AU657558B2 - Pesticides - Google Patents

Description

65755 S F Ref: 218073

AUSTRALIA

PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT

ORIGINAL

*1 IS .555 S. p

S.

S S I S. *S

SI

*I Name and Address of Applicant: Actual Inventor(s): Address for Service: Invention Title: Ciba-Geigy AG Klybeckstrasse 141 CH-4002 Basel

SWITZERLAND

Harald Walter and Mark Havenhand Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Pesticides The following statement is a full description of this invention, including the best method of performing it known to me/us:- 5845/4 1- 18774/A Pesticides The invention relates to compounds of the formula

R

3 R Y4

R

6 in which: one of the radicals R 2

R

3

R

4

R

5

R

6 and R 7 is a group of the formnula

R

9

N

N N -[C(R 12

)(RI

3 )lm-[C(RI 4 5 )ln-C(Rl 6 )(Rl 7 (Ia); the remaining five of the radicals R 2

R

3

R

4

R

5

R

6 and R 7 independently of one another are hydrogen, halogen, C 1

-C

8 alkyl, halo-C 1

-C

8 allcyl, Cj-C 4 alkoxy-C 1

-C

4 alkyl,

C

1

-C

8 alkoxy, halo-C 1

-C

8 alkoxy, Cl-C 8 alkylthio, halo-Cl-C 8 alkylthio, cyano, nitro, phenyl, phenoxy or phenylthio, where the phenyl groups in phenyl, phenoxy and phenylthio are usubsti~ ted or substituted by one, two or three substituents, selected from the group eefflp gqalogen, C 1

-C

4 alkyl and CI-C 4 alkoxy, with the proviso that, of the five radicals from the group of the radical-, R 2

R

3

R

4

R

5

R

6 and R 7 which differ from group la, 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 g1atem," rtdf'ratom or a group of the formula NRI in which R, is hydrogen, 1

C-C

8 alkyl, CI-Cgalkanoyl, Cl-C 8 alkanesulfonyl, halo-C 1 -Cgalkanesulfonyl, cyano--C_ 8 alkanesulfonyl or phenylsulfonyl, wihose phenyl gopis unsuibstitued or substituted by one or two substituents selected from the group empin halogen, Cl-C 4 alkyl, nitro and cyano; R 8 is hydrogen, Cl-C 8 alkyl, Cl-C 8 alkoxy or Cl-C 8 alkylthio; R 9 is hydrogen, C 1

-C

8 alkYl, halo-Cl-C 8 alkyl, C 1

-C

4 alkoxy-Cj-C 4 alkyl, Cj-C 4 alkylthio-C 1

-C

4 aLkyl, Cj-C 4 alkanesulfinyl-C 1

-C

4 alkyl, C 1

-C

4 alkanesulfonyl-C 1

-C

4 alkyl, C 2

-C

8 alkenyl, halo-

CZ-C

8 alkenyl, C 2

-C

8 alkynyl, 02 3

-C

8 cycloalkyl or halogen; RIO is hydrogen, hydroxyl,

C

1 -Cgalkyl, halo-Cl-Cgalkyl, C 1 -C~alkoxy-C 1

-C

4 alkyl, CI-CgaLkoxy, C 1

-C

8 alkylthio, Cl-C 8 alkanesulfinyl, Cl-C 8 alkanesulfonyl, halogen, nitro, cyano, amino, a group of the formula N(H)R 18 a group of the formula N(R 18 )Rlg (Id) or a group of the formula N=C(Rl 9

)R

20

R

11 is hydrogen, Cl-C 8 alkyl, benzyl, Cl-C 8 alkanoyl, phenylcarbonyl whose phenyl group is unsubstituted or substituted by one, two or three substituents selected from the group eefpf6iigalogen and Cl-C 4 alkyl, Or is Cl-C 8 alkylthio, halo-

C

1 -Cgallcylthio, cyano-Cl-Cgalkylthio, phenylthio or benzylthio, where the phenyl groups in phenylthio and benzyltllio are unsubstituted or substituted by one or two substituents selected from the group e ps.,alogen, Cl-C 4 alkyl, nitro and cyano; R 12

R

13 1 R 14

R

15

R

16 and R 17 independently of one another are hydrogen, Cl-C 8 alkyl, halo- C I-C 8 alkyl, Cj-C 4 alkoxy-Cj-C 4 alkyl or C 3

-C

8 cycloalkyl; R 18 is Cl-C 8 alkyl, benzyl, Cl-C 8 alkanoyl, phenylcarbonyl whose phenyl group is uns u1stituted or substituted by one, two or three substituents selected from the group c- Z7 s4~alogen and Cl-C 4 alkyl, Cl-Cgalkylthio, halo-C 1

-C

8 alkylthio, cyano-Cl-C 8 alkylt)-io, phenylthio or benzylthio, where the phenyl groups in pheniylthio and benzylthio are siubstitutpI or substituted by one or two suusiiuents selected from the group ++ialogen, Cl-C 4 alkyl, nitro and cyano; R 19 is CI-COalkyl; R 20 is hydrogen or Cl-C 8 alkyl; mnis 0 or 1; and n isO0 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 ingec ~t is selected from these compounds and tautomers, in each case in free form or in a. hemically usable salt form, and a process for the preparation and the use of these compositions.

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

The compounds I and, if appropriate, the tautomers thereof can exist in the form of salts, in particular agrochemically usable salts. Since the compounds I have at least one basic centre, they can form, for example, acid addition salts. These are formed, for example, with strong inorganic acids such as mineral acids, for example sulfuric acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as

C

1

-C

4 alkanecarboxylic acids, for example acetic acid, which are unsubst;tuted or substituted, for example by halogen, or unsaturated or saturated dicarboxylic acids, for example oxalic acid, malonic acid, maieic 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 C 1

-C

4 alkane- or arylsulfonic acids, for example methane- or p-toluenesulfonic acid, which are unsubstituted or substituted for example by halogen. Furthermore, compounds I \t i.ch 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.

S: 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 S. 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 defined, in each case 1 up to and including 8, preferably 1 up to and including 4, in particular 1 or 2, carbon atoms.

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, alkanesulfinyl, alkanesulfinylalkyl, alkanesulfonyl, cyanoalkanesulfonyl, haloalkanesulfonyl and alkanesulfonylalkyl 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, i.e. methyl, ethyl, propyl, butyl, 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-l-yl, or branched, for example propen-2-yl, but-1-en-2-yl or oct-2-en-4-yl.

S 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-1-yn- -yl, pent-2-yn-1-yl or oct-3-yn-1-yl, or branched, for example propyn-2-yl, But-l-yn-2-yl or oct-2-yn-4-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.

S. In halogen-substituted carbon-containing groups and compounds, such as haloalkyl, haloalkenyl, haloalkoxy, haloalkylthio and haloalkanesulfonyl, at least one of the hydrogen atoms present 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 the 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.

Examples which may be mentioned are -CH 2 F, -CHF 2

-CF

3

-CH

2 CI, -CHCl 2

-CCI

3 -CC1 2 CC1 3

-CH

2 Br, -CH 2

CH

2 Br, -CF BrC1, -CCl=CCl 2

-OCH

2 F, -SCHC12 and -SO 2

CF

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

Preferred compounds of the formula I within the scope of the invention are those in which: one of the radicals R 2

R

3

R

4

R

5

R

6 and R 7 is a group Ia; the other five of the radicals R 2

R

3

R

4

R

5

R

6 and R 7 independently of one another are hydrogen, halogen, Cl-C 4 alkyl, halo-Cl-C 4 alkyl having 1, 2 or 3 halogen atoms, Cj-C 2 akoxy-CjC 4 akyl, Cl-C 4 alkoxy, Halo-C 1

-C

4 alkoxy having 1, 2 or 3 halogen atoms,

C

1

-C

4 alkylthio, halo-C 1

-C

4 alkylthio having 1, 2 or 3 halogen atoms, cyanio, nitro, phenyl, phenoxy or phenylthio, where the phenyl groups i phenyl, phenoxy and phenylthio are unsubstituted or substituted by one, two or three substituents selected from the group C-4fa\aogen, C 1

-C

2 alkyl and Cl-C 2 allcoxy, with the proviso that, of the five :radicals from the group of the radicals R 2

R

3

R

4

R

5

R

6 and R 7 which differ from group Ia, at least two radicals are hydrogen and at least four radicals differ from phenyl which is Vnus.ue.rsbtttdasmnindaoe rmpeox hc susbtttdo unusie rsubstituted as mentioned above,an from phenylthi which is unsubstituted ortite as mentioned above, Y is an o::ygetem a group Ib; R, is hydrogen, Cl-C 4 alkyl, Cl-C 4 alkanoyl, C 1

-C

4 alkanesulfonyl, halo-Cl-C 4 alkanesulfonyl having 1, 2 or *3 halogen atoms, cyano-Cl-C 4 alkanesulfonyl or phenylsulfonyl whose phenyl.Q i unsubstituted or substituted by one or two sub stituents selected from the group~e"A, halogen, Cl-C 2 alkyl, nitro and cyano; R 8 is hydrogen, Cl-C 4 alkyl, Cl-C 4 alkoxy or Cl-C 4 alkylthio; R 9 is hydrogen, Cl-C 4 alkyl, halo-Cl-C 4 alkyl having 1, 2 or 3 halogen atoms, C 1

-C

2 alkoxy-Cj-C 4 alkyl, Cj-C 2 alkylthio-Cj-C 4 alkyl, Cl-C 2 alkanesulfinyl-

C

1

-C

4 alkyl, C 1

-C

2 alkanesulfonyl-Cj-C 4 a~kyl, C 2

-C

4 alkenyl, halo-C 2

-C

4 alkenyl having 1, 2 or 3 halogen atoms, C 2

-C

4 alkynyl, C 3

-C

7 cycloalkyl or halogen; RIO is hydrogen, hydroxyl, Cl-C 4 alkyl, halo-C 1

-C

4 alkyl having 1, 2 or 3 halogen atoms, Cj-C 4 alkoxy-C 1

-C

4 alkyl, Cl-C 4 alkoX'Y, C 1

-C

4 alkylthio, Cl-C 4 alkanesulfinyl, Cl-C 4 alkanesulfonyl, halogen, nitro, cyano, amino, a group Ic, a gr ip Id or a group le,

R

11 is hydrogen, CI-COaikyl, benzyl, Cl-C 4 alkanoyl, phenylcarbonyl whose phenyl group is unsub stituted or substituted by one, two or three substituents selected from the group halogen and CI-C 2 ailkyl, or is Cl-C 4 alkylthio, halo-C,-C~alkylthio having 1, 2 or 3 halogen atoms, cvano-C 1

-C

4 alkylthio, phenylthio or benzylthio, where the phenyl -6groups in phenylthio and benzyhfr-, -unsubstiti~ed or substituted by one or two substituents selected from the group eem ismg 4halogen, CI-C 2 alkyl, nitro and cyano;

R

12

R

13 1 R 14

R

15

R

16 and R1 7 independently of one another are hydrogen, C 1

-C

4 alkyl, halo-Cl-C 4 alkyl having 1, 2 or 3 halogen atoms, Cj-C 4 alkoxy-Cj-C 4 alkyl or

C

3

-C

7 cycloalkyl; R 18 is Cl-C 4 alkyl, benzyi, Cl-C 4 alkanoyl, phenylcarbonyl whose phenyl group is~unsubstited or substituted by one, two or tee substituents selected from the gru om ingogen and CI-C 2 alkyl, or is Cl-C 4 alkylthio, halo-Cl-C 4 alkylthio having 1, 2 or 3 halogen atoms, cyano-Cl-C 4 alkylthio, phenylthio or benzylthio, where the phenyl groups in phenylthio and benzylthio are unsubstituted or substituted by one or two substituents selected from the group s4alogen, CI-C 2 alkyl, nitro and cyano; R 19 is Cl-C 4 aikyl; R- is hydrogen or C 1

-C

4 allcyl; mn isO0 or 1; and n is 0 or 1; and, if appropriate, mautomers thereof, in each case in free f-)rmn or in salt form.

Particularly preferred compounds of the formula I within the scope of the invention are those in which: one of the radicals R 2

R

3

R

5 and R 6 is a group Ia; the other three of the radicals R 2

R

3

R

5 and R 6 and the radicals R 4 and R 7 independently of one another are hydrogen, halogen, Cj-C 4 alkyl, halo-Cl-C 4 alkyl having 1, 2 or 3 halogen atoms, C 1

-C

2 alkoxy-Cj-C 4 alkyl, CI-C 4 alkoxy, halo-Cl-C 4 allcoxy having 1, 2 or 3 halogen atoms, Cl-C 4 alkylthio, halo-Cl-C 4 alkylthio having 1, 2 or 3 halogen atoms, cyano, nitro, phenyl, phenoxy or phenylthio, where the phenyl groups in phenyl, phenoxy and phnlhoare unsubsti ited or substituted by one, two or three substituents selected from the group e alogen, CI-C 2 alkyl and Cl-C 2 alkoxy, with the proviso that, of the five radicals from the group of the radicals R 2

R

3

R

4

R

5

R

6 and R 7 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 .1henoxy which is substituted or unsubstituted as mentioned above, and from phenylthio which is unsubstituted or substituted as mentioned above; Y is an @xygen rte~i', A- a group Ib; R- is hydrogen, Cl-C 4 alkyl, Cl-C 4 allcanoyl, Cl-C 4 alkanesulfonyl, halo-Cl-C 4 alkanesulfonyl having 1, 2 or 3 halogen atoms, cyano-Cl-C 4 alkanesulfonyl or phenylsulfonyl whose phenyl group is unsubstitu ed or substituted by one or two substituents selected from the group Mip alogen, CI-C 2 alkyl, nitro and cyano; R 8 is hydrogen, CI-C 4 alkyl, CI-C 4 alkoxy or Cl-C 4 alkylthio; R 9 is hydrogen, CI-C 4 alkyl, halo-Cl-C 4 alkyl having 1, 2 or 3 halogen atoms, Cl-C 2 alkoxy-CI-C 4 alkyl, CI-C 2 alkylthio- Cl-C 4 alkyl, C 1

-C

2 alkanesulfinyl-Cj-C 4 alkyl, C 1

-C

2 alkanesulfonyl-C 1

-C

4 alkyl,

SC

2

-C

4 alkenyl, halo-C 2

-C

4 alkenyl having 1, 2 or 3 halogen atoms, C 2

-C

4 alkynyl,

C

3

-C

7 cycloallcyl or halogen; RIO is hydrogen, hydroxyl, C 1

-C

4 alkyl, halo-C 1

-C

4 alkyl having 1, 2 or 3 halogen atoms, Cj-C 4 alkoxy-CI-C 4 alkyl, CI-C 4 alkoxy, CI-C 4 alkylthio, Cl-C 4 alkanesulfinyl, Cl-C 4 alkanesulfonyl, halogen, nitro, cyano, amino, a group 1c, a group Id or a group le; R 11 is hydrogen, Cj-C 4 alkyl, benzyl, Cl-C 4 alkanoyl, phenylcarbonyl whose phenyl group is unsubstituted or substituted by one, two or three substituents selected from the group comprising halogen and Cj-C ,alkyl, or is Cl-C 4 alkylthio, halo-C 1

-C

4 alkylthio having 1, 2 or 3 halogen atoms, cyano-Cl-C 4 alkylthio, phenylthio or benzylthio, where the phenyl groups in phenylthio and benzylthio are unsubsti 'ted or substituted by one or two substituents selected from Lne group fftfrtln., CI-C 2 alkyl, nitro and cyano; R 12

R

13

R

14

R

15

R

16 and

R

17 independently of one another are hydrogen, Cl-C 4 alkyl, halo-CI-C 4 alkyl having 1, 2 or 3 halogen atoms, C 1

-C

4 allcoxy-Cj-C 4 alkyl or C 3

-C

7 cycloalkyl; R 18 iS Cl-C 4 alkyl, benzyl, CI-C 4 alkanoyl, phenylcarbonyl whose phenylgrgup is unsubstituted or substituted by 1, 2 or 3 substituents selected from the group c~masm logen and CI-C 2 alkyl, or is Cj-C 4 alkylthio, halo-Cl-C 4 alkylthio having 1, 2 or 3 halogen atoms, cyano-Cl-C 4 alkylthio, phenylthio or benzylthio, where the phenyl groups in phenylthio and ben7ylthio are unsubstituted or substituted by one or two substituents selected from the group c imig\alogen, CI-C 2 alkyl, nitro and cyano;, R1 9 is CI-C 4 alkyl; R 20 is hydrogen or C 1

-C

4 alkyl; mnis 0 or 1; and n isO0 or 1; and, if appropriate, tautomers thereof, in each case in free formn 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 R 3

R

5 and R 6 is a group 1a; the other three of the radicals R 2

R

3

R

5 and R 6 and the radicals R 4 and R 7 independently of one another are hydrogen, halogen, Cj-C 4 alkyl, CI-C 4 alkoxy or unsubstituted phenyl, with the proviso that, of the five radicals from the group of the radicals R 2

R

3

R

4

R

5

R

6 and R-i. wir6"~ differ from the group Ia, Ft least two radicals are hydrogen and at least four radicals differ from unsub~tituted phenyl; Y is anebDUnWa group Ib; R, is hydrogen, C 1

-C

4 alkyl, Cl-C 4 alkanoyl or unsubstituted phenylsulfonyl; R 8 is hydrogen or C 1

-C

4 alkyl; R 9 is Cj-C 4 alkyl, C 3

-C

4 cycloalkyl or halogen; RIO is CI-C 4 alkyl, halogen or nitro; R, I, R 12

R

13

R

14

R

1 5 and R 16 are in each case hydrogen; R 17 is hydrogen or CI-C 4 alkyl; m is 0 or 1; and n is 0 or 1; in free form or in salt form.

SCompounds which are pref~erred in a particular fashion within the scope of the invention are those of the formula I in which: one of the radicals R 2

R

3 and R 6 is a group Ia; the other two of the radicals R 2

R

3 and R 6 and the radicals R 4

R

5 and R 7 independently of one another are hydrogen, halogen, C 1

-C

4 alkyl or C 1

-C

4 alkoxy, with the proviso that, of the five radicals from the group of the radicals R 2

R

3

R

4 Rs, R 6 and R 7 which differ from the group Ia, at least three radicals are hydrogen; Y is a group Ib; R 1 is hydrogen or C 1

-C

4 alkyl; R 8 is hydrogen; R 9 is C 1

-C

4 alkyl; R 1 0 is halogen; R 11 and R 16 in each case are hydrogen; R 17 is CI-C 4 alkyl; 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:

R

2 is a group Ia, R 3 is hydrogen or C 1

-C

4 alkyl, R 4 is hydrogen, R 5 is hydrogen, halogen or C 1

-C

4 alkoxy, R 6 and R 7 in each case are hydrogen, with the 15 proviso that, of the five radicals R 3

R

4

R

5

R

6 and R 7 at least four radicals are hydrogen, Y is a group Ib and R 1 is hydrogen or C 1

-C

4 alkyl; or i' R 2 is hydrogen, R 3 is a group Ia, R 4

R

5

R

6 and R 7 in each case are hydrogen, Y is a group Ib and R 1 is hydrogen or C 1

-C

4 alkyl; or

R

2 and R 3 independently of one another are C 1

-C

4 alkyl, R 4 and R 5 in each S 20 case are hydrogen, R 6 is a group Ia, R 7 is hydrogen, Y is a group Ib and R 1 is hydrogen; and in each case R 8 is hydrogen; R 9 is C 1

-C

4 alkyl; R 1 0 is halogen; R 1 and R 16 in each case are hydrogen; R17 is C 1

-C

4 alkyl; and m and n in each case are 0; Sin free form 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 form, comprises, for example, a) to produce a compound of the formula I in which Ri 1 is hydrogen, C 1

-C

8 alkyl or benzyl, or, if appropriate, a tautomer thereof, in each case in free form or in salt form, reacting a compound of the formula IN:\LbZI00319:BFD R9 N

R

o 10

R

8 N Z in which R 8

R

9 and Rio 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 formula

R

4

R

3 R,9' I 1 (III), R2' Y

R

6 R7' in which Y is as defined in formula I and, with a single exception, R 2 is R 2

R

3 is R 3

R

4 is R 4

R

5 is R 5

R

6 is R 6 and R 7 is R 7 where R 2

R

3

R

4

R

5

R

6 and R 7 are as defined in formula I, the abovementioned exception being that the group la, which is mentioned in the definitions of the variables R 2

R

3

R

4

R

5

R

6 and R 7 of the formula I, is replaced by the group of the formula H(R 11 ')N-[C(R1 2 )(R1 3 5 )]n-C(R1 6

)(R

7 (IIa) in which R 11 is hydrogen, C 1

-C

8 alkyl or benzyl and R 12

R

13

R

14

R

15

R

16

R

1 7 m and n are as defined in formula I, or with a salt thereof, preferably in the presence of a base, or S* b) to prepare a compound of the formula I in which R 1 I is as defined in formula I but differs from hydrogen, C 1 -Cgalkyl and benzyl, or, if appropriate, a tautomer thereof, in each case in free form or in salt form, introducing the desired substituent R 11 which differs from hydrogen, C 1 -Csalkyl and benzyl, into a compound of the formula I in which

R

11 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, and isolating the desired isomer and/or converting a free compound of the formula I or a tautomer thereof which can be obtained according to the process into a salt, or 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 tautoer thereof or into a different salt.

What has been said above for tautomers or salts of compounds I applies 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 0 C to the boiling point of the reaction medium, preferably approximately -20 0 C to approximately +150 0 C, 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.

*i 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 u described below.

Variant a): Suitable examples of radicals Z are: fluorine, chlorine, bromine, iodine, C 1 -Csalkylthio such as methylthio, ethylthio or propylthio, C 1 -Csalkanoyloxy such as acetoxy, (halo-)C 1 -Csalkanesulfonyloxy such as methairesulfonyloxy, ethanesulfonyloxy or trifluoromethanesulfonyloxy, or substituted or unsubstituted phenylsulfonyloxy such as benzenesulfonyloxy or p-toluenesulfonyloxy, furthermore also hydroxyl.

Examples of suitable bases for facilitating the elimination of HZ are hydroxides, hydrides, amides, alkanolates, carbonates, dialkylamides or alkylsilylamides of alkali metals or p /ls>\alkaline earth metals, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, amnionium hydroxides and carbocyclic amines. Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methanolate, sodium carbonate, potassium tert-butanolate, potassium carbonate, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium h)yiride, trimethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl- N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, N-methylmorpholine, benzyltrimethylammonium hydroxide, and 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. However, 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 mentior.nd are: aromatic, aliphatic and alicyclic hydrocarbons and halohydrocarbons such as benzene, toluene, xylene, chlorobenzene, bromohenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, dichloroethane or trichloroethene; ethers such as diethyl ether, tert-butyl methyl ether, tetrahydrofuran or dioxane; ketones such as acetone or methyl ethyl ketone; alcohols such as methanol, S. ethanol, propanl, butanol, ethylene glycol or glycerol; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-me'hylpyrrolidone or hexamethylphosphoric triamide; nitriles such as acetonitrile; and sulfoxides such as dimethyl sulfoxide. Bases which are employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diettylaniline, can also be used as solvents or diluents.

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

In a preferred embodiment of variant 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 an alkylamine, preferably in the presence of triethylamine.

The 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 European Patent Application EP-A-0,470,600.

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

Fur example, ammonia or an amine of the formula H 2

NR

11 (1b) can be reacted in the customary manner in the presence of a reducing agent with a compound of the formula IIIc, where the compounds mc are the compounds III, but have a group of t e formula

R

1 2 6

)R

1 7 (IIId), a group of the formula

R

1 3 4

)(R

1 5 )]n-C(R 1 6

)(R

1 7 (IIIe), a group of the formula

R

14

C(=O)-C(R

1 6

)(R

17 (1mf), a.group of the formula R 15 C(=O)-C(R16)(R 17 (nIg), a group of the formula R 16 (IIIh) or a group of the formula R 17 (hIi) 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 cyanoborchydride, 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 hid, IIIe, IIIf, IIIg, IIIh or Ili by a hydrogen atom and a group of the formula H(R 1 (IIIj) compounds III are S 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 formamide, 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 compound" 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 mi is Sconverted into the group, and this oxime can be reduced to give the corresponding amine, suitable reducing agents being, for example, complex metal S. hydrides such as LiA1H 4 NaBH 4 /TiC1 4 zinc/acetic acid or hydrogen (in the presence of a hydrogenation catalyst, for 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(R 11 (Ihj) is attached and where R 1 1 is hydrogen.

13 In compounds of the formula IIIk, which correspond to compounds III but have a group of the formula NC-[C(R 1 4)(R 15 )]n-C(R 16

)(R

1 7 (III1), a group of the formula

NC-C(R

1 6

)(R

1 7 (Him) or the cyano group instead of the group Ilia in the compounds III, it is furthermore possible to reduce the cyano group in the groups IIll and IIIm, or the cyano group which in the compounds IIk 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 LiAlH 4 sodium ethanolate or hydrogen (in the presence of a hydrogenation catalyst, for example in the presence of Raney nickel or palladium on charcoal). This gives compounds II which have two hydrogen atoms on the carbon atom to which the group HI(R 11 (IHj) is attached and where R 1 1 is hydrogen.

In compounds of the formula IIIn which correspond to compounds III but have a group of the formula HN(R 11 14

)(R

15 )]n-C(R 16

)(R

17 (1Io), a group of the formula

HN(R

1 16 (IIIp) or a group of the formula HN(Ru 1 (IIIq) instead of the group IIa in the compounds II, it is furthermore possible also to reduce the amide group in the groups IIIo, lp and IIIq in the customary manner to give the group

-CH

2

-NH(R

1 1 (IIIr), suitable reducing agents being, for example, complex metal hydrides such as LiAIH 4 This gives compounds III which have two hydrogen atoms on the carbon atom to which the group H(R 1 (IIIj) is attached.

In nitroalkyl compounds of the formula Ills, it is equally possible to reduce the nitroalkyl group in the customary manner to give the aminoalkyl group, where the compounds HIs correspond to the compounds III, but have a group of the formula 0 2

N-[C(R

2

)(R

13 )m-[C(R 4

)(R

5 )]n-C(Ri 6 )(Ri 7 (lit) instead of the group IIIa in the compounds III, suitable reducing agents being, for example, complex metal hydrides such S as LiAIH 4 This gives compounds III in which R 1 is hydrogen.

Compounds III in which R 1 1 is hydrogen can be C 1 -Cgalkylated or benzylated in the customary manner to give compounds III in which R 1 1' is C 1 -Csalkyl or benzyl. In an exemplary procedure to this end, the compound III in which R 11 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 the type given above, with a compound of the formula C 1 -Csalkyl-Z (IIIu) or with a compound of the formula benzyl-Z (IIv), in which Z in each case has the abovementioned meaning.

compounds IIIb, me, 11k, IIIn, IIIs, IIIu and IIIv are known or can be prepared J4analogously to known compounds.

Variant b): The N-dlkanoylation, N-benzoylation, N-alkylthiolation, N-phenylthiolation or N-benzylthiolation of a compound I in which R 11 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 is carried out in the customary manner, for example by reacting a compound I in which R 1 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 in an inert solvent or diluent, for example in an inert solvent or diluent of the type given under variant and in a temperature range of approximately -80 0 C to approximately +180 0 C, preferably approximately 0 C to approximately +130 0 C, in many cases at the reflux teiiiperature of the solvent used, with a compound of the formula C 1 -Cgalkanoyl-Z with a compound of thb formula phenylcarbonyl-Z (Ig) whose phenyl group is unsubstituted or substituted by one, two or three substituents selected from the group comprising halogen and

CZ-C

4 alkyl, with a compound of the formula C1-Cgalkylthio-Z Ih), with a compound of the formula halo-C 1 -Csalkylthio-Z with a compound of the formula cyano-C 1

-C

8 alkylthio-Z with a compound of the formula phenylthio-Z (Ik) or with a compound of the formula benzylthio-Z where the phenyl groups in phenylthio and benzylthio are unsubstituted or substituted by one or two substituents selected from the S: group comprising halogen, C 1

-C

4 alkyl, nitro and cyano.

In the compounds If, Ig, Ih, Ii, Ij, Ik and II, Z in each case has the meaning given under variant a).

The compounds If, Ig, Ih, Ii, Ij, Ik and II 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 in the customary manner by another substituent/other substituents according to the invention.

For example: non-halogen-containing substituents, or unhalogenated aromatic ring part-structures, can -46be 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 ting 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-structures according to the invention; non-(alkoxy-, alkylthio-, alkanesulfinyl-, alkanesulfonyi- 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 substitueiits, 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 aromatic 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 invention, where the phenyl substituent to be .ntroduced 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 S" 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-structures, can be phenylthiolatzd 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 alkanesulfinylated to give >7en 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 aromatic ring part-structures according to the invention, where the phenyl ring of the 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 aromatic 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 S" 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 subidtuted as defined 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 .i ,.haloalkoxylated aromatic ring part-structures according to the invention; S] 0", r7 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-structures are haloalkenylated 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 ring 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, acid addition salts of compounds I are obtained, for example, by treatment with a suitable acid Sor 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 salts with bases, for example by treatment with a suitable acid or a suitable ion exchanger reagent.

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, barium salt or silver salt, an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example 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 appropriate, the tautomers thereof, in each case in free form or in salt form, 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 absolute and relative configuration 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 be resolved 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 carboxylic acid, for :example camphoric acid, tartaric acid or malic acid, or sulfonic acid, for 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 out the process accord'.ng 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 form.

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 carried 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 particular, the invention relates to the preparation processes described in Examples H-1 to H-14.16.

9o 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 *Ci. of the compounds I or salts thereof, and the use and processes for the preparation of these 0 -1, -24starting materials and intermediates.

Preferred intermediates are those of the formula IV

R

4 R3 Rs I I IV R17 S R6

NH

2 R7 in which R 3

R

4

R

5

R

6 and R 7 independently of one another are hydrogen, halogen,

C

1 -Csalkyl, halo-C 1 -Csalkyl, C 1

-C

4 alkoxy-C 1

-C

4 alkyl, C 1 -Csalkoxy, halo-C 1

-C

8 alkoxy,

C

1 -Csalkylthio, halo-C 1 -Csalkylthio, cyano, nitro, phenyl, phenoxy or phenylthio, where the phenyl groups in phe-yl, phenoxy and phenylthio are unsubstituted or substituted by one, two or three substituents selected from the group comprising halogen, CI-C 4 alkyl and

C

1

-C

4 alkoxy, with the proviso that, of the five radicals R 3

R

4

R

5

R

6 and R 7 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 S above; and R 17 is ethyl; *9 in free form or in salt form.

SFrom amongst these, particularly preferred compounds are those in which R 3

R

4

R

5

R

6 and R 7 independently of one another are hydrogen, methyl, ethyl, methoxy or chlorine; in free form or in salt form.

The following are preferred specifically: (d,l)-2-(1-aminopropyl)-benzo[b]thiophene; -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 Patent Application under the publication number 0 126 254. The compounds I of the present invention differ from these known compounds characteristically by the fact that in the former the amino group in the 4-position of the pyrimidine ring is substituted by a benzo[b]furylalkyl, benzo[b]thienylalkyl or indolylalkyl radical; moreover, the compounds I of the present invention have an unexpectedly 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 active ingredients of the formula I according to the invention are distinguished not only by being very effective but also by being well tolerated by plants.

The active ingredients of the formula I have a biocidal spectrum for controlling pests from the order of the Acarina and phytopa hogenic microorganisms, in particular fungi, which Sis 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 forests, in S the protection of stored goods and materials, and in the hygiene field, in particular on i 2 b domestic animals and productive livestock. They are 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 mouiting, 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, sun.flowers, coconut, castor-oil plant, cocoa, groundnuts); cucurbits (pumpkin, crl :umbers, melons); fibre 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, cinnamon, 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 formulation, surfactants or other application-enhancing additives, without the activity of the compounds of the formula I being reduced thereby.

A'3 i^

A

cd3 -24- 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 function of the severity of attack by the pathogen in questic-.. Alternatively, the active 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 flooded 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.

S 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 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 formulations, i.e. tht 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 ingredient 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 C 8 to C 12 such as xylene mixtures or substituted naphthalenes, phthalic esters such as dibutyl p 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 such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or di nethylformamide, and epoxidised or unepoxidised vegetable oils, such as epoxidised coconut oil or soya oil, and water.

Solid carriers which are generally used, for example for dusts and dispersible powders, are ground natural mineral -'ch as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical p perties, 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 S 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 formula I to be formulated. Surfactants are also to be understood as meaning mixtures of surfactants.

Suitable anionic surfactrnts 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-substituent, 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 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 95 percent by weight, of active ingredient of the formula I, 99.9 to 1 percent by weight, in particular 99.8 to 5 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 arc more preferred as commeicial 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 represenrs "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 form of an agrochemically utilisable salt, in particular such a compound, if appropriate in tautomeric form, which is described as prcduct in Examples H-1 to H-9.6.

Examples H-1 to H-18: Preparation of compounds according to the invention Example H-l1 In a sulfurising flask, a mixture of 1.86 g of 4,5-dichloro-6-ethylpyrimidine, 1.80 g of 2-(l-aminoethyl)-l-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 820, 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 T purified by means of flash chromatography on silica gel using ethyl acetate/hexane (1:3) c as mobile phase. This gives 2-[1-(5-chloro-6-ethylpyrimidin-4-ylamino)ethyl]-l-methyl indole, which melts at 129 to 1310.

Example H-2: Other compounds of the general formula 1.1 which can be prepared analogously to the procedure given in Example H-l or by means of another appropriate procedure selected from those indicated hereinbefore are those listed in Table 1 below.

a a.

o Table 1: N R1 R

R

R8 N N YR Ex. R 3

R

4

R

5

R

6

R

7

R

8

R

9 RIO R1 7 Y Physical data 11-2.1 H H H H H H Me Cl Me N(Me) 11-2.2 H H H H H H Et Br Me N(Me) H-2.3 1111 H H H H Me Br Me N(Me) :H-2.4 H H H H H H C1 Et Me N(Me) H-2.5 Me H H H H H Et Cl Me N(H) m.p. 117-119'C 1H-2.6 Me H H H H H Me Cl Me N(H) H1-2.7 Me H H H H H Et Cl Me N(Ac) H1-2.8 Me H H H H H Me Cl Me H 1-2.9 Me H H H H H Et Cl Me H.1-2.10 Me H H H H H Me Cl Me N(Me) H1-2.11 Me H H H H H Et Br Me N(Me) 11-2.12 1111 H H H H F Et Me N(Me) 11-2.13 H H H H H H Et C1 Me S m.p. 82-83'C 11-2.14 H H H H H Me Et Cl Me S 11-2.15 H H H H H H Et Cl Et S oil,IH NMR 11-2.16 1111111111 H Et Br Me S 11-2.17 H H H H H H Et NO 2 Me S H-2.18 Me H H H H H Et Cl Me S m.p. 50-51'C 11-2.19 Me H H H H H Et Cl Et S m.p. 77-78'C 11-2.20 H H Cl H H H Et Cl S H1-2.21 H H Cl H H H Me Cl Me S 11-2.22 1111111111 H Et Cl MeO0 11-2.23 H H H H H H Me Cl Et 0 H-2.24 H H H H H H Et Br Me 0

R

3

R

4

R

5

R

6 R7, R 8

R

9 Rj 1 0

R

17

Y

Physical data

C

C

.e C

C.

C. C

C

C

CC

CC

C

H1-2.25 H-2.26 H1-2.27 H1-2.28 H1-2.29 H-2.30 H1-2.31 H1-2.32 H-2.33 H1-2.34 H1-2. 35 H-2.36 11-2.37 H1-2.38 H-2.39 1-1-2.40 H1-2.41 11-2.42 11-2 .43 11-2.44 H1-2.45 H1-2.46 H1-2.47 H--2.48 H1-2.49 11-2.50 H1-2.51 H1-2.52 H1-2.53 H1-2.54 H1-2.55 H1-2.5 6 1111 H11H 1111 H111 H11H H111 1111 1111 1111 H H1 1111 H H 1111 H11H CI H CI H CI H CI H OMe 11 OMe H OMe H OMe H 1111 H H1 H H1 1111 H H Et "H 1c-Pr H Et H Et H H Me H H Me OMeBH Et OMe H Et OMe H Me OMe H Br

H

11 H Me Cl MeO0 H Et CI MeO0 H OMeNH H OMeAH H OMe H H OMe H MeNH H Me H N Me H H Et H H Et H H Me H CI MelH Cl Me H Cl MeNH Cl.

Me H CI OMeNH OMe H OMe H OMeNH OMeNH OMeNH H N 1111 1111 1111 1111 H H 1111 H H H H H111 H Et 11 Et N Et H Et H Me H Et HNEt N Et H1Me H Et H Et H Et 11 Et N Me 11 Me H Et TIEt 11 Et "HMe N Et CI Et 0 CI MeO0 Cl MeO0 Cl 'Ut 0 NO4e 0 1 MeO0 CI MeO0 Br MeO0 Br MeO0 Et Et 0 Cl MeO0 CI Et 0 Cl MeO0 CI Et 0 CI MeO0 F Et 0 Cl MeO0 CI Et 0 Cl MeO0 Cl MeO0 CI Et 0 CI MeO0 Cl Et 0 CI MeO0 Br Me 0 N0 Me 0 CI MeO0 CI Et 0 Cl M eO Br Me 0 m.P. 135-136'C m.P. 67-69 0

C

m.p. 67-68'C M.P. 99-101'C m.P. 105-106'C m.p. 106-107TC m.p. 87-88'C m.P. 91-92TC Me H Me H MeNH Me H OMe H OMe H OMeNH OMeNH

R

3

R

4

R

5

R

6

R-

7 Rg R 9 RIO R 17 Y Physical data a a a a.

a a a.

a a a.

a 11-2.57 H--2.58 H1-2.59 H1-2.60 H1-2.61 H-2.62 1H-2.63 H-2.64 H-2.65 H-2.66 H1-2.67 H1-2.68 H- 2. 69 H1-2.70 H-2.71 11-2.72 11-2.73 H1-2.74 H-2.75 H1-2.76 Me H Me H 1111 H H Me H- Me H Me H 1 11 1 H 1111 1111 1111 H H 1111 1111 1111 H11H 1111 H H

RHH

OMe H OMe H Cl H C1 11 H H C1 H C1 H1 1111 H H 1111 1111 1111 1111 1111 H111 1111 1111 H H 1111 H H1 Me C1 Me Ci H Et 11 Me Et H Et H Et Et H Et H Et 11 Me "HEt H Me H Et "HMe Me H Et H Et Me Me Me Me 0 Et MeO0 Cl Et S Cl Et S Br Et S imp. 62-63'C Cl Et S oil, 'H NMR Cl Me S m.p. 91-92'C Br Et S C1 Et NH Br Et N11 C1 Et NI- C1 Me NH Cl Me NH Br Me S C1 Et S Br Et S Cl Me N-CH 2 Ph Cl Et N-ClH 2

II

Cl Me N-CH 2 Ph Cl Et N-C11 2 Ph Example H-3. 1: Other compounds of the general formula 1.2 which can be prepared analogously to the procedure described in Example H- I or by means of another appropriate procedure selected from thosc indicated hereinbefore are those listed in Table 2 below.

Table 2: (1.2) Physical data

R

2

R

5

R

6

R

9 RIO R 17

Y~

S. 0 *5 S S *S S

S

*5 *5

S

5*

*SS*

0* S a.

a.

SO

S.

H1-3.1 H1-3.2 H-3.3 H-3.4 H-3.5 H-3.6 H1-3.7 11-3.8 H1-3.9 H-3.10 H-3.11 H-3. 12 11-3.13 H-3.14 H-3. 15 11-3.16 11-3.17 11-3.18 H-3 .19 H-3.20 H-3.2 1 11-3.22 H-3.23 H-3.24 111H 111H H H 1111 1111 H H H111 H H 1111 Me H Me H Me H H111 H111 H H

NHH

111H 1111 H11H Me H MeNH Me H Me H Me H H Et HNEt H Me H1 Me H Et H Et 11 Me H Et H Me H Et H Et H Me H Et 11 Me H Me N C! H Et H1Et H Me H Et H Et H Me H Me "1 Pr Me N(H) Et N(H) Me N(H) Me N(H) Me N(Ac) Et N(Ac) Me N(Ac) Me N(SO 2 Ph) Me N(SO 2 Ph) Me N(Me) Et N(Me) Me N(Me) Me N(Me) Me N(Me) Me N(Wt) Me N(Me) Me S Et S me S Me S, Et S Me S Me S Me S 162-164' refractive index: nD 5 0 1.6022 m.p. 138-140'C /1 k .R1 Ex. R 2

R

5

R

6

R

9 Rj 0

R

17

Y

Physical data

S

*5 SS 9*

S.

S S S.

S

SS

*5SS

S*

S S

S

S S *5 11-3.25 J-1-3.26 11-3.27 11-3.28 H1-3.29 H1-3.30 H1-3.31 H1-3.32 H1-3.33 H-3.34 11-3.35 11-3.3 6 H-3.37 H1-3.38 H1-3.39 H-3.40 H1-3.41 H1-3.42 11-3.43 11-3.44 H1-3.45 11-3.46 11-3.47 11-3.48 11-3.49 H-3.50 11-3.51 H-3.52 11-3.53 11-3.54 H1-3.55 Ph H PhiH Me CI Me CI Me CI Me CI 111H 1111 1111 1111 1111 Me H Me H Me H Me H Ph H Ph H Me Ci Me CI Me CI Me CI Me CI H Et H Er H Et H Er Me "1 Me Er H Et H Me H Me H CI H Er H Et H Me "1 Et "1 Er H Et H Et H Et H Me H Me H Pr Me S Et S Me S Et S Me S Et S MeO0 Er 0 MeO0 MeO0 Et 0 MeO0 Er 0 Me 0 Er 0 Me 0 Er 0 Me 0 Er 0 Me 0 Er 0 Me 0 Me 0 Er 0 Me 0 Me 0 Me 0 Er 0 MeG0 MeG0 MeG0 Me OMe H Er Me OMe H Et Me OMe H Me Me OMe H Me Me H F Er Me H F Er Me H F Me Me H F Me M c H F c-Pr Examples H-4: Other compounds of the general formula 1.3 which can be prepared analogously to the procedure described in Example 1H-1 or by means of another appropriate procedure selected from those indicated hereinbefore are those listed in Table 3 below.

Table 3: (1.3) *O C. C

C.

C C C. C

C.

C. C

CC

CCC.

C

CC

C C

C

C C

C.

Example R 2

R

3

R

6

K~

9

R

10

R

17 Y Physical data H1-4.1 H-4.2 H-4.3 H1-4.4 H1-4.5 H1-4.6 H1-4.7 H-4.8 H1-4.9 H1-4.10 11-4.11 H-4.12 H1-4.13 H1-4.14 H1-4.15 H1-4.16 H1-4.17 11-4.18 11-4.19 H1-4.20

H

H

H1 11

H

11 Me Me Me Me H1

H

H

H1 Ph Ph Ph Ph Me Me Me Et Me Me Et Me Me Et Me Me Me Et Me Et Me *Et Me Me Me Et

S

S

S

0 0 0 0 0 0 0

N(H)

N(H)

N(Ac) N(Ac) 0 0 0 0

N(H)

N(H)

I,,

I'-

Example R 2

R

3

R

6

R

9 Rio R 17 Y Physical data H-4.21 Me Me Me Me Cl 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-5: Other compounds of the general formula 1.4 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 4 below.

S

6 0. 0 o Table 4:

N

(1.4) Example R2 R 3

R

5

R

7

R

9 RIO Y Physical data 0 *0 0 U U U U

U

U. U

U.

U

U.

U. 0O

U.

U.

H-5.1 H1-5.2 H-5.3 H-5.4 H-5 .5 1H-5.6 H-5.7 H1-5.8 H1-5.9 H-5.10 H1-5.11 H1-5.12 13 H1-5.14 H-5.15 H1-5.16 H1-5.17 H1-5.18 11-5.19 H-5.20 11-5.21 11-5.22 H1-5.23 11-5.24 H1-5.25 111H1H HEt C1 1H HH HEt CI 1111111H Me Br "1 H1111 MeGIl "H1H H C1lEt Me Me H H Et Cl Me MeH H Et Cl Me MeH H Me C1 Me Me H H Me Br 111111 Me Et Cl H H H Me Et Cl H H H Me Me Cl 11111H Br Et Cl "H HBr EtC1 111 HH Br Me Br "H 111 Br Pr Cl 1111 Me H Et CI 1111 Me H Et C1 H Me H Me CI H H Me H Me Br "H 1 Me H e F Me Me H H Et C1 MeMeNH H Et Cl Me MeH H Me C1 Me MeH H Me Br Me Et Me Me Me Me Et Me Me Me Et Me Me Et Me Me Me Et Me Me Me Me Et Me Me

S

S

S

S

S

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

N(H)

N(H)

N(H)

N(H)

imp.: 79-80' oil; 1H NMR 128-130" Example R 2

R

3

R

5

R

7

R

9 RIO R 17 Y Physical data H-5.26 H1-5.27 11-5.28 H-5.29 H-5.30 H-5.31 H-5.32 H1-5.33 H-5.34 MVe Me M~e Me Me Me Mie Me Me Me M~e Me M~e Me Me Me Me Me Et Et Me Me Et Et Me Me Et N(Ac) N(Ac) N(Ac) N(Ac) N(Me) N(Me) N(Me) N(Me) S M.P. llO-lll 0

C

S

S.

S

S4 C S

S

S

B. S S S S Examples 11-6: Other compounds of the general formula 1L5 which can be prepared analogously to the procedure described in Example H-i or by means of another appropriate procedure selected from those indicated hereinbefore are those listed in Table 5 below.

Table

CH

2

CH

3

S.

a.

S.

S. S C S

S

*S

S S S. S 54

S.

N

Example R 3 Y Physical date H1-6.1 11 S H1- 6.2 11 0 H--6.3 H N(H1) 11-6.4 Me N(Mve) Examvle, H-7: Other compounds of the general formula 1.6 which can be prepared analogo~isly 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 6 below.

Table 6:

CH

2

CH

3

N

(1.6) 0 .0 3 .61.

Example R 15 Y Physical data 1H-7.1 H S H4-7.2 H 0 H4-7.3 H N(Me) H-7.4 Me S H-7.5 Me 0 H4-7.6 Me N(Me) H4-7.7 Me NH Examples H-8: Other compounds of the general formula 1.7 which can be pr-epared 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 7 below.

Table 7: (1.7)

S

S*

S. S 5 OS 5* 5

S

S

S

S* S *5 S. S

S.

S SO 55.5 S S 5@ S 55 S S 0e 5.55

S

SOS.

OS

S S

S.

OS S

CS

Example R 17 Y Physical data H-8.1 H-8.2 H-8.3 H-8.4 H-8.5 H-8.6

S

S

0 0 N(Me) N(Me) 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: (1.8) V.a

V

V.

Example R 17 Y Physical data H-9.1 Me S H-9.2 H S H-9.3 Me O H-9.4 H O 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 be prepared for example as follows: In an autoclave, 29 g of dry ammonia and 23.5 g of Raney nickel are added to a mixture of 23.5 g of 2-(l-hydroxyiminoethyl)-3-methylbenzo[b]thiophene and 250 ml of absolute methanol. The reaction mixture is then heated to 500, hydrogenated at this temperature for approximately 5 hours under a pressure of approximately 100 bar and subsequently cooled to room temperature, the catalyst is filtered off, and the filtrate is evaporated under a waterpump vacuum. The oily residue. 2-(l-aminoethyl)-3-methylben7o[b]thiophene 1 H NMR), is reacted further without additional purification.

Examples H-11: Other compounds of the general formula Ia.9, which are used, for l-armple, as starting materials in the processes of Examples H-1 and H.2, which can be 7E prepared analogously to the procedure described in Example 1H-10 or by means of another appropriate procedure selected from those indicated hereinbefore are those listed in Table 9 below.

Table 9: (1a.9)

NH

2 Example R 3

R

4

R

5

R

6

R

7

R

17 Y Physical data H-11.1 H- 11.2 11.3 H- 11.4 H-11.5 H- 11.6 H- 11.7 H-11.8 H-i 1.9 H- 11.10 H1-11.11 H- 11.12 H- 11.13 H- 11.14 H- 11.15 H- 11.15 H- 11. 17 H- 11.18 11. 19 11.20 H- 11.21 H H H H H Me S H H H H H Et S Me H H H H Et S "HH Cl H H Me S "HH Cl H H Et S H H H H H MeO0 H H H H H Et 0 "HH Cl H H MeO0 "HH Cl H H Et 0 "HH OMe H H Me G H H OMe H H Et 0 H H H H OMe Me 0 H H H H OMe Et 0 H H H OMe H Me 0 H H H OMeH Et 0 H OMe H 11e H Me 0 H OMe H O~eH1 Et 0 Me H H F1 H. Me 0 Me H H H H EtO0 Et H H H H Me 0 E tH H- H H Et 0 oil; 'H NMR oil; 'H NMR oil; 'H NMR oil; 1H NMR oil; 'H NMR 40-41' oiJ; IH NMR oil; 'H NMR oil; 'H NMR oil; 1H NMR oil; I HNMR Example R 3

R

4

R

5

R

6

R

7

R

17

Y

Physical data H-11.22 Me H Cl H H Me O 1H-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) 92-95° H-11.27 Me H II H H Me N(Ac) H-11.28 H H H H H Me N(Me) oil; 1 H NMR 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 Cl H H Et S oil; 'H NMR H-11.32 Me H H H H Me S oil; H NMR H-11.33 H H H H H Me N-CH 2 Ph H-11.34 H H H H H Et N-CH 2 Ph 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 i 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 below.

I 7 pr Table (Ia. Example R 2

R

5

R

6 R1 7

Y

Physical data t, S

S

S*

S

S

H- 12.1 H-12.2 H- 12.3 H-12.4 H- 12.5 H-12.6 H- 12.7 H-12.8 H-12.9 H-12.10 H- 12. 11 H- 12.12 H- 12.13 H-12.14 H-12.15 -12.16 H- 12.17 H- 12.18 H- 12.19 H- 12.20 H- 12.21 H- 12.22 H-12.23 H-12.24 H- 12.25 H-12.26 H- 12.27 H-12.28 H H H H H H Me H H Me H H Ph H H Ph H H Me Ci H Me Ci H 11 H H H H H Me H H Me H H Ph H H.

Ph H H Me CI H Me CI H Me OMe H Me OMe H Me H F Me H F H H H H H H H H H H H H H H H H H H Me H H Me H H Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Me Me Et

S

S

S

S

S

S

S

S

0 0 0 0 0 0 0 0 0 0 0

N(H)

N(H)

N(Ac) N(Ac) N(S0 2 Ph) N(Me) N(Me) N(Me) oil; 'H NMR oil; 1H NMR -43- Examples H-13: Other compounds of the general formula Ia.11, which are used, for example, 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: (la.ll) Example R 2

R

3

R

6

R

17 Y Physical data H-13.1 H-13.2 H-i3.3 H-13.4 H-13.5 H-13.6 H-13.7 H-13.8 H-13.9 H-13.10 H-13.11 H-13.12 H-13.13 H-13.14 H-13.15 H-13.16

H

H

H

H

Me Me

H

H

Me Me Me Me

H

H

H

H

S

S

0 0 0 0 0 0

N(H)

N(H)

N(Ac) N(Ac)

N(H)

N(H)

N(Ac) N(Ac) N(Ac) Examples H-14: Other compounds of the general formula Ia. 12, which are used, for example, as starting materials in the processes of Examples H-5, which can be prepared -44analogously 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 12 below.

Table 12: (Ia.12)

NH

2 Example R 2

R

3

R

5

R

7 R17 Y Physical data C. 4

S

C

a 4* H-14.1 H-14.2 H-14.3 H-14.4 H-14.5 H-14.6 H-14.7 H-14.8 H-14.9 H-14.10 H-14.11 H-14.12 H-14.13 H-14.14 H-14.15 H-14.16 H-14.17 H H H H H H Me Me H Me Me H H H H H H H H H H H H H H H Me H H Me Me Me H Me Me H Me Me H Me Me H Me Me H Me Me H Me Me H Me Me H- Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me

S

S

0 0 0 0 0 0 0 0

N(H)

N(H)

N(Ac) N(Ac) N(Me) N(Me)

S

oil; 'H NMR oil; 1H NMR oil; 1H NMR oil Examples H-15: Other compounds of the general formula Ia. 13, which are used, for example, as starting materials in the processes of Examples H- 6, 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 4LLq Table 13 below.

Table 13:

H

2

N

Example R 3 Y Physical data H- 15.1 H S H-1'5.2 H 0 H-15.3 H N(H) H- 15.4 Me N(Me) (Ia. 13) S S

S

0* S

S

SS

S

S Examples H- 16: Other compounds of the general formula Ia. 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: Is (Ia. 14) S

S.

S

S

S

.5 5 5*

S.

Example RIS Y Physical data H1-16.1 H S 1H-16.2 H 0 H1-16.3 H N(Me) H- 16.4 Me S H- 16.5 Me 0 H- 16.6 Me N(Me) Fl-16.7 Me NH 0

S.

S S *5

S.

S S 555*

S

S.

5 S *S 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 below.

Table (Ia. Example R 17 Y Physical data H- 17. 1 Me S H- 17.2 H S H- 17.3 Me 0 H- 17.4 H 0 H-17.5 Me N(Me) H-17.6 H N(Me) too.

toS

S

S. S S S *0 S S S. S

S.

S S

SS

S

SS

S S

S

S S S

S.

Examples 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 those listed in Table 16 below.

Table 16: (Ia. 16) Example R 17 Y Physical data H-16.1 Me S H1-16.2 H S H1-16.3 Me 0 H- 16.4 H 0 H- 16.5 Me N(Me) H- 16.6 H N(Me)

S.

S S *5

S

S S *5 *5S* S S

S

S*

*5 *5 0

SO

OS

NMR data: Table 17 which follows contains the 1 H NMR data from the above examples.

The 1 H NMR spectra were recorded in CDCI 3 unless another solvent is indicated.

Table 17: Example 1 H NMR data (ppm/multiplicity/number of protons) H-2.15 H1-2.49 H1-2.62 H--5.7 8.43/s/11H; 7.77/d/111; 7.70/d/1H; 7.32/1111; 7.29/t/lH; 7.23/s/lH; .63/in/11-; 5 .58/m/1H; 2.80/q/2H; 2.07/m/2H; 1.2 7/m/3H; 1 .05/t/3H 8.47/s/1H; 7.67/d/1H; 7.63/d/1H; 7.26/dd/1H; 5.62/q/1H; 5.57/d/1H; 2.7 81q/2H; 2.45/s/3H; 2.08/m/1H; 1 .95/in/iN; 1 .24/t/3H; 1.0 1/t/3H 8.40/s/1H; 7.66/d/1H; 7.62/d/11-; 7.25/dd/1H; 5.62/m/11H; 5.57/m/1H-; 2.7 8/q/2H; 2.47/s/3H; 2.08/in/1H; 1 .95/i-/1H; 1 .23/t/3H; 1.0 l/t/3H 8.37/s/iN; 7.35/d/1H; 7.33/d/lH-; 7.1 8/dd/1H; 5.66/d/lH; 5.2 l/q/1N; 2.77/q/2H; 2.37/s/3H; 2.1l4/s/3H; 1 .97/m/2H; 1 .24/t/3H; 0.95/t/3H H1-10 7.8 i/d/iH; 7.63/d/ll; 7.36/t/ll; 7.28/t/1H; 4.66/m/1H; 2.37/s/3H; 1 .591s/2ll; 1 .48/d/3H H-11.1 7.801d/1H; 7.68/d/1H; 7.27/rn/3H; 4.43/rn/ill; i.60/s/2ll; 1.521d/3H- H1-11.2 7.80/d/1H; 7.68/d/1H; 7.3 1/t/1H; 7.27/t/lH; 7. 12/s/1H; 4.37/rn/liI; 1 .82Irn/2H; O.96/t/3H H1-11.3 7.79/dilH-; 7.64/d/1H; 7.37/t/1H; 7.28It/1ll; 4.40/s/ll; 2,37/s/3ll; l.80/rn/2H; 1.58/s/2ll; U.94t3ll H1-11.4 7.691d/1H; 7.59Id/IH; 7.25/dd/lH; 4.661s/IH; 2.33IsI3H; 1.65IsI2H 1 .47/d/3H H1-11.5 7.70/d/lH; 7.60/s/ll; 7.24/d/1H; 4.33/rn/ll; 2.3 1/s/3H; i.77/m/2H; 1 .60/s/2ll; .93/t/3ll H1-11.8 7.45/d/1l4; 7.33/dll; 7.17/dd/1H; 6.42/s/l-; 4.19/,-n/ll; l.60/s/2H; 1 .45/t/311.

H- 11.9 7.48/dull; 7.33/dull; 7. 17/dd/iH; 6.47/s/1H; 3.96/rn/ll; 1 .85/m/2H; 1 .52/s/2ll; O.96/t/3H H1-11.11 7.32/d/1ll; 6.98/dull; 6.83/dd/ll; 3.95/rn/il; 3.84/s/3H; 1.85/m/2ll; 09 1 .55/s/2ll; O.97/t/3ll H-i11.12 7.12/rn/2H; 6.76/rn/1H; 6.49/s/ll; 4.22/s/ll; 4.Oi/s/3ll; 1.62/s/2H; 1 .52/d/3ll 11 11: -11.14 7.37/d/lll; 6.99/d/ll; 6.83/dd/lll; 6.41/s/ll; 4.22/s/ll; 3.83/s/3ll; I .82/s/2H; 1.5/d/3ll 00* H9: 1-11.16 6.62/d/1H; 6.48/s/il-1; 6.30/d/Ill; 4.14/rn/ll; 3.88/s/3ll; 3.83/s,3ll; 1 .57/s/2ll; 1 .48/d/3ll 0061-11.18 7.42/rn/2H; 7.22/rn/2ll; 4.30/s/ll; 2.2 i/s/3ll; 1 .57/s/2ll; 1 .49/s(broad)/3ll 11-11.28 7.56/Wll; 7.28/rn/ll; 7.18/t/lll; 7.08/t/lll; 6.40/s/ll; 4.28/q/ill; 3.78/s/3ll; 1.55//3ll; 1.47/s/2ll 11-11.30 7.69/Wll; 7.60/Will; 7.24/ddll; 4.67/s/ll; 2.34/s/3H; 1.63/s/2ll; 1 .47/d/311 11.31 7.68/Will; 7.59/Wll; 7.23/ddll; 4.33/s/ill; 2.32/s/3ll; i.77/n/lll; 1 .60/s/2ll, 0.92/t/311 11-11.32 7.81/Wll; 7.63/Wlll; 7.36/i/ill; 7.28/t/iH; 4.66/s/ill; 2.37/s/3H; 1 .59/s/2ll; 1 .48//3ll 11-12.21 8.00/s/ll; 7.75 to 7.07/rn/5ll; 4.50/rn/ll; 1.70/s/2ll; 1.58//3ll 11-12.26 7.68/Will; 7.32 to 7.20/m/2ll; 7.1 1/i/ll; 6.97/s/ll; 4.49/rn/Ill; 3.75/s/3H; I 5-P, L 141.56/s/2ll; i.54/W/31 H- 14.3 7.35/s/lH; 7.33/d/1H; 7.18/dd/1H; 4.2 1/q/bH; 2.37/s/3H; 2.1 31s/3H; l.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; 2.38IsI3H; 2.15/s3-; l.72/m/2H; 1.50/s/2H; G.85/t/3H H-14.11 7.72/s/iN; 7.40/d/lN; 7.25/s/1H; 7.05/dd/lN; 4.20/rn/iN; 2.38/s/3H; 2.20/s/3H; 1.75 to l.31/m/5H t S

S

0 S. 0*

S.

S.

S

0@ *0*S S. *5 S S

S.

S.

S S Si S Examples F-i to F-6: Formulation of compounds according to the invention Examples F-1.1 to F-1.3: Emulsion concentrates Components F-Li. F- 1.2 F- 1.3 Active ingredient according ,o the invention 25% 40% Calcium dodecylbenzeiiesulfonate 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% Xylene mixture 65% 25% Emulsions of any desired concentration can be prepared from these emulsion concentrates by dilution with water.

S-0 "S Example F-2: Emulsion concentrate Components F-2 Active ingredient according to the invention Octylphenol polyethylene glycol ether (4 to 5 mol of ethylene oxide units) 3% Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (36 mol of ethylene oxide units) 4% Cyclohexanone Xylene mixture Emulsions of any desired concentration can be prepared from this emulsion concentrate by dilution with water.

*i Examples F-3.1 to F-3.4: Solutions S. S

S.

S

*55*

S.

S S S. S

S

S

Components F-3.1 F-3.2 F-3.3 F-3.4 Active ingredient according to the invention 80% 10% 5% Propylene glycol monomethyl ether 20% Polyethylene glycol (relative molecular weight: 400 atomic mass units) N-Methylpyrrolid-2-one -20% Epoxidised coconut oil 1% o I; Ori 9 Petroleum spirit (boiling range: 160-190°) 94% The solutions are suitable for use in the form of microdrops.

Examnles F-4.1 to F-4.4: Granules Components F-4.1 F-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.

Examnle F-5.1 and F-5.2: Dusts

C.

C. C

S

Components F-5.1 F-5.2 Active ingredient according to the invention 2% Highly-disperse silica 1% Talc .97% Kaolin Ready-for-use dusts are obtained by intimately mixing all components.

i Examples F-6.1 to F-6.3: Wettable 3owders Components F-6.1 F-6.2 F-6.3 Active ingredient according to the invention 25% 50% Sodium ligninsulfonate 5% Sodium lauryl sulfate 3% Sodium diisobutylnaphthalenesulfonate 6% Octylphenol polyethylene glycol ether (7 to 8 mol of ethylene oxide units) 2% Highly-disperse silica 5% 10% Kaolin 62% 27% All components are mixed thoroughly, and the mixture is ground thoroughly in a suitablt mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.

Examples B-l to B-11: Biological action of comnounds accordina to the invention a.

S

a S. S S S *S a.

Si..

S. a A. Microbicidal action a Example B-1.1: Systemic action against Pythium uitimum on sugar beet Test method: Mycelium of Pythium ultimum is mixed with soil (500 ml of mycelium suspension/101 of soil) and the mixture is filled into 250 ml plastic dishes. The dishes are incubated for four days at 100, 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 solution containing one of the active ingredients according to the invention (0.002% active substance) are then pou'ed into each dish. After an incubation phase at 100 for seven days followed by an incubation phase at 220 for four days, the activity of the active substance is assessed taking into account number and appearance of the emerged plants.

T.e, Test result: Active ingredients according to the invention show a good systemic action 27 /K against Pythium ultimum on sugar beet.

Example B-1.2: Systemic action against Pythium ultimum on maize Test method: The test is carried out analogously to the procedure described in Example B-1.1.

Test result: Active ingredients according to the invention show good systemic action against Pythium ultimum on maize.

Example B-2: Action against Puccinia graminis 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 c. the fungus. After an iilcubation time of 48 hours (conditions: 95 to 100 percent relative atmospheric humidity at the plants are placed in a greenhouse at 220. 12 days after infection, the activity of the active substance is assessed taking into account the development of rust pustule,;.

o 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 In contrast, °e 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 fe 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 huwmidity at 200), the plants are placed in a greenhouse at 220. The activity of the active substance is assessed taking into account the development of rust pustules 12 days after infection.

Test result: Active ingredients according to the invention of Examples H-1, H-2.13, H-2.15 and H-2.18 show a good systemic action against Puccinia graminis on wheat.

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 infection during which a relative atmospheric humidity of 90 to 100 percent and a temperature of 200 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-2.29 reduce the fungus infestation to 5 to 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 volun e) 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 days after infection, during which a relative atmospheric humidity of 90 to 100 percent and a temperature of 200 are mainrained.

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 groundnuts 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 210 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.

IT iTest result: Active ingredients according to the inve-tion show a good residual-protective y 5 action against Cercospora arachidicola on groundnuts.

Example B-5: Action against 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. invent-on (0.02% active substance) 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 6 days after infection, during which a relative atmospheric humidity of 95 to 100 percent and a temperature of 200 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 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 S Test method: Vine seedlings in the 4- to 5-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 200) and then 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). When the spray coating has dried on, Liie 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 Pyricularia oryzae on rice a) Residual-protective action Test method: Rice plants are grown for two weeks and then 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 84 hours later 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 220 are maintained.

S Test result: Active ingredients according to the irnvention show a good residual-protective action against Pyricularia oryzae on rice.

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 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 flooded 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 days after infection, during which a relative atmospheric humidity of 95 to 100 percent and a temperature of 240 are maintained.

Test result: Active ingredients according to the invention show a good systemic action S against Pyricularia oryzae on rice.

Example B-7: Residual-protective action against Venturia inaequalis on aeples 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 S.o. at a relative atmospheric humidity of 90 to 100 percent and placed in a greenhouse at 20 to 240 for a further 10 days. The activity of the active substance is assessed taking into zccount 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 particular H-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 ?repared 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 220.

The activity of the active substance is assessed taking into account the fungus infestation 10 days after infection.

/t 7 -o 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 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 (0.002% 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 dres 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 220. The activity of the active substance is assessed taking into account Sthe fungus infestation 10 days after infection.

STest result: Active ingredients according to the invention show a good systemic action S against Erysiphe graminis on barley.

a SExample B-9: Action against 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 relative atmospheric humidity and 20 0 C. The fungus infestation is assessed 12 days after infection.

Active ingredients of the formula 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 Tetranychus urticae on beans Test method: 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 substarce) 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 2 corresponding numerical values on the control plants which have not been treated with the active substance are determined 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 activity of the active substance).

Test result: Active ingredients according to the invention show a good action against Tetranychus urticae on beans.

Example B-11: Action against Tetranychus cinnabarinus on dwarf beans Test method (dilution series): Dwarf beans in the 2-leaf stage are populated with a mixed population (eggs, larvae/nymphs ai, adults) of an OP-tolerant strain of Tetranychus cinna.barinus. 24 hours later, the active ingredient according to the invention is applied to the plants in an automatic spray cabin at concentrations of 200, 100 and 50 mg/1l (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 active ingredient at the desired concentration) are counted, and the corresponding 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 o reduced at the particular concentration of active ingredient (percentage activity of the active substance).

Test result: Active ingredients according to the inventio. show a good action against Tetranychus cinnabarinus on dwarf beans.

Claims (9)

1. A compound of the formula R 3 R R2 Y R 6 R 7 in which: one of the radicals R 2 R 3 R 4 R 5 R 6 and R 7 is a group of the formula [C(Ri 2 )(Ri 3 )]md[C(Ri 4 )(Ri 5 )]n-C(R 6 )(R 7 -l) 8 N N .:the remaining fr', of the radicals R 2 R 3 R 4 R 5 R 6 and R 7 independently of one another are hydrogen, halugen, CI-C 8 alkyl, halo-C 1 -Csalcyl, Cj-C 4 alkoxy-Cj-C 4 alkyl, Cl-C 8 alkoxy, balo-Cl-C 8 alkoxy, CI-C 8 alkylthio, halo-Cl-C 8 alkylthio, cyano, nitro, phenyl, phenoxy or phenylthio, where the phenyl groups in phenyl, phenoxy and phenylthio are unsubst uted or substituted by one, two or three substituents, selected from the group eeffqfW~g~alogen, CI-C 4 alkyl and C 1 -C 4 alkoxy, with the proviso that, of the five radicals from the group of the radicals R 2 R 3 R 4 R 5 R 6 and R 7 which differ from group la, 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 unsubs~tituted or substituted as mentioned above, and from phenylthio which is unsubstituted or substituted as mentioned above; Y is gtSM; g q a group of the formnula NRI in which R, is hydrogen,\ -sly, Cl-C 8 alkanoyl, Cl-C 8 alkanesulfonyl, halo-Cl-C 8 alkanesulfonyl, cyano-Cl-C~aikanesulfonyl or phenylsulfonyl, whose phenyl gr unsubstituted or substituted by one or two substituents selected from the group oem ww4g~halogen, Cl-CIalkyl, nitro and cyano; R 8 is hydrogen, CI-C 8 alkyl, C 1 -C 8 alkoxy or Cl-C 8 alkylthio; R 9 is hydrogen, C 1 -C 8 alkyl, halo-Cl-COalkYl, C 1 -C 4 alkoxy-Cj-C 4 alkyl, CI-C 4 alkylthio-C 1 -C 4 alkyl, Cl-C 4 alkanesulfinyl-C 1 -C 4 alkyl, CI-C 4 alkanesulfonyl-Cj-C 4 alkyl, C 2 -C 8 alkenyl, halo- C 2 -C 8 allcenyl, C 2 -C 8 alkynyl, C 3 -C 8 cycloalkyl or halogen; RIO is hydrogen, hydroxyl, Cl-C 8 alkyl, halo-Cl-C 8 alkyl, CI-C 4 alkoxy-Cj-C 4 alkyl, Cl-C 8 alkoxy, Cl-C 8 alkylthio, C 1 -C 8 alkanesulfinyl, Cl-C 8 alkanesulfonyl, halogen, nitro, cyano, amino, a group of the formula N(Hi)R 18 a group of the formula N(R, 8 )Rl 9 (Id) or a group of the formula N=C(Rl 9 )R 20 R 11 is hydrogen, CI-C 8 alkyl, benzy), Cl-C 8 alkanoyl, phenylcarbonyl whose phenvi graup is unsubstituted or substituted by one, two or three substituents selected fioi A_ ru eew4i~fialog and CI-C 4 alkyl, or is Cl-C 8 alkylthio, halo- Cl-C~alkylthio, cyano-Cl-C 8 alkylthio, phenylthio or benzylthio, where the phenyl groups in phenylthio and benzylthio arq unsubstituted or substituted by one or two substituents selected from the grop eff4H.&1gi aogen, Cl-C 4 alkyl, nitro and cyano; R 12 R 13 R 14 R1 5 R 16 and R 1 7, independently of one another are hydrogen, Cl-C 8 alkyl, halo-Cl-C~alkyl, Cj-C 4 alkoxy-Cj-C 4 alkyl or C 3 -C 8 cycloalkyl; R1 8 is C 1 -C 8 alkyl, benzyl, Cl-C 8 alkanoyl, **phenylcarbonyl whose phenyl group is ,unsubstituqed or substituted by one, two or three substituents selected from the grou Zep hlogen and Cl-C 4 alkyl, C 1 -C~alkylthio, halo-Cl-C 8 alkylthio, cyano-Cl-C 8 alkylthio, phenylthio or benzylthio, where the phenyl groups in phenylthio and benzylthio are, unsilbstituted or substituted by one or two substituents selected from the gru efftp44Vialogen, CI-C 4 alkyl, nitro and cyano; R 19 is Cl-C 8 alkyl; R 20 is hydrogen or Ci-C 8 alkyl; misO0 or 1; and n is 0 or 1; or, if appropriate, a tautomer thereof, in each case in free form or in salt formn.

2. A compound according to claim 1 of the formula 1, in which: one of the radicals R 2 R 3 R 4 R 5 R 6 an 7 is a group Ia; the other five of the radicals R 2 R 3 R 4 R 5 R 6 and R 7 independently of one another are hydrogen, halogen, CI-C 4 alkyl, hao-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms, C 1 -C 2 alkoxy-Cj-G 4 alkyl, Cl-C 4 alkoxy, Halo-CI-C~alkoxy having 1, 2 or 3 halogen atoms, Cl-C 4 allcylthio, halo-Cl-C 4 alkylthio having 1, 2 or 3 halogen atoms, cyano, nitro, phenyl, phenoxy or phenylthio, where the phenyl groups in phenyl, phenoxy and phenylthio are unsubs ted o~ubstituted by one, two or three substituents selected from the group Cl-G,)alkyl and Cl-C 2 allcoxy, with the proviso that, of the five radicals frmthe group of the radicals R 2 R 3 R 4 R 5 R 6 and R 7 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 orx'gen atom; rufiff rtoiAo@ a group Ib; R, is hydrogen, 0 1 C 1 -C 4 alkyl, Cl-C 4 alkanoyl, C 1 -G 4 alkanesulfonyl, halo-C 1 -C 4 alkanesulfonyl having 1, 2 or 3 halogen atom, cyano-Cl-C 4 allcanesulfonyl or phenylsulfonyl whose phpny1,grou~~ unsubstituted or substituted by one or two substituents selected from the groupreuipsi g halogen, C 1 -C 2 alkyl, nitro and cyano; R 8 is hydrogen, CI-C~atkyl, Cj-C 4 alkoxy or Cl-C~alkylthio; R 9 iv hydrogen, CI-C 4 alkyl, halo-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms, Cj-C 2 alkoxy-Cj-C 4 alkyl, Cl-C 2 alkylthio-CI-C 4 alkyl, Cl-C 2 alkanesulfinyl-C 1 -C 4 alkylA, Cl-C- 2 aikanesulfonyl-C 1 -C 4 alcyl, C 2 -COaW.-nyl, halo-C 2 -C 4 alkenyl having 1, 2 or 3 halogen atoms, C 2 -C 4 allcynyl, C 3 -C 7 cycloalkyl or halogen; R 10 is hydrogen, hydroxyl, Cl-C 4 alkyl, halo-Cl-C 4 alkyl having 1, 2 or 3 halogen atoms, Cj-C 4 alIkoxy-Cj-C 4 alkyl, CI-C 4 alkoxy, Cl-C 4 alkylthio, C 1 -C 4 alkanesulfinyl, Cl-C 4 alkanesulfonyl, halogen, nitro, cyano, amino, a group Ic, a group Id or a group le; R 11 is hydrogen, Cl-C 4 alkyl, benzyl, CI-C 4 alkanoyl, phenylcarbonyl whose phenyl group is unsub~tituted or substituted by one, two or three substituents selected from the group c-r~6\ Cr:5 o -G)Oigaoe and Cl-C 2 alkyl, or is C 1 -C 4 alkylthio, halo-C 1 -C 4 alkylthio having 1, 2 or 3 halogen atoms, cyano-Cl-C 4 alkylthio, phenylthio or benzylthio, where the phenyl groups in phenylthio and benzylthio are undstituted or substituted by one or two substituents selected from the gfoup. 9p~h alogen, CI-C 2 alkyl, nitro and cyano; R 12 R 13 R 14 R 15 R 16 and R 17 independently ofone another are hydrogen, CI-C 4 alkyl, halo-Cl-C 4 alkyl having 1, 2 or 3 halogen atoms, CI-C 4 alkoxy-C 1 -C 4 aIkyl or C 3 -C 7 cycloalkyl; R 18 is CI-C 4 alkyl, benzyl, Cl-C 4 alkanoyl, phenylcarbonyl whose phenyl *group isu btgudor substituted by one, two or three substituents selected from the group coe+49Fg~alogen and C 1 -C 2 alkyl, or is CI-C 4 alkylthio, halo-Cl-C 4 alkylthio having 1, 2 or 3 halogen atoms, cyano-C 1 '-C 4 alkylthio, phenylthio or benzylthio, where the phenyl groups in phenylthio and benzylthio are unsubstituted or substituted by one or two substituents selectedfrom the group iPigalogen, CI-C 2 alkyl, nitro and cyano; R 19 is Cl-C 4 alkyl; R 20 is hydrogen or CI-C 4 alkyl; m is 0 or 1; and n is 0 or 1; or0; 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 R 2 R 3 R 5 and R 6 is a group 1a; the other three of the radicals R 2 R 3 R 5 and R 6 and the radicals R 4 and R 7 independently of one another are hydrogen, halogen, C 1 -C 4 alkyl, halo-Cl-C 4 alkyl having 1, 2 or 3 halogen atcms, CI-C 2 alkoxy-CI-C 4 alkyl, Cj-C~alikoxy, haiO-C 1 C 4 alkoxy having 1, 2 or 3 halogen atoms, Cl-C 4 alkylthio, halo-Cl-C2 4 alkylthio having 1, 2 or 3 halogen atoms, cyano, nitro, phenyl, phenoxy or phenylthio, where the phenyl groups in phenyl, phenoxy phenylthio are unsubstituted or substituted by one, two or three substituents selected V from the group oo si\alogen, CI-C 2 alkyl and C 1 -C 2 alkoxy, with the proviso that of the five radicals from the group of the radicals R 2 R 3 R 4 R 5 R 6 and R 7 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 sii'istituted as menitioned above; Y is an O';g1 1 group 1b; R, is hydrogen, CI-C 4 alkyl, Cl-C 4 alkanoyl, C 1 -COallanesulfonyl, halo-C 1 -C 4 alkanesulfonyl having 1, 2 or 3 halogen atoms, cyano-CI-C 4 alkanesulfonyl or phenylsulfonyl whose phenyl grou unsubstituted or substituted by one or two U9 .V-N IF substituents selected from the group eatflP MI.Nhalogen, Cl-C 2 alkyl, nitro and cyano; R 8 is hydrogen, C, -C- 4 alkyl, C.,-C 4 alkoxy or Cl-C 4 a'iylthio; R 9 is hydrogen, C, -C 4 alkyl, halo-Cl-C 4 alkyl having 1, 2 or 3 halogen atoms, Cj-C 2 alkoxy-C 1 -C 4 alkyl, CI-C 2 alkylthio- C 1 -I lyC-~lknsliy- 1 -C 4 alkyl, Cl-C 2 alkanesulfonyl-C 1 -C 4 alkyl, C 2 -C 4 alkenyl, halo-C 2 -C 4 alkenyl having 1, 2 or 3 halogen atoms, C 2 -C 4 alkynyl, C 3 -C 7 cycloalkyl or halogen; R 10 is hydrogen, hydroxyl, CI-C 4 alkyl, halo-Cl-C 4 alkyl ~having 1, 2 or 3 halogen atoms, Cj-C 4 alkoxy-Cj-C 4 alkyl, C-~loy 1 Caklho :Cl-C 4 alkanesulfinyl, Cl-C 4 alkanesulfonyl, halogen, nitro, cyano, amino, a group Ic, a group Id or a group Ie; R 11 is hydrogen, Cl-C 4 alkyl, benzyl, Cl-C 4 alkanoyl, phenylcarbonyl whose phenyl group is unsubstituted or substituted by one, two or three substituents selected from the group ~p8\halogen and CI-C 2 alkyl, or is CI-C 4 alkylthio, halo-Cl-C 4 alkylthio having 1, 2 or 3 halogen atoms, cyano-C 1 -2 4 alkylrhio, phenylthio or benzylthio, where the phenyl groups in phenylthio and benzylthio are un~substituted or substituted by one or two substituents selected from CF *the group eeipf igalogen, Cl-C 2 alkyl, nitro and cyano; R 12 R 13 R 14 R 15 R 16 and R 17 independently of one another are hydrogen, CI-C 4 alkyl, halo-Cl-C 4 alkyl having 1, 2 S. or 3 halogen atoms, Cj-C 4 alkoxy-C 1 -C 4 alkyl or C 3 -C 7 cycloalkyl; R 18 is CI-C 4 alkyl, benzyl, C 1 -C 4 alkanoyl, phenylcarbonyl whose phenyl group is uilsubstituted or substituted by one, two or three substituents selected from the group- si galogen and Cl-C 2 alkyl, or is Cl-C 4 alkylthio, halo-Cl-C 4 alkylthio having 1, 2 or 3 halogen atoms, cyano-C 1 -C 4 alkylthio, phenylthio or benzylthio, where the phenyl groups in phenylthio and benzylthio are unsubstituted or substituted by one or two substituents selected from the gru a+'s~'aogen, Cl-C 2 alkyl, nitro and cyano; R 19 is CI-C 4 alkyl; R 20 iS hydrogen or CI-C 4 alkyl; 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. -64-

4. A compound according to claim 1 of the formula I, in which: one of the radicals R 2 R 3 R 5 and R 6 is a group Ia; the other three of the radicals R 2 R 3 R 5 and R 6 and the radicals R 4 and R 7 independently of one another are hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or unsubstituted phenyl, with the proviso that, of the five radicals from the group of the radicals R 2 R 3 R 4 R 5 R 6 and R 7 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 atema SulfAMatomIor a group Ib; R 1 is hydrogen, Ci-C 4 alkyl, CI-C 4 alkanoyl or unsubstituted phenylsulfonyl; R 8 is hydrogen or C 1 -C 4 alkyl; R 9 is C 1 -C 4 alkyl, C 3 -C 4 cycloalkyl or halogen; RIo is Ci-C 4 alkyl, halogen or nitro; R 11 R 12 R 13 R 1 4 R 15 and R 16 are in each case hydrogen; R 1 7 is hydrogen or C 1 -C 4 alkyl; m is 0 or 1; and n is 0 or 1; in free form or in salt form. *,oS*S S

5. A compound according to claim 1 of the formula I, in which: one of the radicals R 2 R 3 and R 6 is a group Ia; i the other two of the radicals R 2 R 3 and R 6 and the radicals R 4 R 5 and R 7 independently of one another are hydrogen, halogen, Ci-C 4 alkyl or C 1 -C 4 alkoxy, with the proviso that, of the five radicals from the group of the radicals R 2 R 3 R 4 Rs, R 6 and R 7 which differ from the group Ia, at least three radicals are hydrogen; Y is a-~e'yg ,lfr atom=r a group Ib; R 1 is hydrogen or C 1 -C 4 alkyl; Rg is hydrogen; R 9 is C 1 -C 4 alkyl; R 1 o is halogen; RI and R 1 6 in each case are hydrogen:, R 17 is C 1 -C 4 alkyl; 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: R 2 is a group Ia, R 3 is hydrogen or C 1 -C 4 alkyl, R 4 is hydrogen, R 5 is hydrogen, halogen or C 1 -C 4 alkoxy, R 6 and R 7 in each case are hydrogen, with the proviso that, of the five radicals R 3 R 4 R 5 R 6 and R 7 at least four radicals are hydrogen, Y is an exygea Ate, AM Al Quraiatear a group Ib and R 1 is hydrogen or C 1 -C 4 alkyl; or R 2 is hydrogen, R 3 is a group Ia, R 4 R 5 R 6 and R 7 in each case are hydrogen, Y is a group Ib and RK i, hydrogen or C 1 -C 4 alkyl; or R 2 and R 3 independently of one another are C 1 -C 4 alkyl, R 4 and R 5 in each case are hydrogen R 6 is a group Ia, R 7 is hydrogen, Y is anoxygen-atom=or a group Ib and R 1 is hydrogen; and in each case Rg is hydrogen; R 9 is C 1 -C 4 alkyl; RIo is halogen; R 11 and R 16 in each case are hydrogen; R 17 is C 1 -C 4 alkyl; and m and n in each case are 0; in free form or in salt form. *in each ease in free form or pin lln rm. i- 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 R 1 1 is hydrogen, C 1 -Csalkyl or benzyl, or, if appropriate, a tautomer thereof, in each case in free form or in salt form, reacting a compound of the formula S. S S S S R 8 N in which R 8 R 9 and Rio 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 formula S i (ni), in which Y is as defined in formula I and, with a single exception, R 2 is R 2 R 3 is R 3 R 4 is R 4 R 5 is R 5 R 6 is R 6 and R 7 is R 7 where R 2 R 3 R 4 R 5 R 6 and R 7 are as defined in formula I, the abovementioned exception being that the group Ia, which is mentioned in the definitions of the variables R 2 R 3 R 4 RS, R 6 and R 7 of the formula I, is replaced by the group of the formula H(Rn')N-[C(R1 2 )(R1 3 )]m-[C(R1 4 )(Ri 5 )]n-C(Ri 6 (Ila) in which R 11 is hydrogen, C 1 -Csalkyl or benzyl and R 12 R 13 R 1 4 R 1 5 R 16 R 17 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 R 11 is as defined in formula I but differs from hydrogen, C, Csalkyi and benzyl, or, if appropriate, a tautomer thereof, in each case in free form or in salt form, introducing the desired substituent R 11 which differs from hydrogen, C 1 -Csalkyl and benzyl, into a compound of the formula I in which R 11 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, separatirg an isomer mixture which can be obtained according to the process, and isolating the desired isomer and/or converting a free compound of the formula I or a tautomer thereof which can be obtained according to the process into a salt, or 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. 'IA. 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-appTroprie-in addition to at least one auxiliary. A composition according to claim t\for protecting plants against attack by phytopathogenic microorganisms and/or pests from the order of the Acarina. -5 A process for the preparation of a composition according to claim/ 3, which comprises intimately mixing the active ingredient with the carrier material. \N The use of a compound according to claim 1 or, if appropriate, of a tautomer thereof, in each case in free form or in agroch.emically usable salt form, or of a composition according to claim lkfor protecting plants against attack by pests. 1 The use according to claim 6ifor 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 -66- 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.

14. A method according to claim 13 for protecting plants against attack by phytopathogenic microorganisms and/or pests from the order of the Acarina. A [1-(pyrimidin-4-ylamino) alkyl] indole derivative, substantially as hereinbefore described with reference to any one of examples H1 to H9.

16. A composition for protecting plants against pests, substantially as hereinbefore described with reference to any one of examples F1 to F6.

17. A method of protecting plants against attack by pests, which comprises applying, as active ingredient, a compound according to claim 15, or a composition according to claim 16, to the plants, their locus or to parts of plants. DATED this Twenty third Day of December 1994 S 15 Ciba-Geigy AG Patent Attorneys for the Applicant SPRUSON FERGUSON 0* *000: *o IN:\lbZ10039.S:FO 18774/A Pesticides Abstract Compounds of the formula R 3 R R2) Y R 6 in which: one of the radicals R, 2 R 3 R 4 R 5 R 6 and R 7 is a group of the formula [C(R, 2 )(R1 3 )1,i-[C(RI 4 )(R 15 )lnC(R',16) (Rl 7 (la); R8~: N N the other five of the radicals R 2 R 3 R 4 R 5 R 6 and R 7 independently of one another- are hydrogen, halogen, CI-C 8 alkyl, halo-C 1 -C 8 alkyl, C 1 -C 4 alkoxy-C 1 -C 4 alkyl, CI-C 8 alkoxy, halo-Cl-C 8 alkoxy, Cl-C 8 a'lkylthio, halo-C 1 -Cgalkylthio, cyano, nitro, phenyl, phenoxy or -'henylthio, 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 in which R, is hydrogen, CI-C 8 alkyl, CI-C 8 alkanoyl, Cl-C 8 alkanesulfonyl, halo-Cl-C 8 alkanesulfonyl, cyano-C 1 -C 8 alkanesulfonyl or phenylsulfonyl, whose phenyl group is unsubstituted or substituted by one or two substituents selected from the group comprising halogen, C 1 -C 4 alkyl, nitro and cyano; i is 0 or rind n is 0 or 1; and R 8 to IR 20 have the meaning given herei.n, and, if appropriate, their tautomers, in each case in their free form or in salt form, can be used as agrochemical active ingredients.