AU3705699A

AU3705699A - N-pyridonyl herbicides

Info

Publication number: AU3705699A
Application number: AU37056/99A
Authority: AU
Inventors: Walter Kunz; Kurt Nebel; Jean Wenger
Original assignee: Novartis AG
Current assignee: Novartis AG
Priority date: 1998-04-08
Filing date: 1999-04-06
Publication date: 1999-11-01
Anticipated expiration: 2019-04-06
Also published as: ID27165A; EP1076655A1; CN1295570A; JP2002511461A; AU738222B2; WO1999052893A1; BR9909487A; KR20010042521A

Description

WO 99/52893 PCT/EP99/02313 -1 N-PYRIDONYL HERBICIDES The present invention relates to novel, herbicidally active substituted N-pyridonyl nitrogen heterocycles, to processes for the preparation thereof, to compositions comprising those compounds, and to the use thereof in the control of weeds, especially in crops of useful plants, for example cereals, maize, rice, cotton, soybeans, rape, sorghum, sugar cane, sugar beet, sunflowers, vegetables, plantation crops and fodder plants, or in the inhibition of plant growth, and also in the non-selective control of weeds. N-Pyridyl-pyrazoles and N-pyridyl-tetramethylenetriazolidine-dione compounds having herbicidal activity are described, for example, in DE-A-3 917 469, DE-A-19 518 054, DE-A-19 530 606 and US-A-5 306 694. N-(2-Pyridyl)-pyridazinone compounds having herbicidal activity are described, for example, in JP-A-58-213 776. Novel N-pyridonyl nitrogen heterocycles having herbicidal and growth-inhibiting properties have now been found. The present invention therefore relates to compounds of formula I R1 R, W a2" w (I), N

X

1 R 3 wherein

R

1 is hydrogen, fluorine, chlorine, bromine or methyl;

R

2 iS C 1

-C

4 alkyl, C 1

-C

4 haloalkyl, halogen, nitro, amino, cyano or R 43 0-;

R

43 is hydrogen, C 1 -Coalkyl, C 3

-C

8 alkenyl, C 3 -CBalkynyl, C 3

-C

6 cycloalkyl, Cl-C 8 haloalkyl, cyano-Cl-Cealkyl, C3-C 8 haloalkenyl, hydroxy-C 1

-C

4 alkyl, C -C 4 alkoxy-C 1

-C

4 alkyl, C3-C6 alkenyloxy-C-C 4 alkyl, C 3

-C

6 alkynyloxy-C 1

-C

4 alkyl, C -C 4 alkoxy-Cl-C 4 alkoxy-C -C 4 -alkyl, Cl-C 4 alkylthio-C-C 4 alkyl, Cs-Caalkylcarbonyl, Cl-Coalkoxycarbonyl, C 3

-C

8 alkenyl oxycarbonyl, benzyloxy-Cl- or -C 2 -alkyl, benzylcarbonyl, benzyloxycarbonyl, phenyl, phenyl-C 2

-C

8 alkyl, benzyl, pyridyl, pyrimidinyl, pyrazinyl or pyridazinyl, those aromatic WO 99/52893 PCT/EP99/02313 -2 and heteroaromatic rings being unsubstituted or mono- to tri-substituted by halogen,

C

1

-C

4 alkyl or by C 1

-C

4 haloalkyl; or R44X 1 6 C(0)- [Cl-C 8 alkylene]

R

43 is R44X 6 C(0)-C 1

-C

8 alkyl- or

(C

6

H

s )

X

1 6 is oxygen, sulfur or RN R44 is hydrogen, C 1

-C

8 alkyl, C 3 -Cs 8 alkenyl, C 3

-C

8 alkynyl, C 3

-C

6 cycloalkyl, C-C 8 haloalkyl,

C

3 -Cshaloalkenyl, C 1

-C

4 alkoxy-Cj-C 4 alkyl, C 3

-C

6 alkenyloxy-C 1

-C

4 alkyl, C1 -C 4 alkylthio-C 1 C 4 alkyl, phenyl, phenyl mono- to tri-substituted by halogen, C 1

-C

4 alkyl or by C 1

-C

4 -halo alkyl, benzyl or benzyl mono- to tri-substituted on the phenyl ring by halogen, C 1

-C

4 alkyl or by Cl-C 4 haloalkyl;

R

45 is hydrogen, C 1 -Caalkyl, C 3

-C

8 alkenyl, C 3 -Cs 8 alkynyl, C 3

-C

6 cycloalkyl, Cj-C 8 haloalkyl or benzyl;

R

3 iS hydroxy, C 1

-C

6 alkoxy, C 3

-C

6 alkenyloxy, C 3

-C

6 alkynyloxy, C 1

-C

6 haloalkoxy, C 3

-C

6 haloalkenyloxy, C1-C 6 alkoxy-C 1 -Cealkyl, C 3

-C

6 alkenyloxy-C 1

-C

6 alkyl, C 3

-C

6 alkynyloxy C1-C 6 alkyl, C1-C 6 alkoxy-C 1

-C

6 alkoxy-C 1

-C

6 alkyl, Bl-Cl-C 6 alkoxy, R 4 (Rs)N-, C,-C 6 alkyl,

C

3

-C

6 alkenyl, C 3

-C

6 alkynyl, C 2

-C

6 haloalkyl, C 3

-C

6 haloalkenyl, C 3

-C

6 cycloalkyl, C 3

-C

6 halocycloalkyl, B 1 -C1-C 6 alkyl, OHC-, C1-C 6 alkylcarbonyl, C1-C 6 alkylcarbonyloxy, C -C 6 haloalkylcarbonyl, C 2

-C

6 alkenylcarbonyl, Cl-C 6 alkoxycarbonyl, C1-C 6 alkyl-S(0) 2 -,

C

1

-C

6 haloalkyl-S(O) 2 -, C 3

-C

8 trialkylsilyloxy, (C1-C6alkyl) 2 N-N=CH-, I--CH 2 - , O 0 C, 1

-C

3 alkyl , Bl-CH=N-, (CH 3

)

2 N-CH=N-, (C1-C 5 hydroxyalkyl)-CH 2 -, (B1-Cl-Cs

CH

hydroxyalkyl)-CH 2 -, (B 1 -C1-Cshaloalkyl)-CH 2 -, (hydroxy-Cl-C 5 alkyl)-O- or (B 1

-C

1 -C5 hydroxyalkyl)-O-; B, is cyano, OHC-, HOC(O)-, Cl-C 6 alkylcarbonyl, Cl-C 6 haloalkylcarbonyl, C 1 -C6alkoxy carbonyl, C 3

-C

6 alkenyloxycarbonyl, C 3

-C

6 alkynyloxycarbonyl, benzyloxy, benzyloxy carbonyl, benzyloxycarbonyl mono- to tri-substituted on the phenyl ring by halogen, C1-C 4 alkyl or by Cl-C 4 haloalkyl, benzylthio, benzylthiocarbonyl, benzylthiocarbonyl mono- to tri-substituted on the phenyl ring by halogen, Cl-C 4 alkyl or by C1-C 4 haloalkyl, C1-C 6 haloalkoxycarbonyl, Cl-C 6 alkylthio-C(O)-, R6(R 7 )NC(0)-, phenyl, phenyl mono- to WO 99/52893 PCT/EP99/02313 -3 tri-substituted by halogen, C 1

-C

4 alkyl or by C 1

-C

4 haloalkyl, 0 1

-C

6 alkyl-S(O) 2 -, C1-C6 alkyl-S(O)-, C 1

-C

6 alkylthio-, C 3

-C

6 cycloalkyl, C 1

-C

6 alkoxy, C 3

-C

6 alkenylthio or 0 3

-C

6 alkynylthio;

R

4 and R 5 are each independently of the other hydrogen, Cl-C 6 alkyl, C 3

-C

6 alkenyl, C3-C6 alkynyl, CI-C 6 haloalkyl, C3-C 6 haloalkenyl, C 3

-C

6 cycloalkyl, Cl-C 6 alkoxy-C,-Csalkyl, OHC-, Cl-C 6 alkylcarbonyl, Cl-C 6 haloalkylcarbonyl, Cl-C 6 alkyI-S(O) 2 - or C 1

-C

6 haloalkyl S(0)2-;

R

6 and R 7 are each independently of the other hydrogen, Cl-C 6 alkyl, C 3

-C

6 alkenyl, C 3

-C

6 alkynyl, C 1

-C

6 haloalkyl, C 3

-C

6 haloalkenyl, phenyl, phenyl mono- to tri-substituted by halogen, C 1

-C

4 alkyl or by C 1

-C

4 haloalkyl, benzyl or benzyl mono- to tri-substituted on the phenyl ring by halogen, C 1

-C

4 alkyl or by C 1

-C

4 haloalkyl;

X

1 is oxygen or sulfur;

R

9 R 1 2 R Rs R R 3 16 W is a group (W), X I (W 2 ), N(W3),

X

3 N X 2

X

4 N 1 I I R R20 R22 R2 18R 21 20 R .

2 5 N R4 (W4), 6 N X 5

(W

5 ), (W 6 ), (W7), N X X X 1 o N X N R 1 7 X 8 N II

R

28 R27

R

3

R

29 R 32 R31 kN-N N ,-N (W), N N

(W

9 ) or N (Wio) X t N X N, N X 1 5 13 14

R

8 is C 1

-C

3 alkyl, Cl-C 3 haloalkyl or amino;

R

9 is C 1

-C

3 haloalkyl, C 1

-C

3 alkyl-S(0)ni, C 1

-C

3 haloalkyl-S(O)nl or cyano; or

R

8 and R 9 together form a C3- or C 4 -alkylene bridge or C3- or C 4 -alkenylene bridge, each of which may be substituted by halogen, C 1

-C

3 haloalkyl or by cyano; nj is 0, 1 or2; Rio is hydrogen, C 1

-C

3 alkyl, halogen, C 1

-C

3 haloalkyl or cyano; or WO 99/52893 PCT/EP99/02313 -4

R

1 0 and R 9 together form a C3- or 0 4 -alkylene bridge or C3- or C 4 -alkenylene bridge, each of which may be substituted by halogen, C 1

-C

3 haloalkyl or by cyano;

R

11 is hydrogen, C 1

-C

3 alkyl, halogen or cyano;

R

12 is C 1

-C

3 haloalkyl;

R

1 2 and R 11 together form a C3- or 0 4 -alkylene bridge or C3- or C 4 -alkenylene bridge;

R

13 is hydrogen, C 1

-C

3 alkyl or halogen;

R

1 3 and R 1 2 together form a C3- or C 4 -alkylene bridge or C3- or C 4 -alkenylene bridge;

R

1 4 is hydrogen, C 1

-C

3 alkyl, halogen, C 1

-C

3 haloalkyl, R 3 3 0-, R34S(0)n 2 , R 35

(R

36 )N,

R

3 8(R 39

)N-C(R

37 )=N-, hydroxy, nitro or NE-C-S- ;

R

3 3 is C 1

-C

3 alkyl, Cl-C 3 haloalkyl, C2-C 4 alkenyl, C3- or C 4 -alkynyl or C 1

-C

5 alkoxycarbonyl

C

1

-C

4 alkyl; R34 is C 1

-C

4 alkyl or C 1

-C

4 haloalkyl; n 2 is0, 1 or 2;

R

35 is hydrogen, C 1

-C

4 alkyl, C 1

-C

4 haloalkyl, C 3

-C

6 cycloalkyl, OHC- or C 1

-C

4 alkylcarbonyl;

R

36 , R 37 and R 39 are each independently of the others hydrogen or C 1

-C

4 alkyl;

R

38 is Cl-C 4 alkyl;

R

15 is hydrogen, C 1

-C

4 alkyl, halogen, C 1

-C

4 haloalkyl, C 2

-C

4 alkenyl, C3-C 5 haloalkenyl, C3 or C 4 -alkynyl, C1-C 4 alkoxy, Cl-C 4 alkylcarbonyl, C1-C 4 haloalkylcarbonyl, C 2

-C

4 alkenyl carbonyl, C 2

-C

4 haloalkenylcarbonyl, C 2

-C

4 alkynylcarbonyl, C2-C 4 haloalkynylcarbonyl, Cl-C 4 alkoxycarbonyl, Cl-C 4 alkylcarbamoyl, C!-C 4 alkylS(0)n 3 , C3- or C 4 -alkynylS(0)n 3 , OHC-, nitro, amino, cyano or NE-C-S- ; n 3 is 0,1 or 2;

R

16 and R 17 are each independently of the other hydrogen, C 1

-C

4 alkyl, halogen, C 1

-C

4 halo alkyl or cyano;

R

18 and R 19 are each independently of the other hydrogen, methyl, halogen, hydroxy or =0;

R

2 0 and R 2 1 are each independently of the other hydrogen, C 1

-C

4 alkyl or C 1

-C

4 haloalkyl;

R

2 2 and R 23 are each independently of the other hydrogen, C1-C 3 alkyl, halogen or hydroxy;

R

2 4 and R 25 are each independently of the other hydrogen or Cl-C 4 alkyl; or / R40

R

2 4 and R 2 5 together form the group =C R41 R40 and R41 are each independently of the other Cl-C4alkyl; or WO 99/52893 PCT/EP99/02313 -5

R

40 and R 4 1 together form a C4- or C 5 -alkylene bridge;

R

2 6 is hydrogen or C 1

-C

3 alkyl ; or

R

2 6 together with R 25 forms a 0 3

-C

5 alkylene bridge, which may be interrupted by oxygen and/or substituted by halogen, Cl-C 4 alkyl, C 2

-C

4 alkenyl, C1-C 3 haloalkyl, C1-C 3 alkyl carbonyloxy, C 1

-C

4 alkoxycarbonyl, C 1

-C

3 alkylsulfonyloxy, hydroxy or by =0;

R

2 7 , R 2 8 , R 2 9 and R 30 are each independently of the others hydrogen, C 1

-C

3 alkyl, C3- or C4 alkenyl or C 3 -Csalkynyl; or

R

2 7 and R 28 together and/or R 29 and R 30 together in each case form a C2-C 5 alkylene bridge or C3-Csalkenylene bridge, each of which may be interrupted by oxygen, sulfur or S(0) 2 - and/or substituted by halogen, C 1

-C

4 alkyl, C 2

-C

4 alkenyl, C 1

-C

3 alkylcarbonyloxy,

C-C

3 alkylsulfonyloxy, hydroxy or by =0;

R

3 1 is hydrogen, C 1

-C

4 alkyl, C 1

-C

4 haloalkyl, C3- or C 4 -alkenyl, C3- or C 4 -haloalkenyl or C3 or C 4 -alkynyl;

R

32 is hydrogen, C1-C 4 alkyl, C 1

-C

3 alkoxy-C 1 - or -C 2 -alkyl, C 1

-C

4 haloalkyl, C3- or C 4 -alkenyl, C3- or C 4 -haloalkenyl or C3- or C 4 -alkynyl; or

R

32 and R 3 1 together form a C 3

-C

5 alkylene bridge; and

X

2 , X 3 , X 4 , X 5 , X 6 , X7, X 8 , X 9 , X1 0 , X 11 , X 12 , X 13 , X 1 4 and X 1 5 are each independently of the others oxygen or sulfur, and the agrochemically acceptable salts and stereoisomers of those compounds of formula I. In the above definitions, halogen is to be understood as being iodine or, preferably, fluorine, chlorine or bromine. The alkyl, alkenyl and alkynyl groups in the substituent definitions may be straight-chain or branched, this applying also to the alkyl, alkenyl and alkynyl moiety of the following groups: alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, hydroxyalkyl, cyanoalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, alkylthio, alkenylthio, alkynylthio, alkylthio-C(O)-, alkylsulfinyl, alkylsulfonyl, alkylaminocarbonyl, dialkylaminocarbonyl, (alkyl) 2 N-N=CH-, alkylcarbamoyl, trialkylsilyloxy, B 1 -alkyl and HOC(0)-alkyl. Alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and the various isomeric pentyl and hexyl radicals. Methyl, ethyl, n-propyl, isopropyl and n-butyl are preferred. Examples of alkenyl radicals that may be mentioned are vinyl, allyl, methallyl, 1-methylvinyl, but-2-en-1-yl, pentenyl and 2-hexenyl, with preference being given to alkenyl radicals WO 99/52893 PCT/EP99/02313 -6 having a chain length of from 3 to 5 carbon atoms. Examples of alkynyl radicals that may be mentioned are ethynyl, propargyl, 1-methyl propargyl, 3-butynyl, but-2-yn-1 -yl, 2-methylbutyn-2-yl, but-3-yn-2-yl, 1-pentynyl, pent-4-yn 1-yl and 2-hexynyl, with preference being given to alkynyl radicals having a chain length of from 2 to 4 carbon atoms. Suitable haloalkyl radicals are alkyl groups that are mono- or poly-substituted, especially mono- to tri-substituted, by halogen, halogen being in particular iodine or especially fluorine, chlorine or bromine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2-chloroethyl, 2,2-dichloro ethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl. Suitable haloalkenyl radicals are alkenyl groups mono- or poly-substituted by halogen, halogen being in particular bromine, iodine or especially fluorine or chlorine, for example 2 or 3-fluoropropenyl, 2- or 3-chloropropenyl, 2- or 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl, 4,4,4-trifluorobut-2-en-1-yl and 4,4,4-trichlorobut-2-en-1-yl. Of the alkenyl radicals mono-, di- or tri-substituted by halogen, preference is given to those having a chain length of 3 or 4 carbon atoms. The alkenyl groups may be substituted by halogen at saturated or unsaturated carbon atoms. Suitable haloalkynyl radicals are, for example, alkynyl groups mono- or poly-substituted by halogen, halogen being bromine, iodine or especially fluorine or chlorine, for example 3 fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4 trifluoro-but-2-yn-1-yl. Alkylthio is, for example, methylthio, ethylthio, propylthio or butylthio or a branched isomer thereof. Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl or an isomer of pentyl sulfonyl or hexylsulfonyl; preferably methylsulfonyl or ethylsulfonyl. Haloalkylsulfonyl is, for example, fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoro methylsulfonyl, chloromethylsulfonyl, trichloromethylsulfonyl, 2-fluoroethylsulfonyl, 2,2,2-tri fluoroethylsulfonyl or 2,2,2-trichloroethylsulfonyl. Cyanoalkyl is, for example, cyanomethyl, cyanoethyl, cyanoeth-1-yl or cyanopropyl. Hydroxyalkyl is, for example, hydroxymethyl, 2-hydroxyethyl or 3-hydroxypropyl. Alkylamino is, for example, methylamino, ethylamino or an isomer of propylamino or butyl amino.

WO 99/52893 PCT/EP99/02313 -7 Dialkylamino is, for example, dimethylamino, diethylamino or an isomer of dipropylamino or dibutylamino. Alkenylamino is, for example, allylamino, methallylamino or but-2-en-1-ylamino. Alkynylamino is, for example, propargylamino or 1-methylpropargylamino. Haloalkylamino is, for example, chloroethylamino, trifluoroethylamino or 3-chloropropyl amino. Di(haloalkyl)amino is, for example, di(2-chloroethyl)amino. Alkylcarbonyl is especially acetyl or propionyl. Haloalkylcarbonyl is especially trifluoroacetyl, trichloroacetyl, 3,3,3-trifluoropropionyl or 3,3,3-trichloropropionyl. Alkenylcarbonyl is especially vinylcarbonyl, allylcarbonyl, methallylcarbonyl, but-2-en-1 ylcarbonyl, pentenylcarbonyl or 2-hexenylcarbonyl. Alkynylcarbonyl is especially acetylenecarbonyl, propargylcarbonyl, 1-methylpropargyl carbonyl, 3-butynylcarbonyl, but-2-yn-1-ylcarbonyl or pent-4-yn-1 -ylcarbonyl. Alkoxy is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec butoxy, tert-butoxy or an isomer of pentyloxy or hexyloxy. Alkenyloxy is, for example, allyloxy, methallyloxy or but-2-en-1-yloxy. Alkynyloxy is, for example, propargyloxy or 1-methylpropargyloxy. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl. Alkenyloxyalkyl is, for example, allyloxyalkyl, methallyloxyalkyl or but-2-en-1-yloxyalkyl. Alkynyloxyalkyl is, for example, propargyloxyalkyl or 1-methylpropargyloxyalkyl. Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso propoxycarbonyl or n-butoxycarbonyl, preferably methoxycarbonyl or ethoxycarbonyl. Alkenyloxycarbonyl is, for example, allyloxycarbonyl, methallyloxycarbonyl, but-2-en-1 yloxycarbonyl, pentenyloxycarbonyl or 2-hexenyloxycarbonyl. Alkynyloxycarbonyl is, for example, propargyloxycarbonyl, 3-butynyloxycarbonyl, but-2-yn-1 yloxycarbonyl or 2-methylbutyn-2-yloxycarbonyl. Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoro ethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy or 2,2,2-trichloroethoxy. Suitable haloalkenyloxy radicals are alkenyloxy groups mono- or poly-substituted by halogen, halogen being in particular bromine, iodine or especially fluorine or chlorine, for example 2- or 3-fluoropropenyloxy, 2- or 3-chloropropenyloxy, 2- or 3-bromopropenyloxy, 2,3,3-trifluoropropenyloxy, 2,3,3-trichloropropenyloxy, 4,4,4-trifluoro-but-2-en-1-yloxy or WO 99/52893 PCT/EP99/02313 -8 4,4,4-trichlorobut-2-en-1 -yloxy. The cycloalkyl radicals suitable as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The halocycloalkyl radicals suitable as substituents are, for example, mono-, di- or up to per-halogenated cycloalkyl radicals, for example fluorocyclopropyl, chlorocyclopropyl, bromocyclopropyl, 2,2-dichlorocyclopropyl, 2,2-difluorocyclopropyl, 2,2-dibromocyclopropyl, 2-fluoro-2-chlorocyclopropyl, 2-chloro-2-bromocyclopropyl, 2,2,3,3-tetrafluorocyclopropyl, 2,2,3,3-tetrachlorocyclopropyl, pentafluorocyclopropyl, fluorocyclobutyl, chlorocyclobutyl, 2,2-difluorocyclobutyl, 2,2,3,3-tetrafluorocyclobutyl, 2,2,3-trifluoro-3-chlorocyclobutyl, 2,2 dichloro-3,3-difluorocyclobutyl, fluorocyclopentyl, difluorocyclopentyl, chlorocyclopentyl, perfluorocyclopentyl, chlorocyclohexyl and pentachlorocyclohexyl. Corresponding meanings may also be given to the substituents in combined definitions, such as, for example, alkylcarbonyloxy, alkoxyalkoxyalkyl, alkoxycarbonylalkyl, haloalkoxy carbonyl, haloalkylcarbonyl, haloalkenylcarbonyl, haloalkynylcarbonyl, alkylthio-C(O)-, alkenylthio, alkynylthio, alkyl-S(O)-, alkylsulfonyloxy, R 33 0-, R 4 (Rs)N-, R 35

(R

36 )N-,

R

6

(R

7 )NC(O)-, R 38

(R

39

)N-C(R

37 )=N-, R34S(O)n 2 , B 1 -alkyl, B 1 -alkoxy, Bi-CH=N-, (Bl-haloalkyl)

CH

2 - and (B-hydroxyalkyl)-CH 2 -. In the definition of R 3 , (C 1

-C

5 hydroxyalkyl)-CH 2 -, (B-C 1 -Cshydroxyalkyl)-CH 2 - and

(B

1 -Cl-Cshaloalkyl)-CH 2 - signify that only the Cl-Csalkyl moiety is hydroxylated or halogenated, that is to say the methylene group is not hydroxylated or halogenated. L in the reagents of formulae VI, XI, XIX, XXVIII, XXXIa, XXXIb and XXXXII denotes a leaving group, such as, for example, halogen, preferably chlorine, bromine or iodine,

C

1

-C

3 alkyl- or aryl-sulfonyloxy, preferably CH 3

SO

2 0- or CH 3 - SO 2 0- , or Cl-C 6 alkylcarbonyloxy, preferably acetyloxy.

L

1 in the reagent of formula XX denotes a leaving group, such as, for example, HOS(O) 2 0-,

NO

2

CH

3

NO

2 - or H 3 C OS(O) 2 CH 3

L

2 in the reagents of formulae XXXIIa and XXXIIc denotes a leaving group, such as, for example, hydroxy, Cl-C 4 alkoxy or halogen, preferably chlorine, bromine or iodine.

WO 99/52893 PCT/EP99/02313 -9

L

3 in the reagent of formula XXXVIll denotes a leaving group, such as, for example, chlorine N or bromine, trichloromethoxy or -N N In the definitions of cyanoalkyl, alkylcarbonyl, alkylcarbonyloxy, alkenylcarbonyl, haloalkenylcarbonyl, alkynylcarbonyl, alkoxycarbonyl, alkylthiocarbonyl and haloalkylcarbonyl, the upper and lower limits of the number of carbon atoms given in each case do not include the cyano or carbonyl carbon atom, as the case may be. The invention relates also to the salts that the compounds of formula I having azide hydrogen, especially the derivatives with carboxylic acid and sulfonamide groups (e.g. carboxyl-substituted alkyl and alkoxy groups and alkyl-S(O) 2 NH and haloalkyl-S(O) 2 NH groups) are able to form with bases. Those salts are, for example, alkali metal salts, e.g. sodium and potassium salts; alkaline earth metal salts, e.g. calcium and magnesium salts; ammonium salts, that is to say unsubstituted ammonium salts and mono- or poly-substituted ammonium salts, e.g. triethylammonium and methylammonium salts; or salts with other organic bases. Among the alkali metal and alkaline earth metal hydroxides as salt formers, attention is drawn, for example, to the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially to the hydroxides of sodium and potassium. Suitable salt formers are described, for example, in WO 97/41112. Examples of amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary C 1

-C

18 alkylamines, C 1

-C

4 hydroxyalkylamines and C 2

-C

4 alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomers of butylamine, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonyl amine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanol amine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, WO 99/52893 PCTIEP99/02313 -10 methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, thiomorpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, 0-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and 0-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine. The salts of compounds of formula I having basic groups, especially having basic pyrazolyl rings (W 3 , W 4 ), or the derivatives with amino groups, for example alkylamino and dialkyl amino groups, in the definition of R 3 , R 8 or R 1 4 are, for example, salts with inorganic or organic acids, for example hydrohalic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid, and also sulfuric acid, phosphoric acid and nitric acid, and organic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, citric acid, benzoic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid and methanesulfonic acid. The presence of an asymmetric carbon atom in the compounds of formula I, e.g. in the substituent R 3 where R 3 is a branched alkyl, alkenyl, haloalkyl or alkoxyalkyl group or R 3 is

(B

1

-C

1 -Cshydroxyalkyl)-CH 2 -, wherein e.g. B 1 is C-C 6 alkyI-S(O)-, means that the com pounds may be in the form of optically active individual isomers or in the form of racemic mixtures. In the present invention, "compounds of formula I" is to be understood as including both the pure optical antipodes and the racemates or diastereoisomers. When an aliphatic C=C or C=N-O double bond (syn/anti) is present, geometric isomerism may occur. The present invention relates to those isomers also. Preference is given to compounds of formula 10 R1

R

2 W (0lo), N X1

R

3 wherein

R

1 is hydrogen, fluorine, chlorine, bromine or methyl; R 2 is methyl, halogen, hydroxy, nitro, amino or cyano; and R 3 , X, and W are as defined for formula I.

WO 99/52893 PCT/EP99/02313 -11 Preference is also given to compounds of formula I wherein W is the group R9 R / N, R, o

.(W

1 ); and R 8 , R 9 , Ro 10 , X 2 and X 3 are as defined for formula I. Of those X3 X2 I compounds, special preference is given to those wherein R 8 is methyl; R 9 is trifluoromethyl;

R

1 0 is hydrogen; and X 2 and X 3 are oxygen. Also preferred are compounds of formula I wherein W is a group

R

1 2 R 26

R

2 5 32 R 3 , RN 4 I (W2) (W 7 ) or (W 10 ); X4 N X 1 o N N X 1 5 I I I and R 11 , R 12 , R 13 , R 24 , R 25 , R 26 , R 31 , R 32 , X 4 , Xg, Xio and X 1 5 are as defined for formula I. Preferred compounds of formula I are those wherein W is a group R19 F R2

RR

2 2 R1 R 8

R

21

R

20 N, R1 (W 3 ), (W4), Xs (W 5 ), (W 6 ) or I X N NN R14 X6 NNX

R

28

R

2 7 \ / N-N 2 N Xi (W 8 ); and R 1 4 , Ris, R 1 6 , R 1 7 , R 1 8 , Ri 9 , R 20 , R 21 , R 22 , R 23 , R 2 7 , R 28 , Xs, X 6 , X7, X12 N X I

X

8 , X 1 1 and X 1 2 are as defined for formula I. Also preferred are compounds of formula I wherein R, is hydrogen, fluorine or chlorine; R 2 is chlorine, bromine, cyano or CFa; and X, is oxygen. Of those compounds, special preference is given to those wherein R, is fluorine or chlorine; and R 2 is chlorine, bromine or cyano, and of those compounds special importance is attached to those wherein R 1 is fluorine; and R 2 is chlorine.

WO 99/52893 PCT/EP99/02313 -12 The process according to the invention for the preparation of compounds of formula I R1 R! W() N X1

R

3 wherein Ri, R 2 and W are as defined for formula I; X, is O or S; R 3 is C 1 -Cealkoxy-Cj-C 6 alkyl, Cl-C 6 alkoxy-Cl-C 6 alkoxy-C 1

-C

6 alkyl, C 1

-C

6 alkyl, C 3

-C

6 alkenyl, C3-C 6 alkynyl, C 2

-C

6 haloalkyl, C 3

-C

6 haloalkenyl, C3-Cecycloalkyl, C 3

-C

6 halocycloalkyl, B 1 -- C 6 -Cealkyl, O-- CH2- , O/ CiC 3 a lky l , (C1-Cshydroxyalkyl)-CH 2 -, (B-C 1 -Cshydroxyalkyl)-CH 2 - or 0

CH-

(B-C

1

-C

5 shaloalkyl)-CH 2 -; and B, is as defined for formula I is carried out analogously to known procedures, for example as described in CH Application No. 695/97 and references given therein, and comprises oxidising a compound of formula III Ri

R

2 _. W (), N for example with hydrogen peroxide/urea adduct in the presence of a carboxylic acid and/or a carboxylic acid anhydride, organic peracid or persulfonic acid (Caro's acid) in a suitable solvent, to form a compound of formula V R1

R

2 W (V) 0 O" and then rearranging that compound in an inert solvent in the presence of an anhydride or in the presence of antimony pentachloride (Katada reaction) to yield, after aqueous working-up and purification, a compound of formula II WO 99/52893 PCT/EP99/02313 -13 R1

R

2 N W (l), N OH the radicals R 1 , R 2 and W in the compounds of formulae II, 111 and V being as defined, and then alkylating that compound in the presence of an inert solvent and a base with a com pound of formula VI

R

3 -L (VI), wherein R 3 is as defined and L is a leaving group, preferably chlorine, bromine, iodine,

CH

3

SO

2 0- or CH3 SO20- , in a suitable inert solvent and a base to form the isomeric compounds of formulae I and IV R, R, R / W (I) and R 2 W (IV), N N X1 R 3 OR 3 wherein R 1 , R 2 , R 3 and W are as defined and X, is O, and then, after the compound of formula I has been separated from the pyridol derivative of formula IV, optionally functionalising the pyridono derivative of formula I further in accordance with the definition of X, and R 3 , for example with the aid of a suitable sulfur reagent to form the corresponding pyridinethione derivative (Xi = S). When R 3 in the pyridol derivative of formula IV is an allyl group or a homolog thereof (R 3 =

C

3

-C

6 allyl group), those pyridol derivatives of formula IVb in Reaction Scheme 1 may be rearranged in a manner analogous to that described, for example, in J. Org. Chem. 50, 764 (1985) and Tetrahedron Lett. 1979, 3949, in the presence of a suitable catalyst, for example palladium(ll) chloride/diacetonitrile or palladium(ll) chloride/phenylacetonitrile complex, to form the isomeric N-allylated pyridone derivative of formula I (R 3 = C 3

-C

6 allyl group). That rearrangement reaction is illustrated in Reaction Scheme 1 below. Reaction Scheme 1: WO 99/52893 PCT/EP99/02313 -14 Ri catalyst, e.g. R1 2- PdCI 2

(CH

3

CN)

2 ' R2 W R W solvent N N O-C3 -Callyl group X R 3 IVb I (X,=O, R 3

=C,-C

6 allyl group) The compounds of formula I wherein R 1 , R 2 and W are as defined for formula I, X, is oxygen and R 3 is C 1

-C

6 alkyl, C3-C 6 alkenyl, C 3

-C

6 alkynyl, C 2

-C

6 haloalkyl or C 3

-C

6 haloalkenyl may be obtained in a manner analogous to that described in J. Org. Chem. 38, 3268 (1973), ibid 16, 1143 (1951), Chem. Communic. 1979, 552 or J. Am. Chem. Soc. 78, 416 (1956) from the compounds of formula IVa R

R

2 W (IVa), -N R03 wherein R 1 , R 2 and W are as defined for formula I and R 03 is a lower alkoxy group, e.g. Cj or C 2 -alkoxy, benzyloxy or halogen, e.g. chlorine or bromine, by first reacting a compound of formula IVa with an alkylating agent of formula VI

R

3 -L (VI), wherein R 3 is C 1

-C

6 alkyl, C 3

-C

6 alkenyl, C 3

-C

6 alkynyl, C 2

-C

6 haloalkyl or C3-C 6 haloalkenyl and L is a leaving group, and then either heating or treating with dimethyl sulfoxide, if appropriate in the presence of an alkali metal halide, or with iodine or hydrochloric acid. The compounds of formula I wherein R 1 , R 2 and W are as defined for formula I, X, is oxygen and R 3 is C 1

-C

6 alkyl, C 3

-C

6 alkenyl, C 3

-C

6 alkynyl, C 2

-C

6 haloalkyl, C 3

-C

6 haloalkenyl or

C

3

-C

6 cycloalkyl may, in a further synthesis variant, be obtained in a manner analogous to that described in Heterocycles 45, 1059 (1997) or Chem. Pharm. Bull. 2, 193 (1954) from the compounds of formula Ill R1

R

2 -<7 W (N- W wherein R 1 , R 2 and W are as defined, by reaction with an alkylating reagent of formula VI WO 99/52893 PCT/EP99/02313 - 15

R

3 -L (VI), wherein R 3 is C 1

-C

6 alkyl, C 3 -Cealkenyl, C 3

-C

6 alkynyl, C 2

-C

6 haloalkyl, C 3

-C

6 haloalkenyl or C3-C 6 cycloalkyl and L is a leaving group, and with an oxidising agent, for example manganese dioxide (MnO 2 ) or potassium hexacyanoferrate (K 3 Fe(CN) 6 ). The process according to the invention for the preparation of compounds of formula I R 1 ' R2- W() N X1

R

3 wherein R 1 , R 2 and W are as defined for formula I; X, is S; R 3 is hydroxy, C 1

-C

6 alkoxy,

C

3

-C

6 alkenyloxy, C 3

-C

6 alkynyloxy, C 1

-C

6 haloalkoxy, C 3

-C

6 haloalkenyloxy, B 1

-C

1

-C

6 alkoxy,

C

1

-C

6 alkylcarbonyloxy, C3-Catrialkylsilyloxy, (hydroxy-C-C 5 alkyl)-O- or (B-C-C 5 hydroxy alkyl)-O-; and B! is as defined for formula I is carried out analogously to known procedures, for example as described in WO 98/42698 and references given therein, and comprises first oxidising a compound of formula Ill

R

1

A

2 \\ W(Il N to yield a compound of formula V Ri.

R

2 : -W (V), -- N + O" 0 chlorinating or brominating that compound, for example with phosphorus oxychloride, phosphorus oxybromide, sulfuryl chloride, thionyl chloride or phosphorus pentachloride in phosphorus oxychloride, and then oxidising it again to form a compound of formula VIII WO 99/52893 PCT/EP99/02313 -16 R1

R

2 W (VIII), N+ Hal O0 the radicals Ri, R 2 and W in the compounds of formulae III, V and VIII being as defined and Hal in the compound of formula VIII being chlorine or bromine, then converting that compound in the presence of a solvent, e.g. water, an alcohol or a mixture thereof, or an amide, using a suitable sulfur reagent, e.g. hydrogen sulfide, thiourea, sodium hydrogen sulfide (NaSH) or phosphorus pentasulfide (P 2 Ss), into a compound of formula Im Ri R2 W (Im), N S OH and reacting that compound in the presence of a solvent and a base with a compound of formula Xl R42-L (Xl), wherein R 42 is C 1

-C

6 alkyl, C 3

-C

6 alkenyl, C 3

-C

6 alkynyl, C 1

-C

6 haloalkyl, C 3

-C

6 haloalkenyl,

B

1

-C-C

6 alkyl, Cl-C 6 alkylcarbonyl, C 3 -Catrialkylsilyl, hydroxy-C-Csalkyl or B 1

-C

1 -Cshydroxy alkyl; B 1 is as defined; and L is a leaving group, e.g. halogen, for example chlorine, bromine or iodine, CH 3

SO

2 0-, CH- -SO2 0- or C 1

-C

6 alkylcarbonyloxy. The process according to the invention for the preparation of compounds of formula I R1

R

2 w (I) N X1 R3 wherein R 1 , R 2 , R 3 and W are as defined for formula I and X, is S is carried out analogously to known procedures, for example as described in WO 98/42698 and references given therein, and comprises treating a compound of formula I WO 99/52893 PCT/EP99/02313 -17 R,

R

2 W () N

X

1

R

3 wherein R 1 , R 2 , R 3 and W are as defined and X, is O in an inert solvent with a sulfur reagent, for example phosphorus pentasulfide or Lawesson reagent. For the preparation of the pyridine intermediates of formula Ill, a large number of known standard procedures of heterocyclic chemistry are available, the choice of a suitable preparation procedure being governed by the properties (reactivities) of the substituents in the respective intermediates. The process according to the invention for the preparation of compounds of formula Ill is carried out analogously to known procedures, for example as described in EP-A-0 438 209 or DE-OS 19 604 229, and, for the purpose of preparing compounds of formula III R1

R

2 - N /w (Ill) XN R wherein R, and R 2 are as defined for formula I, W is a group W, -N R 9

(W

1 ) and x 2 R 8 R8, R 9 , Rio, X 2 and X 3 are as defined for formula I (corresponding to the compound of formula Ilia in Reaction Scheme 2), comprises, for example, converting a compound of formula XII RR

R

2 / Hal

-N

WO 99/52893 PCT/EP99/02313 -18 wherein R 1 and R 2 are as defined and Hal is fluorine, chlorine or bromine, in the presence of an inert solvent and ammonia, if appropriate in an autoclave at temperatures of from -10 to 1800C, into a compound of formula XIII Ri R(XIII),

R

2 7 NH 2 N converting that compound in the presence of a base and a solvent a) with a chloroformic acid ester of formula XIV

X

2

C

1

-C

4 alky lO ---- CI (XIV), wherein X 2 is as defined for formula I, into a compound of formula XV R__ X2 (XV), or

R

2 /NH-C-OC-C 4 a l ky l I N b) with oxalyl chloride, phosgene or thiophosgene into a compound of formula XVI R N=C=X (XVI),

R

2 /X Z N=C=X 2 N then cyclising the compound of formula XV or XVI in the presence of from 0.1 to 1.5 equi valents of a base in an inert solvent with an enamine derivative of formula XVII R9 X3 C II / c,C\, (XVll),

NH

2 C OC-C 4 alkyl

R

10 io wherein R 9 and R 10 io are as defined for formula I and X 3 is oxygen, to yield a compound of formula XVIII WO 99/52893 PCT/EP99/02313 -19

R

1

X

3

R

1 0 RN R a 9 (XVIII), N N \N

X

2 H wherein R 1 , R 2 , R 9 , R 10 io, X 2 and X 3 are as defined, and reacting that compound further in the presence of an inert solvent and a base c) with a compound of formula XIX

R

8 -L (XIX), wherein Re is C 1

-C

3 alkyl or C 1

-C

3 haloalkyl and L is a leaving group, or d) with a hydroxylamine derivative of formula XX

NH

2

-L

1 (XX), wherein L, is a leaving group. The process according to the invention for the preparation of compounds of formula Ill is carried out analogously to known procedures, for example as described in DE-A-4 423 934 and JP-A-58 213776, and, for the preparation of compounds of formula Ill R1 RC W

R

2 _ /W (Il) N

X

4

R

1 3 wherein R 1 and R 2 are as defined for formula I, W is a group W 2 -N R 12 (W 2 )

N

R11 and R 11 , R 1 2 , R 13 and X 4 are as defined for formula I (corresponding to the compound of formula Illb in Reaction Scheme 3), comprises, for example, either a) converting a compound of formula XII Ri (XII),

R

2 - Hal CN wherein R 1 and R 2 are as defined and Hal is fluorine, chlorine or bromine, with hydrazine, preferably in a protic solvent, into a compound of formula XXI WO 99/52893 PCT/EP99/02313 - 20 R1 ~(xxI),

R

2

NH-NH

2 N and reacting that compound further with a compound of formula XXII or XXIla 0 0 11 II R II C C\ (XXII) or \C,' C (XXIla), II R12- R 0 Hal Hal 12 wherein R 11 and R 12 are as defined for formula I, and Hal in the compound of formula XXlla is chlorine or bromine, or b) first diazotising a compound of formula XIII R-. (XIII),

R

2 \ NH 2 N wherein R, and R 2 are as defined, and then reacting further with a compound of formula XXIII COOH I CH R R1 1 1 2 (XXIII), 11 II 0 O wherein R 11 and R 12 are as defined, to yield a compound of formula XXIV R1

R

2 O R12 (XXIV), N N-C R11 which is optionally cyclised in the presence of a base, e.g. 4-dimethylaminopyridine, and a compound of formula XXV

X

4 P(phenyl) 3 (XXV), II II (xxy),

C

1

-C

4 alkyl-O-C-C-R 1 3 wherein R 13 is as defined and X 4 is oxygen.

WO 99/52893 PCT/EP99/02313 -21 The process according to the invention for the preparation of compounds of formula III is carried out analogously to known procedures, for example as described in EP-A-0 272 594, EP-A-0 493 323, DE-A-3 643 748, WO 95/23509, US-A-5 665 681 and US-A-5 661 109, and, for the preparation of compounds of formula Ill Ri

R

2 W (Ill) N

X

9 R 2 5 - R 24 wherein R 1 and R 2 are as defined for formula I, W is a group W 7 -N N, R 26

(W

7 ) and ' R26 X10

R

24 , R 25 , R 26 , X 9 and X 1 0 are as defined for formula I (corresponding to the compound of formula IlIg in Reaction Scheme 4), comprises, for example, reacting either a) a compound of formula XVa R NH1° (XVa) R2-- N/ - --OC 1

-C

4 alkyl in the presence of a solvent and a base, or b) a compound of formula XVIa Ri (XVIa),

R

2 N=C=X10 --N if appropriate in a suitable solvent, the radicals R 1 , R 2 and Xo 1 0 in the compounds of formulae XVa and XVIa being as defined, with a compound of formula XXVI R2s X9 1 2511

R

26

NH-C-C-OC

l

-C

4 alky l (XXVI), I R24 wherein R24, R25, R26 and X, are as defined, to yield a compound of formula XXVII WO 99/52893 PCT/EP99/02313 - 22 Rl' X 1 ° R X 9 H 12511 (XXVII), R2i/- NH- C-N- C-OC,-C 4 alky N

R

26

R

24 cyclising that compound in the presence of a suitable solvent and a base and then optionally c) when R 26 is hydrogen, reacting with a compound of formula XXVIII

R

26 -L (XXVIII), wherein R 26 is C 1

-C

3 alkyl and L is a leaving group. The process according to the invention for the preparation of compounds of formula III is carried out analogously to known procedures, for example as described in EP-A-0 210 137, DE-A-2 526 358, EP-A-0 075 267 and EP-A-0 370 955, and, for the preparation of compounds of formula III Ri.

R

2 / W N

X

1 1 R wherein R, and R 2 are as defined for formula I, W is a group W 8 -N N R (W 8 ) and X12

R

27 , R 28 , X 1 and X 12 are as defined for formula I (corresponding to the compound of formula Illh in Reaction Scheme 5), comprises, for example, reacting a) a compound of formula XVb

X

12 (XVb) - I

R

2 -- ( NH-C-OC,-C4 alkyl N in the presence of a solvent and a base, or b) a compound of formula XVIb WO 99/52893 PCT/EP99/02313 - 23 Ri 2"- (XVlb),

R

2 N=C=X1 2 (XVIb), N the radicals R 1 , R 2 and X 12 in the compounds of formulae XVb and XVIb being as defined, if appropriate in a suitable solvent, with a compound of formula XXIX Xli II

R

2 8NH-N-C-OC -C4 alkyl (XXIX), I

R

2 7 wherein R 27 , R 28 and X 11 are as defined, to yield a compound of formula XXX Ri X 2 X 11 SIIxxx), R NH- C-N-N- C-OC -C 4 alkyl (XXX), -N

R

28

R

27 cyclising that compound in the presence of a suitable solvent and a base, and then optionally c) when R 27 and/or R 28 are hydrogen, reacting further with a compound of formula XXXIa or XXXlb

R

2 7 -L (XXXIa) or R 2 a-L (XXXIb), wherein R 27 and R 28 are each independently of the other Cl-C 3 alkyl and L is a leaving group, or with a Michael acceptor. The process according to the invention for the preparation of compounds of formula Ill is carried out analogously to known procedures, for example as described in WO 97/07114, US-A-5 306 694, DE-A-3 832 348, EP-A-0 257 479 and EP-A-0 500 209, and, for the preparation of compounds of formula III RR ~(Ill) R 2-CZ W

N

WO 99/52893 PCT/EP99/02313 - 24 R14 wherein R 1 and R 2 are as defined for formula I, W is a group W 3

R

15 (W3) and -N N R16

R

1 4 , R 1 5 and R 16 are as defined for formula I (corresponding to the compound of formula Ilic in Reaction Scheme 6), comprises, for example, condensing a compound of formula XXI Ri

R

2

-

NHNH

2 (XXI), N wherein R, and R 2 are as defined, a) with a compound of formula XXXII O 0 II II

R

14 C" C R 16 (XXXII), I

R

15 wherein R 14 is hydrogen, CI-C3alkyl or C 1

-C

3 haloalkyl; Rs 15 is hydrogen, Cl-C 4 alkyl, C1-C 4 haloalkyl, C 2

-C

4 alkenyl, C 3 -Cshaloalkenyl or C 3 - or C 4 -alkynyl and R 16 is hydrogen,

C

1

-C

4 alkyl or Cl-C 4 haloalkyl, if appropriate in the presence of an acidic, basic or bifunctional catalyst, e.g. p-toluenesulfonic acid, or b) with a compound of formula XXXIIa O 0 II 11II L CCH 1CR (XXXIIa), L2 I

R

15 wherein Rs 1 5 and R 1 6 are as defined and L 2 is a suitable leaving group, to form a compound of formula XXXIII R N

R

2 N R (XXXIII),

O

WO 99/52893 PCT/EP99/02313 - 25 and functionalising the pyrazolone group further in accordance with the definition of R 14 analogously to known procedures, for example using a halogenating agent, e.g. phosphorus oxychloride, to form the corresponding halogen derivative of formula IIIc R 1 N R 16 R2N -N R R 9 s 14 wherein R 1 , R 2 , R 1 5 and R 16 are as defined and R 1 4 is halogen (Reaction Scheme 6). The process according to the invention for the preparation of compounds of formula III is carried out analogously to known procedures, for example as described in EP-A-0 370 332, EP-A-0 370 955 or DE-A-3 917 469, and, for the preparation of compounds of formula III R1 R, W

R

2 - CX / W N R17 R18 wherein R 1 and R 2 are as defined for formula I, W is a group W 4 -N R \ ..... 19 N

(W

4 ) and R 17 , R 18 and R 19 are as defined for formula I (corresponding to the compound of formula Illd in Reaction Scheme 7), comprises, for example, condensing a compound of formula XXI Rl'

R

2

-

NHNH

2 (XXI), N wherein R, and R 2 are as defined, a) with a compound of formula XXXIlb WO 99/52893 PCT/EP99/02313 - 26 O O II R_ CR 17 (XXXIIb), R19 wherein R 18 and R 19 are as defined and R 17 is hydrogen, C 1

-C

4 alkyl or CI-C 4 haloalkyl, if appropriate in the presence of a catalyst, or b) with a compound of formula XXXlIc O 0 II C.. R 2 (XXXIIc), R19 wherein R 18 and R 1 9 are as defined and L 2 is a suitable leaving group, to form a compound of formula XXXIlla R1 NR N /N R (XXXIlla) O N 1 and treating that compound with a halogenating agent, e.g. a phosphorus oxyhalide or thionyl halide, to yield a compound of formula IllId R i R

R

2 / N Ri (1id), R 1 wherein R 1 , R 2 , RI 8 and R 19 are as defined and R 1 7 is halogen, and optionally reacting that compound with a cyanide of formula XXXIV M(CN), (XXXIV), wherein M is an ammonium cation, an alkali metal ion or a metal ion from sub-group I or II of the Periodic Table of the Elements and s is the number 1 or 2, if appropriate in the presence of an alkali metal iodide (R 17 = cyano) (Reaction Scheme 7).

WO 99/52893 PCT/EP99/02313 -27 The process according to the invention for the preparation of compounds of formula III is carried out analogously to known procedures, for example as described in DE-A-3 917 469, WO 92/00976, US-A-5 069 711 and EP-A-0 260 228, and, for the preparation of compounds of formula III R1 ~(Ill)

R

2 / W N wherein R, and R 2 are as defined for formula I, W is a group W 5 -N (Ws) or X5 R20 X8 R22 W6 - N R 23

(W

6 ) and R 2 0 , R 21 , R 22 , R 23 and Xs to X 8 are as defined for

X

7 formula I (corresponding to the compounds of formulae Ille and Illf, respectively, in Reaction Scheme 8), comprises, for example, reacting a) a compound of formula XXXV 0 R21 S0 (XXXV) or

R

2 0 o b) a compound of formula XXXVa R22 O R23 0 (XXXVa), O 0 the radicals R 20 to R 23 in the compounds of formulae XXXV and XXXVa being as defined, with a compound of formula XIII WO 99/52893 PCT/EP99/02313 - 28 Ri

R

2 ~ (XIII), R2

NH

2 N wherein R 1 and R 2 are as defined, in an inert solvent in the presence of a C 1

-C

4 alkyl carboxylic acid at temperatures of from 200 to 2000C, and optionally converting the resulting compound of formula Ille or IIIf

R

1 X 6

R

1

X

8 RR R 2- N/-"N x(llle) or R 2 (ll), -N -N R3 R 2 5 7 wherein R 1 , R 2 and R 20 to R 23 are as defined and Xs to X 8 are oxygen, with the aid of a suitable sulfur reagent, into the corresponding thiono compound of formula Ille or Ilif wherein Xs and/or X 6 and X 7 and/or X 8 are sulfur respectively (Reaction Scheme 8). The process according to the invention for the preparation of compounds of formula Ill is carried out analogously to known procedures, for example as described in WO 95/00521, EP-A-0 611 708 and WO 94/25467, and, for the preparation of compounds of formula Ill R1

R

2 W N X1 3 /

N

R3 wherein R, and R 2 are as defined for formula I, W is a group W 9 X14 (W 9 ) and -N

R

29 , R3o, X 13 and X 14 are as defined for formula I (corresponding to the compound of formula Illi in Reaction Scheme 9), comprises, for example, reacting a) a compound of formula XVc WO 99/52893 PCT/EP99/02313 - 29 __ Ri X14 II

R

2 / NH-C- OC-C 4 alkyl (XVc) or N b) a compound of formula XVIc Ri. ~(XVIc),

R

2

N=C=X

14 (XVc), N the radicals R 1 , R 2 and X 14 in the compounds of formula XVc and XVIc being as defined, if appropriate in the presence of a solvent and a base, with a compound of formula XXXVI

R

30

-NH-NH-R

29 (XXXVI), wherein R 29 and R 30 are as defined for formula I, to yield a compound of formula XXXVII R1 X 4

R

2 / NH-C- N-NH-R (XXXVII), N 3 and then reacting that compound, if appropriate in a solvent and in the presence of a base, with a (thio)carbonylating reagent of formula XXXVIII L3, / C=X13 (XXXVIII), Lz wherein X 13 is as defined and L 3 is a leaving group (Reaction Scheme 9). The process according to the invention for the preparation of compounds of formula III is carried out analogously to known procedures, for example as described in US-A-5 980 480, DE-A-3 917 469, US-A-4 818 275, US-A-5 041 155 and EP-A-0 610 733, and, for the preparation of compounds of formula III R1 R 2W --- N WO 99/52893 PCT/EP99/02313 - 30 X /R31 wherein R, and R 2 are as defined for formula I, W is a group W 10 _N N (Wo) N N R32 and R 31 , R 3 2 and X 1 s are as defined for formula I (corresponding to the compound of formula IIIk in Reaction Scheme 10), comprises, for example, a) reacting a compound of formula XXI

R

2

NHNH

2 (XXI), N if appropriate in the presence of a catalyst, with a compound of formula XXXIX

R

32 c0=O (XXXIX) HOOC to form a compound of formula XXXX R, 2- (XXXX), R NHN=C' N COOH the radicals R 1 , R 2 and R 32 in the compounds of formulae XXI, XXXIX and XXXX being as defined, and cyclising the compound of formula XXXX by further reaction with an azide of formula XXXXI O N (XXXXI) N-- P(OC 1

-C

4 alky) 2

(X

1 5 = O, R 31 = H), or b) cyclising a compound of formula XXI

R

1

R

2 7

NHNH

2 (XXI) Nwith a compound of formula XXXXII with a compound of formula XXXXIII WO 99/52893 PCT/EP99/02313 -31 OC -C 4 alkyl -C OOCl- 4 alkyl (XXXXIII), R,2 N -COOC, - C4aly the radicals R 1 , R 2 and R 32 in the compounds of formulae XXI and XXXXIII being as defined,

(X

1 s = O, R 31 = H), or c) reacting a compound of formula XXI

R

2

NHNH

2 (XXI) N first with a compound of formula XXXXIV

R

32 -CHO (XXXXIV) to form a compound of formula XXXXa RI

R

2 - / NH-N=CH-R32 (XXXXa), N and then with an alkali metal cyanate to form a compound of formula XXXXV RI

R

2 - N-N= CH-R 32 (XXXXV) & // NH 2 and finally cyclising that compound in the presence of an oxidising agent, to yield a compound of formula IIlk / R_ 1 15 R / N R 31 R / \ N (II1k), N N

R

32 wherein R1, R 2 and R 32 are as defined, Xs 15 is oxygen and Ra 3 1 is hydrogen, and optionally treating that compound with a sulfur reagent (Xs 15 = S) and, in the presence of a base, with an alkylating reagent of formula XXXXII

R

31 -L (XXXXII), WO 99/52893 PCT/EP99/02313 - 32 wherein R 31 is C 1

-C

4 aIkyl, C 1

-C

4 haloalkyl, C3- or C 4 -alkenyl, C3- or C 4 -haloalkenyl or C3- or

C

4 -alkynyl and L is a leaving group. The preparation of the compounds of formula Ilia R X 3

R

1 0

R

2 R NR 9 (Ilia) NN

X

2 R 8 wherein R 1 , R 2 , R 8 , R 9 , Ro 10 , X 2 and X 3 are as defined for formula I is illustrated in Reaction Scheme 2 below.

WO 99/52893 PCT/EP99/02313 - 33 Reaction Scheme 2:

R

1 Ri a) CIC(X 2

)O-C,-C

4 alkyl or R - Hal NH 3 (autoclave) R - NH XIV Slv R2 NH 2 2 solvent, -10-180NC b) oxalyl chloride or C(X 2 )Cl 2 , base, solvent XII XIII X C R 9

X

3 R N O-C-C 4 alkyl O C 1

-C

4 alkyl R 1

X

3

R

10 XV R 1 o R2- /-- \ -N R XVII NN or base, solvent X 2 H

R

1 XVIII c) R.-L or C /lNC=X 2 base, solvent NC=XZ d) NH 2

-L

1 N XX XVI Ri X 3 Rio Ri X3 RIO R X 3 thionation reagent, e.g. R R - NLawesson reagent R N R 9 t solvent R N R 2 9 solvent 2 N ,>N NN X2 R 8 X2 R8 Ilia (X 3 =S) Ilia (X 3 =0) For the preparation of the compounds of formula Ilia according to the invention, a large number of known standard procedures are available, for example as described in EP-A-0 438 209 and DE-OS-19 604 229 (R 9 =cyano). Reaction Scheme 2 shows a selection of suitable preparation procedures, the choice of the reaction routes and the reagents being govemed by the reactivities of the substituents in the intermediates. Starting, for example, from a compound of formula XII, it is possible by reaction with ammonia in an inert solvent, if appropriate in an autoclave at temperatures of from -10 to 180*C, to obtain an aminopyridine of formula XIII. The latter compound may be converted in the presence of a base and a solvent either WO 99/52893 PCT/EP99/02313 -34 a) with a chloroformic acid ester of formula XIV (X 2 = O or S) into a pyridyl carbamate of formula XV, or b) with oxalyl chloride, phosgene (X 2 =0) or thiophosgene (X 2 =S) into an iso(thio)cyanate of formula XVI. Such reactions are described, for example, in Angew. 1971, 407. The carbamate and the iso(thio)cyanate of formulae XV and XVI may be cyclised in the presence of an enamine derivative of formula XVII in an inert solvent to form a uracil derivative of formula XVIII, the reaction of the iso(thio)cyanate of formula XVI advant ageously being carried out in the presence of from 0.1 to 1.5 equivalents of a base, e.g. sodium hydride, potassium tert-butanolate or an alkaline earth metal oxide or hydroxide, e.g. barium hydroxide. The desired compounds of formula Ilia may be prepared in accordance with standard procedures from the uracils of formula XVIII in the presence of an inert solvent and at least one equivalent of a base, for example an alkali metal carbonate, such as potassium carbonate, c) with an alkylating agent of formula XIX to form the N-alkyl derivative of formula Ilia (R 8 =alkyl), or d) analogously to WO 97/05116 with a hydroxylamine derivative of formula XX, wherein L,

NO

2 CH 3 is a leaving group, e.g. HOS(O) 2 0-, NO2-- or H 3 C OS(O) 2 NO2 0-1/

CH

3 for example 2,4-dinitrophenyl-hydroxylamine or hydroxylamine-O-sulfonic acid, to form the N-amino derivative of formula Ilia (R 8 =amino). The desired thiono derivatives of formula Ilia (X 2 , X 3 =S) may be obtained by thionation, for example with phosphorus pentasulfide or Lawesson reagent. The preparation of the compounds of formula IIIb RR X 4

R

1 3 R N\ R 12 (Illb),

N

N N~ R11 WO 99/52893 PCT/EP99/02313 - 35 wherein R 1 , R 2 , R, 1 , R 1 2 , R 13 and X 4 are as defined for formula I, is illustrated in Reaction Scheme 3 below. Reaction Scheme 3: Ri Ri 2" N NH 2

NH

2 '2,"

R

2 Hal H2 2' R2 NHNH 2 N solvent N XII XXI O C R12 O C R 12 I or C Br-C No / R1 O R Br R XXII XXIla X4

R

13 C-C

R

1

X

4

R

13

C

1

-C

4 alkyl-O P(Ph) 3 R1 XXV N R N R2 R NH C-R 2 N NN N=C Rllb XXIV IIIb 1) diazotisation (preferably with exclusion of water) 2) O 0 cR 1 2 2) C R12Japp-Klingemrnann I reaction CH COOH R 1 1 XXIII RI

R

2 - NH 2 N XIII The compounds of formula IIIb may be prepared in accordance with known methods, for example in accordance with Reaction Scheme 3 (variant a)), by reacting a 2-halopyridine WO 99/52893 PCT/EP99/02313 - 36 derivative of formula XII with hydrazine, preferably in a protic solvent, e.g. an alcohol, analogously to GB-A-2 230 261 to form a 2-hydrazino derivative of formula XXI. The latter is reacted with a diketone of formula XXII analogously to DE-OS-19 754 348 or with a dihaloketone of formula XXIIa analogously to WO 97/07104 to form a hydrazone derivative of formula XXIV. The subsequent cyclisation to form the desired compound of formula IIIb is carried out in the presence of a phosphorane derivative of formula XXV if appropriate in the presence of a base, for example 4-dimethylaminopyridine. Then, for the case where X 4 in a compound of formula IIIb = O, thionation (X 4 = S) may be carried out in a manner analogous to that described under Reaction Scheme 2. According to Reaction Scheme 3, the hydrazone derivative of formula XXIV may also be obtained from the 2-aminopyridine derivative of formula XII via diazotisation, preferably with exclusion of water, and subsequent coupling to the ketonic acid of formula XXIII (Japp Klingemann reaction analogously to DE-OS-19 754 348) (variant b) in Reaction Scheme 3). The preparation of the compounds of formula IIIg

R

1

X

9

R

2 5 R / ' / N N (,lIg), R2- _ NCXZ N. N, R24 N 'Y R 2 6 X10 wherein R 1 , R 2 , R 24 , R 25 , R 26 , X 9 and X 1 0 are as defined for formula I, is illustrated in Reaction Scheme 4 below.

WO 99/52893 PCT/EP99/02313 - 37 Reaction Scheme 4: R so a) R2 1 4O a) R Z R-C 4 alkyl XVa O 6 N 0C l Cia l C -C4al kyK

R

2 4 R2

R

2 4 0 orXXVI r base, solvent N N 9

X

10 R 26 b) R 2 N=C=Xo 10 XXVII N base, solvent XVIa

RX

9 5 R alkylation, e.g. R 26 -L R 1

X

9

R

5

R

2 R24 2ill 4C N N base, solvent N N N

X

1 0

R

26

X

10 o R26 IlIg (e.g. X 1 0 = O) IlIg Sthionation e.g. Lawesson reagent

R

1

X

9 R25 X, R2 R,/ N R2

X

1 0 o R 26 lIg (e.g. X 1 0 = S) The compounds of formula IlIg may be prepared analogously to known methods, for example as described in EP-A-0 272 594, EP-A-0 493 323, DE-A-3 643 748, WO 95/23509, US-A-5 665 681 or US-A-5 661 109. For example, in accordance with Reaction Scheme 4 either a) a carbamate derivative of formula XVa may be cyclised in the presence of a solvent and a base, or WO 99/52893 PCT/EP99/02313 - 38 b) an iso(thio)cyanate of formula XVIa may be cyclised, if appropriate in a suitable solvent, with an amino acid derivative of formula XXVI via a compound of formula XXVII in the presence of a base and a suitable solvent to form a compound of formula 111ig. For the case where in a compound of formula IIg R 26 is hydrogen and X 9 and/or X 1 o are oxygen, then optionally alkylation may be carried out at the free N atom of the hydantoin ring using an alkylating reagent of formula XXVIII and the ring carbonyl group may be thionated (X 9 and/or X 1 0 = S). The preparation of compounds of formula IIIh

R

1

X

1 1

R

27

R

2 R / (IIh), N R28

X

12 wherein R 1 , R 2 , R 27 , R 28 , X 1 1 and X 1 2 are as defined for formula I, is illustrated in Reaction Scheme 5 below.

WO 99/52893 PCT/EP99/02313 - 39 Reaction Scheme 5: X X12 a) R 2 N O-C-C 4 alkyl R28N C -C4 N R2NklCakY XVb I R C-C,4alky xvb £ ,__27 R27 0 XXIX N or XX R 2 R 27 base, solvent \ X R

X

12

R~

8 - XXX b) g N=C=X 1 2 N base, solvent XVIb R X R27 alkylation, e.g. R 2 7 -L, R 2 8 -L, or R X 11 R27 N / XXXIa XXXIb / - / R2 R2 Michael acceptor, base, N N N N solvent X12 R28

X

12

R

28 IIIh lIlh (e.g. X 12 = O) thionation, e.g. Lawesson reagent

R

1

X

11

R

27 N /

R

2 \/ N X12 R28 IIIh (e.g. X 12 = S) The compounds of formula IIIh may be prepared analogously to known procedures, for example as described in EP-A-0 210 137, DE-OS-2 526 358, EP-A-0 075 267 or EP-A-0 370 955. For example, in accordance with Reaction Scheme 5 either WO 99/52893 PCT/EP99/02313 -40 a) a carbamate derivative of formula XVb may be cyclised in the presence of a solvent and a base, or b) an iso(thio)cyanate of formula XVIb may be cyclised, if appropriate in a suitable solvent, with a carbazate of formula XXIX via a compound of formula XXX in the presence of a base and a suitable solvent to form a compound of formula IIIh. For the case where in a compound of formula Illh R 27 and/or R 28 are hydrogen and X 1 1 and/or X 1 2 are oxygen, then alkylation may be carried out at the free N atoms using an alkylating agent of formula XXXla or XXXIb and the ring carbonyl groups may be thionated (Xa and/or X 1 2 = S) using a thionating reagent. For the preparation of compounds of formula IIIh in Reaction Scheme 5 wherein R 27 and R 28 together form an alkylene bridge that is interrupted e.g. by -S(O) 2 -, for example a compound of formula lllh wherein R 27 and R 28 are hydrogen may be reacted with a corresponding Michael acceptor, for example CH 2

=CH-S(O)

2

CH

3 or CH 2

=CH-S(O)

2

-CH=CH

2 , and the resulting Michael addition products may be functionalised further. The preparation of the compounds of formula IIIc

R

1 - N R 16 N R14

R

1 5 14 wherein Ri, R 2 and R 1 4 to R 16 are as defined for formula I, is illustrated in Reaction Scheme 6 below.

WO 99/52893 PCT/EP99/02313 -41 Reaction Scheme 6: 0 0 II II a'C, C~" a) R, CCH 'R Ri 14 1 16 l

R

1 5 R16 R2 NHNH 2 XR11R R 2 N N XXI R14 15 O O IIIc II II 'C, .. b)

CC

H C'R1 I R15 XXXIla R 1 ' R i RN RR6 halogenation reagent, e.g. N R RR6 R N b R 2 / N h POdN O 1R R15 R14 XXXIII IIIc (R 14 = halogen) In accordance with Reaction Scheme 6, the pyrazole compounds of formula IlIc may be prepared, for example, either from the hydrazinopyridine derivatives of formula XXI by means of condensation with a 1,3-dicarbonyl derivative of formula XXXII (variant a)), or by means of condensation with a -carbonylcarboxylic acid derivative of formula XXXlla wherein L 2 is a leaving group, for example Cl-C 4 alkoxy, hydroxy or halogen, e.g. chlorine or bromine, (variant b)) and subsequent treatment of the resulting pyridylpyrazolone derivative of formula XXXIII with a halogenating agent, for example phosphorus oxychloride

(R

1 4 =halogen). The two reaction steps a) and b) in Reaction Scheme 6 are effected, if appropriate, in the presence of an acidic, basic or bifunctional catalyst, e.g. p toluenesulfonic acid. The compounds of formula IIIc obtained in this way may be functionalised further in accordance with the definitions of the substituents R 1 4 to R 1 6 by means of standard procedures. The compounds of formula IlIc in Reaction Scheme 6 wherein R 15 is hydrogen may be functionalised further in accordance with the definition of Rs 1 5 , for example with an electrophilic reagent, e.g. a halogenating agent, such as elemental halogen or sulfuryl WO 99/52893 PCT/EP99/02313 - 42 halide, to form the corresponding compounds of formula IIIc wherein R 15 is halogen, or with a nitrating agent, such as nitric acid, if appropriate in admixture with a further strong acid, such as sulfuric acid, to form the corresponding compounds of formula IIIc wherein Rs 15 is nitro. The corresponding pyridono derivatives of formula Ic N RR X R 3

R

14 15 wherein R, to R 3 , R 14 to R 16 and X, are as defined for formula I, may be obtained, as described above, from compounds of formula IIIc by means of oxidation of the pyridyl moiety. In a further variant, the pyridono derivatives of formula Ic may also be obtained directly from the corresponding pyridonylhydrazines of formula XXla R, R2 NHNH 2 (XXIa), N

X

1 R 3 wherein R 1 to Ra and X, are as defined, analogously to the variants shown in Reaction Scheme 6. The required pyridonylhydrazine of formula XXIa may readily be obtained from the corres ponding pyridonyl halide of formula XIIa R, R2 " Hal (Xlla), N

X

1 R 3 wherein Ri, R 2 and Ra are as defined and Hal is fluorine, chlorine or bromine, with hydrazine, preferably in a protic solvent. In certain cases, the compounds of formula Ic may also be obtained in manner analogous to that described in J. Het. Chem. 15, 1221 (1978) and in Reaction Scheme 11, by substitution of a pyridonyl derivative of formula XIIa that is provided with a leaving group L4, WO 99/52893 PCT/EP99/02313 -43 e.g. a halide, a C 1

-C

4 alkyl- or phenyl-sulfonyl group or an unsubstituted or substituted C 1 C 4 alkyl- or phenyl-sulfonyloxy group, (variant c) in Reaction Scheme 11), or by substitution of a pyridine derivative of formula XII that is provided with a leaving group L 4 , e.g. a halide, a C 1

-C

4 alkyl- or phenyl-sulfonyl group or an unsubstituted or substituted C 1

-C

4 alkyl- or phenyl-sulfonyloxy group, (variant d) in Reaction Scheme 11), with a pyrazole of formula

W

03 a or an alkali metal salt thereof, and in the case of variant d) by subsequent functionalisation (oxidation) of the pyridyl moiety of the compound of formula IIc. The substitution reactions according to variants c) and d) may optionally be carried out in the presence of a suitable solvent and a base. Reaction Scheme 11:

R

2 L 4 7 - NNR NN X R 3

R

1 4

R

1 5 HN solvent, base NN d) RI

•

N N R1WR 2 )RR R R2 /L 4

R

1 4 15 XII IIc The preparation of the compounds of formula IIld

NR

18 R NR (lId) N R17 R 19 wherein R 1 , R 2 and R17 to R 19 are as defined for formula I is illustrated in Reaction Scheme 7 below.

WO 99/52893 PCT/EP99/02313 - 44 Reaction Scheme 7: 0 0 R17 a) R 18 R R 1

R

18 R118RR R

R

2

NHNH

2 XXXIb R 2 N- N N N XXI

R

17 R19 O O IIId b) L2

R

18

R

1 9 / i N R 18 R 1 R2 / N halogenation, e.g. R N 2N XXXIlla R17 Ri IIId (R17= halogen)

M(CN)

s XXXIV IIId (R 1 7 = CN) In accordance with Reaction Scheme 7, the tetrahydroindazole compounds of formula IIId may be obtained according to known procedures from the hydrazinopyridine derivatives of formula XXI, for example either by condensation with a cyclohexanone derivative of formula XXXIIb that is acylated in the 2-position, wherein R 17 is as defined for formula I with the exception of R 17 as halogen or cyano, (variant a)), or by condensation with a cyclohexanone derivative of formula XXXIIc wherein L 2 is a leaving group, for example Cl-C 4 alkoxy, hydroxy or halogen, e.g. chlorine or bromine, and subsequent halogenation (variant b)) in a manner analogous to that described under Reaction Scheme 6. The halogen derivatives of formula Ild wherein R 1 7 is halogen may be converted into the corresponding cyano-substituted derivatives of formula Illd (R 17 =CN) according to known methods with an alkali metal cyanide, ammonium cyanide or a metal cyanide, the metal being selected from sub-groups I and II of the Periodic Table of the Elements, if appropriate with the addition of an alkali metal iodide.

WO 99/52893 PCT/EP99/02313 - 45 The preparation of the compounds of formulae Ille and IIIf

R

1

X

6 R 1

X

8 R2"- \ , N II(llR) R

R

2 N j (Ille)and R 2 N / (Illf), N rN X5 R 2 0 X wherein R 1 , R 2 , R 20 to R 23 and X 5 to X 8 are as defined for formula I, is illustrated in Reaction Scheme 8 below. Reaction Scheme 8:

R

1 O R2

NH

2 R, X6 R21- N a) XIII N - R R 21 solvent, propionic acid, 2 R2 20-200*C N 0 R20 5 XXXV Ille (X 5 , X 6 =0) R1

R

2 - N H 2 R22 O N R1 X 8 b) XIII solvent, propionic acid, 2 , 20-200*C N 23 O

X

7 R23 XXXVa IIIf (X 7 , X 8 = O) In accordance with Reaction Scheme 8, the pyrrolinedione derivatives of formula Ille and the tetrahydroisoindolinedione derivatives of formula IIIf may be obtained analogously to known procedures, for example by reaction of an anhydride of formula XXXV (variant a)) or XXXVa (variant b)) with an aminopyridine of formula XIII in an inert solvent, for example an ether, e.g. dioxane, or a lower alkylcarboxylic acid, e.g. propionic acid, at temperatures of from 20 to 2000C. The compounds of formulae Ille and Illf (Xs to X 8 = O) obtained in accordance with Reaction Scheme 8 may optionally be thionated with a suitable sulfur reagent (Xs to X 8 = S).

WO 99/52893 PCTIEP99/02313 - 46 The corresponding pyridono derivatives of formulae le and If

R

1

X

6 R 1 X8 R22

R

2 / / (le) and R N N N X1 R 3

X

5

R

20 X R3 X7 R2 3 1X3 5 XXR may be obtained from the compounds of formulae Ille and Illf as described above, by means of oxidation of the pyridyl moiety. In a further variant, the pyridono derivatives of formulae le and If may also be obtained directly from the corresponding aminopyridone derivatives of formula Xllla R1 R NH 2 (Xllla), N X1

R

3 wherein R 1 , R 2 , R 3 and X 1 are as defined for formula I, analogously to the method as described in Reaction Scheme 8. The preparation of the compounds of formula Illi R1, R

-

X14

X

1 3 R N - , N N-N R29 wherein R 1 , R 2 , R 2 9 , R 30 , X 13 and X 14 are as defined for formula I is illustrated in Reaction Scheme 9 below.

WO 99/52893 PCT/EP99/02313 - 47 Reaction Scheme 9:

R

l X 4 a) R 2 < / O--0C,-C 4 alkyl R X14 XVc R14NH-NHR29 NHR XXXVI / solvent, N - I 1 base 30 XXXVII b) R 2 N=C=X 14

-

N solvent, 3 XVIc base = X13 L3 XXXVIII 1 X14 X1

R

2 N N N

-

N / R R29 Illi In accordance with Reaction Scheme 9, the compounds of formula Illi may be prepared according to known procedures, for example by first reacting a carbamate of formula XVc (variant a)) or an isothiocyanate of formula XVIc (variant b)) with a hydrazine derivative of formula XXXVI to form a semicarbazide derivative of formula XXXVII and then reacting the latter in the presence of a carbonylating or thiocarbonylating reagent of formula XXXVIII. Both reaction steps are advantageously carried out in a suitable solvent and in the presence of a base. As (thio)carbonylating reagent of formula XXXVIII there come into consideration e.g. phosgene, diphosgene, thiophosgene and carbonyldiimidazole. L 3 in formula XXXVIII is therefore a leaving group, for example halogen, e.g. chlorine or bromine, trichloromethoxy or .N The corresponding pyridono derivatives of formula li WO 99/52893 PCT/EP99/02313 -48 R, R2-4

X

1 4 X N N-N

X

1

R

3

R

29 wherein R 1 to R 3 , R 29 , R 30 , X 1 , X 13 and X 14 are as defined for formula I, may be obtained from the compounds of formula Ilili in the manner described above, by means of oxidation of the pyridyl moiety. In a further variant, the pyridono derivatives of formula li may also be obtained directly from the corresponding pyridone carbamates of formula XVd R, x 1 4 R2 NH-C-OC,-C4alkyl (XVd) N Xl

R

3 or from the iso(thio)cyanates of formula XVId R1 R2 N=C=X 1 4 (XVId), N X1

R

3 the radicals R 1 to R 3 , X, and X 14 in the compounds of formulae XVd and XVId being as defined for formula I, in a manner analogous to that described in Reaction Scheme 9. The required starting compounds of formulae XVc and XVIc are known and are described, for example, in EP-A-0 468 924 and EP-A-0 304 920. The preparation of the compounds of formula IIIk R1 N R~ R2 NR3 (IIlk), N Xi

R

31 X15 3 wherein R 1 , R 2 , R 31 , R 32 and X 1 5 are as defined for formula I, is illustrated in Reaction Scheme 10 below.

WO 99/52893 PCT/EP99/02313 - 49 Reaction Scheme 10: R, R, a) 6,cO-mOOH~ NPoc,- N R oaw .x x NHN -< - xx - N ***f N COOH N N XXXX Xs IIIk(X 1 s=O, R 31 =H) FR,-L, base b) OC,-Cak La ws reagers ) N ,cooc,-cR1 R1 R N H N H 2 -• R 2 X - N N N ',As rR N XXI XI s 1 X 15 111Ik (X 15 =0, R 3 1 =H) 111Ik (Xs--S, R1) 4-L. base c) ) .. Lawe R1 R s1 o reage 2) a..metaI ware -0)s N.0a ,N 2 Na*ok c F -- --N-N=CHR, g N t e.g. Na*OCN ",N\\ / &y " *=.9 - N CONH N CFzCOOH 2 // R )xxx(V X15 IIIk (X 15 --O, R 31 =H) In accordance with Reaction Scheme 10, the triazolone derivatives of formula IIIk may be prepared analogously to known procedures, for example by using as starting material a hydrazinopyridine derivative of formula XXI which, in accordance with variant a), is reacted with a keto acid of formula XXXIX, advantageously in the presence of an acid catalyst, e.g. a lower alkylcarboxylic acid, e.g. propionic acid, a mineral acid, e.g. sulfuric acid or hydrochloric acid, or a sulfonic acid, e.g. p-toluenesulfonic acid, to form a hydrazone derivative of formula XXXX. The latter may then be cyclised with an azide of formula XXXXI to form a triazolone derivative of formula Illk wherein Xs 15 is oxygen and R 31 is hydrogen and then optionally derivatised further in accordance with standard procedures with an alkylating reagent of formula XXXXII or with a sulfur reagent. In accordance with variant b), a hydrazinopyridine derivative of formula XXI may be cyclised with an imino ether of formula XXXXIII to form a triazolone derivative of formula Illk wherein

X

1 5 s is oxygen and R 3 1 is hydrogen and then optionally alkylated or thionated as described under variant a). In accordance with variant c), in Reaction Scheme 10 a hydrazinopyridine derivative of formula XXI may be converted first with an aldehyde of formula XXXXIV, then in the presence of a lower alkylcarboxylic acid, e.g. acetic acid, with an alkali metal cyanate to form a compound of formula XXXXV, which may or may not be isolated, and finally cyclised WO 99/52893 PCT/EP99/02313 -50 with an oxidising agent, e.g. an alkali metal hypochlorite (Javelle), to form a compound of formula IIlk wherein Xs 15 is oxygen and R 3 1 is hydrogen. The resulting compound of formula IIIk may then optionally be alkylated or thionated as described under variant a). The corresponding pyridono derivatives of formula Ik R, R2 N R32 R2/- , ')" NY'

R

2 N (1k), N X X1 R 3 15 R31 wherein R, to R 3 , R 31 , R 32 , X, and X 1 5 s are as defined for formula I, may be obtained from the compounds of formula Illk as described above, by means of oxidation of the pyridyl moiety. As a further variant, the pyridono derivatives of formula Ik may also be obtained directly from the corresponding pyridonylhydrazines of formula XXIa R, R / NHNH 2 (XXIa), N X1 R 3 wherein R, to Ra and X, are as defined, in a manner analogous to the variants shown in Reaction Scheme 10. The compounds of formulae XII and XII are known or may be prepared in accordance with known methods, for example as described in DE-A-3 917 469; WO 97/07114; WO 92/00976; JP-A-58-213 776; EP-A-0 012 117; EP-A-0 306 547; EP-A-0 030 215; EP-A-0 272 824; EP-A-0 500 209; US-A-4 996 323; US-A-5 017 705; WO 97/05112; J. Het. Chem. 11, 889 (1974); J. Het. Chem 21, 97 (1984); Tetrahedron 41, 4057 (1985); Heterocycles 22,117; Synth. 1988, 938; J. Med. Chem. 25, 96. The 2-aminopyridines of formula XIII may also be prepared by degradation reactions according to Curtius, Hofmann or Lossen from corresponding pyridine derivatives with carboxylic acid, carboxylic acid chloride, carboxylic acid azide, carboxylic acid ester or carboxylic acid amide functions in the 2-position. The compounds of formulae XII and Xlla in Reaction Scheme 11 wherein L4 is a leaving group, e.g. a C 1

-C

4 alkyl- or phenyl-sulfonyl group, are known or may be prepared in accordance with known methods, for example by oxidation of the corresponding thioethers WO 99/52893 PCT/EP99/02313 -51 with hydrogen peroxide or Javelle water or by means of the synthesis of the heterocycle. Such syntheses are described, for example, in Synthesis 1989, 623 or in WO 98/11071. The reagents of formulae XIV, XVa, XVb, XVIa, XVIb, XVII, XIX, XX, XXII, XXlla, XXIII, XXV, XXVI, XXVIII, XXIX, XXXIa, XXXIb, XXXII, XXXlla, XXXIIb, XXXIIc, XXXIV, XXXV, XXXVa, XXXVI, XXXVIII, XXXIX, XXXXI, XXXXII, XXXXIII and XXXXIV used in Reaction Schemes 2 to 10 are either known or may be prepared in analogy to known methods. The intermediates of formula II RT R,

R

2 / W - R 2 - ' W (1l), N NH OH O in which R 1 , R 2 and W are as defined for formula I and which may be in the tautomeric keto-enol form, are novel. The invention therefore relates to those compounds also. The reactions to form compounds of formula I are advantageously carried out in aprotic, inert organic solvents. Such solvents are hydrocarbons, such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles, such as acetonitrile or propionitrile, amides, such as N,N-dimethylformamide, N,N-diethylformamide or N-methylpyrrolidinone. The reaction temperatures are preferably from -20'C to +120 0 C. The reactions are generally slightly exothermic and may usually be carried out at room temperature. In order to shorten the reaction time or alternatively to initiate the reaction, the reaction mixture may be heated to its boiling point for a short time. The reaction times may likewise be shortened by the addition of a few drops of base as reaction catalyst. Suitable bases are especially tertiary amines, such as trimethylamine, triethylamine, quinuclidine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene or 1,5 diazabicyclo[5.4.0]undec-7-ene, but it is also possible to use inorganic bases, such as hydrides, e.g. sodium or calcium hydride, hydroxides, such as sodium or potassium hydroxide, carbonates, such as sodium or potassium carbonate, or hydrogen carbonates, such as potassium or sodium hydrogen carbonate.

WO 99/52893 PCT/EP99/02313 - 52 The compounds of formula I can be isolated in customary manner by concentration and/or evaporation of the solvent and can be purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydro carbons or chlorinated hydrocarbons, or by means of column chromatography and a suitable eluant. For the use according to the invention of the compounds of formula I, or of compositions comprising them, there come into consideration all methods of application customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and also various methods and techniques such as, for example, the controlled release of active ingredient. For that purpose a solution of the active ingredient is applied to mineral granule carriers or polymerised granules (urealformaldehyde) and dried. If required, it is also possible to apply a coating (coated granules), which allows the active ingredient to be released in metered amounts over a specific period of time. The compounds of formula I may be used as herbicides in their unmodified form, that is to say as obtained in the synthesis, but they are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, on pages 9 to 13 of WO 97/34485. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The formulations, that is to say the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, for example solvents or solid carriers. Surface-active compounds (surfactants) may also be used in addition in the preparation of the formulations. Examples of solvents and solid carriers are given, for example, on page 6 of WO 97/34485. Depending on the nature of the compound of formula I to be formulated, suitable surface active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 99/52893 PCT/EP99/02313 - 53 WO 97/34485. In addition, the surfactants conventionally employed in formulation technology, which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981, Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, MunichVienna 1981, and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-Ill, Chemical Publishing Co., New York, 1980-81, are also suitable for the preparation of the herbicidal compositions according to the invention. The herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of herbicide, from 1 to 99.9 % by weight, especially from 5 to 99.8 % by weight, of a solid or liquid formulation adjuvant, and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients, such as stabilisers, for example vege table oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), anti foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients. The compounds of formula I are generally applied to plants or the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha. The concentration required to achieve the desired effect can be determined by experiment. It is dependent on the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters. The compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control. The term "crops" is to be understood as including also crops that have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic techniques. The weeds to be controlled may be either monocotyl edonous or dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.

WO 99/52893 PCT/EP99/02313 - 54 The following Examples further illustrate but do not limit the invention. Preparation Examples: Example Pl: Preparation of 2-N-ethoxycarbonylamino-3-fluoro-5-chloro-pyridine Cl F N) F S NH

OC

2

H

5 294 g of 2-amino-3-fluoro-5-chloro-pyridine are dissolved in 1 litre of dry pyridine and cooled to 0oC; 220 g of ethyl chloroformate are added dropwise, with stirring, and the mixture is stirred at 220C until reaction is complete. The reaction mixture is then poured into ice-water, adjusted to pH 4-5 with 2N hydrochloric acid and extracted with ethyl acetate. The combined extracts are washed with water, dried over sodium sulfate, concentrated by evaporation and caused to crystallise by the addition of n-hexane. The resulting precipitate is filtered off, washed with n-hexane and dried in vacuo, yielding the desired title compound having a melting point of 1320C. Example P2: Preparation of 1-(3-fluoro-5-chloro-pyridin-2-yl)-3-methyl-4-trifluoromethyl pyrimidine-2,6-dione CI F 0 F ,j" CHF, NN O CF 3 Under a nitrogen atmosphere, with cooling and stirring, a solution of 22.7 g of 4,4,4-trifluoro 3-amino-2-butenoic acid ethyl ester is added dropwise at 0-5°C to 5.1 g of a previously prepared sodium hydride dispersion (60%) in 60 ml of N-methylpyrrolidine and the mixture is stirred at 220C until the evolution of hydrogen has ceased. 23.7 g of 2 ethoxycarbonylamino-3-fluoro-5-chloro-pyridine (Example P1) are then added and the reaction mixture is heated at 1200C for about 5 hours. The mixture is then cooled, 16.7 g of methyl iodide are added dropwise and stirring is carried out at 220C overnight. The reaction mixture is taken up in ethyl acetate and then washed with ice-water, dried over sodium sulfate, filtered and concentrated by evaporation. The resulting residue is recrystallised from ethyl acetate/n-hexane, yielding the desired title compound having a melting point of 133 1340C.

WO 99/52893 PCT/EP99/02313 - 55 Example P3: Preparation of 1-(3-fluoro-5-chloro-2-pyridyl-N-oxide)-3-methyl-4 trifluoromethyl-pyrimidine-2,6-dione Cl F F ,NCH3 O"N N+ N N I~ O CF 3 24 g of 1-(3-fluoro-5-chloro-pyridin-2-yl)-3-methyl-4-trifluoromethyl-pyrimidine-2,6-dione (Example P2) in 150 ml of dichloromethane are cooled to -50C and 2 g of hydrogen peroxide/urea adduct are added. 2.7 ml of trifluoroacetic acid anhydride dissolved in 2 ml of dichloromethane are then metered in dropwise and after the exothermic reaction has subsided the reaction mixture is stirred overnight to complete the reaction. A further 5 g of hydrogen peroxide/urea adduct and 3 ml of trifluoroacetic acid anhydride are then added in two portions in the course of 3 hours and after the exothermic reaction has subsided the reaction mixture is heated at 25-350C until the reaction is complete. The reaction mixture is then cooled and at -50C adjusted to pH 7.5 first with 2N sodium hydroxide solution and then with saturated sodium hydrogen carbonate solution and partitioned between dichloro methane and ice-water; the organic phase is separated off, dried over sodium sulfate, filtered and concentrated by evaporation. The solid residue that remains is recrystallised from ethyl acetate/n-hexane, yielding the desired product having a melting point of 142 143 0 C. Example P4: Preparation of 1 -(3-fluoro-5,6-dichloro-2-pyridyl)-3-methyl-4-trifluoromethyl pyrimidine-2,6-dione Cl F C N N ' NCH3 O CF 0 /J_ -- F3 6.8 g of 1-(3-fluoro-5-chloro-2-pyridyl-N-oxide)-3-methyl-4-trif luoromethyl-pyrimidine-2,6 dione (Example P3) are added in portions to a solution, heated to 700C, of 2.4 ml of phosphorus oxytrichloride in 20 ml of 1,2-dichloroethane and the mixture is maintained at that temperature overnight; a further 4.0 ml of phosphorus oxytrichloride is added and the mixture is heated for a further 20 hours. The mixture is then cooled, poured into ice-water and extracted with dichloroethane and the combined extracts are washed with ice-cold 2N WO 99/52893 PCT/EP99/02313 - 56 sodium hydroxide solution and water, dried over sodium sulfate and concentrated by evap oration. The residue is purified by means of silica gel chromatography (eluant: hexane/ethyl acetate 9/1), yielding the desired title compound having a melting point of 113-1150C. Example P5: Preparation of 1-(2-hydroxy-3-chloro-5-fluoro-pyridin-6-yl)-3-methyl-4 trifluoromethyl-pyrimidine-2,6-dione CI F ,l CH3 HO n NN O CF3 182 g of trifluoroacetic acid anhydride are added dropwise to a solution, cooled to -30'C, of 29.6 g of 1-(3-fluoro-5-chloro-2-pyridyi-N-oxide)-3-methyl-4-trifluoromethyl-pyrimidine-2,6 dione (Example P3) in 400 ml of dimethylformamide and the mixture is then stirred overnight at -30C and on the following day at 220C. The mixture is then freed of excess trifluoroacetic acid anhydride in vacuo, cooled to -50C and cautiously neutralised first with dilute sodium hydroxide solution and then with sodium hydrogen carbonate solution. After the addition of ice-water, extraction is carried out with ethyl acetate and the combined extracts are washed with water and dried over sodium sulfate. Filtration is then carried out and the filtrate is concentrated by evaporation; the resulting residue is purified over a column of silica gel (eluant: n-hexane/ethyl acetate 8/2, with an increasing gradient with respect to ethyl acetate). The desired title compound having a melting point of 1780C is obtained.

WO 99/52893 PCT/EP99/02313 -57 Example P6: Preparation of 1-(2-proparqyloxy-3-chloro-5-fluoro-pyridin-6-yl)-3-methyl-4 trifluoromethyl-pyrimidine-2,6-dione, 1-(2-chloro-3-proparqyloxy-5-fluoro-pyridin-6-yl)-3 methyl-4-trifluoromethyl-pyrimidine-2,6-dione and 1-(1-proparqyloxy-3-chloro-5-fluoro-2 pyridon-6-yl)-3-methyl-4-trifluoromethyl-pyrimidine-2,6-dione CI F HCOkC 2 HHC SF CH 3 F O N N N Ond

CH

2 IN,3CH and O CF3 C N N" 0i N C CH CF 3 CI F C2 / CF 3 C 0 CH 4.5 ml of propargyl bromide are added dropwise to a suspension of 10.2 g of a mixture of 1 (2-hydroxy-3-chloro-5-fluoro-pyridin-6-yi)-3-methyl-4-trifluoromethyl-pyrimidine-2,6-dione and 1-(2-chloro-3-hydroxy-5-fluoro-pyridin-6-yl)-3-methyl-4-trifluoromethyl-pyrimidine-2,6 dione (Example P5), 7.5 g of potassium carbonate and 0.08 g of 18-crown-6 in 180 ml of acetonitrile and the mixture is then heated at 650C overnight. Concentration by evaporation in vacuo is then carried out, and an ethyl acetate/ice-water mixture and 1N hydrochloric acid are added to the resulting residue until a pH of 7 is obtained; the aqueous phase is separated off and extracted with ethyl acetate and the combined organic phases are washed with water, dried over sodium sulfate, filtered and concentrated by evaporation. The residue is purified by silica gel chromatography (eluant: n-hexane/ethyl acetate 8/2), yielding the desired isomers 1-(2-propargyloxy-3-chloro-5-fluoro-pyridin-6-yl)-3-methyl-4 trifluoromethyl-pyrimidine-2,6-dione having a melting point of 121-1220C, 1-(2-chloro-3 propargyloxy-5-fluoro-pyridin-6-yl)-3-methyl-4-trifluoromethyl-pyrimidine-2,6-dione having a melting point of 69-710 C and 1-(1-propargyloxy-3-chloro-5-fluoro-2-pyridon-6-yl)-3-methyl-4 trifluoromethyl-pyrimidine-2,6-dione having a melting point of 223-224oC.

WO 99/52893 PCT/EP99/02313 - 58 Example P7: Preparation of 1-(1-allyloxy-3-chloro-5-fluoro-2-pyridon-6-yl)-3-methyl-4 trifluoromethyl-pyrimidine-2,6-dione CI F 0

SCH

3 O N N N H

C-C

H O

CF

3 H, C A solution of 0.62 g of 1-(2-allyloxy-3-chloro-5-fluoro-pyridin-6-yl)-3-methyl-4-trifluoromethyl pyrimidine-2,6-dione in 5 ml of dioxane is stirred at 200C with 0.02 g of palladium(II) chloride/diacetonitrile complex until reaction is complete. The reaction mixture is then filtered over silica gel and concentrated by evaporation. The title compound is purified by silica gel chromatography (eluant: ethyl acetate/hexane). The title compound is obtained in pure form with a melting point of 115-1170C. Example P8: Preparation of 2-(5-chloro-3-fluoro-1l-oxy-pyridin-2-yl)-4,5,6,7-tetrahydro isoindolo-1,3-dione (intermediate) ClIF 0 N N o 004 With cooling at -250 to -15°C, 15 g of trifluoroacetic acid anhydride are added in the course of 30 minutes to a suspension of 10.1 g of 2-(5-chloro-3-fluoro-pyridin-2-yl)-4,5,6,7-tetra hydroisoindolo-1,3-dione (prepared analogously to Chem. Abstr. 114, 164251f) and 6.6 g of hydrogen peroxide/urea adduct in 100 ml of 1,2-dichloroethane. Stirring is carried out at +100C overnight, and then a further 3.3 g of hydrogen peroxide/urea adduct is added and stirring is continued at 200C until reaction is complete. Everything is then poured into ice water and neutralised with aqueous 2N sodium hydroxide solution. The product is extracted with ethyl acetate, washed with water and dried. Concentration by evaporation yields a solid, which is purified by means of silica gel chromatography (eluant: hexane/ethyl acetate 7/3). The desired 2-(5-chloro-3-fluoro-1 -oxy-pyridin-2-yl)-4,5,6,7-tetrahydroisoindolo-1,3 dione having a melting point of 162-1640C is obtained.

WO 99/52893 PCT/EP99/02313 - 59 Example P9: Preparation of 2-(5-chloro-3-fluoro-6-hydroxy-pyridin-2-yl)-4,5,6,7-tetrahydro isoindolo-1,3-dione and 2-(5-hydroxy-6-chloro-3-fluoro-pyridin-2-yl)-4,5,6,7-tetrahydro isoindolo-1,3-dione Cl F HO F 0 0 HO N N and Cl N N O O 3.6 ml of trifluoroacetic acid anhydride are added dropwise, with cooling at -300 to -200C, to a solution of 0.79 g of 2-(5-chloro-3-fluoro-1-oxy-pyridin-2-yl)-4,5,6,7-tetrahydroisoindolo 1,3-dione (Example P8) in 12 ml of dimethylformamide and the mixture is stirred at +100C overnight. A further 3 ml of trifluoroacetic acid anhydride is then added dropwise and stirring is continued at +100C for 15 hours. Concentration by evaporation is then carried out; ethyl acetate is added to the resulting residue and the mixture is rendered basic with aqueous 1N sodium hydroxide solution. Extraction is then carried out with ethyl acetate and the combined extracts are washed with water, dried and concentrated by evaporation. The residue is purified by silica gel chromatography, yielding the isomeric mixture of the two title compounds having a melting point of 190-1930C. The mixture can either be separated or further reacted directly. In an analogous manner, and in accordance with methods as shown in the general Reaction Schemes 1-10 and in the references indicated, it is also possible to obtain the preferred compounds listed in the following Tables. Table 1: A preferred group of compounds of formula I corresponds to general formula Rio F Cl N F (li), wherein the meanings of the corresponding N N F X 1 R 3 o CH 3 substituents R 1 , X, and R 3 are given in Table A, so that 423 specific compounds of formula I, are disclosed.

WO 99/52893 PCT/EP99/02313 - 60 Table 2: A further preferred group of compounds of formula I corresponds to general Rio F formula Br / " N F (12), wherein the meanings of the corresponding N N F X R 3 0 CH 3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 12 are disclosed. Table 3: A further preferred group of compounds of formula I corresponds to general Rio F formula NC N F (13), wherein the meanings of the corresponding N. N F X,

R

3 o

CH

3 substituents R 1 , X 1 and R 3 are indicated in Table A, so that 423 specific compounds of formula 13 are disclosed. Table 4: A further preferred group of compounds of formula I corresponds to general

R

1 0 F formula CH3 N F (14), wherein the meanings of the fr-ma / H / N -N F X/ R 3 0 CH3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 14 are disclosed. Table 5: A further preferred group of compounds of formula I corresponds to general R,O S F formula CI -N -F (5Is), wherein the meanings of the corresponding N N F X R 3 S CH 3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 15 are disclosed.

WO 99/52893 PCT/EP99/02313 -61 Table 6: A further preferred group of compounds of formula I corresponds to general R 1 S F formula CIl \ N F (16), wherein the meanings of the corresponding N >-N F X R 3 0

CH

3 substituents RI, X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 16 are disclosed. Table 7: A further preferred group of compounds of formula I corresponds to general / R q O F Rio F F formula Cl /N F (17), wherein the meanings of the N N FF X R 30 CH 3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 17 are disclosed. Table 8: A further preferred group of compounds of formula I corresponds to general R 1 S F formula Cl / \ N F (la), wherein the meanings of the corresponding N -N F X * R 3 S CH 3 substituents RI, X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 18 are disclosed. Table 9: A further preferred group of compounds of formula I corresponds to general

R

1 0 FF formula OH 3 N F (19), wherein the meanings of the N. N\ FF X R 3 O CH 3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 19 are disclosed.

WO 99/52893 PCT/EP99/02313 - 62 Table 10: A further preferred group of compounds of formula I corresponds to general

R

1 0o c l / \ F formula CI N H (110), wherein the meanings of the corresponding N. N \ F X R 30 CHF 2 substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 110 are disclosed. Table 11: A further preferred group of compounds of formula I corresponds to general

R

1 CH 3 /F formula CI N F (I11), wherein the meanings of the corresponding N N F X R 30

CH

3 substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula I, are disclosed. Table 12: A further preferred group of compounds of formula I corresponds to general R 1 0 Cl F formula Cl N F (112), wherein the meanings of the corresponding N F R 30

CH

3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 112 are disclosed. Table 13: A further preferred group of compounds of formula I corresponds to general

R

1 0 formula Cl N CN (113), wherein the meanings of the corresponding N~N\ Xl R 3 0 CH 3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 113 are disclosed.

WO 99/52893 PCT/EP99/02313 - 63 Table 14: A further preferred group of compounds of formula I corresponds to general

R

1 0

CH

3 formula Br N CN (114), wherein the meanings of the corresponding 'ormul N N X R 3 O CH 3 substituents R 1 , X 1 and R 3 are indicated in Table A, so that 423 specific compounds of formula 114 are disclosed. Table 15: A further preferred group of compounds of formula I corresponds to general

R

1 0 / '__ formula NC N CN (115s), wherein the meanings of the corresponding N. N, X I R 3 O CH 3 substituents R 1 , X 1 and R 3 are indicated in Table A, so that 423 specific compounds of formula 115 are disclosed. Table 16: A further preferred group of compounds of formula I corresponds to general

R

1 0 formula CH 3 N c N (116), wherein the meanings of the corresponding N - N x , R 3 O CH 3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 116 are disclosed. Table 17: A further preferred group of compounds of formula I corresponds to general R in formula Cl / N (117), wherein the meanings of the corresponding N~N\ X 1 R 3 0 CH 3 substituents R 1 , X 1 and R 3 are indicated in Table A, so that 423 specific compounds of formula 117 are disclosed.

WO 99/52893 PCT/EP99/02313 - 64 Table 18: A further preferred group of compounds of formula I corresponds to general Ro formula CI N (118), wherein the meanings of the corresponding N -N

X

1

R

3 0 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 118 are disclosed. Table 19: A further preferred group of compounds of formula I corresponds to general Rio formula Cl / N (119), wherein the meanings of the corresponding N N

X

1

R

3 S substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 119 are disclosed. Table 20: A further preferred group of compounds of formula I corresponds to general Ro 1 0 CH 3 /- F formula Cl ' N -F (120), wherein the meanings of the corresponding N N F XI R3 H 3 substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 120 are disclosed. Table 21: A further preferred group of compounds of formula I corresponds to general Ro 1 0 F formula Cl \N F (121), wherein the meanings of the corresponding N N- F X R 3

H

3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 121 are disclosed.

WO 99/52893 PCT/EP99/02313 - 65 Table 22: A further preferred group of compounds of formula I corresponds to general

R

1 0 /\ \ F formula Br N F (122), wherein the meanings of the N N F X R3 CH 3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 122 are disclosed. Table 23: A further preferred group of compounds of formula I corresponds to general

R

1 0 F Br N F formula BN N F (123), wherein the meanings of the corresponding X

R

3

CH

3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 123 are disclosed. Table 24: A further preferred group of compounds of formula I corresponds to general Rio /. \ F formula Br N F (124), wherein the meanings of the N N F X1 R 3 corresponding substituents R 1 , X 1 and R 3 are indicated in Table A, so that 423 specific compounds of formula 124 are disclosed. Table 25: A further preferred group of compounds of formula I corresponds to general R 1 0i CH 3 F formula Br N " F (125), wherein the meanings of the corresponding N N F X, R3 substituents RI, X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 125 are disclosed.

WO 99/52893 PCT/EP99/02313 - 66 Table 26: A further preferred group of compounds of formula I corresponds to general

CH

3 Rio F formula Br N F (126), wherein the meanings of the Br -N FN- N N- F X,

R

3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 126 are disclosed. Table 27: A further preferred group of compounds of formula I corresponds to general Rio formula O O N FF(127), wherein the meanings of N N F X, R, the corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 127 are disclosed. Table 28: A further preferred group of compounds of formula I corresponds to general

CH

3

R

1 0 F formula N F(128), wherein the meanings of the N,1 IN F N N- F X, R 3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 128 are disclosed. Table 29: A further preferred group of compounds of formula I corresponds to general Ro 1 0 Cl F formula Cl / N F (129), wherein the meanings of the corresponding N N- F X/ R

CH

3 substituents RI, X 1 and Ra are indicated in Table A, so that 423 specific compounds of formula 129 are disclosed.

WO 99/52893 PCT/EP99/02313 - 67 Table 30: A further preferred group of compounds of formula I corresponds to general R 1 S CH 3 F formula Cl (130), wherein the meanings of the corresponding N N- F X R 3 H 3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 13o are disclosed. Table 31: A further preferred group of compounds of formula I corresponds to general R S F formula CI N (131), wherein the meanings of the corresponding N N-- F X R 3 CH 3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 131 are disclosed. Table 32: A further preferred group of compounds of formula I corresponds to general R S F CI NF formula CN N F (132), wherein the meanings of the corresponding " 1 R 3

CH

3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 132 are disclosed. Table 33: A further preferred group of compounds of formula I corresponds to general R S F C formuN F formulaN N F (I), wherein the meanings of the corresponding " 1 R 3

XR

3

CH

3 substituents R 1 , X 1 and R 3 are indicated in Table A, so that 423 specific compounds of formula 133 are disclosed.

WO 99/52893 PCT/EP99/02313 - 68 Table 34: A further preferred group of compounds of formula I corresponds to general Rio F formula c / \ N (l34), wherein the meanings of the corresponding F N N F X, R 3 substituents R 1 , X 1 and R 3 are indicated in Table A, so that 423 specific compounds of formula 134 are disclosed. Table 35: A further preferred group of compounds of formula I corresponds to general R 1 S F formula CH 3 N F (3las), wherein the meanings of the corresponding N N F X, R 3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 135 are disclosed. Table 36: A further preferred group of compounds of formula I corresponds to general Ro 1 0 formula NC - N F (136), wherein the meanings of the N N F X, R, S1 R3 corresponding substituents RI, X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 136 are disclosed. Table 37: A further preferred group of compounds of formula I corresponds to general Rio Cl F formula ci N F (137), wherein the meanings of the corresponding N N F N.CN X R 3 CN substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 137 are disclosed.

WO 99/52893 PCT/EP99/02313 - 69 Table 38: A further preferred group of compounds of formula I corresponds to general Rio F formula CI N F (138l), wherein the meanings of the N N- F x R cl corresponding substituents RI, X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 138 are disclosed. Table 39: A further preferred group of compounds of formula I corresponds to general R 1 0 Cl F formula CI NF (139), wherein the meanings of the corresponding N N- F X 1 R c substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 139 are disclosed. Table 40: A further preferred group of compounds of formula I corresponds to general R10 F NC N F formula N N-- F (140), wherein the meanings of the X, R 3

CH

3 corresponding substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 140 are disclosed. Table 41: A further preferred group of compounds of formula I corresponds to general Rio R10 formula Cl- / N (141), wherein the meanings of the corresponding N N x1 R3 substituents RI, X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 141 are disclosed.

WO 99/52893 PCT/EP99/02313 -70 Table 42: A further preferred group of compounds of formula I corresponds to general RIS formula CI- / \ N (142), wherein the meanings of the corresponding N N x R3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 142 are disclosed. Table 43: A further preferred group of compounds of formula I corresponds to general

R

1 o formula CI N (143), wherein the meanings of the corresponding N N~ X/ 1 "R 3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 143 are disclosed. Table 44: A further preferred group of compounds of formula I corresponds to general Rio formula NC N (144), wherein the meanings of the corresponding N N Xl R3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 144 are disclosed. Table 45: A further preferred group of compounds of formula I corresponds to general

R

1

CH

3 Br formula C N (14s), wherein the meanings of the corresponding N N CH 3 X, R substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 145 are disclosed.

WO 99/52893 PCT/EP99/02313 - 71 Table 46: A further preferred group of compounds of formula I corresponds to general R1 Cl formula Cl N (146), wherein the meanings of the corresponding N N

CH

3 X,

R

3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 146 are disclosed. Table 47: A further preferred group of compounds of formula I corresponds to general R 1 CF 3 Cl formula Cl N (147), wherein the meanings of the corresponding N N

CH

3 X,

R

3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 147 are disclosed. Table 48: A further preferred group of compounds of formula I corresponds to general R 1 Cl formula NC N ' CH (148), wherein the meanings of the corresponding N N

CH

3 X, R 3 substituents RI, X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 148 are disclosed. Table 49: A further preferred group of compounds of formula I corresponds to general R, N.Br formula Cl N (149), wherein the meanings of the corresponding N N

CH

3

R

3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 149 are disclosed.

WO 99/52893 PCT/EP99/02313 - 72 Table 50: A further preferred group of compounds of formula I corresponds to general R 1 CH 3 COOEt formula CI N (15o), wherein the meanings of the corresponding N. N

CH

3 X,

R

3 substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 15o are disclosed. Table 51: A further preferred group of compounds of formula I corresponds to general R 1 N0 2 formua Cl / \

H

3 formula C N (151), wherein the meanings of the corresponding N N Cl

X

1 R 3 substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 5Is are disclosed. Table 52: A further preferred group of compounds of formula I corresponds to general R 1

C

2

H

5 /

OH

3 formula Cl N (152), wherein the meanings of the corresponding N N C 2

H

5 X, R3 substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 152 are disclosed. Table 53: A further preferred group of compounds of formula I corresponds to general R 1 C 2 Hs formula Cl - N (153), wherein the meanings of the corresponding N N C 2 Hs X, R 3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 153 are disclosed.

WO 99/52893 PCT/EP99/02313 -73 Table 54: A further preferred group of compounds of formula I corresponds to general R 1

NO

2 formula NC N (Is4), wherein the meanings of the corresponding N. N

CH

3 X, R 3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula Is~ are disclosed. Table 55: A further preferred group of compounds of formula I corresponds to general

R

1

CH

3 0 formula C / N (5Iss), wherein the meanings of the corresponding N N CH 3 X, R 3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 5Is5 are disclosed. Table 56: A further preferred group of compounds of formula I corresponds to general R 1 C 2 H 5 Br formula N (156), wherein the meanings of the corresponding N N

CH

3 X1 R 3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 156 are disclosed. Table 57: A further preferred group of compounds of formula I corresponds to general R 1

NH

2 formula Cl- / -N (157), wherein the meanings of the corresponding N N

CH

3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 5Is7 are disclosed.

WO 99/52893 PCT/EP99/02313 - 74 Table 58: A further preferred group of compounds of formula I corresponds to general CH 3 1 CH:T-N Ri N formula (15s), wherein the meanings of the corresponding CI- N N N CH 3 X R3 substituents R 1 , X 1 and R 3 are indicated in Table A, so that 423 specific compounds of formula le8 are disclosed. Table 59: A further preferred group of compounds of formula I corresponds to general R 1 N0 2 Cl formula N (159Is), wherein the meanings of the corresponding N N C 2 Hs

X

1 R 3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 159 are disclosed. Table 60: A further preferred group of compounds of formula I corresponds to general

R

1 l formula Cl/ R N (160), wherein the meanings of the corresponding N N N X1 R3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 160 are disclosed. Table 61: A further preferred group of compounds of formula I corresponds to general R CN formula Cl N (161), wherein the meanings of the corresponding N N X, R3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 161 are disclosed.

WO 99/52893 PCT/EP99/02313 - 75 Table 62: A further preferred group of compounds of formula I corresponds to general R Cl formula NC N ? (162), wherein the meanings of the corresponding N. N X, R 3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 162 are disclosed. Table 63: A further preferred group of compounds of formula I corresponds to general R Cl CI formula Cl N (163), wherein the meanings of the N, N corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 163 are disclosed. Table 64: A further preferred group of compounds of formula I corresponds to general R Cl OH formula NC N N (164), wherein the meanings of the N N corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 164 are disclosed. Table 65: A further preferred group of compounds of formula I corresponds to general R Cl F formula Cl N c(1 65), wherein the meanings of the N N

XR

3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 165 are disclosed.

WO 99/52893 PCT/EP99/02313 -76 Table 66: A further preferred group of compounds of formula I corresponds to general R 1Cl formula Cl N CH (166), wherein the meanings of the -N N X1 R3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 166 are disclosed. Table 67: A further preferred group of compounds of formula I corresponds to general R 1

CH

3 Cl

OH

3 formula Cl N (167), wherein the meanings of the N. N corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 167 are disclosed. Table 68: A further preferred group of compounds of formula I corresponds to general F R1 formula Cl N (168), wherein the meanings of the N. N " 1 R"3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 168 are disclosed. Table 69: A further preferred group of compounds of formula I corresponds to general

R

1 , O / \ CH 3 formula Cl N CH(169), wherein the meanings of the N CH 3 X

R

3 o corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 169 are disclosed.

WO 99/52893 PCT/EP99/02313 - 77 Table 70: A further preferred group of compounds of formula I corresponds to general

R

1 o CH 3 formula CH 3 N (170), wherein the meanings of the corresponding N

CH

3 X, R, O substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 170 are disclosed. Table 71: A further preferred group of compounds of formula I corresponds to general

R

1 o

CH

3 formula NC N CH3 (171), wherein the meanings of the corresponding N R 3 0 substituents RI, X 1 and R 3 are indicated in Table A, so that 423 specific compounds of formula 17, are disclosed. Table 72: A further preferred group of compounds of formula I corresponds to general

R

1 o Cl formula Cl N (172), wherein the meanings of the N

CH

3 X, R 3o X R/ "= 3 0 corresponding substituents R 1 , X 1 and R 3 are indicated in Table A, so that 423 specific compounds of formula 172 are disclosed. Table 73: A further preferred group of compounds of formula I corresponds to general

R

1 o CF3 formula NC \ N (173), wherein the meanings of the corresponding N. C F 3 X 1

R

3 0 substituents RI, X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 173 are disclosed.

WO 99/52893 PCT/EP99/02313 -78 Table 74: A further preferred group of compounds of formula I corresponds to general R, s -/ ' OH 3 formula CI N C H3 (174), wherein the meanings of the corresponding N

CH

3 X) R 3 S substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 174 are disclosed. Table 75: A further preferred group of compounds of formula I corresponds to general

R

1 o

CH

3 formula NC /N (17s), wherein the meanings of the corresponding N.

CH

3

X

1 R 3 O substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 175 are disclosed. Table 76: A further preferred group of compounds of formula I corresponds to general R o formula Cl N (176), wherein the meanings of the corresponding N. CH3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 176 are disclosed. Table 77: A further preferred group of compounds of formula I corresponds to general R 1 O, formula Cl N (177), wherein the meanings of the corresponding N

X

1

R

3 0 substituents RI, X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 177 are disclosed.

WO 99/52893 PCT/EP99/02313 -79 Table 78: A further preferred group of compounds of formula I corresponds to general

R

1 o formula Cl N CC (178), wherein the meanings of the N X, R, O corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 178 are disclosed. Table 79: A further preferred group of compounds of formula I corresponds to general R S formula Cl N (179), wherein the meanings of the corresponding N

CF

3 X, R 3 S substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 179 are disclosed. Table 80: A further preferred group of compounds of formula I corresponds to general

R

1 o

CH

3 formula CI N (180), wherein the meanings of the N.

CH

3 X, R 3 0 corresponding substituents RI, X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 180 are disclosed. Table 81: A further preferred group of compounds of formula I corresponds to general R o formula CI / N (181), wherein the meanings of the corresponding N X1 R 3 0 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 181 are disclosed.

WO 99/52893 PCT/EP99/02313 - 80 Table 82: A further preferred group of compounds of formula I corresponds to general R o formula CH 3 , N (182), wherein the meanings of the corresponding N XC RN 0 substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 182 are disclosed. Table 83: A further preferred group of compounds of formula I corresponds to general R o formula NC / N | (183), wherein the meanings of the corresponding N

X

1

R

3 0 substituents R 1 , X 1 and Ra are indicated in Table A, so that 423 specific compounds of formula 183 are disclosed. Table 84: A further preferred group of compounds of formula I corresponds to general R o CI formula CI / N (184), wherein the meanings of the N vXi

R

3 0 corresponding substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 184 are disclosed. Table 85: A further preferred group of compounds of formula I corresponds to general R o OH formula NC /' N (l15), wherein the meanings of the N XI R 3 0 corresponding substituents RI, X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 185 are disclosed.

WO 99/52893 PCT/EP99/02313 -81 Table 86: A further preferred group of compounds of formula I corresponds to general R o F formula Cl /N (186), wherein the meanings of the N X R O 3 0 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 186 are disclosed. Table 87: A further preferred group of compounds of formula I corresponds to general

R

1 ,

CH

3 formula NC N (187), wherein the meanings of the N X, R 3 0 corresponding substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 187 are disclosed. Table 88: A further preferred group of compounds of formula I corresponds to general R o

OH

3 formula Cl /, N (188), wherein the meanings of the N X

R

3 0 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 188 are disclosed. Table 89: A further preferred group of compounds of formula I corresponds to general R o formula Br / N (189), wherein the meanings of the N X 1 R 3 O corresponding substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 189 are disclosed.

WO 99/52893 PCT/EP99/02313 - 82 Table 90: A further preferred group of compounds of formula I corresponds to general R s formula Cl N (19I), wherein the meanings of the corresponding N X R 3 S substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 190 are disclosed. Table 91: A further preferred group of compounds of formula I corresponds to general

R

1 o formula Cl N (191), wherein the meanings of the N,

CH

3 X, R 3 0 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 191 are disclosed. Table 92: A further preferred group of compounds of formula I corresponds to general

R

1 0 N ,CH3 formula Cl N\ (192), wherein the meanings of the corresponding N 1 a 3 0 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 192 are disclosed. Table 93: A further preferred group of compounds of formula I corresponds to general R O / \ NH formula Cl N (193), wherein the meanings of the corresponding NN

X

I

R

3 0 1 3 0 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 193 are disclosed.

WO 99/52893 PCT/EP99/02313 - 83 Table 94: A further preferred group of compounds of formula I corresponds to general

R

1 0 / \N ,CH 3 formula Cl N N (194), wherein the meanings of the corresponding N X R 3 O CH 3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 194 are disclosed. Table 95: A further preferred group of compounds of formula I corresponds to general RiO / N / CH 3 formula Cl N/ N (195), wherein the meanings of the corresponding N

X

i R R CH 2

CH

3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 195 are disclosed. Table 96: A further preferred group of compounds of formula I corresponds to general R O /- N"CH 3 formula Cl N N (196), wherein the meanings of the X R 3

CH

2 CH 2 CH 3 corresponding substituents RI, X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 196 are disclosed. Table 97: A further preferred group of compounds of formula I corresponds to general RiO R

CH

3 / \ 7~-N 3 formula Cl N-N (197), wherein the meanings of the XK R3 O CH 2 CH2CH 3 corresponding substituents R 1 , X 1 and R 3 are indicated in Table A, so that 423 specific compounds of formula 197 are disclosed.

WO 99/52893 PCT/EP99/02313 - 84 Table 98: A further preferred group of compounds of formula I corresponds to general

R

1 0

/-NCH

3 formula Cl N CH3 (198), wherein the meanings of the N X R 3 CH 2

CH

2

CH

3 CH corresponding substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 198 are disclosed. Table 99: A further preferred group of compounds of formula I corresponds to general

R

1 0 / i NCH formula NC NJ (199), wherein the meanings of the

X

i R O

C

H

2

CH

3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 199 are disclosed. Table 100: A further preferred group of compounds of formula I corresponds to general R 0 //NCH2CH 3 formula CI- N CH2CH3 (11oo), wherein the meanings of the N CHCH

X

1

R

3 0 2 corresponding substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula o1100 are disclosed. Table 101: A further preferred group of compounds of formula I corresponds to general R O / \ NH formula Cl N (o1101), wherein the meanings of the X R O CH 2

CH

2

CH

3 corresponding substituents RI, X, and R 3 are indicated in Table A, so that 423 specific compounds of formula lo, are disclosed.

WO 99/52893 PCT/EP99/02313 - 85 Table 102: A further preferred group of compounds of formula I corresponds to general R S N,CH formula CI N\ (1102), wherein the meanings of the corresponding 1 R 3H substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1102 are disclosed. Table 103: A further preferred group of compounds of formula I corresponds to general R 10 N ,CH3 formula NC N O..CH 3 (1103), wherein the meanings of the corresponding N X R 3 0 CH 3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1103 are disclosed. Table 104: A further preferred group of compounds of formula I corresponds to general

R

1 0 NCH3 / \ -N 3 NC N formula N (l104), wherein the meanings of the corresponding X

R

3 O0 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 114 are disclosed. Table 105: A further preferred group of compounds of formula I corresponds to general R O / /'NCH3 Cl N formula N(1105), wherein the meanings of the corresponding X i R 3 0 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula has are disclosed.

WO 99/52893 PCT/EP99/02313 - 86 Table 106: A further preferred group of compounds of formula I corresponds to general R0 / R NCH3 formula N CH (1106), wherein the meanings of the X R O / 3

R

3 CH 3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1106 are disclosed. Table 107: A further preferred group of compounds of formula I corresponds to general R S N N ,CH3 formula Br N ] (1107), wherein the meanings of the corresponding N X R 3 S H 3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1107 are disclosed. Table 108: A further preferred group of compounds of formula I corresponds to general

R

1 0 //NCH3 CIl N formula N (lo8), wherein the meanings of the corresponding X R 3 0 O substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula lo8 are disclosed. Table 109: A further preferred group of compounds of formula I corresponds to general RiO formula Cl- N (11o9), wherein the meanings of the corresponding N

X

1

R

3 0 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1109 are disclosed.

WO 99/52893 PCT/EP99/02313 - 87 Table 110: A further preferred group of compounds of formula I corresponds to general R 0 formula Cl N (1110), wherein the meanings of the corresponding N O

R

3 0 Xi R 3 O substituents R 1 , X 1 and Ra are indicated in Table A, so that 423 specific compounds of formula 1110 are disclosed. Table 111: A further preferred group of compounds of formula I corresponds to general R O formula CI N (1111), wherein the meanings of the OH

X

1

R

3 0 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula I,,, are disclosed. Table 112: A further preferred group of compounds of formula I corresponds to general R 0 formula Cl N (1112), wherein the meanings of the N CI

X

1 R 3 0 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1112 are disclosed. Table 113: A further preferred group of compounds of formula I corresponds to general R10 formula Br N (1113), wherein the meanings of the N Cl Xi R 3 0 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1113 are disclosed.

WO 99/52893 PCT/EP99/02313 - 88 Table 114: A further preferred group of compounds of formula I corresponds to general RO formula NC N (1114), wherein the meanings of the N.p Cl X R 3 0 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1114 are disclosed. Table 115: A further preferred group of compounds of formula I corresponds to general R0 formula NC N (1115), wherein the meanings of the corresponding N

X

1

R

3 0 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula I1,s are disclosed. Table 116: A further preferred group of compounds of formula I corresponds to general R o formula Br N (1116), wherein the meanings of the corresponding N F F

X

1

R

3 0 substituents RI, X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1116 are disclosed. Table 117: A further preferred group of compounds of formula I corresponds to general RO formula Cl N (1117), wherein the meanings of the corresponding N. ' F X, R 3 o substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1117 are disclosed.

WO 99/52893 PCT/EP99/02313 - 89 Table 118: A further preferred group of compounds of formula I corresponds to general RO formula CI N F (1118), wherein the meanings of the corresponding N F

X

1

R

3 0 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula hI8 are disclosed. Table 119: A further preferred group of compounds of formula I corresponds to general RO formula NC N F (1119), wherein the meanings of the N. ' F

X

1 R 3 0 corresponding substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1119 are disclosed. Table 120: A further preferred group of compounds of formula I corresponds to general R S formula NC N F (1120), wherein the meanings of the N F F Xi

R

3 0 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1120 are disclosed. Table 121: A further preferred group of compounds of formula I corresponds to general R S formula Cl N F (1121), wherein the meanings of the corresponding N. ' F X R 3 S substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1121 are disclosed.

WO 99/52893 PCT/EP99/02313 - 90 Table 122: A further preferred group of compounds of formula I corresponds to general

R

1 O / \ >No formula CI N (1122), wherein the meanings of the ON CH 3 1

R

3 0 corresponding substituents R 1 , X 1 and R 3 are indicated in Table A, so that 423 specific compounds of formula 1122 are disclosed. Table 123: A further preferred group of compounds of formula I corresponds to general R0 formula CI N (1123), wherein the meanings of the

X

1

R

3 0 O CH 3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1123 are disclosed. Table 124: A further preferred group of compounds of formula I corresponds to general R0 formula Br N (1124), wherein the meanings of the N. CH 3

X

1

R

3 0 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1124 are disclosed. Table 125: A further preferred group of compounds of formula I corresponds to general R0 formula Cl N (1125), wherein the meanings of the N Os

CH

3 1

R

3 0 O0 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 112s are disclosed.

WO 99/52893 PCT/EP99/02313 -91 Table 126: A further preferred group of compounds of formula I corresponds to general R O0 formula Br N F (1126), wherein the meanings of the N F

X

1

R

3 O FF corresponding substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1126 are disclosed. Table 127: A further preferred group of compounds of formula I corresponds to general R 0 -N 0 formula CI N (1127), wherein the meanings of the corresponding N,

X

1

R

3 0 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1127 are disclosed. Table 128: A further preferred group of compounds of formula I corresponds to general R0 formula CI N \\ SO (1128), wherein the meanings of the N OS N 0 CH

X

1 R 30 OH3 1 3 o corresponding substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1128 are disclosed. Table 129: A further preferred group of compounds of formula I corresponds to general R 0 formula Cl- N (1129), wherein the meanings of the corresponding N 1 3 O Xi R a 3O substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1129 are disclosed.

WO 99/52893 PCT/EP99/02313 - 92 Table 130: A further preferred group of compounds of formula I corresponds to general R 0 formula CI N 0 (1130), wherein the meanings of the 1 3 O corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1130 are disclosed. Table 131: A further preferred group of compounds of formula I corresponds to general R 0 -N F formula Cl- N F (1131), wherein the meanings of the corresponding N F

X

1

R

3 0 substituents R 1 , X 1 and R 3 are indicated in Table A, so that 423 specific compounds of formula 1131 are disclosed. Table 132: A further preferred group of compounds of formula I corresponds to general Ri 0 formula Cl -N F (1132), wherein the meanings of the IN

X

1

R

3 0 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1132 are disclosed. Table 133: A further preferred group of compounds of formula I corresponds to general R O formula NC N -F (1133), wherein the meanings of the N.,PD

X

1

R

3 0 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1133 are disclosed.

WO 99/52893 PCTIEP99/02313 - 93 Table 134: A further preferred group of compounds of formula I corresponds to general R formula CH 3 - F (1134), wherein the meanings of the N

X

1

R

3 0 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1134 are disclosed. Table 135: A further preferred group of compounds of formula I corresponds to general RO formula Cl- N (1135s), wherein the meanings of the corresponding N

X

1

R

3 0 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1135 are disclosed. Table 136: A further preferred group of compounds of formula I corresponds to general RO formula Cl N~ (1136), wherein the meanings of the corresponding N

X

1

R

3 0 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1136 are disclosed. Table 137: A further preferred group of compounds of formula I corresponds to general RO0 formula Cl N 0 (1137), wherein the meanings of the N

X

1

R

3 0 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1137 are disclosed.

WO 99/52893 PCT/EP99/02313 - 94 Table 138: A further preferred group of compounds of formula I corresponds to general R, O formula Cl- N Cl (1a3), wherein the meanings of the N

X

1

R

3 0 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula l1a are disclosed. Table 139: A further preferred group of compounds of formula I corresponds to general RO formula Cl N F (1139), wherein the meanings of the N

X

1 R 3 0 corresponding substituents RI, X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1139 are disclosed. Table 140: A further preferred group of compounds of formula I corresponds to general Ri S / -NH formula Cl N (1140), wherein the meanings of the corresponding N iC X1 R 3 S substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1140 are disclosed. Table 141: A further preferred group of compounds of formula I corresponds to general R0 formula Cl N N (1141), wherein the meanings of the N NCH

X

1

R

3 O corresponding substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 114, are disclosed.

WO 99/52893 PCT/EP99/02313 - 95 Table 142: A further preferred group of compounds of formula I corresponds to general

R

1 / N formula Cl N 1 (1142), wherein the meanings of the N > CH3 3 corresponding substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1142 are disclosed. Table 143: A further preferred group of compounds of formula I corresponds to general R1 0 / \ /N CH3 formula Cl N I (1143), wherein the meanings of the N NCH Xi R 3 O corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1143 are disclosed. Table 144: A further preferred group of compounds of formula I corresponds to general R 0 / N formula CH- N N (1144), wherein the meanings of the N 'NCH3

X

1

R

3 0 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1144 are disclosed. Table 145: A further preferred group of compounds of formula I corresponds to general

R

1 S / N formula Cl N 1 (1145), wherein the meanings of the N 'CH, Xi

R

3 s corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1145 are disclosed.

WO 99/52893 PCT/EP99/02313 - 96 Table 146: A further preferred group of compounds of formula I corresponds to general Ri formula Cl NO 1 (1146), wherein the meanings of the corresponding X R 3 O substituents R 1 , X 1 and R 3 are indicated in Table A, so that 423 specific compounds of formula 1146 are disclosed. Table 147: A further preferred group of compounds of formula I corresponds to general R O formula Cl N \ (1147), wherein the meanings of the corresponding xi R 3 0 substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1147 are disclosed. Table 148: A further preferred group of compounds of formula I corresponds to general R 0

CH

3 /N CH formula Cl N I (1148), wherein the meanings of the SN CH II 3

X

1

R

3 O corresponding substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1148 are disclosed. Table 149: A further preferred group of compounds of formula I corresponds to general R0 formula NC --- N 1 (1149), wherein the meanings of the corresponding NN

X

1

R

3 O substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1149 are disclosed.

WO 99/52893 PCT/EP99/02313 - 97 Table 150: A further preferred group of compounds of formula I corresponds to general R0 formula Cl N (115o), wherein the meanings of the corresponding X R 3 O0 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula s1150 are disclosed. Table 151: A further preferred group of compounds of formula I corresponds to general R formula CH, 3 N (11s51), wherein the meanings of the corresponding

X

1

R

3 0 substituents RI, X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 15, are disclosed. Table 152: A further preferred group of compounds of formula I corresponds to general

R

1 0 / N ,0 formula Cl N I S\ (1152), wherein the meanings of the N N

X

1

R

3 0 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1152 are disclosed. Table 153: A further preferred group of compounds of formula I corresponds to general RO R1 O formula CI IN I SN (11s), wherein the meanings of the corresponding N, o Xi R 3 0 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1153 are disclosed.

WO 99/52893 PCT/EP99/02313 - 98 Table 154: A further preferred group of compounds of formula I corresponds to general R 0 /N formula Cl N I O (115), wherein the meanings of the corresponding NN Xi R 3 0 substituents R 1 , X 1 and Ra are indicated in Table A, so that 423 specific compounds of formula 1,4 are disclosed. Table 155: A further preferred group of compounds of formula I corresponds to general R O /- N,CH3 formula Cl N 1 (115s), wherein the meanings of the corresponding N 'I CH

X

1

R

3 substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1155 are disclosed. Table 156: A further preferred group of compounds of formula I corresponds to general R10 / N ,CH3 formula NC --- N (1156), wherein the meanings of the corresponding N C X R 3 0 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1156 are disclosed. Table 157: A further preferred group of compounds of formula I corresponds to general R0

-

CH3 formula CH 3 / N I -C (1157), wherein the meanings of the corresponding N C X N 3 X Co substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1157 are disclosed.

WO 99/52893 PCTIEP99/02313 - 99 Table 158: A further preferred group of compounds of formula I corresponds to general R 0 fru , N CH3 formula Br N I (1sl), wherein the meanings of the corresponding N > CH3 Xl R o substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1158 are disclosed. Table 159: A further preferred group of compounds of formula I corresponds to general R0 /\ NH formula NC N (sq1159), wherein the meanings of the corresponding N NCH X R 3 0 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1159 are disclosed. Table 160: A further preferred group of compounds of formula I corresponds to general RO /_( N, CH(CH)3)2 formula Cl N I (1160), wherein the meanings of the N >N-CH(CH3)2 Xl R3 0 corresponding substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1160 are disclosed. Table 161: A further preferred group of compounds of formula I corresponds to general R 0 formula Cl N O (1161), wherein the meanings of the corresponding N N-,/

X

1

R

3 O substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1161 are disclosed.

WO 99/52893 PCT/EP99/02313 -100 Table 162: A further preferred group of compounds of formula I corresponds to general R S - NCH 3 formula CI / \ N 1 (1162), wherein the meanings of the corresponding N N CH Xl R 3 S substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1162 are disclosed. Table 163: A further preferred group of compounds of formula I corresponds to general R O formula Cl N IN CH 3 (1163), wherein the meanings of the N xi R 3 0 corresponding substituents R 1 , X, and Rs are indicated in Table A, so that 423 specific compounds of formula 1163 are disclosed. Table 164: A further preferred group of compounds of formula I corresponds to general RO 0 / N CH 3 formula OH 3 N I (1164), wherein the meanings of the corresponding N '-ICH3

X

1

R

3 O substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1164 are disclosed. Table 165: A further preferred group of compounds of formula I corresponds to general R 0 formula NC N I S (1165), wherein the meanings of the corresponding SN N Xi R 3 0 substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1165 are disclosed.

WO 99/52893 PCT/EP99/02313 - 101 Table 166: A further preferred group of compounds of formula I corresponds to general R S formula CI N I S (1166), wherein the meanings of the corresponding N Xi R 3 S substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1166 are disclosed. Table 167: A further preferred group of compounds of formula I corresponds to general R 0 formula OH 3 . N I S :O (1167), wherein the meanings of the N Xi R 3 0 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1167 are disclosed. Table 168: A further preferred group of compounds of formula I corresponds to general

R

1 0 formula Cl N N (1168), wherein the meanings of the corresponding

X

1

R

3 O substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1168 are disclosed. Table 169: A further preferred group of compounds of formula I corresponds to general RO formula CI N 1N S (1169), wherein the meanings of the corresponding NN

X

1

R

3 O substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1169 are disclosed.

WO 99/52893 PCT/EP99/02313 - 102 Table 170: A further preferred group of compounds of formula I corresponds to general

R

1 O formula Cl N : ON (1170), wherein the meanings of the N xi R 3 O corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1170 are disclosed. Table 171: A further preferred group of compounds of formula I corresponds to general

R

1 O / N /0 formula NC NN I /\ (1171), wherein the meanings of the NN Xi R 3 0 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1l17 are disclosed. Table 172: A further preferred group of compounds of formula I corresponds to general RO formula NC /N (1172), wherein the meanings of the corresponding N N O

X

1

R

3 O substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1172 are disclosed. Table 173: A further preferred group of compounds of formula I corresponds to general R CH 3 \ CH N

/

3 formula CH 3 N N< (1173), wherein the meanings of the N. X, R 3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1173 are disclosed.

WO 99/52893 PCT/EP99/02313 -103 Table 174: A further preferred group of compounds of formula I corresponds to general R CH3-\ /

NNCH

3 formula Cl N SS (1174), wherein the meanings of the X R corresponding substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1174 are disclosed. Table 175: A further preferred group of compounds of formula I corresponds to general R, formula / N N (1175), wherein the meanings of the corresponding Xl R substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1175 are disclosed. Table 176: A further preferred group of compounds of formula I corresponds to general

R

1 formula NC N S N (1176), wherein the meanings of the corresponding NC; N X, R 3 substituents RI, X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1176 are disclosed. Table 177: A further preferred group of compounds of formula I corresponds to general

R

1 formula Cl / N N (1im), wherein the meanings of the corresponding N/ N _, s-A" X 1/ 'R 3 substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 11n are disclosed.

WO 99/52893 PCT/EP99/02313 -104 Table 178: A further preferred group of compounds of formula I corresponds to general _0 R 1) formula Cl N N (1178), wherein the meanings of the corresponding X, R 3 N substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1178 are disclosed. Table 179: A further preferred group of compounds of formula I corresponds to general 0 R 1 formula N (1179), wherein the meanings of the corresponding C l N S O N X, R 3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1179 are disclosed. Table 180: A further preferred group of compounds of formula I corresponds to general R 0 formula C / N S (11,o), wherein the meanings of the corresponding N S

X

1

R

3 substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1180 are disclosed. Table 181: A further preferred group of compounds of formula I corresponds to general S R 8) formula / \ N (1181), wherein the meanings of the corresponding N S x 1

R

WO 99/52893 PCT/EP99/02313 -105 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1181 are disclosed. Table 182: A further preferred group of compounds of formula I corresponds to general 0 \\ ,O R formula N (1182), wherein the meanings of the corresponding CI N s o X, R3 substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1182 are disclosed. Table 183: A further preferred group of compounds of formula I corresponds to general R, formula Cl NN (1183), wherein the meanings of the corresponding N S X1 R3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1183 are disclosed. Table 184: A further preferred group of compounds of formula I corresponds to general R, N_ formula C /, N N (1184), wherein the meanings of the corresponding X R 3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1184 are disclosed.

WO 99/52893 PCT/EP99/02313 - 106 Table 185: A further preferred group of compounds of formula I corresponds to general R, formula NC /\ N ~N , (115), wherein the meanings of the corresponding N S S x R3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1185s are disclosed. Table 186: A further preferred group of compounds of formula I corresponds to general R1 CN formula CHz -NS g (11se), wherein the meanings of the X, R 3 corresponding substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1186 are disclosed. Table 187: A further preferred group of compounds of formula I corresponds to general R, formula CH( N N (1187), wherein the meanings of the /-N s'---o x / RN corresponding substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1187 are disclosed. Table 188: A further preferred group of compounds of formula I corresponds to general R, formula Cl / -N N S N (1s), wherein the meanings of the corresponding N R x1 R 3 WO 99/52893 PCT/EP99/02313 - 107 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1188 are disclosed. Table 189: A further preferred group of compounds of formula I corresponds to general RO0 /N ' ,CH3 formula Cl N/ CH 3 (l89), wherein the meanings of the corresponding N N C H 3

X

1

R

3 substituents RI, X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1189 are disclosed. Table 190: A further preferred group of compounds of formula I corresponds to general

R

1 / N,CH3 formula NC N \ (1190), wherein the meanings of the corresponding N N CH 3 Xi

R

3 substituents R 1 , X 1 and R 3 are indicated in Table A, so that 423 specific compounds of formula 1190 are disclosed. Table 191: A further preferred group of compounds of formula I corresponds to general RiO0 N CH3 formula CH 3 N\ (1191), wherein the meanings of the corresponding N N: CH3 N Xi

R

3 substituents RI, X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 119, are disclosed. Table 192: A further preferred group of compounds of formula I corresponds to general

R

1 0 //N ,CHF2 formula C I/ N\ l (1192), wherein the meanings of the corresponding N N C 2

H

s Xi

R

3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1192 are disclosed.

WO 99/52893 PCTIEP99/02313 - 108 Table 193: A further preferred group of compounds of formula I corresponds to general

R

1 / N,CHF2 formula NC N \ (1193), wherein the meanings of the corresponding N N 'CH 3

X

1 R 3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1193 are disclosed. Table 194: A further preferred group of compounds of formula I corresponds to general

R

1 S / \NCHF 2 formula CI N -N CH (114), wherein the meanings of the corresponding N N CH 3 Xi

R

3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 194 are disclosed. Table 195: A further preferred group of compounds of formula I corresponds to general

R

1 /\CHF formula CI N\ (1195), wherein the meanings of the corresponding N N OH 3 XK R3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1195 are disclosed. Table 196: A further preferred group of compounds of formula I corresponds to general R O / 1 ,CH3 formula Cl N\ (1196), wherein the meanings of the corresponding N N CF 3 Xl R substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1196 are disclosed.

WO 99/52893 PCT/EP99/02313 -109 Table 197: A further preferred group of compounds of formula I corresponds to general

R

1 O /N, , CH(CH3)2 formula Cl N\ CHF 2 (1197), wherein the meanings of the N N CHF 2 Xi

R

3 corresponding substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1197 are disclosed. Table 198: A further preferred group of compounds of formula I corresponds to general R0 / 'WNCHF 2 formula CF 3- N-N CH (1198), wherein the meanings of the N N CH

X

1 R 3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1198 are disclosed. Table 199: A further preferred group of compounds of formula I corresponds to general

R

1 0o formula Cl N (1199), wherein the meanings of the N N OH 3

X

1 R3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1199 are disclosed. Table 200: A further preferred group of compounds of formula I corresponds to general

R

1 0 formula Cl N \ (1200), wherein the meanings of the N N COH 3 Xi R 3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1200 are disclosed.

WO 99/52893 PCT/EP99/02313 -110 Table 201: A further preferred group of compounds of formula I corresponds to general Ro 0 / N formula Cl N1 C (1201), wherein the meanings of the N N CH 3 Xi R3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1201 are disclosed. Table 202: A further preferred group of compounds of formula I corresponds to general R0 formula CH 3 N (1202), wherein the meanings of the N N CH 3 corresponding substituents RI, X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1202 are disclosed. Table 203: A further preferred group of compounds of formula I corresponds to general R0 \R / NCHF 2 formula CF 30 N (1203), wherein the meanings of the N N CH 3 Xi

R

3 corresponding substituents RI, X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1203 are disclosed. Table 204: A further preferred group of compounds of formula I corresponds to general

R

1 O formula Cl N \. (1204), wherein the meanings of the corresponding N N Xi

R

3 substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1204 are disclosed.

WO 99/52893 PCT/EP99/02313 -111 Table 205: A further preferred group of compounds of formula I corresponds to general

R

0 formula Cl N (1205), wherein the meanings of the corresponding //,, - - N N Xl

R

3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1205 are disclosed. Table 206: A further preferred group of compounds of formula I corresponds to general R 10 CH3

R

1 O s formula Br N\ N , CHF 2 (1206), wherein the meanings of the corresponding N N CHF 2 Xi

R

3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 120o are disclosed. Table 207: A further preferred group of compounds of formula I corresponds to general RO formula NC N j (1207), wherein the meanings of the corresponding N N Xi

R

3 substituents RI, X 1 and R 3 are indicated in Table A, so that 423 specific compounds of formula 1207 are disclosed. Table 208: A further preferred group of compounds of formula I corresponds to general R0 formula Cl N (1208), wherein the meanings of the corresponding N N xl

R

3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1208 are disclosed.

WO 99/52893 PCT/EP99/02313 -112 Table 209: A further preferred group of compounds of formula I corresponds to general R 1 0 C H 3 F formula ,o / \ N F (1209), wherein the meanings of the corresponding

CH

3 N N F X, R 3 substituents R 1 , X 1 and R 3 are indicated in Table A, so that 423 specific compounds of formula 1209 are disclosed. Table 210: A further preferred group of compounds of formula I corresponds to general

R

1 0 CH 3 F formula 0 N , NF (1210), wherein the meanings of the N N F X1

R

3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1210 are disclosed. Table 211: A further preferred group of compounds of formula I corresponds to general

R

1 0 F formula (CH 3) 2 CHO N F (1211), wherein the meanings of the N" ,>- N\ F X I R zo corresponding substituents Ri, X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1211 are disclosed. Table 212: A further preferred group of compounds of formula I corresponds to general

R

1 0 CH 3 F / F formula F N F (1212), wherein the meanings of the F N N F X/ 1 'R 3 corresponding substituents R 1 , X, and Ra are indicated in Table A, so that 423 specific compounds of formula 1212 are disclosed.

WO 99/52893 PCT/EP99/02313 -113 Table 213: A further preferred group of compounds of formula I corresponds to general RO formula (CH 3 /N (1213), wherein the meanings of the x R3 0 X1 N3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1213are disclosed. Table 214: A further preferred group of compounds of formula I corresponds to general

R

1 O

OH

3 F formula (CH 3) 3 C \ F (1214), wherein the meanings of the NN F

X

1 R 3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1214 are disclosed. Table 215: A further preferred group of compounds of formula I corresponds to general Rio F formula CI R N F (1215), wherein the meanings of the N N F X

R

3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 121s are disclosed. Table 216: A further preferred group of compounds of formula I corresponds to general R0 F formula F F N (1216), wherein the meanings of the corresponding F N

X

1 R 0 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1216 are disclosed.

WO 99/52893 PCT/EP99/02313 -114 Table 217: A further preferred group of compounds of formula I corresponds to general RO0 N

,

C HF , NN 2 formula O N\. (1217), wherein the meanings of the N N CH3 Xi R3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1217 are disclosed. Table 218: A further preferred group of compounds of formula I corresponds to general

R

1 0 CH 3 formula 0/ N F (1218) wherein the meanings of the F N N F FX R 1 3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1218 are disclosed. Table 219: A preferred group of compounds of formula I corresponds to general formula

R

1 0 F F F N H (1219), wherein the meanings of the corresponding F N -N F X , R 3 O CH 3 substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1219 are disclosed. Table 220: A preferred group of compounds of formula I corresponds to general formula

R

1 0 F 0/ N F (1220), wherein the meanings of the N/ N )-N\ F N X 1 R 3 0 CH 3 corresponding substituents R 1 , X, and R 3 are indicated in Table A, so that 423 specific compounds of formula 1220 are disclosed.

WO 99/52893 PCT/EP99/02313 -115 Table A Comp. No. R 1 X, Ra .001 H O CH 3 .002 F O CH 3 .003 CI O CH 3 .004 F O CH 2

CH

3 .005 Cl O CH 2

CH

3 .006 H O CH 2

CH

3 .007 F O CH 2

CH

2

CH

3 .008 CI O CH 2

CH

2

CH

3 .009 H O CH 2

CH

2

CH

3 .010 F O CH 2

CH

2

CH

2

CH

3 .011 CI O CH 2

CH

2

CH

2

CH

3 .012 F O CH 2

CH

2

CH

2

CH

2

CH

3 .013 CI O CH 2

CH

2

CH

2

CH

2

CH

3 .014 F O CH 2

CH

2

CH

2

CH

2

CH

2

CH

3 .015 F O CH 2

CH

2

CH(CH

3

)

2 .016 Cl O CH 2

CH

2

CH(CH

3

)

2 .017 H O CH 2

CH

2

CH(CH

3

)

2 .018 F O CH 2

CH(CH

3

)CH

2

CH

3 .019 CI O CH 2

CH(CH

3

)CH

2

CH

3 .020 H O CH 2 CH(CHa)CH 2

CH

3 .021 F O CH 2

CH(CH

3

)CH

2

CH

2

CH

3 .022 F O CH 2

CH

2

CH(CH

3

)CH

2

CH

3 .023 F O CH 2

CH

2

CH

2

CH(CH

3

)

2 .024 F O CH(CHa)CH 2

CH

2

CH

2

CH

3 .025 CI O CH(CHa)CH 2

CH

2

CH

2

CH

3 .026 H O CH(CH 3

)CH

2

CH

2

CH

2

CH

3 .027 F O CH 2 C(CHa) 3 .028 Cl O CH 2 C(CHa) 3 .029 H O CH 2

CH(CH

3

)

2 .030 Cl O CH 2 CH(CHa) 2 .031 F O CH 2

CH(CH

3

)

2 .032 F O CH 2 C(CHa) 2

CH

2

CH

3 .033 CI O CH 2 C(CHa) 2

CH

2

CH

3 .034 H O CH 2 C(CHa) 2

CH

2

CH

3 WO 99/52893 PCT/EP99/02313 -116 Comp. No. R 1 X, R 3 .035 F O CH 2

CH

2 C(CHa) 3 .036 CI O CH 2

CH

2

C(CH

3

)

3 .037 F O CH 2

CH

2

CHCH

2 .038 F O CH 2

CH

2

CH

2

CH

3 .039 F O CH(CHa) 2 .040 CI O CH(CHa) 2 .041 H O CH(CH 3

)

2 .042 F O CH 2

CF

3 .043 CI O CH 2

CF

3 .044 H O CH 2 CF3 .045 F O CH 2 CCl 3 .046 F O CH 2

CH

2

CF

3 .047 F O CH 2

CH

2

CH(OH)CH

3 .048 F O CH 2

CH(OH)CH

2

CH

3 .049 CI O CH 2

CH(OH)CH

2

CH

3 .050 F O CH 2

CH(OH)CH

3 .051 H O CH 2

CH

2

CHCICH

3 .052 CI O CH 2

CH

2

CHCICH

3 .053 F O CH 2

CH

2

CHCICH

3 .054 F O CH 2

CH

2

CHFCH

3 .055 F O CH 2

CHFCH

2

CH

3 .056 CI O CH 2

CHFCH

2

CH

3 .057 H O CH 2

CHFCH

2

CH

3 .058 F O CH 2

CHCICH

2

CH

3 .059 F O CH 2

CH

2 F .060 Cl O CH 2

CH

2 F .061 F O CH 2

CHF

2 .062 H O CH 2

CHCH

2 .063 Cl O CH 2

CHCH

2 .064 F O CH 2

CHCH

2 .065 F O CH 2 CH(CHa)CH 2 .066 F O CH 2

CHCH(CH

3 ) .067 Cl O CH 2

CH

2 0H .068 F O CH 2

CH

2 OH .069 F O CH 2

CHCHCI

WO 99/52893 PCT/EP99/02313 -117 Comp. No. R 1 X, R3 .070 CI O CH 2 CHCHCI .071 F O CH 2 0CH 2

C

6

H

5 .072 H O CH 2 CCH .073 CI O CH 2 CCH .074 F O CH 2 CCH .075 F O CH 2

CH

2 CCH .076 CI O CH 2

CH

2

C

6

H

5 .077 F O CH 2

CH

2

C

6

H

5 .078 F O CH 2

CH

2

CH

2

C

6 Hs .079 F O CH 2

CH

2

CH(CH

3

)C

6 Hs .080 F O CH 2

CH

2

CH

2

CH

2 (p-F-C 6

H

4 ) .081 H O CH 2

C

6 Hs .082 CI O CH 2

C

6

H

5 .083 F O CH 2

C

6

H

5 .084 F O CH 2 (o-F-C 6

H

4 ) .085 H O CH 2 (p-CI-C 6

H

4 ) .086 F O CH 2 (m-CF 3

-C

6 Hs) .087 H O CH 2 CN .088 CI O CH 2 CN .089 F O CH 2 CN .090 F O CH 2

CH

2 CN .091 F O cyclopropyl .092 F O cyclopentyl .093 F O CH 2 -cyclopentyl .094 F O CH 2 -cyclopropyl .095 F O CH 2

CH

2 Cl .096 F O CH 2 CHCl 2 .097 H O CH 2

OCH

3 .098 Cl O CH 2

OCH

3 .099 F O CH 2 0CH 3 .100 F O CH 2

CH

2 0CH 3 .101 F O CH 2

CH

2

OCH

2

CH

3 .102 F O CH 2

CH(CH

3

)OCH

3 .103 H O CH 2

CH

2

OCH

2

CH

2 0CH 3 .104 CI O CH 2

CH

2 0CH 2

CH

2

OCH

3 WO 99/52893 PCT/EP99/02313 -118 Comp. No. R 1 X, R 3 .105 F O CH 2

CH

2

OCH

2

CH

2

OCH

3 .106 H O CH 2

SCH

3 .107 CI O CH 2

SCH

3 .108 F O CH 2

SCH

3 .109 H O CH 2 S(0)CH 3 .110 Cl O CH 2 S(0)CH 3 .111 F O CH 2 S(0)CH 3 .112 H O CH 2 S(0) 2

CH

3 .113 CI O CH 2 S(0) 2

CH

3 .114 F O CH 2 S(0) 2

CH

3 .115 F O CH 2

SCH

2

CH

3 .116 F O CH 2

CH

2

SCH

3 .117 F O CH 2

CH

2

SCH

2

CH

3 .118 CI O CH 2

CH

2

SCH

2

CH

3 .119 H O CH 2

CH

2

SCH

2

CH

3 .120 Cl O CH 2

CH

2

SCH

3 .121 H O CH 2

CH

2

SCH

3 .122 F O CH 2

CH

2 S(0)CH 3 .123 F O CH 2

CH

2 S(0) 2

CH

3 .124 CI O CH 2

CH

2 S(0)CH 3 .125 CI O CH 2

CH

2 S(0) 2

CH

3 .126 F O CH 2

CH

2 S(0)CH 2

CH

3 .127 Cl O CH 2

CH

2 S(0)CH 2

CH

3 .128 H O CH 2

CH

2 S(0)CH 2

CH

3 .129 F O CH 2

CH

2 S(0) 2

CH

2

CH

3 .130 Cl O CH 2

CH

2 S(0) 2

CH

2

CH

3 .131 H O CH 2

CH

2 S(0) 2

CH

2

CH

3 .132 F O CH 2

CH(CH

3

)SCH

3 .133 H O CH 2 COOH .134 CI O CH 2 COOH .135 F O CH 2 COOH .136 F O CH 2

COOCH

3 .137 H O CH 2

COOCH

2

CH

3 .138 CI O CH 2

COOCH

2 CHa .139 F O CH 2

COOCH

2

CH

3 WO 99/52893 PCT/EP99/02313 -119 Comp. No. R 1 X, R3 .140 F O CH 2

COOC(CH

3

)

3 .141 F O CH 2

COOCH

2

CHCH

2 .142 F O CH 2

COOCH

2 CCH .143 F O CH 2

COOCH

2

C

6

H

5 .144 H O CH 2 CHO .145 CI O CH 2 CHO .146 F O CH 2 CHO .147 H O CH 2 C(0)CH 3 .148 CI O CH 2 C(0)CH 3 .149 F O CH 2 C(0)CH 3 .150 F O CH 2

COSCH

2

CH

3 .151 H O CH 2

COSCH(CH

3

)

2 .152 CI O CH 2

COSCH(CH

3

)

2 .153 F O CH 2

COSCH(CH

3

)

2 .154 F O CH 2

COSCH

2

C

6

H

5 .155 F O CH 2

CONH

2 .156 F O CH 2 CON(CHa) 2 .157 Cl O CH 2

CON(CH

3

)

2 .158 F O CH 2

CON(CH

2

CH

3

)

2 .159 CI O CH 2

CON(CH

2

CH

3

)

2 .160 H O CH 2

CON(CH

2

CH

3

)

2 .161 F O CH 2 0CH 2

C

6 Hs .162 CI O CH 2

CONHCH

2 CCH .163 F O CH 2

CONHCH

2 CCH .164 CI O CH 2

CH

2 COOH .165 F O CH 2

CH

2 COOH .166 F O CH 2

CH

2

COOCH

2

CH

3 .167 H O CH 2

CH

2 CN .168 CI O CH 2

CH

2 CN .169 F O CH 2

CH

2 CN .170 F O CH 2

CH(CH

3 )CN .171 Cl O CH(CH 3

)CH

2 CN .172 CI O CH 2

CH

2 CHO .173 F O CH 2

CH

2 CHO .174 F O CH 2

CH

2 C(0)CH 3 WO 99/52893 PCT/EP99/02313 - 120 Comp. No. R 1 X, Ra .175 Cl O CH 2

CH

2

C(O)CH

3 .176 F O CH 2

COCH

2

CH

3 .177 CI O CH 2

COCH

2

CH

3 .178 H O CH 2

COCH

2

CH

3 .179 F O CH 2

COCH

2

CH

2

CH

3 .180 F O CH 2

CH

2

COCH

2

CH

3 .181 F O CH 2

CH

2

COCH

2

CF

3 .182 F O CH 2

CHCICOCH

2

CH

3 .183 F O CH 2

CH

2

COCHCICH

3 .184 F O CH 2 CH(CHa)COOCH 3 .185 F O CH 2

CH

2

CH

2

COOCH

3 .186 F O CH 2

CH

2

CH

2

COSCH

2

CH

3 .187 F O CH 2

CH

2

CH

2 CON(CHa) 2 .188 F O CH 2

CH

2

CH(CH

3

)COOCH

2

CH

3 .189 H O CH 2 CH(OH)COOH .190 Cl O CH 2 CH(OH)COOH .191 F O CH 2 CH(OH)COOH .192 CI O CH 2 CH(CI)COOH .193 F O CH 2 CH(CI)COOH .194 CI O CH 2

CH(CI)COOCH

2

CH

3 .195 F O CH 2

CH(CI)COOCH

2 CHs .196 F O CH 2 CH(CI)COOH .197 F O CH 2 C(CHa)(CI)COOH .198 F O CH 2

CH(CI)COOCH

2

CHCH

2 .199 F O CH 2 CH(Cl)COOCH 2 CCH .200 F O CH 2

CH(CI)COOCH

2

C

6

H

5 .201 F O CH 2 CH(CI)C(0)SCH(CHa) 2 .202 F O CH 2 CH(CI)C(0)NH(CH 2 CCH) .203 F O CH 2 CH(CHa)C(0)N(CH 3

)(CH

2

CHCH

2 ) .204 F O CH 2 CH(Br)COOC(CHa) 3 .205 F O CH 2 CH(Br)COOCH 2

CHCH

2 .206 F O CH 2

COOCH

2

CH

2 CI .207 F O CH 2

COOCH

2

CF

3 .208 H O

CH-<'CO

WO 99/52893 PCT/EP99/02313 -121 Comp. No. R 1 X, R 3 .209 H O \ CH .210 CI O CH2KO 20 .211 F O CH2-<l 20 .212 F O CH .213 F O S(O) 2

CH

3 .214 F O S(O) 2

CH

2

CH

3 .215 CI O S(0) 2

CF

3 .216 CI O S(0) 2

CH

2

CH

3 .217 F O S(0) 2 CH(CHa) 2 .218 H O C(0)CH 3 .219 CI O C(0)CH 3 .220 F O C(0)CH 3 .221 F O C(0)CF 3 .222 F O C(0)CH 2

CH

3 .223 CI O OH .224 F O OH .225 H O OCH 3 .226 CI O OCH 3 .227 F O OCH 3 .228 H O OCH 2

CH

3 .229 CI O OCH 2

CH

3 .230 F O OCH 2

CH

3 .231 F O OCH 2 CH(CHa) 2 .232 F O OCF 3 .233 F O OCHF 2 .234 F O OCH 2

CHCH

2 .235 F O OCH 2 C(CHa)CH 2 .236 F O OCH 2 CHCHCI .237 Cl O OCH 2

OCH

3 .238 F O OCH 2

OCH

3 .239 F O OCH 2

SCH

3 WO 99/52893 PCT/EP99/02313 - 122 Comp. No. R 1 X, R3 .240 F 0 OCH 2 CCH .241 F 0 OCH 2 COOH .242 F 0 OCH 2

COOCH

3 .243 F O OCH 2

COOCH

2

CH

3 .244 F O OCH 2 COOCH(CHa) 2 .245 CI O OCH(CHa)COOH .246 F O OCH(CHa)COOH .247 F O OCH(CH 3

)COOCH

2

CH

3 .248 F O OCH(CHa)COOCH 2 CCH .249 F O OCH(CH 3

)COOCH

2

CHCH

2 .250 F O OCH 2

COSCH

2

CH

3 .251 F O OCH 2 COSCH(CHa) 2 .252 F O OCH 2

COSCH

2

C

6

H

5 .253 F O OCH 2

CONH

2 .254 F O OCH 2 CON(CHa) 2 .255 CI O OCH 2

CONHCH

2 CCH .256 F O OCH 2

CONHCH

2 CCH .257 F O OCH 2

C

6 Hs .258 F O OCH 2 (p-CH 3 0-C 6

H

4 ) .259 F O OCH 2 (o-F-C 6

H

4 ) .260 Cl O OCH 2 (m-CF 3

-C

6

H

4 ) .261 F O OCH 2

CH

2

C

6 Hs .262 H O OCH 2 CN .263 F O OCH 2 CN .264 F O OCH 2

CH

2 CI .265 Cl O OCH 2

CH

2 OH .266 F O OCH 2

CH

2 0H .267 H O OCH 2

CH

2 CN .268 Cl 0 OCH 2

CH

2 CN .269 F 0 OCH 2

CH

2 CN .270 Cl 0 OCH 2

CH(OCH

3

)(CH

3 ) .271 F 0 OCH 2 CH(OCHa)(CHa) .272 H 0 OC(0)CH 3 .273 Cl 0 OC(0)CH 3 .274 F 0 OC(0)CH 3 WO 99/52893 PCT/EP99/02313 - 123 Comp. No. R, X, R 3 .275 H S CH 3 .276 Cl S CH 3 .277 F S CH 3 .278 H S CH 2

CH

3 .279 Cl S CH 2

CH

3 .280 F S CH 2

CH

3 .281 F S CH 2

CH

2

CH

3 .282 F S CH 2

CH(CH

3

)

2 .283 F S CH 2

CH

2

CF

3 .284 F S CH(CH 3

)

2 .285 F S CH 2

CH(CH

3

)

2 .286 F S CH 2

CH(CI)CH

3 .287 Cl S CH 2

CHCH

2 .288 F S CH 2

CHCH

2 .289 F S CH 2

C(CH

3

)CH

2 .290 H S CH 2 CCH .291 Cl S CH 2 CCH .292 F S CH 2 CCH .293 F S CH 2

CH

2 CCH .294 F S CH(CH 3 )CCH .295 H S CH 2

CH

2 OH .296 Cl S CH 2

CH

2 OH .297 F S CH 2

CH

2 OH .298 F S CH 2

CH(OH)CH

3 .299 H S CH 2

C

6 Hs .300 CI S CH 2

C

6 H5 .301 F S CH 2

C

6 Hs .302 Cl S CH 2 (o-F-C 6

H

4 ) .303 F S CH 2 (o-F-C 6

H

4 ) .304 F S CH 2 (m-CF 3

-C

6

H

4 ) .305 F S CH 2 (p-CH3-C 6

H

4 ) .306 F S CH 2 (2,4-di-F-C 6

H

3 ) .307 F S CH 2

CH

2

CH(CH

3

)C

6

H

5 .308 F S CH 2

CH

2

CH

2

CH

2 (p-F-C 6

H

4 ) .309 Cl S CH 2

CN

WO 99/52893 PCT/EP99/02313 - 124 Comp. No. R 1 X, R3 .310 F S CH 2 CN .311 F S cyclopropyl .312 CI S CH 2 -cyclopropyl .313 F S CH 2 -cyclopropyl .314 F S CH 2 CI .315 H S CH 2 0CH 3 .316 CI S CH 2 0CH 3 .317 F S CH 2

OCH

3 .318 F S CH 2 0CH 2

CHCH

2 .319 F S CH 2

CH

2

OCH

3 .320 F S CH 2 CH(OCHa)CH 3 .321 F S CH 2

CH(OCH

2

CCH)CH

3 .322 H S CH 2

CH

2

OCH

2

CH

2

OCH

3 .323 CI S CH 2

CH

2

OCH

2

CH

2

OCH

3 .324 F S CH 2

CH

2 0CH 2

CH

2

OCH

3 .325 H S CH 2

SCH

3 .326 CI S CH 2

SCH

3 .327 F S CH 2 SCHa .328 F S CH 2

SCH

2

CHCH

2 .329 F S CH 2

SCH

2 CCH .330 F S CH 2

CH

2

SCH

3 .331 F S CH 2

CH

2

S(O)CH

3 .332 F S CH 2

CH

2

S(O)

2

CH

3 .333 F S CH 2 COOH .334 F S CH 2

COOCH

3 .335 F S CH 2

COOCH

2 CHa .336 F S CH 2 COOC(CHa)a .337 F S CH 2

COOCH

2

C

6 Hs .338 F S CH 2

COOCH

2 (p-Cl-C 6

H

4 ) .339 F S CH 2 C(O)SCHa .340 F S CH 2 C(O)SCH(CHa) 2 .341 F S CH 2

C(O)SCH

2

C

6

H

5 .342 F S CH 2

C(O)NH

2 .343 F S CH 2 C(O)NH(CHa) .344 CI S CH 2

C(O)NH(CH

2

CCH)

WO 99/52893 PCT/EP99/02313 - 125 Comp. No. R 1 X, R 3 .345 F S CH 2

C(O)NH(CH

2 CCH) .346 F S CH 2

C(O)N(CH

2

CH

3

)

2 .347 F S CH 2 CHO .348 F S CH 2

C(O)CH

3 .349 H S CH 2

CH

2 COOH .350 CI S CH 2

CH

2 COOH .351 F S CH 2

CH

2 COOH .352 F S CH 2

CH

2

COOCH

3 .353 F S CH 2

CH

2

COOCH

2

C

6 Hs .354 Cl S CH 2

CH

2

C(O)SCH

2

CH

3 .355 F S CH 2

CH

2

C(O)SCH

2

CH

3 .356 F S CH 2 CH(OH)COOH .357 F S CH 2 CH(CI)COOH .358 Cl S CH 2

CH(CI)COOCH

2

CH

3 .359 F S CH 2

CH(CI)COOCH

2

CH

3 .360 F S CH 2 CH(CI)COOH .361 F S CH 2 C(CHa)(CI)COOH .362 F S CH 2

CH(CI)COOCH

2

CHCH

2 .363 CI S CH 2 CH(Cl)COOCH 2 CCH .364 F S CH 2

CH(CI)COOCH

2 CCH .365 F S CH 2

CH(CI)COOCH

2

C

6

H

5 .366 F S CH 2 CH(Br)COOH .367 F S CH 2 CH(CI)C(O)SCH(CHa) 2 .368 F S CH 2

CH(CI)C(O)NH(CH

2 CCH) .369 F S CH 2 CH(CHa)C(O)N(CH 3

)(CH

2

CHCH

2 ) .370 F S CH 2

CH

2

C(O)NH(CH

2 CCH) .371 H S CH2-< .372 Cl SH CH' .373 F S CH2-< .374 CI S CH2 O 0 .375 F S CH' 1 2 <CH WO 99/52893 PCT/EP99/02313 - 126 Comp. No. R 1 X, R 3 .376 F S OH .377 H S OCH 3 .378 CI S OCH 3 .379 F S OCH 3 .380 F S OCH 2

CH

3 .381 CI S OCH 2

CH(CH

3

)

2 .382 F S OCH 2

CH(CH

3

)

2 .383 F S OCH(CH 3

)

2 .384 F S OCF 3 .385 H S OCH 2

OCH

3 .386 CI S OCH 2 0CH 3 .387 F S OCH 2

OCH

3 .388 F S OCH 2

SCH

3 .389 Cl S OCH 2

CHCH

2 .390 F S OCH 2

CHCH

2 .391 CI S OCH 2 CCH .392 F S OCH 2 CCH .393 F S OCH(CH 3

)CHCH

2 .394 F S OCH(CH 3 )CCH .395 F S OCH 2 CHCH(CI) .396 F S OCH 2 COOH .397 F S OCH 2

COOCH

2

CH

3 .398 F S OCH(CH 3 )COOH .399 F S OCH(CH 3

)COOCH

2 CCH .400 F S OCH 2

C(O)NH

2 .401 F S OCH 2

C(O)NH(CH

3 ) .402 F S OCH 2

C(O)NH(CH

2 CCH) .403 F S OCH 2

C(O)SCH

3 .404 F S OCH 2

C(O)SCH

2

CH

3 .405 F S OCH 2

C(O)SCH(CH

3

)

2 .406 CI S OCH 2

C(O)SCH

2

C

6 Hs .407 F S OCH(CH 3

)C(O)SCH

2

C

6 Hs .408 F S OCH 2

CH

2 OH .409 F S OCH 2

CH(CH

3 )OH .410 F S OCH 2

CH

2

CI

WO 99/52893 PCT/EP99/02313 - 127 Comp. No. R 1 X, R3 .411 Cl S OCH 2

CH

2 CN .412 F S OCH 2

CH

2 CN .413 CI S OCH 2

CH

2

CF

3 .414 F S OCH 2

CH

2

CF

3 .415 F S OCH 2

CH(OH)(C

6 Hs) .416 F O CH 2

COCH

3 .417 F O CH 2

CONHCH

2

CH=CH

2 .418 CI O CH 2

CONHCH

2

CH=CH

2 .419 Cl S CH 2

CONHCH

2

CH

3 .420 Cl O CH 2

CONHCH

2

CH

3 .421 F O CH 2

CONHCH

2

CH

3 .422 F O CH 2

CONHCH

3 .423 Cl O CH 2

CONHCH

3 Table B: Prepared compounds from the preceding Tables with physico-chemical data. The figure before the point indicates the number of the Table, e.g. 1.002 indicates in Table 1 compound No. 002 of Table A. Comp. No. physical data 1.002 m.p. 159-160 0 C 1.007 m.p. 123-125 0 C 1.064 m.p. 115-1160C 1.071 nD(30 0 C) 1.5431 1.074 m.p. 218-220 0 C 1.139 nD(30 0 C) 1.5131 34.074 'H-NMR (CDCI 3 ): 8,14 ppm (s, 1H); 7,72 ppm (d, 1H); 7,36 ppm (s, 1H); 4,90 ppm (s, 2H); 2,21 ppm (s, 1H) Examples of specific formulations for compounds of formula I, such as emulsifiable concen trates, solutions, wettable powders, coated granules, extruder granules, dusts and suspen sion concentrates, are described on pages 9 to 13 of WO 97/34485. Biological Examples Example B1: Herbicidal action prior to emergence of the plants (pre-emergence action) WO 99/52893 PCT/EP99/02313 - 128 Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastics pots. Immediately after sowing, the test compounds, in the form of an aqueous suspension (prepared from a 25 % wettable powder (Example F3, b), as described, for example, in WO 97/34485), or in the form of an emulsion (prepared from a 25 % emulsifiable concentrate (Example Fl, c), as described, for example, in WO 97/34485), are applied by spraying in a concentration corresponding to 2000 g of active ingredient/ha (500 litres water/ha). The test plants are then grown in a greenhouse under optimum conditions. After a test duration of 3 weeks, the test is evaluated in accordance with a scale of nine ratings (1 = total damage, 9 = no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action. In this test the compounds of formula I exhibit strong herbicidal action. Test plants: Lolium, Setaria, Sinapis, Solanum, Ipomoea Examples of the good herbicidal activity of the compounds of formula I are given in Table B1. Table BI: Pre-emergence action: Test plant: Lolium Setaria Sinapis Solanum Ipomoea conc. [g a.i./ha] Comp. No. 1.002 1 1 1 1 2 2000 1.007 3 1 1 1 1 2000 1.064 3 1 1 1 1 2000 1.071 6 1 1 1 3 2000 1.074 1 1 1 1 1 2000 1.139 1 1 1 1 1 2000 The same results are obtained when compounds of formula I are formulated in accordance with Examples F2 and F4 to F8 according to WO 97/34485. Example B2: Post-emergence herbicidal action In a greenhouse, monocotyledonous and dicotyledonous test plants are grown in standard soil in plastics pots and at the 4- to 6-leaf stage are sprayed with an aqueous suspension of the test compounds of formula I, prepared from a 25 % wettable powder (Example F3, b) according to WO 97/34485), or with an emulsion of the test compounds of formula I, prepared from a 25 % emulsifiable concentrate (Example Fl, c) according to WO 99/52893 PCT/EP99/02313 - 129 WO 97/34485), in a concentration corresponding to 2000 g of active ingredient/ha (500 litres water/ha). The test plants are then grown on in a greenhouse under optimum conditions. After a test duration of about 18 days, the test is evaluated in accordance with a scale of nine ratings (1 = total damage, 9 = no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action. Test plants: Lolium, Setaria, Sinapis, Solanum, Ipomoea In this test too, the compounds of formula I according to the invention exhibit strong herbicidal action. Examples of the good herbicidal activity of the compounds of formula I are given in Table B2. Table B2: Post-emergence action: Test plant: Lolium Setaria Sinapis Solanum lpomoea conc. [g a.i./ha] Comp. No. 1.002 1 1 1 1 1 2000 1.007 2 2 1 1 1 2000 1.064 4 4 3 1 1 2000 1.071 2 2 1 1 3 2000 1.074 1 1 1 1 1 2000 1.139 1 1 1 1 1 2000 The same results are obtained when compounds of formula I are formulated in accordance with Examples F2 and F4 to F8 according to WO 97/34485. The compounds of formula I according to the invention can also be used for weed control in admixture with known herbicides as co-herbicides, for example in the form of ready prepared formulations or in the form of a 'tank-mix'. Suitable mixing partners for the compounds of formula I include, for example, the following co-herbicides: compound of formula I + acetochlor, compound of formula I + acifluorfen, compound of formula I + aclonifen, compound of formula I + alachlor, compound of formula I + ametryn, compound of formula I + aminotriazole, compound of formula I + amidosulfuron, compound of formula I + asulam, compound of formula I + atrazine, compound of formula I + BAY FOE 5043, compound of formula I + benazolin, compound of formula I + bensulfuron, compound of WO 99/52893 PCTIEP99/02313 -130 formula I + bentazone, compound of formula I + bifenox, compound of formula I + bispyribac-sodium, compound of formula I + bialaphos, compound of formula I + bromacil, compound of formula I + bromoxynil, compound of formula I + bromophenoxim, compound of formula I + butachlor, compound of formula I + butylate, compound of formula I + cafenstrole, compound of formula I + carbetamide, compound of formula I + chloridazone, compound of formula I + chlorimuron-ethyl, compound of formula I + chlorbromuron, compound of formula I + chlorsulfuron, compound of formula I + chlortoluron, compound of formula I + cinosulfuron, compound of formula I + clethodim, compound of formula I + clodinafop, compound of formula I + clomazone, compound of formula I + clopyralid, compound of formula I + cloransulam, compound of formula I + cyanazine, compound of formula I + cyhalofop, compound of formula I + dalapon, compound of formula I + 2,4-D, compound of formula I + 2,4-DB, compound of formula I + desmetryn, compound of formula I + desmedipham, compound of formula I + dicamba, compound of formula I + diclofop, compound of formula I + difenzoquat metilsulfate, compound of formula I + diflufenican, compound of formula I + dimefuron, compound of formula I + dimepiperate, compound of formula I + dimethachlor, compound of formula I + dimethametryn, compound of formula I + dimethenamid, compound of formula I + S-dimethenamid, compound of formula I + dinitramine, compound of formula I + dinoterb, compound of formula I + dipropetryn, compound of formula I + diuron, compound of formula I + diquat, compound of formula I + DSMA, compound of formula I + EPTC, compound of formula I + esprocarb, compound of formula I + ethalfluralin, compound of formula I + ethametsulfuron, compound of formula I + ethephon, compound of formula I + ethofumesate, compound of formula I + ethoxysulfuron, compound of formula I + fenclorim, compound of formula I + flamprop, compound of formula I + fluazasulfuron, compound of formula I + fluazifop, compound of formula I + flumetralin, compound of formula I + flumetsulam, compound of formula I + fluometuron, compound of formula I + flurochloridone, compound of formula I + fluoxaprop, compound of formula I + fluroxypyr, compound of formula I + fluthiacet-methyl, compound of formula I + fluxofenim, compound of formula I + fomesafen, compound of formula I + glufosinate, compound of formula I + glyphosate, compound of formula I + halosulfuron, compound of formula I + haloxyfop, compound of formula I + hexazinone, compound of formula I + imazamethabenz, compound of formula I + imazapyr, compound of formula I + imazaquin, compound of formula I + imazethapyr, compound of formula I + imazosulfuron, compound of formula I + ioxynil, compound of formula I + isoproturon, compound of formula I + isoxaben, compound of formula I + isoxaflutole, compound of formula I + karbutylate, compound of formula I + lactofen, compound of formula I + lenacil, compound of formula I + linuron, compound of formula I + MCPP, compound of formula I + metamitron, WO 99/52893 PCT/EP99/02313 -131 compound of formula I + metazachlor, compound of formula I + methabenzthiazuron, compound of formula I + methazole, compound of formula I + metobromuron, compound of formula I + metolachlor, compound of formula I + S-metolachlor, compound of formula I + metosulam, compound of formula I + metribuzin, compound of formula I + metsulfuron methyl, compound of formula I + molinate, compound of formula I + MCPA, compound of formula I + MSMA, compound of formula I + napropamide, compound of formula I + NDA 402989, compound of formula I + nefenacet, compound of formula I + nicosulfuron, compound of formula I + norflurazon, compound of formula I + oryzalin, compound of formula I + oxadiazon, compound of formula I + oxasulfuron, compound of formula I + oxyfluorfen, compound of formula I + paraquat, compound of formula I + pendimethalin, compound of formula I + phenmedipham, compound of formula I + phenoxaprop-P-ethyl (R), compound of formula I + picloram, compound of formula I + pretilachlor, compound of formula I + primisulfuron, compound of formula I + prometon, compound of formula I + prometryn, compound of formula I + propachlor, compound of formula I + propanil, compound of formula I + propazine, compound of formula I + propaquizafop, compound of formula I + propyzamide, compound of formula I + prosulfuron, compound of formula I + pyrazolynate, compound of formula I + pyrazosulfuron-ethyl, compound of formula I + pyrazoxyphen, compound of formula I + pyridate, compound of formula I + pyriminobac methyl, compound of formula I + pyrithiobac-sodium, compound of formula I + quinclorac, compound of formula I + quizalofop, compound of formula I + rimsulfuron, compound of formula I + sequestrene, compound of formula I + sethoxydim, compound of formula I + simetryn, compound of formula I + simazine, compound of formula I + sulcotrione, compound of formula I + sulfosate, compound of formula I + sulfosulfuron-methyl, compound of formula I + tebutam, compound of formula I + tebuthiuron, compound of formula I + terbacil, compound of formula I + terbumeton, compound of formula I + terbuthylazine, compound of formula I + terbutryn, compound of formula I + thiazafluron, compound of formula I + thiazopyr, compound of formula I + thifensulfuron-methyl, compound of formula I + thiobencarb, compound of formula I + tralkoxydim, compound of formula I + triallate, compound of formula I + triasulfuron, compound of formula I + trifluralin, compound of formula I + tribenuron-methyl, compound of formula I + triclopyr, compound of formula I + triflusulfuron, and compound of formula I + trinexapac-ethyl, and esters and salts of those mixing partners for the compound of formula I that are mentioned e.g. in The Pesticide Manual, Eleventh Edition, 1997, BCPC.

Claims

1. A compound of formula I Ri W R2 N W(I), N X 1 R 3 wherein R 1 is hydrogen, fluorine, chlorine, bromine or methyl; R 2 is 0 1 -C 4 alkyl, C 1 -C 4 haloalkyl, halogen, nitro, amino, cyano or R 43 0-; R 43 is hydrogen, C1-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 6 cycloalkyl, Cl-C 8 haloalkyl, cyano-C 1 -Csalkyl, C 3 -Cahaloalkenyl, hydroxy-Cl-C 4 alkyl, C -C 4 alkoxy-Cl-C 4 alkyl, C3-C6 alkenyloxy-C,-C 4 alkyl, C 3 -C 6 alkynyloxy-Cj-C 4 alkyl, C1 -C 4 alkoxy-C-C 4 alkoxy-C l -C 4 -alkyl, Cl-C 4 alkylthio-C,-C 4 alkyl, C -C 8 alkylcarbonyl, Cl-C 8 alkoxycarbonyl, C 3 -Coalkenyl oxycarbonyl, benzyloxy-C - or -C 2 -alkyl, benzylcarbonyl, benzyloxycarbonyl, phenyl, phenyl-C 2 -Cealkyl, benzyl, pyridyl, pyrimidinyl, pyrazinyl or pyridazinyl, those aromatic and heteroaromatic rings being unsubstituted or mono- to tri-substituted by halogen, CI-C 4 alkyl or by C-C 4 haloalkyl; or R44X 16 C(O)- [C 1 -Calkylene] R 43 is R4X 1 6 C(O)-C-C 8 alkyl- or I (C6 H 5 ) X 16 is oxygen, sulfur or R N R44 is hydrogen, C 1 -C 8 alkyl, C3-C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 8 haloalkyl, C 3 -C 8 haloalkenyl, CI-C 4 alkoxy-Cj-C 4 alkyl, C3-C6alkenyloxy-Cl-C 4 alkyl, Cl -C 4 alkylthio-Cl C 4 alkyl, phenyl, phenyl mono- to tri-substituted by halogen, CI-C 4 alkyl or by Cl-C 4 -halo alkyl, benzyl or benzyl mono- to tri-substituted on the phenyl ring by halogen, C 1 -C 4 alkyl or by CI-C 4 haloalkyl; R 45 is hydrogen, C 1 -C 8 alkyl, C 3 -Cealkenyl, C 3 -Cealkynyl, C 3 -C 6 cycloalkyl, Cl-Cshaloalkyl or benzyl; WO 99/52893 PCT/EP99/02313 -133 R 3 is hydroxy, Cl-C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C1-C 6 haloalkoxy, C3-C6 haloalkenyloxy, C 1 -Csalkoxy-C,-C 6 alkyl, C 3 -C 6 alkenyloxy-Cl-C 6 alkyl, C 3 -C 6 alkynyloxy C 1 -C 6 alkyl, C 1 -C 6 alkoxy-Cl-C 6 alkoxy-Cl-C 6 alkyl, B 1 -C1-C 6 alkoxy, R 4 (Rs)N-, Cy-C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 2 -C 6 haloalkyl, C 3 -C 6 haloalkenyl, C 3 -C 6 cycloalkyl, C3-06 halocycloalkyl, By-Cl-C 6 alkyl, OHC-, C1-C 6 alkylcarbonyl, Cl-C 6 alkylcarbonyloxy, C -C 6 haloalkylcarbonyl, C 2 -C 6 alkenylcarbonyl, CI-C 6 alkoxycarbonyl, Cy-C 6 alkyl-S(O) 2 -, Cl-C6haloalkyl-S(O) 2 -, C 3 -C8trialkylsilyloxy, (Cl-C 6 alkyl) 2 N-N=CH-, >-cH 2 - , O oCl-C 3 alkyl , Bl-CH=N-, (CH 3 ) 2 N-CH=N-, (C 1-C 5 hydroxyalkyl)-CH 2 -, (B1-C1-C 5 CH-- hydroxyalkyl)-CH 2 -, (Bj-C1-C 5 haloalkyl)-CH 2 -, (hydroxy-Cl-Csalkyl)-O- or (By-Cl-Cs hydroxyalkyl)-O-; B, is cyano, OHC-, HOC(O)-, C1-C 6 alkylcarbonyl, C 1 -C 6 haloalkylcarbonyl, C1-C 6 alkoxy carbonyl, C 3 -C 6 alkenyloxycarbonyl, C 3 -C 6 alkynyloxycarbonyl, benzyloxy, benzyloxy carbonyl, benzyloxycarbonyl mono- to tri-substituted on the phenyl ring by halogen, C1-C 4 alkyl or by Cl-C 4 haloalkyl, benzylthio, benzylthiocarbonyl, benzylthiocarbonyl mono- to tri-substituted on the phenyl ring by halogen, Cl-C 4 alkyl or by Cl-C 4 haloalkyl, Cl-C 6 haloalkoxycarbonyl, C1-C 6 alkylthio-C(O)-, R 6 (R 7 )NC(O)-, phenyl, phenyl mono- to tri-substituted by halogen, C1-C 4 alkyl or by C1-C 4 haloalkyl, Cl-C 6 alkyI-S(O) 2 -, C1-C 6 alkyl-S(O)-, C1-C 6 alkylthio-, C 3 -C 6 cycloalkyl, Cy-C 6 alkoxy, C 3 -C 6 alkenylthio or C 3 -C 6 alkynylthio; R 4 and Rs are each independently of the other hydrogen, Cl-C 6 alkyl, C 3 -C 6 alkenyl, C3-C6 alkynyl, Cl-C 6 haloalkyl, C 3 -C 6 haloalkenyl, C 3 -C 6 cycloalkyl, Cl -C 6 alkoxy-Cl-C 6 alkyl, OHC-, Cl-C 6 alkylcarbonyl, Cl-C 6 haloalkylcarbonyl, C 1 -C 6 alkyl-S(O) 2 - or C1-C 6 haloalkyl S(0)2-; R 6 and R 7 are each independently of the other hydrogen, Cl-C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, Cl-C 6 haloalkyl, C 3 -C 6 haloalkenyl, phenyl, phenyl mono- to tri-substituted by halogen, Cl-C 4 alkyl or by Cl-C 4 haloalkyl, benzyl or benzyl mono- to tri-substituted on the phenyl ring by halogen, C1-C 4 alkyl or by C 1 -C 4 haloalkyl; X, is oxygen or sulfur; WO 99/52893 PCT/EP99/02313 -134 R9 R12 R R 1 5 RIO NR8 R 13 R1 W is a group (W), I (W2), N (W3), .11 .,N 'N\ R14 X 3 N X2 X4 I II RR2 2 R 18 R 2 1 R 2 0 2 6 N R2 (W4)X (W), (W 6 , (W7), I X5 X N X,9 N N X N X70 | | R 28 R 27 R30 R29R 32 R31 N-N N (WN) or N X N (W.), N(W 9 ) O(W10) X N X 1 i x X : N X 1 5 1 13 14 R 8 is C-C 3 alkyl, C 1 -C 3 haloalkyl or amino; R 9 is Cl-C 3 haloalkyl, Cl-C 3 alkyl-S(O)nl, C 1 -C 3 haloalkyl-S(O)nl or cyano; or R 8 and R 9 together form a C 3 - or C 4 -alkylene bridge or C3- or C 4 -alkenylene bridge, each of which may be substituted by halogen, C-C 3 haloalkyl or by cyano; nj is 0, 1 or2; R 10 is hydrogen, CI-C 3 alkyl, halogen, Ci-C 3 haloalkyl or cyano; or R 10 and R 9 together form a C3- or C 4 -alkylene bridge or C3- or C 4 -alkenylene bridge, each of which may be substituted by halogen, Ci-C 3 haloalkyl or by cyano; R 11 i is hydrogen, CI-C 3 alkyl, halogen or cyano; R 12 is C 1 -C 3 haloalkyl; R 1 2 and R 11 together form a C3- or C 4 -alkylene bridge or C3- or C 4 -alkenylene bridge; R 13 is hydrogen, CI-C 3 alkyl or halogen; R 13 and R 12 together form a C3- or C 4 -alkylene bridge or C3- or C 4 -alkenylene bridge; R 14 is hydrogen, Cl-C 3 alkyl, halogen, Cl-C 3 haloalkyl, R 33 0-, R34S(O)n 2 , R 35 (R 36 )N, R 38 (R 39 )N-C(R 37 )=N-, hydroxy, nitro or NEC----S- ; R 3 3 is C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 2 -C 4 alkenyl, C3- or C 4 -alkynyl or Cl-Csalkoxycarbonyl C,-C 4 alkyl; WO 99/52893 PCT/EP99/02313 - 135 R34 is C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; n 2 is 0, 1 or 2; R 35 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C3-C 6 cycloalkyl, OHC- or C 1 -C 4 alkylcarbonyl; R 36 , R 37 and R 39 are each independently of the others hydrogen or C 1 -C 4 alkyl; R 38 is C 1 -C 4 alkyl; R 15 is hydrogen, C 1 -C 4 alkyl, halogen, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 3 -C 5 haloalkenyl, C3 or C 4 -alkynyl, Cl-C 4 alkoxy, Cl-C 4 alkylcarbonyl, C1-C 4 haloalkylcarbonyl, C 2 -C 4 alkenyl carbonyl, C 2 -C 4 haloalkenylcarbonyl, C 2 -C 4 alkynylcarbonyl, C 2 -C 4 haloalkynylcarbonyl, Cl-C 4 alkoxycarbonyl, C1-C 4 alkylcarbamoyl, CI-C 4 alkylS(0)n 3 , C3- or C 4 -alkynylS(O)n 3 , OHC-, nitro, amino, cyano or N-EC-S- ; n 3 is 0, 1 or 2; R 16 and R17 are each independently of the other hydrogen, C1-C 4 alkyl, halogen, C1-C 4 halo alkyl or cyano; R1 8 and R1 9 are each independently of the other hydrogen, methyl, halogen, hydroxy or =0; R 20 and R21 are each independently of the other hydrogen, C 1 -C 4 alkyl or Cl-C 4 haloalkyl; R 22 and R 23 are each independently of the other hydrogen, C 1 -C 3 alkyl, halogen or hydroxy; R 24 and R 25 are each independently of the other hydrogen or Cy-C 4 alkyl; or / R40 R 24 and R 2 5 together form the group =C, R41 R 40 and R 4 1 are each independently of the other C 1 -C 4 alkyl; or R 40 and R 41 together form a C4- or C 5 -alkylene bridge; R 26 is hydrogen or Cj-C 3 alkyl; or R 26 together with R 25 forms a C 3 -C 5 alkylene bridge, which may be interrupted by oxygen and/or substituted by halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 1 -C 3 haloalkyl, C1-C 3 alkyl carbonyloxy, C 1 -C 4 alkoxycarbonyl, Cl-C 3 alkylsulfonyloxy, hydroxy or by =0; R 27 , R 28 , R 29 and R 30 are each independently of the others hydrogen, CI-C 3 alkyl, C3- or C4 alkenyl or C 3 -Csalkynyl; or R 2 7 and R 28 together and/or R 29 and R 3 0 together in each case form a C 2 -C 5 alkylene bridge or C 3 -Csalkenylene bridge, each of which may be interrupted by oxygen, sulfur or S(0) 2 - and/or substituted by halogen, Cl-C 4 alkyl, C 2 -C 4 alkenyl, Cl-C 3 alkylcarbonyloxy, C 1 -C 3 alkylsulfonyloxy, hydroxy or by =0; WO 99/52893 PCT/EP99/02313 - 136 R 3 1 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C3- or C 4 -alkenyl, C3- or C 4 -haloalkenyl or C3 or C 4 -alkynyl; R 32 is hydrogen, C 1 -C 4 alkyl, C 1 -C 3 alkoxy-C 1 - or -C 2 -alkyl, C 1 -C 4 haloalkyl, C3- or C 4 -alkenyl, C3- or C 4 -haloalkenyl or C3- or C 4 -alkynyl; or R 3 2 and R 3 1 together form a C 3 -Csalkylene bridge; and X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , X 9 , X 10 o, X 11 , X 1 2 , X 13 , X 14 and X 1 5 are each independently of the others oxygen or sulfur, or an agrochemically acceptable salt or stereoisomer of such a compound of formula I.

2. A compound according to claim 1 of formula o10 R, R -- W (10), N X 1 R 3 wherein R, is hydrogen, fluorine, chlorine, bromine or methyl; R 2 is methyl, halogen, hydroxy, nitro, amino or cyano; and R 3 , X, and W are as defined in claim 1.

3. A process for the preparation of a compound of formula I R I R 2 w (I), N X1 R 3 wherein R 1 , R 2 and W are as defined in claim 1; X, is O or S; R 3 is C1-Cealkoxy-C,-C 6 alkyl, Cl-C 6 alkoxy-Cl-C 6 alkoxy-C 1 -C 6 alkyl, C1 -C 6 alkyl, C 3 -C 6 alkenyl, C3-C6alkynyl, C 2 -C 6 haloalkyl, C 3 -C 6 haloalkenyl, C3-C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, B-C, -C 6 alkyl, I>- CH 2 o WO 99/52893 PCT/EP99/02313 - 137 O C-C 3 alkyl , (C 1 -Cshydroxyalkyl)-CH 2 -, (Bi-Cj-Cshydroxyalkyl)-CH 2 - or CH2 (B-C 1 -Cshaloalkyl)-CH 2 -; and B 1 is as defined in claim 1, which process comprises oxidising a compound of formula Ill RR R --- W (Ill) N in a suitable solvent to form a compound of formula V R 1 R N W (V) O" and then rearranging that compound in an inert solvent in the presence of an anhydride or in the presence of antimony pentachloride to yield, after aqueous working-up, a compound of formula II R, R 2 / W (II), N OH the radicals R 1 , R 2 and W in the compounds of formulae II, III and V being as defined, and then alkylating that compound in the presence of an inert solvent and a base with a com pound of formula VI R 3 -L (VI), wherein R 3 is as defined and L is a leaving group, in a suitable inert solvent and a base to form the compounds of formulae I and IV Ri R, R W (I) and R ~N W (IV), N N X R 3 OR 3 WO 99/52893 PCT/EP99/02313 -138 wherein R 1 , R 2 , R 3 and W are as defined and X, is O, and then, after the compound of formula I has been separated from the pyridol derivative of formula IV, optionally functionalising the pyridono derivative of formula I further in accordance with the definitions of X, and R 3 .

4. A compound of formula II R1 R 1 R 2 - / W " R W (II), N NH OH O wherein R 1 , R 2 and W are as defined in claim 1.

5. A herbicidal and plant-growth-inhibiting composition, comprising a herbicidally effective amount of a compound of formula I on an inert carrier.

6. A herbicidal and plant-growth-inhibiting composition according to claim 5, comprising at least one further co-herbicide as additional component.

7. A method of controlling undesired plant growth, which method comprises applying a compound of formula I, or a composition comprising such a compound, in a herbicidally effective amount to plants or to the locus thereof.

8. Use of a composition according to claim 5 in the control of undesired plant growth.