It has already been known that certain dihalogeno-triazolo-pyrimidine derivatives have fungicidal properties (see WO 94-20 501 and EP-A 0 834 513). Further, it has been described already that such known triazolopyrimidine derivatives can be used as intermediates for the synthesis of other fungicidally active compounds (see EP-A 0 770 615, US-A 5 756 509, US-A 5 593 996 and EP-A 0 782 997). The fungicidal activity of the known dihalogeno-triazolo-pyrimidine derivatives, however, is not always satisfactory when they are applied at low dosages.

There have now been found novel triazolopyrimidine derivatives of the formula in which X represents halogen, Y represents hydrogen or halogen, R'represents phenyl or naphthyl, each of which may optionally be substituted by halogen, Cl 6 alkyl, C,4 haloalkyl, Cl 4 alkoxy, Cl 4 haloalkoxy, Cl 4 alkylene- dioxy, C,4haloalkylenedioxy and/or phenyl, R2 represents a group of the formula in which R3 represents hydrogen or phenyl, R4 and R5 independently of each other represent C l 6-alkyl or phenyl, or R4 and R5 form, together with the nitrogen atom to which they are bonded, a 5- or 6- membered aliphatic heterocyclic ring, which may further contain 1 or 2 heteroatoms selected from nitrogen and oxygen, and which heterocyclic ring may be substituted by Cl 4 alkyl.

Furthermore, it has been found that triazolopyrimidine derivatives of the formula (I) can be prepared by a) reacting amino-triazolopyrimidines of the formula in which RI, X and Y have the above-mentioned meanings, with compounds of the formula

in which R3, R4 and R5 have the above-mentioned meanings and M represents XI or a group of the formula wherein xi is chlorine or bromine, in the presence of an inert diluent, or b) reacting hydroxy-triazolopyrimidine derivatives of the formula in which

Rl, R3, R4 and R5 have the above-mentioned meanings and Z represents hydrogen or hydroxy, with a halogenating agent in the presence of an inert diluent.

Finally, it has been found that the triazolopyrimidine derivatives of the formula (I) are oustandingly active as fungicides, which can be used in agriculture and horticul- turne : Surprisingly, the compounds according to the invention have a much better fungi- cidal activity than the already known compounds which are structurally most similar and have the same type of action.

In the present context,"halogen"represents fluoro, chloro, bromo or iodo, preferably fluoro, chloro or bromo.

"Alkyl"represents straight-chain or branched groups. The term"alkyl"includes methyl, ethyl, n-propyl, isopropyl, n-(iso-, sec- and tert-) butyl, n- (iso-, sec-, neo- and tert-) pentyl, n-hexyl, iso-hexyl etc.

The terms"haloalkyl"and"haloalkoxy"represent straight-chain or branched groups with 1 to 4 carbon atoms and 1 to 6 fluoro and/or chloro atoms. As examples there may be mentioned difluoromethyl, trifluoromethyl, 2, 2, 2-trifluoroethyl, dichloro- methyl, 2-chloro-1,1,2-trifluoroethyl, 1,1,2,3,3,3-hexafluoropropyl, etc.

The term"alkoxy"represents straight-chain or branched groups having 1 to 4 carbon atoms. As examples there may be mentioned methoxy, ethoxy, n-propoxy, iso- propoxy, n- (iso-, sec- and tert-) butoxy.

"Alkylenedioxy"represents straight-chain or branched groups with 1 to 4 carbon atoms, wherein the oxygen atoms are separated by at least one carbon atom and wherein the oxygen atoms are bonded to adjacent carbon atoms of a phenyl or naph- thyl ring. As examples there may be mentioned methylenedioxy, ethylenedioxy, methylmethylenedioxy, dimethylmethylenedioxy, propylenedioxy, tetramethyleth- ylenedioxy, etc.

"Haloalkylenedioxy"represents straight-chain or branched groups having 1 to 4 car- bon atoms and 1 to 4 halogen atoms, wherein the oxygen atoms are separated by at least one carbon atom and wherein the oxygen atoms are bonded to adjacent carbon atoms of a phenyl or naphthyl ring. As examples there may be mentioned difluo- romethylenedioxy, tetrafluoroethylenedioxy, trifluoromethyl-methylenedioxy etc.

A"5- or 6-membered aliphatic heterocyclic group"in the present context is an ali- phatic heterocyclic ring having 5 or 6 ring members and 1 to 3 hetero atoms selected from nitrogen and oxygen. As examples there may be mentioned pyrrolidino, piperidino, morpholino, piperazin-1-yl etc. These heterocyclic rings may be substi- tuted by one or more alkyl groups having 1 to 4 carbon atoms.

Formula (I) provides a general definition of the triazolopyrimidine derivatives ac- cording to the invention. Preferred compounds of the formula (I) are those, in which X represents chloro or bromo, Y represents hydrogen, chloro or bromo, Rl represents phenyl or naphthyl, each of which may be substituted by 1 to 5 radicals selected from fluoro, chloro, bromo, iodo, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, difluoromethoxy, trifluoromethoxy, 2- chloro-1,1,2-trifluoroethoxy, 1,1,2,3,3,3-hexafluoropropoxy and phenyl, or

may be substituted by a radical selected from methylenedioxy, ethylenedioxy, difluoromethylenedioxy and tetrafluoroethylenedioxy, and R2 represents a group of the formula in which R3 represents hydrogen or phenyl, and R4 and R5 independently of each other represent methyl, ethyl, n-propyl, iso- propyl, n-butyl, isobutyl, n-pentyl or phenyl, or R4 and R5 form, together with the nitrogen atom to which they are bonded, a pyrrolidino, piperidino, 4-methyl-piperidin-1-yl or a morpholino group.

Particularly preferred triazolopyrimidine derivatives of the formula (I) are those, in which X represents chloro or bromo, Y represents hydrogen or chloro, RI represents phenyl or naphthyl, each of which may be substituted by 1 to 5 radicals selected from fluoro, chloro, bromo, iodo, methyl, tert-butyl, trifluo- romethyl, methoxy, ethoxy, difluoromethoxy or phenyl, or may be substituted

by a radical selected from methylenedioxy, difluoromethylenedioxy or tetra- fluoroethylenedioxy, and R2 represents a group of the formula , in which R3 represents hydrogen or phenyl, and R4 and R5 independently of each other represent methyl, ethyl, n-propyl, isopropyl, n-butyl or phenyl, or R4 and R5 form, together with the nitrogen atom to which they are bonded, a pyrrolidino, piperidino, 4-methyl-piperidin-1-yl or a morpholino group.

Specific examples of triazolopyrimidine derivatives according to the invention are listed in the following Tables 1 and 2.

Table 1

Table 1 (continued) X Y R6 R2 Cl H 4-F N=CHN (CH3) 2 Cl H 2-CH3 N=CHN (CH3) 2 Cl H 3-CH3 N=CHN (CH3) 2 Br H 4-CH3 N=CHN(CH3)2 Cl H 4-CH3 N=CHN (CH3) 2 -N=C-N N H N Cl H 4-CH3 N H N Cl H 4-CH3 N=CHNX Cl H 4-CH3 - N=-N \-CH, Cl H 4-CH3 H / Cl H 4-CH3 H Cl H 4-CH3 N=CHN(C2H5)2 Cl H 4-CH3 N=CHN(iSo-C3H7)2 Cl H 4-CH3 N=CHN(n-C4H9)2 N(CH3)2 \NX Cl H 4-CH3 " Cl H 3-CF3 N=CHN(CH3)2 Cl H 4-CF3 N=CHN(CH3)2 Cl H 4-tert-C4Hg N=CHN(CH3)2 Cl H 4-OCH3 N=CHN (CH3) 2 Cl H 4-OCHF2 N=CHN (CH3) 2 Cl H 4-OC2Hs N=CHN(CH3)2

Table 1 (continued) X Y R6 R2 Cl H 2,4-Cl2 N=CHN(CH3)2 Br H 3, 4-Cl2 N=CHN (CH3) 2 Cl H 3, 4-Cl2 N=CHN (CH3) 2 Cl H 3, 4-Cl2"3 N H N Cl H 3,4-Cl2 Fi N Cl H 3,4-Cl2 N=HCN xNCH3 Cl H 3,4-Cl2 - N=C-N O Cl H 3, 4-Cl2 Cl H 354-C'2 N=CHN (C2H5) 2 Cl H 3,4-Cl2 N=CHN(iSo-C3H7)2 Cl H 3,4-C12 N=CHN(n-C4H9)2 N(CH3)2 \NX Cl H 3,4-Cl2 Cl H 3-Cl,4-CF3 N=CHN(CH3)2 Cl H 334-F2 N=CHN (CH3) 2 Cl H 2,5-(CH3)2 N=CHN(CH3)2 Cl H 3,5-(CH3)2 N=CHN(CH3)2 Cl H 3, 4- (OCH3) 2 N=CHN (CH3) 2 Cl Cl H N=CHN(CH3)2 Cl Cl 2-Cl N=CHN(CH3)2 Cl Cl 3-Cl N=CHN (CH3) 2 Cl Cl 4-Cl N=CHN(CH3)2 Cl Cl 2-CH3 N=CHN(CH3)2

Table 1 (continued) X Y R6 R2 Cl Cl 3-CH3 N=CHN (CH3) 2 Cl Cl 4-CH3 N=CHN (CH3) 2 Cl H 4--o N=CHN (CH3) 2 Cl H 2-F N=CHN (CH3) 2 Cl H 2-F N=CHN(C2H5)2 Cl H 2-F N H N Cl H 2-F H C Cl H 2-F - N=C-N 0 Cl H 2-F - NC-N N-CH, Cl H 2-F Cl H 2-F N=CHN (CH3) (C2H5) Cl H 2-F N=CHN (iso-C-, H7) 2 Cl H 2-F N=CHN (n-C3H7) 2 Cl H 2-F N=CHN (n-C4H9) 2 Cl H 2-F N=CHN (CH3) (iso-CH7) Cl H 2-F N=CHN (CH3) (n-C3H7) Cl H 2-F N=CHN (CH3) (n-C4H9) Cl H 3-F N=CHN (CH3) 2 Cl H 3-F N=CHN (CH3) (n-C3H7) Cl H 4-F N=CHN (C2H5) 2

Table 1 (continued) X Y R6 R2 H C C1 H 4-F H S C1 H 4-F H X C1 H 4-F - N=C-N O Cl H 4-F N=HCN xNCH3 Cl H 4-F Cl H 4-F N=CHN (n-C3Hy) 2 Cl H 4-F N=CHN (iso-C3Hy) 2 Cl H 4-F N=CHN (n-C4H9) 2 Cl H 4-F N=CHN (CH3) (C2H5) Cl H 4-F N=CHN (CH3) (iso-C3Hy) Cl H 4-F N=CHN (CH3) (n-C4H9) Cl H 2-Br N=CHN (CH3) 2 Cl H 3-Br N=CHN (CH3) 2 Cl H 2, 4-F2 N=CHN (CH3) 2 Cl H 2, 4-F2 N=CHN (CH3) (C2H5) Cl H 2) 4-F2 N=CHN (isO-C3H7) 2 -N=C-N 0 Cl H 2,4-F2 Cl H 2, 4-F N=CHN (CH3) (iso-C3Hy) Cl H 2, 5-F2 N=CHN (CH3) 2 Cl H 3, 5-F2 N=CHN (CH3) 2

Table 1 (continued) X Y R6 R2 Cl H 2-CF3 N=CHN (CH3) 2 Cl H 2-CF3 N=CHN (iso-C3H7) 2 Cl H 2-OCH3 N=CHN (CH3) 2 Cl H 3-OCH3 N=CHN(CH3)2 Cl H 3, 4- (OCH20) N=CHN (CH3) 2 Cl H 3, 4- (OCH2CH20) N=CHN (CH3) 2 Cl H 2,4-(OCH3)2 N=CHN(CH3)2 Cl H 3, 5- (OCH3) 2 N=CHN (CH3) 2 Cl H 3, 4, 5- (OCH3) 3 N=CHN (CH3) 2 <BR> <BR> <BR> <BR> Cl H 3, 4- (OCF20) N=CHN (CH3) 2 <BR> <BR> <BR> <BR> <BR> <BR> <BR> Cl H 3, 4- (OCF2CF20) N=CHN (CH3) 2 Cl H 4-iso-C3H7 N=CHN(CH3)2 Cl H 2-I N=CHN(CH3)2 Cl H 4-I N=CHN(CH3)2 Cl H 4-Cl N=CHN(n-C3H7)2 Cl H 4-CH3 N=CHN(n-C3H7)2 Cl H 3,4-Cl2 N=CHN(n-C3H7)2 Cl H 4-Cl N=CHN(CH3)(iso-C3H7) Cl H 4-CH3 N=CHN(CH3)(iso-C3H7) Cl H 3,4-Cl2 N=CHN(CH3)(iso-C3H7) Br H 2-F N=CHN(CH3)2 Br H 2,4-F N=CHN(CH3)2

Table 1 (continued) X Y R6 R2 Cl Cl 2-F N=CHN (CH3)2 Cl Cl 3-F N=CHN(CH3)2 Cl Cl 4-F N=CHN (CH3) 2 Cl Cl 2,4-F2 N=CHN(CH3)2 Cl Cl 2, 6-F2 N=CHN (CH3) 2 Cl Cl 2,3,4,5,6-F5 N=CHN(CH3)2 Cl Cl 2-Cl, 6-F N=CHN(CH3)2 Cl Cl 2,4-Cl2 N=CHN(CH3)2 Cl Cl 3,4-Cl2 N=CHN(CH3)2 Cl Cl 2,6-C12 N=CHN(CH3)2

Table 2 If 2-amino-5, 7-dichloro-6-phenyl 1, 2, 4 triazol 1, 5-a pyrimidine and (chlorometh- ylene) -dimethylammonium chloride are used as starting materials process (a) accord- ing to the invention can be illustrated by the following formula scheme.

If 2- (N, N-dimethylaminophenyl-methylideneamino) -6- (4-methylphenyl) 1, 2, 4 tri- azolo 1, 5-a pyrimidin-5-ol and phosphorus oxychloride are used as starting materials, process (b) according to the invention can be illustrated by the following formula scheme : Formula (II) provides a general definition of the amino-triazolopyrimidines, which are required as starting materials for carrying out process (a) according to the inven- tion. In this formula, RI, X and Y preferably have those meanings, which have al- ready been mentioned as preferred for these substituents.

The following compounds may be mentioned as examples of amino triazolopyr- imidines of the formula (II).

2-Amino-5-chloro-6-phenyl 1, 2, 4 triazolo 1, 5-a pyrimidine, 2-amino-5-chloro-6- (4-methylphenyl) 1, 2, 4 triazolo 1, 5-a pyrimidine, 2-amino-5-chloro-6-(4-tert-butylphenyl)[1,2,4]triazolo[1,5-a ]pyrimidine, 2-amino-5-chloro-6- (4-trifluoromethylphenyl) 1, 2, 4 -triazolo 1, 5-a pyrimidine,

2-amino-5-chloro-6-(3,4-dimethoxyphenyl)1,2,4triazolo-1,5-ap yrimidine, 2-amino-5-chloro-6- (4-difluoromethoxyphenyl) 1, 2, 4 -triazolo 1, 5-a pyrimidine, 2-amino-5,7-dichloro-6-(2-chlorophenyl)[1,2,4]triazolo[1,5-a ]pyrimidine.

The compounds of the formula (II) are novel. They can be prepared by c) reacting triazolopyrimidines of the formula in which R1 and Z have the above-mentioned meanings, with halogenating agents, such as phosphorus oxychloride, phosphorus oxybromide, phosphorus trichloride, phosphorus tribromide, phosgene, carbonyl bromide, oxalyl dichloride, thionyl chloride or thionyl bromide.

The triazolopyrimidines of the formula (V) are novel too. They can be prepared by d) either reacting esters of the formula in which R1 has the above-mentioned meanings,

with 3, 5-diamino-1, 2, 4-triazole in the presence of a diluent, such as acetic acid, or e) by reacting diesters of the formula in which Rl has the above-mentioned meanings, with 3, 5-diamino-1, 2, 4-triazole in the presence of a base, such as tributyl- amine.

The esters of the formula (VI) are known or can be synthesized according to known processes (see Japanese laid-open Patent Publication No. 25 095/1994).

The diesters of the formula (VII) are also known or can be prepared according to known processes (see Organic Synthesis, Coll. Volume II, 288 (1943) and Heterocy- cles 1979, Vol. 43, page 1036).

Process (d) can be carried out according to a method, which is principally known (see WO 94-21 640).

Process (e) can also be carried out according to a method, which is principally known (see Japanese Laid-open Patent Publication No. 152 489/1998 and EP-A 0 770 615).

Formula (III) provides a general definition of the compounds, which are also required as starting materials for carrying out process (a) according to the invention. In this formula, R3, R4 and R5 preferably have those meanings, which have already been mentioned as preferred for these substituents.

M preferably represents XI or a group of the formula wherein Xl is chloro or bromo.

The following compounds may be mentioned as examples of substances of the for- mula (III).

Chloromethylene) dimethylammonium chloride, (bromomethylene) dimethylammonium bromide, (chloromethylene) dimethylammonium dichlorophosphate, (chloromethylene) dimethylammonium dichlorophosphite, (chloromethylene) dimethylammonium chlorosulfinate, 1 - (chloromethylene) piperidinium chloride, 4- (chloromethylene) morpholinium chloride, (chloromethylene) methylphenylammonium chloride, (chloromethylene) diethylammonium chloride,

(chloromethylene) di (isopropyl) ammonium chloride, (chloromethylene) di (n-butyl) ammonium chloride, and (1 -chloro-1 -phenylmethylene) dimethylammonium chloride.

The compounds of the formula (III) can be prepared according to the known process for synthesizing Vilsmeier complexes. Thus, the compounds of the formula (III) can be prepared by reacting amides of the formula in which R3, R4 and R5 have the above-mentioned meanings, with halogenating agents such as phosphorus oxychloride, phosphorus oxybromide, phosphorus trichloride, phosphorus tribromide, phosgene, carbonyl bromide, oxalyl dichloride, thionyl chloride or thionyl bromide.

The amides of the formula (VIII) are known or can be prepared according to princi- pally known processes.

Formula (IV) provides a general definition of the hydroxy-triazolopyrimidine deriva- tives, which are required as starting materials for carrying out process (b) according to the invention. In this formula, Rl, R3, R4 and R5 preferably have those meanings. which have already been mentioned as preferred for these substituents. Z represents hydrogen or hydroxy.

The following compounds may be mentioned as examples of hydroxy-triazolo- pyrimidine derivatives of the formula (IV).

2- (Morpholin-4-ylmethylideneamino) -6- (4-chlorophenyl) - 1, 2, 4 triazolo 1, 5-a pyr- imidin-5-ol, 2- (N, N-dimethylaminomethylideneamino) -6- (3-trifluoromethylphenyl) 1, 2, 4 tri- azolo l, 5-a pyrimidin-5-ol, 2- (N, N-diethylaminomethylideneamino) -6- (3, 4-dichlorophenyl) 1, 2, 4 triazolo 1, 5- a pyrimidin-5-ol, 2-(N,N-dimethylaminophenylmethylideneamino)-6-(4-methylpheny l)1,2,4tri- azolo 1, 5-a pyrimidin-5-ol, 2 (N-methylanilinomethylideneamino) -6- (4-chlorophenyl) - 1, 2, 4 triazolo 1, 5-a pyr- imidin-5-ol, 2- (N, N-dimethylaminomethylideneamino) -6- (4-ethoxyphenyl) - 1, 2, 4 triazolo 1, 5- a pyrimidin-5-ol, 2-(piperidinylmethylideneamino)-6-(4-methylphenyl)1,2,4-tria zolo1,5-apyr- imidin-5-ol, 2- (N, N-dimethylaminomethylideneamino) -6 (4difluoromethoxyphenyl) 1, 2, 4 tria- zolo 1, 5-a pyrimidin-5-ol, 2- (N, N-di (isopropyl) aminomethylideneamino) -6- (4-methylphenyl) 1, 2, 4 tri- azolo 1, 5-a pyrimidin-5-ol, 2-(N,N-di(n-butyl)aminomethylideneamino)-6-(3,4-dichlorophen yl)1,2,4tri- azolo 1, 5-a pyrimidin-5-ol, 2- (N, N-dimethylaminomethylideneamino) -6-phenyl 1, 2, 4 -triazolo 1, 5-a pyrimidin- 5,7-dol.

The hydroxy-triazolopyrimidine derivatives of the formula (IV) are novel com- pounds. They can be prepared by f) reacting tirazolopyrimidines of the formula

in which R1 and Z have the above-mentioned meanings, with compounds of the formula in which R3, R4 and R5 have the above-mentioned meanings and M represents X1 or a group of the formula wherein X1 is chlorine or bromine, in the presence of an inert diluent.

Process (f) can be carried out under conditions corresponding to that of process (a) according to the invention.

Preferred halogenating agents for carrying out process (b) according to the invention are phosphorus oxychloride, phosphorus oxybromide, phosphorus trichoride, phosphorus tribromide, phosgene, carbonyl bromide, oxalyl dichloride, thionyl chlorid, thionyl bromide etc.

All inert organic solvents customary for such reactions can be used as diluents for carrying out process (a) according to the invention. Suitable solvents preferably in- clude aliphatic, alicyclic and aromatic hydrocarbons (optionally chlorinated), such as pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, chloroben- zene, dichlorobenzene etc. ; ethers, such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), dieth- ylene glycol dimethyl ether (DGM) etc. ; esters, such as ethyl acetate, amyl acetate etc.

In carrying out process (a) according to the invention, the reaction temperatures can be varied within a substantially wide range. The reaction is generally carried out at a temperature between about 10°C and about 200°C, preferably between about 50°C and about 160°C.

Process (a) according to the invention is generally carried out under atmospheric pressure but, if desired, can also be carried out under elevated or reduced pressure.

Upon carrying out process (a) according to the invention, in general 1 mol of amino- triazolopyrimidine of the formula (II) is reacted with 1 to 15 mol of a compound of

the formula (III) in the presence of an inert diluent. Working up is carried out by customary methods.

In a preferred variant, process (a) according to the invention can be carried out by starting from amides of the formula (VIII), reacting same with halogenating agents and reacting the Vilsmeier complexes of the formula (III) thus obtained, without iso- lation with amino-triazolopyrimidines of the formula (II).

In a further preferred variant, process (a) according to the invention can be carried out-by starting from triazolopyrimidines of the formula (V), reacting same with halo- genating agents and reacting the amino-triazolopyrimidines of the formula (II) thus obtained, without isolation with Vilsmeier complexes of the formula (III).

Process (b) according to the invention can also be carried out in the presence of all inert organic diluents customary for such reactions. Suitable diluents preferably are those, which have already been mentioned as preferred for carrying out process (a) according to the invention.

In carrying out process (a) according to the invention, the reaction temperatures can be varied within a substantially wide range. The reaction is generally carried out at a temperature between about 10°C and about 200°C, preferably between about 50°C and about 160°C.

Process (b) according to the invention is generally carried out under atmospheric pressure but, if desired, can also be carried out under elevated pressure.

Upon carrying out process (b) according to the invention, in general 1 mol of hy- droxy-triazolopyrimidine derivative of the formula (IV) is reacted with 1 to 50 mol of a halogenating agent in the presence of an inert diluent. Working up is carried out by customary methods.

In a preferred variant, process (b) according to the invention can be carried out by starting from triazolopyrimidines of the formula (V), reacting same with Vilsmeier complexes of the formula (III) and reacting the hydroxy-triazolopyrimidine deriva- tives of the formula (IV) thus obtained, without isolation, with halogenating agents.

When preparing hydroxy-triazolopyrimidine derivatives of the formula (IV), it is also possible to start from amides of the formula (VIII), reacting same with halogenating agents and reacting the Vilsmeier complexes of the formula (III) thus obtained, with- out isolation, with triazolopyrimidines of the formula (V).

The Vilsmeier complexes of the formula (III) may also be used as halogenating agents.

The compounds according to the present invention exhibit strong fungicidal activity and thus can be used for the control of phytopathogenic fungi and plant disease germs in agricultural and horticulture.

Generally, the compounds according to the invention can be used as fungicides for combating phytopathogenic fungi, such as Plasmodiophoromycetes, Oomycetes, Chytridiomycetes. Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Some pathogens causing fungal diseases which come under the generic names listed above are mentioned as examples, but not by way of limitation : Erwinia species, such as, for example, Erwinia amylovora ; Pythium species, such as, for example, Pythium ultimum ; Phytophthora species, such as, for example, Phytophthora infestans ; Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis ; Plasmopara species, such as, for example, Plasmopara viticola ; Bremia species, such as, for example, Bremia Lactucae ;

Peronospora species, such as, for example, Peronospora pisi or P. brassicae ; Erysiphe species, such as, for example, Erysiphe graminis ; Sphaerotheca species, such as, for example, Sphaerotheca fuliginea ; Podosphaera species, such as, for example, Podosphaera leucotricha ; Venturia species, such as, for example, Venturi inaequalis ; Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea (conidia form : Drechslera, syn : Helminthosporium) ; Cochliobolus species, such as, for example, Cochliobolus sativus (conidia form : Drechslera, syn : Helminthosporium) ; Uromyces species, such as, for example, Uromyces appendiculatus ; Puccinia species, such as, for example, Puccinia recondita ; Sclerotinia species, such as, for example, Sclerotinia sclerotiorum ; Tilletia species, such as, for example, Tilletia caries ; Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae ; Pellicularia species, such as, for example, Pellicularia sasakii ; Pyricularia species, such as, for example, Pyricularia oryzae ; Fusarium species, such as, for example, Fusarium culmorum ; Botrytis species, such as, for example, Botrytis cinerea ; Septoria species, such as, for example, Leptosphaeria nodorum ; Cercospora species, such as, for example, Cercospora canescens ; Alternaria species, such as, for example, Altemaria brassicae ; and Pseudocercosporella species, such as, for example, Pseudocercosporella herpo- trichoides.

The fact that the active compounds are well tolerated by plants at the concentrations required for controlling plant diseases permits the treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.

Moreover, the active compounds, according to the present invention have a low tox- icity against warm-blooded animals and therefore can be used safely.

The active compounds, according to the present invention can be converted into the customary formulations for actual application. As such customary formulations, for example, solutions, wettable powders, emulsions, suspensions, powders, foams, pastes, tablets, granules, aerosols, natural and synthetic materials impregnated with active compounds, microcapsules, coating compositions for use on seeds, ULV [cold mist, warm mist etc. may be mentioned.

The formulations can be prepared according to known methods, for example, by mixing the active compound with extenders, namely liquid diluents, solid diluents or carriers, optionally with the use of surface-active agents, namely emulsifiers and/or dispersants and/or foaming agents. In case of using water as extender, for example, organic solvents can be used as auxiliary solvents.

As liquid diluents or carriers, for example, aromatic hydrocarbons (for example, xy- lene, toluene or alkylnaphthalene etc. ), chlorinated aromatic hydrocarbons or chlorin- ated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides or methylene chloride etc. ), aliphatic hydrocarbons [for example, cyclohexane etc. or paraffins (for example, mineral oil fractions) ], alcohols (for example, butanol, glycol etc. ) and their ethers and esters etc. , ketones (for example, acetone, methyl ethyl ke- tone, methyl isobutyl ketone, cyclohexanone etc. ), strongly polar solvents (for ex- ample, dimethylformamide, dimethylsulphoxide etc. ) and water may be mentioned.

Liquefied gaseous diluents are gases at normal temperature and normal pressure and, for example, butane, propane, nitrogen gas, carbon dioxide, and aerosol propellants such as halogenated hydrocarbons may be mentioned.

As solid diluents, for example, ground natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth etc. ), ground synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates etc.) etc. may be mentioned.

As solid carriers for granules, for example, crushed and fractionated rocks (for ex- ample, calcite, marble, pumice, sepiolite, dolomite etc. ), synthetic granules of inor- ganic and organic meals, granules of organic material (for example, sawdust, coconut shells, maize and tobacco stalks etc. ) etc. may be mentioned.

As emulsifiers and/or foaming agents, for example, nonionic and anionic emulsifiers [for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers (for example, alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsul- phonates etc. )], albumin hydrolysis products etc. may be mentioned.

As dispersants, for example, ligninsulphite waste liquor, methyl cellulose etc. are included.

Adhesives may also be used in formulations (powders, granules, emulsions). As said adhesives, for example, carboxymethyl cellulose, natural and synthetic polymers (for example, gum arabic, polyvinyl alcohol, polyvinyl acetate etc. ), may be mentioned.

Colorants may also be used. As said colorants, for example, inorganic pigments (for example, iron oxide, titanium oxide, Prussian Blue), organic dyestuffs such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and further trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum, zinc etc. may be mentioned.

The formulations in general contain from 0. 1 to 95 percent by weight of active com- pound, preferably from 0. 5 to 90 percent by weight.

The active compound according to the invention can be present in the formulations or in the various use forms as a mixture with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repel- lents, growth factors, plant nutrients and agents for improving soil structure.

The active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in the custom- ary manner, for example by water, immersion, spraying, atomising, misting, vapor- izing, injecting, forming a slurry, brushing on, dusting, scattering, dry dressing, moist dressing, wet dressing, slurry dressing or encrusting.

In the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are, in general, from 1 to O : E1001 % by weight, preferably from 0. 5 and 0. 001%.

For the treatment of seed, amounts of active compound of 0. 001 to 50 g, especially 0. 01 to 10 g, are generally employed per kilogram of seed.

For the treatment of soil, active compound concentrations, at the point of action, of 0. 00001 to 0. 1 % by weight, especially of 0. 0001 to 0. 02%, are generally employed.

The preparation and use of the active compounds according to the invention can be seen from the following examples. The invention, however, is not limited to said examples in any way.

Synthesis Example 1

To a mixture of 2-amino-6- (4-methylphenyl) l, 2, 4 triazolo- l, 5-a pyrimidin-5-ol (3. 0 g) and phosphorus oxychloride (20 ml), N, N-dimethylbenzamide (6. 0 g) was added at room temperature and the mixture was stirred for 1 hour. Then, after heat- ing the reaction mixture to 110°C for 3 hours, the excess amount of phosphorus oxy- chloride was distilled off under reduced pressure. The residue was poured into water and the resulting mixture was basified with 40% aqueous solution of sodium hy- droxide. The mixture was extracted with chloroform and, after washing the combined organic phases with water, the organic phase was dried with anhydrous magnesium sulphate. After the solvent had been distilled off, the residue was treated with silica gel column chromatography (eluting solvent : chloroform) to obtain 5-chloro-2- (N, N- dimethylaminophenyl methylideneamino) -6- (4-methylphenyl) 1, 2, 4 -triazolo 1, 5- a pyrimidine (2. 5 g). (mp. 242-244°C).

Synthesis Example 2 To a mixture of 2-amino-6-phenyl 1, 2, 4 triazolo 1, 5-a pyrimidin-5, 7-diol (3. 0 g) and phosphorus oxychloride (15 ml), N, N-dimethylformamide (3 ml) was added drop by drop at room temperature. After the addition, the reaction mixture was stirred at room temperature for 30 minutes, and then stirred at 110°C for 1 hour. After the

excess amount of phosphorus oxychloride was distilled off under reduced pressure, the obtained residue was poured into water. The resulting mixture was basified with 40% aqueous solution of sodium hydroxide. After extraction with chloroform, the combined organic phases were washed with water and dried over anhydrous magne- sium sulphate. After the solvent had been distilled off, the residue was treated with silica gel column chromatography (eluting solvent : chloroform) to obtain 5, 7- dichloro-2- (N, N-dimethylaminomethylideneamino) -6-phenyl 1, 2, 4 triazolo 1, 5- a pyrimidine (1. 2 g). (mp. 197-198°C).

The following Table 3 shows compounds of the formula (Ia), which were synthesized according to the processes mentioned above.

Table 3 Comp. Melting point No. X Y Z R2 (°C) 1 Cl H H N=CHN (CH3) 2 180-182 2 Cl H 2-Cl N=CHN(CH3)2 192-198 3 Cl H 4-Cl N=CHN (CH3) 2 213-216 (decomp. ) 4 Cl H 2-CH3 N=CHN (CH3) 2 148-150 5 Cl H 3-CH3 N=CI-IN (CH3) 2 178-180 6 Br H 4-CH3 N=CHN(CH3)2 >250 7 Cl H 4-CH3 N=CHN(CH3)2 246-247 (decomp. ) 8 Cl H 4-CH3 H in 198-204 H X 9 Cl H 4-CH3 228-229 (decomp.) 3 P) - N=C-N O 10 Cl H 4-CH3 <- 183-185 11 Cl H 4-CH3 N=CHN(C2H5)2 190-193 12 Cl H 4-CH3 N=CITN (isO-C3H7) 2 129-133 13 Cl H 4-CH3 N=CHN (n-C4H9) 2 nD 'N \N I \ 14 Cl H 4-CH3 W 242-244

Table 3 (continued) Comp. Melting point No. X Y Z R2 (°C) 15 Cl H 3-CF3 N=CHN (CH3) 2 159-161 16 Cl H 4-CF3 N=CHN(CH3)2 232-236 (decomp. ) 17 Cl H 4-tert-C4H9 N=CHN (CH3) 2 203-211 18 Cl H 4-OCH3 N=CHN(CH3)2 240-242 19 Cl H 4-OCHF2 N=CHN(CH3)2 167-176 2@ Cl H 4-OC2Hs N=CHN(CH3)2 175-180 21 Cl H 3,4-Cl2 N=CHN(CH3)2 194- 198 22 Cl H 3 -Cl,4-CF3 N=CHN(CH3)2 210-211 23 Cl H 3,4-(OCH3)2 N=CHN(CH3)2 179-180 24 Cl Cl H N=CHN(CH3)2 197- 198 25 Cl Cl 2-Cl N=CHN(CH3)2 189-201 26 Cl Cl 2-CH3 N=CHN(CH3)2 193- 195 27 Cl Cl 4-Cl N=CHN (CH3) 2 217-222 28 Cl H 2-F N=CHN(CH3)2 207-209 29 Cl H 3-F N=CHN (CH3) 2 180-182 30 Cl H 4-F N=CHN(CH3)2 204-206 31 Cl H 4-Br N=CHN(CH3)2 243-248 32 Cl H 4-CH3 N=CHN(CH3)(C3H7-iso) 127-130 33 Cl H 2,5-(CH3)2 N=CHN(CH3)2 103-106 34 Cl H 3,5-(CH3)2 N=CHN(CH3)2 163-166 35 Cl H 4 4 N=CHN(CH3)2 246-248 (decomp.) H H C \ X zCH 36 Cl H 2, 3"N=CHN (CH3) 2 amorphous Synthesis Example 3 (Raw material for the compound of Synthesis Example 1)

A solution of ethyl 4-methylphenylacetate (13. 2 g), methyl formate (70 g) and di- methylformamide (40 ml) was added dropwise at room temperature to a suspension of-60% sodium hydride (6. 4 g) in dimethylformamide (40 ml), and the mixture was stirred for 2 hours. After being kept standing for a night, the reaction solution was acidified by adding water and concentrated hydrochloric acid. Then it was extracted with ethyl acetate. After washing with water, the organic layer was dried over anhydrous magnesium sulphate. To the residue obtained after elimination of solvent by distillation, 3,5-diamino-1,2,4-triazole (8.0 g) and acetic acid (200 ml) were added, and the mixture was refluxed by heating for 5 hours. Water was added to the mixture and the precipitate was filtered, washed with water and then with n-hexane and dried in the air to obtain 2-amino-6- (4-methylphenyl) I,. 2, 4 triazolo 1, 5- a pyrimidin-5-ol (15. 0 g). (mp. > 250. ) Synthesis Example 4 (Raw material for the compound of Synthesis Example 2) A mixture of diethyl phenylmalonate (5. 2 g), 3, 5-diamino-1, 2, 4-triazole (2. 1 g) and tri-n-butylamine (4. 4 g) was stirred at 180. for 6 hours. After addition of water and chloroform to the reaction mixture, the solid formed was filtered, washed with water and then with chloroform and dried in the air to obtain 2-amino-6- phenyl 1, 2, 4 triazolo 1, 5-a pyrimidin-5, 7-diol (3. 4g). (mp. >250.) The following Table 4 shows compounds of the formula (Va), which were synthe- sized according to the process mentioned above.

Table 4

Comp.

No,YZ(mp.°C)(IRcm') V-1 H H >250 1682 V-2 H 2-Cl >250 1669 V-3 H 3-Cl >250 1678 V-4 H 4-Cl >250 1668 V-5 H 2-CH3 >250 1660 V-6 H 3-CH3 >250 1678 V-7 H 4-CH3 >250 1671 V-8 H 3-CF3 >250 1668 V-9 H 4-CF3 >250 1682 V-10 H 4-tert-C4H9 >250 1673 V-11 H 4-OCH3 >250 1670 V-12 H 4-OCHF2 >250 V-13 H 4-OC2H5 >250 1674 V-14 H 3,4-Cl2 >250 1685 V-15 H 3-Cl,4-CF3 >250 1677 V-16 H 3,4-(OCH3)2 >250 V-17 OH H >250 1660 V-18 OH 2-Cl >250

Table 4 (continued) Comp. No. Y Z (mp. °C) (IR cm~1) V-19 H 2-F >250 1682 V-20 H 3-F >250 1673 V-21 H 4-F >250 1673 V-22 H 2,4-F2 >250 1682 V-23 H 2-Br >250 1662 V-24 H 4-Br >250 1668 V-25 H 2,5-(CH3)2 >250 1668 V-26 H 3,5-(CH3)2 >250 1669 V-27 H >250 1669 H C sC"CH cCH V-28 H 2, 3">250 1671

Biological Test Examples Test Example A Test of foliar spray effect against rice blast Preparation of formulations of the compounds tested.

Active compound : 30 - 40 parts by weight Carrier : mixture of diatomaceous earth and kaolin (1 : 5), 55-65 parts by weight Emulsifier : polyoxyethylene alkyl phenyl ether, 5 parts by weight.

Each of the wettable powders is prepared by pulverizing and mixing the above amounts of active compound, carrier and emulsifier. A portion of the wettable pow- der containing the prescribed amount of the active compound is diluted with water, followed by mixing.

Testing procedure Seedlings of paddy rice (variety : Kusabue) were cultivated in plastic pots each hav- ing a diameter of 7 cm. The previously prepared solution of the prescribed concen- tration of active compound was sprayed over the seedlings in the 3-4 leaf stage, at a rate of 50 ml per 1 pots. 1 day after the application, a suspension of artificially cul- tured Pyricularia oryzae spores was spray-inoculated once on the seedlings, and the seedlings were maintained at 25°C and 100% relative humidity for infection. 7 days after the inoculation, the degree of infection per pot was examined and rated accord- ing to the following criteria. Further, the control value (%) was calculated, and the phytotoxicity was tested at the same time. The data are average values of the results of 3 pots in one plot.

Evaluation of the degree of infection Degree of Infection Percentage of lesion (spot) area (%) 0 0 0. 5 less than 2 1 2 - less than 5 2 5 - less than 10 3 10 - less than 20 4 20 - less than 40 5 more than 40 Control value (%) = {1- (degree of infection in treated plot : degree of infection in non-treated plot)} x 100 As a result, Compounds No. 1,7, 8,16, 17,18, 21 and 25 showed a control value of higher than 80% at an active compound concentration of 500 ppm.

Test Example B Test of foliar spray effect against Helminthosporium leaf spot Test method Paddy rice (variety : Kusabue) was cultivated in plastic pots each havng a diameter of 7 cm. At the 3-4 leaf stage the plants were sprayed with a diluted solution of the pre- scribed concentration of active compound, which solution had been prepared in the same manner as in Test Example A. The solution was sprayed in an amount of 50 ml per 3 pots. 1 day after the application, a suspension of spores of artificially cultured Cochliobolus miyabeanus was spray-inoculated once on the seedlings, and the seed- lings were maintained at 25°C and 100% relative humidity for infection. 4 days after the inoculation, the degree of infection per pot was examined and rated according to

the following standard. Further, the control value was calculated in %, and the phy- totoxicity was tested at the same time. The data are average values of the results of 3 pots in one plot.

Evaluation of the degree of infection : Degree of Infection Degree of Damage 0 no damage 1 slight 2 little 3 medium 4 much 5 tremendous Control value (%) = { 1-(degree of infection in treated plot - degree of infec- tion in non-treated plot} x 100 As a result, Compounds No. 1,2, 3,7, 16,18, 21,25, 28,31, 33,34 and 36 showed a control value of higher than 80 % at an active compound concentration of 500 ppm.

Test Example C Test of foliar spray effect against Alternaria brassicicola Test method About 15 seeds of Brassica compestris (variety : Misugi) were sown in plastic pots each having a diameter of 7 cm, and were cultivated in a green-house at 15-25°C.

Two weeks after sowing, the seedligs were sprayed with a diluted solution of the prescribed concentration of active compound, which solution had been prepared in

the same manner as in Test Example A. The solution was sprayed in an amount of 25 ml per 3 pots. 1 day after the application, a suspension of spores of artificially cultured Alternaria brassicicola was spray inoculated once on the seedlings, and the seedlings were maintained at 25°C and 100% relative humidity for infection. 4 days after the inoculation, the degree of infection per pot was examined and evaluated according to the standard set forth in Test Example B. The phytotoxicity was tested at the same time. The data are average values of the results of 3 pots per one plot.

As a result, Compounds No. 3,7, 10,18, 19,21, 26,28, 29,30, 31, 32, 33 and 34 showed a control value of higher than 80% at an active compound concentration of 500 ppm.

Test Example D Test of foliar spray effect against Alternaria leaf spot Test method Three weeks after complete spread, a leaf of an apple (variety : Oregon Super deli- cious) that had been cultivated in a green-house at 15-25°C was put into a glass tube having a diameter of 2 cm and being filled with water. Each leaf was then sprayed with 2 ml of a diluted solution of the prescribed concentration of active compound, which solution had been prepared in the same manner as in Test Example A. 1 day after the application, a suspension of spores of artificially cultured Alternaria mali was spray inoculated once, and the leaves were maintained at 25°C and 100% rela- tive humidity for infection. 2 days after the inoculation, the degree of infection per leaf was examined and evaluated according to the standard set forth in Test Example B. The phytotoxicity was tested at the same time. The data are average values of the results of 3 leaves per one plot.

As a result, Compounds No. 3,7, 18 and 21 showed a control value of higher than 80% at an active compound concentration of 500 ppm.

Formulation Examples Formulation Example I (Granules) 25 parts by weight of water were added to a mixture of 10 parts by weight of Com- pound No. 1 according to the invention, 30 parts by weight of bentonite (montmoril- lonite), 58 parts by weight of talc and 2 parts by weight of lignin sulphonic acid salt, and the mixture was kneaded thoroughly. The resulting product was granulated by means of an extrusion granulator to form granules having a size of from 10 to 40 meshes. The granules were dried at a temperature between 40 and 50°C.

Formulation Example II (Granules) 95 parts by weight of a clay mineral having a particle size distribution within a range of from 0. 2 to 2 mm were introduced into a rotary mixer. This product was uniformly wetted by spraying thereto under rotation a mixture of 5 parts by weight of Com- pound No. 21 according to the invention and a liquid diluent. The granules obtained in this manner were dried at a temperature between 40 and 50°C.

Formulation Example III (Emulsion) An emulsion was obtained by mixing 30 parts by weight of Compound No. 18 ac- cording to the invention, 5 parts by weight of xylene, 8 parts by weight of poly- oxyethylene alkyl phenyl ether, 7 parts by weight of calcium alkylbenzene sulpho- nate and 50 parts by weight of water with stirring.

Formulation Example IV (Wettable Powder) A wettable powder was prepared by thoroughly mixing 15 parts by weight of Com- pound No. 10 according to the invention, 80 parts by weight of a mixture (1 : 5) of White Carbon (fine powder of hydrated non-crystalline silicon oxide) and powdery clay, 2 parts by weight of sodium alkylbenzene sulphonate and 3 parts by weight of a condensate of sodium alkylnaphthalene sulphonate and formaldehyde in powdery state.

Formulation Example V (Water Dispersible Granules) 20 parts by weight of Compound No. 25 according to the invention, 30 parts by weight of sodium lignin sulphonate, 15 parts by weight of bentonite and 35 parts by weight of calcined diatomaceous earth powder were thoroughly mixed with water.

The resulting product was granulated by means of extrusion through a 0. 3 mm screen. After drying the product, water dispersible granules were obtained.