CA2077111A1 - Pesticides - Google Patents

Abstract

Pesticides Abstract Compounds of the formula (I), in which:
one of the radicals R2, R3, R4, R5, R6 and R7 is a group of the formula (Ia);

the other five of the radicals R2, R3, R4, R5, R6 and R7 independently of one another are hydrogen, halogen, C1-C8alkyl, halo-C1-C8alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C8alkoxy, halo-C1-C8alkoxy, C1-C8alkylthio, halo-C1-C8alkylthio, cyano, nitro, phenyl, phenoxy or phenylthio, where the phenyl groups in phenyl, phenoxy and phenylthio are unsubstituted or substituted by one, two or three substituents; Y is an oxygen atom, a sulfur atom or a group of the formula NRI (Ib); in which R1 is hydrogen, C1-C8alkyl, C1-C8alkanoyl, C1-C8alkanesulfonyl, halo-C1-C8alkanesulfonyl, cyano-C1-C8alkanesulfonyl or phenylsulfonyl, whose phenyl group is unsubstituted or substituted by one or twosubstituents selected from the group comprising halogen, C1-C4alkyl, nitro and cyano; m is 0 or 1; and n is 0 or 1; and R8 to R20 have the meaning given herein, and, if appropriate, their tautomers, in each case in their free form or in salt form, can be used as agrochemical active ingredients.

Description

2~77~

Pesticides The invention relates to compounds of the formula R3 ~Rs in which:
one of the radicals R2, R3, R4, Rs, R6 and R7 is a group of the fo~nula Rg N~R10 J~ Jl~ , [c(Rl2)(Rl3)]m-[c(Rl4)(Rls)]n-c(Rl6)(Rl7) (Ia);

R-the remaining five of the radicals R2, R3, R4, Rs, R6 and R7 independently of one another are hydrogen, halogen, Cl-C8alkyl, halo-CI-C8alkyl, Cl-C4allcoxy-Cl-C4alkyl, Cl-C8alXoxy, halo-Cl-C8alkoxy, Cl-C8alkylthio, halo-Cl-C8alkylthio, cyano, nitro, phenyl, phenoxy or phenylthio, where the phenyl groups in phenyl, phenoxy and phenylthio are unsubstituted or substituted by one, two or three substituents, selected from the group comprising halogen, C1-C4aL~cyl and Cl-C4alkoxy, with the proviso that9 of the five radicals from the group of the radicals R2, R3, R4, Rs, R6 and R7, which differ from group Ia, at least two radicals are hydrogen and at least four radicals differ fr~m phenyl which is unsubstituted or substituted as men~ioned above, from phenoxy which is unsubstituted or substituted as mentioned above, and from phenyl~hio which is unsubstituted or substituted as mentioned above; Y is an oxygen atom, a sulfur atom or a group of the formula NRl ~Ib); in which Rl is hy~rogen, Cl-C8alkyl, Cl-C8alkanoyl, 20~7~ ~

Cl-C8alkanesulfonyl, halo-CI-C8alkanesulfonyl, cyano-CI-C8alkanesulfonyl or phenylsulfonyl, whose phenyl group is unsubstituted or substituted by one or twosubstituents selected from the group comprising halogen, Cl-C4alkyl, nitro and cyano; R8 is hydrogen, Cl-C8alkyl, Cl-C8alkoxy or Cl-C8alkylthio; Rg is hydrogen, Cl-C8alkyl, halo-CI-C8alkyl, Cl-C~alkoxy-Cl-C4alkyl, Cl-C4alkylthio-Cl-C4alkyl, Cl-C4alkanesulfinyl-Cl-C4alkyl, Cl-C4alkanesulfonyl-Cl-C4alkyl, C2-C8alkenyl, halo-C2-C8alkenYI, C2-C8alkYnYI, C3-cscycloalkyl or halogen; Rlo is hydrogen, hydroxyl, Cl-C8alkyl, halo-CI-C8alkyl, Cl-C4alkoxy-CI-C4alkyl, Cl-C8alkoxy, Cl-C8alkylthio, Cl-C8alkanesulfinyl, C~-C8alkanesulfonyl, halogen, nitro, cyano, amino, a group of the forrnula-N(H)RI8 (Ic), a group of the formula N(~,8)R,9 (Id) or a group of the formula N=C(R1g)R20 (Ie); Rll is hydrogen, Cl-C8alkyl, benzyl, Cl-C8alkanoyl, phenylcarbonyl whose phenyl group is unsubstituted or substituted by one, two or three substituents selected from the group comprising halogen and Cl-C4allcyl, or is Cl-C8alkylthio, halo-C1-C8alkylthio, cyano-C1-C8alkylthio, phenylthio or benzylthio, where the ph~nyl groups in phenylthio and benzylthio are unsubstituted or substituted by one or two substituents selected from the group comprising halogen, Cl-C4alkyl, nitro and cyano; R12, Rl3, Rl4, R15, Rl6 and ~17 independently of one another are hydrogen, Cl-C8alkyl, halo-Cl-C8alkyl, Cl-C4alkoxy-Cl-C4alkyl or C3-C8cycloalkyl; Rl8 is Cl-C8alkyl, benzyl, Cl-C8alkanoyl, phenylcarbonyl whose phenyl group is unsubstituted or substituted by one, two or three substituents selected from the group comprising halogen and Cl-C4a1kyl, Cl-~8alkylthio, halo-CI-C8alkylthio, cyano-CI-C8alkylthio, phenylthio or benzylthio, where the phenyl groups in phenylthio and benzylthio are unsubstituted or substituted by one or two substituents selected from the group comprising halogen, Cl-C4alkyl, nitro and cyano; R19 is Cl-C8alkyl; R20 is hydrogen or Cl-~8alkyl; m is O or 1; and n is O or 1;
and, if appropriate, tautomers thereof, in each case in free form or in salt form, a process for their preparation and the use of these compounds and tautomers, and pesticides whose active ingredient is selected from these compounds and tautomers, in each case in free form or in agrochemically usabl~ salt form, and a process for the preparation and the use of ~hese compositions.

Some of the compounds I can exist in the form of tautomers. If, for example, the radical Rlo in group Ia is hydroxyl, such compounds can b~ in equilibrium with the tautomeric oxo derivatives, i.e. the corresponding pyrimid-5-ones. Accordingly, compounds Ihereinafter are also to be understood as meaning, if appropriate, corresponding tautomeTs, even when the laner are not mentioned specifically in each case.

, , -3 20771~ 1 The compounds I and, if appropriate, the tautomers thereof can exist in the form of salts, in particular agrochem.ically usable salts. Since the compounds I have at least one basic centre, they can form, for exarnple, 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 C1-C4alkanecarboxylic acids, for example acetic acid, which are unsubstituted orsubstituted, for example by halogen, or unsaturated or saturated dicarboxylic acids, for example oxalic acid, malonic acid, maleic acid, fumaric acid or phthalic acid, or hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or benzoic acid, or with organic sulfonic acids such as C1-C4alkane- or arylsulfonic acids, for example methane- or p-toluenesulfonic acid, which are unsubstituted or substituted for example by halogen. Furthermore, compounds 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 magnesium salts, or salts with ammonia or an organic amine such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethylamine, diethylamine, triethylamine or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example monoethanolamine, diethanolamine or triethanolamine. Moreover, corresponding internal salts may be formed, if appropriate.
The invention furthermore embraces salts which are not suitable for agrochemical uses and which are employed, for example, for the isolation or purification of free compounds I
or agrochemically usable salts thereof. Due to the close relation between the compounds I
in free form and in the form of their salts, the free compounds I or the salts thereof are also to be understood hereinbefore and hereinafter as meaning, if appropriate, the corresponding salts or the free compounds I, both analogously and with regard to their intended use. The same applies to tautomers of compounds I and salts thereof.

The general terms used hereinabove and hereinafter have the meanings given below, unless defined otherwise.

Halogen is fluorine, chlorine, bromine or iodine.

Carbon-containing groups and compounds contain, unless otherwise def1ned, in each case 1 up to and including 8, preferably 1 up to and including 4, in particular 1 or ~, carbon atoms.

- -~4~ 20771~ 1 Alkyl - as a group per se and as structural element of other groups and compounds such as haloalkyl, alkoxy, haloalkoxy, alkoxyalkyl, alkylthio, cyanoalkylthio, haloalkylthio, alkylthioalkyl, alkanesul~myl, alkanesulfinylalkyl, alkanesulfonyl, cyanoalkanesulfonyl, haloalkanesulfonyl and ~Ikanesulfonylalkyl - is, in each case with due consideration of the number of carbon atoms contained in the particlllar group or compound existing in each individual case, either straight-chain, i.e. methyl, ethyl, propyl, butyI, pentyl, hexyl, heptyl or octyl, or branched, for example isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isooctyl.

Alkenyl - as a group per se and as structural element of other groups and compounds such as haloalkenyl - is, in each case with due consideration of the number of carbon atoms contained in the particular group or compound existing in each individual case, either straight-chain, for example ethenyl, propen-1-yl, but-1-en-1-yl, pent-2-en-1-yl or oct-3-en-1-yl, or branched, for example propen-2-yl, but-1-en-2-yl or oct-2-en-4-yl.

Alkynyl, in each case with due consideration of the number of carbon atoms existing in each individual case, is either straight-chain, for example ethynyl, propyn-1-yl, but- I -yn- 1-yl, pent-2-yn- 1 -yl or oct-3-yn- 1 -yl, or branched, fo} example propyn-2-yl, But-l-yn-2-yl or oct-2-yn-~-yl.

Alkanoyl, in each case with due consideration of the number of carbon atoms existing in each individual case, is either straight-chain or branched, for example formyl, acetyl, propionyl, butyryl, pivaloyl or octanoyl.

Cycloalkyl, in each case with due consideration of the number of carbon atoms existing in each individual case, is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

In halogen-substituted carbon-containing groups and compounds, such as haloaL~cyl, haloalkenyl, haloalkoxy, haloalkylthio and haloalkanesulfonyl, at least one of the hydrogen atoms p~esent in the underlying non-halogenated skeleton is replaced by a halogen atom; however, it is also possible for two or more than two, for example - in ~he case of perhalogenation - of all the hydrogen atoms present in the underlying non-halogenated skeleton, to be replaced independently of one another by halogen atoms.
E~camples which may be mentioned are -CH2F, -OEIF2, -CF3, -CH2Cl, -CHCl2, -CCI3,-CCl2CCl3, -CH2Br, -CH2CH2Br, -CHBrCI,-CCI=CCI~, -OCH2F, -SCHCl2 and-SO2CF3.

..:- ~. .:

2 ~

In alkoxy-, alkylthio-, alkanesulfinyl-, alkanesulfonyl- or cyano-substituted carbon-containing groups and compounds such as alkoxyalkyl, alkylthioalkyl, alkanesulfinylalkyl, alkanesulfonylalkyl, cyanoalkylthio and cyanoalkanesulfonyl, one of the hydrogen atoms present in the underlying unsubstituted skeleton is replaced by alkoxy, alkylthio, alkanesulfinyl, alkanesulfonyl or cyano.

Prefe~ed compounds of the for~nula I within the scope of the invention are those in which:
one of the radicals R2, R3, R4, Rs, R6 and R7 is a group Ia;
the other five of the radicals R2, R3, R4, Rs, R6 and R7 independently of one another are hydrogen, halogen, Cl-C4alkyl, halo-CI-C4alkyl having 1, 2 or 3 halogen atoms, Cl-C2alkoxy-Cl-C4alkyl, Cl-C4alkoxy, Halo-Cl-C4alkoxy having 1, 2 or 3 halogen atoms, Cl-C4alkylthio, halo-Cl-C4alkylthio having 1, 2 or 3 halogen atoms, cyano, nitro, phenyl, phenoxy or phenylthio, where the phenyl groups in phenyl, phenoxy and phenylthio are unsubstituted or substitllted by one, two o~ three substituents selected from the group comprising halogen, Cl-C2alkyl and Cl-C2alkoxy, with the proviso that, of the five radicals from the group of the radicals R2, R3, R4, R5, R6 and R7, which differ from group Ia, at least two radicals are hydrogen and at least four radicals differ from phenyl which is unsubstituted or substituted as mentioned above, from phenoxy which is unsubstituted or substituted as mentioned above, and from phenylthio which is unsubstituted or substituted as mentioned above; Y is an oxygen atom, a sulfur atom or a group Ib; Rl is hydrogen, Cl-C4alkyl, Cl-C4alkanoyl, Cl-C4alkanesulfonyl, halo-CI-C4alkanesulfonyl having 1, 2 or 3 halogen atoms, cyano-CI-C4alkanesulfonyl or phenylsulfonyl whose phenyl group is unsubstituted or substituted by one or two substituents selected from the group comprising halogen, Cl-C2alkyl, nitro and cyano; R8 is hydrogen, Cl-C4alkyl, Cl-C4alkoxy orCl-C4alkylthio; Rg is hydrogen, Cl-C4alkyl, halo-Cl-C4alkyl having 1, 2 or 3 halogen atoms, Cl-C2alkoxy-Cl-C4alkyl, Cl-C2alkylthio-Cl-C4alkyl, Cl-C2alkanesulfinyl-Cl-C4alkyl, Cl-C2alkanesulfonyl-Cl-C4alkyl, C2-C4alkenyl, halo-C2-C4alkenyl having 1, 2 or 3 halogen atoms, C2-C4alkynyl, C3-C7cycloalkyl or halogen; Rlo is hydrogen,hydroxyl, Cl-C4alkyl, halo-Cl-C4alkyl having 1, 2 or 3 halogen atoms, Cl-C4alkoxy-Cl-C4alkyl, Cl-(:4aikoxy, CI-C4alkylthio, Cl-C4alkanesulfinyl, Cl-C4alkanesulfonyl, halogen, nitro, cyano, amino, a group Ic, a group Id or a group Ie;
R,l is hydrogen, Cl-C4alkyl, benzyl, Cl-C4alkanoyl, phenylcarbonyl whose phenyl group is unsubstituted or substituted by one, two or three substituents selected from the group comprising halogen and Cl-C2alkyl, or is Cl-C4aL~ylthio, halo-Cl-C4alkylthio having 1, 2 or 3 halogen atoms, cyano-Cl-C4alkylthio, phenylthio or benzylthio, where the phenyl : '.' ', '- ' .

-6- 2~77~

groups in phenylthio and benzylthio are unsubstituted or substituted by one or two substituents selected from the group comprising halogen, Cl-C2alkyl, nitro and cyano;
Rl2, Rl3, Rl4, Rls, Rl6 and Rl7 independently of one another are hydrogen, C1-C4alkyl, halo-CI-C4alkyl having 1, 2 or 3 halogen atoms, Cl-C4alkoxy-CI-C4alkyl or C3-C7cycloalkyl; Rl8 is Cl-C4alkyl, benzyl, C1-C4alkanoyl, phenylcarbonyl whose phenyl group is unsubstituted or substituted by one, two or three substituents selected from the group comprising halogen and Cl-C2alkyl, or is Cl-C4alkylthio, halo-CI-C4alkylthio having 1, 2 or 3 halogen atoms, cyano-CI-C4aLlsylthio, phenylthio or benzylthio, where the phenyl groups in phenylthio and benzylthio are unsubstituted or substituted by one or two substituents selected ~rom the group comprising halogen, Cl-C2alkyl, nitro and cyano; Rlg is Cl-C4alkyl; R20 is hydrogen or Cl-C4alkyl; rn is O or 1; and n is O or 1;
and, if appropriate, tautomers thereof, in each case in free forrn or in salt forrn.

Particularly preferred compounds of the fonnula I within the scope of the invention are those in which:
one of the radicals R2, R3, R5 and R6 is a group Ia;
the other three of the radicals R2, R3, Rs and R6 and the radicals R4 and R7 independently of one another are hydrogen, halogen, Cl-C4alkyl, halo-CI-C4alkyl having 1, 2 or 3 halogen atoms, Cl-C2alkoxy-CI-C4alkyl, Cl-C4alkoxy, halo-CI-C4alkoxy having 1, 2 or 3 halogen atoms, Cl-C4alkylthio, halo-CI-C4alkylthio having 1, 2 or 3 halogen atoms, cyano, nitro, phenyl, phenoxy or phenylthio, where the phenyl groups in phenyl, phenoxy and phenylthio are unsubstituted or substituted by one, two or three substituents selected from the group comprising halogen, Cl-C2alkyl and Cl-C2alkoxy, with the proviso that, of the five radicals from the group of the radicals R2, R3, R4, R5, R6 and R7, which differ from group Ia, at least t~vo radicals are hydrogen and at least four radicals differ from phenyl which is unsubstituted or substituted as mentioned above, from phenoxy which is substituted or unsubstituted as mentioned above, and from phenylthio which is unsubstituted or substituted as mentioned above; Y is an oxygen atom, a sulfur atom or a group Ib; Rl is hydrogen, Cl-C4alkyl, Cl-C4alkanoyl, Cl-C4alkanesulfonyl, halo-Cl-C4-alkanesulfonyl having 1, 2 or 3 halogen atoms, cyano-C1-C4alkanesulfonyl or phenylsulfonyl whose phenyl group is unsubstituted or substituted by one or two substituents selected from the group cornprising halogen, Cl-C2alkyl, nitro and cyano; R8 is hydrogen, Cl-C4alkyl, Cl-C4alkoxy or C1-C4alkylthio; R9 is hydrogen, C1-C4alkyl, halo-Cl-C4alkyl having 1, 2 or 3 halogen atoms, Cl-C2alkoxy-CI-C4alkyl, Cl-C2alkylthio-Cl-C4alkyl, Cl-C2alkanesulfinyl-CI-C4alkyl, Cl-C2alkanesulfonyl-CI-C4alkyl, C2-C4alkenyl, halo-C2-C4alkenyl having 1, 2 or 3 halogen atoms, C2-C4alkynyl, .. , :, ............................ . .
.

2077~1~
C3-C7cycloallcyl or halogen; Rlo is hydrogen, hydroxyl, Cl-C4alkyl, halo-Cl-C4alkyl having 1, 2 or 3 halogen atoms, Cl-C4alkoxy-CI-C4alkyl, Cl-C4alkoxy, Cl-C4alkylthio, Cl-C4aLkanesul~myl, Cl-C4alkanesulfonyl, halogen, nitro, cyano, amino, a group Ic, a group Id or a group Ie; Rll is hydrogen, Cl-C4alkyl, benzyl, Cl-C4alkanoyl, phenylcarbonyl whose phenyl group is unsubstituted or substituted by one, two or three substituents selected from the group comprising halogen and Cl-C2alkyl, or is Cl-C4alkylthio, halo-CI-C4alkylthio having 1, 2 or 3 halogen atoms, cyano-CI-C4alkylthio, phenylthio or benzylthio, where the phenyl groups in phenylthio and benzylthio are unsubstituted or substituted by one or two substituents selected from the group comprising halogen, Cl-C2alkyl, nitro and cyano; Rl2, R13, Rl4, Rl5, Rl6 and Rl7 independently of one another are hydrogen, Cl-C4alkyl, halo-CI-C4alkyl having 1, 2 or 3 halogen atoms, Cl-C4alkoxy-CI-C4alkyl or C3-C7cycloalkyl; Rl8 is Cl-C4alkyl, benzyl, Cl-C4alkanoyl, phenylcarbonyl whose phenyl group is unsubstituted or substituted by 1, 2 or 3 substituents selected from the group comprising halogen and Cl-C2alkyl, or is Cl-C4alkylthio, halo-CI-C4alkylthio having 1, 2 or 3 halogen atoms, cyano-CI-C4alkylthio, phenylthio or benzylthio, where the phenyl groups in phenylthio and benzylthio are unsubstituted or substituted by one or two substituents selected from the g,roup comprising halogen, Cl-C2alkyl, nitro and cyano; Rlg is Cl-C4alkyl; R20 is hydrogen or Cl-C4alkyl; m is O or 1; and n is O or 1;
and, if appropriate, tautomers thereof, in each case in free forrn or in salt form.

Especially preferred compounds of the formula I within the scope of the invention are those in which:
one of the radicals R2, R3, Rs and R6 is a group Ia;
the other three of the radicals R2, R3, Rs and R6 and the radicals R4 and R7 independently of one another are hydrogen, halogen, Cl-C4alkyl, C1-C4alkoxy or unsubstituted phenyl, with the proviso that, of the five radicals from the group of the radicals R2, R3, R4, Rs, R6 and R7, which differ from the group Ia, at least two radicals are hydrogen and at least four radicals differ ~rom unsllbstituted phenyl; Y is an oxygen atom, a sulfur atom or a group Ib; R1 is hydrogen, Cl-C4alkyl, Cl-C4alkanoyl or unsubstituted phenylsulfonyl; R~ is hydrogen or Cl-C4alkyl; R9 is C1-C4alkyl, C3-C4cycloalkyl or halo~en; Rlo is Cl-C4alkyl, halogen or nitro; Rll, Rl2, Rl3, Rl4, Rls and Rl6 are in each case hydrogen; Rl7 is hydrogen or Cl-C4alkyl; m is O or 1; and n is O or 1;
in free form or in salt form.

Compounds which are prefelTed in a particular fashion within the scope of the invention -8- 2~7711~

are those of th~- formula I in which:
one of the radicals R2, R3 and R6 is a group Ia;
the other two of the radicals R2,R3 and R6 and the radicals R4,Rs and R7 independently of one another are hydrogen, halogen, Cl-C4alkyl or Cl-C4alkoxy, with the proviso that, of the five radicals from the group of the radicals R2, R3,R4,Rs, R6 and R7 which differ from the group Ia, at least three radicals are hydrogen; Y is an oxygen atom, a sul~ur atom or a group Ib; Rlis hydrogen or Cl-C4alkyl; R8 is hydrogen; Rg is Cl-C4alkyl; Rlo is halogen;
Rll and Rl6 in each case are hydrogen; Rl7is Cl-C4alkyl; and m and n in each case are 0;
in free form or in salt form.

Particularly preferred compounds of the formula I within the scope of the invention are those in which:
(a) R2 is a group Ia, R3is hydrogen or cl-c4alkyL R4is hydrogen, Rsis hydrogen, halogen or Cl-C4alkoxy, R6 and R7 in each case are hydrogen, with the proviso that, of the five radicals R3,R4, Rs, R6 and R7 at least four radicals are hydrogen, Y is an oxygen atom, a sulfur atom or a group I~ and Rlis hydrogen or Cl-C4alkyl; or (b) R2 is hydrogen, R3is a group Ia, R4,Rs,R6 and R7 in each case are hydrogen, Y is a group Ib and Rlis hydrogen or Cl-C4alkyl; or (c) R2 and R3 independently of one another are Cl-C4alkyl, R4 and Rs in each case are hydrogen, R6 is a group Ia, R7 is hy(1rogen, Y is an oxygen atom or a group Ib and Rl is hydrogen;
and in each case R8 is hydrogen; Rg is Cl-C4alkyl; Rlo is halogen; Rll and Rl6 in each case are hydrogen; Rl7 is Cl-C4alkyl; and m and n in each case are 0;
in free form or in salt forrn.

Very particularly preferred compounds of the formula I within the scope of the invention are those in which:
(d) R2 is a group Ia, R6 is hydrogen and either R3is hydrogen or Cl-C4alkyl, Rs is hydrogen and Y is a sulfur atom or R3is hydrogen, R~is halogen or Cl-C4alkoxy and Y is an oxygen atom; or (e) R2 and R3 independendy of one another are Cl-C4alkyl,Rsis hydrogen, R6 is a group Ia and Y is an oxygen atom; and in each case R4,R7 and R8 in each case are hydrogen; Rgis Cl-C4a~yl;RIOis halogen; Rll and Rl6 in each case are hydrogen; Rl7is cl-c4alkyl; and m and n in each case are O;
in *ee form or in salt fonn.

.. . .. . :

: - ' 9 ~77~

Especially preferred compounds of the formula I within the scope of the invention are those in which:
either R3 is C1-C4alkyl, R5 is hydrogen and Y is a sulfur atom or R3 is hydrogen, Rs is Cl-C4aLkoxy and Y is an oxygen atom; and in each case R2 is a group Ia; R4, R6, Pc7 and R8 in each case are hydrogen; Rg is Cl-C4alkyl; Rlo is halogen; Rll and Rl6 in each case are hydrogen; ~17 iS Cl-C4alkyl; and m and n in each case are 0;
in free form or in salt form.

Very especially preferred compounds of the formula I within the scope of the invention are those in which:
Y is a sulfur atorn; R~ is a group Ia; R3 is Cl-C4alkyl; R4, R5, R6, R7 and R8 in each case are hydrogen; R9 is Cl-C4alkyl; Rlo is halogen; Rll and Rl6 in each case are hydrogen;
Rl7 is Cl-C4alkyl; and m and n in each case are 0;
in free forrn or in salt forrn.

First and foremost preferred compounds within the scope of the invention are those of the formula I, mentioned in Examples H-1 to H-9.6, in free form or in salt form.

Individually preferred compounds within the scope of the invention are the following:
(d,1)-2-[ 1-(5-chloro-6-ethylpyrimidin-4-ylamino)ethyl]-3-methylbenzo[b]thiophene, (d,1)-2-~ 1 -(5-chloro-6-ethylpyrimidin-4-ylarnino)ethyl]-5-methoxybenzo[b]furan, (d,1)-2-[ 1 -(5-chloro-6-ethylpyrimidin-4-ylamino)ethyl]benzo[b]thiophene, (d,1)-2-[ 1 -(5-chloro-6-ethylpyrimidin-4-ylamino)propyl]benzo[b]thiophene, (-)-2-[1-(5-chloro-6-ethylpyrimidin-4-ylamino)propyl]benzo[b]thiophene, in each case in free forrn or in salt form.

As a further subject of the invention, the process for the preparation of the compounds of the formula I and, if appropriate, the tautomers thereof, in each case in free form or in salt forrn, comprises, for exarnple, a) to produce a compound of the forrnula I in which Rl1 is hydrogen, Cl-C8alkyl or benzyl, or, if appropriate, a tautomer thereof, in each case in free form or in salt form, reacting a compound of the formula . ' . , , ' ' 2~77~ ~ ~

~- Rg N~R10 ll ' (II), R8 ~N~Z

in which R8, Rg and Rlo are as defined in formula I and Z is an easily detachable nucleofugic radical, or, if appropriate, a tautomer thereof, with a compound of the forrnula Rz ~Rs (111), R7~

in which Y is as defined in fonnula I and, with a single exception, R2' is R2, R3' is R3, R~' isR4,Rs'isRs,R6'isR6andR7'isR7,whereR2,R3,R4,Rs,R6andR7areasdefinedin formula I, the abovementioned exception being that the group Ia, which is mentioned in the definitions of the variables R2, R3, R4, Rs, R6 and R7 of the formula I, is replaced by the group of the forrnula H(Rll~)N-[c(Rl2)(Rl3)lm-[c(Rl4)~Rls)]n-~(Rl6)(Rl7)- (IIIa) in which Rll' is hydrogen, Cl-C8alkyl or benzyl and Rl2, Rl3, Rl4, Rls, Rl6, Rl7, m and n are as defined in formula I, or with a salt thereof, preferably in the presence of a base, or b) to prepare a compound of the formula I in which Rll is as defined in forrnula I but differs from hydrogen, Cl-C8alkyl and benzyl, or, if appropriate, a tautomer thereof, in each case in free forrn or in salt fo~rn, introducing the desired substituent Rll, which differs from hydrogen, Cl-C8alkyl and benzyl, into a compound of the formula I in which Rll is hydrogen, or, if appropriate, into a tautomer thereof, in each case in free forrn or in salt form, by means of N-alkanoylation, N-benzoylation, N-alkylthiolation, N-phenylthiolation or N-benzylthiolation, and, in each case, if desir~d, converting a compound of the forrnula I or a tautomer thereof which can be obtained according to the process or by other means, in each case in free form or in salt forrn, into another compound of the~ formula I or a tautomer thereof, .

~

11 2~77~

separating an isomer mixture which can be obtained according to the process, andisolating the desired isomer andlor converting a free compound of the fonnula I or a tautomer thereof which can be obtained according to the process into a salt, or a salt which can be obtained according to the process, of a compound of the formula I or of a tautomer thereof, 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 I aMlies analogously to starting materials listed hereinbefore and hereinafter with regard to their tautomers or salts.

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

The starting material listed hereinbefore and hereinafter which is used for the preparation of the compounds I and, if appropriate, the tautomers thereof, in each case in free form or in salt form, is known or can be prepared by methods known per se, for example as described below.

Variant a):
Suitable examples of radicals Z are: fluorine, chlorine, bromine, iodine, C1-C8alkylthio such as methylthio, ethylthio or propylthio, C~l-C8alkanoyloxy such as acetoxy, (halo-)Cl-C8alkanesulfonyloxy such as methanesulfonyloxy, ethanesulfonyloxy or trifluoromethanesulfonyloxy, or substituted or unsubstituted phenylsulfonyloxy such as benzenesulfonyloxy or p-toluenesulfonyloxy, ~urthermore also hydroxyl.

Examples of suitable bases for ~acilitating the elimination of HZ are hydroxides, hydrides, amides, alkanolates, carbonates, dialkylamides or alkylsilylamides of alkali metals or aLkaline earth metals, alkylamines, alkylenediamines, free or N-alkylated saturated or 2~771~ 1 unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methanolate, sodium carbonate, po~assium tert-butanolate, potassium carbonate, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, trimethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, N-methylmorpholine, ben~yltrimethylammonium hydroxide, and 1,5-diaza-bicyclo[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, for example in the melt. Howe~er, in most cases it is advantageous to add an inert solvent or diluent or a mixture thereof. 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, dichloromethane, trichloromethane, dichloroethane or trichloroethene; ethers such as diethyl ether, tert-butyl me~hyl ether, tetrahydrofuran or dioxane; ketones such as acetone or methyl ethyl ketone; alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol or glycerol; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles such as acetonitlile; and sulfoxides such as dimethyl sulfoxide. Bases which are employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, can also be used as solvents or diluents.

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

In a prefelTed embodiment of variant a), a compound III is reacted with a compound II in which Z is halogen, preferably chlorine, at reflux temperature in an alcohol, preferably in isopropanol, and in the presence of a~ alkylamine, preferably in the presence oftriethylamine.

~he compounds II and, if appropriate, their tautomers, in each case in free form or in salt form, are known or can be prepared analogously to known compounds; information in this context can be found, for example, on the one hand in D.J. Brown, "The Pyrimidines", in "Heterocyclic Compounds" and, on the other hand, in Eu~opean Patent ~pplication 2077~

EP-A-0,470,60û.

The compounds III, in free form or in salt form, are known or can be prepared analogously to known compounds, for example as described below.

For example, ammonia or an amine of the formula H2NRll' (IIIb) can be reac~ed in the customary manner in the presence of a reducing agent with a compound of the formula IIIc, where the compounds IIIc are the compounds III, but have a group of the forrnula ~l2C(=O)-[C~Rl4)(Rl~)]n-C(Rl6)(Rl7~- (IIId), a group of the formula Rl3C(=O)-[C(Rl4)(Rls)]n-C(Rl6)(Rl7)- (IIIe), a group of the formula R~4C(=O)-C(RI6)(RI7)- (IIIf), a.group of the formula RlsC(=O)-C(R,6)(RI7)- (IIIg), a group of the formula Rl6C(=O)- (IIIh) or a group of the formula Rl7C(=O)- (IIIi) instead of the group IIIa in the compounds III. Examples of suitable reducing agents are hydrogen (in the presence of a hydrogenation catalyst), zinc/hydrochloric acid, sodium cyanoborohydride, sodium borohydride (in the presence or absence of titanium tetrachloride), iron pentacarbonyl/alcoholic potassium hydroxide or formic acid. In this way - by formally replacing the carbonyl function in the groups IIId, IIIe, IIIf, IIIg, IIIh or IIIi by a hydrogen atom and a group of the formula H(RI I ')N- (IIIj) - compounds III are obtained which have at least one hydrogen atom on the carbon atom to which the group (IIIj) is attached. A "combined compound" - which may have been prepared before - of the reducing agent and the compound IIIb, for example a corresponding ammonium formate or formarnide, can also be used for this reaction, and primary products having an N-formylated group IIIj, which may have been formed after the reaction of this "combined compoundl' with the compound IIIc, can subsequently be N-deformylated hydrolytically in the customary manner to give the desired compounds III.

Hydroxylamine can also be reacted with a compound IIIc in the customary manner, by which process the carbonyl function in the groups IIId, IIIe, IIIf, IIIg, IIIh or IIIi is converted into the (~O-N=) group, and this oxime can be reduced to give the corresponding amine, suitable reduciT~g agents being, for example, complex metalhydrides such as LiAlH4, NaBH4/TiCI4, zinc/acetic acid or hydrogen (in the presence of a hydrogenation catalyst, fM example in the presence of Raney nickel, in the presence or absence of ammonia, or palladium on charcoal). This gives compounds III which have at least one hydrogen atom on the carbon atom to which the group H(Rl,')N- (IIIj) is attached and where Rll' is hydrogen.

2~77~ 11 In compounds of the formula IIIk, which correspond to compounds III but have a group of the formula NC-~(Rl4)(RI5)]n-C(Rl6)(RI7)- (IIII), a group of the formula NC-C(Rl6)(Rl7)- (IIIm) or the cyano group instead of the group IIIa in the compounds III, it is furthermore possible to reduce the cyano group in the groups IIII and IlIm, or the cyano group which in the compounds IIIk replaces the group IIIa in the compounds III, in the customary manner to give the aminomethyl group, suitable reducing agents being, for example, complex metal hydrides such as LiAlH4, sodium ethanolate or hydrogen (in the presence of a hydrogenation catalyst, for exarnple in the presence of Raney nickel or palladium on charcoal). This gives compounds III which have two hydrogen atoms on the carbon atom to which the group H(Rll')N- (Illj) is attached and where Rll' is hydrogen.

In compounds of the forrnula IIIn which correspond to compounds III but have a group of the formula HN(R11')-C~=O)-[C(R14)(RIs)ln-C(Rl6)(Rl7)- (IIIo), a group of the formula HN(R11')-C(=O)-C(RI6)(Rl7)- (IIIp) or a group of the formula HN(Rll')-C(=O)- (ITIq) instead of the group IIIa in the c~mpounds III, it is furthermore possible also to reduce the amide group in the groups lIIo, IIIp and IIIq in the customary manner to give the group -CH2-NH(Rll') (IIIr), suitable reducing agents being, for example, complex metalhydrides such as LiAlH4. This gives compounds III which have two hydrogen atoms on the carbon atom to which the group H(RIl')N- (IIIj) is attached.

In nitroaL~cyl compounds of the forrnula IIIs, it is equally possible to reduce the nitroalkyl group in the customary manner to give the aminoaLkyl group, where the compounds IIIs correspond to the compounds III, but have a group of the formula 02N~[C(R12)(RI3)]m~[C(RI4)(RIs)]n~C(Rl6)(R17)~ (IIIt) instead of the group IlIa in the compounds III, suitable reducing agents being, for example, complex metal hydrides such as LiAl~ . This gives compounds III in which Rll' is hydrogen.

Compounds III in which R11' is hydrogen can be C1-C8alkylated or benzylated in the customary manner to give compounds III in which R11' is C1-C8alkyl or benzyl. In an exemplary procedure to this end, the compound III in which Rll~ is hydrogen is reacted, advantageously in the presence of a base, for example in the presence of one of the bases mentioned above, and in an inert solvent or diluent, for example of tlle type given above, with a compound of the formula Cl-C8alkyl-Z (IIIu) or with a compound of the forrnula benzyl-Z (IIIv), in which Z in each case has the abovementioned meaning.

The compounds IIIb, IIIc, IIIk, IIIn, IIIs, IIIu and IIIv are known or can be prepared 2~771~

analogously tO known compounds.

Variant b):
The N-alkanoylation, N-benzoylation, N-alkylthiolation, N-phenylthiolation or N-benzylthiolation of a compound I in which Rll is hydrogen or, if appropriate, a tautomer thereof, in each case in free form or in salt form, obtainable, for example, according to process variant a), is carried out in the customary manner, for example by reacting a compound I in which Rl is hydrogen or, if appropriate, a tautomer thereof, in each case in free form or in salt form, advantageously in the presence of a base, for example in the presence of one of the bases given under variant a), in an inert solvent or diluent, for example in an inert solvent or diluent of the type given under variant a), and in a temperature range of approximately -80C to approximately -7rl80C~ preferablyapproximately 0C to approximately +130C, in many cases at the reflux temperature of the solvent used, with a compound of the formula Cl-C8alkanoyl-Z (If), with a compound of the for nula phenylcarbonyl-Z (Ig) whose phenyl group is unsubstituted or substituted by one, two or three substituents selected from the group comprising halogen andCl-C4alkyl, with a compound of the formula Cl-C8alkylthio-Z (Ih), with a compound of the forrnula halo-CI-C8alkylthio-Z (Ii), with a compound of the formula cyano-Cl-C8alkylthio-Z (Ij), with a compound of the formula phenylthio-Z (Ik) or with a compound of the formula benzylthio-Z (Il), where the phenyl groups in phenylthio and benzylthio are unsubstituted or substituted by one or two substituents selecte~t from the group comprising halogen, Cl-C4alkyl, nitro and cyano.

In the cornpounds If, ~g, Ih, Ii, Ij, Ik and Il, Z in each case has the meaning given under variant a).

The compounds If, Ig, Ih, Ii, Ij, Ik and Il are known or can be prepared analogously to known compounds.

A compound I or, if appropriate, a tautomer thereof, obtainable according to the process or by other means, can be converted into a different compound I in a manner known per se by replacing one or more substituents of the starting compound I in the customary manner by another substituen~/other substituents according to the invention.

For example:
- non-halogen-containing substituents, or unhalogenated aromatic ring part-structures, can . . ' ' : ' . ' ,. :
.~ :

~7~ ~

be halogenated to give halogen-containing substituents, or halogenated aromatic ring part-structures, according to the invention;
- non-cyano-containing substituents, or non-cyano-substituted aromatic ring part-structures, can be converted into cyano-containing substituents, or cyano-substituted aromatic ring part-structures, according to the invention;
- non-nitrated aromatic ring part-structures can be nitrated to give nitrated aromatic ring part-struc~ures according to the invention;
- non-~alkoxy-, alkylthio-, alkanesulfinyl-, alkanesulfonyl- or halo-)alkylated aromatic ring part-structures can be (alkoxy-, alkylthio-, alkanesulfinyl-, alkanesulfonyl- or halo-)alkylated to give (alkoxy-, alkylthio-, alkanesulfinyl-, alkanesulfonyl- or halo-)alkylated aromatic ring part-structures according to the invention;
- non-alkoxylated substituents, or non-alkoxylated aromatic ring part-structures, can be alkoxylated to give alkoxylated substituents, or alkoxylated aromatic ring part-structures, according to the Invention;
- non-alkylthiolated substituents, or non-alkylthiolated aromatic ring part-structures, can be alkylthiolated to give alkylthiolated substituents, or alkylthiolated arornatic ring part-structures, according to the invention;
- alkylthio-substituents can be oxidised to give alkylsulfinyl or alkylsulfonyl substituents;
- alkylsulfinyl substituents can be oxidised to give alkylsulfonyl substituents;- non-phenylated aromatic ring part-structures can be phenylated to give phenylated aromatic ring part-structures according to the inventis~n, where the phenyl substituent to be introduced is unsubstituted or substituted as defined in the corresponding variables of the compounds I;
- non-phenoxylated aromatic ring part-structures can be phenoxylated to give phenoxylated aromatic ring part-structures according to the invention, where the phenyl ring of the phenoxy substituent to be introduced is unsubstituted or substituted as defined in the corresponding variables of the compounds I;
- non-phenylthiolated substituents, or non-phenylthiolated aromatic ring part-stlllctures, can be phenylthiolated to give phenylthiolated substituents, or phenylthiolated aromatic ring part-structures, according to the invention, where the phenyl ring of the phenylthio substituent to be introduced is unsubstituted or substituted as defined in the corresponding variables of the compounds I;
- non-alkanoylated substituents, or non-alkanoylated aromatic ring part-structures, can be alkanoylated to give alkanoylated substituents, or alkanoylated aromatic ring part-structures according to the invention;
- non-alkanesulfinylated aromatic ring part-structures can be alkanesul~lnylated to give .
.
.
.

2~77~1 alkanesulfinylated aromatic ring part-structures according to the invention;
- non-alkanesulfonylated aromatic ring part-structures can be alkanesulfonylated to give alkanesulfonylated aromatic ring part-structures according to the invention;
- non-phenylsulfonylated aromatic ring part-structures can be phenylsulfonylated to give phenylsulfonylated arornatic ring part-structures according to the invention, where the phenyl ring of thç phenylsulfonyl substituent to be introduced is unsubstituted or substituted as defined in the corresponding variables of the compounds I;
- non-cycloalkylated substituents or non-cycloalkylated aromatic ring part-structures can be cycloalkylated to give cycloalkylated substituents or cycloalkylated aromatic ring part-structures according to the invention;
- non-alkenylated aromatic ring part-structures can be alkenylated to give alkenylated aromatic ring part-structures according to the invention;
- non-alkynylated aromatic ring part-structures can be alkynylated to give alkynylated aromatic ring part-structures according to the invention;
- non-hydroxylated aromatic ring part-structures can be hydroxylated to give hydroxylated aromatic ring part-structures according to the invention;
- non-amino-substituted aromatic ring part-structures can be amino-substituted to give amino-substituted arornatic ring part-structures according to the invention, where amino in "amino-substituted" is amino, a group Ic, a group Id or a group Ie;
- non-alkylated substituents can be alkylated to give alkylated substituents according to the invention;
- non-benzylated substituents can be benzylated to give benzylated substituents according to the invention;
- non-phenylcarbonylated substituents can be phenylcarbonylated to give phenylcarbonylated substituents according to the invention, where the phenyl ring of the phenylcarbonyl substituent to be introduced is unsubstituted or substituted as defined in the corresponding variables of the compounds I;
- non-benzylthiolated substituents can be benzylthiolated to give benzylthiolated substituents according to the invention, where the phenyl ring of the benzylthio substituent to be introduced is unsubstituted or substituted as deflned in the corresponding variables of the compounds I;
- non-haloalkylthiolated substituents, or non-haloalkylthiolated aromatic ring part-structures, are haloalkylthiolated to give haloalkylthiolated substituents, or haloalkylthiolated aromatic ring part-structures, according to the invention;
- non-haloalkoxylated aromatic ring part-structures are haloalkoxylated to give :
haloalkoxylated aromatic ring part-structures according to the invention;

.
: .
- . ., 2~

- non-(halo- or cyano)alkanesulfonylated aromatic ring part-structures are (halo- or cyano)alkanesulfonylated to give (halo- or cyano)alkanesulfonylated aromatic ring part-structures according to the invention;
- non-haloalkenylated aromatic ring part-stmctures are haioalkenylated to give haloalkenylated aromatic ring part-structures according to the invention;
- non-cyanoalkylthiolated substituents are cyanoalkylthiolated to give cyanoalkylthiolated substituents according to the invention;
- non-(alkoxy- or halo)alkylated substituents are (alkoxy- or halo)alkylated to give (alkoxy- or halo)alkylated substituents according to the invention;
- halogen substituents in halogenated aromatic ring part-structures can be replaced by alkylthio, alkoxy, cyano, phenoxy or phenylthio substituents according to the invention, where the phenyl ring of the phenoxy or phenylthio substituent to be introduced is unsubstituted or substituted as defined in the corresponding variables of the compounds I.

In this context it is possible, depending on the reaction conditions and starting materials which are suitable in each case, to replace only one substituent by another substituent according to the invention per reaction step, or several substituents can be replaced by other substituents according to the invention in the same reaction step. For example, two or more identical halogen substituents can be introduced simultaneously into the same, or, if present, into different substituents and/or rings. Equally, a substituent or ling - within the scope of the definitions of the variables according to the invention - which is already substituted, for example monosubstituted, by a certain substituent, for example chlorine, can be additionally substituted, for example chlorinated, by one or more further identical substituents, i.e. for example converted into the disubstituted, for example dichlorinated, or into an even higher substituted, for example higher chlorinated, state.

Salts of compounds I can be prepared in a manner known per se. For example, acidaddition salts of compounds I are obtained, for example, by treatment with a suitable acid or a suitable ion exchanger reagent, and salts with bases are obtained by treatment with a suitable base or a suitable ion exchanger reagent.

Salts of compounds I can be converted into the free compounds I in a customary manner, for example acid addition salts by treatment with a suitable basic agent or a suitable ion exchanger reagent, and saits with bases, for example by treatment with a suitable acid or a suitable ion exchanger reagent.

2~77~

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

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

The compounds I and, if appropAate, the tautomers thereof, in each case in free forrn or in salt fonn, can exist in some cases in the form of one of the isomers which are possible or in the form of an isomer mixture, for example depending on the number and the absoll~te and relative con~lguration of the asymmetric carbon atoms in the form of pure isomers such as antipodes and/or diastereomers, or in the form of isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures;
the invention relates to the pure isomers and to all isomer mixtures which are possible and is in each case hereinbefore and hereinafter tO be understood analogously, even when stereochemical details are not mentioned specifically in each case.

Diastereomer mixtures and racemate mixtures of compounds I and, if appropriate, 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 substances and procedures -or by other means can be resolved into the pure diastereomers or racemates in a known manner on the basis of the physicochemical differences of the components, for example by fractional crystallisation, distillation and/or chromatography.

Enantiomer mixtures which can be obtained analogously, such as racemates, can beresolved by known methods into the optical antipodes, for example by recrystallisation from an optically active solvent, by chromatography on chiral adsorbants, for example high-pressure liquid chromatography ~HPLC) on acetylcellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilised enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is sequestered, or by conversion into diastereomeric salts, for example by reaction of a basic end substance racemate with an optically active acid such as carboxyl;c acid, for example camphoric acid, tartaric acid or malic acid, or sulfonic acid, ~or example .

camphorsulfonic acid, and resolution of the diastereomer mixture obtained in this way, for example on the basis of their different solubilities by fractional crystallisation, to give the diastereomers, and the desired enantiomer can be set free from the diastereomers by the action of suitable, for example basic, agents.

Another method for obtaining pure diastereomers or enantiomers according to the invention is, apart from the resolution of suitable isomer mixtures, by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying Ollt the process according to the invention with educts which are suitable from the stereochemical point of view.

It is possible that the biological activity of diastereomers and of enantiomers, respectively, differs. In this case, it is advantageous to isolate, or synthesise, in each case the biologically more active isomer, for example enantiomer or diastereomer.

The compounds I and, if appropriate, the tautomers thereof, in each case in free form or in salt form, can also be obtained in the form of their hydrates and/or can include other solvents, for example those which may be used for the crystallisation of compounds in solid forrn.

The invention relates to all those embodiments of the process in which the starting compound is a compound which can be obtained in any stage of the process as starting material or intermediate, and in which all or some of the missing steps are carlied out or a starting material is used in the form of a derivative or salt and/or a racemate or antipode thereof, or, in particular, formed under the reaction conditions.

The process of the present invention uses preferably those starting materials and intermediates, in each case in free form or in salt form, which lead to the compounds I or salts thereof which have been described at the outset as being particularly valuable.

In particul~r, the invention relates to the preparation processes descri~ed in Examples H-l to H-1~.16.

Another object of the invention is novel starting materials and intermediates, in each case in free form or in salt form, which are used according to the invention for the preparation of the compounds I or salts thereof, and the use and processes for the preparation of these -21- %~711~
starting materials and intermediates.
Preferred intermediates are those of the formula IV

R17 ~ R IV

in which R3, R4, Rs, R6 and R7 independently of one another are hydrogen, halogen, Cl-C8allcyl, halo-CI-C8alkyl, Cl-C4alkoxy-CI-C4alkyl, Cl-C8alkoxy, halo-CI-C8alkoxy, Cl-C8alkylthio, halo-CI-C8alkylthio, cyano, nitro, phenyl, phenoxy or phenylthio~ where the phenyl groups in phenyl, phenoxy and phenylthio are unsubstituted or substituted by one, two or three substituents selected from the ~oup comprising halogen, Cl-C4alkyl and Cl-C4alkoxy, with the proviso that, of the five radicals R3, R4, Rs, R6 and R7 at least two radicals are hydrogen and at least four radicals differ from phenyl which is unsubstituted or substituted as mentioned above, from phenoxy which is unsubstituted or substituted as mentioned above, and from phenylthio which is unsubstituted or substituted as mentioned above; and Rl7 is ethyl;
in free forrn or in salt forrn.

From amongst these, particularly p~eferred compounds are those in which R3, R4, Rs7 R6 and R7 independently of one another are hydrogen, methyl, ethyl, methoxy or chlo~ine;
in free form or in salt form.

The following are prefelTed specifically:
(d,1)-2-(1-aminopropyl)-benzo[b]thiophene;
(-)-2-(1-aminopropyl)-benzo~b]thiophene, in free form or in salt form.

Pyrimidines which are amino-substituted in the 4-position have already been disclosed, for example in the European Paten~ Application under the publication number 0 126 254. The compounds I of the present invention differ from these lcnown compounds characteristically by the fact that in the fonner the amino group in the 4-position of the 20771 ~1 . .
pyrimidine ring is substituted by a benzo[b]furylalkyl, benzo[b]thienylalkyl or indolylalkyl radical; moreover, the compounds I of the present invention have anunexpectedly powerful microbicidal and acaricidal activity.

The compounds I and, if appropriate, their tautomers, in each case in free form or in solid form, of the present invention are oils, resins or solids which are stable at room temperature. They can be used in the agricultural sector and related fields preventively and/or curatively as active ingredients in the control of plant-injurious microorganisms and of pests of the order of the Acarina. Even when used at low concentrations, the acti~/e ingredients of the fonnula I according to the invention are distinguished not only by being very effectiYe but also by being ~,vell tolerated by plants.

The active ingredients of the formula I have a biocidal spectrum for controlling pests from the order of the Acarina and phytopathogenic microorganisms, in particular fungi, which is highly favourable for practical requirements. They have very advantageous, in particular systemic, properties and can be used for the protection of a large number of crop plants.
The active ingredients of the formula I can be used for inhibiting, or destroying the pests which occur on plants or parts of plants (fruits, flowers, foliage, stalks, tubers, roots) of various crops of useful plants, and the protection, for example against phytopathogenic microorganisms, also extends to parts of the plants which form at a later point in time.

Compounds I are active for example against the phytopathogenic fungi belonging to the following classes: Fungi imperfecti (for example Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (for example Rhizoctonia, Hemileia, Puccinia). Moreover, they act against the classes of the Ascomycetes (for example Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes (for example Phytophthora, Pythium, Plasmopara).

Furthermore, the compounds I can be used as seed-dressing agents for treating seed (fruits, tubers, grains) and plant cuttings as a protection against fungal infections and against soil-borne phytopathogenic fungi.
~, Moreover, the compounds I according to the invention are valuable active ingredients in the control of pests from the order of the Acarina on useful plants and ornamentals in agriculture, in particular in cotton plantations, vegetable fields and orchards, in ~orests, in the protection of stored goods and materials, and in the hygiene field, in particular on , 2~771~1 domestic animals and productive livestock. They a~e active against various stages of development. Their action can become apparent by immediately destroying the pests or only after some time has elapsed, for example during moulting, or in markedly reduced oviposition and/or hatching rate. The order of the Acarina includes, for example, Boophilus spp. and Tetranychus spp.; this enumeration is not by way of limitation.

The invention also relates to the compositions which comprise compounds I as active ingredient, in particular crop-protecting compositions, and to their use in the agricultural sector and in related fields. Moreover, the invention also includes the preparation of these compositions, which comprises intimately mixing the active substance with one or more of the substances or substance groups described below. A process for the treatment of plants, which comprises applying the novel compounds I or the novel compositions, is also part of the invention.

Examples of plant species which are target crops for crop-protective use within the scope of the invention are the following: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomaceous fruit, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); pulses (beans, lentils, peas, soya beans); oil crops (oilseed rape, mustard, poppy, olives, sunflowers, coconut, castor-oil plant, cocoa, groundnuts), cucurbits (pumpkin, cucumbers, melons); flbre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, tangerines); vegetables (spinach, lettuce, asparagus, cabbage species, carrots, onions, tomatoes, potatoes, bell peppers); Lauraceae (avocado, cinna~lon, camphor) and plants such as tobacco, nuts, coffee, egg plants, sugar cane, tea, pepper, vines, hops, Musaceae and latex plants, and ornamentals, and lawns.

Active ingredients I are customarily used in the form of compositions and can be applied to the area of plant to be treated simultaneously or in succession with other active ingredients. These other active ingredients can be, for example, fertilisers, trace element promoters or other preparations which have an effect on the growth of plants. However, other substances which can be used are selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of a plurality of these preparations, if desired with other carriers customarily used in the art of forrnulation, surfactants or other application-enhancing additives, without the activity of the compounds of the formula I being reduced thereby.

- .. : . ~

-24- 2~77111 Suitable carriers and additives can be solid or liquid and are those substances which are expedient in the art of formulation, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilisers.

A preferred process for applying an active ingredient of the formula I, or an agrochemical composition comprising at least one of these active ingredients, is applying it to the plant foliage (foliar application). The frequency of application and the dosage rate are a ~unction of the severity of attack by the pathogen in question. Alternatively, the actiYe ingredients I
can reach the plant via the soil through the root system (systemic action), by drenching the locus of the plant with a liquid preparation or incorporating the substances into the soil in solid form, for example in the form of granules (soil application). In the case of crops of paddy rice, such granules can be metered into the 1ooded rice field. Alternatively, the compounds of the formula I can be applied to seeds (coating) either by soaking the grains in a liquid preparation of the active ingredient or by coating them with a solid preparation.

The compounds I are employed as pure active ingredients or, preferably, together with the auxiliaries conventionally used in the art of formulation. To this end, they are expediently processed in a known manner, for example to give emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts or granules, for example by encapsulation in, for example, polymeric substances. The application methods such as spraying, atomising, dusting, scattering, painting on or pouring, as well as the nature of the compositions are selected to suit the intended aims and the prevailing circumstances.

Advantageous application rates are generally 5 g to 2 kg of active substance (AS) per hectare (ha), preferably 10 g to 1 kg of AS/ha, in particular 20 g to 600 g of AS/ha; or, in the case of seed treatment, 10 mg to 1 g of AS per kg of seed.

The forrnulations, i.e. the compositions, preparations or combinations comprising the active ingredient of the formula I and, if desired, a solid or liquid additive, are prepared in a known manner, for example by intimately mixing and/or grinding the active ingredien~
with extenders such as solvents, solid carriers and, if appropriate~ surface-active compounds (surfactants).

The following are suitable as solvents: aromatic hydrocarbons, preferably the fractions C8 to Cl2, such as xylene mixtures or substituted naphthalenes, phthalic esters such as dibutyl . - , ~

20771~

phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, 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 sach as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylforrnamide, and epoxidised or unepoxidised vegetable oils, such as epoxidised coconut oil or soya oil, and water.

~olid carriers which are generally used, for example for dusts and dispersible powders, are ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly disperse silica or highly disperse absorbent polymers. Possible particulate, carriers for granules are porous types such as pumice, brick grit, sepiolite or bentonite, and possible non-sorptive carrier materials are, for example, calcite or sand. Moreover, a large number of pregranulated materials of inorganic nature such as dolomite or comminuted plant residues can be used.

Suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties, depending on the nature of the active ingredient of the forrnula I to be forrnulated. Surfactants are also to be understood as meaning mixtures of surfactants.

Suitable anionic surfactants can be either so-called water-soluble soaps or water-soluble synthetic surface-active compounds.

Examples of non-ionic surfactants which may be mentioned are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethyleneethanol, polyethylene glycol and octylphenoxypolyethoxyethanol .

Other suitable substances are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are mainly quaternary ammonium salts which contain, as N-substituellt, at least one alkyl radical having 8 to 22 C atoms and as further substituent lower, free or halogenated alkyl, benzyl or lower hydroxyalkyl radicals.

Other surfactants conventionally used in the art of formulation are those known to those ' ~';
.. . . . .-. , ~, . .
:

-~6- 2~77~

skilled in the art or can be found in the relevant specialist literature.

As a rule, the agrochemical preparations comprise 0.1 to 99 percent by weight, in particular 0.1 to 9S percent by weight, of active ingredient of the formula I, 99.9 to 1 percent by weight, in particular 99.8 to S percent by weight, of a solid or liquid additive and 0 to 25 percent by weight, in particular 0.1 to 25 percent by weight, of a surfactant.

While concentrated compositions are more preferred as commercial goods, the end consumer generally uses dilute compositions.

The compositions can also comprise further additives such as stabilisers, defoamers, viscosity regulators, binders or adhesives, as well as fertilisers or other active ingredients for achieving specific effects.

The examples which follow illustrate the invention described above without imposing any limitation to the scope of the latter. Temperatures are given in degrees centigrade. The following abbreviations are used: Ac = acetyl; d = doublet; dd = doubleted doublet; Et =
ethyl; m = multiplet; Me = methyl; Ph = phenyl; c-Pr = cyclopropyl; Pr = n-propyl; q =
quartet; s = singlet; t = triplet; m.p. = melting point. In Examples F-1. 1 to F-6.3, the term "%" represents "percent by weight", ditto when concentrations of solutions are given in Examples B-1.1 to B-11, unless the concentrations in question are not given in a different unit. The term "active ingredient according to the invention" in Examples F-1.1 to F-6.3 and B-1.1 to B-11 is to be understood in each case as meaning a compound I or, if appropriate, a tautomer thereof, in each case in the free form or in the forrn of an agrochemically utilisable salt, in particular such a compound, if appropriate in tautomeric form, which i3 described as product in Examples H-1 to H-~.6.

Examples H-1 to H-18: Preparation of compounds accordin~ to the invention Example H-1: In a sulfurising flask, a mixture of 1.86 g of ~,5-dichloro-6-ethylpyrimidine, 1.80 g of 2-(1-aminoethyl)-1-methylindole, 1.21 g of triethylamine and 25 g of absolute isopropanol is heated to reflux, stirred for 12 hours at an internal temperature of 80 to 82, and then freed from the solvent under a water pump vacuum. The residue is taken up in a mixture of 250 ml of ethyl acetate and 80 ml of water, the organic phase is extracted twice using water, and the extract is dried over sodium sulfate and evaporated. The residue is purified by means of flash chromatography on silica gel using ethyl acetate/hexane (1:3) ,,, ' -27- 2~77~ ~

as mobile phase. This gives 2-[1-(5-chloro-6-ethylpyrimidin-4-ylamino)ethyl]-1-methyl indole, which melts at 129 to 131.

Example H-2: Other compounds of the general formula I. 1 which can be prepared analogously to the procedure given in Example H- 1 or by means of another appropriate procedure selected from those indicated hereinbefore are those listed in Table 1 below.

.

.. . .
' '~-.'" , , ~

20771~

Tablel:
Rg R4 Rs l~ N r~ ¦ a. l ~

Ex.R3 R4 Rs R6 R7 Rs E~s Rlo Rl7 Y Physical data . , _ .

H-2.1 H H H H H H Me Cl Me N(Me) H-2.2 H H H H H H Et Br Me N(Me) H-2.3 H H H H H H Me Br Me N(Me) H-2.4 H H H H H H Cl Et Me N(Me) H-2.5 Me H H H H H Et Cl Me N(H) m.p.117-119C
H-2.6 Me H H H H H Me Cl Me N(H) H-2.7 Me H H H H H Et Cl Me N(Ac) H-2.8 Me H H H H H Me Cl Me N(Ac) H-2.9 Me H H H H H Et Cl Me N(Me) H-2.10 Me H H H H H Me Cl Me N(Me) H-2.11 Me H H H H H Et Br Me N(Me) H-2.12 H H H H H H F Et Me N(Me) H-2.13 H H H H H H Et Cl Me S m.p.82-83C
H-2.14 H H H H H Me Et C1 Me S
H-2.15 H H H H H H Et Cl Et S oil, lHNMR
H-2.16 H H H H H H Et Br Me S
H-2.17 H H H H H H Et NO2 Me S
H-2.18 Me H H H H H Et Cl Me S m.p.50-51C
H-2.19 Me H H H H H Et Cl Et S m.p.77-78C
H-2.20 H H Cl H H H Et Cl Me S
H-2.21 H H Cl H H H Me Cl Me S
H-2.22 H H H H H H Et Cl Me O
H-2.23 H H H H H H Me Cl Et O
H-2.24 H H H H H H Et Br Me O

;.
-' . . ~ , , ~
~ ' ., - `

2~77~

Ex. R3 R4 Rs R6 R7 R~ Rg R1o Rl7 Y Physical - data _ H~2.25 H H Cl H H H Me Cl Me O
H-2.26 H H Cl H H H Et Cl Me O m.p. 135-136C
~I-2.27 H H Cl H H H Et Cl Et O m.p. 67-69C
H-2.28 H H Cl H H H c-Pr Cl Me O
H-2.29 H H OMe H H H Et Cl Me O m.p. 67-68C
H-2.30 - H H OMe H H H Et Cl Et O m.p. 99-101C
H-2.31 H H OMe H H H Me NO2 Me O
H-2.32 H H OMe H H H Me I Me O
H-2.33 H H H H OMe H Et Cl Me O m.p. 105-1û6C
H-2.34 H H H H OMe H Et Br Me O
H-2.35 H H H H OMe H Me Br Me O
H-2.36 H H H H OMe H Br Et Et O
H-2.37 H H H OMe H H Et Cl Me O m.p. 106-107C
H-2.38 H H H OMe H H Et Cl Et O
H-2.39 H OMe H OMe H H Et Cl Me O m.p. 87-88C
H-2.40 H OMe H OMe H H Et Cl Et O
H-2.41 H OMe H OMe H H Me Cl Me O
H-2.42 H OMe H OMe H H Et F Et O
H-2.43 Me H H H H H Et Cl Me O m.p.91-92C
H-2.44 Me H H H H H Et Cl Et O
H-2.45 Me H H H H H Me Cl Me O
H-2.46 Et H H H H H Et Cl Me O
H-2.47 Et H H H H H Et Cl Et O
H-2.48 Me H Cl H H H Et Cl Me O
H-2.4g Me H Cl H H H Et Cl Et O
H-2.50 Me H Cl H H H Me Cl Me O
H-2.51 Me H Cl H H H Me Br Me O
H-2.52 Me H Cl H H H Et N 2 Me O
H-2.53 Me H OMe H H H Et Cl Me O
H-2.54 Me H OMe H H H Et Cl Et O
H-2.55 Me H OMe H H H Me Cl Me O
H-2.56 Me H OMe H H H Et Br Me O
' , . . , . , ~,: .
- ` : ., ~, j . ~ . ~ '' .
.. . . . .
: - . , .

-30- 2~177 ~ ~

Ex. R3 R4 Rs R6 R7 Rg Rg Rlo R17 Y Physical : data H-2.57 Me H OMe H H Me Cl Me Me O
H-2.58 Me H OMe H H Me Cl Et Me O
H-2.59 H H Cl H H H Et Cl Et S
H-2.60 H H Cl H H H Me Cl Et S
H-2.61 Me H H H H H Et Br Et S m.p. 62-63C
H-2.62 - Me H Cl H H H Et Cl Et S oil,1H NMR
H-2.63 Me H Cl H H H Et Cl Me S m.p. 91-92C
H-2.64 H H H H H H Et Br Et S
H-2.65 H H H H H H Et C1 Et NH
H-2.66 H H H H H H Et Br Et NH
H-2.67 H H H H H H Me Cl Et NH
H-2.68 H H H H H H Et Cl Me NH
H-2.69 H H H H H H Me Cl Me NH
H-2.70 H H H H H H Et Br Me S
H-2.71 H H H H H H Me Cl F.t S
H-2.72 H H H H H H Me Br Et S
H-2.73 H H H H H H Et Cl Me N-CH2Ph H-2.74 H H H H H H Et Cl Et N-CH2Ph H-2.75 H H H H H H Me Cl Me N-CH2Ph H-2.76 H H H H H H Me Cl Et N-CH2Ph . _ Example H-3.1: Other compounds of the general formula I.2 which can be prepared analogously to the procedure described in Example H-1 or by means of another appropriate procedure selected from those indicated hereinbefore are those listed in Table 2 below.

- . . . ~ .

~ ` `' '' ` ' ~
.

-31- 20771:L~

Table 2:
~9 H~ R6 Ex. R2 Rs R6 R9Rlo Rl7 Y Physical data ~-. . _ H-3.1 H H H Et C1 Me N(H) m.p.: 162-164 H-3.2 H H H Et Cl Et N(H) H-3.3 H H H Me Br Me N(H) H-3.4 H H H Me Cl Me N(H) H-3.~ H H H Et Cl Me N(Ac) H-3.6 H H H Et Cl Et N(Ac) H-3.7 H H H Me Cl Me N(Ac) H-3.8 H H H Et Cl Me N(SO2Ph) H~3.9 H H H Me C1 Me N(SO2Ph) H-3.10 Me H H Et Cl Me N(Me) ~ .
H-3.11 Me H H Et Cl Et N(Me) H-3.12 Me H H Me C1 Me N(Me) H-3.13 H H H Et Cl Me N(Me) refractive index:
: ~ ~ nD50 = 1.6û22 H-3.14 H H H ~ Me Cl Me N(Me) H-3.15 H H H Me Br Me N(Me) H-3.16 H H H Cl Et Me N(Me) H-3.17 H H H Et Cl Me S m.p. 138-140(;
H-3.18 H H H Et Cl Et S
H-3.19 H H H Me C1 Me S
:~ : : ~ :
H-3.20 ~ Me H H Et ~1 Me S
H-3.21 Me H H Et Cl Et S
H-3.22 Me H H Me Cl Me S
H-3.23 ~Me H H Me Br Me S
I-3,24 ~ Me H H ~ Pr Cl Me S
:
::

, `.: :' ` `'` `,: ~ ' ~

2~77~

Ex. R2 R5 R6 Rg Rlo Rl7 Y Physic~ data H-3.25 Ph H H Et Cl Me S
H-3.26 Ph H H Et Cl Et S
H-3.27 Me Cl H Et Cl Me S
H-3.28 Me Cl H Et Cl Et S
H-3.29 Me Cl H Me Cl Me S
H-3.30 Me Cl H Me Br Et S
H-3.31 H H H Et Cl Me O
H-3.32 H H H Et Cl Et O
H-3.33 H H H Me Cl Me O
H-3.34 H H H Me Br Me O
H-3.35 H H H Cl Et Et O
H-3.36 Me H H Et Cl Me O
H-3.37 Me H H Et Cl Et O
H-3.38 Me H H Me Cl Me O
H-3.39 Me H H Et Br Et O
H-3.40 Ph H H Et Cl Me O
H-3.41 Ph H H Et Cl Et O
H-3.42 Me Cl H Et Cl Me O
H-3.43 Me Cl H Et Cl Et O
H-3.44 Me Cl H Me Br Me O
H-3.45 Me Cl H Me I Et O
H-3.46 Me Cl H Pr Cl Me O
H-3.47 Me OMe H Et Cl Me O
H-3.48 Me OMe H Et Cl Et O
H-3.49 Me OMe H Me Cl Me O
H-3.50 Me OMe H Me Br Me O
H-3.51 Me H F Et Cl Me O
H-3.52 Me H F Et Cl Et O
H-3.53 Me H F Me Cl Me O
H-3.54 Me H F Me Br Me O
H-3.55 Me H F c-Pr Cl Me O

2~77~

Examples H-4: Other compounds of the general fonnula I.3 which can be prepared analogously to the procedure described in Example H-l or by means of another appropnate procedure selected from those indicated hereinbefore are those listed in Table 3 below.

Table 3:
Rg R

~\N~ R2 (1.3) Example R2 R3 R~ Rg Rlo Rl7 Y Physical data H-4.1 H H Me Et Cl Me S
H-4.2 H H Me Et Cl Et S
H-4.3 H H Me Me Cl Me S
H-4.4 H H H Et Cl Me O
H-4.5 H H H Et Cl Et O
H-4.6 H H H Me Br Me O
H-4.7 Me Me Me Et Cl Me O
H-4.8 Me Me Me Et Cl Et O
H-4.9 Me Me Me Me Cl Me O
H-4.10 Me Me Me Me Br Me O
H-4. 11 H H H Et Cl Me N(H) H-4.12 H H H Et Cl Et N(H) H-4.13 H H H Et Cl Me N(Ac) H-4.14 H H H Et Cl Et N(Ac) H-4.15 Ph H Me Et Cl Me O
H-4.16 Ph H Me Et Cl Et O
H-4.17 Ph H Me Me Cl Me O
H-4.18 Ph H Me Me Br Me O
H-4.19 Me Me Me Et Cl Me N(H) H-4.2Q Me Me Me Et Cl Et N(~I) ' ' - : .
: : .

- 34 - ~177 ~1~

ExampleR2 R3 R6 Rg Rlo Rl7 Y Physical data _ H-4.21 Me Me Me Me C1 Me N(H) H-4.22 Me Me Me Me Br Me N(H) H-4.23 Me Me Me Et Cl Me N~Ac) H-4.24 Me-Me Me Et Cl Et N(Ac) H-4.25 Me Me Me Me Cl Me N(Ac) H-4.26 Me Me Me Me Br Me N(Ac) Examples H-S: Other compounds of the general formula I.4 which can be prepared analogously tothe procedure described in Example H-1 or by means of another appropriate procedure selected from those indicated hereinbefore are those listed in Table 4 below.

- . : : : :

.

-35 2077~1~

Table 4: ~-Rg ~N~V~R32 (1.4) Example R2 R3 Rs R7 Rg Rlo Rl7 Y Physical data H-S.l H H H H Et Cl Me S
H-5.2 H H H H Et Cl Et S
H-5.3 H H H H Me Br Mc S
H-5.4 H H H H Me Cl Me S
H-S.5 H H H H Cl Et Me S
H-5.6 Me Me H H Et Cl Me O m.p.: 79-80 H-5.7 Me Me H H Et Cl Et O oil; lH NMR
H-5.8 Me Me H H Me Cl Me O
H-5.9 Me Me H H Me Br Me O
H-S.10 H H H Me Et Cl Me O
H-5.11 H H H Me Et Cl Et O
H-5.12 H H H Me Me Cl Me O
H-S.13 H H H Br Et Cl Me O
H-5. 14 H H H Br Et Cl Et O
H-S.lS H H H Br Me Br Me O
H-5.16 H H H Br Pr Cl Me O
H-5.17 H H Me H Et Cl Me O
H-5.18 H H Me H Et Cl Et O
H-S.l9 H H Me H Me Cl Me O
H-5.20 H H Me H Me Br Me O
H-5.21 H H Me H Me ~ Me O
H-5.22 Me Me H H Et Cl Me N(H) m.p.: 128-130 H-5.23 Me Me H H Et 1 Et N(H) H-5.24 Me Me H H Me Cl Me N(H) H-5.25 Me Me H H Me Br Me N(H) ~ ~;

.. , ~ . .

Example R2 R3 Rs R7 Rg Rlo R17 Y Physical data H-5.26 Me Me H H Et C1 Me N(Ac) H-5.27 Me Me H H Et Cl Et N(Ac) H-5.28 Me Me H H Me Cl Me N(Ac) H-5.29 Me Me H H Me Br Me N(Ac) H-5.30 Me Me H H Et Cl Me N(Me) H-5.31 Me Me H H Et Cl Et N(Me) H-5.32 Me Me H H Me Cl Me N(Me~
H-5.33 Me Me H H Me Br Me N(Me) H-5.34 Me Me H H Et Cl Me S m.p. 110-111C

.

Examples H-6. Other compounds of the general formula I.S which can be prepared analogously to the procedure described in Example H-1 or by means of another appropriate procedure selected from those indicated hereinbefore are those listed in Table S below.

Table 5:

~C~ ~ (1.5) H

Example R3 Y Physical data H-6.1 H S
H-6.2 H O
H-6.3 H N(H~
H-6.4 Me N~Me) - . -- ; ~ , ) , . . -.

2077~ ~ ~

Examples H-7: Other cornpounds of the general formula I.6 which can be prepared analogously to the procedure described in Example H-1 or by means of anoeher appropriate procedure selected from those indicated hereinbefore are those listed in Table 6 below.

Table 6:

~N I ~ (1.6) _ _ Example R17 Y Physical data H-7~1 H S
H-7.2 H O
H-7.3 H N(Me) H-7.4 Me S
H-7.5 Me O
H-7.6 Me N(Me) H-7.7 Me NH
. .

- ,, .

:.
' ~ : ' : ' 2~771~

Examples H-8: Other compounds of the general formula L7 which can be prepared analogously to the procedure desclibed in Example H- 1 or by means of another appropriate procedure selected from those indicated hereinbefore are those listed in Table 7 below.

Table 7:

N~ ", ~ (1.7) _ Example R17 Y Physical data .
H-8.1 Me S
H-8.2 H S
H-8.3 Me O
H-8.4 H O
H-8.5 Me N(Me) H-8.6 H N(Me) .
. : , . . .

., . -- -. .. .-~ :, . ~ .

.: . . ; - .

39 ` 2~'7~

Examples H-9: Other compounds of the general formula 1.8 which can be prepared analogously to the procedure described in Example H-1 or by means of another appropriate procedure selected from those indicated hereinbefore are those listed in Table 8 below.

Table 8:
~H2CH3 ~ ~~ (1.8) .
Example Rl7 Y Physical data H-9. 1 Me S
H-9.2 H S
H-9.3 Me O
H-9.4 H O
H-9.5 Me N(Me) H-9.6 H N(Me) .
Example H-10: The starting material used in the process of Example H-2.18 can beprepared for example as follows:
In an autoclave, 20 g of dry ammonia and 23.5 g of Raney nickel are added to a mixture of 23.5 g of 2-(1-hydroxyiminoethyl)-3-methylbenzo[b]thiophene and 250 ml of absolute methanol. The reaction mixture is then heated to ~0, hydrogenated at this temperature for approximately 5 hours under a pressure of approximately 100 bar and subsequently cooled to room ternperature, the catalyst is filtered off, and the filtrate is evaporated under a waterpump vacuum. The oily residue, 2-(1-aminoethyl)-3-methylbenzoLb]thiophene (lH NMR), is reacted further without additional purification.

Examples H-11: Other compounds of the general formula Ia.9, which are used, for example, as starting materials in the processes of Examples H-1 and H.2, which can be .' ' .'' 2~771~1 prepared analogously to-the procedure described in Example H-10 or by means of another appropriate procedure selected from those indicated hereinbefore are those listed in Table 9 below.

Table 9:

R3 ___~ Rs ~ .

~YJ~ R6 (Ia 9) Example R3 R4Rs R6 R7 Rl7 Y Physical data -H~ l H H H H H Me S oil; lHNMR
H-11.2 H H H H H Et S oil; IH NMR
H-11.3 Me H H H H Et S oil; IHNMR
H- 11.4 H H Cl H H Me S
H- l l.S H H Cl H H Et S
H- 11.6 H H H H H Me O
H- 11.7 H H H H H Et O
H-11.8 H H Cl H H Me O oil; IH NMR
H-11.9 H H Cl H H Et O oil; IHNMR
H-11.10 H H OMe H H Me O m.p.: 40-41 H-11.11 H H OMeH H Et O oil;lHNMR
H-11.12 H H H H OMe Me O oil; lH NMR
H-11.13 H H H H OMe Et O
H-11.14 H H H OMe H Me O oil; lH NMR
H-11.15 H H H OMe H Et O
H-l 1.16 H OMe H OMe H Me O oil; IH NMR
H-11.17 H OMe H OMe ~I Et O
H-11.18 Me H H H H Me O oil; IH NMR
H-11.19 Me H H H H Et O
H- 11 .2n Et H H H H Me O
H-11.21 Et H H H H Et O
:-' . , 2~77~ ~1 Example R3 R4 Rs R6 R7 R17 Y Physical data H-11.22 Me H C1 H H Me O
H-11.23 Me H Cl H H Et O
H-11.24 Me H OMe H H Me O
H-11.25 Me H OMe H H Et O
H-11.26 Me H H H H Me N(H) m.p.:92-95 H-11.27 Me H H H H Me N(Ac) H-11.28 H H H H H Me N(Me) oil; IHNMR
H-11.29 Me H H H H Me N(Me~ oil H-11.30 Me H Cl H H Me S oil; 1H NMR
H-11.31 Me H C1 H H Et S o11; lHNMR
H-11.32 Me H H H H Me S oil; 1HNMR
H- 11.33 H H H H H Me N-CH2Ph H- 11.34 H H H H H Et N-CH2Ph Examples H-12: Other compounds of the general formula Ia. 10, which are used, for example, as starting materials in the processes of Examples H-3, which can be prepared analogously to the procedure described in Example H-10 or by means of another appropriate procedure selected from those indicated hereinbefore are those listed in Table 10 below.

2~77~

Table 10:

H2N ~J3~R5 (Ia.10) Example R2 Rs R6 Rl7 Y Physical data H-12.1 H H H Me S
H-12.2 H H H Et S
H-12.3 Me H H Me S
H-12.4 Me H H Et S
H-12.5 Ph H H Me S
H-12.6 Ph H H Et S
H-12.7 Me Cl H Me S
H-12.8 Me Cl H Et S
H-12.9 H H H Me O
H-12.10 H H H Et O
H-12.11 Me H H Me O
H-12.12 Me H H Et O
H-12.13 Ph H H Me O
H-12.14 Ph H H Et O
H-12.15 Me Cl H Me O
H-12.16 Me Cl H Et O
H-12.17 Me OMeH Me O
H-12.18 Me OMeH Et O
H-12.19 Me H F Me O
H-12.20 Me H F Et O :, H-12.21 H ~I H Me N(H) oil; lH NMR
H-12.22 H H H E$ N(H) H-12.23 H H H Me N(Ac) H- 12.24 H H H Et N(Ac) H-12.25 H H H Me N(SO2Ph) H-12.26 H H H Me N(Me) oil; IH NMR
H-12.27 Me H H Me N(Me) H-12.28 Me H H Et N(Me) ..
- : . .
.

- , ~ :
, 2~771~

Examples H-13: Other compounds of the general formula la.11, which are used, forexample, as starting materials in the processes of Examples H-4, which can be prepared analogously to the procedure described in Example H-10 or by means of another appropriate procedure selected from those indicated hereinbefore are those listed in Table 11 below.

Table 11:
~17 H2N ~ (la.l l) Example R2 R3 R6 Rl7 Y Physical data H-13.1 H H Me Me S
H-13.2 H H Me Et S
H-13.3 H H H Me O
H-13.4 H H H Et O
H-13.5 Me Me Me Me O
H-13.6 Me Me Me Et O
H-13.7 Ph H Me Me O
H-13.8 Ph H Me Et O
H-13.9 Me Me Me Me N(H) H-13.10 Me Me Me Et N~H) H-13.11 Me Me Me Me N(Ac) H-13.12 Me Me Me Et N(Ac) H-13.13 H H H Me N(H) H-13.14 H H H Et N(H) H-13.15 H H H Me N(Ac) H-13.16 H H H Et N(Ac) .

Examples H-14: Other compounds of the general formula Ia.12, which are used, forexample, as starting materials in the processes of Examples H-S, which can be prepared .
.:
, ~

-44- 2~77~

analogously to the procedure describe~ in Fxample H-10 or by means of another appropriate procedure selected from those indicated hereinbefore are those listed in Table 12 below.

Table 12:
Rl7 ~R32 (la.~ 2) Example R2 R3 Rs R7 Rl7 Y Physical data H-14.1 H H H H Me S
H-14.2 H H H H Et S
H-14.3 Me Me H H Me O oil; lHNMR
H-14.4 Me Me H H Et O oil; lHNMR
H-14.5 H H H Me Me O
H-14.6 H H H Me Et O
H- 14.7 H H H Br Me O , H-14.8 H H H Br Et O
H-14.9 H H Me H Me O
H-14.10 H H Me H Et O
H-14.11 Me Me H H Me N(H) oil; lHNMR
H-14.12 Me Me H H Et N(H) H-14.13 Me Me H H Me N(Ac) H-14.14 Me Me H H Et N(Ac) H-14.15 Me Me H H Me N(Me) ~ . .
H-14.16 Me Me H H Et N(Me) ~ .:
H-14.17 Me Me H H Me S oil Examples H-15: Other compounds of the general formula la.l3, which are used, forexample, as starting materials in the processes of Examples H-3, whi~h can be prepared analogously to the procedure described in Example H-10 or by means of another appropriate procedure selected from those indicated hereinbefore are those listed in .: :
.

.

~077~

Table 13 below.

Table 13:
R3 ~, H2N ~~Y J~ (la.13) Example R3 Y Physicaldata . . . . ..
H-15.1 H S
H-15.2 H O
H-15.3 H N(H) H-15.4 Me N(Me) . .

: ' :

2~77111 Examples H-16: Other compounds of the general formula la.14 which can be prepared analogously to the procedure described in Example H-10 or by means of another appropriate procedure selected from those indicated hereinbefore are those listed in Table 14 below.

Tabelle 14:

H2N ~--~ (la.14) Example Rl7 Y Physical data H-16.1 H S
H-16.2 H O
H- 16.3 H N(Me) H-16.4 Me S
H-16.5 Me O
H- 16.6 Me N(Me) H-16.7 Me NH

, 2~7~
- ~7 -Examples H-17: Other compounds of the general formula Ia.15 which can be prepared analogously to the procedure described in Example H-10 or by means of another appropriate procedure selected from those indicated hereinbefore are those listed in Table 15 below.

Table 15:

H2N "'--~J~ (Ia. 15) Example Rl7 Y Physical data H-17.1 Me S
H-17.2 H S
H- 17.3 Me O
H-17.4 H O
H- 17.5 Me N(Me) H- 17.6 H N(Me) ,~

-',, ' ~ ' ' 2~77~

E~camples H- 18: Other compounds of the general formula Ia.16 which can be prepared analogously to the procedure described in Example H-10 or by means of another appropriate procedure selected from those indicated hereinbefore are ~ose listed in Table 16 below.

Table 16:

H2N ~ (la.16) Example Rl7 Y Physical data H-16.1 Me S
H-16.2 H S
H-16.3 Me O
H-16.4 H O
H-16.5 Me N(Me) H- 16.6 H N(Me) NMR data: Table 17 which follows contains the IH NMR data from the above examples.
The IH NMR spectra were lecorded in CDCl3, unless another solvent is indicated.

7 ~ble 17 -Example IH NMR data (ppm/multiplicity/number of protons) H-2.15 8.43/s/lH; 7.77/d/lH; 7.70/d/lH; 7.32/lllH; 7.29/tllH; 7.23/s/lH;

- 5.63/m/lH; 5.58/m/lH; 2.80/q/2H; 2.07/m/2H; 1.27/m/3H; 1.05/t/3H
H-2.49 8.47/s/lH; 7.67/~/lH; 7.63/d/lH; 7.26/dd/lH; 5.62/q/lH; 5.57/dllH;
2.78/q/2H; 2.45/s/3H; 2.08/m/lH; 1.95/m/lH; 1.24/~3H; 1.01/tl3H
H-2.62 8.40/s/lH; 7.66/d/lH; 7.62/d/lH; 7.25/dd/lH; 5.62/m/lH; 5.57/m/lH;
2.78/q/2H; 2.47/s/3H; 2.08/m/lH; 1.95/m/lH; 1.23/t13H; 1.01/tl3H
H-5.7 8.37/s/lH; 7.35/dflH; 7.33/d/lH; 7.18/dd/lH; 5.66/d/lH; 5.21/q/lH;

.

.
.

20~7~

2.77/q~H;2.37/s/3H;2.14/s/3H;1.97/m/2H;1.24/t/3H;0.95/~3H
H-10 7.81/~lH;7.63/~lH;7.36/t/lH;7.28/t/lH;4.66/m/lH;2.37/s/3H;
l.S9/s/2H;1.48/~3H
H-ll.l 7.80/~lH;7.68/d/lH;7.27/m/3H;4.43/m/lH;1.60/s/2H;1.52/d/3H
H-11.2 7.80/~lH;7.68/d/lH;7.31/~lH;7.27/t/lH;7.12/s/lH;4.37/m/lH;
1.821m/2H;0.96/~3H
H-11.3 7.79/d/lH;7.64/~lH;7.37/t/lH;7.28/t/lH;4.40/s/lH;2.37/s/3H; 1.80/m/2H;1.58/s/2H;0.94/~3H
H-11.4 7.69/d/lH;7.59/~lH;7.25/dd/lH;4.66/s/lH;2.33/s/3H;}.65/s/2H 1.47/~3H
H-ll.S 7.70/d/lH;7.60/s/lH;7.24/~lH;4.33/m/lH;2.31/s/3H;1.77/m/2H; 1.60/s/2H;0.93/t/3H
H-11.8 7.45/d/lH;7.33/d/lH;7.17/dd/lH;6.42/s/lH;4.19/m/lH;1.60/s/2H;
1.45/~3H.
H-ll.9 7.48/d/lH;7.33/d/lH;7.17/d~lH;6.47/s/lH;3.96/m/lH;1.85/m/2H;
1.52/s/2H;0.96/~3H
H-ll.ll 7.32/d/lH;6.98/~lH;6.83/dd/lH;3.95/m/lH;3.84/s/3H;1.85/m/2H;
l.SS/s/2H;0.97/t/3H
H-11.12 7.12/m/2H;6.76/m/lH;6.49/s/lH;4.22/s/lH;4.01/s/3H;1.62/s/2H;
1.52/d/3H
H-11.14 7.37/d/lH;6.99/~lH;6.83/dd/lH;6.41/s/lH;4.22/s/lH;3.83/s/3H;
1.82/s/2H;1.50/d/3H
H-11.16 6.62/d/lH;6.48/s/lH;6.30/~lH;4.14/m/lH;3.88/s/3H;3.83/s/3H; 1.57/s/2H;1.48/~3H
H-11.18 7.42/m/2H;7.22/m/2H;4.30/s/lH;2.21/s/3H;1.57/s/2H;1.49/s(broad)/3H
H-11.28 7.56/d/lH;7.28/m/lH;7.18/t/lH;7.08/t/lH;6.40/s/lH;4.28/q/lH;
3.78/s/3H,1.55/~3H;1.47/s/2H
H-11.30 7.69/dJlH;7.60/~lH;7.24/d~lH;4.67/s/lH;2.34/s/3H;1.63/s/2H; 1.47/d/3H
H-11.31 7.68/~lH;7.59/d/lH;7.23/dd/lH;4.33/s/lH;2.32/s/3H;1.77/m/lH;
1.60/s/2H,0.92/t/3H
H-11.32 7.81/~lH;7.63/~lH;7~36/~lH;7.28/t/lH;4.66/s/lH;2.37/s/3H;
l.S9/s/2H;1.48/~3H
H-12.21 8.00/s/lH;7.75to7.07/m/SH;4.50/m/lH;1.70/s/2H;1.58/d/3H
H-12.2S 7.68/~lH;7.32to7.20/m/2H;7.11/t/lH;6.97/s/lH;4.49/m/lH;3.75/s/3~;
1.56/s/2H;1.54/~3H

' - . ~

2~7 H-14.3 7.35/s/1~ 7.33/d/lH; 7.18/dd/lH; 4.21/q/lH; 2.37/s/3H; 2.13/s/3H;
1.53/s/2H; 1.42/d/3H
H-14.4 7.34/d/lH; 7.32/s/lH; 7.14/dd/lH; 3.88/m/lH; 2.38/s/3H; 2.15/s/3H;
1.72/m/2H; 1.50/s/2H; 0.85/~3H
H-14.11 7.72/s/lH; 7.40/dllH; 7.25/s/lH; 7.05/dd/lH; 4.20/m/lH; 2.38/s/3H;
2.20/s/3H; 1.75 to 1.31/m/5H

.

Examples F-1 to F-6: Formulation of compounds accordin~ to the invention Examples F-1.1 to F-1.3: Emulsion concentrates Components F- 1.1 F- 1.2 F- 1.3 .
Active ingredient according to the invention 25% 40% 50%
Calcium dodecylbenzenesulfonate 5% 8% 6%
Castor oil polyethylene glycol ether (36 mol of ethylene oxide units) 5%
Tributylphenol polyethylene glycol ether (30 mol of ethylene oxide units) - 12% 4%
Cyclohexanone - 15% 20%
Xylene mixture 65% 25% 20%
.

Emulsions of any desired concentration can be prepared from these emulsion concentrales by dilution with water.

.

-- 207~

Example F-2: Emulsion concentrate Components F-2 -Active ingredient according to the invention 10%
Octylphenol polyethylene glycol ether (4 to 5 mol of ethylene oxide units) 3%
Calcium dodecylbenzenesulfonate 3%
Castor oil polyglycol ether (36 mol of ethylene oxicle units) 4%
Cyclohexanone 30%
Xylene mixture 50%

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

Examples F-3.1 to F-3.4: Solutions ~ .
Components F-3.1 F-3.2 F-3.3 F-3.4 . ~ . .
Active ingredient according to the invention 80% 10% 5% 95%
Propylene glycol monomethyl ether 20%
Polyethylene glycol (relative molecular weight: 400 atomic -:
mass units) - 70%
N-Methylpyrrolid-2-one - 20%
Epoxidised coconut oil - - 1% S%

2~'77~

Petroleum spirit (boiling range: 160-190) - - 94%

The solutions are suitable for use in the form of microdrops.

Examples F-4.1 tO F-4.4: Granules Components F-4. 1 P-4.2 F-4.3 F-4.4 .
Active ingredient according to the invention 5% 10% 8% 21%
Kaolin 94% - 79% 54%
Highly-disperse silica 1% - 13% 7%
Attapulgite - 90% - 18%

The active ingredient according to the invention is dissolved in dichloromethane, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated in vacuo.

Example F-5.1 and F-5.2: Dusts Components F-5. 1 F-5.2 Active ingredient according to the invention 2% 5%
Highly-disperse silica 1% 5%
Talc 97%
Kaolin 90%

Ready-for-use dusts are obtained by intimately mixing all components.

2~7~ 1~

Examples F-6. 1 tO F-6.3 Wettable powders , Components F-6.1 F-6.2 F-6.3 Active ingredient according to the invention 25% 50% 75%
Sodium ligninsulfonate 5% 5% -Sodium lauryl sulfate 3% - 5%
Sodium diisobutylnaphthalene-sulfonate - 6% 10%
Octylphenol polyethylene glycol ether (7 to 8 mol of ethylene oxide units) - 2%
Highly-disperse silica 5% 10% 10%
Kaolin 62% 27%

~11 components are mixed thoroughly, and the mixture is ground thoroughly in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any des*ed concentration.

Examples B-l to B-l l: Biolo~ical action of compounds according to the invention A. Microbicidal action Example B-l.l: Systemic action against PYthium ultimum on su~ar beet Test method: Mycelium of PYthium ultimum is mixed with soil t500 ml of mycelium suspcnsion/10 1 of soil) and the mixture is filled into 250 ml plastic dishes. The dishes are incubated ~or four days at 10, and 10 seeds of the sugar beet plant to be tested are then placed into each dish. The next day, 50 ml portions of an aqueous spray solutioncontaining one of the active ingredients according to the invention (0.002% active substance) are then poured into each dish. After an incubation phase at 10 for seven days followed by an incubation phase at 22 for four days, the activity of the active substance is assessed taking into account number and appearance of the emerged plants.
Test result: Active ingredients according to the invention show a good systemic action ':

20771~

against Pythium ultimwn on sugar beet.

Example B-1.2: Systemic action against ~y~ on maize Test method: The test is carried out analogously to the procedure described in F,xample B-l.l.
est result: Active ingredients according to the invention show good systemic action against Pythium ultimum on maize.

Example B-2: Action against Puccinia ~raminis on wheat a) Residual-protective action Test method: 6 days after sowing, wheat plants are sprayed with an aqueous spray mixture comprising one of the active ingredients according to the invention (0.02% active substance) to drip point and 24 hours later infected with a uredospore suspension of the fungus. After an incubation time of 48 hours (conditions: 95 to 100 percent relative atmospheric humidity at 20), the plants are placed in a greenhouse at 22. 12 days after infection, the activity of the active substance is assessed taking into account the development of rust pustules.
Test result: Active ingredients according to the invention show a good residual-protective action against Puccinia graminis on wheat, for example the active ingredients of Examples H- 1, H-2. 13, H-2.15 and H-2. 18 reduce the fungus infestation to 20 to 5%. In contrast, control plants which were infected but not treated with the active substance show a fungus infestation of 100%.

b) Systemic action Test method: 5 days after sowing, an aqueous spray mixture prepared with one of the wettable powders comprising one of the active ingredients according to the invention (0.006% active substance relative to the soil volume) is poured next to wheat plants. Care is taken that the spray mixture is not brought into contact with aerial parts of the plants. 48 hours later, the plants are infected with a uredospore suspension of the fungus. After an incubation time of 48 hours (conditions: 95 to 100 percent relative atmospheric humidity at 20), the plants are placed in a greenhouse at 22. The activity of the active substance is ~ ;
assessed taking into account the development of rust pustules 12 days afte~ infection.
Test result: Active ingredients according to the invention of Examples H-l, H-2. 13, H-2.15 and H-2.18 show a good systemic action against Puccinia graminis on wheat.

. ~ ;

-55- ~077~ ~ ~

Example B-3: Action against Phytophthora infestans on tomatoes a) Residual-protective action Test methods: Tomato plants which have been grown for three weeks are sprayed with an aqueous spray mixture prepared with a wettable powder comprising one of the active ingredients according to the invention (0.02% active substance) to drip point and 24 hours later infected with a sporangia suspension of the fungus. The activity of the active substance is assessed taking into account the fungus infestation 5 days after infec~ion duAng which a relative atmospheric humidity of 90 to 100 percent and a temperature of 20 are maintained.
Test result: Active ingredients according to the invention show a good residual-protective action against Phyophthora infestans on tomatoes, for example the active ingredients of Examples H-2.15, H-2.18 and H-2.2g reduce the fungus infestation to 5 to 0%. In contrast, control plants which have been infected but not treated with the active substance show a fungus infestation of 100%.

b) SYstemic action Test method: An aqueous spray mixture prepared with a wettable powder comprising one of the active ingredients according to the invention (0.006% active substance relative to the soil volume) is poured next to tomato plants which have been grown for three weeks.
Care is taken that the spray mixture is not brought into contact with aerial parts of the plants. 48 hours later, the plants are infected with a sporangia suspension of the fungus.
The activity of the active substance is assessed taking into account the fungus infestation 5 days after infection, during which a relative atmospheric humidity of 90 to 100 percent and a temperature of 20 are maintained.
Test result: Active ingredients according to the invention show a good systemic action against Phytophthora infestans on tomatoes.

Example B-4: Residual-protective action against Cercospora arachidicola on ~roundnuts Test method: Groundnut plants 10 to 15 cm in height are sprayed to drip point with an aqueous spray mixture prepared with a wettable powder comprising one of the active ingredients according to the invention (0.02% active substance) and 48 hours later infected with a conidia suspension of the fungus. The plants are incubated for 72 hours at 21 and high atmospheric humidity and then placed in a greenhouse until the typical foliar lesions appear. The activity of the active ingredient is assessed 12 days after infection taking into account number and size of the foliar lesions.
Test resul~: Active ingredients according to the invention show a good residual-protective :

207~

action against Cercospora arachidicola on groundnuts.

Example B-S: Action a.gainst Plasmopara viticola on vines a) Residual-protective action Test method: Vine seedlings in the 4- to 5-leaf-stage are sprayed to drip point with an aqueous spray mixture prepared with a wettable powder comprising one of the active ingredients according to the invention (0.02% active substance) and 24 hours later infected with a sporangia suspension of the fungus. The activity of the active substance is assessed tal~ing into account the fungus infestation 6 days after infection, during which a relative atmospheric humidity of 9S to 100 percent and a temperature of 20 are maintained.
Test result: Active ingredients according to the invention show a good preventive residual-protective action against Plasmopara viticola on vines, for example the active ingredient of Example H-2.29 reduces the fungus infestation to 20 to 0%. In contrast, control plants which have been infected but not treated with the active substance show a fungus infestation of 100%.

b) Residual-protective action Test method: Vine seedlings in the 4- to S-leaf stage are infected with a sporangia suspension of the fungus, incubated for 24 hours in a humid chamber (conditions: 95 to 100 percent relative atmospheric humidity at 20) and then sprayed to drip point with an aqueous spray mixture prepared with a wettable powder comprising one of the active in~redients according to the invention (0.02% active substance). When the spray coating has dried on, the plants are returned to the humid chamber. The activity of the active substance is assessed taking into account the fungus infestation 6 days after infection.
Test result: Active ingredients according to the invention show a good curative residual-protective action against Plasmopara viticola on vines.

Example B-6: Action against ~yricularia oryzae on rice a) ~esidual-protective action 'rest method: Rice plants are grown for two weeks and then sprayed to drip point with an aqueous spray mixture preparedi with a wettable powder comprising one of the active ingredients according to the invention (0.02% active substance) and 84 hours later infected with a conidia suspension of the fungus. The activity of the active substance is assessed takiag into account the fungus infestation S days after infection, during which a relative atmospheric humidity of 9S to 100 percent and a temperature of 22 are maintained.
Test result: Active ingredients according to the invention show a good residual-protective , 2977~

action against Pyricularia oryzae on rice.

b) Systemic action Test method: ~n aqueous spray mixture prepared with a wettable powder comprising one of the active ingredients according to the invention (0.006% active substance relative to the soil volume) is poured next to 2-week-old rice plants. Care is taken that the spray mixture is not brought into contact with aerial parts of the plants. The pots are then floodes3 with water to such an extent that the stem bases of the rice plants are covered with water. After 96 hours, the plants are infected with a conidia suspension of the fungus. The activity of the active substance is assessed taking into account the fungus infestation 5 days after infection, during which a relative atmospheric humidity of 95 to 100 percent and a temperature of 24 are maintained.
Test result: Active ingredients according to the invention show a good systemic action against Pyricularia oryzae on rice.

Example B-7: Residual-protective action against Venturia inaequalis on apples Test method: Apple cuttings with young shoots 10 to 20 cm in length are sprayed to drip point with an aqueous spray mixture prepared with a wettable powder comprising one of the active ingredients according to the invention (0.02 % active substance) and 24 hours later infected with a conidia suspension of the fungus. The plants are incubated for 5 days at a relative atmospheric humidity of 90 to 100 percent and placed in a greenhouse at 20 to 24 for a ~urther 10 days. The activity of the active substance is assessed taking into account the extent of scab 15 days after infection. ?
Test result: Active ingredients according to the invention of Examples H-1 and Tables 1, 2 and 4, in particularH-2.13, H-2.15, H-2.18, H-2.19, H-2.26, H-2.27, H-2.39, H-2.61, H-2.65, H-2.68, H-3.1, H-3.13, H-5.6 and H-5.7, show a good residual-protective action against Venturia inaequalis on apples.

Example B-8: Action against ErYsiphe graminis on barleY
a) Residual-protective action Test method Barley plants approximately 8 cm in height are sprayed to drip point with an aqueous spray mixture prepared from a wettable powder comprising one of the active ingredients according to the invention (0.02% active substance) and 3 to 4 hours later dusted with conidia of the fungus. The infected plants are placed in a greenhouse at 22.
The activity of the active substance is assessed taking into acco~mt the fungus infestation 10 days after infection.

..
.. .

-58- 2~7'7~ ~ ~

Test result: Active ingredients according to the invention show a good residual-protective action against Erysiphe graminis on barley, for example the active ingredients of Examples H-2.18 and H-2.29 reduce the fungus infestation to 5 to 0%. In contrast, control plants which have been infected b.lt not treated with the active substance show a fungus infestation of 100%.

b) SYstemic action Test method: An aqueous spray mixture prepared with a wettable powder comprising one of the active ingredients according to the invention (0.002~ active substance relative to the soil volume) is poured next to barley plants approximately 8 cm in height. Care is taken that the spray mixture does not come into contact with aerial parts of the plants. 48 hours later, the plants are dusted with conidia of the fungus. The infected plants are placed in a greenhouse at 22. The activity of the active substance is assessed taking into account the fungus infestation 10 days after infection.
Test result: Active ingredients according to the invention show a good systemic action against Erysiphe graminis on barley~

Example B-9: Action a~ainst Podosphaera leucotricha on apple shoots Residual-protective action Apple cuttings having new shoots approx. 15 cm in length are sprayed with a spray mixture (0.06% active substance). After 24 hours, the treated plants are infected with a conidia suspension of the fungus and placed in a controlled-environment cabinet at 70%
relative atmospheric humidity and 20C. The fungus infestation is assessed 12 days after infection.
Active ingredients of the fonnula I from Tables 1~ 2 and 4 reduce the disease level to less than 20%. Control plants show a fungus infestation of 100%.

B. Acaricidal action Example B-10: Action against Tetranvchus urticae on beans Test mothod: Young bean plants are populated with a mixed population of Tetranychus urticae, sprayed one day later to drip point with an aqueous emulsion spray mixture prepared with a wettable powder comprising one of the active ingredients according to the invention (0.04% active substance) and subsequently incubated for 6 days at 25. The activity of the active substance is then evaluated based on a count of the pests. The dead eggs, the dead larvae and the dead adults on the treated plants are counted and the : . ' ~ .. , .. ' :

. : .

207~
~9 corresponding numerical values on the control plants which have not been treated with the active substance are deterrnined analogously. The individual pairs of values for the treated and the untreated plants are used for calculating the percentage by which the pest population on the treated plants has been reduced (percentage ac~ivity of the acdve substance).
Test result: Active ingredients according to the invention show a good action against .
Tetranychus urticae on beans.

Example B-11: Action against Tetranvchus cinnabarinus on dwarf beans Test method (dilution series): Dwarf beans in the 2-leaf stage are populated with a mixed population (eggs, larvae/nymphs and adults) of an OP-tolerant strain of Tetranychus cinnabarinus. 24 hours later, the active ingredient according to the invention is applied to the plants in an automatic spray cabin at concentrations of 2~0, 100 and 50 mg/l (the active substance is formulated and is diluted in each case with water to the desired concentration) are counted. The activity of the active substance is evaluated 2 and 7 days after application based on a count of the pests. In each case the dead eggs, dead larvae/nymphs and dead adults on the plants (which have been treated with activeingredient at the desired concentration) are counted, and the col~esponding numerical values are determined analogously on control plants which have not been treated with the active substance. The individual pairs of values for the plants which have been treated (with active ingredient at the desired concentration) and untreated plants is used for calculating the percentage by which the pest population on the treated plants has been reduced at the particular concentration of active ingredient (percentage activity of the active substance).
Test result: Active ingredients according to the invention show a good action against Tetranychus cinnabarinus on dwarf beans.

.
. ' '.:', ' - :
., .
. . . ~, . ':, . . ' ' ,. . . . .

: '.' ' : .

Claims (22)

1. A compound of the formula in which:
one of the radicals R2, R3, R4, R5, R6 and R7 is a group of the formula (Ia);

the remaining five of the radicals R2, R3, R4, R5, R6 and R7 independently of one another are hydrogen, halogen, C1-C8alkyl, halo-C1-C8alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C8alkoxy, halo-C1-C8alkoxy, C1-C8alkylthio, halo-C1-C8alkylthio, cyano, nitro, phenyl, phenoxy or phenylthio, where the phenyl groups in phenyl, phenoxy and phenylthio are unsubstituted or substituted by one, two or three substituents, selected from the group comprising halogen, C1-C4alkyl and C1-C4alkoxy, with the proviso that, of the five radicals from the group of the radicals R2, R3, R4, R5, R6 and R7, which differ from group Ia, at least two radicals are hydrogen and at least four radicals differ from phenyl which is unsubstituted or substituted as mentioned above, from phenoxy which is unsubstituted or substituted as mentioned above, and from phenylthio which is unsubstituted or substituted as mentioned above; Y is an oxygen atom, a sulfur atom or a group of the formula NR1 (Ib); in which R1 is hydrogen, C1-C8alkyl, C1-C8alkanoyl, C1-C8alkanesulfonyl, halo-C1-C8alkanesulfonyl, cyano-C1-C8allcanesulfonyl or phenylsulfonyl, whose phenyl group is unsubstituted or substituted by one or twosubstituents selected from the group comprising halogen, C1-C4alkyl, nitro and cyano; R8 is hydrogen, C1-C8alkyl, C1-C8alkoxy or C1-C8alkylthio; R9 is hydrogen, C1-C8alkyl, halo-C1-C8alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkylthio-C1-C4alkyl, C1-C4alkanesulfinyl-C1-C4alkyl, C1-C4alkanesulfonyl-C1-C4alkyl, C2-C8alkenyl, halo-C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl or halogen; R10 is hydrogen, hydroxyl, C1-C8alkyl, halo-C1-C8alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C8alkoxy, C1-C8alkylthio, C1-C8alkanesulfinyl, C1-C8alkanesulfonyl, halogen, nitro, cyano, amino, a group of the formula N(H)R18 (Ic), a group of the formula N(R18)R19 (Id) or a group of the formula N=C(R19)R20 (Ie); R11 is hydrogen, C1-C8alkyl, benzyl, C1-C8alkanoyl, phenylcarbonyl whose phenyl group is unsubstituted or substituted by one, two or three substituents selected from the group comprising halogen and C1-C4alkyl, or is C1-C8alkylthio, halo C1-C8alkylthio, cyano-C1-C8alkylthio, phenylthio or benzylthio, where the phenyl groups in phenylthio and benzylthio are unsubstituted or substituted by one or two substituents selected from the group comprising halogen, C1-C4alkyl, nitro and cyano; R12, R13, R14, R15, R16 and R17 independently of one another are hydrogen, C1-C8alkyl, halo-C1-C8alkyl, C1-C4alkoxy-C1-C4alkyl or C3-C8cycloalkyl; R18 is C1-C8alkyl, benzyl, C1-C8alkanoyl, phenylcarbonyl whose phenyl group is unsubstituted or substituted by one, two or three substituents selected from the group comprising halogen and C1-C4alkyl, C1-C8alkylthio, halo-C1-C8alkylthio, cyano-C1-C8alkylthio, phenylthio or benzylthio, where the phenyl groups in phenylthio and benzylthio are unsubstituted or substituted by one or two substituents selected from the group comprising halogen, Cl-C4alkyl, nitro and cyano; R19 is C1-C8alkyl; R20 is hydrogen or C1-C8alkyl; m is 0 or 1; and n is 0 or 1;
or, if appropriate, a tautomer thereof, in each case in free form or in salt form.

2. A compound according to claim 1 of the formula I, in which:
one of the radicals R2, R3, R4, R5, R6 and R7 is a group Ia;
the other five of the radicals R2, R3, R4, R5, R6 and R7 independently of one another are hydrogen, halogen, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl, C1-C4alkoxy, Halo-C1-C4alkoxy having 1, 2 or 3 halogen atoms, C1-C4alkylthio, halo-C1-C4alkylthio having 1, 2 or 3 halogen atoms, cyano, nitro, phenyl, phenoxy or phenylthio, where the phenyl groups in phenyl, phenoxy and phenylthio are unsubstituted or substituted by one, two or three substituents selected from the group comprising halogen, C1-C2alkyl and C1-C2alkoxy, with the proviso that, of the five radicals from the group of the radicals R2, R3, R4, R5, R6 and R7, which differ from group Ia, at least two radicals are hydrogen and at least four radicals differ from phenyl which is unsubstituted or substituted as mentioned above, from phenoxy which is unsubstituted or substituted as mentioned above, and from phenylthio which is unsubstituted or substituted as mentioned above; Y is an oxygen atom, a sulfur atom or a group Ib; R1 is hydrogen, C1-C4alkyl, C1-C4alkanoyl, C1-C4alkanesulfollyl, halo-C1-C4-alkanesulfonyl having 1, 2 or 3 halogen atom, cyano-Cl-C4alkanesulfonyl or phenylsulfonyl whose phenyl group is unsubstituted or substituted by one or two substituents selected from the group comprising halogen, C1-C2alkyl, nitro and cyano; R8 is hydrogen, C1-C4alkyl, C1-C4alkoxy orC1-C4alkylthio; R9 is hydrogen, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl, C1-C2alkylthio-C1-C4alkyl, C1-C2alkanesulfinyl-C1-C4alkyl, C1-C2alkanesulfonyl-C1-C4alkyl, C2-C4alkenyl, halo-C2-C4alkenyl having 1, 2 or 3 halogen atoms, C2-C4alkynyl, C3-C7cycloalkyl or halogen; R10 is hydrogen, hydroxyl, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C4alkoxy-C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkanesulfinyl,C1-C4alkanesulfonyl, halogen, nitro, cyano, amino, a group Ic, a group Id or a group Ie;
R11 is hydrogen, C1-C4alkyl, benzyl, C1-C4alkanoyl, phenylcarbonyl whose phenyl group is unsubstituted or substituted by one, two or three substituents selected from the gronp comprising halogen and C1-C2alkyl, or is C1-C4alkylthio, halo-C1-C4alkylthio having 1, 2 or 3 halogen atoms, cyano-C1-C4alkylthio, phenylthio or benzylthio, where the phenyl groups in phenylthio and benzylthio are unsubstituted or substituted by one or two substituents selected from the group comprising halogen, C1-C2alkyl, nitro and cyano;
R12, R13, R14, R15, R16 and R17 independently of one another are hydrogen, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C4alkoxy-C1-C4alkyl or C3-C7cycloalkyl; R18 is C1-C4alkyl, benzyl, C1-C4alkanoyl, phenylcarbonyl whose phenyl group is unsubstituted or substituted by one, two or three substituents selected from the group comprising halogen and C1-C2alkyl, or is C1-C4alkylthio, halo-C1-C4alkylthio having 1, 2 or 3 halogen atoms, cyano-C1-C4alkylthio, phenylthio or benzylthio, where the phenyl groups in phenylthio and benzylthio are unsubstituted or substituted by one or two substituents selected from the group comprising halogen, C1-C2alkyl, nitro and cyano; R19 is C1-C4alkyl; R20 is hydrogen or C1-C4alkyl; m is 0 or 1; and n is 0 or 1;
or, if appropriate, a tautomer thereof, in each case in free form or in salt form.

3. A compound according to claim 1 of the formula I, in which:
one of the radicals R2, R3, R5 and R6 is a group Ia;
the other three of the radicals R2, R3, R5 and R6 and the radicals R4 and R7 independently of one another are hydrogen, halogen, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy-CI-C4alkyl, C1-C4alkoxy, halo-C1-C4alkoxy having 1, 2 or 3 halogen atoms, C1-C4alkylthio, halo-C1-C4alkylthio having 1, 2 or 3 halogen atoms, cyano, nitro, phenyl, phenoxy or phenylthio, where the phenyl groups in phenyl, phenoxy and phenylthio are unsubstituted or substituted by one, two or three substituents selected from the group comprising halogen, C1-C2alkyl and C1-C2alkoxy, with the proviso that of the five radicals from the group of the radicals R2, R3, R4, R5, R6 and R7 which differ from group Ia, at least two radicals are hydrogen and at least four radicals differ from phenyl which is unsubstituted or substituted as mentioned above, from phenoxy which is substituted or unsubstituted as mentioned above, and from phenylthio which is unsubstituted or substituted as mentioned above; Y is an oxygen atom, a sulfur atom or a group Ib; R1 is hydrogen, C1-C4alkyl, C1-C4alkanoyl, C1-C4alkanesulfonyl, halo-C1-C4-alkanesulfonyl having 1, 2 or 3 halogen atoms, cyano-C1-C4alkanesulfonyl or phenylsulfonyl whose phenyl group is unsubstituted or substituted by one or two substituents selected from the group comprising halogen, C1-C2alkyl, nitro and cyano; R8 is hydrogen, C1-C4alkyl, C1-C4alkoxy or C1-C4alkylthio; R9 is hydrogen, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl, C1-C2alkylthio-C1-C4alkyl, C1-C2alkanesulfinyl-C1-C4alkyl, C1-C2alkanesulfonyl-C1-C4alkyl, C2-C4alkenyl, halo-C2-C4alkenyl having 1, 2 or 3 halogen atoms, C2-C4alkynyl, C3-C7cycloalkyl or halogen; R10 is hydrogen, hydroxyl, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C4alkoxy-C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkanesulfinyl, C1-C4alkanesulfonyl, halogen, nitro, cyano, amino, a group Ic, a group Id or a group Ie; R11 is hydrogen, C1-C4alkyl, benzyl, C1-C4alkanoyl, phenylcarbonyl whose phenyl group is unsubstituted or substituted by one, two or three substituents selected from the group comprising halogen and C1-C2alkyl, or is C1-C4alkylthio, halo-C1-C4alkylthio having 1, 2 or 3 halogen atoms, cyano-C1-C4alkylthio, phenylthio or benzylthio, where the phenyl groups in phenylthio and benzylthio are unsubstituted or substituted by one or two substituents selected from the group comprising halogen, C1-C2alkyl, nitro and cyano; R12, R13, R14, R15, R16 and R17 independently of one another are hydrogen, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C4alkoxy-C1-C4alkyl or C3-C7cycloalkyl; R18 is C1-C4alkyl, benzyl, C1-C4alkanoyl, phenylcarbonyl whose phenyl group is unsubstituted or substituted by one, two or three substituents selected from the group comprising halogen andC1-C2alkyl, or is C1-C4alkylthio, halo-C1-C4alkylthio having 1, 2 or 3 halogen atoms, cyano-C1-C4alkylthio, phenylthio or benzylthio, where the phenyl groups in phenylthio and benzylthio are unsubstituted or substituted by one or two substituents selected from the group comprising halogen, C1-C2alkyl, nitro and cyano; R19 is C1-C4alkyl; R20 is hydrogen or C1-C4alkyl; m is 0 or 1; and n is 0 or 1;
or, if appropriate, a tautomer thereof, in each case in free form or in salt form.

4. A compound according to claim 1 of the formula 1, in which:
one of the radicals R2, R3,R5 and R6 is a group Ia;
the other three of the radicals R2,R3,R5 and R6 and the radicals R4 and R7 independently of one another are hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy or unsubstituted phenyl, with the proviso that, of the five radicals from the group of the radicals R2, R3,R4,R5,R6 and R7, which differ from the group Ia, at least two radicals are hydrogen and at least four radicals differ from unsubstituted phenyl; Y is an oxygen atom, a sulfur atom or a group Ib; R1 is hydrogen, C1-C4alkyl, C1-C4alkanoyl or unsubstituted phenylsulfonyl; R8 is hydrogen or C1-C4alkyl; R9 is C1-C4alkyl, C3-C4cycloalkyl or halogen; R10 is C1-C4alkyl, halogen or nitro; R11, R12, R13, R14, R15 and R16 are in each case hydrogen; R17is hydrogen or C1-C4alkyl; m is 0 or 1; and n is 0 or 1;
in free form or in salt form.

5. A compound according to claim 1 of the formula I, in which:
one of the radicals R2, R3 and R6 is a group Ia;
the other two of the radicals R2, R3 and R6 and the radicals R4, R5 and R7 independently of one another are hydrogen, halogen, C1-C4alkyl or C1-C4alkoxy, with the proviso that, of the five radicals from the group of the radicals R2, R3, R4, R5, R6 and R7 which differ from the group Ia, at least three radicals are hydrogen; Y is an oxygen atom, a sulfur atom or a group Ib; R1 is hydrogen or C1-C4alkyl; R8 is hydrogen; R9 is C1-C4alkyl; R10 is halogen;
R11 and R16 in each case are hydrogen; R17 is C1-C4alkyl; and m and n in each case is 0;
in free form or in salt form.

6. A compound according to claim 1 of the formula I, in which:
(a) R2 is a group Ia, R3 is hydrogen or C1-C4alkyl, R4 is hydrogen, R5 is hydrogen, halogen or C1-C4alkoxy, R6 and R7 in each case are hydrogen, with the proviso that, of the five radicals R3,R4,R5,R6 and R7 at least four radicals are hydrogen, Y is an oxygen atom, a sulfur atom or a group Ib and R1 is hydrogen or C1-C4alkyl; or (b) R2 is hydrogen, R3 is a group Ia, R4, R5, R6 and R7 in each case are hydrogen, Y is a group Ib and R1 is hydrogen or C1-C4alkyl; or (c) R2 and R3 independently of one another are C1-C4alkyl,R4 and R5 in each case are hydrogen, R6 is a group Ia, R7is hydrogen, Y is an oxygen atom or a group Ib and R1 is hydrogen;
and in each case R8 is hydrogen; R9is C1-C4alkyl;R10 is halogen; R11 and R16 in each case are hydrogen; R17 is C1-C4alkyl; and m and n in each case are 0;
in free form or in salt form.

7. A compound according to claim 1 of the formula I, in which:
(d) R2 is a group Ia, R6 is hydrogen and either R3 is hydrogen or C1-C4alkyl, R5 is hydrogen and Y is a sulfur atom or R3 is hydrogen, R5 is halogen or C1-C4alkoxy and Y is an oxygen atom; or (e) R2 and R3 independently of one another are C1-C4alkyl, R5 is hydrogen, R6 is a group Ia and Y is an oxygen atom; and in each case R4, R7 and R8 in each case are hydrogen; R9 is C1-C4alkyl; R10 is halogen; R11 and R16 in each case are hydrogen; R17 is C1-C4alkyl; and m and n in each case are 0;
in free form or in salt form.

8. A compound according to claim 1 of the formula I, in which:
either R3 is C1-C4alkyl,R5 is hydrogen and Y is a sulfur atom or R3 is hydrogen, R5 is C1-C4alkoxy and Y is an oxygen atom; and in each case R2 is a group Ia; R4, R6, R7 and R8 in each case are hydrogen; R9 is C1-C4alkyl; R10 is halogen; R11 and R16 in each case are hydrogen; R17 is C1-C4alkyl; and m and n in each case are 0;
in free form or in salt form.

9. A compound according to claim 1 of the formula I, in which:
Y is a sulfur atom; R2 is a group Ia; R3 is C1-C4alkyl;R4,R5,R6,R7 and R8 in each case are hydrogen; R9 is C1-C4alkyl; R10 is halogen; R11 and R16 in each case are hydrogen;
R17 is C1-C4alkyl; and m and n in each case are 0;
in free form or in salt form.

10. A compound from the group comprising (d,1)-2-[1-(5-chloro-6-ethylpyrimidin-4-ylamino)ethyl]-3-methylbenzo[b]thiophene, (Example H-2.18) (d,1)-2-[1-(5-chloro-6-ethylpyrimidin-4-ylamino)ethyl]-5-methoxybenzo[b]furan, (Example H-2.29) in each case in free form or in salt form.

11. A compound from the group comprising (d,1)-2-[1-(5-chloro-6-ethylpyrimidin-4-ylamino)ethyl]benzo[b]thiophene, (Example H-2.13) (d,1)-2-[1-(5-chloro-6-ethylpyrimidin-4-ylamino)propyl]benzo[b]thiophene, (Example H-2.15) (-)-2-[1-(5-chloro-6-ethylpyrimidin-4-ylamino)propyl]benzo[b]thiophene, in each case in free form or in salt form.

12. A process for the preparation of a compound of the formula I or, if appropriate, of a tautomer thereof, in each case in free form or in salt form, which comprises a) to produce a compound of the formula I in which R11 is hydrogen, C1-C8alkyl or benzyl, or, if appropriate, a tautomer thereof, in each case in free form or in salt form, reacting a compound of the formula (II), in which R8, R9 and R10 are as defined in folmula I and Z is an easily detachable nucleofugic radical, or, if appropriate, a tautomer thereof, with a compound of the formula (III), in which Y is as defined in formula I and, with a single exception, R2' is R2, R3' is R3, R4' is R4, R5' is R5, R6' is R6 and R7' is R7, where R2, R3, R4, R5, R6 and R7 are as defined in formula I, the abovementioned exception being that the group Ia, which is mentioned in the definitions of the variables R2, R3, R4, R5, R6 and R7 of the formula I, is replaced by the group of the formulaH(R11')N-[C(R12)(R13)]m-[C(R14)(R15)]n-C(R16)(R17)- (IIIa) in which R11' is hydrogen, C1-C8alkyl or benzyl and R12, R13, R14, R15, R16, R17, m and n are as defined in formula I, or with a salt thereof, preferably in the presence of a base, or b) to prepare a compound of the formula I in which R11 is as defined in formula I but differs from hydrogen, C1-C8alkyl and benzyl, or, if appropriate, a tautomer thereof, in each case in free form or in salt form, introducing the desired substituent R11, which differs from hydrogen, C1-C8alkyl and benzyl, into a compound of the formula I in which R11 is hydrogen, or, if appropriate, into a tautomer thereof, in each case in free form or in salt form, by means of N-alkanoylation, N-benzoylation, N-alkylthiolation, N-phenylthiolation or N-benzylthiolation, and, in each case, if desired, converting a compound of the formula I or a tautomer thereof which can be obtained according to the process or by other means, in each case in free form or in salt form, into another compound of the formula I or a tautomer thereof, separating an isomer mixture which can be obtained according to the process, andisolating 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 a salt which can be obtained according to the process, of a compound of the formula I or of a tautomer thereof, 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.

13. A composition for protecting plants against attack by pests, which comprises, as active ingredient, at least one compound according to claim 1 or, if appropriate, a tautomer thereof, in each case in free form or in agrochemically usable salt form, if appropriate in addition to at least one auxiliary.

14. A composition according to claim 13 for protecting plants against attack by phytopathogenic microorganisms and/or pests from the order of the Acarina.

15. A process for the preparation of a composition according to claim 13, which comprises intimately mixing the active ingredient with the carrier material.

16. The use of a compound according to claim 1 or, if appropriate, of a tautomer thereof, in each case in free form or in agrochemically usable salt form, or of a composition according to claim 13 for protecting plants against attack by pests.

17. The use according to claim 16 for protecting plants against attack by phytopathogenic microorganisms and/or pests from the order of the Acarina.

18. A method of protecting plants against attack by pests, which comprises applying, as active ingredient, a compound according to claim 1 or, if appropriate, a tautomer thereof, in each case in free form or in agrochemically usable salt form, to the plants, their locus or to parts of the plants.

19. A process according to claim 18 for protecting plants against attack by phytopathogenic microorganisms and/or pests from the order of the Acarina.

20. A compound of the formula IV

IV

in which R3, R4, R5, R6 and R7 independently of one another are hydrogen, halogen, C1-C8alkyl, halo-C1-C8alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C8alkoxy, halo-C1-C8alkoxy, C1-C8alkylthio, halo-C1-C8alkylthio, cyano, nitro, phenyl, phenoxy or phenylthio, where the phenyl groups in phenyl, phenoxy and phenylthio are unsubstituted or substituted by one, two or three substituents selected from the group comprising halogen, C1-C4alkyl and C1-C4alkoxy, with the proviso that, of the five radicals R3, R4, R5, R6 and R7 at least two radicals are hydrogen and at least four radicals differ from phenyl which is unsubstituted or substituted as mentioned above, from phenoxy which is unsubstituted or substituted as mentioned above, and from phenylthio which is unsubstituted or substituted as mentioned above; and R17 is ethyl;
in free form or in salt form.

21. A compound according to claim 20, in which:
R3, R4, R5, R6 and R7 independently of one another are hydrogen, methyl, ethyl, methoxy or chlorine, R17 is ethyl;
in free form or in salt form.

22. A compound according to claim 21 from the group comprising (d,1)-2-(1-aminopropyl)benzo[b]thiophene;
(-)-2-(1-aminopropyl)benzo[b]thiophene;

in each case in free form or in salt form.

FD 4.5/HS/md