OCH3 Cl OCH3 CH C - CH
112 OC6H4-p-Cl CH3 OCH3 H
113 ~Cl CH3 So2c2Hs C~3 m.p. 91-96C

TabeUe 3: Verbindungen der Formel ~S~O

R' ~ ~<N--N Z
\~_ N
R3 ~R7 Comp. R8 R2 R3 Z R7 Physical No. data 114* CH3 F OH ~CH3 CH3 m.p.170-173C
llS* CH3 Cl CH3 sO2-n-C4Hs CH3 m.p.g0-91C
116* CH3 Cl CH3 SO2-n-C4Hg CH3 m.p.129-132C
117 CH3 Cl CH3 . SO2CH3 ~H3 m.p.115-142C
118 C~I3 Cl CH3 SO2N(CH3~2 CH3 m.p.73-82C
119 CH3 Cl CH3 SO2C2Hs ` CH3 m.p.ll2-143C
120 n-C3H7 Cl OH NH2 CH3 Table 4: Compounds of the ~ormula Rl ~ (R2)P

~/ ~N--N O - R9 O - S - O \~--N
CF3 R3 ~R7 Comp. Rl R2 R3 R~ R7 Physical No. data 121 H 2,4-Cl2 H CH3 CH3 122 2-C1 4-Cl H CH3 CH3 123 H 4-Cl Cl C~3 CH3 124 6-Cl 4-C1 CH3 CH3 C~3 12~ H 2,4-F2 CH3 CH3 CH3 126 H 3-Cl H CH3 CH3 127 H 2?4-C12 CH3 CH3 C2Hs 128 H 4-F OH C2Hs CH3 129 H 4-Cl c-C3Hs CH3 ~H3 .

Table ~: Compounds of the fonnula ,~ (R2)p --N o- CH3 ) n ~ N~CH

_ Comp. Rl R2 R3 Physical No. da~a 130 3,4-(OCF2O) 4-Cl CH3 oil 131 4-OC6Hs 4-CI CH3 honey 134 2,4-(OSO2CF3~2 4-Cl CH3 135 2,4-(OSO2CF3)2 4-Cl Cl 136 2,4-(OSO2CF3)2 4-CI OH
137 2,4-(OSO2CF3)2 4-Cl H

139 4~OCF2CHFCF3 4-Cl C~3 141 4-OCF2CHFCF~ 4-F CH3 142 4-OCF2CHFCF3 4-CI OH m.p. 86-102C
143 4-OCF2CHFCP3 . 4-F OH m.p. 81-88C

2 ~

Formulation Examples (~O = per cent by weight) Exarnple Fl: Emulsion concentrates a) b) c) Active ingredient according to the Preparation Examples 25% 40 % 50 %
Calcium dodecylbenzenesulfonate 5 % 8 % S %
Castor oil polyethylene glycol ether (36 mol EO) 5 %
Tributylphenol polyethylene glycol ether (30 mol EO) - 12 % 4 %
Cy lohexanone - 15 % 20 %
Xylene mixture 65 % 25 % 20 %

Emulsions ~f any desired concentration can be prepared from such concentrates bydilution with water.

Example F2: Solutions a) b) c) d) Active ingredient according to the Preparation Examples 80 % 10 ~ 5 % 95 %
Ethylene glycol monomethyl ether 20 %
Polyethylene glycol MW 400 - 70 %
N-Me~yl-2-pylTolidone - 20 %
Epoxidised COCOllUt oil - - 1 % 5 %
Pe~ol (boiling range 160-190C) - - 94 %

The solutions are suitable for use in ~e form of microdrops.

Example F3: Granules a) b) Active ingredient accordin~
to the Preparation Examples 5 % 10 %
Kaolin 94 %
Highly-disperse silica 1 %
Attapulgite - 90 %

The ac~ive ingredient is dissolve in dichloromethane, the solution is sprayed onto the carrier, and ~e solvent is subsequently evaporated in vacuo.

Exam~leF4: Dusts a) b) ~ctive LngIedient according to the Preparation Examples 2 % 5 %
Highly-dispersesilica 1% 5 %
Talc 97 %
Kaolin - 90 %

Ready-to-use dusts a~e obta~ned by intimately mixing the carriers with the active ingredient.

Example F5: Wettable ~owders a) b) c) Active ingredient according to the Preparation Examples 25% 50 % 75 %
Sodiumligninsulfonate 5 % 5 %
Sodium lauryl sulfate 3 % - 5 %
Sodium diisobutylnaphthalene-sulfonate - 6 % 10 %
Octylphenol polyethylene glycol e~.er (7-8 mol EO) - 2 %
Highly-disperse silica 5 % 10 % 10 ~o Kaolin 62 % 27 %

The active ingredient is mixed with the additives and the mixture is ground thoroughly in a suit~ble mill. This gives a wettable powder which can be diluted with water to give suspensions of any desired concentration.

Example F6: Emulsion concentrate Active ing~edient according to the Preparation Exarnples 10 %
Octylphenol polyethylene glycol ether (4-5 mol EO) ~ %
Calcium dodecylbenzenesulfonate 3 %

2 ~

Castor oil polyglycol ether ~36 mol EO) 4 %
Cyclohexanone 30 %
Xylene mixt~e 50 %

Fmulsions of any desired concentration can be prepared from this concentrate by dilution with water.

Example F7: Dusts a) b) Active ingredient according to ~e Preparation ExamplPs 5 % 8 %
Talc 95 %
Kaolin - 92 %

Ready-to-use dusts are obtained by mixing the active ingredient with the carlier and grlnding the mixture in a suitable mill.

Exarnple F8: Extruder ~ranules Active ingredient according to the Preparation Examples 10 %
Sodiom ligninsulfonate 2 %
Carboxymethylcellulose 1 %
Kaolin 87 %

The active ingredient is mLl~ed with the additives, and ~e mixture is ground and moistened with water. This mixture is extruded, granulated and subseguently dried in a stream of air.

Example F9: Coated ~ranules Active ingredient according to the Preparation ~xarnples 3 %
Polyethylene glycol (MW 200) 3 %
Kaolin 94 ~o In a mixer, ~e finely ground active ingredient is applied uniformly to the kaolin which has been moistened with polyethylene glycol. In this marmer, dust-free coated granules are obtained.

: . .

2 ~

Exarnple F10: Suspension concentrate Active ingredient according to the Preparation Exarnples 40 %
~.thylene glycol 10 %
Nonylphenol polyethylelle glycol ether (15 mol EO) 6 a/o Sodiurn ligninsulfonate 10 %
Carboxymethylcellulose 1 %
37 % aqueous formaldehyde solution 0.2 %
Silicone oil in the form of a 75 %
aqueous emulsion 0.8 %
Water 32 %

The flmely ground active ingredient is mixed intimately with the additives. This gives a suspension concentrate frorn which su~spensions of any desired concentration can be prepared by dilution with water.

Biolo~ical Examples Exarnple Bl: Ovicida arvicidal activitY on Heliothis virescens Heliothis virescens eggs which have been deposited on cotton are sprayed with an aqueous ernulsion spray mixture comprising 400 ppm of the active ingredient. After 8 days, the hatching percentage of the eggs and the survival rate of the caterpillars are evaluated in comparison with untreated control batches (~o reduction of the population). In this test, compounds of Tables 1, 2, 3 and 5 are very effective.

Example B2: ActivitY against Spodoptera littoralis caterp ars Young soya plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of the active ingredient. ~fter the spray coating has dried on, the soya plants are populated with 10 Spodoptera littoralis caterpillars in the third stage and placed in a plastic container. After 3 days, the test is evaluated. The percentage reduction of the population, or the percentage reduction of the feeding damage (% acdvity), is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with those of the untreated plants.

In this test, a good ac~ivity is shown by compounds 1, 4 to 8, 19, 23, 25, 26, 29, 41, 51,54, 55, 56, 60, 62 to 71, 73,74,76 100 and 104.

Examp~B3: Activity a~ainst Diabrotica balteata larvae Maize seedlings are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of the active ingredient. After the spray coating has dried on, the maize seedlings are populated with lû Diabrotica balteata larvae in the second stage and placed in a plastic container. 6 days later, the test is evaluated. The percentage reduction of the population (%
activity), is determined by comparing the number of dead larvae on the treated plants with those on the untreatecl plants.
In this test, an activity of over 80 % is shown by the compounds 1, 4 to 8, 13, 19,22, 23, 25, 26, 28, 29, ~1, Sl, 54, 55,56, 61, 62, 64, 65, 66, 6~,70,71,73,74, 100, 102,104, 113 and 130.

~: ActivitY a~ainst Heliothis virescens caterpillars Young ~oya plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of the active ingrsdient. After the spray coating has dried on, the soya plants are populated with 10 Heliothis virescens caterpillars in the first stage and placed in a plastic container. After 6 days, the test is evaluated. The percentage reduction of the population, or the percentage reducdon of the feeding damage (% activity), is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with those of the untreated plants.
In ~is test, a good activity is shown by compounds 1, 4 to 8, 13, 17, 19, 22, 23,25, 26,29, ~1, 51, 54, 55, 56, 61 to 71,73,74, 100, 101, 103, 104, 113 and 130.

Exam le B5: Ovicidal activitv a~ainst Heliothis virescens Heliothis virescens e~ggs which have been deposited on ~llter paper are briefly immersed in a test solution which comprises 400 ppm of the active ingredient to be tested dissolved in ace~one/water. After the test solution has dried on, the eggs are incubated in Petli dishes.
After 6 days the hatching percentage of the eggs is evaluated in companson with untreated control batches (% reduction of hatching rate).
In this test, an activity of over 8Q % is shown by the compounds 1, 4 to 8, 19, 23, 25, 29, 41,51,54,55,56,60,62,64to70,73and74.

Example B6: Activity a~nst Plutella xylostella cate~pillars Young cabbage plants are sprayed with an aqueous emulsion spray mixture comprising 2 ~

400 ppm of the active ingredient. After the spray coating has dried on, the cabbage plants are populated with 10 Plutella xylostella caterpillars in the third stage and placed in a plastic container. 3 days later, the test is evaluated. The percentage reduction of the population, or the percentage reduction of the feeding damage (% activity), is determined by comparing the number of dead caterpillars and the feeding d~nage on the treated plants with those of the untreated plants.

In this test, an activity against Plutella xylostella of over 80 % is shown by the compounds 1,4to8, 19,23,25,26,29,41,51,54,55,56,60,62to71,73,74and76.

Example B7: Activity a~ainst Blattella ~ermanica A Petri dish is f~lled with such an amount of 0.1 % solution of the active ingredient in acetone that the amount corresponds to a rate of application of 2 g/m2. When the solvent has evaporated, 20 Blattella germanica nymphs (final nymph stage) are placed into the dish which has been prepared in this manner and then exposed for 2 hours to the action of the test substance. The nymphs are then anaesthetised using CO2, transferred to a new Petri dish and kept in the dark at 25C and an atmospheric humidity of 50 to 70 %. After 48 hours, the insecticidal action is determined by calculating the mort~lity rate.

In this test, a good activity against Blattella germanica is exhib;ted by compounds of Tables 1 to 3 and ~.

E~ample B8: ActivitY a~ainst ~reenbottle flies Lucilia cupr;na Small portions (30 to S0 eggs) of freshly deposited eggs of the greenbottle fly species Lucilia cuprina are placed into test tubes in which previously 4 ml of nu~ient medium have been mixed with I ml of test solution comprising 16 ppm of the active ingredient to be tested. After the medium had been inoculated, the tes~ tubes were sealed with a cotton wool plug and incubated for 4 days in an incubator at 30C. At this point in time, larvae approximately 1 cm in length (stage 3) develop in ~e untreated medium. If the substance is active, then the larvae are either dead at this point in time or noticeably delayed in their development. After 96 hours, the test is evaluated.

In this test, a good acti~,rity against Lucilia cuprina is exhibited by the compounds of Tables 1 to 3 and S.

2~

-41 ~

Example B9: Activity a~ainst Ctenocephalides felis 20 to 25 flea eggs are placed in a horizontally positioned 50 ml dssue culture flask into which lS g of flea larvae nutrient medium comprising 100 ppm of the active ingredient to be tested have been introduced. The flasks are incubated in an incubator at 26 to 27C at an a~ospheric humidity of 60-70 %. After 21 days, they are checked for the presence of adult fleas, unhatched pupae and larvae.

In this test, a good activity against Ctenocephalides felis is shown by the compounds of Tables 1 to 3 and S.

Example B10: Activity a~ainst Musca domestica A lump of sugar is treated wilh a solution of the test substance in such a way thatt after drying overnight, the concentration of test substance in ~he sugar is 250 ppm. This treated lump and a moist cotton wool ball and 10 adult Musca domestica of an OP-resistant strain are placed on an aluminium dish, covered with a glass beaker and incubated at 25C. The mortality rate is determined after 24 hours.

In this test, a good activity against Musca domestica is shown by the compounds of Tables 1 to3andS.

Claims

1. A compound of the formula (I), in which o and p independently of one another are 0, 1, 2, 3, 4 or 5, where, if o is greater than 1, the radicals Rl are identical or different and where, if p is greater than 1, the radicals R2 are identical or different;
R1 and R2 independently of one another are C1-C4alkyl, halo-C1-C4alkyl, C1-C4alkoxy, halo-C1-C4alkoxy, C1-C4alkylthio, halo-C1-C4alkylthio, halogen, -OH, nitro, cyano, phenoxy, -O-S(=O)-R8 or -O-S(=O)2-R8, C2-C4alkynyl, or C2-C4alkynyl which is substituted by phenyl or halogen, or are C2-C4alkenyl, halo C2-C4alkenyl, and/or two substituents R1 which are bonded to adjacent C atoms of the phenyl ring and/or two substituents R2 which are bonded to adjacent C atoms of the phenyl ring independently of one another together are -Y1-Z-Y2-;
R3 is hydrogen, halogen, -OH, -SH, C1-C4alkyl, C3-C6cycloalkyl, halo-C1-C4alkyl,C1-C4alkoxy, C1-C4alkoxy-C1-C4alkyl, C1-C4alkoxy-C1-C4alkoxy, C1-C4alkylthio or -N(R4)R5;
R4 and R5 independently of one another are hydrogen, C1-C4alkyl or -OH;
R6 is -OR9, -S(O)nR10, -P(O)R11R12 or -NR13R14;
R7 is hydrogen, C1-C4alkyl, C3-C6cycloalkyl, halo-C1-C4alkyl, C1-C4alkcoxy-C1-C4alkyl, allyl, C1-C3alkylallyl, haloallyl or propargyl;
R8 is C1-C8alkyl or halo-C1-C8allyl;
R9 is hydrogen, C1-C4alkyl, halo-C1-C4alkyl, C1-C4alkoxy-C1-C4alkyl, C3-C6cycloalkyl, C2-C6alkenyl, halo-C2-C6alkenyl or propargyl;
R10 is hydrogen, C1-C4alkyl, halo-C1-C4alkyl, phenyl or -NR13R14;
R11 and R12 independently of one another are C1-C4alkoxy;
R13 and R14 independently of one another are hydrogen, C1-C4alkyl, halo-C1-C4alkyl, phenyl, C1-C4alkylamido, C1-C4dialkylamido or -NH2;
nis 0, 1 or 2;
Y1 and Y2 independently of one another are O or S; and Z is methylene, eth-1,2-ylene; halomethylene or haloeth-1,2-ylene, a tautomer of the compound of the formula I, and a salt of the various tautomers.

2. A compound according to claim 1, of the formula I in which the radicals R1 independently of one another are C1-C4alkyl, halo-C1-C4alkyl, C1-C4alkoxy, halo-Cl-C4alkoxy, halogen, -O-S(=O)2-CI-C4alkyl or -O-S(=0)2-halo-C1-C4alkyl, phenoxy or two radicals R1 together are -OCF2O-, or, where appropriate, a tautomer thereof.

3. A compound according to claim 2, of the formula I in which the radicals R1 independently of one another are halo-C1-C4alkyl, halo-C1-C4alkoxy, halogen, -O-S(=O)2-C1-C2alkyl or-O-S(=O)2-halo-C1-C2alkyl, or, where appropriate, a tautomer thereof.

4. A compound according to claim 1, of the formula I in which the radicals R2 independently of one another are C1-C4alkyl, halo-C1-C4alkyl, C1-C4alkoxy, halo-C1-C4alkoxy, halogen, -O-S(=O)2-C1-C2,alkyl or -O-S(=O)2-halo-C1-C2alkyl, or, where appropriate, a tautormer thereof.

5. A compound according to claim 1, of the formula I in which R3 is hydrogen, halogen, -OH, -SH, C1-C4alkyl, C3-C6cycloalkyl, halo-C1-C4alkyl, C1-C4alkoxy, C1-C4alkoxy-C1-C4alkoxy, C1-C4alkylthio, -NH2, -NH(C1-C2alkyl), -N(C1-C2alkyl)2 or -NHOH, or, where appropriate, a tautomer thereof.

6. A compound according to claim 1, of the formula I in which R6 is -OR9 and R9 is hydrogen, C1-C4alkyl, C2-C6alkenyl or halo-C2-C6alkenyl, or, where appropriate, a tautomer thereof.

7. A compound according to claim 1, of the formula I in which R6 is -SO2-C1-C4alkyl, -SO2NH(CH3), -P(O)(OC2H5)2, -NH2, -N(CH3)NH2 or -NHCON(CH3)2, or, where appropriate, a tautomer thereof.

8. A compound according to claim 1, of the formula I in which R7 is hydrogen, C1-C2alkyl, C1-C2alkoxy-C1-C2alkyl, allyl, 2-methylallyl, haloallyl or propargyl, or, where appropriate, a tautomer thereof.

9.A compound according to claim 1, of the formula I in which R1 is -O-S(=O)2-C1-C2alkyl, -O-S(=O)2-halogen-C1-C2alkyl or C1-C3fluoroalkoxy;
R2 is fluorine or chlorine;
R3 is hydrogen, -OH, -SH, C1-C2alkyl, cyclopropyl, C1-C2alkoxy, C1-C2alkoxy-C1-C2alkoxy, C1-C2alkylthio, -NH2, -NH(CH3), -N(CH3)2 or -NHOH;
R6 is -OR9, -SO2-C1-C4alkyl, -SO2NH(CH3), -P(O)(OC2H5)2, -NH2, -N(CH3)NH2 or -NHCON(CH3)2;
R7 is hydrogen, methyl or ethyl; and R9 is hydrogen, C1-C2alkyl, C2-C3alkenyl or halo-C2-C3alkenyl and o and p are 1 or 2, or, where appropriate, a tautomer thereof.

10. A compound according to claim 9, of the formula I in which R1 is -O-S(=O)2-CH3,-O-S(=O)2-CF3 or-OCF2CHFCF3;
R2 is chlorine;
R3 is hydrogen, -OH, -SH, C1-C2alkyl, cyclopropyl, C1-C2alkoxy, C1-C2alkoxy-C1-C2alkoxy, C1-C2alkylthio, -NH2, -NH(CH3), -N(CH3)2 or -NHOH;
R6 is -OR9, -SO2-C1-C4alkyl, -SO2NH(CH3), -P(O)(OC2H5)2, -NH2, -N(CH3)NH2 or -NHCON(CH3)2;
R7 is hydrogen, methyl or ethyl; and R9 is hydrogen, C1-C2alkyl, C2-C3alkenyl or halogen-C2-C3alkenyl und o and p are 1 or 2, or, where appropriate, a tautomer thereof.

11. A compound according to claim 10, of the formula I in which R1 is O-S(=O)2-CF3 which is bonded in the 4-position;
R2 is chlorine which is bonded in the 4-position;
R3 is hydrogen, -OH, -SH, C1-C2alkyl, cyclopropyl, C1-C2alkoxy, C1-C2alkoxy-C1-C2alkoxy, C1-C2alkylthio, -NH2, -NH(CH3), -N((CH3)2 or -NHOH;
R6 is -OR9, -SO2-C1-C4alkyl, -SO2NH(CH3), -P(O)(OC2H5)2, -NH2, -N(CH3)NH2 or -NHCON(CH3)2;
R7 is hydrogen, methyl or ethyl; and R9 is hydrogen, C1-C2alkyl, C2-C3alkenyl or halo-C2-C3alkenyl, and o and p are 1, or, where appropriate, a tautomer thereof.

12. A compound according to claim 1, of the formula I, selected from the group of compounds comprising (a) 1-(4-chlorophenyl)-4-hydroxy-5-methyl-6-oxa-2,3,5-triaza-1-(4-trifluoromethane-sulfonyloxyphenyl)hepta-1,3-diene, or 1-(4-chlorophenyl)-5-methyl-6-oxa-4-oxo-2,3,5-triaza-1-(4-trifluoromethanesulfonyl-oxyphenyl)hept-1-ene;
(b) 1-(4-chlorophenyl)-4,5-dimethyl-6-oxa-2,3,5-triaza-1-(4-trifluoromethanesulfonyl-oxyphenyl)hepta-1,3-diene;
(c) 1-(4-chlorophenyl)-4-hydroxy-5-methyl-6-oxa-2,3,5-triaza-1-(4-methanesulfonyl-oxyphenyl)hepta-1,3-diene, or 1-(4-chlorophenyl)-5-methyl-6-oxa-4-oxo-2,3,5-triaza-1-(4-methanesulfonyl-oxyphenyl)hept-1-ene;
(d) 1-(4-fluorophenyl)-4-hydroxy-5-methyl-6-oxa-2,3,5-triaza-1-(4-trifluoromethane-sulfonyloxyphenyl)hepta- 1 ,3-diene, or 1-(4-fluorophenyl)-5-methyl-6-oxa-4-oxo-2,3,5-triaza-1-(4- trifluoromethanesulfonyl-oxyphenyl)hept-l-ene;
(e) 1-(4-chlorophenyl)-4,5-dimethyl-6-oxa-2,3,5-triaza-1-(4-methanesulfonyloxyphenyl)-hepta-1,3-diene;
(f) 1-(4-chlorophenyl)-4-cyclopropyl-5-methyl-6-oxa-2,3,5-triaza-1-(4-trifluoromethane-sulfonyloxyphenyl)hepta-1,3-diene;
(g) 1-(4-fluorophenyl)-4,5-dimethyl-6-oxa-2,3,5-triaza-1-(4-trifluoromethanesulfonyl-oxyphenyl)hepta- 1,3-diene;
(h) 1-(4-chlorophenyl)-4-cyclopropyl-5-ethyl-6-oxa-2,3,5-triaza-1-(4-trifluoromethane-sulfonyloxyphenyl)hepta-1,3-diene;
(i) 1-(4-chlorophenyl)-4,5-dimethyl-6-oxa-2,3,5-triaza-1-(4-trifluoromethanesulfonyl-oxyphenyl)octa- 1 ,3-diene;
(j) 1-(4-chlorophenyl)-5-ethyl-4-methyl-6-oxa-2,3,5-triaza-1-(4 trifluoromethanesulfonyl-oxyphenyl)hepta-1,3-diene, and (k) 1-(4-chlorphenyl)-4-hydroxy-5-methyl-6-oxa-2,3,5-triaza-1-(4-trifluoromethane-sulfonyloxyphenyl)nona-1,3,8-triene, or 1-(4-chlorophenyl)-5-methyl-6-oxa-4-oxo-2,3,5-triaza-1-(4-trifluoromethanesulfonyl-oxyphenyl)nona-1,8-diene.

13. A process for the preparation of a compound according to claim 1, of the formula I, or, where appropriate, of a tautomer thereof, in each case in free form or in salt form, which comprises a) to prepare a compound of the formula I in which R3 is -OH, -SH, -NHR4 or -NHR5, reacting, preferably in the presence of a base, a compound of the formula (II) or a salt thereof with a compound of the formula (III), in which Y is O, S, -NR4 or -NR5 and Z is halogen, C1-C8alkoxy, C1-C8alkylthio, C1-C8alkanoyloxy, C1-C8alkanesulfonyloxy, halo-C1-C8alkanesulfonyloxy, benzenesulfonyloxy or toluenesulfonyloxy, or with a salt and/or, where appropriate, a tautomer thereof, or b) reacting a compound of the formula (IV), with a compound of the formula (V) or with a salt and/or, where appropriate, a tautomer thereof, or c) to prepare a compound of the formula I in which R3 is -OH, -SH, C1-C4alkoxy, C1-C4alkylthio or -N(R4)R5, reacting, a compound of the formula (VI), in which X is halogen, or a salt and/or, where appropriate, a tautomer thereof, with water, H2S, a C1-C4 alkanol, a C1-C4alkoxy-C1-C4alcohol, a mercapto-C1-C4alkane or a compound of the formula HN(R4)R5 or a salt thereof, or d) to prepare a compound of the formula I in which R3 is hydrogen, C1-C4alkyl, halo-C1-C4alkyl or C3-C6cycloalkyl, reacting a compound of the formula (VII), in which X is halogen, or a salt thereof, with a compound of the formula HN(R6)R7 or a salt thereof, or e) to prepare a compound of the formula I in which R3 is halogen, reacting a compound of the formula I in which R3 is -OH or -SH, or a salt and/or, where appropriate, a tautomer thereof, with a halogenating agent, and in each case, if desired, converting a compound of the formula I or a tautomer thereof which can be obtained by the process or by a different route, in each case in free form or in salt form, into a different compound of the formula I or a tautomer thereof, resolving an isomer mixture which can be obtained according to the process, isolating the desired isomer, and/or converting a free compound of the formula I or a tautomer thereof, which can be obtained according to the process, into a salt, or converting a salt of a compound of the formula I or of a tautomer thereof, which can be obtained according to the process, into the free compound of the formula I or a tautomer thereof or into a different salt.

14. A composition for protection against attack by pests, which comprises at least one compound of the formula I according to claim 1 or, where appropriate, a tautomer thereof, in each case in free form or in agrochemically utilisable salt form, as active ingredient and at least one auxiliary.

15. A composition according to claim 14 for protection against attack by insects and/or arachnids.

16. A process for the preparation of a composition according to claim 14, which comprises intimately mixing the active ingredient with the auxiliary or auxiliaries.

17. Use of a compound of the formula I according to claim 1 or, where appropriate, of a tautomer thereof, in each case in free form or in agrochemically utilisable salt form, or of a composition according to claim 14 for protection against attack by pests.

18. Use according to claim 17 for protection against attack by insects and/or arachnids.

19. A method for protection against attack by pests, which comprises applying a compound of the formula I according to claim 1 or, where appropriate, a tautomer thereof, in each case in free form or in agrochemically utilisable salt form, or a composition according to claim 14, to the pests and/or their environment.

20. A method according to claim 19 for protection against attack by insects and/or arachnids.

FD 4.5/FF