AU2008201017A1 - 5-phenylpyrimidines, their preparation, intermediate for their preparation, and their use for controlling harmful fungi - Google Patents

Description

P001 Section 29 Regulation 3.2(2)

AUSTRALIA

0 O 8- 0O

(N

00 Patents Act 1990 COMPLETE SPECIFICATION STANDARD PATENT Application Number: Lodged: 13 March 2002 Invention Title: 5-phenylpyrimidines, their preparation, intermediate for their preparation, and their use for controlling harmful fungi The following statement is a full description of this invention, including the best method of performing it known to us: P111AHAU/1107 00 their preparation, intermediates for their preparation, and their use for controlling harmful fungi The present invention relates to 5-phenylpyrimidines of the formula 1,

N

2 in which the substituents have the following meanings: 00 10 R' 1,2,3-triazine, 1,2,4-triazine, pyridazine, pyrimidine or pyrazine, it being possible for R1 to be substituted by one to three identical or difference groups Ra, Ra is halogen, hydroxyl, cyano, oxo, nitro, amino, mercaptol, 01-06alkyl, Cl-0 6 -haloalkyl, 0 2 -0 6 -alkenyl, 0 2 -0 6 -alkynyl, 03-06- 1 5 cycloalkyl, 0 1 -0 6 -alkoxy, C,-0 6 ,-haloalkoxy, carboxyl, 01-07alkoxycarbonyl, carbamoyl, Cl-C 7 -alkylaminocarbonyl, 0 1 -C6-alkyl- 0 1 -0 6 -alkylamincarbonyl, morpholinocarbonyl, pyrrolidinocarbonyl, Cl-C 7 -alkylcarbonylamino, Cl-0 6 -alkylamino, di(0 1

-C

6 -alkyl)amino, 0 1 -0 6 -alkylthio, Cl-0 6 -alkylsulfinyl, Cl-C 6 -alkylsulfonyl, hydroxysulfonyl, aminosulfonyl, 0 1 -0 6 -alkylaminosulfonyl, di(Cl-0 6 alkyl)aminosulfonyl; R 2 is hydrogen, halogen, cyano, Cl-0 6 -alkyl, Cl-0 6 -haloalkyl, Cl-0 6 -alkoxy, Cl-0 4 -haloalkoxy or C 3 -0 6 -alkenyloxy;

R

3 R 4 independently of one another are hydrogen, Cl-0 6 -alkyl, Cl-0 6 -haloalkyl, 0 3

-C

6 -cycloalkyl, 0 3 -0 6 -halocycloalkyl, 0 2 -0 6 -alkenyl, C 2 -0 6 -haloalkenyl,

C

3

-C

6 -cycloa Ikenyl, C 2

-C

6 -alkynyl, 0 2 -C6-ha loalkynyl or C3-Cecycloalkynyl, R 3 and R 4 may also, together with the nitrogen atom to which they are bonded, form a five- or six-membered ring which can be interrupted by a hetero atom selected from the group consisting of 0, N and S and/or which can have 00 2 attached to it one or more substituents selected from the C 1group consisting of halogen, Ci-C 6 -alkyl, Ci-C6-haloalkyl and oxyCi-C 3 -alkylenoxy or in which two adjacent C atoms S or one N atom and one adjacent C atom can be linked by a

C

1

-C

4 -alkylene chain;

R

5

R

6 independently of one another are hydrogen, halogen, Ci-C 6 -alkyl, Cl-C 6 -haloalkyl or C 1

-C

6 -alkoxy;

R

7

R

8 independently of one another are hydrogen, halogen, Ci-C 6 -alkyl or Ci-C6-haloalkyl; 00 R 9 is hydrogen, halogen, Cl-C 6 -alkyl, Cl-C 6 -alkoxy, 0 C 3

-C

6 -cycloalkoxy, Ci-C 6 -haloalkoxy, C 1

-C

6 -alkoxycarbonyl 0. 15 or C 1 -C6-alkylaminocarbonyl.

Moreover, the invention relates to processes and intermediates for the preparation of these compounds and to their use for controlling harmful fungi.

Fungicidally active 2-pyridyl-4-amino pyridine derivatives are disclosed in EP-A 407 899, pyridylpyrimidine derivatives are disclosed in DE-A 39 37 284, DE-A 39 37 285, DE-A 40 29 649, DE-A 40 34 762, DE-A 42 27 811, EP-A 481 405 and WO-A 92/10490.

The compounds described in the abovementioned publications are suitable as crop protection agents against harmful fungi.

In many cases, however, their action is not satisfactory. It is therefore an object of the present invention to provide compounds with an improved activity.

We have found that this object is achieved by the phenylpyrimidine derivatives I defined at the outset. Moreover, we have found processes and intermediates for their preparation and compositions comprising them for controlling harmful fungi, and their use.

The compounds of the formula I have an improved activity against harmful fungi compared with the known compounds.

The compounds I can be obtained via various routes.

Compounds of the formula I in which R I is heterocycles bonded via nitrogen and R 2 is chlorine can be prepared, for example, by the following process; 00 3 The cyclocondensation of thiourea with alkyl phenylmalonates of C( the formula II gives compounds of the formula III O 5 R R 7

R

5

R

H N RR S R 9 2 N NH 2 R-O R HN R 9 e8 II B III 0 R 6

R

8 O R' 8 where, in formula II, R is C 1

-C

6 -alkyl. The reaction is usually carried out in a protic solvent such as, for example, alcohols, in particular ethanol. However, it may also be carried out in Saprotic solvents such as, for example, pyridine, 00 N,N-dimethylformamide, N,N-dimethylacetamide, or mixtures of Sthese [cf. US 4,331,590; Org. Prep. and Proced. Int., Vol. -q 15 pp. 21-27 (1978); Collect. Czech. Chem. Commun., Vol. 48, pp. 137-143 (1983); Heteroat. Chem., Vol. 10, pp. 17-23 (1999); Czech. Chem. Commun., Vol. 58, pp. 2215-2221 (1993).

It may be advantageous to carry out the process in the presence of a base, which may be employed in equimolar amounts or else in excess. Examples of suitable bases are alkali metal carbonates, alkaline earth metal carbonates, alkali metal hydrogen carbonates and alkaline earth metal hydrogen carbonates, for example the potassium and sodium salts, in particular Na 2

CO

3 and NaHCO 3 or else nitrogen bases such as, for example, pyridine and tributylamine. The reaction temperature is normally 20-250 0

C,

preferably 70-220 0

C.

The reactants are usually employed in an approximately stoichiometric ratio. However, it may be advantageous to employ thiourea in excess. The arylmalonates required are known (cf. EP-A 1002 788) or can be prepared by methods known from the literature.

Compounds III were reacted by means of alkylating agents IV to give the thiobarbituric acid derivatives. In formula IV, R is

C

1

-C

6 -alkyl and X is a leaving group which can be eliminated nucleophilically. Formula IV generally represents customary alkylating agents such as CI-C 6 -alkyl halides, in particular methyl chloride and methyl bromide, di(Cl-C 6 -alkyl) sulfates, such as dimethyl sulfate, or a Ci-C 6 -alkyl methanesulfonate, such as methyl methanesulfonate.

4 00 0 R R7 III R-X R-S V

IV

The reaction can be carried out in water or else in a dipolar aprotic solvent such as, for example, N,N-dimethylformamide [cf. US 5,250,689], it is advantageously carried out in the presence of a base, which may be employed in O 10 equimolar amounts or else in excess. Suitable bases are alkali metal hydroxides, O alkaline earth metal hydroxides, alkali metal hydrogen carbonates and alkaline earth 0 metal hydrogen carbonates, such as, for example, KOH, NaOH, NaHCO 3 and 0 Na 2

CO

3 but also nitrogen bases such as pyridine. The reaction temperature is usually 0-1000C, preferably 10-60C. The reactants are usually employed in an approximately stoichiometric ratio. However, it may be advantageous to employ the alkylating agent in excess.

Compounds V are converted into dichloropyrimidines of the formula VI [cf.

US 4,963,678; EP-A 745 593; DE-A 196 42 533; WO-A 99/32458; J.Org. Chem. Vol.

58, (1993), pp. 3785-3786; Helv. Chim. Acta, Vol. 64, (1981), pp. 113-152].

ci R

N-

[cl] R-S-

R

9

VI

Examples of suitable chlorinating agents [CI] are POCI3, PCI 3

/CI

2 or PC15, or mixtures of these. The reaction can be carried out in an excess of chlorinating agent (POCl 3 or an inert solvent such as, for example, acetonitrile or 1,2-dichloroethane.

Carrying out the reaction in POCI 3 is preferred.

This reaction is usually carried out at between 10 and 180 0 C. For practical reasons, the reaction temperature usually corresponds to the boiling point of the chlorinating agent employed (POCl 3 or of the solvent employed. The process is advantageously carried out with addition of N,N-dimethylformamide in catalytic or substoichiometric amounts or with addition of nitrogen bases such as, for example, N,N-dimethylaniline.

By amination with VII, the dichloro compounds of the formula VI are converted into the compounds of the formula VIII.

00 R

N

R R'

R

3 4 t VI N R-S R 9

VIII

H VII N c1 R 6

R

8 This reaction is usually carried out at from 0 to 1500C, preferably at from 20 to 120 0 C [cf. J. Chem. Res. S (1995), pp. 286-287, Liebigs Ann. Chem., (1995), pp. 1703-1705] in an inert solvent, if appropriate in the presence of an auxiliary base.

0 00 Suitable solvents are protic solvents, such as alcohols, for 0 example ethanol, or aprotic solvents, such as aromatic hydrocarbons or ethers, for example toluene, m- and p-xylene, diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane or tetrahydrofuran, in particular tert-butyl methyl ether or tetrahydrofuran. Examples of suitable auxiliary base [sic] are the following: NaHCO 3 Na 2

CO

3 Na 2

HPO

4 Na 2

B

4 0 7 diethylaniline or ethyldiisopropylamine.

The reactants are normally employed in an approximately stoichiometric ratio. However, it may be advantageous to employ the amine in excess.

The amines of the formula VII are commercially available or known from the literature or can be prepared by known methods.

The thio compounds VIII are oxidized to give the sulfones of the formula IX.

3 R4 RN Rs R [Ox) N 9 R-SO-/ R

IX

c1 R' R IX The reaction is usually carried out at from 0 to 100 0 C, preferably at from 10 to 500C, in the presence of protic or aprotic solvents B. Kor. Chem. Soc., Vol. 16, (1995), pp. 489-492; Z. Chem., Vol. 17, (1977), p. 63].

Suitable solvents are alkylcarboxylic acids such as acetic acid or alcohols such as methanol, water or halogenated hydrocarbons such as dichloromethane or chloroform. Mixtures of these may also 00 6 be employed. Preferred are acetic acid and a methanol/water mixture.

S Examples of suitable oxidants are hydrogen peroxide, pertungstic acid, peracetic acid, 3-chloroperbenzoic acid, perphthalic acid, chlorine, oxygen and Oxone® (KHSOs). The oxidant is usually employed in an approximately stoichiometric ratio. However, it may be advantageous to carry out the process with an excess of oxidant.

Pyrimidine derivatives of the formula IX are converted into the Scompounds I by reaction with heterocycles of the formula X. In 00 formula X, the cycle A is a five- to ten-membered saturated, Spartially unsaturated or aromatic nitrogen-containing ring.

C R4 RN/ R 5

R'

N

R-SO- R 9 -H I

N=

cl R 6 R IX x This reaction is usually carried out at from 0 to 2000C, preferably at from 10 to 1500C, in the presence of a dipolar aprotic solvent such as N,N-dimethylformamide, tetrahydrofuran or acetonitrile [cf. DE-A 39 01 084; Chimia, Vol. 50, (1996), pp. 525-530; Khim. Geterotsikl. Soedin, Vol. 12, (1998), pp. 1696-1697].

The reactants are usually employed in an approximately stoichiometric ratio. However, it may be advantageous to employ the nitrogen heterocycle of the formula X in excess.

The reaction is usually carried out in the presence of a base, which may be employed in equimolar amounts or else in excess.

Suitable bases are alkali metal carbonates and alkali metal halogen carbonates, for example Na 2

CO

3 and NaHCO 3 nitrogen bases such as triethylamine, tributylamine and pyridine, alkali metal alkoxides such as sodium ethoxide or potassium tert-butoxide, alkali metal amides such as NaNH 2 or else alkali metal hydrides such as LiH or NaH.

Compounds of the formula I in which R' is bonded to the pyrimidine ring via a carbon atom can be synthesized for example as follows: r 00 7

O

S0 R 5

R

7 2NH HN S II R' Vb XII 0 6 R 8 In formulae vb and XII, the cycle B is a five- to ten-membered saturated, partially unsaturated or aromatic heterocycle ring which is bonded via carbon.

The reaction is usually carried out at from 50 to 250 0

C,

O preferably at from 100 to 200 0 C in the presence of a inert solvent 0 Austr. J. Chem., Vol. 32, (1979), pp. 669-679; J. Org.

SChem., Vol. 58, (1993), pp. 3785-3786; Arm. Xim. ZH, Vol. 38, 0 15 N11, (1985), 718-719].

The following are suitable as solvents: protic solvents such as alcohols, preferably methanol or ethanol, or aprotic solvents such as tributylamine or ethylene glycol dimethyl ether.

As a rule, it is advantageous to carry out the process in the presence of a base, which can be employed in equimolar amounts or else in excess. Suitable bases are alkali metal alkoxides and alkaline earth metal alkoxides such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide, in particular sodium methoxide, or else nitrogen bases such as triethylamine, triisopropylethylamine and N-methylpiperidine, in particular pyridine and tributylamine.

Usually, the reactants are employed in approximately stoichiometric amounts. However, it may also be advantageous to employ one of the reactants in excess.

ci R 5

R

7 Vb B R' VIb ci R6 RB The chlorination of Vb to give VIb is carried out under the same conditions as the chlorination of V to give VI.

3 R4 N RS R 7 N VIb VII R VIIib N R C1 R 6 00 8 The amination of the dichloropyrimidine VIb with VII is carried g out under the same conditions as the amination of VI to give

VIII.

Compounds of the formula VI in which R 2 is alkoxy are obtained T from the corresponding chloro compounds of the formula VI (R 2 Cl) by reaction with alkali metal alkoxides or alkaline earth metal alkoxides Heterocycles, Vol. 32, (1991), pp.

17- 1327-1340; J. Heterocycl. Chem. Vol. 19, (1982), pp. 1565-1567; Geterotsikl. Soedin, (1991) pp. 400-402].

Compounds of the formula I in which R 2 is cyano are obtained from 00 the corresponding chloro compounds of the formula VI (R 2 Cl) by Sreaction with alkali metal cyanides, alkaline earth metal cyanides or metal cyanides, such as NaCN, KCN or Zn(CN) 2 [cf.: Heterocycles, Vol. 39, (1994), pp. 345-356; Collect. Czech. Chem.

Commun. Vol. 60, (1995), pp. 1386-1389; Acta Chim. Scand., Vol.

(1996), pp. 58-63].

Compounds of the formula I in which R 2 is hydrogen are obtained from the corresponding chloro compounds of the formula VI (R 2 Cl) by catalytic hydrogenation J. Fluorine Chem. Vol. (1989), pp. 417-430; J. Heterocycl. Chem. Vol. 29, (1992), pp. 1369-1370], or by reduction with zinc in acetic acid (cf.: Org. Prep. Proced. Int., Vol. 27, (1995), pp. 600-602; JP-A 09/165 379].

Compounds of the formula I in which R 2 is C 1

-C

6 -alkyl or

C

1

-C

6 -haloalkyl can be prepared in analogy to the above-described synthesis sequence to give the compounds I in which R 2 is chlorine by suitably altering the starting materials of the formula II.

Instead of the phenylmalonates of the formula II, phenyl-p-ketoesters of the formula XIII in which R 2 is alkyl are used [sic) with thiourea or the amidine of the formula XII. The reactions which follow are carried out analogously to the compounds where R 2 chlorine.

0 R 5

R

7 0 R5 R' S R-0 HN 4 0 A 0 R 2 R S N RR 9 4 2R o0 N R 2 a pp 8 X I II v p

III

00 9 0 R 5

R'

2 N S NH XIII R 5 XI2 R8 vb' XII R R6 R Vb' The reaction mixtures are worked up in the customary fashion, for example by mixing with water, separating the phases and, if appropriate, chromatographic purification of the crude products.

Some of the intermediates and end products are obtained in the Sform of colorless or pale brown viscous oils, which are freed or 00 purified from volatile constituents under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, they may also be purified by recrystallization or digestion.

If individual compounds I cannot be obtained via the above-described routes, they can be prepared by derivatizing other compounds I.

In the definitions of the symbols given for the above formulae, collective terms were used which generally represent the following substituents: Halogen: fluorine, chlorine, bromine and iodine; Alkyl: saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 6 or 8 carbon atoms, for example Ci-C 6 -alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, l-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-l-methylpropyl and l-ethyl-2-methylpropyl; Haloalkyl: straight-chain or branched alkyl groups having 1 to 8 carbon atoms (as mentioned above), it being possible for some or all of the hydrogen atoms in these groups to be replaced by halogen atoms as mentioned above, for example Cl-C 2 -haloalkyl such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorfluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 00 0 1-bromoethyl, 1-fluoroethyl, 2-f luoroethyl, 2,2-difluoroethyl, -hor--looty,2cir.

22,2-rifluoroethyl, 22-chloro-2-fluoroethyl, -ho 2 ,2,2-trichloroethyl, pentafluoroethyl and 1,1,1-trifluoroprop-2-yl; Alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 6 or 8 carbon atoms and a double bond in any position, for example C 2

-C

6 -alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-rethylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-l-propenyl, 2-methyl-l-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 00 3-pentenyl, 4-pentenyl, 1-rethyl-l-butenyl, 2-methyl-1-butenyl, 00ehl1btnl 1mty--uey, -ehl2btnl 13-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-23-butenyl, 3-methyl-3-butenyl, 1, l-diniethyl-2-propenyl, 1, 2-dimethyl-1-propenyl, 1 ,2-dimethyl-2-propenyl, l-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, l-methyl-l-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, l-rethyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4--pentenyl, 1, 1-dirnethyl-2-butenyl, 1, I-dimethyl-3-butenyl, 1, 2-dimethyl-1-butenyl, 1, 2-dirnethyl-2-butenyl, 1, 2-dimethyl-3.-butenyl, 1, 3-dimethyl-l-butenyl, 1, 3-dimethyl-2-butenyl, 1, 3-dimethyl-3-butenyl, 2,2-dirnethyl-3-butenyl, 2,3-dinmethyl-1-butenyl, 2, 3-dimethyl-2-butenyl, 2, 3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-l-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, l,l,2-trimethyl-2-propenyl, l-ethyl-l-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl; Alkynyl: straight-chain or branched hydrocarbon groups having 2 to 4, 6 or 8 carbon atoms and a triple bond in any position, for example c 2 -c 6 -alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-l-butynyl, 1, 1-dimethyl-2-propynyl, l-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, l-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-J.-pentynyl, 3-niethyl-4-pentynyl, 4-methyl-l-pentynyl, 4-methyl-2-pentynyl, 1, 1-dimethyl-2-butynyl, 00 11 1, 1-dimethyl-3-butynyl, 1,2-dirnethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimnethyl-1--butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl und l-ethyl-l-methyl-2-propynyl; Cycloalkyl: monocyclic, saturated hydrocarbon groups having 3 to 6 cabonringmemerssuch as cyclopropyl, cyclobutyl, cycopetylandcyclohexyl; Alkoxycarbonyl: an alkoxy group having 1 to 6 carbon atoms (as mentioned above) which is bonded to the skeleton via a carbonyl group 00 Oxyalkylenoxy: divalent unbranched chains of 1 to 3 CH 2 groups, both valencies being bonded to the skeleton via an oxygen atom, for example OCH 2 O, OCH 2

CH

2 O and OCH 2

CH

2

CH

2

O;

five- to ten-membered saturated or partially unsaturated heterocycle containing one to four hetero atoms selected from the group consisting of oxygen, nitrogen or sulfur: mono- or bicyclic heterocycles (heterocyclyl) containing, in addition to carbon ring members, one to three nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms, for example 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidyinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1,2, 4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl, 1,],4-thiadiazolidin-2-yl, 1,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2, 3-dihydrothien-3-yl, 2, 4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 4-isoxazolin-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl, 3-isothiazolin-5-yl, 2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl, 2, 3-dihydropyrazol-3-yl, 2, 3-dihydropyrazol-4-yl, 00 12 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4 -iyrprzo--y,4 -ihdoyao--l 54 ,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol--yl, 2 3-dihydrooxazol--yl, 2, 3-dihydrooxazol--yl, 2, 3-dihydrooxazol-5-yl, 23 -dihydrooxazol-2-yl, 23 -dihydrooxazol-3-yl, 3, 4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 13,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2pprdnl 3-piperidinyl, 4-piperidinyl, 1, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl, 00 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2 -hexahydropyrimidinyl, 4 -hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl, 1,3,5-hexahydrotriazin-2-yl and 1,2,4-hexahydrotriazin-3-yl; five- to ten-membered aromatic heterocycle containing one to four hetero atoms selected from the group consisting of oxygen, nitrogen or sulfur: mononuclear or binuclear heteroaryl, for example 5-membered heteroaryi containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom: heteroaryl ring groups which, in addition to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, l,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, l,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl und 1,3,4-triazol-2-yl; benzo-fused 5-membered heteroaryl containing one to three nitrogen atoms or one nitrogen atom and one oxygen or sulfur atom: 5-membered heteroaryl ring groups which, in addition to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members and in which two adjacent carbon ring members or one nitrogen and one adjacent carbon ring member may be bridged by a buta-1,3-dien-l,4-diyl group in which one or two C atoms can be replaced by N atoms; 5-membered heteroarv. which is bonded via nitrogen and which contains one to four nitrogen atoms. or benzo-fused heteroaryl which is bonded via nitrogen and contains one to 00 13 three nitrogen atoms: 5-membered heteroaryl ring groups which, CN in addition to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms as ring members and in S which two adjacent carbon ring members or one nitrogen and one adjacent carbon ring member may be bridged by a buta-1,3-dien-l,4-diyl group, in which one or two C atoms can be replaced by N atoms, these rings being bonded to the skeleton via one of the nitrogen ring members; 6-membered heteroaryl containing one to three, or one to four, nitrogen atoms: 6-membered heteroaryl ring groups which, in addition to carbon atoms, may contain one to three, or one to Sfour, nitrogen atoms as ring members, for example 00 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl; The especially preferred embodiments of the intermediates with regard to the variables correspond to those of radicals R 1 to R 9 of the formula I.

with regard to the intended use of the phenylpyrimidines of the formula I, the following meanings of the substituents are especially preferred, in each case alone or in combination: Preferred compounds I are those in which R 1 is an aromatic heterocycle.

Furthermore preferred compounds I are those in which R 1 is a fiveto six-membered, in particular a five-membered, heterocycle.

Particularly preferred compounds of the formula I are those in which R 1 is a nitrogen-containing heterocycle.

In addition, preferred compounds I are those in which R I is a heterocycle which is bonded to the pyrimidine ring via nitrogen.

Equally preferred are compounds I in which R 1 is [lacuna] the following groups: pyrrole [sic], pyrazole [sic], imidazole [sic], 1,2,4-triazole [sic], 1,2,3-triazole [sic], tetrazole [sic], 1,2,3-triazine [sic], 1,2,4-triazine [sic], oxazole [sic], isoxazole [sic], 1,3,4-oxadiazole [sic], furan [sic], thiophene [sic], thiazole (sic], isothiazole [sic], it being possible for the heterocycle to be bonded to the pyrimidine ring via C or N.

00 14 Preferred compounds I are furthermore those in which the cycle RI rN2~ is pyridazine [sic], pyrimidine [sic] or pyrazine (sic], in particular 2-pyrimidine [sic].

Equally preferred compounds I are those in which RI is pyrazole (sic], pyrrole [sic], imidazole [sic], 1,2,3-triazole [sic], 1,2,4-triazole (sic], tetrazole [sic), 2-pyridine (sic], 2-pyrimidine (sic], pyrazine [sic] or 3-pyridazine [sic], each of which is optionally substituted by up to three groups Ra or Ra&.

Especially preferred compounds I are those in which an RI is pyrazole [sic], 1,2,3-triazole [sic] or 1,2,4-triazole (sic], in 00 particular 1-pyrazole (sic].

In addition, especially preferred compounds I are those in which the cycle R 1 is substituted by one to three identical or different groups Ra from among those which follow: halogen, hydroxyl, cyano, nitro, amino, mercapto, Cl-C 6 -alkyl, Cl-C 6 -haloalkyl, C 2

-C

6 -alkenyl, C 2

-C

6 -alkynyl,

C

3

-C

6 -cycloalkyl, Cl-C 6 -alkoxy, Cl-C 6 -haloalkoxy, carboxyl, Cl-C 7 -alkoxycarbonyl, carbainoyl, Ci-C 7 -alkylaminocarbonyl, Cl-C 6 -alkyl-Cl-C 6 -alkylamincarbonyl, morpholinocarbonyl, pyrrolidinocarbonyl, Cl-C7-alkylcarbonylanino, Cl-C 6 -alkylamfino, di(Cl-C 6 -alkyl)amino, CI-C 6 -alkylthio, Cl-C 6 -alkylsulfinyl, Cl-C 6 -alkylsulfonyl, hydroxysulfonyl, aminosulfonyl, Cl-C6-alkylaminosulfonyl or di (C 1

-C

6 alkyl )aminosulfonyl.

Especially preferred compounds I are, in particular, those in which the cycle R 1 is substituted by one to three identical or different groups Ra," from amongst those which follow: halogen, cyano, nitro, amino, C 1

-C

6 -alkyl, Cl-C 6 -haloalkyl, Cl-C 6 -alkoxy, carboxyl, C 1

-C

7 -alkoxycarbonyl, carbamoyl, Cl-C 7 -alkylaminocarbonyl, di(CI-C 6 -alkyl)amincarbonyl or Cl-C 7 -alkylcarbonylamino.

Especially preferred compounds I are those in which RI is unsubstituted or monosubstituted by halogen, cyano, nitro, methyl or methoxy.

Equally preferred compounds I are those in which R 2 is other than hydrogen.

00 Moreover, especially preferred compounds I are those in which R 2 is halogen, Ci-C 6 -alkyl or C 1

-C

6 -alkoxy, in particular halogen.

SEspecially preferred compounds of the formula I are those in which R 2 is chlorine.

Moreover, preferred compounds of the formula I are those in which

R

3 is hydrogen.

Equally especially preferred compounds I are those in which R 3 and

R

4 independently of one another are Ci-C 6 -alkyl, C 1

-C

6 -haloalkyl,

C

3

-C

6 -cycloalkyl, C 2

-C

6 -alkenyl.

00 SParticularly preferred compounds I are those in which R 3 is hydrogen and R 4 is C 1

-C

4 -halogenalkyl.

Furthermore, preferred compounds I are those in which R 3 and R 4 together with the nitrogen atom to which they are bonded form a five- or six-membered ring which can be interrupted by an oxygen atom and can have attached to it one or two Ci-C 6 -alkyl substituents.

Furthermore, preferred compounds I are also those in which not both R 5 and R 6 are hydrogen.

Especially preferred compounds I are those in which R 5 is hydrogen.

Equally, especially preferred compounds I are those in which R 5 is hydrogen and R 6 is halogen or methyl.

Compounds of the formula I which are especially preferred are furthermore those in which R 7 and R 8 are identical or different and are hydrogen or halogen.

Moreover, especially preferred compounds I are those in which R 9 is hydrogen, halogen or Ci-C 4 -alkoxy.

Equally, compounds I' in which R 1 to R 4 are as defined for formula I and RA is [lacuna] the following combinations of radicals: 2-chloro,6-fluoro; 2,6-difluoro; 2,6-dichloro; 2-methyl,4-fluoro; 2-methyl,6-fluoro; 2-fluoro,4-methyl; 2,4,6-trifluoro; 2,6-difluoro, 4-methoxy, 2,4-dimethyl and pentafluoro are especially preferred.

00 M.

N In addition, compounds of the formula I' which are especially preferred are those in which RA is 2,4,6-trifluoro.

Particularly preferred with regard to their use are the compounds I compiled 0 in the tables which follow. In the tables, the groups mentioned for a substituent

(N

00 additionally constitute an especially preferred embodiment of the substituent in 0question per se, independently of the combination in which they are mentioned.

Table 1 Compounds of the formula I1-1 in which R 5 is fluorine, R 6 is chlorine and R 7

R

8 and R 9 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Rp

R

5

R

Il-i Table 2 Compounds of the formula I1-1 in which R 5 and R 6 are fluorine, and R 7

R

8 and R 9 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table 3 Compounds of the formula I1-1 in which R 5 and R 6 are chlorine and R 7

R

8 and R 9 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table 4 Compounds of the formula I1-1 in which R 5 is fluorine, R 6 is methyl and R 7

R

8 and R 9 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A 00 Table 0Compounds of the formula 11-1 in which R 5

R

6 and R 9 are fluorine and R 7 and

R

8 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 C corresponds to one line of Table A 5 Table 6 Compound of the formula 11-1 in which R 5 and R 6 are fluorine, R 7 and R 8 are t- hydrogen and R 9 is methoxy and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table 7 0o 10 Compounds of the formula 11-1 in which R 5

R

6

R

7

R

8 and R 9 are fluorine and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table 8 Compounds of the formula 11-1 in which R 5 is methyl, R 6

R

7 and R 8 are hydrogen and R 9 are fluorine and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table 9 Compounds of the formula 11-1 in which R 5 is fluorine, R 6

R

7 and R 8 are hydrogen and R 9 are methyl and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table Compounds of the formula 11-1 in which R 5 and R 9 are methyl and R 6

R

7 and

R

8 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table 11 Compounds of the formula 11-2 in which R 5 is fluorine, R 6 is chlorine and R 7

R

8 and R 9 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A R- R N, 11-2 00 Table 12 Compounds of the formula 11-2 in which R 5 and R 6 are fluorine and R 7

R

8 and R 9 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table 13 Compounds of the formula 11-2 in which R 5 and R 6 are chlorine and R 7

R

8 and R 9 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table 14 0 10 Compounds of the formula 11-2 in which R 5 is fluorine and R 6 is methyl and

R

7

R

8 and R 9 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table Compounds of the formula 11-2 in which R 5

R

6 and R 9 are fluorine and R 7 and R 8 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table 16 Compounds of the formula 11-2 in which R 5 and R 6 are fluorine, R 7 and R 8 are hydrogen and R 9 is methoxy and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table 17 Compounds of the formula 11-2 in which R 5

R

6

R

7

R

e and R 9 are fluorine and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table 18 Compounds of the formula 11-2 in which R 5 is methyl, R 6

R

7 and R 8 is hydrogen and R 9 is fluorine and, for each compound, the combination of the radicals

R

3 and R 4 corresponds to one line of Table A Table 19 Compounds of the formula 11-2 in which R 5 is fluorine, R 6

R

7 and R 8 are hydrogen and R 9 is methyl and, for each compound, the combination of the radicals

R

3 and R 4 corresponds to one line of Table A 00 Table 0Compounds of the formula 11-2 in which R 5 and R 9 are methyl and R 6

R

7 and

R

8 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 C corresponds to one line of Table A Table 21 Compounds of the formula 11-3 in which R 5 is fluorine, R 6 is chlorine and R 7

R

8 and R 9 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A

R

4 IR R7 10 10 N N oo FNL 'N 11-3 Table 22 Compounds of the formula 11-3 in which R 5 and R 6 are fluorine and R 7

R

8 and R 9 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table 23 Compounds of the formula 11-3 in which R 5 and R 6 are chlorine and R 7

R

e 8 and R 9 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table 24 Compounds of the formula 11-3 in which R 5 is fluorine and R 6 is methyl and

R

7

R

8 and R 9 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table Compounds of the formula 11-3 in which R 5

R

6 and R 9 are fluorine and R 7 and R 8 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table 26 Compounds of the formula 11-3 in which R 5 and R 6 are fluorine, R 7 and R 8 are hydrogen and R 9 is methoxy and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table 27 Compounds of the formula 11-3 in which R 5

R

6

R

7

R

8 and R 9 are fluorine and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A 00 Table 28 0Compounds of the formula 11-3 in which R 5 is methyl, R 6

R

7 and R 8 is

(N

hydrogen and R 9 is fluorine and, for each compound, the combination of the radicals

SR

3 and R 4 corresponds to one line of Table A 5 Table 29 Compounds of the formula 11-3 in which R 5 is fluorine, R 6

R

7 and R 8 is hydrogen and R 9 is methyl and, for each compound, the combination of the radicals

SR

3 and R 4 corresponds to one line of Table A Table 00 10 Compounds of the formula 11-3 in which R 5 and R 9 are methyl and R 6

R

7 and are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table 31 Compounds of the formula 11-4 in which R 5 is fluorine, R 6 is chlorine and R 7

R

8 and R 9 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A R3'RI q"rN R 5 R7 ~R9 11-4 Table 32 Compounds of the formula 11-4 in which R 5 and R 6 are fluorine and R 7

R

8 and R 9 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table 33 Compounds of the formula 11-4 in which R 5 and R 6 are chlorine and R 7

R

8 and R 9 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table 34 Compounds of the formula 11-4 in which R 5 is fluorine and R 6 is methyl and

R

7

R

8 and R 9 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table Compounds of the formula 11-4 in which R 5

R

6 and R 9 are fluorine and R 7 and R 8 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A 00 Table 36 SCompounds of the formula 11-4 in which R 5 and R 6 are fluorine, R 7 and R 8 are hydrogen and R 9 is methoxy and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table 37 Compounds of the formula 11-4 in which R 5

R

6

R

7

R

8 and R 9 are fluorine I- and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A 38 oo 10 Compounds of the formula 11-4 in which R 5 is methyl, R 6

R

7 and R 8 are hydrogen and R 9 is fluorine and, for each compound, the combination of the radicals

R

3 and R 4 corresponds to one line of Table A Table 39 Compounds of the formula 11-4 in which R 5 is fluorine, R 6

R

7 and R 8 are hydrogen and R 9 is methyl and, for each compound, the combination of the radicals

R

3 and R 4 corresponds to one line of Table A Table Compounds of the formula 11-4 in which R 5 and R 9 are methyl and R 6

R

7 and

R

8 are hydrogen and, for each compound, the combination of the radicals R 3 and R 4 corresponds to one line of Table A Table A No. R3R 4 A-1 CH 2

CH

3

H

A-2 CH 2

CH

3

CH

3 A-3 CH 2 CH3 CH 2

CH

3 A-4 CH 2

CH

2

CH

3

H

CH

2

CH

2

CH

3

CH

3 A-6 CH 2

CH

2

CH

3

CH

2

CH

3 A-7 CH 2

CH

2

CH

3

CH

2

CH

2

CH

3 A-8 CH 2

CH

2 F H A-9 CH 2

CH

2 F CH 3

CH

2

CH

2 F CH 2

CH

3 A-1l CH 2 CF3 H A-12 CH 2

CF

3

CH

3 A-13 CH 2

CF

3

CH

2

CH

3 A-14 C11 2

CF

3

CH

2

CH

2

CH

3

CH

2 CC1 3

H

A-16 CH 2 CCl 3

CH

3 A-17 CH 2 CC1 3

CH

2

CH

3 A-18 CH 2 CC1 3

CH

2

CH

2

CH

3 A-19 CH(CH 3 2

H

CH(CH

3 2

CH

3 A-21 CH(CH 3 2

CH

2

CH

3 A-22 CH(CH 3 2

CH

2

CH

2

CH

3 A-23 CH 2

C(CH

3 3

H

A-24 CH 2 C(C11 3 3

C!

3

CH

2

C(CH

3 3

CH

2

CH

3 A-26 Cf1 2

CH(CH.

3 2

H

A-27 CH 2

CH(CH

3 2

CH

3 A-28 CH 2

CH(CH

3 2

CH

2

CH

3 A-29 CH(CH 2

CH

3

)CH

3

H

±)CH(CH

2

CH

3

)CH

3

CH

3 A-31 CH(CH 2

CH

3

)CH

3

CH

2

CH

3 A-32 CH(CH 2

CH

3

)CH

3

H

A-33 CH(CH 2

CH

3

)CH

3

CF!

3 A-34 CH(CH 2

CH

3

)CH

3

CH

2

CH

3

CH(CH

2

CH

3

)CH

3

H

A-36 CH(CH 2

CH

3

)CH

3

OH

3 A-37 CH(CH 2

CH

3

)CH

3

CH

2

CH

3 No. R 3

R

4 A-38 ()CH(CH 3

)-CH(CH

3 2

H

A-39 ()CH(CH 3

)-CH(CH

3 2

CH

3

()CH(CH

3

)-CH(CH

3 2

CH

2

CH

3 A-41 CH(CH3)-CH(CH 3 2

H

A-42 CH(CH3)-CH(CH 3 2

CH

3 A-43 CH(CH 3

)-CH(CH

3 2

CH

2

CH

3 A-44 CTI(CH 3

)-CH(CH

3 2

H

CH(CH

3

)-CH(CH

3 2

CH

3 A-46 CH(C11 3

)-CH(CH

3 2

CH

2

CH

3 A-47 ()CH(CH 3

)-C(CH

3 3

H

A-48 ()CH(CH 3

)-C(CH

3 3

CH

3 A-49 ()CH(CH 3

)-C(CH

3 3 CH2CH 3

CH(CH

3

)-C(CH

3 3

H

A-51 CH(CH 3

)-C(CH

3 3

CH

3 A-52 CH(CH 3

)-C(CH

3 3

CH

2

CH

3 A-53 CH(CH 3

)-C(CH

3 3

H

A-54 CH(CH 3

)-C(CH

3 3

CH

3

CH(CH

3

)-C(CH

3 3

CH

2

CH

3 A-56 ()CH(CH 3

)-CF

3

H

A-57 ()CH(CH 3

)-CF

3

CH

3 A-58 ()CH(CH 3

)-CF

3

CH

2

CH

3 A-59 CH(CH 3

)-CF

3

H

CH(CH

3

)-CF

3

CH

3 A-61 CH(CH 3

)-CF

3

CH

2

CH

3 A-62 CH(CH 3

)-CF

3

H

A-63 CH(CH 3

)-CF

3

CH

3 A-64 CH(CH 3

)-CF

3

CH

2

CH

3 ()CH (CH 3 -CC 1 3

H

A-66 (00 CH(CH 3 )-CC1 3

CH

3 A-67 CH(CH 3 )-CC1 3

CH

2

CH

3 A-68 CH (CH 3 -CC 1 3

H

A-69 CH(CH 3 )-CC1 3

CH

3

CH(CH

3 )-CC1 3

CH

2

CH

3 A-71 CH(CH 3 )-CC1 3

H

A-72 CH(CH 3 )-CC1 3

CH

3 A-73 CH(CH 3 )-CC1 3

CH

2

CH

3 A-74 CH 2

C(CH

3

)=CH

2

H

CH

2

C(CH

3

)=CH

2

OH

3 A-76 CH 2

C(CH

3

)=CH

2

CH

2

CH

3 No. R 3

R

A-77 Cyclopentyl H A-78 Cyclopentyl

CH

3 5A-79 Cyclopentyl CH 2

CH

3 A- 80 -(CH 2 )4- A-81 -(CH 2 2

-CH(CH

3

)-CH

2 A-82 -(CH 2 2

-CH(CH

3

)-CH

2 10A-83

-(CH

2 2

-CH(CH

3

)-CH

2 A10-C22CHOH)C2

-(CH

2 2

-CH(OHCH

3

)-CH

2 A-86 -(CH 2 2

-CHCH(CH

3 )2-CH 2 A- 87 -CH 2

-CH=CH-CH

2 A-88 -(CH 2 5 A-89 -(CH 2 2

-CH(CH

3

)-(CH

2 2

-(CH

2 3

-CH(CH

3

)-CH

2 A-91 -(CH 2 3 -CH(CH3)-CH 2 A-92 -(CH 2 3

-CH(CH

3

)-CH

2 A-93 -(CH 2 2 -C(0[CH 2

I

2 0)-(CH 2 2 A-94 -(CH 2 2

-C(O[CH

2 ]30) -(CH 2 )2- C2 CH 2

C

A-96 -(CH 2 2

-CH=CH-CH

2 A-97 -CH-CHC 3 )2-O-C(CH )-C A-98 cs -CH 2

-CH(CH

3

)-O-CH(CH

3

)-CH

2 30A-99 (tras) -CH 2

-CH(CH

3

)-O-CH(CH

3

)-CH

2 30A-1001tas -CH 2 A-101 -(CH 2 2

-NH-(CH

2 2 A-102 -(CH 2 2 -SH3-(CH 2 2 A-103 -(C1 2 2

-CH-(CH

2 2 35A-104 -(CH 2

)-CHF-CH

2 A-105 -(CH 2

)-CHF)-CH

2 A-106 -(CH 2 2

-CH(CHF)-(CH

2 2 A-107 -(CH 2 2

-HCHF-(CH

2 2 401A10j (H)-F-C22 The compounds I are suitable as fungicides. They are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the 4Ascomycetes, Deuterornycetes, Phycomycetes and Basidiornycetes.

Some of them act systemically, and they can be employed in crop protection as foliar- and soil-acting fungicides.

They are especially important for controlling a large number of fungi on a variety of crop plants such as wheat, rye, barley, oats, rice, maize, grass, bananas, cotton, soya, coffee, sugar cane, grapevines, fruit species, ornamentals and vegetables such as cucumbers, beans, tomatoes, potatoes and cucurbits, and on the seeds of these plants.

Specifically, they are suitable for controlling the following plant diseases: Alternaria species on vegetables and fruit, Botrytis cinerea (gray mold) on strawberries, vegetables, ornamentals and grapevines, Cercospora arachidicola on peanuts, Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits, Erysiphe graminis (powdery mildew) on cereals, Fusarium and Verticillium species on various plants, Helminthosporium species on cereals, Mycosphaerella species on bananas and peanuts, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on grapevines, Podosphaera leucotricha on apples, Pseudocercosporella herpotrichoides on wheat and barley, Pseudocercosporella species on hops and cucumbers, Puccinia species on cereals, Pyricularia oryzae on rice, Rhizoctonia species on cotton, rice and turf, Septoria nodorum on wheat, Uncinula necator on grapevines, Ustilago species on cereals and sugar cane, and Venturia species (scab) on apples and pears.

Moreover, the compounds I are suitable for controlling harmful fungi such as Paecilomyces variotii in the protection of materials (eg. timber, paper, paint dispersions, fibers and fabrics) and in the protection of stored products.

The compounds I are applied by treating the fungi, or the plants, seeds, materials or the soil to be protected against fungal infection with a fungicidally active amount of the active ingredients. Application can be effected either before or after infection of the materials, plants or seeds by the fungi.

In general, the fungicidal compositions comprise between 0.1 and preferably between 0.5 and 90, by weight of the active ingredient.

00 26 When used in crop protection, the application rates are from 0.01 C to 2.0 kg of active ingredient per hectare, depending on the nature of the desired effect.

In the treatment of seed, amounts of active ingredient of from 0.001 to 0.1 g, preferably 0.01 to 0.05 g, are generally required per kilogram of seed.

When used in the protection of materials or stored products, the rate of application of active ingredient depends on the nature of the field of application and on the desired effect. Rates of application conventionally used in the protection of materials 00 are, for example, from 0.001 g to 2 kg, preferably 0.005 g to S1 kg, of active ingredient per cubic meter of material treated.

CM The compounds I can be converted into the customary formulations, eg. solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the intended purpose; it is intended to ensure in each case a fine and uniform distribution of the compound according to the invention.

The formulations are prepared in a known manner, eg. by extending the active ingredient with solvents and/or carriers, if desired using emulsifiers and dispersants, it also being possible to use other organic solvents as auxiliary solvents if water is used as the diluent. Auxiliaries which are suitable are essentially: solvents such as aromatics (eg. xylene), chlorinated aromatics (eg. chlorobenzenes), paraffins (eg. mineral oil fractions), alcohols (eg. methanol, butanol), ketones (eg. cyclohexanone), amines (eg. ethanolamine, dimethylformamide) and water; carriers such as ground natural minerals (eg. kaolins, clays, talc, chalk) and ground synthetic minerals (eg. highly disperse silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (eg. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin-sulfite waste liquors and methylcellulose.

Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids and their alkali metal and alkaline earth metal salts, salts of sulfated fatty alcohol glycol ether, condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of napthalenesulfonic acid with phenol or formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated 00 27 isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol CA ethers, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide t condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as Skerosene or diesel oil, furthermore coal tar oils and oils of OO vegetable or animal origin, aliphatic, cyclic and aromatic 0 hydrocarbons, eg. benzene, toluene, xylene, paraffin, 15 tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents, eg. dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and water.

Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.

Granules, eg. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Examples of solid carriers are mineral earths, such as silicas, silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, eg.

ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.

In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active ingredient.

The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

The following are examples of formulations: 0 O 28 I. 5 parts by weight of a compound according to the invention C are mixed intimately with 95 parts by weight of finely Sdivided kaolin. This gives a dust which comprises 5% by Sweight of the active ingredient.

II. 30 parts by weight of a compound according to the invention are mixed intimately with a mixture of 92 parts by weight of pulverulent silica gel and 8 parts by weight of paraffin oil which had been sprayed onto the surface of this silica gel.

This gives a formulation of the active ingredient with good adhesion properties (comprises 23% by weight of active C- ingredient).

00 III. 10 parts by weight of a compound according to the invention C 15 are dissolved in a mixture composed of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol of oleic acid N-monoethanolamide, 2 parts by weight of calcium dodecylbenzenesulfonate and 2 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil (comprises 9% by weight of active ingredient).

IV. 20 parts by weight of a compound according to the invention are dissolved in a mixture composed of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 5 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil (comprises 16% by weight of active ingredient).

V. 80 parts by weight of a compound according to the invention are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalene-a-sulfonate, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill (comprises 80% by weight of active ingredient).

VI. 90 parts by weight of a compound according to the invention are mixed with 10 parts by weight of N-methyl-a-pyrrolidone, which gives a solution which is suitable for use in the form of microdrops (comprises 90% by weight of active ingredient).

VII. 20 parts by weight of a compound according to the invention are dissolved in a mixture composed of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by 00 29 weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of mol of ethylene oxide and 1 mol of castor oil. Pouring S the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.

VIII. 20 parts by weight of a compound according to the invention are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalene-a-sulfonate, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste Sliquor and 60 parts by weight of pulverulent silica gel, and 00 the mixture is ground in a hammer mill. Finely distributing Sthe mixture in 20,000 parts by weight of water gives a spray mixture which comprises 0.1% by weight of the active ingredient.

The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, eg. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the active ingredients according to the invention.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.

The active ingredient concentrations in the ready-to-use products can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1%.

The active ingredients may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active ingredient, or even to apply the active ingredient without additives.

00 various types of oils, herbicides, fungicides, other pesticides, or bactericides may be added to the active ingredients, if appropriate just immediately prior to use (tank mix). These agents can be admixed with the agents according to the invention in a weight ratio of 1:10 to 10:1.

In the use form as fungicides, the compositions according to the invention can also be present together with other active ingredients, eg. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers. Mixing the compounds I or the compositions comprising them in the use form as fungicides with other fungicides frequently results in a 00 broader fungicidal spectrum of action.

The following list of fungicides together with which the compounds according to the invention can be used is intended to illustrate the possible combinations, but not to impose any limitation: "sulfur, dithiocarbamates and their derivatives, such as iron(III) dimethyldithiocarbanate, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbanate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediaminebisdithiocarbaiate, tetramethylthiuram disulfide, ammonia complex of zinc (N,N-ethylenebisdithiocarbamate), amrmonia complex of zinc (N,N'-propylenebisdithiocarbamate), zinc N -propylenebisdithiocarbaiate), N,N' -polypropylenebis(thiocarbamoyl)disulfide; nitro derivatives, such as dinitro(-methylheptyl)phenyl crotonate, 2-sec-butyl--4,6-dinitrophenyl 3,3-dimethylacrylate, 2-sec-butyl-4 ,6-dinitrophenylisopropyl carbonate, diisopropyl itro-isophthalate; heterocyclic substances, such as 2-heptadecyl-2--imidazoline acetate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, 0, 0-diethyl phthalimidophosphonothioate, 5-amino-1-[bis (dimethylamino)phosphinyl ]-3-phenyl- 1,2,4- triazole, 2,3-dicyano-l,4-dithioanthraquinone, 2-thio-l,3-dithiolo[4,5-b)- quinoxaline, methyl 1- (butylcarbanoyl -benzimidazolecarbamate, 2-methoxycarbonylaminobenzimidazole, 2-(2-furyl)benzimidazole, 4-thiazolyl)benzimidazole, 1,2,2-tetrachloroethylthio)tetrahydrophthalimide, N-tni- chloromethylthiotetrahydrophthalimide, N-trichlorornethylthiophthalimide; 0 N-dichlorofluoromethylthio-N' ,N'-dimethyl-N--phenylsulfodiamide, 5-ethoxy-3-trichloromethyl-1, 2, 3-thiadiazole, 2 -thiocyanatomethylthiobenzothiazole, 00 31 1, 4-dichloro-2, 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, Ct pyridine-2-thiol 1-oxide, 8-hydroxyquinoline or its copper salt, 2, 3-dihydro-5-carboxanilido-6-methyl-1 ,4-oxathiine, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine 4,4-dioxide, 6-dihydro-4H-pyran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2, 5-dimethyifuran-3-carboxanilide, 2,4, 5-trimethylfuran-3-carboxanilide, 2, 5-direthylfuran-3-carbocyclohexylamide, N-cyclohexyl-N-methoxy-2 ,5-dimethylfuran-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, 00 N-formyl-N-morpholine-2, 2, 2-trichioroethyl acetal, piperazine-1,4-diylbis-1-(2,2,2-trichloroethyl)formamide, 1-(3,4-dichloroanilino)-l-formylanino-2,2,2-trichloroethane, 2,6-dixnethyl-N-tridecylmorpholine or its salts, 2 ,6-dimethyl-N-cyclododecylm~orpholine or its salts, N-f p-tert-butylphenyl)-2-methylpropyl]-cis- 2, 6-dixnethylmorpholine, N-I 3-(p-tert-butylphenyl) 2-methyipropyl ]piperidine, 4-dichiorophenyl 4ehl1,3-dioxolan-2-yl-ethyl] 1H-l, 2,4-triazole, 1-f 2, 4-dichlorophenyl )-4-n-propyl-l, 3-dioxolan-2-yl-ethyl 1- N-(n-propyl)-N-(2,4,6-trichlorophefloxyethyl)-N'-imidazolylurea, l-(4-chlorophenoxy)-3,3-dimethyl-l-(lH-1,2,4-triazol-1-yl)- 2-butanone, l-(4-chlorophenoxy)-3,3-dimethyl-l-(lH-1,2,4-triazol-1-yl)- 2 -butanole, (2RS,3R5)-1-[3-(2-chlorophenyl)-2-(4-fluorophelyl)-oxiral- 2-ylrnethyl]J-1H-l, 2, 4-triazole, cL-( 2-chlorophenyl)--Q-(4-chlorophenyl)-5-pyrimidinemethanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis (p-chlorophenyl) -3-pyridinernethanol, 1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene, 1, 2-bis( 3-rethoxycarbonyl- 2-thioureido)benzene; strobilurins such as methyl E-methoxyimino- (QL-(o-tolyl-oxy) -o-tolyl ]acetate, methyl-E-2-{2-[6-(2-cyanopheloxy)pyrimidil-4-yloxy-phelyl}- 3-methoxyacrylate, N-methyl-E-methoxyimino-[QL-( 2-phenoxyphenyl) Jacetamide, N-methyl E-methoxyimino- 5-dimethylphenoxy) -o-tolyljacetamide, methyl E--2[-rfurmtypriy--oyehlpeyl 3 -methoxyacrylate, methyl (E,E)-methoximilo-{2-[ 1-(3-trifluoromethylphenyl)ethylidene- 00 32 aminooxymethyllphenyi }acetate, rethyl-N-(2-{[l-(4-chlorophelyl)- Ct H-pyrazol-3-yIoxymethyl}phel)N-methoxycarbamate; 0anilinopyrimidiles such as N- (4 6.dimethylpyrimlidifl-2-yl) aniline, 4-methyl-6-cyclopropylpyrmidil-2-yl]anilile; 0phenylpyrroleS such as 4-(2,2-difluoro-1,3-beflzodioxol- 4-yl)pyrrole-3-carboflitrile; cinnaxnamides such as 3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl) acryloylmorpholine; 0 and a variety of fungicides such as dodecylguanidine acetate, hexachlorobenzele, methyl 2, 6-dirnethyiphenyl) N-(2-furoyl)-DL-alaninate, DL-N-(2, 6-dimethyiphenyl methoxyacetyl)-alanine methyl ester, N- (2 ,6-dimethyiphenyl )-N-chloroacetyl-D, L-2-aminobutyrolactone, DL-N-(2 ,6-dimethylphenyl) -N-(phenylacetyl) alanine methyl ester, 5-methyl-.5-vinyl-3-(3,5-dichlorophefl)-2,4-dioxo- 1, 3-oxazolidine, 3-13, 5-dichiorophenyl (5-methyl-5-methoxymethyl] 1,3-oxazolidine-2,4-dione, 3-(3,5-dichlorophenyl)- 1-isopropylcarbaxnoylhydantoin, N-(3,5-dichlorophenyl)-1,2-dimfethylcyclopropane- 1, 2-dicarboximide, 2-cyano-[N-(ethylaminocarbonyl 2-methoximino] acetaxnide, 1-(2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole, 2,4-difluoro-t-( 1H-1,2,4-triazolyl-1-methyl)benzhydryl alcohol, 3-chloro-2, 6-dinitro-4-trifluoromethylphenyl) 5-trifluoromethyl-3-chloro-2-aminopyridine, l-((bis(4-fluorophenyl)methylsilyl)Inethyl-lH-1,2,4-triazole.

Synthesis examples with due modification of the starting compounds, the protocols shown in the synthesis examples below were used for obtaining further compounds 1. The compounds obtained in this way are listed in the following tables with physical data.

Example 1: 6-Chloro-5-( 2-chloro-6-fluorophenyl )-4-isopropylaminol-pyrazolyl)pyrimidine [I-1] a) 5-(2-Chloro-6-fluorophenyl)-2-methylthio-4,6( pyrimidinedione 00 0 33 060.0 g (208 mmol) of ethyl 2 2 -chloro-6-fluorophenyl)malonate and 19.0 g (249 mmol) of thiourea were heated for 2.5 hours at 1500C in 77 g (416 mmol) of n-tributylamine. Most of the ethanol formed was distilled off. 180 ml of an aqueous solution of 24.9 g (623 mmol) of NaOH were added to the reaction mixture once it had cooled down. After the aqueous phase had been treated with 50 ml of cyclohexane and stirred for approximately 30 minutes, it was separated off, treated with 35.4 g (142 mmol) of methyl iodide and stirred for approximately 16 hours at approximately 20 to 250C. After acidification with dilute HC1 solution and stirring for approximately 30 minutes, the precipitate was filtered off.

C Washing with water and drying gave 16.7 g of the title compound 00 as white crystals of m.p. 250 0 C (decomp.).

CN 15 b) 4,6-Dichloro-5-(2-chloro-6-fluorophenyl)- 2-methylthiopyrimidine A solution of 48.8 g (170 mmol) of the product of step a in 200 ml of phosphorus oxychloride was refluxed for 40 hours after addition of 3 ml of dimethylformamide (DMF). After most of the phosphorus oxychloride had been distilled off and the residue had been diluted with ethyl acetate, water was added with stirring at to 200C. After phase separation, the organic phase was washed with water and dilute NaHCO 3 solution and then dried and freed from solvent. This gave 37.5 g of the title compound as an oil which was employed in step c without further purification.

IR (film): y (cm- 1 1558, 1477, 1449, 1353, 1252, 900, 816, 783.

c) 6-Chloro-5-(2-chloro-6-fluorophenyl)-4-isopropylamino- 2-methylthiopyrimidine A solution of 37.5 g (324 mmol) of the product of step b in 150 ml of anhydrous dichloromethane was treated with 24 g (406 mol) of isopropylamine and stirred for five hours at approximately 20 to 250C. Then, the solvent was distilled off, the residue was taken up in ethyl acetate and washed with dilute HC1, water and dilute NaHC03 solution, dried and freed from solvent.

Following chromatography on silica gel (cyclohexane/methyl tert-butyl ether 100:1 to 19:1), 13.4 g of the title compound were obtained from the residue in the form of colorless crystals of m.p. 94-980C, which were employed in the next step without further purification.

d) 6-Chloro-5-(2-chloro-6-fluorophenyl)-4-isopropylamino- 2-methylsulfonylpyrimidine 00 34 A solution of 13.3 g (38.4 mmol) of the product of step c in C1 240 ml of anhydrous dichloromethane was treated with 17.2 g (76.8 mmol) of 3-chloroperbenzoic acid at 0 to 50C. The mixture Swas stirred for one hour at 0 to 5 0 C and for 14 hours at approximately 20 to 250C. After the solvent was distilled off, the residue was taken up in ethyl acetate and then washed with strength NaHCO 3 solution. After phase separation, the organic phase was dried and freed from solvent. The residue was digested with diisopropyl ether/hexane. This gave 11.3 g of the title compound as colorless crystals of m.p. 145-1490C.

e) 6-Chloro-5-(2-chloro-6-fluorophenyl)-4-isopropylamino- 00 2-(l-pyrazolyl)pyrimidine eC 15 A solution of 180 mg (2.64 mmol) of pyrazole in 4 ml of anhydrous DMF was treated with 106 mg (2.64 mmol) of NaH (60% suspension in mineral oil), with ice-cooling. After the mixture had been stirred for one hour, 500 mg (1.32 mmol) of the product of step d were added and the mixture was stirred for approximately 14 hours at 20 to 250C. The product was precipitated by adding water.

Filtration, washing with water and drying gave 450 mg of the title compound as colorless crystals of m.p. 185-1870C.

Example 2: (S)-6-Chloro-4-(2,2,2-trifluoro-l-methylethyl)amino- 5-(2,4,6-trifluorophenyl)-2-(l-pyrazolyl)pyrimidine [1-2] a) 5-(2,4,6-Trifluorophenyl)-2-methylthio-4,6(1H,5H)pyrimidinedione Analogously to Example 1 (step 200.0 g of diethyl 2-(2,4,6-trifluorophenyl)malonate, 62.9 g of thiourea and 117.4 g of methyl iodide gave 115 g of white crystals of m.p. 275 0

C

(decomp.).

b) 4,6-Dichloro-5-(2,4,6-trifluorophenyl)-2-methylthiopyrimidine The following Example 1 (step 64.8 g of the product of step a gave, after chromatography on silica gel with cyclohexane, 43 g of white crystals of m.p. 750C.

c) (5)-6-Chloro-5-(2,4,6-trifluorophenyl)-4-(2,2,2-trifluoro- 2-methylethylamino)-2-methylthiopyrimidine A solution of 90.0 g (277 mmol) of the product of step b and 120.0 g (113 mmol) of 2,2,2-trifluoro-l-methylethylamine was stirred for five days at 150oC. After dilution with methyl tert-butyl ether and washing with 5m [sic] hydrochloric acid, the 00 3 phases were separated. The organic phase was dried and then freed from solvent. Chromatography on silica gel (cyclohexane, then ct cyclohexanelmethyl tert-butyl ether 85:15) gave 90 g of the title compound as colorless crystals of m.p. 94-960C.

d) (S)-6-Chloro-5-(2,4,6-trifluorophenyl)-4--(2,2,2-trifluoro- 1-methylethylamino) -2-methylsulfonylpyrimidine Analogously to Example 1 (step 90.0 g (424 mmol) of the product of step c gave 89 g (92% of theory) of white crystals of M.P. 159 0

C.

00e) (S)-6-Chloro-4-(2,2,2-trifluoro-l-fethylethyl)amino- 5-(2,4,6-trifluorophenyl)-2-(l-pyrazolyl)pyrimfidine Analogously to Example 1 (step 17.0 g (39.2 mmol.) of the product of step d and 4.00 g (58.8 mxnol) of pyrazole gave 14.9 g of theory) of the tit].e compound in the form of colorless crystals of M.p. 209 0 C (purity 97% according to HPLC analysis).

Example 3: (S)-6-Chloro-4-(2,2,2-trifluoro-l-methylethyl)amino- 5-(2,4,6-trifluorophenyl)-2-(l-imidazolyl)pyrimidile [1-3) Analogously to Example 1 (step 89.8 mg of imidazole and 249.5 g of the sulfone of Example 1, in step d, gave 0.22 g (91% of theory) of the title compound in the form of colorless crystals of m.p. 172-1730C.

Example 4: (S)-6-chloro-4-(2,2,2--trifluoro-1-methylethyl)amino- 5-(2,4,6-trifluorophenyl)-2-(l,2,4-triazol-l-yl)pyrimidine (1-4] Analogously to Example 1 (step 91.1 mg of 1,2,4-triazole and 24.95 g of the sulfone of Example 1, step d, gave 0.22 g (91% of theory) of the title compound in the form of colorless crystals of M.p. 176-177 0

C.

Example 6-Chloro-5-(2,4,6-trifluorophenyl)-4-[ (S)-1,2-dimethyl-propyl]amino-2-(pyridazin-3-yl)-pyrimidile a) Pyridazine-3-carboxamfidine A solution of 1.60 g (0.068 mol) of sodium in 300 ml of anhydrous methanol was treated with a solution of 53.5 g (0.510 mol) of pyridazine-3-carbonitrile in 100 ml of methanol and the mixture was stirred for 8 hours at 350C. Then, 29 g of ammonium chloride were added and the mixture was ref luxed for approximately 00 36 14 hours. The hot mixture was filtered and the solid was Cr discarded. 53.3 g of the title compound were obtained from the cold mother liquor by means of filtration.

1 H NMR: 6 (ppm, DMSO-d 6 9.75 9.6 8.6 8.1 b) 4,6-Dihydroxy-5-(2,4,6-trifluorophenyl)-2-(3-pyridazinyl)pyrimidine A mixture of 18.1 g (0.063 mol) of diethyl 2-(2,4,6-trifluorophenyl)malonate, 12 g (0.063 mol) of O tributylamine and 10.0 g (0.063 mol) of the amidine of Ex. 5a was 00 heated for approximately 6 hours at 1800C, during which process ethanol distilled off. After cooling to 60-700C, the mixture was C 15 treated with 6.3 g (0.158 mol) of sodium hydroxide, dissolved in ml of water, and stirring was continued for 30 minutes. After cooling to 20-250C, the mixture was extracted with MTBE, and the reaction product was precipitated from the aqueous phase by acidification. Filtration gave 6.0 g of the title compound.

1 H NMR: 6 (ppm, DMSO-d 6 9.5 8.2 8.0 7.2 c) 4,6-Dichloro-5-(2,4,6-trifluorophenyl)-2-(3-pyridazinyl)pyrimidine A suspension of 5.7 g (0.018 mol) of the dihydroxypyrimidine of Ex. 5b in 37 g (0.23 mol) of phosphorus oxychloride was heated for 8 hours at 1200C and then concentrated in vacuo. The residue was taken up in dichloromethane and water, and the organic phase was dried and freed from solvent. Chromatography on silica gel (cyclohexane/ethyl acetate) gave 2.0 g of the title compound.

1 H NMR: 6 (ppm, CDC1 3 9.2 8.7 7.8 6.9 d) 6-Chloro-5-(2,4,6-trifluorophenyl)-4-[(S)-1,2-dimethylpropyljamino-2-(pyridazin-3-yl)-pyrimidine A solution of 200 mg (0.568 mmol) of the dichloride of Ex. 5c in ml of DMF was treated with 100 mg (1.2 mmol) of (S)-3-methyl-2-butylamine and the mixture was then stirred for 72 hours at 50 0 C and then cooled to 20-250C. The reaction product was precipitated by addition of water. Filtration gave 200 mg (100% of theory) of the title compound.

1H NMR: 6 (ppm, CDC1 3 9.3 8.5 7.6 6.9 4.4 1.8 1.1 0.9 2008201017 04 Mar 2008 Table I

R~RR

5

R

7

N-

R'R9 2 6 8 Physical data No. R R 2

R

3 R R R 6

R

7

R

8

R

9 (M-p.[OCJ, 1 H NMM[ppml; 1ogP 0 I-1 pyrazolyl-1 Cl CH(CH 3 2 H C1 F H H H 185-187 1-2 pyrazolyl-l Cl CH(CH 3

)CF

3 H F F H H F 159 1-3 imidazolyl-l Cl CH(CH 3 )CF3 H F F H H F 203-205 1-4 1,2,4-triazolyl-1 Cl CH(CH 3

)CF

3 H F F H H F 112-114 pyridazinyl-3 Cl F F H H F 176

CH(CH

3

)CH(CH

3 2 1-6 pyrimidinyl-2 Cl(R) H Cl F H H H 228 3

)CH(CH

3 2 1-7 pyrimidinyl-2 Cl CH(CH 3 2 H Cl F H H H 157 1-8 pyrimidinyl-2 Cl C-C 5

H

9 H Cl F H H H 167 1-9 pyrimidinyl-2 Cl CH 2

CH

3

CH

2

CH

3 C1 F H H H logP 0 w 3. 86 pyrimidinyl-2 C1 F H H H 224-226

CH(CH

3

)C(CH

3 3 I-i pyrimidinyl-2 Cl CH(CH 3 2 H F F IH H IF logP 0 3. 2008201017 04 Mar 2008 Physical data No. RR2R 3

R

4

R

5

R

6

R

7

R

8

R

9 (M.p-[OCJ, 1 H NMR[ppMJ; 0.9 1.1 (dd,3H); 11 yaiy 1(S) H 1 F H H H 4.4 7.2 (m,1H); 1-12pyrziny Cl CH(CH 3

)C(CH

3 3 H7.45H H 8.7 (s,1H); 8.8 9.7 (s,LH) 1-13 pyrazinyl Cl CH(CH 3 2 H CI F H H H 153 1-14 pyrazinyl Cl CH 2

CH

3

CH

2

CH

3 C1 F H H H logP 0 w 4.49 0.9 1.1 (m,2H); 1.6 (ni,3H); 2.9 (rn,2H); 1-15 pyrazinyl C1 -(CH 2 2

-CH(CH

3

)-(CH

2 2 C1 F H H H 4.1 7.1 (t,1H); 7.4 8.7 (s,1H); 8.8 9.65 (s,1H) 1.1 1.45 (s,3H); 3.3 3.6 (m,1H); 1-16 pyrainy C1 H2C=CH2CH3 CH2C3 C F H H H 3.'9 (dd,2H); 4.8 (m,2H); 1-1 pyaziyl l C 2 C(CH)CH CHCH 3 Cl H H 7.1 7.3 (rn,1H); 7.4 8.65 (d,1H); 8.8 9.6 (s,1H) 1.15 4.7 (d,1H); 1-17 pyrzinl C (S CH(H3)F3 C1 F H H H 5.3 7.2 (m,1H); 1-1 pyaznylCl S)CH(H 3

CF

3 H C F H7HH 5 8.7 (s,1H); 8.8 9.6 (s,1H) 1-18 pyrazinyl Cl CH(CH 3 2 H F F H H F logP 0 w 4. 7 1-19 pyrazinyl Cl CH(CH 3

)CH

2

CH

3 H F F H H F 175-176 1-20 prznlC1 CH 2

CH

3

CH

2

CH

3 F F H H F ogP,, 4.41 2008201017 04 Mar 2008 Physical data No. RI R2 3 R4 RS R 6

R

7 R8 R 9 0 1 H NMRfppm]; 1-21 pyrazinyl C1 CH(CH 3 2

CH

3 F F H H F logP 0 w 4.48 1-22 pyrazinyl C1 CH 2

C(CH

3 3 H F F H H F logP,, 4.72 1-23 pyrazinyl C1 CH(CH 3

)CF

3 H F F H H F 188 1.1 1.4 (s,3H); 3.9 (s,2H); 1-24 pyrazinyl Cl CH 2 C (=CH 2

)CH

3

CH

2

CH

3 F F H H F 4.8 6.8 (t,2H); 8.7 8.8 (s,1H); 9.6 (s,1H) 1-25 pyrazinyl Ci. H F F H H F 128

~~~~CH(CH

3

)C(CH

3 3 1-26 pyridaziriyl-3 Cl CH(CH 3

)C(CH

3 3 H F F H H F 126 1-27 pyrazoly.-1 Cl H H F F H H F 317-319 1-28 imidazolyl-1 Cl CH(CH 3 2 H C1 F H Hi H 172-173 1-29 1,2,4-triazolyl-1 Cl CH(CH 3 2 H Cl F H H H 176-177 1-30 Tetrazolyl-1 Cl CH(CH 3 2 H Cl F H H H 171-175 1-31 1,2,5-triazolyl-1 C1 CH(CH 3 2 H Cl F H H H 170-173 1-32 1,2,3-triazolyl-1 C1 CH(CH 3 2 H Cl F H H H 153-157 1-33 3-CF 3 -pyrazolyl-1 C1 CH(CH 3 2 H Cl F H H H 184-186 1-34 4-Br-pyrazolyl-1 Cl CH(CH 3 2 H Cl F H H H 128-132 1-35 3-CH 3 -pyrazolyl-1 C1 CH(CH 3 2 H Cl F H H H 174-179 1-36 pyrazolyl-1 Cl CH(CH 3 2 H F F H H F 206-209 2008201017 04 Mar 2008 I Physical data No. RI 2 R3R 4 R~S R 6

R

7 R8 R 9 (M-P.[OCJ, 1 H Nl.R[ppmj; I___logP" 1-37 1,2,4-triazolyl-1 C1 CH(CH 3 2 H F T F H H F 212-214 1-38 irnidazolyl-1 C1 CH(CH 3 2 H F F H H F 215-216 1-39 3-CF 3 -pyrazolyl-1 CI CH(CH 3 2 H F F H H F 234-236 1.2 (d,6 4.3 (m,1H); 1-40 4-Br-pyrazolyl-1 Cl CH(CH 3 2 H F F H H F 4.7 6.85 (m,2H); 7.8 8.4 (S..1H) 1.2 (d,6 4.3 (m,2H); 1-41 3-CH 3 -pyrazolyl-1 C1 CH(CH 3 2 H F F H H F 6.2 6.8 (m,2H); 8.4 (d,1H) 1-42 3, 5-(CH 3 2 ,4-Cl- Cl CH(CH 3 2 H F F H H F 241-244 pyrazolyl-1 1-43 3, 5-(CH 3 2 C1 CH(CH 3 2 H F F H H F 206-211 pyrazolyl-1 1-44 N Cl CH(CH 3 2 H F F H H F 179-184 1-45 3-[CH(CH 3 2 Cl CH(CH3) 2 H F F H H F 229-235 pyrazolyl-1 1-46 5-N0 2 -pyrazolyl-1 Cl CH(CH3) 2 H F F H H F 188-194 1-47 4-CH 3 -pyrazolyl-1 Cl CH(CH 3 2 Hi F F H H F 172-174 1-48 4-(4-CH 3

-C

6

H

4 Cl CH(CH 3 2 H F F H H F 197-201 pyrazolyl- 1 1-49 1H-Indazolyl-1 Cl CH(CH 3 2 H F F IH IH IF 192-194 2008201017 04 Mar 2008 Physical data No. R 1 RR3R 4

R

5

R

6

R

7

R

8

R

9 (M.p.[OCJ, 1 H NMR[ppml; ogp" 1-50 3-C 6

H

5 -pyrazolyl-1 C1 CH(CH 3 2 H F F H H F 196-198 1-51 11,2,3-triazolyl-1 C1 CH(CH 3

)CF

3 H F F H H F 160-163 1-52 1,2,5-triazolyl-l Cl CH(CH 3

)CF

3 H F F H H F 172-173 1-53 4-CH 3 -pyrazolyl-l C1 CH(CH 3

)CF

3 H F F H H F 214-218 1-54 4-Br-pyrazolyl-l Cl CH(CH 3

)CF

3 H F F H H F 160-163 1-55 3,5-(CH 3 2 ,4-C1- Cl CH(CH 3

)CF

3 H F F H H F 235-238 pyrazolyl-1 1-56 3-C 6

H

5 -pyrazolyl-l C1 CH(CH 3

)CF

3 H F F H H F 185-190 1-57 0 2 N -Q N Cl CH(CH 3

)CF

3 H F F H H F 165-168 1-8 3[HC32- Cl CH(CH 3

)CF

3 H F F H H F 270-273 1-59 3-CF 3 -pyrazolyl-1 C1 CH(CH 3

)CF

3 H F F H H F 253-255 1-60 5-N0 2 -pyrazolyl-1 Cl CH(CH 3

)CF

3 H F F H H F 222-224 N, 1.3 2.3 (s,3H); ,NN# 3.0 3.8 (s,3H); 1-61 H 3 C -Cl CH(CH3)CF 3 H F F H H F 4.8 (bm,1H);

CH

3 0: CH 3 5.2 (bm,1H); 6.9 (m,2H); 7.1-7.4 (bm,4H) 1-62 4-(4-CH 3

-C

6

H

4 Cl CH(CH 3

)CF

3 H F F H H F 214-216 pyrazolyl-1 I__I _III_ _II

III

2008201017 04 Mar 2008 Physical data No. RR2R 3

R

4 RS R 6

R

7 RS R 9 (M-p.[OCI, 1 H NMR[pprnl; logPOW 1-63 3, 5-(CH 3 2 4-1I- Cl CH(CH 3

)CF

3 H F F H H F 228-232 pyrazolyl-1 1-64 pyrazoly-r Cl CH(CH 3

)CF

3 H F F H H F 242-244 1-65 4-I-pyrazolyl-1 Cl CH(CH 3

)CF

3 H F F H H F 194-196

F

3 C )N 1-66 Cl CH(CH 3

)CF

3 H F F H H F 214-6

H

3

CODC

1-67 Br 3 -pyrazolyl-1 Cl CH(CH 3

)CF

3 H F F H H F 206-209 1-68 3,5-(CH 3 2 ,4-Br- Cl CH(CH 3

)CF

3 H F F H H F 258-261 pyrazolyl-l 1-69 4-Cl-pyrazolyl-1 Cl CH(CH 3

)CF

3 H F F H H F 185-188 1-70 H 3 C /Cl

CH(CH

3

)CF

3 H F F H H F 180-182

______COOCH

2 CH 3 1-71 3-CH 3 4-Cl- C (S HC3F H F F H H F247-249 pyrazolyl-1 Cl H F F H H F 1-72 3-NO 2 C S HCAF 3-3 1,2,4-triazolyl-1 Cl IS

CIC

3 )F 1 F1 3-3 1-73 3-N0 2 ,5-Br- ()C(HC3 H FIF H ___1,2.4-triazolyl-1 Cl 1S

HC

3

C

3 H F F H H 2008201017 04 Mar 2008 Physical data No. RIR 2

R

3

R

4 RS R 6

R

7 RO R 9 0 CJ, 1 H NMR[ppmj; 1-74 6-ll-ez-raCl CH(CHA 3

CF

3 H F F H H F 140-142 1-75 1 H-benzo- Cl CH(CH 3

)CF

3 H F F H H F 100-102 triazolyl-1 1-76 6-CH 3 -1H-benzo-tri Cl CH(CH 3

)CF

3 H F F H H F 118-121 azolyl-1 1-77 6 azo2lyl.eno..1 Cl CH(CH 3

)CF

3 H F F H H F 130-133 1-78 7jj>Cl CH(CH 3

)CF

3 H F F H H F 140-143 1-79 1Hlbenzo- l H F F H H F 127-130 imidazolyl-1 Cl HCHCF 1-80 imidazolyl-1 Cl CH(CH 3

)CF

3 H F F H H F 132-135 0 H C 1-81 30)Cl CH(CH 3

)CF

3 H F F H H F 125-127 0.9 1.1 (m,2H); 1-82 imidazolyl-1 C1 -(CH 2 2

-CH(CH

3

)-(CH

2 2 F F H H F 4.0 6.8 (rn,2H); 7.9 8.4 (5,1H) 2008201017 04 Mar 2008 Physical data No. R1R 2 R3R 4

R

5

R

6

R

7

R

8

R

9 0 Cj, IH NMR~ppm]; logP" 1-83 1,2,4-triazolyl-1 C1 (CH 2 2 -CH (CH 3

-(CH

2 2 F F H H F 95-98 1-84 1.2,3-triazolyl-1 C1 -(CH 2 2

-CFI(CH

3

)-(CH

2 2 F F H H F 124-128 1-85 3,5r(CHo)2,-Cl C1 -(CH 2 2

-CH(CH

3

)-(CH

2 F F H H F 146-148 1-86 3,yrazoly Cl -(CH 2 2 -CH (CH 3

-(CH

2 2 F F H H F 127-131 1-87 3-C 6

H

5 -pyrazolyl-1 Cl -(CH 2 2

-CH(CH

3

-(CH

2 2 F F H H F 179-181 1-88 3-CF 3 -pyrazolyl-1 Cl -(CH 2 2 -CH (CH 3

-(CH

2 2 F F H H F 101-102 1-89 5-N0 2 -pyrazolyl-1 C1 -(CH 2 2 -CH (CH 3

-(CH

2 2 F F H H F 158-161 1-90 H 3 COOC /N C1 -(CH 2 2

-CH(CH

3

)-(CH

2 2 F F H H F 110-112

OH

1-91 1H-indazolyl-1 C1 -(CH 2 2

-CEI(CH

3

-(CH

2 2 F F H H F 145-150 1-92 3,5- (CH 3 2 1 4-1- C1 -(CH 2 2

-CH(CH

3

-(CH

2 2 F F H H F 158-161 pyrazolyl-1 1-93 pyrazolyl..1 C1 -(CH 2 2 -CH(C11 3

-(CH

2 2 F F H H F 136-138 1-94 Br 3 -pyrazolyl-1 Cl -(CH 2 2

-CH(CH

3

-(CH

2 2 F F H H F 121-125 4-I-pyrazolyl-1 Cl -(CH 2 2

-CH(CH

3

)-(CH

2 2 F IF IH IH F 174-177 2008201017 04 Mar 2008 Physical data No. R1 2 R 3 R 4 RS R 6 R7 R8 R 9 (M.P.1 0 1 H NMR[ppmJ; logp 0.9 1.1 (ni,2H); 1.4 2.4 (s,3H); 1-96 3-CH 3 -pyrazolyl-1 C1 -(CH 2 2

-CH(CH

3

)-(CH

2 2 F F H H F 2.8 4.1 (m,2H); 6.2 6.8 (ni,2H); 8.3 (d,1H) 1-97 4-Br-pyrazolyl-1 C1 -(CH 2 2

-CH(CH

3

)-(CH

2 2 F F H H F 131-134 0.9 1.1 (m,2H); 3-[CHCH3)21.2 1.4 (m,3H); 1-98 3[CH(CH 3 2 C1 -(CH 2 2

-CH(CH

3

)-(CH

2 2 F F H H F 2.9 (rn,2H); 4.0 (m,2H); pyrzoll-16.2 6.8 (m,2H); 8.4 (S,LH) 1-99 3,5-(CH 3 2 ,4-Br C1 -(CH 2 2

-CH(CH

3

)-(CH

2 2 F F H H F 131-134 pyrazolyl-1 I-100 4-CI-pyrazolyl-1 C1 -(CH 2 2

-CH(CH

3

)-(CH

2 2 F F H IH F 150-152

C-C

5

H

9 =cyclopentyl denotes the bond with the pyrimidinyl skeleton of formula I 00 46 C The lipophilicity parameters logPow (Table I) were determined as specified by OECD directive test guidelines using the RP-HPLC run time method.

To this end, a logk'/logPow correlation curve based on ten reference substances was plotted and validated with the aid of the lipophilicity parameters of eight comparative substances, which had been established by the extraction method.

0 -4 A commercially available reversed-phase Ce stationary phase was Sused as stationary phase. Chromatographic separation was carried 00 out with methanol and a buffer solution as mobile phase at pH 7.4 under isocratic conditions.

Cq The retention times of the standards tR were converted in accordance with equation into the capacity factors where to, as reaction time of the solvent unretarded on the reversed-phase C 18 stationary phase, represents the dead time of the chromatographic system: tR to k' to The linear correlation of the logk' values with the logPow values of the standards published in the appendix to the Directive 92/69/EEC yields the correlation curve through linear regression.

The lipophilicity parameters logPow of the analytes were interpolated from the correlation curve of the standards after calculation of the logarithmic capacity logk'.

The validation of the RP-HPLC analytical method described, and of the standards used, is carried out with the aid of eight comparison active compounds, the distribution behavior of which was determined with the aid of the extraction method.

Examples for the action against harmful fungi The fungicidal action of the compounds of the general formula I was demonstrated by the following experiments: The active compounds were prepared, separately or together, as a 10% emulsion in a mixture of 70% by weight of cyclohexanone, by weight of Nekanil® LN (Lutensol® AP6, wetting agent with emulsifying and dispersing action, based on ethoxylated 00 47 alkylphenols) and 10% by weight of wettol® EM (nonionic C emulsifier, based on ethoxylated castor oil) and were diluted Swith water to give the desired concentration.

Use example 1 Activity against Alternaria solani on tomatoes Leaves of pot plants cv. "GroJe Fleischtomate St. Pierre" were sprayed to runoff point with.an aqueous suspension prepared from Sa stock solution consisting of 10% of active compound, 63% of cyclohexanone and 27% of emulsifier. On the following day, the leaves were infected with an aqueous suspension of Alternaria solani zoospores in 2% Biomalz solution at a concentration of 00 0.17 x 106 spores/ml. The plants were subsequently placed in a water-vapor-saturated chamber at temperatures between 20 and 220C.

15 After 5 days, early blight in the untreated, but infected, control plants had developed to such an extent that the disease level could be determined visually in In this test, the plants treated with 63 ppm of the active substances I-1, 1-4, 1-12 to 1-14, 1-19 bis 1-23, 1-29, 1-31, 1-32, 1-35 to 1-37, 1-40, 1-41, 1-46, 1-47, 1-51, 1-52, 1-54 and 1-60 showed no disease or a disease level of up to while the untreated plants showed a disease level of 100%.

Use example 2 Curative activity against Puccinia recondita on wheat (wheat leaf rust) Leaves of wheat seedlings cv. "Kanzler" in pots were dusted with leaf rust (Puccinia recondita) spores. Thereafter, the pots were placed for 24 hours into a chamber with high atmospheric humidity (90-95%) and 20 to 220C. During this time, the spores germinated, and the germination tubes penetrated the plant tissue. On the next day, the infected plants were sprayed to runoff point with an aqueous active substance preparation prepared from a stock solution consisting of 10% of active substance, 63% of cyclohexanone and 27% of emulsifier. After the spray coating had dried on, the test plants were grown in the greenhouse for 7 days at temperatures between 20 and 220C and a relative atmospheric humidity of 65 to 70%. The extent of rust development on the leaves was then determined.

In this test, the plants treated with 63 ppm of the active substances I-1 and I-2 showed a disease level of not more than while the untreated plants showed a disease level of O0 48 0 Use example 3 Activity against barley net blotch disease SLeaves of barley seedlings cv. "Igri" in pots were sprayed to Srunoff point with an aqueous suspension prepared from a stock solution consisting of 10% of active substance, 63% of cyclohexanone and 27% of emulsifier and, 24 hours after the spray coating had dried on, inoculated with an aqueous spore suspension of Pyrenophora teres, the net blotch disease pathogen.

The test plants were subsequently placed in the greenhouse at temperatures between 20 and 24 0 C and a relative atmospheric «s humidity of 95 to 100%. After 6 days, the extent of the disease 00 level was determined visually in diseased overall leaf area.

CA 15 In this test, the [lacuna] with 63 ppm of the active substances I-1, I-4, 1-12 to 1-14, 1-19 to 1-23, 1-29, 1-32, 1-35 to 1-37, 1-40, 1-41, 1-47, 1-51, 1-52, 1-54 and I-60 showed no disease or a disease level of up to 10%, while the untreated plants showed a disease level of Use example 4: Activity against Botrytis cinerea on capsicum leaves Capsicum seedlings cv. "Neusiedler Ideal Elite" were allowed to fully develop 4 to 5 leaves and then sprayed to runoff point with an aqueous active substance preparation which had been prepared from a stock solution consisting of 10% of active compound, of cyclohexanone and 5% of emulsifier. On the next day, the treated plants were inoculated with a spore suspension of Botrytis cinerea, which contained 1.7 x 106 spores/ml in a 2% aqueous Biomalz solution. The test plants were subsequently placed into a control/environment cabinet at 22-24 0 C and high atmospheric humidity. After 5 days, the extent of fungal infection on the leaves was determined visually in In this test, the (lacuna] with 250 ppm of the active substances I-1, 1-3, 1-4, I-7 to 1-9, I-11 to 1-14, I-18 to 1-23, 1-29 to 1-32, 1-35 to 1-37, 1-40, 1-47, 1-51, 1-52, 1-54, 1-60, 1-77, 1-78 and I-80 showed no disease or a disease level of up to 7%, while the untreated plants showed a disease level of Use example 5: Protective activity against powdery mildew of cucumbers caused by Sphaerotheca fuliginea Leaves of cucumber seedlings cv. "Chinesiche Schlange" in pots were sprayed, at the cotyledon stage with an aqueous active substance preparation which had been made with a stock solution 00 49 0 consisting of 10% active substance, 85% of cyclohexanone and C of emulsifier. 20 hours after the spray coating had dried on, the plants were inoculated with an aqueous spore suspension of Scucumber powdery mildew (Sphaerotheca fuliginea). The plants were subsequently grown in the greenhouse for 7 days at temperatures between 20 and 240C and a relative atmospheric humidity of 60 to The extent of mildew development was then determined visually in diseased cotyledon area.

In this test, the [lacuna] with 63 ppm of the active substances I-1, 1-4, 1-12 to 1-14, 1-19 to 1-23, 1-29, 1-31, 1-32, 1-35, 1-36, 1-41, 1-47, 1-52, 1-54 and I-60 showed no disease, while 00 the untreated plants showed a disease level of 100%.

(C 49a 1. Experimental Report (bioloQical testinQ) Example 1-1 -Action against grey mould on pepper leaves caused by Botrytis cinerea Pepper seedlings of the "Neusiedler Ideal Elite" variety were sprayed to runoff with an aqueous suspension having the below mentioned concentration of active ingredient after 4 to 5 leaves had developed sufficiently. The suspension or emulsion was prepeared from a stock solution with 10 active ingredient in a mixture containing 85 cyclohexanone and 5 emulsifier. On the following day, the treated plants were inoculated with a spore suspension of Botrytis cinerea containing 1.7 x 106 spores/ml in a 2 aqueous Biomalz solution. The test plants were then placed in a climatic chamber at 22 to 24"C and high humidity. After 5 days the extent of fungus attack on the leaves could be assessed visually in Compounds tested and results:

R

3 attack after application of compd aqueous No. R 1

R

3

R

4

R

s

R

6 R' preparation (table I) containing 63 ppm active ingredient pyridazin-3-yl CH(CH 3 )CH H F F F 0

(CH

3 2 1-12 pyrazinyl CH(CH 3 H Cl F H 0

C(CH

3 3 1-13 pyrazinyl CH(CH 3 2 H Cl F H 0 1-14 pyrazinyl CH 2

CH

3

CH

2

CH

3 Cl F H 0 1-19 pyrazinyl CH(CH 3

)CH

2

CH

3 H F F F 0 1-20 pyrazinyl CH 2

CH

3

CH

2

CH

3 F F F 0 1-21 pyrazinyl CH(CH 3 2

CH

3 F F F 0 1-22 pyrazinyl CH 2

C(CH

3 3 H F F F 0 1-35 3-methylpyrazol-l-yl CH(CH 3 3 H CI F H 3 untreated control 100 49b Example 1-2 Action against mildew of wheat caused by Erysiphe [svn. Blumeria] graminis forma specialis tritici Leaves of pot plants of wheat seedling cv. "Kanzler" were sprayed until dripping with an aqueous suspension having a concentration of the active ingredient as given below. The suspension or emulsion was prepared from a stock solution with 10 active ingredient in a mixture containing cyclohexanone and 5 emulsifier. 24 hours after the spray coating had dried on, the test plants were dusted with spores of mildew of wheat (Erysiphe [syn. Blumeria] graminis forma specialis. triticl). Thereafter, the test plants were placed in a greenhouse at temperatures between and 24"C and a relative atmospheric humidity of 60 to 90 After 7 days, the extent of mildew development was determined visually in of the whole leaf area.

Compounds tested and results: attack after compd. application of No. R 1

R

3

R

4

R

5

R

6

R

9 aqueous preparation (table 1) containing 63 ppm active ingredient 1-20 pyrazinyl CH 2 CH3 CH 2

CH

3 F F F 1-21 pyrazinyl CH(CH 3 2

CH

3 F F F 7 1-22 pyrazinyl CH 2

C(CH

3 3 H F F F 1-24 pyrazinyl CH 2

C(=CH

2

)CH

3

CH

2

CH

3 F F F 0 1-35 3-methyl pyrazol-l-yl CH(CH 3 2 H Cl F H untreated control 49c 00 2. Experimental report (biological testing)

O

The active compounds were prepared as a stock solution with 25 mg topped up ad 10 ml with a mixture of c acetone and/or DMSO and the emulsifier Uniperol® EL (wetting agent having emulsifying and dispersing action based on ethoxylated alkyl phenols) having a volume ratio solvent-emulsifier of 99 to 1. Then, the 5 solution was topped up ad 100 ml with water. This stock solution was diluted with the described mixture of solvent-emulsifier-water to the below concentration of active ingredient.

Example 2-1 Action against early blight on tomatoes caused by Alternaria solani (protective application) Leaves of pot plants cv. "Goldene Konigin" were sprayed until dripping with an aqueous suspension having a concentration of active ingredient as given below. On the following day, the leaves were OO inoculated with an aqueous spore suspension of Alternaria solani in 2 Biomalz solution with a density of S0.17 x 106 spores/ml. Then, the plants were placed in a water vapor-saturated chamber at temperatures l between 20 and 22°C. After 5 days, the disease had developed strongly on the untreated but inoculated control plants such that the attack could be determined visually in Example 2-2 Action against grey mould on pepper leaves caused by Botrytis cinerea (protective application) Pepper seedlings of the "Neusiedler Ideal Elite" variety were sprayed to runoff with an aqueous suspension having the below mentioned concentration of active ingredient after 2 to 3 leaves had developed sufficiently. On the following day, the treated plants were inoculated with a spore suspension of Botrytis cinerea containing 1.7 x 106 spores/ml in a 2 aqueous Biomalz solution. The test plants were then placed in a climatic chamber at 22 to 24°C, darkness and high humidity. After 5 days the extent of fungus attack on the leaves could be assessed visually in Example 2-3 Action on downy mildew on grape vines caused by Plasmopara viticola Leaves of potted vines were sprayed until dripping with an aqueous suspension having the below mentioned concentrations of active ingredients. On the following day, the undersides of the leaves were inoculated with an aqueous zoospore suspension of Plasmopara viticola. Then, the vines were first kept in a water vapor-saturated chamber at 24*C for 48 h, and then placed in a greenhouse at temperatures between 20 and 30°C for 5 days. To accelerate the sporangiophore discharge, the plants were then again placed in the moist chamber for 16 hours. The extent of fungus attack development was then assessed visually on the undersides of the leaves.

Example 2-4 Action on barley net blotch caused by Pyrenophora teres (protective application) Leaves of potted barley seedlings were sprayed until dripping with an aqueous suspension having the below mentioned concentration of active ingredients. 24 h after the spray coating had dried on, the test plants were inoculated with an aqueous spore suspension of the barley net blotch pathogen Pyrenophora [syn. Drechslera] teres. Then, the test plants were placed in the greenhouse at temperatures between and 24"C and 95 to 100 relative humidity. After 6 days the extent of the disease development was assessed visually in infection on the total leaf area.

49d Compounds tested: N R H4 R NI R H compound R3 R 4 R_ 5 R a thiazol-2-yI 4-methylpiperidin-1 -yI F F F b 5-methyl-[1 ,3,4]-oxadiazol-2-yI CH(CH 3

)(C

2

H

5 H F F F

C

2-furyl CH(CH 3

)CH(CH

3 2 H F F F 3,5-diaminoisoxazol-4-y 4-methylpiperidin-I -yI F F jF Results: attack at attack at attack at attack at compound 250 ppm 250 ppm 250 ppm 250 ppm Ex. 2-1 Ex. 2-2 Ex. 2-3 Ex. 2-4 a 0 b 0 3 c 3 d untreated control 100 75 80 49e oo 3. Experimental report (biological testing microtiter tests)

O

The active compounds were formulated separately as a stock solution having a concentration of 10 000 ppm in DMSO for the microtiter test (MT).

"t 5 Example 3-1 Activity against the rice blast pathogen Pyricularia oryzae in the microtiter test The stock solution was pipetted onto a microtiter plate (MTP) and diluted to the stated active compound concentrate using a malt-based aqueous nutrient medium for fungi. An aqueous spore suspension of SPyricularia oryzae was then added. The plates were placed in a water vapor-saturated chamber at 00 10 temperatures of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm on day 7 0after the inoculation. The measured parameters were compared to the growth of the active compound- CN free control variant and the fungus- and active compound-free blank value to determine the relative growth in of the pathogens in the individual active compounds.

Example 3-2 Activity against the speckled leaf blotch pathogen Septoria tritici in the microtiter test The stock solution was pipetted onto a microtiter plate (MTP) and diluted to the stated active compound concentrate using a malt-based aqueous nutrient medium for fungi. An aqueous spore suspension of Septoria tritici was then added. The plates were placed in a water vapor-saturated chamber at temperatures of 18*C. Using an absorption photometer, the MTPs were measured at 405 nm on day 7 after the inoculation. The measured parameters were compared to the growth of the active compound-free control variant and the fungus- and active compound-free blank value to determine the relative growth in of the pathogens in the individual active compounds.

Compounds tested:

R

3 R N

R

5

H

N

N-

Cl R 6

H

compound R' R 3

R

4 R' R' R e thien-2-yl CH(CH 3 2 H F F F f N-methylpyrrol-2-yl CH(CH 3

)CH(CH

3 2 H F F F (isomer 1) g N-methylpyrrol-2-yl Cyclopentyl H F F F h N-methylpyrrol-2-yl CH(CH 3

)CH(CH

3 2 H F F F (isomer 2)_ Results: growth in growth In compound atl125 ppm atl125 ppm Ex. 3-1 Ex. 3-2 e 1 f 0 0 g 0 0 h 1 4. Experimental report (physical data) Physical data of the inventive compounds to (h) compound physical data a melting point 159-1 60 TC b melting point 153-1 57 00 c melting point 112-1 14 00 d melting point 171-1 74 00 e melting point 103-105 TC f, (isomer 1) RT-MSD* 4,463; mass 409,15 g RT-MSD* 4,434; mass 407,15 h, (Isomer 2) RT-MSD* 4,461; mass 409,15 *RT-MSD: retention times resulting from HPLC-mass spectrometer (elektrospray) Physical data of inventive compounds compounds to (n) 3-amino-pyrazol-1-yi CI 2,6-dimethyl-morpholin-4- F F F yl 1,2,3-tdazol-1-yl Br 4-methylpiperidin-1-yl F F F k 3,5-dimethyl-[1,2,4]-tnazol-1 -yl Br 4-methylpiperidin-1 -yl F F F L1 ,2,4-triazol-1-yI Br (S HC3C3 H F F F M1 ,2,4-triazol-1-yl I (S HC3C3 H F F F npyrazol-1 -yl -F F S HC3C3 H F F ,F 49g compound physical data melting point 206 °C melting point 100-106 "C melting point 164-170 °C melting point 126-134 °C melting point 101-106 °C melting point 219-227 °C Comparative Examples against US 5,250,530 The active compounds were prepared as a stock solution with 0.25 by weight of active compound in acetone or DMSO. 1 by weight of the emulsifier Uniperol® EL (wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols) was added to this solution, and the solution was diluted with water to the desired concentration.

Example 1: Action aqainst mildew of wheat caused by Ervsiphe fsvn. Blumerial qraminis forma specialis tritici Leaves of pot plants of wheat seedling cv. "Kanzler" were sprayed until dripping with an aqueous suspension having a concentration of the active ingredient as given below. The suspension or emulsion was prepared as given above. 24 hours after the spray coating had dried on, the test plants were dusted with spores of mildew of wheat (Erysiphe [syn. Blumeria] graminis forma specialis. tritici). Thereafter, the plants were placed in a greenhouse at temperatures between 20 and 24 C and a relative atmospheric humidity of 90 After 7 days, the extent of mildew development was determined visually in of the whole leaf area.

"Al N NH F according to F 32 70 US 5,250,530 N N prior art Cl F control (untreated) NH F N N32 100 compound of the present N N' _F 32 invention N N Cl F NH F compound of the present N F 32 invention N N Cl F 49h Example 2: Protective activity against Puccinia recondita on wheat (wheat leaf rust) Leaves of wheat seedlings cv. "Kanzler" in pots were sprayed until dripping wet with an aqueous suspension having a concentration of the active ingredient as given below. On the following day, the treated leaves were dusted with wheat leaf rust (Puccinia recondita) spores. Thereafter, the plants were placed for 24 hours into a chamber with high atmospheric humidity (90 to 95 at 20 and 22 C. During this time, the spores germinated, and the germination tubes penetrated the plant tissue. On the next day, the test plants where placed into the greenhouse again and cultivated at temperatures of 20 to 22 °C and a relative atmospheric humidity of 65 to 70 for additional 7 days. Then, the extent of rust development on the leaves was determined visually in control (untreated) 90

"A"

according to US 5,250,530 32 90 prior art

"B"

Compound of the present 32 20 invention

"C"

Compound of the present 32 40 invention Comprises/comprising and grammatical variations thereof when used in this specification are to be taken to specify the presence of stated features, integers, steps or components or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.

Claims (7)

1. 2. A compound of the formula I as claimed in claim 1, where the variables have the following meanings: R 1 is 2-pyrimidinyl, pyrazinyl or 3-pyridazinyl, R 2 is halogen, C1-CG-alkyl or C1-C 6 -alkoxy; R 3 R 4 independently of one another are hydrogen, C 1 -C 6 -alkyl, C1-C 6 -haloalkyl, C 3 -C 6 -cycloalkyl or C 2 -C 6 -alkenyl; R 3 and R 4 may also, together with the nitrogen atom to which they are bonded, form a five- or six-membered ring which can be interrupted by an oxygen atom and have attached to it a C 1 -C 6 -alkyl substituent; R 5 R 6 independently of one another are hydrogen, halogen or C1-C 6 -alkyl; R 7 R 8 independently of one another are hydrogen or halogen; R 9 is hydrogen, halogen, C1-C 6 -alkyl or C1-C 6 -alkoxy.
2. 3. A compound of the formula I as claimed in claims 1 and 2, where R 2 is chlorine.
3. 4. A compound of the formula I as claimed in any one of claims 1 to 3, where the combination of the substituents R 5 to R 9 have the following meanings: 2- chloro,6-fluoro; 2,6-difluoro; 2,6-dichloro; 2-methyl,4-fluoro; 2-methyl,6-fluoro; 2- fluoro,4-methyl; 2,4,6-trifluoro; 2,6-difluoro, 4-methoxy; 2,4-dimethyl and pentafluoro. A process for the preparation of 5-phenylpyridine of the formula I as claimed in claim 1, in which R' is bonded via carbon and R 2 is chlorine, which process comprises cyclizing a compound of formula XII, where has the meaning of R 1 and is bonded through carbon with an alkyl phenylmalonate of the formula II. NH 2 B NH X11 o 5 R 7 R- R-O o0zfr R in which R is C 1 -C 6 -alkyl to give compounds of the formula Vb O R 5 R o R 1 5 which are converted with chlorinating agents to give the dichloropyrimidines of the formula VIb Cl R 5 R 7 N I Vlb which are reacted with amino compounds of the formula VII 43 RN to give the pyrimidine derivatives of the formula I
4. 6. A 5-phenylpyrimidine of the formula I as claimed in claim 1, substantially as hereinbefore described with reference to the Examples. 00 0 7. Composition suitable for controlling phytopathogenic harmful fungi, the 0 composition comprising a solid or liquid carrier and a compound of the formula I as claimed in claim 1.
5. 8. Composition suitable for controlling phytopathogenic harmful fungi comprising a compound of the formula I as claimed in claim 1, the composition r- being substantially as hereinbefore described with reference to the Examples.
6. 9. A method of controlling phytopathogenic harmful fungi, the method oo comprising treating the fungi or the materials, plants, soil or seeds to be protected 0 against fungal infection with an effective amount of a compound of the formula I as claimed in claim 1 or of a composition as claimed in claim 7 or claim 8. A method of controlling phytopathogenic harmful fungi with an effective amount of a compound of the formula I as claimed in claim 1, the method being substantially as hereinbefore described with reference to the Examples.
7. 11. A process for the preparation of 5-phenylpyridine of the formula I as claimed in claim 1, the process being substantially as hereinbefore described with reference to the Examples. BASF AKTIENGESELLSCHAFT WATERMARK PATENT TRADE MARK ATTORNEYS P23194AU00