ZA200307981B

ZA200307981B - 5-phenylpyrimidine, methods and intermediate products for the production thereof and use of the same for controlling pathogenic fungi.

Info

Publication number: ZA200307981B
Application number: ZA200307981A
Authority: ZA
Inventors: Eberhard Ammermann; Markus Gewehr; Thomas Grote; Andreas Gypser; Gisela Lorenz; Bernd Mueller; Joachim Rheinheimer; Ingo Rose; Hubert Sauter; Frank Schieweck; Peter Schaefer; Reinhard Stierl; Siegfried Strathmann; Jordi Tormo I Blasco
Original assignee: Basf Ag
Priority date: 2001-03-15
Filing date: 2003-10-14
Publication date: 2004-10-14
Also published as: UA76453C2

Description

- 0050/52348 » h,.2003/7981 5-Phenylpyrimidines, their preparation, intermediates for their preparation, and their use for controlling harmful fungi

The present invention relates to 5-phenylpyrimidines of the formula I, 4

RJ R® Rr

N

SC :

N=

R? R® R° in which the substituents have the following meanings:

R1 is a five- to ten-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocycle comprising one to four hetero atoms selected from the group consisting of O, N or S, except for pyridyl, it being possible for R! to be substituted by one to three identical or different groups R?,

R2 is halogen, hydroxyl, cyano, oxo, nitro, amino, mercapto, C;-Cg-alkyl, C;-C¢-haloalkyl, C,-Cg¢-alkenyl,

C,-Cg—-alkynyl, C3-Cg-cycloalkyl, C;-Cgs-alkoxy,

C;-Cs-haloalkoxy, carboxyl, C;-Cy-alkoxycarbonyl, carbamoyl, C;-Cy-alkylaminocarbonyl,

C1-Cg-alkyl-C;-Cg-alkylamincarbonyl, morpholinocarbonyl, pyrrolidinocarbonyl,

C,-C;-alkylcarbonylamino, C;-Cg-alkylamino, di(C;~-Cg-alkyl)amino, C;-Cg-alkylthio,

C;-Cg-alkylsulfinyl, C;-Cg-alkylsulfonyl, hydroxysulfonyl, aminosulfonyl,

C;-Cg-alkylaminosulfonyl, ] di(C;~Ceg-alkyl)aminosulfonyl;

R? is hydrogen, halogen, cyano, C;-Cg-alkyl, C;-Ce-haloalkyl,

C;-C¢-alkoxy, C;-Cy-haloalkoxy or Cj3-Cg-alkenyloxy;

R3, R4 independently of one another are hydrogen, C;-Cg-alkyl, 40 C;-Cg-haloalkyl, C;3-Cg-cycloalkyl, C3-Cg¢-halocycloalkyl,

C,-Cg-alkenyl, C,-Cg-haloalkenyl, C3-Cg-cycloalkenyl,

C,-Cg¢-alkynyl, Cy-Cg¢-haloalkynyl or C3;-Cg-acycloalkynyl,

R3 and R? may also, together with the nitrogen atom to 45 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 O, N and S and/or which can have

0050/52348 AMENDED SHEET ’ attached to it one or more substituents selected from the ) group consisting of halogen, C,-C,-alkyl, C,-Cs-haloalkyl and oxy-C;-C,-alkylenoxy or in which two adjacent C atoms or one N atom and one adjacent C atom can be linked by a

C,-C,-alkylene chain;

R®, R® independently of one another are hydrogen, halogen,

C,-C¢-alkyl, C,-Cs-haloalkyl or C,-Cs-alkoxy;

Rr’, R® independently of one another are hydrogen, halogen,

C,-C.-alkyl or C,-C.-haloalkyl;

R’® is hydrogen, halogen, C,-C,-alkyl, C,-C.-alkoxy,

C,-Cs-cycloalkoxy, C,-C¢-haloalkoxy, C,-C,-alkoxycarbonyl or C,-Cq-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.

Therefore a need exists to provide compounds with an improved activity.

We have found that this need is fulfilled 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 40 harmful fungi compared with the known compounds.

The compounds I can be obtained via various routes.

Compounds of the formula I in which R' is heterocycles bonded via 45 nitrogen and R® is chlorine can be prepared, for example, by the following process:

. 0050/52348 ® ;

The cyclocondensation of thiourea with alkyl phenylmalonates of the formula II gives compounds of the formula III o RR ® 0 R° FR

S R-0 HN

HN NH, R-O HN oO 4s R° II o Xx R° III where, in formula II, R is C;-Cg-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 aprotic solvents such as, for example, pyridine,

N,N-dimethylformamide, N,N-dimethylacetamide, or mixtures of these [cf. US 4,331,590; Org. Prep. and Proced. Int., Vol. 10, 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,CO; and NaHCO3, or else nitrogen bases such as, for example, pyridine and tributylamine. The reaction temperature is normally 20-250°C, preferably 70-220°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;-C¢-alkyl and X is a leaving group which can be eliminated nucleophilically. Formula IV generally represents customary alkylating agents such as C;-Cg-alkyl halides, in particular 40 methyl chloride and methyl bromide, di(C;-Ce¢-alkyl) sulfates, such as dimethyl sulfate, or a C;-C¢-alkyl methanesulfonate, such as methyl methanesulfonate. 45 dd

} 0050/52348 eo a o R Rr

HN

III + RX — R-S—( <r

IV N Y x6 R® Vv

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 equimolar amounts or else in excess. Suitable bases are alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal hydrogen carbonates and alkaline earth metal hydrogen carbonates, such as, for example,

KOH, NaOH, NaHCO; and Na,CO3, but also nitrogen bases such as pyridine. The reaction temperature is usually 0-100°C, preferably 10-60°C. 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° FR

N—

Iv [ely R—S—{ Io VI

N c1 Rr® R®

Examples of suitable chlorinating agents [Cl] are POCl3, PCl3/Cl; or PCls, or mixtures of these. The reaction can be carried out in an excess of chlorinating agent (POClj) or an inert solvent such as, for example, acetonitrile or 1,2-dichloroethane. Carrying out the reaction in POCl; is preferred.

This reaction is usually carried out at between 10 and 180°C. For practical reasons, the reaction temperature usually corresponds to the boiling point of the chlorinating agent employed (POCl3) or of the solvent employed. The process is advantageously carried 40 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 45 are converted into the compounds of the formula VIII. a

0050/52348 AMENDED SHEET [ 3 R - RNY R® R

N

3 4

VI + RNR —_— rs \ R® VIII & VII = 6 8 cl R

This reaction is usually carried out at from 0 to 150°C, preferably at from 20 to 120°C [cf. J. Chem. Res. S (7), (1995), pp. 286-287, Liebigs Ann. Chem., (1995), pp. 1703-1705] in an inert solvent, if appropriate in the presence of an auxiliary base.

Suitable solvents are protic solvents, such as alcohols, for example ethanol, or aprotic solvents, such as aromatic hydrocarbons or ethers, for example toluene, o-, 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 bases are the following: NaHCO,, Na,CO,, Na,HPO,, Na,B,0,, 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. 4 3 R

A» ow

Ox N 3 VIII 10x51 R-s0~/ A\ R®

N= IX cl s R°

The reaction is usually carried out at from 0 to 100°C, preferably at from 10 to 50°C, in the presence of protic or aprotic solvents 40 [cf.: 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 45 such as dichloromethane or chloroform. Mixtures of these may also

} 0050/52348 ® : be employed. Preferred are acetic acid and a methanol/water mixture.

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 compounds I by reaction with heterocycles of the formula X. In formula X, the cycle A is a five- to ten-membered saturated, partially unsaturated or aromatic nitrogen-containing ring. 4

RL R® rR’

N

R—505</ Sr + (3 wen _— I

N= ca R® RIX X

This reaction is usually carried out at from 0 to 200°C, preferably at from 10 to 150°C, 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;CO3 and NaHCOj, 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,, or else alkali metal hydrides 40 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: 45 gd

_ 0050/52348 ® , o R FR

NH, HN

N

XII 0 gr¢ R®

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 2500C, preferably at from 100 to 200°C in the presence of a inert solvent (cf.: Austr. J. Chem., Vol. 32, (1979), pp. 669-679; J. Org.

Chem., Vol. 58, (1993), pp. 3785-3786; Arm. Xim. ZH, Vol. 38,

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 RB FR

N— vb _tetl OPS es VIb

N cr r® R®

The chlorination of Vb to give VIb is carried out under the same 40 conditions as the chlorination of V to give VI. ; R*

RY R® Rr

Vib + VII —= OC VIIIb 45 N= c1 R® R

. 0050/52348 ® .

The amination of the dichloropyrimidine VIb with VII is carried out under the same conditions as the amination of VI to give

VIII.

Compounds of the formula VI in which R? is alkoxy are obtained from the corresponding chloro compounds of the formula VI (R? =

Cl) by reaction with alkali metal alkoxides or alkaline earth metal alkoxides [cf.: Heterocycles, Vol. 32, (1991), pp. 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? is cyano are obtained from the corresponding chloro compounds of the formula VI (R? = Cl) by reaction with alkali metal cyanides, alkaline earth metal cyanides or metal cyanides, such as NaCN, KCN or Zn(CN),, [cf.:

Heterocycles, Vol. 39, (1994), pp. 345-356; Collect. Czech. Chem.

Commun. Vol. 60, (1995), pp. 1386-1389; Acta Chim. Scand., Vol. 50, (1996), pp. 58-63].

Compounds of the formula I in which R? is hydrogen are obtained from the corresponding chloro compounds of the formula VI (RZ =

Cl) by catalytic hydrogenation [cf.: J. Fluorine Chem. Vol. 45, (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 RZ is C;-Cg-alkyl or

C1-Cg-haloalkyl can be prepared in analogy to the above-described synthesis sequence to give the compounds I in which R2? is chlorine by suitably altering the starting materials of the formula ITI.

Instead of the phenylmalonates of the formula II, phenyl-f-ketoesters of the formula XIII in which R? 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 RZ? = chlorine. 0 Rk x o R ®

S R-0O HN

Le 40 yg N” TNH, 0 N= "2 he RS XIII R24 Re III’

_ 0050/52348 od ; o R FR

NH, N

Gy + XIII — R’

N=

XII R? gs R* VP

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 form of colorless or pale brown viscous oils, which are freed or 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 C;-Cg-alkyl such as methyl, ethyl, propyl, l-methylethyl, butyl, l-methylpropyl, 2-methylpropyl, 1,l-dimethylethyl, pentyl, l-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, l-ethylpropyl, hexyl, 1,l-dimethylpropyl, 1,2-dimethylpropyl, l-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, l-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, l-ethyl-l-methylpropyl and l-ethyl-2-methylpropyl; 40

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 C;-Cp-haloalkyl such 45 as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorfluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, l-chloroethyl,

_ 0050/52348 ® 10 l-bromoethyl, l-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluorocethyl, 2-chloro-2-fluoroethyl, 2-chloro- 2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 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,-Cg-alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1l-methylethenyl, l-butenyl, 2-butenyl, 3-butenyl, l-methyl-l-propenyl, 2-methyl-l-propenyl, l-methyl-2-propenyl, 2-methyl-2-propenyl, l-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, l-methyl-l-butenyl, 2-methyl-l-butenyl, 3-methyl-1l-butenyl, l-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, l-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,l-dimethyl-2-propenyl, 1,2-dimethyl-1l-propenyl, 1,2-dimethyl-2-propenyl, l-ethyl-l-propenyl, l-ethyl-2-propenyl, l-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, l-methyl-l-pentenyl, 2-methyl-1-pentenyl, 3-methyl-l-pentenyl, 4-methyl-l-pentenyl, l-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, l-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, l-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1l-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-l-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, l-ethyl-1-butenyl, l-ethyl-2-butenyl, l-ethyl-3-butenyl, 2-ethyl-l-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, l-ethyl-l-methyl-2-propenyl, l-ethyl-2-methyl-l-propenyl and l-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,-Cg-alkynyl such as ethynyl, l-propynyl, 2-propynyl, 40 1-butynyl, 2-butynyl, 3-butynyl, l-methyl-2-propynyl, l-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-l-butynyl, 1,1-dimethyl-2-propynyl, l-ethyl-2-propynyl, l-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2-pentynyl, 45 l-methyl-3-pentynyl, l-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-l-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,l-dimethyl-2-butynyl,

~ 0050/52348 o 11 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, l-ethyl-2-butynyl, l-ethyl-3-butynyl, 2-ethyl-3-butynyl und l-ethyl-1l-methyl-2-propynyl;

Cycloalkyl: monocyclic, saturated hydrocarbon groups having 3 to 6 carbon ring members such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;

Alkoxycarbonyl: an alkoxy group having 1 to 6 carbon atoms (as mentioned above) which is bonded to the skeleton via a carbonyl group (-CO-);

Oxyalkylenoxy: divalent unbranched chains of 1 to 3 CH, groups, both valencies being bonded to the skeleton via an oxygen atom, for example OCH,0, OCH,CH,0 and OCH,CH,;CH,0; 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, S-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-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-yl1l, 1,2,4-triazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl, 1,3,4-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, 40 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-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, 2-isothiazolin-5-yl, 45 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl,

~ 0050/52348

J 12 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1l-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-vyl1, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1,3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl, 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 heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen 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, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-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 40 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-1,4-diyl group in which one or two C atoms can be replaced by N atoms; 45 - 5-membered heteroaryl which is bonded via nitrogen and which contains one to four nitrogen atoms, or benzo-fused 5-membered heteroaryl which is bonded via nitrogen and contains one to

0050/52348 AMENDED SHEET i o 13 three nitrogen atoms: 5-membered heteroaryl ring groups which, i in addition to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms 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-1,4-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 four, nitrogen atoms as ring members, for example 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-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' to R° 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® is an aromatic heterocycle.

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

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

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

Equally preferred are compounds I in which R! is one of the following groups: pyrrolyl, pyrazolyl, imidazolyl, 1,2,4-triazolyl, 1,2,3-triazolyl, tetrazolyl, 1,2,3-triazinyl, 40 1,2,4-triazinyl, oxazolyl, isoxazolyl, 1,3,4-oxadiazolyl, furanyl, thiophenyl, thiazolyl, isothiazolyl, it being possible for the heterocycle to be bonded to the pyrimidine ring via C or N.

0050/52348 AMENDED SHEET ® 14

Preferred compounds I are furthermore those in which the cycle R! ) is pyridazinyl, pyrimidinyl or pyrazinyl, in particular 2-pyrimidinyl.

Equally preferred compounds I are those in which R' is pyrazolyl, pyrrolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, 2-pyridinyl, 2-pyrimidinyl, pyrazinyl or 3-pyridazinyl, each of which is optionally substituted by up to three groups R® or R*.

Especially preferred compounds I are those in which an R' is pyrazolyl, 1,2,3-triazolyl or 1,2,4-triazolyl, in particular 1-pyrazolyl.

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

C,-C¢-haloalkyl, C,-C.,-alkenyl, C,-Cs-alkynyl,

C;-Cs-cycloalkyl, C,-Ci-alkoxy, C,-Cs-haloalkoxy, carboxyl,

C,-C,-alkoxycarbonyl, carbamoyl, C,-C,-alkylaminocarbonyl,

C,-Cs-alkyl-C,-C,-alkylamincarbonyl, morpholinocarbonyl, pyrrolidinocarbonyl, C,-C,-alkylcarbonylamino,

C,-C¢-alkylamino, di (C;-C4-alkyl)amino, C,-Ci-alkylthio,

C,-C¢-alkylsulfinyl, C,-C,-alkylsulfonyl, hydroxysulfonyl, aminosulfonyl, C,-C,-alkylaminosulfonyl or di (C,-C¢-alkyl)aminosulfonyl.

Especially preferred compounds I are, in particular, those in which the cycle R' is substituted by one to three identical or different groups R*/’ from amongst those which follow: halogen, cyano, nitro, amino, C,-C¢-alkyl, C,-Cs-haloalkyl,

C,-Cs-alkoxy, carboxyl, C,-C,-alkoxycarbonyl, carbamoyl,

C,-C,-alkylaminocarbonyl, di (C,-C,-alkyl)amincarbonyl or

C,-C,-alkylcarbonylamino.

Especially preferred compounds I are those in which R! is 40 unsubstituted or monosubstituted by halogen, cyano, nitro, methyl or methoxy.

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

0050/52348 AMENDED SHEET ® 15

Moreover, especially preferred compounds I are those in which R? is halogen, C,-C,-alkyl or C,-C.,-alkoxy, in particular halogen.

Especially preferred compounds of the formula I are those in which R® is chlorine.

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

R’ is hydrogen.

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

R* independently of one another are C,-C¢-alkyl, C,-C.,-haloalkyl,

C;-C¢-cycloalkyl, C,-C.-alkenyl.

Particularly preferred compounds I are those in which R*® is hydrogen and R* is C,-C,-halogenalkyl.

Furthermore, preferred compounds I are those in which R* and R* 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 C,-Cs-alkyl substituents.

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

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

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

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

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

Equally, compounds I’ in which R' to R* are as defined for formula 40 I and R® is one of the following combinations of radicals: 2-chloro, 6-fluoro; 2,6-diflucro; 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.

3 0050/52348 ® 16

RY \

N—R

N R? ,

R—( A I

N=

R?

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

Particularly preferred with regard to their use are the compounds

I compiled in the tables which follow. In the tables, the groups mentioned for a substituent additionally constitute an especially preferred embodiment of the substituent in question per se, independently of the combination in which they are mentioned.

Table 1 compounds of the formula I-1 in which R5 is fluorine, R6 is chlorine and R7, R® and R? are hydrogen and, for each compound, the combination of the radicals R3 and R% corresponds to one line of Table A

RrR®

RNY RrR° R’

N c1 RR

Table 2

Compounds of the formula I-1 in which R> and R® are fluorine, and

R7, R8 and RY? are hydrogen and, for each compound, the combination of the radicals R3 and R* corresponds to one line of Table A

Table 3

Compounds of the formula I-1 in which R5 and R® are chlorine and

R7, R8 and R? are hydrogen and, for each compound, the combination of the radicals R3 and R3 corresponds to one line of Table A 40 Table 4

Compounds of the formula I-1 in which R> is fluorine, R® is methyl and R7, R8 and RY are hydrogen and, for each compound, the combination of the radicals R3 and RY corresponds to one line of

Table A 45

. 0050/52348 ® -

Table 5

Compounds of the formula I-1 in which R5, R® and R? are fluorine and R?7 and R8 are hydrogen and, for each compound, the combination of the radicals R3 and R% corresponds to one line of Table A

Table 6

Compound of the formula I-1 in which R> and R6 are fluorine, R7 and R8 are hydrogen and R? is methoxy and, for each compound, the combination of the radicals R3 and R% corresponds to one line of

Table A

Table 7

Compounds of the formula I-1 in which R5, R¢, R7, R® and R? are fluorine and, for each compound, the combination of the radicals

R3 and R% corresponds to one line of Table A

Table 8

Compounds of the formula I-1 in which RS is methyl, R®, R7 and R® are hydrogen and R? are fluorine and, for each compound, the combination of the radicals R3 and R? corresponds to one line of

Table A

Table 9 compounds of the formula I-1 in which R> is fluorine, R6, R7 and

R8 are hydrogen and R? are methyl and, for each compound, the combination of the radicals R3 and R? corresponds to one line of

Table A

Table 10

Compounds of the formula I-1 in which R5 and R® are methyl and RS,

R7 and R® are hydrogen and, for each compound, the combination of the radicals R3 and R% corresponds to one line of Table A

Table 11

Compounds of the formula I-2 in which R5 is fluorine, R® is chlorine and R7, R® and R? are hydrogen and, for each compound, the combination of the radicals R3 and R? corresponds to one line of Table A 4 3 R 40 RY ®» w

N N

[Cn 7 \ R® I-2 x~/ = c1 6 R° 45 rl

. 0050/52348 ® 18

Table 12

Compounds of the formula I-2 in which R> and R® are fluorine and

R7, R8 and R? are hydrogen and, for each compound, the combination of the radicals R3 and R? corresponds to one line of Table A

Table 13

Compounds of the formula I-2 in which R> and R6 are chlorine and

Table 14

Compounds of the formula I-2 in which R5 is fluorine and R® is methyl and R7, R® and R? are hydrogen and, for each compound, the combination of the radicals R3 and R% corresponds to one line of

Table A

Table 15

Compounds of the formula I-2 in which R35, R® and R? are fluorine and R?7 and R8 are hydrogen and, for each compound, the combination of the radicals R3 and R% corresponds to one line of Table A

Table 16

Compounds of the formula I-2 in which R> and R® are fluorine, R’ and R8 are hydrogen and RY is methoxy and, for each compound, the combination of the radicals R3 and R% corresponds to one line of

Table A

Table 17

Compounds of the formula I-2 in which R53, Rf, R7, R8 and R? are fluorine and, for each compound, the combination of the radicals

R3 and RY corresponds to one line of Table A

Table 18

Compounds of the formula I-2 in which R5 is methyl, RS, R7 and R® is hydrogen and R? is fluorine and, for each compound, the combination of the radicals R3 and R¢ corresponds to one line of

Table A

Table 19 40 Compounds of the formula I-2 in which R53 is fluorine, RS, R7 and

R8 are hydrogen and R? is methyl and, for each compound, the combination of the radicals R3 and R% corresponds to one line of

Table A

. 0050/52348 ® 19

Table 20

Compounds of the formula I-2 in which R> and R? are methyl and RS,

R7 and R8 are hydrogen and, for each compound, the combination of the radicals R3 and R? corresponds to one line of Table A

Table 21

Compounds of the formula I-3 in which RS is fluorine, R® is chlorine and R7, R8 and R? are hydrogen and, for each compound, the combination of the radicals R3 and R? corresponds to one line of Table A 4

Rf R® R’ =N N

OC “ cl 6 R°

Table 22

Compounds of the formula I-3 in which R5 and R® are fluorine and

R7, R8 and RY? are hydrogen and, for each compound, the combination of the radicals R3 and R% corresponds to one line of Table A

Table 23

Compounds of the formula I-3 in which R> and R® are chlorine and

R7, R® and R? are hydrogen and, for each compound, the combination of the radicals R3 and R% corresponds to one line of Table A

Table 24

Compounds of the formula I-3 in which R5 is fluorine and RS is methyl and R7, R® and RY are hydrogen and, for each compound, the combination of the radicals R3 and R% corresponds to one line of

Table A

Table 25

Compounds of the formula I-3 in which R35, R® and R? are fluorine and R?7 and R® are hydrogen and, for each compound, the combination of the radicals R3 and R% corresponds to one line of Table A

Table 26 compounds of the formula I-3 in which R® and R® are fluorine, R’ 40 and R8® are hydrogen and R? is methoxy and, for each compound, the combination of the radicals R3 and R? corresponds to one line of

Table A

Table 27 45 Compounds of the formula I-3 in which R3, R6, R7, R8 and RY are fluorine and, for each compound, the combination of the radicals

R3 and R%? corresponds to one line of Table A

. 0050/52348 ® ”

Table 28

Compounds of the formula I-3 in which R> is methyl, R6, R7 and RS is hydrogen and R? is fluorine and, for each compound, the combination of the radicals R3 and R! corresponds to one line of

Table A

Table 29

Compounds of the formula I-3 in which R5 is fluorine, RS, R7 and

R8 is hydrogen and R? is methyl and, for each compound, the combination of the radicals R3 and R% corresponds to one line of

Table A

Table 30

Compounds of the formula I-3 in which R5 and R® are methyl and RS,

R7 and R8 are hydrogen and, for each compound, the combination of the radicals R3 and R% corresponds to one line of Table A

Table 31

Compounds of the formula I-4 in which R5 is fluorine, R® is chlorine and R7, R8 and R? are hydrogen and, for each compound, the combination of the radicals R3 and R% corresponds to one line of Table A 4 3 R

RNY RS R?

N— N a A\ 9 I-4

Oe

C1 6 R°

Table 32

Compounds of the formula I-4 in which R®> and R® are fluorine and

R7, R8 and R? are hydrogen and, for each compound, the combination of the radicals R3 and R% corresponds to one line of Table A

Table 33 compounds of the formula I-4 in which R> and R® are chlorine and

R7, R8 and R? are hydrogen and, for each compound, the combination of the radicals R3 and R? corresponds to one line of Table A 40 Table 34

Compounds of the formula I-4 in which R5 is fluorine and R® is methyl and R7, R® and R? are hydrogen and, for each compound, the combination of the radicals R3 and R! corresponds to one line of

Table A

. 0050/52348 ® 21

Table 35

Compounds of the formula I-4 in which R3, RS and R’ are fluorine and R7 and R8 are hydrogen and, for each compound, the combination of the radicals R3 and R? corresponds to one line of Table A

Table 36

Compounds of the formula I-4 in which R> and R¢ are fluorine, R’ and R8 are hydrogen and R? is methoxy and, for each compound, the combination of the radicals R3 and R? corresponds to one line of

Table A

Table 37

Compounds of the formula I-4 in which R5, R6, R7, R® and R? are fluorine and, for each compound, the combination of the radicals

R3 and R4 corresponds to one line of Table A

Table 38 compounds of the formula I-4 in which R5 is methyl, R®, R7 and R® are hydrogen and R? is fluorine and, for each compound, the combination of the radicals R3 and R? corresponds to one line of

Table A

Table 39

Compounds of the formula I-4 in which R3 is fluorine, R%, R7 and

R8 are hydrogen and R% is methyl and, for each compound, the combination of the radicals R3 and R! corresponds to one line of

Table A

Table 40

Compounds of the formula I-4 in which R> and R® are methyl and RS,

R7 and R8 are hydrogen and, for each compound, the combination of the radicals R3 and R% corresponds to one line of Table A 40

.. 0050/52348 ® 2

Table A

EX

EE ES EE SE

EE CS EE

0

Ae | mom | 8

EE I A I SA

1s ome, | 8 as omen, | w® 2s mem, | ®&

Em mem); [om

EE SR I

3s oacmemon [8 40

EE CTR I

CTC ER SR

. 0050/52348 ® 23

EN ES mw oeacmy-acemy, | ow , am acme), | ow ai | oAcm)-oamy, | ow *

Am acmyo(omy, [ow is 50 ® omempc(omy, [ow 0 [a5 ® Cm) Cer), | ow

Ase | momcmyon, | w ”

Ass | moememp-on, [ow

Ae | momcmyon, [om i I CIC I ei | Gy cacmyon, | omom

Aes | momemycon, [wm 3s

Ae | moomcmp-cen, | wm 40 eam, | ow

ATi | omcmyeom | w ©

. 0050/52348 ® 24

EX

Go Gelepenyt | w ] ;

EE Re Pe TC * [2-90 | (#) -(CHp)y-CH(CHj)-CH-

CH,

Fee | empower s0 as 40

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

Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. 45 Some of them act systemically, and they can be employed in crop protection as foliar- and soil-acting fungicides. od

. 0050/52348 ® 25

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 40 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 95, preferably between 0.5 and 90, % by weight of the active 45 ingredient. &

. 0050/52348 ® 26

When used in crop protection, the application rates are from 0.01 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 are, for example, from 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active ingredient per cubic meter of material treated.

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, 40 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 45 naphthalene derivatives with formaldehyde, condensates of naphthalene or of napthalenesulfonic acid with phenol or formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated

. 0050/52348 od . isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide 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 kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. benzene, toluene, xylene, paraffin, 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 40 100%, preferably 95% to 100% (according to NMR spectrum).

The following are examples of formulations: 45 i

. 0050/52348 ® 25

I. 5 parts by weight of a compound according to the invention are mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dust which comprises 5% by weight 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 ingredient).

III. 10 parts by weight of a compound according to the invention 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).

Vv. 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 40 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). 45 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

. 0050/52348 od " weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring 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 liquor and 60 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill. Finely distributing the 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 40 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, 45 or even to apply the active ingredient without additives.

. 0050/52348 ® 30

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 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: e sulfur, dithiocarbamates and their derivatives, such as iron(III) dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediaminebisdithiocarbamate, tetramethylthiuram disulfide, ammonia complex of zinc (N,N-ethylenebisdithiocarbamate), ammonia complex of zinc (N,N’-propylenebisdithiocarbamate), zinc (N,N’-propylenebisdithiocarbamate),

N,N’-polypropylenebis(thiocarbamoyl)disulfide; e nitro derivatives, such as dinitro(l-methylheptyl)phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl 5-nitro-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-1,4-dithiocanthraquinone, 2-thio-1,3-dithiolo[4,5-b]- quinoxaline, methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate, 40 2-methoxycarbonylaminobenzimidazole, 2-(2-furyl)- benzimidazole, 2-(4-thiazolyl)benzimidazole,

N-(1,1,2,2-tetrachloroethylthio)tetrahydrophthalimide,

N-tri- chloromethylthiotetrahydrophthalimide,

N-trichloromethylthiophthalimide; 45 * N-dichlorofluoromethylthio-N’,N’-dimethyl-N-phenylsulfo- diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-thiocyanatomethylthiobenzothiazole,

. 0050/52348 ® on 1,4-dichloro-2,5-dimethoxybenzene, 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, pyridine-2-thiol 1l-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, 2-methyl-5, 6-dihydro-4H-pyran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide, 2,4,5-trimethylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carbocyclohexylamide,

N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide,

N-formyl-N-morpholine-2,2,2-trichloroethyl acetal, piperazine-1,4-diylbis-1-(2,2,2-trichloroethyl) formamide, 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecylmorpholine or its salts, 2,6-dimethyl-N-cyclododecylmorpholine or its salts,

N-[3-(p-tert-butylphenyl)-2-methylpropyl]-cis- 2,6-dimethylmorpholine, N-[3-(p-tert-butylphenyl)- 2-methylpropyllpiperidine, 1-[{2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl-ethyl]- 1H-1,2,4-triazole, 1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl-ethyl]- 1H-1,2,4-triazole,

N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N’-imidazolylurea, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)~- 2-butanone, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)- 2-butanole, (2RS,3RS)-1-[3-(2-chlorophenyl)-2-(4~-fluorophenyl)-oxiran- 2-ylmethyl}-1H-1,2,4-triazole, 0-(2~-chlorophenyl)-a-(4-chlorophenyl)-5-pyrimidinemethanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis (p-chlorophenyl)-3-pyridinemethanol, 1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene, 1,2-bis(3-methoxycarbonyl- 2-thioureido)benzene; * strobilurins such as methyl E-methoxyimino- [a-(0o-tolyl-oxy)-o-tolyl]acetate, methyl-E-2-{2-[6-(2~-cyanophenoxy)pyrimidin-4-yloxy]-phenyl}- 40 3-methoxyacrylate, N-methyl-E-methoxy- imino-[0-(2-phenoxyphenyl) Jacetamide, N-methyl E-methoxyimino- [o-(2,5-dimethylphenoxy)-o-tolyl]acetamide, methyl

E-2-{2-[2-trifluoromethylpyridyl-6-]oxymethyl]phenyl}- 3-methoxyacrylate, methyl 45 (E,E)-methoximino-{2-[1-(3-trifluoromethylphenyl)ethylidene-

. 0050/52348 aminooxymethyl ]phenyl}acetate, methyl-N-(2-{[1-(4-chlorophenyl)~ 1H-pyrazol-3-yl]oxymethyl}phenyl)N-methoxycarbamate; * anilinopyrimidines such as

N-(4,6-dimethylpyrimidin-2-yl)aniline,

N-[4-methyl-6-(1l-propynyl)pyrimidin-2-yljaniline,

N-[4-methyl-6-cyclopropylpyrimidin-2-yljaniline; * phenylpyrroles such as 4-(2,2-difluoro-1,3-benzodioxol- 4-yl)pyrrole-3-carbonitrile; * cinnamamides such as 3-(4-chlorophenyl)-3-(3,4-dimethoxy- phenyl)acryloylmorpholine; * and a variety of fungicides such as dodecylguanidine acetate, 3-13-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutarimide, hexachlorobenzene, methyl N-(2,6-dimethylphenyl)-

N-(2-furoyl)-DL-alaninate, DL-N-(2,6-dimethylphenyl)-

N-(2’'- methoxyacetyl)-alanine methyl ester, )

N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-amino- butyrolactone, DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)- alanine methyl ester, 5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2, 4~-dioxo- 1,3-oxazolidine, 3-[3,5~-dichlorophenyl(5-methyl-5-methoxymethyl]- 1,3-oxazolidine-2,4-dione, 3-(3,5-dichlorophenyl)- l-isopropylcarbamoylhydantoin,

N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane- 1,2-dicarboximide, 2-cyano-[N-(ethylaminocarbonyl)- 2-methoximino jacetamide, 1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole, 2,4-difluoro-a-(1H-1,2,4-triazolyl-l-methyl)benzhydryl alcohol,

N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)- 5-trifluoromethyl-3-chloro-2-aminopyridine, 1-( (bis (4~-fluorophenyl)methylsilyl)methyl-1H-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 I. The compounds obtained in this way are listed in the following tables with physical data. 40

Example 1: 6-Chloro-5-(2-chloro-6-fluorophenyl)-4-isopropylamino- 2-(l-pyrazolyl)pyrimidine [I-1] a) 5-(2-Chloro-6-fluorophenyl)-2-methylthio-4,6(1H,5H)- 45 pyrimidinedione i

. 0050/52348 * " 60.0 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 150°C 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 25°C. After acidification with dilute HCl solution and stirring for approximately 30 minutes, the precipitate was filtered off.

Washing with water and drying gave 16.7 g of the title compound as white crystals of m.p. 2500C (decomp.). 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 15 to 20°C. After phase separation, the organic phase was washed with water and dilute NaHCO; 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-l] = 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 25°C. Then, the solvent was distilled off, the residue was taken up in ethyl acetate and washed with dilute HCl, water and dilute NaHCO; 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 40 were obtained from the residue in the form of colorless crystals of m.p. 94-98°C, which were employed in the next step without further purification. d) 6-Chloro-5-(2-chloro-6-fluorophenyl)-4-isopropylamino- 45 2-methylsulfonylpyrimidine

0050/52348 AMENDED SHEET

A solution of 13.3 g (38.4 mmol) of the product of step c¢ in ) 240 ml of anhydrous dichloromethane was treated with 17.2 g (76.8 mmol) of 3-chloroperbenzoic acid at 0 to 5°C. The mixture was stirred for one hour at 0 to 5°C and for 14 hours at approximately 20 to 25°C. After the solvent was distilled off, the residue was taken up in ethyl acetate and then washed with 10% strength NaHCO, 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. 145-149°C. e) 6-Chloro-5-(2-chloro-6-fluorophenyl) -4-isopropylamino- 2-(l-pyrazolyl) pyrimidine

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 25°C. 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. 185-187°C.

Example 2: (S)-6-Chloro-4-(2,2,2-trifluoro-1l-methylethyl)amino- 5-(2,4,6-trifluorophenyl) -2- (1-pyrazolyl) pyrimidine [I-2] a) 5-(2,4,6-Trifluorophenyl)-2-methylthio-4, 6 (1H, 5H) - pyrimidinedione

Analogously to Example 1 (step a), 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°C (decomp. ) . b) 4,6-Dichloro-5-(2,4,6-trifluorophenyl) -2-methylthiopyrimidine

The following Example 1 (step b), 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. 75°C. 40 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 45 120.0 g (113 mmol) of 2,2,2-trifluoro-l-methylethylamine was stirred for five days at 150°C. After dilution with methyl tert-butyl ether and washing with 5M hydrochloric acid, the

. 0050/52348 ® ” phases were separated. The organic phase was dried and then freed from solvent. Chromatography on silica gel (cyclohexane, then cyclohexane/methyl tert-butyl ether 85:15) gave 90 g of the title compound as colorless crystals of m.p. 94-96°C. d) (S)-6-Chloro-5-(2,4,6-trifluorophenyl)-4-(2,2,2-trifluoro- l-methylethylamino)-2-methylsulfonylpyrimidine

Analogously to Example 1 (step d), 90.0 g (424 mmol) of the product of step c gave 89 g (92% of theory) of white crystals of m.p. 1590C. e) (S)-6-Chloro-4-(2,2,2-trifluoro-1l-methylethyl)amino- 5-(2,4,6-trifluorophenyl)-2-(1l-pyrazolyl)pyrimidine

Analogously to Example 1 (step e), 17.0 g (39.2 mmol) of the product of step d and 4.00 g (58.8 mmol) of pyrazole gave 14.9 g (90% of theory) of the title compound in the form of colorless crystals of m.p. 209°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-(1l-imidazolyl)pyrimidine [I-3]

Analogously to Example 1 (step e), 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. 172-173°C.

Example 4: (S)-6-Chloro-4-(2,2,2-trifluoro-l-methylethyl)amino- 5-(2,4,6-trifluorophenyl)-2-(1,2,4-triazol-1-yl)pyrimidine [I-4]

Analogously to Example 1 (step e), 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°C.

Example 5: 6-Chloro-5-(2,4,6-trifluorophenyl)-4-[ (S)-1,2-dimethyl-propyl]- amino-2-(pyridazin-3-yl)-pyrimidine [I-5] 40 a) Pyridazine-3-carboxamidine

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 45 pyridazine-3-carbonitrile in 100 ml of methanol and the mixture was stirred for 8 hours at 35°C. Then, 29 g of ammonium chloride were added and the mixture was refluxed for approximately

. 0050/52348 ® ” 14 hours. The hot mixture was filtered and the solid was discarded. 53.3 g of the title compound were obtained from the cold mother liquor by means of filtration. 1H NMR: 8 (ppm, DMSO-dg¢) = 9.75 (bs); 9.6 (d); 8.6 (d); 8.1 (m). 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 tributylamine and 10.0 g (0.063 mol) of the amidine of Ex. 5a was heated for approximately 6 hours at 180°C, during which process ethanol distilled off. After cooling to 60-70°C, the mixture was treated with 6.3 g (0.158 mol) of sodium hydroxide, dissolved in 70 ml of water, and stirring was continued for 30 minutes. After cooling to 20-25°C, 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. lH NMR: 6 (ppm, DMSO-dg¢) = 9.5 (d); 8.2 (d); 8.0 (dd); 7.2 (m). 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 120°C 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. lH NMR: 6 (ppm, CDCl3) = 9.2 (d); 8.7 (d); 7.8 (dd); 6.9 (t). d) 6-Chloro-5-(2,4,6-trifluorophenyl)-4-[(S)-1,2-dimethyl- propyl)amino-2-(pyridazin-3-yl)-pyrimidine

A solution of 200 mg (0.568 mmol) of the dichloride of Ex. 5c in 5 ml of DMF was treated with 100 mg (1.2 mmol) of 40 (S)-3-methyl-2-butylamine and the mixture was then stirred for 72 hours at 50°C and then cooled to 20-25°C. The reaction product was precipitated by addition of water. Filtration gave 200 mg (100% of theory) of the title compound. 45 lH NMR: 0 (ppm, CDCl3) = 9.3 (d); 8.5 (d); 7.6 (dd); 6.9 (t); 4.5 (m); 4.4 (m); 1.8 (m); 1.1 (d); 0.9 (4d).

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TT An

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N 0050/52348 ®

The lipophilicity parameters logP,, (Table I) were determined as specified by OECD directive test guidelines using the RP-HPLC run time method.

To this end, a logk’/logP,, 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.

A commercially available reversed-phase C;g stationary phase was used as stationary phase. Chromatographic separation was carried out with methanol and a buffer solution as mobile phase at pH 7.4 under isocratic conditions.

The retention times of the standards ty were converted in accordance with equation ® into the capacity factors k’, where tp, as reaction time of the solvent unretarded on the reversed-phase C;g stationary phase, represents the dead time of the chromatographic system: tr - to k! = crm 0) to :

The linear correlation of the logk’ values with the logP,, values of the standards published in the appendix to the Directive 92/69/EEC yields the correlation curve through linear regression.

The lipophilicity parameters logP,, 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 40

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 45 10% emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weight of Nekanil® LN (Lutensol® AP6, wetting agent with emulsifying and dispersing action, based on ethoxylated

N 0050/52348 [ alkylphenols) and 10% by weight of Wettol® EM (nonionic emulsifier, based on ethoxylated castor oil) and were diluted with water to give the desired concentration.

Use example 1 - Activity against Alternaria solani on tomatoes

Leaves of pot plants cv. ”"GroBe Fleischtomate St. Pierre” were sprayed to runoff point with an aqueous suspension prepared from a 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 0.17 x 106 spores/ml. The plants were subsequently placed in a water-vapor-saturated chamber at temperatures between 20 and 22°C.

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, I-4, I-12 to I-14, I-19 bis I-23, 1-29, I-31, 1-32, 1-35 to 1-37, 1-40, I-41, 1-46, I-47, I-51, I-52, I-54 and

I-60 showed no disease or a disease level of up to 7%, 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 22°C. 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 22°C and a relative atmospheric humidity of 65 to 70%. The extent of rust development on the 40 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 7%, while the untreated plants showed a disease level of 90%.

0050/52348 AMENDED SHEET

Use example 3 - Activity against barley net blotch disease

Leaves of barley seedlings cv. ‘‘Igri’’ in pots were sprayed to runoff 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°C and a relative atmospheric humidity of 95 to 100%. After 6 days, the extent of the disease level was determined visually in % diseased overall leaf area.

In this test, the plants which had been treated with 63 ppm of the active substances I-1, I-4, I-12 to I-14, I-19 to I-23, I-29,

I-32, I-35 to I-37, I-40, I-41, I-47, I-51, I-52, I-54 and I-60 showed no disease or a disease level of up to 10%, while the untreated plants showed a disease level of 90%.

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, 85% 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 10° spores/ml in a 2% aqueous Biomalz solution. The test plants were subsequently placed into a control/environment cabinet at 22-24°C and high atmospheric humidity. After 5 days, the extent of fungal infection on the leaves was determined visually in %.

In this test, the plants treated with 250 ppm of the active substances I-1, I-3, I-4, I-7 to I-9, I-11 to I-14, I-18 to I-23,

I-29 to I-32, I-35 to I-37, 1-40, I-47, I-51, I-52, I-54, I-60,

I-77, I-78 and I-80 showed no disease or a disease level of up to 40 7%, while the untreated plants showed a disease level of 90%.

Use example 5: Protective activity against powdery mildew of cucumbers caused by Sphaerotheca fuliginea 45 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

0050/52348 AMENDED SHEET consisting of 10% active substance, 85% of cyclohexanone and 5% of emulsifier. 20 hours after the spray coating had dried on, the plants were inoculated with an aqueous spore suspension of cucumber powdery mildew (Sphaerotheca fuliginea). The plants were subsequently grown in the greenhouse for 7 days at temperatures between 20 and 24°C and a relative atmospheric humidity of 60 to 80%. The extent of mildew development was then determined visually in % diseased cotyledon area.

I-31, I-32, 1-35, I-36, I-41, 1-47, I-52, I-54 and I-60 showed no disease, while the untreated plants showed a disease level of 100%. "Comprises/comprising" when used in this specification is taken to specify the presence of stated features, integers, steps or components but does not preclude the presence or addition of one or more other features, integers, steps or components or groups thereof.

Claims

\ 0050/52348 We claim:

1. A 5-phenylpyrimidine of the formula I, ; R* RNY R° R’ SAA I R: / R® N= R? RE RS in which the substituents have the following meanings: R1 is a five- to ten-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocycle comprising one to four hetero atoms selected from the group consisting of O, N or S, except for pyridyl, it being possible for Rl to be substituted by one to three identical or different groups R23, R2 is halogen, hydroxyl, cyano, oxo, nitro, amino, mercapto, C;-Cg-alkyl, C;-Cg¢-haloalkyl, C,-Cg—-alkenyl, C;-Cg-alkynyl, C3-Cg¢-cycloalkyl, C;~-Cg¢-alkoxy, C;-Cg-haloalkoxy, carboxyl, C;-Cy-alkoxycarbonyl, carbamoyl, C;-Cyj—-alkylaminocarbonyl, C;-Cg-alkyl-C;-Cg-alkylamincarbonyl, morpholinocarbonyl, pyrrolidinocarbonyl, C,-Cy-alkylcarbonylamino, C;-Cg¢-alkylamino, di(C;-Cg-alkyl)amino, C;-Cg-alkylthio, C;-Cg-alkylsulfinyl, C;-Cg¢-alkylsulfonyl, hydroxysulfonyl, aminosulfonyl, C;-Cg-alkylaminosulfonyl, di(C;-Cg-alkyl)aminosulfonyl; RZ? is hydrogen, halogen, cyano, C;-Cg-alkyl, Ci1-C¢-haloalkyl, C;-Cg-alkoxy, C;-Cys-haloalkoxy or C3-Cg¢-alkenyloxy; R3, R4 independently of one another are hydrogen, 40 C1-C¢-alkyl, C;-Cg-haloalkyl, C3-Cg¢-cycloalkyl, C3-Cg-halocycloalkyl, Cz-Cg¢-alkenyl, C,-Cg-haloalkenyl, C3-Cg-cycloalkenyl, C,-Cg¢-alkynyl, C,-Cg~haloalkynyl or C3-Cg-cycloalkynyl, 45 R3 and RY 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

0050/52348 ® 51 hetero atom selected from the group consisting of O, N and S and/or which can have attached to it one or more substituents selected from the group consisting of halogen, C;-Cg-alkyl, C;-Cg-haloalkyl and oxy-C;-Ciz-alkylenoxy or in which two adjacent C atoms or one N atom and one adjacent C atom can be linked by a C;-Cs-alkylene chain; R35, R6 independently of one another are hydrogen, halogen, C;-Cg¢-alkyl, Ci-Cg-haloalkyl or C;-Cg-alkoxy; R7, RS independently of one another are hydrogen, halogen, C;-Cg¢-alkyl or C;-Cg-haloalkyl; R? is hydrogen, halogen, C;-Cg¢-alkyl, C;-Cg-alkoxy, C3-Cg-cycloalkoxy, C;-Cg¢-haloalkoxy, C;-Cg-alkoxycarbonyl or C;-Cg-alkylaminocarbonyl.

2. A compound of the formula I as claimed in claim 1, where R! has the following meaning: Rl is a five- or six-membered aromatic heterocycle which has attached to it up to three substituents R2’, R28’ is halogen, hydroxyl, cyano, nitro, amino, mercapto, C;-Cg-alkyl, C;-Cg¢—-haloalkyl, C,-Cg-alkenyl, Cy-Cg-alkynyl, C3-Cg-cycloalkyl, C;-Cg-alkoxy, C;-Cg-haloalkoxy, carboxyl, C;-C;-alkoxycarbonyl, carbamoyl, C;-C;-alkylaminocarbonyl, C;-Cg-alkyl-C;-Cg-alkylamincarbonyl, morpholinocarbonyl, pyrrolidinocarbonyl, C;~Cy-alkylcarbonylamino, C;-Cg-alkylamino, di(C,-Cg-alkyl)amino, C;-Cg¢-alkylthio, C;-Cg-alkylsulfinyl, C;-Cg-alkylsulfonyl, hydroxysulfonyl, aminosulfonyl, C;-Cg¢-alkylaminosulfonyl or di(C;-Cg-alkyl)aminosulfonyl.

3. A compound of the formula I as claimed in claim 2, where the 40 variables have the following meanings: R! is pyrazole [sic], pyrrole [sic], imidazole [sic], 1,2,3-triazole [sic], 1,2,4-triazole [sic] or tetrazole [sic] which are bonded via C or N, or 45 2-pyrimidine [sic], pyrazine [sic] or 3-pyridazine [sic],

- 0050/52348 o 52 in which R! can have attached to it up to three substituents R2’ as claimed in claim 2; R2 is halogen, C;-Cg-alkyl or C;-Cg-alkoxy; R3, R4 independently of one another are hydrogen, C,-Cg-alkyl, C;-C¢-haloalkyl, C3-Cg-cycloalkyl or C,-Cg-alkenyl; R3 and RY 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;-Cg-alkyl substituent; R53, RS® independently of one another are hydrogen, halogen or C;-Cg-alkyl; R7, R8 independently of one another are hydrogen or halogen; RY is hydrogen, halogen, C;-Cg-alkyl or C;-Cg-alkoxy.

4. A compound of the formula I as claimed in claim 1 to 3, where R2 is chlorine.

5. A compound of the formula I as claimed in claims 1 to 4, where the combination of the substituents R> to R? 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.

6. A process for the preparation of 5-phenylpyridine of the formula I as claimed in claim 1, in which R! is bonded via nitrogen and R? is chlorine, which comprises cyclizing thiourea with an alkyl phenylmalonate of the formula II, o R F R’ II 40 R-0 0 R¢ R® in which R is C;-Cg-alkyl to give compounds of the formula III

- 0050/52348 o R FR HN s=( rR’ III HN O RrS® R® which are reacted with alkylating agents of the formula IV, R—X Iv in which R is C;-Cg-alkyl and X is a nucleophilically exchangeable group to give compounds of the formula V o R x

HN . R—5—( R v N 0 RS¢ R® which are converted with chlorinating agents to give the dichloropyrimidines of the formula VI ca R° ®’ N— R—S—( R’ VI \ c1 RS R® which are reacted with amino compounds of the formula VII rRi___R* N VII H to give the pyrimidine derivatives of the formula VIII rR RA RS R’ N R—S ~ A\ Rr VIII N= c1 R® R° and oxidizing VIII to give the sulfones of the formula IX 4 3 R 40 ANY RB go N R—s05</ \ R® 1X N= c1 R® R° 45 which are converted by reaction with heterocyclic compounds of the formula X

. 0050/52348 IN nd ss (2 en X in which the cycle A is a five- to ten-membered nitrogen-containing ring to give the compounds of the formula

I.

7. A process for the preparation of 5-phenylpyridines of the formula I as claimed in claim 1, where is a heterocycle which is bonded via nitrogen, which process comprises reacting a dichloropyrimidine of the formula IVa, ci R° R’ G< os : VIa \ \—4 c1 r¢® R® where the variables have the meanings stated in claim 1 with an amine of the formula VII as set forth in claim 6.

8. An intermediate of the formulae VI, VIa, VIII and IX as set forth in claims 6 and 7, where the combination of the substituents R5 to RY? have [sic] the meanings as set forth in claim 5.

9. Composition suitable for controlling phytopathogenic harmful fungi, comprising a solid or liquid carrier and a compound of the formula I as claimed in claim 1.

10. A method of controlling phytopathogenic harmful fungi, which comprises treating the fungi or the materials, plants, soil or seeds to be protected against fungal infection with an effective amount of a compound of the formula I as claimed in claim 1. 40

“ 0050/52348

® i 55 5-Phenylpyrimidines, their preparation, intermediates for their preparation, and their use for controlling harmful fungi

Abstract

5-Phenylpyrimidines of the formula I, s R BY rw N rR? R® R° in which the substituents have the following meanings:

Rl is a five- to ten-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocycle comprising one to four hetero atoms selected from the group consisting of O, N or S, which heterocycle can be substituted as defined in the description,

R2 is hydrogen, halogen, cyano, alkyl, haloalkyl or alkoxy; R3, R4 are hydrogen, alkyl, haloalkyl, cycloalkyl,

halocycloalkyl, alkenyl, haloalkenyl, cycloalkenyl, alkynyl, haloalkynyl or cycloalkynyl, R3 and R* together with the nitrogen atom to which they are bonded may also form a five- or six-membered ring which can be interrupted by a hetero atom and have attached to it one or more substituents;

R5, R® are hydrogen, halogen, alkyl, haloalkyl or alkoxy; R7, R8 are hydrogen, halogen, alkyl or haloalkyl;

RY is hydrogen, halogen, alkyl, alkoxy, cycloalkoxy, haloalkoxy or alkoxycarbonyl, Processes and intermediates for the preparation of these 40 compounds, and their use for controlling harmful fungi.