The novel compounds of formula I: ##STR1## (A, L, n and R.sup.1 through R.sup.4 are defined in the specification) show selective fungicidal activity. The new compounds can be combined with carriers and adjuvants to form fungicidal compositions.

BACKGROUND OF THE INVENTION 
This invention relates to certain triazolopyrimidine compounds, a process 
for their preparation, compositions containing such compounds, a method 
for combating a fungus at a locus comprising treating the locus with such 
compounds and their use as fungicides. 
U.S. Pat. No. 4,567,263 claims compounds of the general formula 
##STR2## 
in which R.sup.1 represents alkyl, halogen, alkoxy, cyano, cycloalkyl, 
aryl, aryloxy, arylthio, aralkyl, arylalkyl, arylalkyloxy or arylalkylthio 
each optionally substituted by halogen or alkoxy; or (R.sup.1).sub.n 
represents a benzene, indane or tetrahydronaphthalene ring fused with the 
phenyl ring, aromatic moieties in the above groups being optionally 
substituted by alkyl, alkoxy, halogen or cyano; n is 1 or 2; R.sup.2 and 
R.sup.3 are each hydrogen, alkyl or aryl, A represents a nitrogen atom or 
a CR.sup.4 group, and R.sup.4 is as R.sup.2 but can also be halogen, cyano 
or alkoxycarbonyl or together with R.sup.3 can form an alkylene chain 
containing up to two double bonds. The compounds are said to be active 
against various phytopathogenic fungi, especially those of the phycomycete 
class. However evidence of fungicidal activity is only provided for these 
compounds against Plasmopara viticola, a member of the oomycete class of 
fungi. 
U.S. Pat. No. 5,593,996 claims compounds of the general formula 
##STR3## 
in which R.sup.1 represents an optionally substituted alkyl, alkenyl, 
alkadienyl, cycloalkyl, bicycloalkyl or heterocyclyl group; R.sup.2 
represents a hydrogen atom or an alkyl group; or R.sup.1 and R.sup.2 
together with the interjacent nitrogen atom represent an optionally 
substituted heterocyclic ring; R.sup.3 represents an optionally 
substituted phenyl or naphthyl group; and R.sup.4 represents a halogen 
atom or a group --NR.sup.5 R.sup.6 where R.sup.5 represents a hydrogen 
atom or an amino, alkyl, cycloalkyl or bicycloalkyl group and R.sup.6 
represents a hydrogen atom or an alkyl group. 
SUMMARY OF THE INVENTION 
The present invention provides a compound of formula I 
##STR4## 
in which R.sup.1 represents an optionally substituted alkyl, alkenyl, 
alkynyl, alkadienyl, aryl, heteroaryl, cycloalkyl, bicycloalkyl or 
heterocyclyl group, 
R.sup.2 represents a hydrogen atom or an optionally substituted alkyl, 
alkenyl, alkynyl, alkadienyl, aryl, heteroaryl, cycloalkyl, bicycloalkyl 
or heterocyclyl group, or 
R.sup.1 and R.sup.2 together with the interjacent nitrogen atom represent 
an optionally substituted heterocyclic ring, 
R.sup.3 represents an alkyl group, 
R.sup.4 represents hydrogen or an alkyl or aryl group, 
L represents halogen or an optionally substituted alkyl or alkoxy group, 
A represents N or CR.sup.5, wherein R.sup.5 has the meaning given for 
R.sup.4, and 
n is 0 or an integer from 1 to 5. 
The new compounds show an excellent selective fungicidal activity in 
various crops. 
It is an object of the present invention to provide novel, selective 
fungicidal compounds. 
It is also an object of the invention to provide methods for controlling 
undesired fungus by contacting said plants with a fungicidally effective 
amount of the new compounds. 
It is another object of the invention to provide selective fungicidal 
compositions containing the new compounds as active ingredients. 
These and other objects and features of the invention will be more apparent 
from the detailed description set forth hereinbelow, and from the appended 
claims. 
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
It has surprisingly been found that the compounds of formula I 
##STR5## 
in which R.sup.1 through R.sup.4, A, L and n have the meaning given above 
for formula I show an excellent fungicidal activity against a broad range 
of fungi. 
In general terms, unless otherwise stated, as used herein the term halogen 
atom may denote a bromine, iodine, chlorine or fluorine atom, and is 
especially a bromine, chlorine or fluorine atom. 
Optionally substituted moieties may be unsubstituted or have from one up to 
the maximal possible number of substituents. Typically, 0 to 2 
substituents are present. 
In general terms, unless otherwise stated herein, the terms alkyl, alkenyl, 
alkynyl, alkadienyl as used herein with respect to a radical or moiety 
refer to a straight or branched chain radical or moiety. As a rule, such 
radicals have up to 10, in particular up to 6 carbon atoms. Suitably an 
alkyl moiety has from 1 to 6 carbon atoms, preferably from 1 to 3 carbon 
atoms. A preferred alkyl moiety is an ethyl or especially a methyl group. 
Suitably an alkenyl moiety has from 2 to 6 carbon atoms. A preferred 
alkenyl moiety is allyl or especially a 2-methylallyl group. 
Unless otherwise stated herein, the term aryl, as used herein with respect 
to a radical or moiety,refers to an aryl group having 6, 10 or 14 carbon 
atoms, preferably 6 or 10 carbon atoms, in particular phenyl being 
optionally substituted by one or more halogen atoms, nitro, cyano, alkyl, 
preferably C.sub.1-6 alkyl, alkoxy, preferably C.sub.1-6 alkoxy. 
Generally, unless otherwise stated herein, the term heteroaryl, as used 
herein with respect to a radical or moiety, refers to a heteroaryl group 
having 5 or 6 ring atoms selected from carbon, nitrogen, oxygen and 
sulfur, at least one of which being nitrogen, oxygen or sulfur. 
Unless otherwise stated herein, the term cycloalkyl, as used herein with 
respect to a radical or moiety, refers to a cycloalkyl group having 3 to 8 
carbon atoms, preferably 5 to 7 carbon atoms, in particular cyclohexyl 
being optionally substituted by one or more halogen atoms, nitro, cyano, 
alkyl, preferably C.sub.1-6 alkyl, alkoxy, preferably C.sub.1-6 alkoxy. 
Furthermore, unless otherwise stated herein, the term heterocyclyl or 
heterocyclic ring, as used herein with respect to a radical or moiety, 
refers to a saturated heterocyclyl group having 5 or 6 ring atoms selected 
from carbon, nitrogen, oxygen and sulfur, at least one of which being 
nitrogen, oxygen or sulfur being optionally substituted by one or more 
halogen atoms, nitro, cyano, alkyl, preferably C.sub.1-6 alkyl, alkoxy, 
preferably C.sub.1-6 alkoxy, in particular pyrrolidinyl, pyrazolidinyl, 
piperidinyl, piperazinyl or morpholin-4-yl. 
The invention especially relates to compounds of the general formula I in 
which any alkyl part of the groups R.sup.1 through R.sup.4 which may be 
straight chained or branched, contains up to 10 carbon atoms, preferably 
up to 9 carbon atoms, more preferably up to 6 carbon atoms, any alkenyl or 
alkynyl part of the substituents R.sup.1 through R.sup.4 contains up to 10 
carbon atoms, preferably up to 9 carbon atoms, more preferably up to 6 
carbon atoms, any cycloalkyl part of the substituents R.sup.1 through 
R.sup.4 contains from 3 to 10 carbon atoms, preferably from 3 to 8 carbon 
atoms, more preferably from 3 to 6 carbon atoms, and any aryl part of the 
substituents R.sup.1 through R.sup.4 contains 6, 10 or 14 carbon atoms, 
preferably 6 or 10 carbon atoms, and in which each optionally substituted 
group independently is substituted by one or more halogen atoms or nitro, 
cyano, alkyl, preferably C.sub.1-6 alkyl, cycloalkyl, preferably C.sub.3-6 
cycloalkyl, cycloalkenyl, preferably C.sub.3-6 cycloalkenyl, haloalkyl, 
preferably C.sub.1-6 haloalkyl, halocycloalkyl, preferably C.sub.3-6 
halocycloalkyl, alkoxy, preferably C.sub.1-6 alkoxy, haloalkoxy, 
preferably C.sub.1-6 haloalkoxy, phenyl, halo- or dihalo-phenyl or pyridyl 
groups. Any alkyl, alkenyl or alkynyl group may be linear or branched. A 
4- to 6- membered heterocyclic group may be any heterocyclic group with 4 
to 6 ring atoms, interrupted by one or more heteroatoms selected from 
sulfur, nitrogen, and oxygen, preferably oxygen. A halogen atom suitably 
denotes a fluorine, chlorine or bromine atom. 
The invention especially relates to compounds of the general formula I in 
which R.sup.1 represents a C.sub.1-10 alkyl, C.sub.1-10 haloalkyl, 
C.sub.3-6 cycloalkyl, C.sub.3-8 cycloalkyl-C.sub.1-6 alkyl, C.sub.1-10 
alkoxy-C.sub.1-6 alkyl or phenyl group, in particular a fluorinated 
C.sub.1-10 alkyl group and R.sup.2 represents a C.sub.1-10 alkyl, 
C.sub.3-6 cycloalkyl, C.sub.3-8 cycloalkyl-C.sub.1-6 alkyl, C.sub.1-10 
alkoxy-C.sub.1-6 alkyl or phenyl group, in particular a hydrogen atom. 
Particularly preferred are compounds of formula I, in which the phenyl 
group 
##STR6## 
is selected from 
##STR7## 
The compounds according to general formula I are oils, gums, or, 
predominantly crystalline solid materials. They are superior through their 
valuable fungicidal properties, in particular their enhanced systemicity 
and enhanced fungitoxicity against tomato early blight. For example, they 
can be used in agriculture or related fields for the control of 
phytopathogenic fungi such as Alternaria solani, Botrytis cinerea, 
Cercospora beticola, Cladosporium herbarum, Corticium rolfsii, Erysiphe 
graminis, Helminthosporium tritici repentis, Leptosphaeria nodorum, 
Micronectriella nivalis, Monilinia fructigena, Mycosphaerella ligulicola, 
Mycosphaerella pinodes, Pyricularia grisea f.sp. oryzae, Rhizoctonia 
solani and Sclerotinia sclerotiorum, in particular for the control of 
Alternaria solani and Botrytis cinerea. The compounds of general formula I 
according to the invention possess a high fungicidal activity within a 
wide concentration range and may be used in agriculture without any 
difficulties. 
Moreover, the compounds according to the invention show enhanced residual 
control of fungi compared with conventional fungicides. 
Good results in terms of control of phythopathogenic fungi are obtained 
with a compound as defined in formula I wherein: 
R.sup.3 represents a methyl group; 
R.sup.1 represents straight chained or branched C.sub.1 -C.sub.6 -alkyl, in 
particular ethyl or isopropyl, C.sub.3-7 -cycloalkyl, in particular 
cyclopentyl, straight chained or branched C.sub.1 -C.sub.6 -haloalkyl, in 
particular 2,2,2-trifluoroethyl or 1,1,1-trifluoroprop-2-yl, or straight 
chained or branched C.sub.2 -C.sub.6 -alkenyl, in particular allyl or 
2-methylallyl, and R.sup.2 represents hydrogen or C.sub.1 -C.sub.6 -alkyl, 
in particular nydrogen methyl or ethyl; or 
R.sup.1 and R.sup.2 together with the interjacent nitrogen atom represent a 
heterocyclic ring with 5 or 6 carbon atoms being optionally substituted 
with one or two C.sub.1 -C.sub.6 -alkyl groups, in particular in which 
R.sup.1 and R.sup.2 together with the interjacent nitrogen atom represent 
an optionally substituted pyridin-1-yl group, such as piperidin-1-yl or 
4-methylpiperidin-1-yl; 
A is N, and R.sup.4 is hydrogen; 
In particularly preferred are the compounds of formula IA, 
##STR8## 
in which R.sup.1 and R.sup.2 have the meaning given, and 
L.sup.1, L.sup.2 and L.sup.3 each independently represent hydrogen, 
fluorine or chlorine at least one of which being fluorine or chlorine. 
Especially good results in terms of control of phytopathogenic fungi are 
obtained by using, for example, the following compounds of formula I: 
6-(2-chloro-6-fluorophenyl)-5-methyl-7-(4-methylpiperidin-1-yl)-[1,2,4]tri 
azolo[1,5-a]pyrimidine; 
6-(2-fluorophenyl)-5-methyl-7-(4-methylpiperidin-1-yl)-[1,2,4]triazolo[1,5 
-a]pyrimidine; 
6-(2-chlorophenyl)-5-methyl-7-(4-methylpiperidin-1-yl)-[1,2,4]triazolo[1,5 
-a]pyrimidine; 
6-(2-chloro-6-fluorophenyl)-5-methyl-7-(N,N-diethylamino)-[1,2,4]triazolo[ 
1,5-a]pyrimidine; 
6-(2-chloro-6-fluorophenyl)-5-methyl-7-(N-ethylamino)-[1,2,4]triazolo[1,5- 
a]pyrimidine; 
6-(2-chloro-6-fluorophenyl)-5-methyl-7-(N-(2,2,2-trifluoroethyl)-amino)-[1 
,2,4]triazolo[1,5-a]pyrimidine; 
6-(2,6-difluorophenyl)-5-methyl-7-(4-methylpiperidin-1-yl)-[1,2,4]triazolo 
[1,5-a]pyrimidine; 
6-(2,6-dichlorophenyl)-5-methyl-7-(4-methylpiperidin-1-yl)-[1,2,4]triazolo 
[1,5-a]pyrimidine; 
6-(2-chloro-6-fluorophenyl)-5-methyl-7-(N-isopropylamino)-[1,2,4]triazolo[ 
1,5-a]pyrimidine; 
6-(2-chloro-6-fluorophenyl)-5-methyl-7-(N-cyclopentylamino)-[1,2,4]triazol 
o[1,5-a]pyrimidine; 
6-(2,6-difluorophenyl)-5-methyl-7-(N,N-diethylamino)-[1,2,4]triazolo[1,5-a 
]pyrimidine and 
6-(2-chloro-6-fluorophenyl)-5-methyl-7-(N-ethyl-N-2-methylallyl-amino)-[1, 
2,4]triazolo[1,5-a]pyrimidine, 
6-(2,4,6-trifluorophenyl)-5-methyl-7-(4-methylpiperidin-1-yl)-[1,2,4]triaz 
olo[1,5-a]pyrimidine; 
(2,4,6-trifluorophenyl)-5-methyl-7-(piperidin-1-yl)-[1,2,4]triazolo[1,5-a] 
pyrimidine; 
(2-chloro-6-fluorophenyl)-5-methyl-7-(piperidin-1-yl)-[1,2,4]triazolo[1,5- 
a]pyrimidine; 
(2-fluorophenyl)-5-methyl-7-(piperidin-1-yl)-[1,2,4]triazolo[1,5-a]pyrimid 
ine; 
6-(2-chloro-6-fluorophenyl)-5-methyl-7-(N-(1,1,1-trifluoroprop-2-yl)-amino 
)-[1,2,4]triazolo[1,5-a]pyrimidine; 
6-(2,6-difluorophenyl)-5-methyl-7-(N-(1,1,1-trifluoroprop-2-yl)-amino)-[1, 
2,4]triazolo[1,5-a]pyrimidine; 
6-(2,4,6-trifluorophenyl)-5-methyl-7-(N-(1,1,1-trifluoroprop-2-yl)-amino)- 
[1,2,4]triazolo[1,5-a]pyrimidine; 
6-(2,4,6-trifluorophenyl)-5-methyl-7-(N,N-diethylamino)-[1,2,4]triazolo[1, 
5-a]pyrimidine; 
6-(2,4,6-trifluorophenyl)-5-methyl-7-(N-ethylamino)-[1,2,4]triazolo[1,5-a] 
pyrimidine. 
The present invention further provides a process for the preparation of a 
compound of formula I, wherein R.sup.3 represents a methyl group, which 
comprises 
(a) treating a 5-halo-azolopyrimidine of formula II, 
##STR9## 
in which A, R.sup.1, R.sup.2 R.sup.4, L and n have the meaning given for 
formula I, with an alkyl malonate in the presence of a base, 
(b) heating the resulting aminoazolopyrimidin-5-ylmalonate of formula III, 
##STR10## 
in which R.sup.1, R.sup.2, R.sup.4, A, L and n have the meaning given in 
the preceding claims, and R represents an alkyl group in the presence of 
an acid. 
Furthermore, the compounds of formula I may also be prepared from the 
7-aminotriazolopyrimidines of formula IV, 
##STR11## 
in which R.sup.3, R.sup.4, A, L and n have the meaning given in the 
preceding claims, which are treated with a halogenating agent in the 
presence of a diazotising agent, and treating the resulting compound of 
the general formula V 
##STR12## 
in which R.sup.3, R.sup.4, A, L and n are as defined above; and 
Hal represents a chlorine or bromine atom, 
with an amine of the general formula VI 
##STR13## 
in which R.sup.1 and R.sup.2 are as defined above. 
Compounds of formula IV are known e.g. from U.S. Pat. No. 4,567,263. 
The reaction between the 5- halo-7-amino-6-phenyl-triazolopyrimidines of 
formula II, which are known from U.S. Pat. No. 5,593,996, and the alkyl 
malonate is conveniently carried out in the presence of a solvent. 
Suitable solvents include ethers, such as dioxane, diethyl ether and, 
especially, tetrahydrofuran, optionally halogenated hydrocarbons such as 
mineral oil, dichloromethane and aromatic hydrocarbons, for example 
toluene, nitrites such as acetonitrile or mixtures of these solvents. The 
reaction is suitably carried out at a temperature in the range from 
0.degree. C. to 100.degree. C., the preferred reaction temperature being 
from 20.degree. C. to 70.degree. C. It is also preferred that the reaction 
is carried out in the presence of a strong base. Suitable strong bases 
include hydrides such as sodium hydride and organometallic compounds such 
as butyllithium and amides such as sodium amide or lithium 
diisopropylamide. 
The compounds of general formula I have been found to have fungicidal 
activity. Accordingly the invention further provides a fungicidal 
composition which comprises a carrier and, as active ingredient, at least 
one compound of formula I as defined above. A method of making such a 
composition is also provided which comprises bringing a compound of 
formula I as defined above into association with at least one carrier. 
Such a composition may contain a single compound or a mixture of several 
compounds of the present invention. It is also envisaged that different 
isomers or mixtures of isomers may have different levels or spectra of 
activity and thus compositions may comprise individual isomers or mixtures 
of isomers. 
A composition according to the invention preferably contains from 0.5% to 
95% by weight of active ingredient. 
A carrier in a composition according to the invention is any material with 
which the active ingredient is formulated to facilitate application to the 
locus to be treated, which may for example be a plant, seed or soil, or to 
facilitate storage, transport or handling. A carrier may be a solid or a 
liquid, including material which is normally gaseous but which has been 
compressed to form a liquid, and any of the carriers normally used in 
formulating fungicidal compositions may be used. 
The compositions may be manufactured into e.g. emulsion concentrates, 
solutions which may be sprayed directly or diluted, diluted emulsions, 
wettable powders, soluble powders, dusts, granulates, water-dispersible 
granulates, microencapsulates by well-established procedures. The form of 
application such as spraying, atomizing, dispersing, pouring may be chosen 
like the compositions according to the desired objectives and the given 
circumstances. 
The formulations, i.e. the compositions which comprise at least one 
compound according to general formula I and optionally solid and/or liquid 
auxiliaries and adjuvants, may be prepared by well-established procedures, 
e.g. intensive mixing and/or grinding of the active ingredients with other 
substances, such as fillers, solvents, solid carriers, and optionally 
surface-active compounds (tensides). 
Solvents may be aromatic hydrocarbons, preferably the fractions C.sub.8 to 
C.sub.12, e.g. xylenes or xylene mixtures, substituted naphthalenes, 
phthalic acid esters, such as dibutyl or dioctyl phthalate, aliphatic 
hydrocarbons, e.g. cyclohexane or paraffins, alcohols and glycols as well 
as their ethers and esters, e.g. ethanol, ethyleneglycol mono- and 
dimethyl ether, ketones such as cyclohexanone, strongly polar solvents 
such as N-methyl 2-pyrrolidone, dimethyl sulfoxide, alkyl formamides, 
epoxidized vegetable oils, e.g. epoxidized coconut or soybean oil, water. 
Mixtures of different liquids are often suitable. 
Solid carriers, which may be used for dusts or dispergible powders, may be 
mineral fillers, such as calcite, talc, kaolin, montmorillonite, 
attapulgite. The physical properties may be improved by addition of highly 
dispersed silica gel or highly dispersed polymers. Carriers for granulates 
may be porous material, e.g. pumice, broken brick, sepiolite, bentonite, 
non-sorptive carriers may be calcite or sand. Additionally, a multitude of 
pre-granulated inorganic or organic materials may be used, such as 
dolomite or crushed plant residues. 
Fungicidal compositions are often formulated and transported in 
concentrated form which is subsequently diluted by the user before 
application. The presence of small amounts of a carrier which is a 
surface-active agent facilitates this process of dilution. Thus, 
preferably one carrier in a composition according to the invention is a 
surface active agent. For example, the composition may contain at least 
two carriers, at least one of which is a surface active agent. 
Suitable surface-active substances may be non-ionogenic, anionic or 
cationic tensides with good dispersing, emulgating and wetting properties 
depending on the nature of the compound according to general formula I to 
be formulated. Tensides may also mean mixtures of tensides. 
Suitable tensides may be so-called water-soluble soaps as well as 
water-soluble synthetic surface-active compounds. 
Soaps usually are alkali, earth alkali or optionally-substituted ammonium 
salts of higher fatty acids (C.sub.10 -C.sub.20), e.g. the sodium or 
potassium salts of oleic or stearic acid or of mixtures of natural fatty 
acids which are prepared, for example, from coconut or tallow oil. 
Furthermore, methyl-taurine salts of fatty acids may be used. 
However, so-called synthetic tensides are preferably used, especially fatty 
sulphonates, fatty sulfates, sulfonated benzimidazole derivatives or alkyl 
aryl sulphonates. 
The fatty sulfates or fatty sulphonates are normally used as alkali, earth 
alkali or optionally-substituted ammonium salts and have an alkyl moiety 
of 8 to 22 carbon atoms, whereby alkyl also means the alkyl moiety of acyl 
residues, such as the sodium or calcium salt of lignin sulfonic acid, of 
sulfuric acid dodecylate or of a mixture of fatty alcohols prepared from 
natural fatty acids. This also includes the salts of sulfuric acid esters, 
sulfonic acids and adducts of fatty alcohols and ethylene oxide. The 
sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid 
residues and a fatty acid residue with 8 to 22 carbon atoms. Alkyl aryl 
sulphonates are, for example, the sodium, calcium or triethyl ammonium 
salts of dodecyl benzene sulfonic acid, dibutyl naphthalene sulfonic acid 
or of a condensate of naphthalene sulfonic acid and formaldehyde. 
Furthermore, phosphates, such as the salts of the phosphoric acid ester of 
a p-nonylphenol-(4-14)-ethylene oxide adduct or phospholipids, may be 
used. 
Non-ionic tensides are preferably polyglycolether derivatives of aliphatic 
or cycloaliphatic alcohols, saturated or non-saturated fatty acids and 
alkylphenols, which have 3 to 10 glycol ether groups and 8 to 20 carbon 
atoms in the (aliphatic) hydrocarbon residue and 6 to 18 carbon atoms in 
the alkyl residue of the alkyl phenols. 
Other suitable non-ionic tensides are the water-soluble, 20 to 250 ethylene 
glycol ether groups containing polyadducts of ethylene oxide and 
polypropylene glycol, ethylene diamino polypropylene glycol and alkyl 
polypropylene glycol with 1 to 10 carbon atoms in the alkyl moiety, the 
substances normally contain 1 to 5 ethylene glycol units per propylene 
glycol unit. 
Examples of non-ionic tensides are nonylphenol polyethoxy ethanols, castor 
oil polyglycol ether, polyadducts of ethylene oxide and polypropylene, 
tributyl phenoxy polyethoxy ethanol, polyethylene glycol, octyl phenoxy 
polyethoxy ethanol. 
Furthermore, fatty acid esters of polyoxy ethylene sorbitan, such as 
polyoxy ethylene sorbitan trioleate may be used. 
Cationic tensides preferably are quaternary ammonium salts, which have at 
least one alkyl residue with 8 to 22 carbon atoms and, furthermore, low, 
optionally-halogenated alkyl, benzyl or hydroxyalkyl residues. The salts 
are preferably halides, methyl sulfates or alkyl sulfates, e.g. stearyl 
trimethyl ammonium chloride or benzyl bis(2-chloroethyl) ethyl ammonium 
bromide. 
The compositions of the invention may for example be formulated as wettable 
powders, dusts, granules, solutions, emulsifiable concentrates emulsions, 
suspension concentrates and aerosols. Wettable powders usually contain 
25%, 50% or 75% w/w of active ingredient and usually contain in addition 
to solid inert carrier, 3%-10% w/w of a dispersing agent and, where 
necessary, 0%-10% w/w of stabilizer(s) and/or other additives such as 
penetrants or stickers. Dusts are usually formulated as a dust concentrate 
having a similar composition to that of a wettable powder but without a 
dispersant, and may be diluted in the field with further solid carrier to 
give a composition usually containing 0.5%-10% w/w of active ingredient. 
Granules are usually prepared to have a size between 10 and 100 mesh ASTM 
(approx. 2.00 mm-0.15 mm), and may be manufactured by agglomeration or 
impregnation techniques. Generally, granules will contain 0.5%-75% active 
ingredient and 0-10% w/w of additives such as stabilizer, surfactants, 
slow release modifiers and binding agents. The so called "dry flowable 
powders" consist of relatively small granules having a relatively high 
concentration of active ingredient. Emulsifiable concentrates usually 
contain, in addition to a solvent or a mixture of solvents, 1%-50% w/v 
active ingredient, 2%-20% w/v emulsifiers and 0%-20% w/v of other 
additives such as stabilizers, penetrants and corrosion inhibitors. 
Suspension concentrates are usually compounded so as to obtain a stable, 
non-sedimenting flowable product and usually contain 10%-75% w/w active 
ingredient, 0.5%-15% w/w of dispersing agents, 0.1%-10% w/w of suspending 
agents such as protective colloids and thixotropic agents, 0%-10% of other 
additives such as defoamers, corrosion inhibitors, stabilizers, penetrants 
and stickers, and water or an organic liquid in which the active 
ingredient is substantially insoluble; certain organic solids or inorganic 
salts may be present dissolved in the formulation to assist in preventing 
sedimentation or as antifreeze agents for water. 
Aqueous dispersions and emulsions, for example compositions obtained by 
diluting a wettable powder or a concentrate according to the invention 
with water, also lie within the scope of the invention. The said emulsions 
may be of the water-in-oil or of the oil-in-water type, and may have a 
thick `mayonnaise` like consistency. 
The composition of the invention may also contain other ingredients, for 
example other compounds possessing herbicidal, insecticidal or fungicidal 
properties. 
Of particular interest in enhancing the duration of the protective activity 
of the compounds of this invention is the use of a carrier which will 
provide slow release of the fungicidal compounds into the environment of a 
plant which is to be protected. Such slow-release formulations could, for 
example, be inserted in the soil adjacent to the roots of a plant, or 
could include an adhesive component enabling them to be applied directly 
to the stem of a plant. 
As commodity the compositions may preferably be in a concentrated form 
whereas the end-user generally employs diluted compositions. The 
compositions may be diluted to a concentration of 0.001% of active 
ingredient (a.i.). The doses usually are in the range from 0.01 to 10 kg 
a.i./ha. 
The compositions of this invention can comprise also other compounds having 
biological activity, e.g. compounds having similar or complementary 
fungicidal activity or compounds having plant growth regulating, 
herbicidal or insecticidal activity. 
These mixtures of fungicides can have a broader spectrum of activity than 
the compound of general formula I alone. Furthermore, the other fungicide 
can have a synergistic effect on the fungicidal activity of the compound 
of general formula I. 
Examples of the other fungicidal compound are carbendazim, benomyl, 
thiophanate-methyl, thiabendazole, fuberidazole, etridiazole, 
dichlofluanid, cymoxanil, oxadixyl, ofurace, metalaxyl, furalaxyl, 
benalaxyl, fosetyl-aluminium, fenarimol, iprodione, procymidione, 
vinclozolin, penconazole, myclobutanil, R0151297, S3308, pyrazophos, 
ethirimol, ditalimfos, tridemorph, triforine, nuarimol, triazbutyl, 
guazatine, triacetate salt of 1,1'-iminodi(octamethylene)-diguanidine, 
propiconazole, prochloraz, flutriafol, hexaconazole, flusilazole, 
triadimefon, triadimenol, diclobutrazol, fenpropimorph, pyrifenox, 
cyproconazole, tebuconazole, epoxiconazole, 
4-chloro-N-(cyano(ethoxy)methyl)benzamide, fenpropidin, chlorozolinate, 
diniconazol, imazalil, fenfuram, carboxin, oxycarboxin, methfuroxam, 
dodemorph, blasticidin S, kasugamycin, edifenphos, kitazin P, 
cycloheximide, phthalide, probenazole, isoprothiolane, tricyclazole, 
pyroquilon, chlorbenzthiazon, neoasozin, polyoxin D, validamycin A, 
mepronil, flutolanil, pencycuron, diclomezin, phenazineoxide, nickel 
dimethyldithiocarbamate, techlofthalam, bitertanol, bupirimate, 
etaconazole, streptomycin, cypofuram, biloxazol, quinomethionate, 
dimethirimol, 1-(2-cyano-2-methoxyimino-acetyl)-3-ethyl urea, fenapanil, 
tolclofosmethyl, pyroxyfur, polyram, maneb, mancozeb, captafol, 
chlorothalonil, anilazin, thiram, captan, folpet, zineb, propineb, sulfur, 
dinocap, binapacryl, nitrothalisopropyl, dodine, dithianon, fentin 
hydroxide, fentin acetate, tecnazene, quintozen, dichloran, 
copper-containing compounds such as copper oxychloride, copper sulfate and 
Bordeaux mixture as well as organic mercury compounds, kresoxim-methyl, 
azoxystrobin, SSF-126, pyrimethanil, cyprodinil, spiroxamine, fludioxonil, 
quinoxyfen, BION, carpropamid, metconazole, dimethomorph, famoxadone, 
propanocarb, flumetover, fenpiclonil, fluazinam, mepanipyrim, triazoxide, 
chlorothalonil. 
The compounds of general formula I can be mixed with soil, peat or other 
rooting media for the protection of the plants against seed-borne, 
soil-borne or foliar fungal diseases. 
The invention still further provides the use as a fungicide of a compound 
of the general formula I as defined above or a composition as defined 
above, and a method for combating fungus at a locus, which comprises 
treating the locus, which may be for example plants subject to or 
subjected to fungal attack, seeds of such plants or the medium in which 
such plants are growing or are to be grown, with such a compound or 
composition. 
The present invention is of wide applicability in the protection of crop 
and ornamental plants against fungal attack. Typical crops which may be 
protected include vines, grain crops such as wheat and barley, rice, sugar 
beet, top fruit, peanuts, potatoes and tomatoes. The duration of the 
protection is normally dependent on the individual compound selected, and 
also a variety of external factors, such as climate, whose impact is 
normally mitigated by the use of a suitable formulation. 
The following examples further illustrate the present invention. It should 
be understood, however, that the invention is not limited solely to the 
particular examples given below.

EXAMPLE 1 
6-(2-Chloro-6-fluorophenyl)-5-methyl-7-(4-methylpiperidin-1-yl)-[1,2,4]tria 
zolo[1.5a]pyrimidine 
1A Diethyl 
[6-(2-chloro-6-fluorophenyl)-7-(4-methylpiperidin-1-yl)-[1,2,4-triazolo[1. 
5a]pyrimidine-5-yl]-malonate 
Sodium hydride (0.27 g of a 50% dispersion in mineral oil, 5.65 mmol) is 
added to diethylmalonate (20 ml). The mixture is diluted with acetonitrile 
and 
6-(2-chloro-6-fluorophenyl)-5-chloro-7-(4-methylpiperidin-1-yl)-[1,2,4]tri 
azolo[1.5a]pyrimidine (obtained according to U.S. Pat. No. 5,593,996, 2.0 
g, 4.71 mmol) is added. The reaction mixture is heated to 60.degree. C. 
and stirred for 20 hours. Aqueous ammonium chloride (50 ml) is added and 
the mixture is acidified with diluted hydrochloric acid. The reaction 
mixture is extracted with ethyl acetate (3.times.50 ml). The combined 
organic phases are dried and concentrated. The residue is purified by 
column chromatography (silica, toluene:ethyl acetate, 9:1). The pure 
product is obtained as tan crystals (0.95 g) with a melting point of 
162-163.degree. C. 
1B 
6-(2-Chloro-6-fluorophenyl)-5-methyl-7-(4-methylpiperidin-1-yl)-[1,2,4]tri 
azolo[1.5a]pyrimidine 
A mixture of 1A (0.5 g, 1 mmol) and concentrated hydrochloric acid is 
heated to 80.degree. C. for 24 hours. The reaction mixture is cooled and 
adjusted to pH of 5 by addition of aqueous sodium hydroxide. The reaction 
mixture is extracted with ethyl acetate. The combined organic phases are 
dried and concentrated. The residue is purified by column chromatography 
(silica, toluene:ethyl acetate, 2:1). The pure product is obtained as tan 
crystals (0.27 g) with a melting point of 177-178.degree. C. 
EXAMPLES 2-12 
The following examples (Table I; structure and melting point) are 
synthesized analogously to Example 1. 
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#STR14## 
Exam- melting 
ple R.sup.1 R.sup.2 L.sup.1 L.sup.2 L.sup.3 point (.degree. 
______________________________________ 
C.) 
2 --(CH.sub.2).sub.2 --CH(CH.sub.3)--(CH.sub.2).sub.2 -- 
F H H 197-199 
3 --(CH.sub.2).sub.2 --CH(CH.sub.3)--(CH.sub.2).sub.2 -- Cl H H 
201-202 
4 C.sub.2 H.sub.5 -- 
C.sub.2 H.sub.5 -- 
F Cl H 147-148 
5 C.sub.2 H.sub.5 -- H F Cl H 140-141 
6 F.sub.3 C--CH.sub.2 -- H F Cl H 
7 --(CH.sub.2).sub.2 --CH(CH.sub.3)--(CH.sub.2).sub.2 -- 
F F H 
8 --(CH.sub.2).sub.2 --CH(CH.sub.3)--(CH.sub.2).sub.2 -- Cl Cl H 
9 2-propyl H F Cl H 
10 cyclopentyl H F Cl H 
11 C.sub.2 H.sub.5 -- C.sub.2 H.sub.5 -- F F H 
12 CH.sub.2 .dbd.C(CH.sub.3)--CH.sub.2 -- C.sub.2 H.sub.5 -- F Cl 
H 
13 --(CH.sub.2).sub.2 --CH(CH.sub.3)--(CH.sub.2).sub.2 -- 
F F F 
14 --(CH.sub.2).sub.5 -- F F F 
15 --(CH.sub.2).sub.5 -- F Cl H 
16 --(CH.sub.2).sub.5 -- F H H 
17 --(CH.sub.2).sub.5 -- F F H 
18 1,1,1-trifluoroprop-2-yl 
H F Cl H 
19 1,1,1-trifluoroprop-2-yl H F F H 
20 1,1,1-trifluoroprop-2-yl H F F F 
21 C.sub.2 H.sub.5 -- C.sub.2 H.sub.5 -- F F F 
22 C.sub.2 H.sub.5 -- H F F F 
______________________________________ 
Biological Investigations 
Determination of Effective Dosis for 90% Inhibition by Test Compounds in 
the Serial Dilution Test with Various Phytopathogenic Fungi 
The ED&gt;90 (Effective Dosis&gt;90%)-value is determined by serial dilution 
tests using Microtiter plates with 24 or 48 wells per plate. The dilution 
of the test compounds in the nutrient solution and the distribution to the 
wells is carried out by a TECAN RSP 5000 Robotic Sample Processor. The 
following test compound concentrations are used: 0.05, 0.10, 0.20, 0.39, 
0.78, 1.56, 3.13, 6.25, 12.50, 25.00, 50.00 and 100.00 mg/ml. For 
preparation of the nutrient solution, V8 vegetable juice (333 ml) is mixed 
with calcium carbonate (4.95 g), centrifuged, the supernatant (200 ml) 
diluted with water (800 ml) and autoclaved at 121.degree. C. for 30 min. 
The respective inocula (Alternaria solani, ALTESO; Botrytis cinerea, 
BOTRICI; Leptosphaeria nodorum, LEPTNO; Phytophthora infestans, PHYTIN; 
Pyrenophora teres, PYRNTE; Rhizoctonia solani, RHIZSO;) are added into the 
wells as spore suspensions (50 ml; 5.times.10.sup.5 /ml) or agar slices (6 
mm) of an agar culture of the fungus. 
After 6-12 days incubation at suitable temperatures (1 8-25.degree. C.), 
the ED&gt;90 values are determined by visual inspection of the plates. The 
lowest concentration in the dilution series with mycelial growth of less 
than 10% is defined to be the ED&gt;90 alue (Table II; n. t.=not tested). 
TABLE II 
__________________________________________________________________________ 
Ex.No. 
ALTESO 
BOTRCI 
LEPTNO 
PHYTIN 
PYRNTE 
RHISZO 
__________________________________________________________________________ 
0.2 0.78 1.56 n.t. 0.78 50 
2 3.13 12.5 n.t. 100 100 n.t. 
3 0.78 1.56 n.t. n.t. 100 n.t. 
4 25 n.t. n.t. n.t. n.t. 3.13 
5 50 25 n.t. 100 n.t. 50 
__________________________________________________________________________