Fungicidal pyrimidine compounds

1. A compound of formula I

wherein:

R a2 is hydrogen, halogen, CN, NO 2 , OH, SH, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -haloalkylthio, C 1 -C 4 -alkylsulfinyl, C 1 -C 4 -haloalkylsulfinyl, C 1 -C 4 -alkylsulfonyl, C 1 -C 4 -haloalkylsulfonyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxy, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -haloalkynyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkyloxy, C 3 -C 8 -cycloalkyl-C 1 -C 4 -alkyl, NR A R B , C(═O)R′, C(═NOR″)R′″ or —C(═NH)—O—R′″;

R A , R B independently of each other are hydrogen, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, phenyl, benzyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkenyl or —C(═O)—R′;

R′ is hydrogen, OH, NH 2 , C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylamino or di(C 1 -C 4 -alkyl)amino;

R″ is hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl or C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl;

R′″ is hydrogen or C 1 -C 4 -alkyl;

R a5 , R a6 together with two ring member carbon atoms to which they are attached, form a fused 5-membered saturated, partially unsaturated or aromatic carbocycle or heterocycle, wherein the ring member atoms of the fused heterocycle include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N and O and wherein the fused carbocycle or heterocycle is unsubstituted or carries 1, 2, 3 or 4 identical or different radicals selected from the group consisting of halogen, CN, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl and C 1 -C 4 -haloalkoxy;

R is hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -haloalkoxy-C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -alkynyl, C 2 -C 4 -haloalkynyl, CN, CH 2 CN, NR A R B or CH 2 —O—C(═O)R′; wherein

R A ,R B independently of each other are hydrogen, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, phenyl, benzyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkenyl or —(C═O)—R′;

R′ is hydrogen, NH 2 , C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylamino or di(C 1 -C 4 -alkyl)amino;

R 1 , R 2 independently of each other are hydrogen, halogen, CN, OH, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -haloalkoxy-C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -alkynyl, C 2 -C 4 -haloalkynyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkyl-C 1 -C 4 -alkyl, C 3 -C 8 -cycloalkyloxy, NR A R B , C(═O)R′, C(═NOR″)R′″, —C(═NH)−O−R′″ or benzyl wherein the phenyl moiety of benzyl is unsubstituted or carries 1, 2, 3, 4, or 5 substituents selected from the group consisting of CN, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, (C 1 -C 4 -alkoxy)carbonyl and di(C 1 -C 4 -alkyl)aminocarbonyl;

or two radicals R 1 and R 2 that are bound to the same carbon atom form together with said carbon atom a saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered carbocycle or a saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered heterocycle, wherein the ring member atoms of the abovementioned heterocycle include beside carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the abovementioned cycle is unsubstituted or carries 1, 2, 3 or 4 substituents selected from halogen, CN, OH, SH, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -alkylthio; and one or two CH 2 groups of the abovementioned cycles may be respectively replaced by one or two C(═O) or C(═S) groups;

X is a divalent group selected from —CR 3 R 4 —, —C(═O)—, —C(═S)—, —C(═NR D )— and —C(═NOR D )—, wherein

R D is hydrogen or C 1 -C 4 -alkyl;

R 3 and R 4 independently of each other are hydrogen, CN, C 1 -C 4 -hydroxyalkyl, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -haloalkoxy-C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -alkynyl, C 2 -C 4 -haloalkynyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkyl-C 1 -C 4 -alkyl, C 3 -C 8 -cycloalkyloxy, NR A R B , C(═O)R′, C(═NOR″)R′″, —C(═NH)—O—R′″ or benzyl wherein the phenyl moiety of benzyl is unsubstituted or carries 1, 2, 3, 4, or 5 substituents selected from the group consisting of CN, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, (C 1 -C 4 -alkoxy)carbonyl and di(C 1 -C 4 -alkyl)aminocarbonyl, or

two radicals R 3 and R 4 that are bound to the same carbon atom form together with said carbon atom a saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered carbocycle or a saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered heterocycle, wherein the ring member atoms of the abovementioned heterocycle include beside carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the abovementioned cycle is unsubstituted or carries 1, 2, 3 or 4 substituents selected from halogen, CN, OH, SH, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -alkylthio; and one or two CH 2 groups of the abovementioned cycles may be respectively replaced by one or two C(═O) or C(═S) groups;

n indicates the number of substituents R b on the phenyl ring and n is 0, 1, 2, 3 or 4;

R b is halogen, CN, NO 2 , C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 2 -C 4 -alkenyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -alkynyl, C 2 -C 4 -haloalkynyl, NR A R B , C(═NOR″)R′″ or —C(═NH)—O—R′″,

it being possible for n=2, 3 or 4 that R b are identical or different;

Het is a 5- or 6-membered heteroaryl, wherein the ring member atoms of the heteroaryl include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S and wherein the heteroaryl is unsubstituted or carries 1, 2, 3 or 4 identical or different groups R c :

R c is halogen, CN, NO 2 , NH 2 , C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 1 -C 6 -alkylamino, di(C 1 -C 6 -alkyl)amino, C 1 -C 6 -alkylthio, C 1 -C 6 -haloalkylthio, C 1 -C 6 -alkylsulfinyl, C 1 -C 6 -haloalkylsulfinyl, C 1 -C 6 -alkylsulfonyl, C 1 -C 6 -haloalkylsulfonyl, C 1 -C 6 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 6 -haloalkoxy-C 1 -C 4 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C(═O)R′, C(═NOR″)R′″, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkyl-C 1 -C 4 -alkyl, phenyl, phenoxy, phenoxy-C 1 -C 4 -alkyl or a 5- or 6-membered heteroaryl, wherein the ring member atoms of the heteroaryl include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the aforementioned cyclic radicals are unsubstituted or carry 1, 2, 3 or 4 identical or different substituents R d :

R d is halogen, CN, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -haloalkoxy;

or two radicals R c that are bound to adjacent ring member atoms of the Het group form together with said ring member atoms a fused 5-, 6- or 7-membered saturated, partially unsaturated or aromatic carbocycle or heterocycle, wherein the ring member atoms of the fused heterocycle include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the fused carbocycle or heterocycle is unsubstituted or carries 1, 2, 3 or 4 identical or different radicals groups R e :

R e is halogen, CN, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -haloalkoxy;

and the N-oxides and the agriculturally acceptable salts of the compounds of formula I.

2. The compound of claim 1 , wherein R a2 is selected from the group consisting of Cl, F, CH 3 , CH 2 CH 3 , OCH 3 , OCF 3 , CH 2 OCH 3 , CN, OCH 2 OCH, CF 3 , CHFCH 3 , COOCH 3 and COOCH 2 CH 3 .

3. The compound of claim 1 , wherein X is —CH 2 — or —C(═O)—.

4. The compound of claim 1 , wherein R 1 and R 2 are hydrogen.

5. The compound of claim 1 , wherein Het is selected from pyrimidin-2-yl, pyrimidin-3-yl, pyrimidin-4-yl, pyridin-2-yl, pyridin-3-yl, thiazol-2-yl, pyrazin-2-yl, pyridazin-3-yl, 1,3,5-triazin-2-yl, and 1,2,4-triazin-3-yl.

6. The compound of claim 1 , wherein Het carries 1 or 2 radicals R e , which are selected from F, Cl, Br, CN, C 1 -C 2 -alkylsulfonyl, C 1 -C 2 -alkoxycarbonyl, aminocarbonyl, C 1 -C 2 -alkylaminocarbonyl, di(C 1 -C 2 -alkyl)aminocarbonyl, C 1 -C 2 -alkoxy, CF 3 , CHF 2 , OCF 3 and OCHF 2 .

7. The compound of claim 1 , wherein R is hydrogen.

8. A process for preparing compounds I as defined in claim 1 , wherein X is —C(═O)—, which comprises reacting a compound of formula II

wherein R a2 , R as and R a6 are as defined in claim 1 , Hal is fluorine, chlorine or bromine, with a compound of formula III

wherein R, R 1 , R 2 , R b , R f , n and Het are as defined in claim 1 and X is —CR 3 R 4 — or —C(═O)— as defined in claim 1 in the presence of a base or a catalyst or a combination of a base and a catalyst in a solvent.

9. A process for preparing compounds I as defined in claim 1 in which X is —C(═O)—, which comprises reacting a compound of formula IIa

wherein R a2 , R a5 and R a6 is as defined in claim 1 with a compound of the formula Ma,

wherein Z is hydrogen or C 1 -C 4 -alkyl and R 1 , R 2 , R b , R c , R f1 , R f2 , n, m and Het are as defined in claim 1 .

10. An agrochemical composition which comprises an auxiliary and at least one compound of claim 1 .

11. An agrochemical composition according to claim 10 comprising at least one further active substance.

12. A method for combating phytopathogenic harmful fungi, which method comprises treating the fungi or the materials, plants, the soil or seeds to be protected against fungal attack, with an effective amount of at least one compound of formula I of an or an N-oxide or an agriculturally acceptable salt thereof, according to claim 1 .

13. The method of claim 12 , wherein, in the compound of formula I, R a2 is selected from the group consisting of Cl, F, CH 3 , CH 2 CH 3 , OCH 3 , OCF 3 , CH 2 OCH 3 , CN, OCH 2 OCH, CF 3 , CHFCH 3 , COOCH 3 and COOCH 2 CH 3 .

14. The method of claim 12 , wherein, in the compound of formula I, X is —CH 2 — or —C(═O)—.

15. The method of claim 12 , wherein, in the compound of formula I, R 1 and R 2 are hydrogen.

16. The method of claim 12 , wherein, in the compound of formula I, Het is selected from pyrimidin-2-yl, pyrimidin-3-yl, pyrimidin-4-yl, pyridin-2-yl, pyridin-3-yl, thiazol-2-yl, pyrazin-2-yl, pyridazin-3-yl, 1,3,5-triazin-2-yl, and 1,2,4-triazin-3-yl.

17. The method of claim 12 , wherein, in the compound of formula I, Het carries 1 or 2 radicals R e , which are selected from F, Cl, Br, CN, C 1 -C 2 -alkylsulfonyl, C 1 -C 2 -alkoxycarbonyl, aminocarbonyl, C 1 -C 2 -alkylaminocarbonyl, di(C 1 -C 2 -alkyl)aminocarbonyl, C 1 -C 2 -alkoxy, CF 3 , CHF 2 , OCF 3 and OCHF 2 .

18. The method of claim 12 , wherein, in the compound of formula I, R is hydrogen.