Title of Invention

TRIAZOLOPYRIMIDINES

Abstract 5,6-Dialkyl-7-aminotriazolopyrimidines of the formula I in which the substituents are as defined below: R1 is alkyl or alkoxyalkyl, where the aliphatic groups may be substituted as defined in the description; R2 is CHR3CH3, cyclopropyl, CH=CH2 or CH2CH=CH2; R3 is hydrogen, CH3 or CH2CH3; processes for preparing these compounds, compositions comprising them and their use for controlling phytopathogenic harmful fungi.
Full Text Description
The present invention relates to 5,6-dialkyI-7-aminotriazolopyrimidines of the formula I

in which the substituents are as defined below:
R1 is C5-C12-alkyl or C5-C14-alkoxyalkyl, where the aliphatic groups may be
substituted by 1 to 3 of the following groups:
cyano, nitro, hydroxyl, C3-C6-cycloalkyl, C1-C6-alkylthio and NRaRb;
Ra, Rb are hydrogen or C1-C6-alkyl;
R2 is CHR3CH3, cyclopropyl, CH=CH2 or CH2CH=CH2;
R3 is hydrogen, CH3 or CH2CH3.
Moreover, the invention relates to processes for preparing these compounds, to
compositions comprising them and to their use for controlling phytopathogenic harmful
fungi.
5,6-Dialkyl-7-aminotriazolopyrimidines are proposed in a general manner in
GB 1 148 629. Individual fungicidally active 5,6-dialkvl-7-aminotriazolopyrimidjnes are
known from EP-A 141 317JHowever, in many cases their activity is unsatisfactory.
Based on this, it is an object of the present invention to provide compounds having
improved activity and/or a widened activity spectrum.
We have found that this object is achieved by the compounds defined at the outset.
Furthermore, we have found processes and intermediates for their preparation,
compositions comprising them and methods for controlling harmful fungi using the
compounds I.

The compounds of the formula I differ from those in the abovementioned publications
by the specific arrangement of the substituent in the 5-position of the triazolopyrimidine
skeleton.
Compared to the known compounds, the compounds of the formula I are more
effective against harmful fungi.
The compounds according to the invention can be obtained by different routes.
Advantageously, the compounds according to the invention are obtained by converting
substituted fi-keto esters of the formula II with 3-amino-1,2,4-triazole of the formula III
to give 7-hydroxytriazolopyrimidines of the formula IV. The groups R1 and R2 in
formulae II and IV are as defined for formula I and the group R in formula II is C1-C4-
alkyl; for practical reasons, preference is given here to methyl, ethyl or propyl.

The reaction of the substituted fi-keto esters of the formula II with the aminoazoles of
the formula III can be carried out in the presence or absence of solvents. It is
advantageous to use solvents to which the starting materials are substantially inert and
in which they are completely or partially soluble. Suitable solvents are in particular
alcohols, such as ethanol, propanols, butanols, glycols or glycol monoethers,
diethylene glycols or their monoethers, aromatic hydrocarbons, such as toluene,
benzene or mesitylene, amides, such as dimethylformamide, diethylformamide,
dibutylformamide, N,N-dimethylacetamide, lower alkanoic acids, such as formic acid,
acetic acid, propionic acid, or bases, such as alkali metal and alkaline earth metal
hydroxides, alkali metal and alkaline earth metal oxides, alkali metal and alkaline earth
metal hydrides, alkali metal amides, alkali metal and alkaline earth metal carbonates
and also alkali metal bicarbonates, organometallic compounds, in particular alkali metal
alkyls, alkylmagnesium halides and also alkali metal and alkaline earth metal alkoxides
and dimethoxymagnesium, moreover organic bases, for example tertiary amines, such
as trimethylamine, triethylamine, triisopropylamine, tributylamine and N-
methylpiperidine, N-methylmorpholine, pyridine, substituted pyridines, such as
collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines and mixtures
of these solvents.with water. Suitable catalysts are bases, as mentioned previously, or
acids, such as sulfonic acids or mineral acids. With particular preference, the reaction
is carried out without solvent or in chlorobenzene, xylene, dimethyl sulfoxide or N-
methylpyrrolidone. Particularly preferred bases are tertiary amines, such as
triisopropylethylamine, tributylamine, N-methylmorpholine or N-methylpiperidine. The

temperatures are from 50 to 300°C, preferably from 50 to 180°C, if the reaction is
carried out in solution [cf. EP-A 770 615; Adv. Het. Chem. 57 (1993), 81-ffl.
The bases are generally employed in catalytic amounts; however, they can also be
employed in equimolar amounts, in excess or, if appropriate, as solvent.

In most cases, the resulting condensates of the formula IV precipitate from the reaction
solutions in pure form and, after washing with the same solvent or with water and
subsequent drying, they are reacted with halogenating agents, in particular chlorinating
or brominating agents, to give the compounds of the formula V in which Hal is chlorine
or bromine, in particular chlorine. The reaction is preferably carried out using
chlorinating agents such as phosphorus oxychloride, thionyl chloride or sulfonyl
chloride at from 50°C to 150°C, preferably in excess phosphorus oxytrichloride at reflux
temperature. After evaporation of excess phosphorus oxytrichloride, the residue is
treated with ice-water, if appropriate with addition of a water-immiscible solvent. In
most cases, the chlorinated product isolated from the dried organic phase, if
appropriate after evaporation of the inert solvent, is very pure and is subsequently
reacted with ammonia in inert solvents at from 100°C to 200°C to give the 7-amino-
triazolo[1,5-a]pyrimidines. This reaction is preferably carried out using a 1- to 10-molar
excess of ammonia, under a pressure of from 1 to 100 bar.
The novel 7-aminoazolo[1,5-a]pyrimidines are, if appropriate after evaporation of the
solvent, isolated as crystalline compounds, by digestion in water.
The fi-keto esters of the formula II can be prepared as described in Organic Synthesis
Coll. Vol. 1, p. 248, and/or they are commercially available.
Alternatively, the novel compounds of the formula I can be obtained by reacting
substituted acyl cyanides of the formula VI in which R1 and R2 are as defined above
with 3-amino-1,2,4-triazole of the formula III.

The reaction can be carried out in the presence or absence of solvents. It is
advantageous to use solvents to which the starting materials are substantially inert and
in which they are completely or partially soluble. Suitable solvents are in particular
alcohols, such as ethanol, propanols, butanols, glycols or glycol monoethers,
diethylene glycols or their monoethers, aromatic hydrocarbons, such as toluene,
benzene or mesitylene, amides, such as dimethylformamide, diethylformamide,

dibutylformamide, N,N-dimethylacetamide, lower alkanoic acids, such as formic acid,
acetic acid, propionic acid, or bases, such as those mentioned above, and mixtures of
these solvents with water. The reaction temperatures are from 50 to 300°C, preferably
from 50 to 150°C, if the reaction is carried out in solution.
The novel 7-aminotriazolo[1,5-a]pyrimidines are, if appropriate after evaporation of the
solvent or dilution with water, isolated as crystalline compounds.
Some of the substituted alkyl cyanides of the formula VI required for preparing the
7-aminoazolo[1,5-a]pyrimidines are known, or they can be prepared by known methods
from alkyl cyanides and carboxylic esters using strong bases, for example alkali metal
hydrides, alkali metal alkoxides, alkali metal amides or metal alkyls (cf.: J. Amer.
Chem. Soc. 73, (1951), p. 3766).
If individual compounds I cannot be obtained by the routes described above, they can
be prepared by derivatization of other compounds I.
If the synthesis yields mixtures of isomers, a separation is generally not necessarily
required since in some cases the individual isomers can be interconverted during work-
up for use or during application (for example under the action of light, acids or bases).
Such conversions may also take place after use, for example, in the case of treatment
of plants, in the treated plants, or in the harmful fungus to be controlled.
In the definitions of symbols given above, collective terms were used which are
generally representative of the following substituents:
halogen: fluorine, chlorine, bromine and iodine;
alkyl: saturated straight-chain or mono- or dibranched hydrocarbon radicals having 1 to
4 or 5 to 12 carbon atoms, for example C1-C6-alkyl such as methyl, ethyl, propyl,
1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl,
1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl,
1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl,
4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethyl-
butyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethyl-
propyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;
halomethyl: a methyl group in which some or all of the hydrogen atoms may be
replaced by halogen atoms as mentioned above; in particular chloromethyl,
bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl,
trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl;

cycloalkyl: mono- or bicyclic saturated hydrocarbon groups having 3 to 6 carbon ring
members, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
alkoxyalkyl: a saturated straight-chain or mono-, di- or tribranched hydrocarbon chain
which is interrupted by an oxygen atom, for example C5-C12-alkoxyalkyl: a hydrocarbon
chain as described above having 5 to 12 carbon atoms which may be interrupted by an
oxygen atom in any position, such as propoxyethyl, butoxyethyl, pentoxyethyl,
hexyloxyethyl, heptyloxyethyl, octyloxyethyl, nonyloxyethyl, 3-(3-ethylhexyloxy)ethyl,
3-(2,4,4-trimethylpentyloxy)ethyl, 3-(1-ethyl-3-methylbutoxy)ethyl, ethoxypropyl,
propoxypropyl, butoxypropyl, pentoxypropyl, hexyloxypropyl, heptyloxypropyl, octyloxy-
propyl, nonyloxypropyl, 3-(3-ethylhexyloxy)propyl, 3-(2,4,4-trimethylpentyloxy)propyl,
3-(1-ethyl-3-methyibutoxy)propyl, ethoxybutyl, propoxybutyl, butoxybutyl, pentoxybutyl,
hexyloxybutyl, heptyloxybutyl, octyloxybutyl, nonyloxybutyl, 3-(3-ethylhexyloxy)butyl,
3-(2,4,4-trimethylpentyloxy)butyl, 3-(1-ethyl-3-methylbutoxy)butyl, methoxypentyl,
ethoxypentyl, propoxypentyl, butoxypentyl, pentoxypentyl, hexyloxypentyl, heptyloxy-
pentyl, 3-(3-methylhexyloxy)pentyl, 3-(2,4-dimethylpentyloxy)pentyl, 3-(1-ethyl-
3-methylbutoxy)pentyl.
The scope of the present invention includes the (R)- and (S)-isomers and the
racemates of compounds of the formula I having chiral centers.
With a view to the intended use of the triazolopyrimidines of the formula I, particular
preference is given to the following meanings of the substituents, in each case on their
own or in combination:
Preference is given to compounds I in which the group R1 has at most 12 carbon
atoms.
The alkyl groups in R1 in formula I are preferably straight-chain or mono-, di-, tri- or
polybranched, in particular a straight-chain alkyl group.
In addition, preference is given to compounds of the formula I which, in R1, are
branched at the a carbon atom. They are described by formula la:

in which R11 is C3-C10-alkyl or C5-C10-alkoxyalkyl and R12 is C1-C4-alkyl, in particular
methyl, where R11 and R12 together have at most 12 carbon atoms and are
unsubstituted or may be substituted like R1 in formula I.

If R1 is a cyano-substituted alkyl group, the cyano group is preferably located at the
terminal carbon atom.
Preference is given to compounds I in which R1 is a straight-chain or mono-, di-, tri- or
polybranched C5-C12-alkyl group which does not carry any further substituents.
In one embodiment of the compounds I according to the invention, R1 is C5-C12-alkyl or
C1-C11-alkoxy-C1-C11-alkyl, the total number of carbon atoms preferably being from 5 to
12. Particular preference is given in this case to C2-C9-alkoxypropyl groups.
Particular preference is given to compounds I in which R1 is n-pentyl, 1-methylbutyl,
2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethyl-
propyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methyl-
pentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,
2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,
1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl.
In addition, preference is given to compounds of the formula I in which R1 is n-heptyl,
1-methylhexyl, n-octyl, 1-methylheptyl, n-nonyl, 1-methyloctyl, 3,5,5-trimethylhexyl,
n-decyl, 1-methylnonyl, n-undecyl, 1-methyldecyl, n-dodecyl or 1-methylundecyl.
In one preferred embodiment of the compounds I according to the invention, R2 is
ethyl.
In a further preferred embodiment of the compounds I according to the invention, R2 is
isopropyl.
In a further embodiment of the compounds I according to the invention, R2 is 1-methyl-
propyl.
In a further embodiment of the compounds I according to the invention, R2 is
cyclopropyl.
In particular with a view to their use, preference is given to the compounds I compiled
in the tables below. Moreover, the groups mentioned for a substituent in the tables are
per se, independently of the combination in which they are mentioned, a particularly
preferred embodiment of the substituent in question.
Table 1
Compounds of the formula I in which R1 for each compound corresponds to one row of
Table A and R2 is ethyl

Table 2
Compounds of the formula I in which R1 for each compound corresponds to one row of
Table A and R2 is isopropyl
Table 3
Compounds of the formula I in which R1 for each compound corresponds to one row of
Table A and R2 is 1-methylpropyl
Table 4
Compounds of the formula I in which R1 for each compound corresponds to one row of
Table A and R2 is ethenyl
Table 5
Compounds of the formula I in which R1 for each compound corresponds to one row of
Table A and R2 is allyl
Table 6
Compounds of the formula I in which R1 for each compound corresponds to one row of
Table A and R2 is cyclopropyl.













The compounds I are suitable as fungicides. They are distinguished by an outstanding
effectiveness against a broad spectrum of phytopathogenic fungi, especially from the
classes of the Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes,
especially from the class of the Oomycetes. Some are systemically effective and they
can be used in plant protection as foliar, fungicide, as fungicide for seed dressing and
soil fungicides.
They are particularly important in the control of a multitude of fungi on various
cultivated plants, such as wheat, rye, barley, oats, rice, corn, grass, bananas, cotton,
soya, coffee, sugar cane, vines, fruits and ornamental plants, and vegetables, such as
cucumbers, beans, tomatoes, potatoes and cucurbits, and on the seeds of these
plants.
They are especially suitable for controlling the following plant diseases:
• Alternaria species on fruit and vegetables,
• Bipolaris and Drechslera species on cereals, rice and lawns,
• Blumeria graminis (powdery mildew) on cereals,
• Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and
grapevines,
• Bremia lactucae on salad,
• Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,
• Fusarium and Verticillium species on various plants,
• Mycosphaerella species on cereals, bananas and peanuts,
• Peronospora species on cabbage and onions,

• Phakopsora pachyrhizi and P. meibomiae on soybeans,
• Phytophthora infestans on potatoes and tomatoes,
• Phytophthora capsici on peppers,
• Plasmopara viticola on grapevines,
• Podosphaera leucotricha on apples,
• Pseudocercosporella herpotrichoides on wheat and barley,
• Pseudoperonospora species on hops and cucumbers,
• Puccinia species on cereals,
• Pyricularia oryzae on rice,
• Pythium aphanidermatum on lawns,
• Rhizoctonia species on cotton, rice and lawns,
• Septoria tritici and Stagonospora nodorum on wheat,
• Uncinula necator on grapevines,
• Ustilago species on cereals and sugar cane, and
• Venturia species (scab) on apples and pears.
They are particularly suitable for controlling harmful fungi from the class of the
Oomycetes, such as Peronospora species, Phytophthora species, Plasmopara viticola
and Pseudoperonospora species.
The compounds I are also suitable for controlling harmful fungi, such as Paecilomyces
variotii, in the protection of materials (e.g. wood, paper, paint dispersions, fibers or
fabrics) and in the protection of stored products.
The compounds I are employed by treating the fungi or the plants, seeds, materials or
soil to be protected from fungal attack with a fungicidally effective amount of the active
compounds. The application can be carried out both before and after the infection of
the materials, plants or seeds by the fungi.
The fungicidal compositions generally comprise between 0.1 and 95%, preferably
between 0.5 and 90%, by weight of active compound.
When employed in plant protection, the amounts applied are, depending on the kind of
effect desired, between 0.01 and 2.0 kg of active compound per ha.
In seed treatment, amounts of active compound of 1 to 1000 g/100 kg, preferably 5 to
100 g/100 kg of seed are generally required.
When used in the protection of materials or stored products, the amount of active
compound applied depends on the kind of application area and on the desired effect.
Amounts customarily applied in the protection of materials are, for example, 0.001 g to

2 kg, preferably 0.005 g to 1 kg, of active compound per cubic meter of treated
material.
The compounds I can be converted into the customary formulations, for example
solutions, emulsions, suspensions, dusts, powders, pastes and granules. The
application form depends on the particular purpose; in each case, it should ensure a
fine and uniform distribution of the compound according to the invention.
The formulations are prepared in a known manner, for example by extending the active
compound with solvents and/or carriers, if desired using emulsifiers and dispersants.
Solvents/auxiliaries which are suitable are essentially:
- water, aromatic solvents (for example Solvesso products, xylene), paraffins (for
example mineral oil fractions), alcohols (for example methanol, butanol, pentanol,
benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone),
pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid
dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may
also be used,
- carriers such as ground natural minerals (for example kaolins, clays, talc, chalk)
and ground synthetic minerals (for example highly disperse silica, silicates);
emulsifiers such as nonionogenic and anionic emulsifiers (for example
polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and
dispersants such as lignosulfite waste liquors and methylcellulose.
Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of
lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid,
dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty
alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore
condensates of sulfonated naphthalene and naphthalene derivatives with
formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol
and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol,
octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ether,
tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty
alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl
ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol
esters, lignosulfite waste liquors and methylcellulose.
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, for example toluene, xylene, paraffin,
tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol,

propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents,
for example dimethyl sulfoxide, N-methylpyrrolidone and water.
Powders, materials for spreading and dustable products can be prepared by mixing or
concomitantly grinding the active substances with a solid carrier.
Granules, for example coated granules, impregnated granules and homogeneous
granules, can be prepared by binding the active compounds to solid carriers. Examples
of solid carriers are mineral earths such as 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, such as,
for example, 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 compound. The active compounds are employed in a
purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
The following are examples of formulations: 1. Products for dilution with water
A Water-soluble concentrates (SL)
10 parts by weight of a compound according to the invention are dissolved in water or
in a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The
active compound dissolves upon dilution with water.
B Dispersible concentrates (DC)
20 parts by weight of a compound according to the invention are dissolved in
cyclohexanone with addition of a dispersant, for example polyvinylpyrrolidone. Dilution
with water gives a dispersion.
C Emulsifiable concentrates (EC)
15 parts by weight of a compound according to the invention are dissolved in xylene
with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each
case 5%). Dilution with water gives an emulsion.
D Emulsions (EW, EO)
40 parts by weight of a compound according to the invention are dissolved in xylene
with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each
case 5%). This mixture is introduced into water by means of an emulsifying machine
(Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an
emulsion.

E Suspensions (SC, OD)
In an agitated ball mill, 20 parts by weight of a compound according to the invention are
comminuted with addition of dispersants, wetters and water or an organic solvent to
give a fine active compound suspension. Dilution with water gives a stable suspension
of the active compound.
F Water-dispersible granules and water-soluble granules (WG, SG)
50 parts by weight of a compound according to the invention are ground finely with
addition of dispersants and wetters and made into water-dispersible or water-soluble
granules by means of technical appliances (for example extrusion, spray tower,
fluidized bed). Dilution with water gives a stable dispersion or solution of the active
compound.
G Water-dispersible powders and water-soluble powders (WP, SP)
75 parts by weight of a compound according to the invention are ground in a rotor-
stator mill with addition of dispersants, wetters and silica gel. Dilution with water gives a
stable dispersion or solution of the active compound.
2. Products to be applied undiluted
H Dustable powders (DP)
5 parts by weight of a compound according to the invention are ground finely and
mixed intimately with 95% of finely divided kaolin. This gives a dustable product.
I Granules (GR, FG, GG, MG)
0.5 part by weight of a compound according to the invention is ground finely and
associated with 95.5% carriers. Current methods are extrusion, spray-drying or the
fluidized bed. This gives granules to be applied undiluted.
J ULV solutions (UL)
10 parts by weight of a compound according to the invention are dissolved in an
organic solvent, for example xylene. This gives a product to be applied undiluted.
The active compounds can be used as such, in the form of their formulations or the use
forms prepared therefrom, for example in the form of directly sprayable solutions,
powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable
products, materials for spreading, or granules, by means of spraying, atomizing,
dusting, spreading or pouring. The use forms depend entirely on the intended
purposes; the intention is to ensure in each case the finest possible distribution of the
active compounds 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 a 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 compound concentrations in the ready-to-use preparations can be varied
within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from
0.01 to 1%.
The active compounds may also be used successfully in the ultra-low-volume process
(ULV), by which it is possible to apply formulations comprising over 95% by weight of
active compound, or even to apply the active compound without additives.
Various types of oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or
bactericides may be added to the active compounds, if appropriate not until
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.
The compositions according to the invention can, in the use form as fungicides, also be
present together with other active compounds, e.g. with herbicides, insecticides, growth
regulators, fungicides or else with fertilizers. Mixing the compounds I or the
compositions comprising them in the application form as fungicides with other
fungicides results in many cases in an expansion of the fungicidal spectrum of activity
being obtained.
The following list of fungicides, in conjunction with which the compounds according to
the invention can be used, is intended to illustrate the possible combinations but not
limit them:
• acylalanines, such as benalaxyl, metalaxyl, ofurace or oxadixyl,
• amine derivatives, such as aldimorph, dodine, dodemorph, fenpropimorph,
fenpropidin, guazatine, iminoctadine, spiroxamine or tridemorph,
• anilinopyrimidines, such as pyrimethanil, mepanipyrim or cyprodinyl,
• antibiotics, such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin
or streptomycin,
• azoles, such as bitertanol, bromoconazole, cyproconazole, difenoconazole,
dinitroconazole, enilconazole, epoxiconazole, fenbuconazole, fluquinconazole,
flusilazole, hexaconazole, imazalil, metconazole, myclobutanil, penconazole,

propiconazole, prochloraz, prothioconazole, tebuconazole, triadimefon, triadimenol,
triflumizole or triticonazoie,
• dicarboximides, such as iprodione, myclozolin, procymidone or vinclozolin,
• dithiocarbamates, such as ferbam, nabam, maneb, mancozeb, metam, metiram,
propineb, polycarbamate, thiram, ziram or zineb,
• heterocyclic compounds, such as anilazine, benomyl, boscalid, carbendazim,
carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadone, fenamidone,
fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol,
probenazole, proquinazid, pyrifenox, pyroquilon, quinoxyfen, silthiofam,
thiabendazole, thifluzamide, thiophanate-methyl, tiadinil, tricyclazole or triforine,
• copper fungicides, such as Bordeaux mixture, copper acetate, copper oxychloride
or basic copper sulfate,
• nitrophenyl derivatives, such as binapacryl, dinocap, dinobuton or nitrophthal-
isopropyl,
• phenylpyrroles, such as fenpiclonil or fludioxonil,
• sulfur,
• other fungicides, such as acibenzolar-S-methyl, benthiavalicarb, carpropamid,
chlorothalonil, cyflufenamid, cymoxanil, diclomezine, diclocymet, diethofencarb,
edifenphos, ethaboxam, fenhexamid, fentin acetate, fenoxanil, ferimzone,
fluazinam, phosphorous acid, fosetyl, fosetyl-aluminum, iprovalicarb,
hexachlorobenzene, metrafenone, pencycuron, propamocarb, phthalide, tolclofos-
methyl, quintozene or zoxamide,
• strobilurins, such as azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin,
kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or
trifloxystrobin,
• sulfenic acid derivatives, such as captafol, captan, dichlofluanid, folpet or
tolylfluanid,
• cinnamides and analogous compounds, such as dimethomorph, flumetover or
flumorph.
Synthesis examples
The procedures described in the following synthesis examples were used to prepare
further compounds I by appropriate modification of the starting materials. The
compounds thus obtained are listed in the table below, together with physical data.
Example 1: Preparation of 4-cyanoundecan-3-one
At -70°C, a solution of 0.495 mol of butyllithium in hexane was added to a solution of
0.45 mol of decanitrile in 300 ml of tetrahydrofuran (THF), the mixture was stirred at
this temperature for about 3 hours and 0.45 mol of ethyl propionate was then added.

The mixture was subsequently stirred at 20-25°C for about 16 hours, 200 ml of water
were then added and the mixture was acidified with dil. HCI solution. After the phases
had separated, the organic phase was removed, washed with water, dried and freed
from the solvent. 91 g of the title compound remained.
Example 2: Preparation of 7-amino-5-ethyl-6-octyl[1,2,4]triazolo[1,5-a]pyrimidine
A mixture of in each case 1.27 mol of 5-cyanoundecan-3-one from Example 1 and
3-amino-1,2,4-triazole and 0.25 mol of p-toluenesulfonic acid in 900 ml of mesitylene
was heated at 170°C for about 4 hours. After cooling to about 20-25°C, the precipitate
was filtered off and then taken up in dichloromethane. After washing with water and
drying, the solvent was distilled off from the solution, giving, as residue, 124 g of the
title compound of m.p. 196°C.

The fungicidal action of the compounds of the formula I was demonstrated by the
following experiments:

The active compounds were prepared as a stock solution comprising 25 mg of active
compound which was made up to 10 ml using a mixture of acetone and/or DMSO and
the emulsifier Uniperol® EL (wetting agent having emulsifying and dispersing agent
based on ethoxylated alkylphenols) in a ratio by volume of solvent/emulsifier of 99/1.
The mixture was then made up to 100 ml with water. This stock solution was, using the
solvent/emulsifier/water mixture described, diluted to the active compound
concentration stated below.
Use Example 1 - Activity against peronospora of grapevines caused by Plasmopara
viticola
Leaves of potted vines were sprayed to runoff point with an aqueous suspension
having the concentration of active compound stated below. The next day, the
undersides of the leaves were inoculated with an aqueous sporangia suspension of
Plasmopara viticola. The vines were then initially placed in a water-vapor-saturated
chamber at 24°C for 48 hours and then in a greenhouse at temperatures between 20°C
and 30°C for 5 days. After this time, the plants were once more placed in a humid
chamber for 16 hours to promote the eruption of sporangiophores. The extent of the
development of the infection on the undersides of the leaves was then determined
visually.
In this test, the plants which had been treated with 250 ppm of the compounds 1-1 or I-2
showed no infection, whereas the untreated plants were 95% infected.
Use Example 2: Activity against late blight of tomatoes caused by Phytophthora
infestans, protective treatment
Leaves of potted tomato plants were sprayed to runoff point with an aqueous suspension
having the concentration of active compounds stated below. The next day, the leaves
were infected with an aqueous sporangia suspension of Phytophthora infestans. The
plants were then placed in a water-vapor-saturated chamber at temperatures between
18°C and 20°C. After 6 days, the late blight on the untreated, but infected control plants
had developed to such an extent that the infection could be determined visually in %.
In this test, the plants which had been treated with 250 ppm of the compounds 1-1,1-2,1-8,
I-9,1-10 or 1-11 showed no infection, whereas the untreated plants were 100% infected.
Use Example 3 - Activity against peronospora of grapevines caused by Plasmopara
viticola, protective application
Leaves of potted vines of the cultivar "Muller-Thurgau" were sprayed to runoff point with
an aqueous suspension having the concentration of active compounds stated below. To

be able to assess the persistency of the substances, the plants were, after the spray
coating had dried on, placed in a greenhouse for 7 days. Only then were the leaves
inoculated with an aqueous zoospore suspension of Plasmopara viticola. The vines were
then initially placed in a water-vapor-saturated chamber at 24°C for 48 hours and then in
the greenhouse at temperatures between 20°C and 30°C for 5 or 7 days. After this time,
the plants were once more placed in a humid chamber for 16 hours to promote the
eruption of sporangiophores. The extent of the development of the infection on the
undersides of the leaves was then determined visually.
In the test arrangement where there is a 5 day protective application, the plants which
had been treated with 250 ppm of the compound I-4 showed an infection of 5%,
whereas the untreated plants were 75% infected. In the test arrangement where there
is a 7 day protective application, the plants which had been treated with 250 ppm of the
compounds I-8,1-9,1-10,1-11,1-12 or 1-13 showed an infection of at most 7%, whereas
the untreated plants were 80% infected.

WE CLAIM:
1. A triazolopyrimidine of the formula I

in which the substituents are as defined below:
R1 is C5-C12-alkyl or C5-C14-alkoxyalkyl, where the aliphatic groups may be
substituted by 1 to 3 of the following groups:
cyano, nitro, hydroxyl, C3-C6-cycloalkyl, C1-C6-alkylthio, and NRaRb;
Ra, Rb are hydrogen or C1-C6-alkyI;
R2 is CHR3CH3, cyclopropyl, CH=CH2 or CH2CH=CH2;
R3 is hydrogen or CH3.
2. The compound of the formula I as claimed in claim 1, in which R2 is ethyl.
3. The compound of the formula I as claimed in claim 1, in which R1 is an
unsubstituted straight-chain or mono-, di- or tribranched alkyl chain having up to
12 carbon atoms.
4. Triazolopyrimidines of the formula I as claimed in claim 1 selected from the group
consisting of:
5-ethyl-6-(1-methylheptyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine;
5-ethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine;
5-ethyl-6-(3,5,5-trimethylhexyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine;
5-ethyl-6-pentyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine;
5-ethyl-6-hexyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine;
5-ethyl-6-heptyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine;
5-ethyl-6-nonyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine;
5-ethyl-6-undecyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine;
5-ethyl-6-(3-pentyloxypropyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine.
5. A process for preparing compounds of the formula I as claimed in any of claims 1
to 4 wherein ß-keto esters of the formula II,


in which R is C1-C4-alkyl are reacted with 3-amino-1,2,4-triazole of the formula III

to give 7-hydroxytriazolopyrimidines of the formula IV

which are halogenated to give compounds of the formula V

in which Hal is chlorine or bromine and V is reacted with ammonia.
6. A fungicidal composition comprising a solid or liquid carrier and a compound of
the formula I as claimed in any of claims 1 to 4.


5,6-Dialkyl-7-aminotriazolopyrimidines of the formula I

in which the substituents are as defined below:
R1 is alkyl or alkoxyalkyl, where the aliphatic groups may be substituted as defined
in the description;
R2 is CHR3CH3, cyclopropyl, CH=CH2 or CH2CH=CH2;
R3 is hydrogen, CH3 or CH2CH3;
processes for preparing these compounds, compositions comprising them and their
use for controlling phytopathogenic harmful fungi.

Documents:

02286-kolnp-2006 abstract.pdf

02286-kolnp-2006 claims.pdf

02286-kolnp-2006 correspondence others.pdf

02286-kolnp-2006 description[complete].pdf

02286-kolnp-2006 form-1.pdf

02286-kolnp-2006 form-3.pdf

02286-kolnp-2006 form-5.pdf

02286-kolnp-2006 international publication.pdf

02286-kolnp-2006 international search authority report.pdf

02286-kolnp-2006 pct form.pdf

02286-kolnp-2006 priority document.pdf

02286-kolnp-2006-correspondence-1.1.pdf

02286-kolnp-2006-form-5-1.1.pdf

2286-kolnp-2006-assignment-1.1.pdf

2286-KOLNP-2006-ASSIGNMENT.pdf

2286-KOLNP-2006-CLAIMS 1.1.pdf

2286-KOLNP-2006-CORRESPONDENCE 1.1.pdf

2286-kolnp-2006-correspondence.pdf

2286-KOLNP-2006-DESCRIPTION (COMPLETE) 1.1.pdf

2286-KOLNP-2006-DRAWINGS.pdf

2286-kolnp-2006-examination report.pdf

2286-KOLNP-2006-FORM 1.1.1.pdf

2286-KOLNP-2006-FORM 1.1.2.pdf

2286-KOLNP-2006-FORM 13-1.1.pdf

2286-kolnp-2006-form 13-1.2.pdf

2286-KOLNP-2006-FORM 13.pdf

2286-kolnp-2006-form 18.pdf

2286-KOLNP-2006-FORM 3.1.1.pdf

2286-kolnp-2006-form 3.pdf

2286-KOLNP-2006-FORM 5.1.1.pdf

2286-kolnp-2006-form 5.pdf

2286-KOLNP-2006-FORM-27.pdf

2286-kolnp-2006-gpa.pdf

2286-kolnp-2006-granted-abstract.pdf

2286-kolnp-2006-granted-claims.pdf

2286-kolnp-2006-granted-description (complete).pdf

2286-kolnp-2006-granted-form 1.pdf

2286-kolnp-2006-granted-specification.pdf

2286-kolnp-2006-others-1.1.pdf

2286-KOLNP-2006-OTHERS.pdf

2286-KOLNP-2006-PA.pdf

2286-KOLNP-2006-PETITION UNDER RULE 137.pdf

2286-kolnp-2006-reply to examination report-1.1.pdf

2286-KOLNP-2006-REPLY TO EXAMINATION REPORT.pdf

abstract-02286-kolnp-2006.jpg


Patent Number 247504
Indian Patent Application Number 2286/KOLNP/2006
PG Journal Number 15/2011
Publication Date 15-Apr-2011
Grant Date 12-Apr-2011
Date of Filing 10-Aug-2006
Name of Patentee BASF AKTIENGESELLSCHAFT
Applicant Address 67056 LUDWIGSHAFEN
Inventors:
# Inventor's Name Inventor's Address
1 TORMO I BLASCO JORDI HORAZWEG 5, 69469 WEINHEIM
2 MULLER BERND STOCKINGER STR.7, 67227 FRANKENTHAL
3 GEWEHR MARKUS GOETHESTR.21, 56288 KASTELLAUN
4 GRAMMENOS WASSILIOS ALEXANDER-FLEMING-STR.13, 67071 LUDWIGSHAFEN
5 GROTE THOMAS IM HOHNHAUSEN 18, 67157 WACHENHEIM
6 RHEINHEIMER JOACHIM MERZIGER STR.24, 67063 LUDWIGSHAFEN
7 SCHAFER PETER ROMERSTR.1,67308 OTTERSHEIM
8 SCHIEWECK FRANK BURGUNDERWEG 18, 67098 BAD DÜRKHEIM
9 SCHWOGLER ANJA MEDARDUSTRIG 262, 67112 MUTTERSTADT
10 NIEDENBRUCK MATTHIAS ALBERT-EINSTEIN-ALLEE 3, 67117 LIMBURGERHOF
11 SCHERER MARIA HERMANN-JURGENS-STR.30, 76829 GODRAMSTEIN
12 STRATHMANN SIEGFRIED SUDETENSTR 2, 67117 LIMBURGERHOF
13 SCHOFL ULRICH 100 HOSOKEN CT, APEX NC 27523
14 STIERTL REINHARD DONG SHAN ROAD, NO. 1-G, 83345 NIAO SONG, ROC, TAIWAN
15 BLETTNER CARSTEN RICHARD-WAGNER-STR.48, 68165 MANNHEIM
PCT International Classification Number C07D 487/04
PCT International Application Number PCT/EP2005/002427
PCT International Filing date 2005-03-08
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 102004012011.0 2004-03-10 Germany