Note: Descriptions are shown in the official language in which they were submitted.
2~8338
.iOECHST AKTI~NGES2LLSCHAF~ ~OE 89/F 359
~e~criptio7a
?yridine derivatives, process for their preparation,
~gents containing them and their use as fungicides
The present invention relates to novel pyridine deriva-
ti-~es, a process for their prepara~ion, agents containing
them and their use as fungicides.
Pyridine derivatives are already known as acti~e
components in fungicidal agents (cf. EP-A-270,362,
EP-A 278,610, EP-A-259,139, EP-A 234,104). However, the
action of these cornpounds is not always satisfactory, in
particular at low application rates.
Novel pyridine derivatives have now been found which have
advantageous effects in the control of a wide spectrum of
phytopathogenic fungi, in particular at low dosages.
The present inven~ion therefore relates to the compounds
of the formula I,
~5
~ ~` R9
R~R 2 ~ 8
in which
R1, R2, R3 and R4 are independently of one another,
hydrogen, halogen, nitro, (C~-C4)alkyl,
(Cl-C4~alkoxy, (cl-c4)alkylthio~ (Cl-C4)haloalkoxy
or (C1 -C4 ) haloalkyl,
R5, R6 and R7 are independently of one another hydrogen,
(C1 C6)alkyl or phenyl, it being possible for the
phenyl radical to be monosubstituted to
2~33~
trisubstituted by halogen, nitro, (C1-C4)alkyl,
(C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4 ) haloalkyl,
or (Cl-C4)haloalkoxy,
R8 and R9 are independently of one another hydrogen,
(C1-C6)alkyl, ( C3-C7 ) cycloalkyl, ( C3-C7 ) cycloalkyl-
(C,-C4)alkyl, it being possible for the ~wo last-
mentioned radicals to be monosu~stituted to
trisubstituted in the cycloalkyl moiety by
(C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy,
(Cl-C4)alkylthio, (C1-C4)alkoxy-(C1-C4)alkyl,
(C1-C4)alkylthio-(C1-C4)alkyl, halogen, (C2-C6)al-
kenyl, (C2-C6)alkynyl, phenyl, phenoxy, phenoxy-
(C1-C4)alkyl, phenylmercapto-(Cl-C4)alkyl, phenyl-
mercapto, phenyl-(C1-C4)alkoxy or phenyl-
(C1-C4)alkylthio, it being po~sible for the seven
last-mentioned radical to be monosubstituted to
trisubstituted in the phenyl moiety by halogen,
nitro, cyano, (C1-C4)alkyl, (Cl-C4)alkoxy,
(C1 C4)alkylthio, (Cl-C4)haloalkyl or
(C1-C4)haloalkoxy, or (c2-c4)alkenyloxy~
~C2-C4)alkynyloxy, (Cl-C4)haloalkoxy, (Cl-C4)alkoxy-
(Cl-C4)alkoxy or (C1-C4)alkylthio-(C1-C4)alkylthio,
Rl is hydrogen, (C1-C4)alkyl, (C1-C4)alkoxy, (C2-C6)-
alkenyloxy, (C2-C6)alkynyloxy, (C1-C4)alkylthio,
halogen, phenyl, it beinq possible for the phenyl
radical to be monosubstituted to trisubstituted
by halogen, nitro, cyano, (C1-C4)alkyl, (Cl-C4)alk-
oxy, (C1-C4)alkylthio, (Cl-C4)haloalkyl or
(Cl-C4)haloalkoxy, or
30 R8 and R10 together form a polymethylene chain of the
formula -(CH2) m- where m = 3 - 4,
Rl1 and R12 are independently of one another hydrogen or
(C1-C4)alkyl,
Y is N or -CRl and
n is 1-3, and their acid addition salts.
The alkyl, alkenyl or alkynyl radicals here can be both
straight-~hain and branched. Halogen is F, Cl, Br and I,
preferably F, Cl and Br. The prefix "halo~' in the
2~833~
3 --
description of a substituent here and in the following
means that this substituent can occur once or several
times with the s~ne or a different meaning. The prefix
'halo" comprises fluorine, chlorine, bromine or iodine,
in particular fluorine, chlorine or bromine. Examples of
haloalkyl which may be mentioned are: CF3, CF2CHF2, CF2CF3,
CC13, CC12F, CFzCF2CF3~ CF2CHFCF3 and (CF2)3CF3- ExampleS of
haloalkoxy are OCF3, OCF2CHF2 or OCF2CF2CF3.
Preferred compounds of the formula I are those in which
Rl, R2, R3 and R4 are independently of one another hydro-
qen, halogen, (C1-C2)haloalkyl or (C1-C3)alkyl,
R5 and R6 are independently of one another hydrogen,
~C1-C3)alkyl or phenyl, it being possible for the
phenyl radical to be monosubstituted to trisub-
stituted by halogen or (C1-C4)alkyl,
R7 is hydrogen,
R3 and R9 are independently of one another hydrogen,
(Cl-C6)alkyl, (C3-C6jcycloalkyl, (Cs-C6)cycloalkyl-
(C1-C3~alkyl, halogen, phenyl which can be mono-
substituted to tri~ubstituted by halogen,
(C1-C4)alkyl or (Cl-C4)alkoxy, or (C2-C4)alkenyloxy,
(C2-C4)alkynyloxy, ( C~-C4 ) haloalkoxy or ( Cl-c4 ) alk-
oxy-(C1-C4)alkoxy
R10 is hydrogen, (C1-C4)alkyl, halogen, phenyl, it
being possible for the phenyl radical to be
monosubstituted to trisubstituted by halogen or
(Cl-C3)alkyl, or (C1 C3 ) alkoxy or
R3 and R10 together form a polymethylene chain of the
formula -(CH2) m~ where m - 3 - 4,
Rl1 and Rl2 are hydrogen,
Y is N or -CR10
and n = 1, and their acid addition salts.
The following acids are suitable for the preparation of
the acid addition salts of the compounds of the formula
I:
hydrohalic acid such as hydrochloric acid or hydrobromic
20~8338
acid, and in addition phosphoric acid, nitric acid,
sulfuric acid, mono or bifunctional carboxylic acids and
hydroxycarboxylic acids such as ~cetic acid, maleic acid,
succinic acid, fumaric acid, tartaric acid, citric acid,
salicylic acid, sorbic acid or lactic acid, and sulfonic
acids such as p-toluenesulfonic acid or 1,5-naphthalene-
disulfonic acid. The acid addition salts of the compounds
of the formula I can be obtained in a simple manner by
customary salt formation methods, for example by dis-
solving a compound of the formula I in a suitable organic
solvent and adding the acid and are isolated in a known
manner, for example by filtering off, and, if desired,
purified by washing with an inert organic solvent.
The present invention also relates to a process for the
preparation of the compounds of the formula I.
These compounds can be prepared by the following
variants:
1~ Pyridine derivatives of the formula I where R9 = H
and Y = -CR10 can be obtained by reductive dehalogen-
ation of appropriate halopyrimidines of the formula
I in which R9 - halogen (for example Cl, Br, or I)
and the remaining substituents are as defined in
formula I.
The dehalogenation can be carried out with hydrogen
in the presence of catalysts (for example
palladium/carbon) in an inert solvent, for example
water, lower alcohol (such as methanol and ethanol),
ethyl acetate or toluene or mixtures thereof. The
addition of base~ such as alkali metal hydroxides or
alkali metal carbonates or alkaline earth metal
hydroxides or alkaline earth metal carbonates is
advantageous. The reaction i~ carried out in the
range 15-60C under a pressure of 1 to 5 bar.
2) Pyridine derivatives of the -formula I, in which R9
2~83~
is (C~-C4)alkoxy, (Cl-C4)alkylthio, phenoxy, phenyl-
mercapto,phenyl-(C1-C4)alkoxyorphenyl-(Cl-C4)alkyl
thio, it being possible for the 4 last-mentioned
radicals in the phenyl moiety to be mono~ubstituted
to trisubstituted by halogen, nitro, cyano,
(Cl-C4)alkyl, (Cl-C4)alkoxy, (C1-C4)alkylthio,
(Cl-4)haloalkylor(C1-C4)haloalkoxy,or(C2-C4)alkenyl-
oxy (C2-C4)alkynyloxy, ( C~-C4 ) haloalkoxy, (C1-C4)alk-
oxy-(Cl-C4)alkoxy or(C1-C4)alkylthio-(C1-C4)alkylthio
and Y is -CRl, can be prepared by reaction of the
appropriate halopyrimidines I (R9 = halogen) with an
alkali metal compound of the formula II RaM (II), in
which R9 has the abovementioned meaning and M is an
alkali metal (for example Li, Na or K).
The reaction can be carried out between 0~C and
130C in the course of 0.5 h to 72 h. The alkali
metal compound (II) can be employed in amounts of 1
to 2 mol equivalents relative to 1 equivalent of the
halopyrimidine (I) (R9 = halo~en). The reaction is
usually carried out in the presence of a solvent.
In the cases in which an alkali metal compound R9M
is employed in which R9 is (Cl-C4)alkoxy, phenyl-
(C1-C4)alkoxy, (C2~C4)alkenyloxyl (C2-C4)-alkynyloxy,
(C1-C4)haloalkoxy or (C1-C4)alkoxy-(Cl-C4)alkoxy, the
corresponding alcohol R9OH or an ether (for example
diethyl ether, dioxane or tetrahydrofuran) or a
mixture thereof is used as the solvent.
In the cases in which an alkali metal compound is
employed in which R9 is (Cl-C4)alkylthio, phenoxy,
phenylmercapto, phenyl-(Cl-C4)alkoxy or phenyl-
(C1-C4)alkylthio, an ether (for example diethyl
ether, dioxane or tetrahydrofuran), a nitrile (for
example acetonitrile), an aromatic hydrocar~on (for
example toluene or xylene) or a mixture thereof is
used as the solvent.
~g338
3) Pyridlne derivatives of the formula I, in which R9
is (Cl-C6)alkyl, ( C3-c7 ) cycloalkyl, 1 C3-C7 ) cycloalkyl-
(cl-c4)alkyl~(cl~c4)alkoxy-(cl-c4)alkylr(cl-c4)alkyl-
thio-(Cl-C4)alkyl or phenyl, it being possible for
the last-mentioned radical to be monosubstituted to
trisubstituted by (Cl-C4)alkyl or (Cl-C4)alkoxy, and
Y is -CR10, can be obtained by reaction of appropri-
ate halopyrimidines I (R9 = halogen) with Grignard
compounds R9MgX (III), where R9 is defined a~ indi-
cated above and X is halogen (Cl, Br or I), in the
presence of nickel-phosphine complexes such as, for
example, 1,2-bi~(diphenylphosphino)ethane-nickel(II)
chloride or 1,3-bis(diphenylphosphino)propane-
nickel(II) chloride (cf. Chem. Pharm. Bull. 26, 2160
(1978)).
The reaction can be carried out in the course of
2 - 48 h between 0C and 80C or at the boiling
point of the solvent. The Grignard compound R9MgX is
in this case employed in amounts of 1-2.5 mol
equivalents relative to 1 equivalent of halo-
pyrimidine (I). Suitable solvents are ethers such
as, for example, diethyl ether, THF, dioxane and
dime~hoxyethane.
The halopyrimidines I (R9 = halogen) can be obtained
by reaction of the appropriate hydroxypyrimidines
(I), in which R9 is the radical OH and the other
substituents have the meanings as in formula I, with
halogenating agents. Halogenating agents which can
be employed are, for example, thionyl chloride,
phosgene, phosphorus oxychloride, phosphorus pen-
tachloride, phosphorus oxybromide or phosphorus
tribromide. The reactions can be carried out in a
solvent, but also without solvent. The halogenating
agent is employed in amounts of 1 to ~ equivalents
relative to 1 equivalent of the hydroxypyrimidine
lI) (R9 = 0~). The reactions can be carried out in a
temperature range from 25 to 160C. Solvents used
~0~833~
are, for example, aromatic hydrocarbons (for example
benzene or toluene, inter alia) or halogenated
hydrocarbons (for example chlorobenzene).
The hydroxypyrimidines (I) (R9 = OH) can be prepared
by condensation of the amidine derivatives (IV) with
~-oxocarboxylates V
; - _7
.. I `
;.; ~R
' - _ 3 ? ^ 2
:~3 :~
. ~
I~ V
in which Rl-R8, R10-Rl2 and n are as defined in formula
I, X is halogen (for example chlorine, bromine or
iodine) and Rl3 is lower alkyl radicals such as
methyl, ethyl and propyl.
The reactions are carried out in the temperature
range from 20 to 110C within the course of
2 - 72 h. The ~-oxocarboxylate (V) can be employed
in amounts of 1 - 1.5 equivalents relative to 1
equivalent of amidine derivative (IV). The reaction
is carried out in the presence of a base and of a
solvent. Bases used can be, for example, inorganic
bases such as alkali metal hydroxide6 and carbonates
or organic ba~es such as ~odium alkoxides,
trialkylamines and N,N-dialkylanilines. Solvents
used are lower alcohols (such as methanol and
ethanol), cyclic ethers (such as dioxane and THF),
pyridine, N,N-dimethylformamide, water or mixtures
thereof. The amidine derivatives t~V) and the
~oxocarboxy:Late~ can be prepared by proces6es known
per se (cf. J. Org. Chem. 32, 1591 (1967) and
~8~3~
S~-~nthesis 1982, 451 and Organikum 1986, 516 et
seq.).
4) Pyridine derivatives of the formula (I), in which R~
= R9 and is (Cl-C4)alkyl, phenyl-(C1-C4)alkyl or
phenyl, it being possible for the two last-mentioned
radicals to be monosubstituted to trisubstituted in
the phenyl moiety by halogen, nitro, [lacuna]
(C1-C4)alkyl, (Cl-C4)alkoxy, (Cl-C4)alkylthio,
(Cl-C4)haloalkyl or (C1-C4)haloalkoxy, and Y is N, can
be prepared by reaction of the amidine derivatives
IV with an imidate derivative of the formula VI in
which R9 [sic]
?~ C~ 3 (VI),
has the abovementioned meaning and R13 is as defined
in formula v (cf. also JOC 27, 3608 (1962~).
lS The reaction can be carried out in the presence of
a solvent or, alternatively, without solvent.
Suitable solvents are lower alcohols such as
methanol and ethanol. The reaction is carried out in
the temperature range from 10C to 100C. The
imidate derivative (VI) can be employed in amounts
of 2 to 5 equivalents relative to 1 equivalent of
amidine derivative IV.
The compounds of the formula (I) according to the inven-
tion are distinguished by an excellent fungicidal action.
Causative organisms of fungal disease which have already
penetrated into the plant tissue can be successfully
controlled in a curative manner~ This is particularly
important and advantageous in those fungal diseases
which, after infection has occurred, can no longer be
controlled effectively with the otherwise customary
~68338
funaicides. The spectrum of action of the compounds
claimed includes a plurality of various economically
important phytopathogenic fungi, such as, for example,
Piricularla oryzae, Venturia inaequalis, Cercospora
beticola, powdery mildew species, Fusarium species,
Plasmopora viticola, Pseudoperonospra cubensis [sic],
Leptosphaeria nodorum, Drechslera, various rust fungi and
Pseudocercosporella herpotrichoides. Benzimidazole- and
dicarboximide- sensitive and -resistant Boytritis cinerea
[sic] strains are particularly well controlled.
The compounds according to the invention are in addition
also suitable for use in industrial fields, for example
as wood preservatives, as preservatives in paints, in
cooling lubricants for metal processing or as preserva-
tives in drilling and cutting oils.
The invention also relates to agents which contain thecompounds of the formula I in addition to suitable
formulation auxiliaries.
The agents according to the invention in general contain
the active compounds of the formula I in amounts of 1 to
95% by weight.
They can be variously formulated, depending on how it is
prespecified by the biological and/or physicochemical
parameters. Suita~le formulation possibilities are
therefore:
Wettable powders (WP), emulsifiable concentrates (EC),
aqueous solutions ~SC), emulsions, sprayable solutions,
dispersions having an oil or water base (SC), ~uspo-
emulsions (SC), dusting agents (DP), seed dressings,
granules in the form of micro-, spray, absorption and
adsorption granules, water-dispersible granules (WG), ULV
formulations, microcapsules, waxes or baits.
These individual formulation types are known in principle
2~833~
- 10 -
and are described, for example, in: Winnacker-Kuchler,
"Chemische Technologie" (Chemical Technology), Volume 7,
C- Hauser Verlag Munich, 4th Ed. 1986; van Falkenburg,
"Pesticides Formulations", Marcel Dekker N.Y., 2nd Ed.
1972-73; K. Martens, "Spray Drying Handbook", 3rd Ed.
1979, G. Goodwin Ltd. London.
The formulation auxiliaries required such as inert
materials, surfactants, solvents and other additives are
likewise known and are described, for example, in:
Watkins, "Handbook of Insecticide Dust Diluents and
Carriers , 2nd Ed., Darland Books, Caldwell N.J.; H.Y.
Olphen, "Introduction to Clay Colloid Chemistry", 2nd
Ed., J. Wiley & Sons, N.Y.; Marschen [sic], "Solvents
Guide", 2nd Ed., Interscience, N.Y. 1950; McCutcheon's,
"Detergents and Emulsifiers Annual", MC Publ. Corp.,
Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface
Active Agents", Chem. Publ. Co. Inc., N.Y. 1964;
Schonfeldt, "Grenzflachenaktive Athylenoxidaddukte"
(Surface-active ethylene oxide adducts), Wiss.
Verlagsgesell., Stuttgart 1976; Winnacker-Kuchler,
"Chemische Technologie~ (Chemical Technology), Volume /,
C. ~auser Verlag Munich, 4th Ed. 1986.
On the basis of these formulations, combinations with
other pesticidally active substances, fertilizers and/or
gro~th regulators can also be prepared, for example in
the form of a finished formulation or as a tank mix.
Wettable powders are preparations which can be uniformly
dispersed in water and, apart from the active compound
and a diluent or inert substance, additionally contain
wetting agents, for example polyoxyethylated alkyl-
phenols, polyoxyethylated fatty alcohols, alkyl- or
alkylphenolsulfonates and dispersing agents, for example
sodium ligninsulfonate, sodium 2,2'-dinaphthylmethane-
6r6'-disulfonate, sodium dibutylnaphthalenesulfonate or,
alternatively, sodium oleylmethyltaurate. Emulsifiable
; concentrates are prepared by dissolving the active
2~3C~8
compound in an organic solvent, ~or example butanol,
cyclohexanone, dimethylformamide, xylene or, alter-
natively, higher-boiling aromatics or hydrocarbons with
the addition of one or more emulsifiers. Examples of
emulsifiers which can be used are.
alkylarylsulfonic acid calcium salts such as Ca dodecyl-
benzenesulfonate or nonionic emulsifiers such as fatty
acid polyglycol esters, alkylaryl pol~glycol ethers,
fatty alcohol polyglycol ethers, propylene oxide-ethylene
oxide [lacuna] sorbitan fatty acid esters, polyoxy-
ethylene sorbitan fatty acid esters or polyoxyethylene
sorbitol e~ters.
Dusting agents are obtained by grinding the active
compound with finely divided solid substances, for
example talc, natural clays such as kaolin, bentonite,
poryphillite [sic] or diatomaceous earth. Granules can
either be prepared by spraying the active compound onto
adsorptive granulated inert material or by applying
active compound concentrates by means of adhesives, for
example polyvinyl alcohol, sodium polyacrylate or,
alternatively, mineral oils, to the surface of support
substances such as sand or kaolinites or of granulated
inert material. Suitable active compounds can also be
granulated in the customary manner for the pre~aration of
fertilizer granules - if desired mixed with fertilizers.
In wettable powders the active compound concentration is,
~or exarnple, about 10 to 90% by weight, the remainder to
100~ by weight is composed of customary formulat.ion com-
ponents. In the case of emulsifiable concentrates, the
active compound concentration can be about 5 to 80% by
weight. Dust-like formulations contain mostly 5 to 20~ by
weight of active compound, sprayable solutions about 2 to
20~ by weight of active compound. In the case of
granules, the active compound content partially depends
on whether the active compound is liquid or solid and
which granulation auxiliaries, fillers etc. are used.
20~8~3~
- 12 -
In addition, said active compound formulations optionally
contain the adhesives, wetting agents, dispersants,
emulsifiers, penetrants, solvents, filler~ or support
substances customary in each ca~e.
For application, the concentrates present in commercial
form are optionally diluted in a customary manner, for
example by means of water in the case of wettable pow^
ders, emulsifiable concentrates, dispersions and some-
times even in the case of microgranulates. Dust-like and
granulated preparations, and sprayable solutions are
customarily not diluted further with other inert substan-
ces before application.
The application rate required varies with the external
conditions such as temperature, humidity and the like. It
can vary within wide limits, for example between 0.005
and 10.0 kg/ha or more of active substance, but it is
preferably between 0.01 and 5 k~/ha.
The active compounds according to the invention in their
commercial formulations can be applied either alone or in
combination with other fungicides known from the litera-
ture.
Examples of fungicides known from the literature which,
according to the invention, can be combined with the
compounds of the formula I are the following products:
imazalil, prochloraz, fenapanil, SSF 105, triflumizol,
PP 969, flutriafol, BAY-ME~ 6401, propiconazole,
etaconazole, diclobutrazol, bitertanol, triadimefon,
triadimenol, fluotrimazole, tridemorph, dodemorph,
fenpropimorph, falimorph, S-32165, chlobenzthiazone,
parinol, buthio~ate, fenpropidin, triforine, fenarimol,
nuarimol, triarimol, ethirimol, dimethirimol,
bupirimate, rabenzazole, tricyclazole, fluobenzimine,
pyroxyfur, NK-483, PP~389, pyroquilon, hymexazole,
fenitropan, UHF-8227, cymoxanil, dichlorunanid [sic],
captafol, captan, folpet, tolylfluanid, chlorothaloni],
2~3~8
- 13 -
etridiazole, iprodione ~formula II), procymidone,
vinclozolin, metomeclan, myclozolin, dichlozolinate,
fluorimide, drazoxolan, quinomethionate, nitrothal-
i~opropyl, dithianon, dinocap, binapacryl,
fentin acetate, fentin hydroxide, carboxin, oxycarboxin,
pyracarbolid, methfuroxam, ~enfura [sic], furmecyclox,
benodanil, mebenil, mepronil, flutalanil, fuberidazole,
thiabendazole, carbendazim, benomyl, thiofante [sic],
thiofanate-methyl [sic], CGD-94340 F, IKF-1216,
mancozeb, maneb, zineb, nabam, thiram, probineb,
prothiocarb, propamocarb, dodine, guazatine, dicloran,
quintozene, chloroneb, tecnazene, biphenyl, ~nilazlne,
2-phenylphenol, copper compounds such as Cu oxychloride,
oxine Cu, Cu oxides, sulfur, fosetylaluminum [sic],
sodium dodecylbenzenesulfonate,
sodium dodecyl sulfate,
sodium C13/C15 alcohol ether sulfonate,
sodium cetostearylphosphate ester,
dioctyl sodium sulfosuccinate,
sodium isopropylnaphthalenesulfonate,
sodium methylenebisnaphthalenesulfcnate,
cetyltrimethylammonium chloride,
Salts of long-chain primary, secondary or tertiary
amines, alkylpropylenamines, laurylpyridinium bromide,
ethoxylated quaternized fatty amines, alkyldimethyl-
benzylammonium chloride and 1-hydroxyethyl-2-alkylimid-
azoline.
The abovementioned combination components are known
active compounds, many of which are described in
CH [sic].~. Worthing, U. [sic]S.B. Walker, ~The Pesticide
Manual", 7th Edition (1983), British Crop Protection
Council.
The active compounds according to the invention, in
particular those of the examples mentioned, can in
addition be present in their commercial formulations and
3 3 ~
- 14 -
in the application forms prepared from these formulations
mixed with other active compounds, such as insecticides,
attractants, sterilants, acaricides, nematicides, fun
gicides, growth-regulating substances or herbicides. The
insecticides include, for example, phosphoric acid
esters, carbamates, carboxylic acid esters, formamidines,
tin cornpounds, substances produced by microorganisms and
the like. Preferred mixture components are:
1. from the phosphoric acid ester group
azinphos-2 ethyl, azinphos-2 methyl, 1-(4-chloro-
phenyl)-4-(O-ethyl, S-propyl)phosphoryl-oxypyrazole
(TIA-230), chlorpyrifos, coumaphos, demeton,
demeton-S-methyl, diazinon, dichlorvo~, dimethoate,
ethoprophos, etrimfos, fenitrothion, fenthion,
heptenophos, parathion, parathion-methyl, phosalone,
pirimiphos-ethyl, pirimiphos-methyl, profenof GS,
prothiofos, sulprofos, triazophos or trichlorophon.
2. from the carbamate group
aldicarb, bendiocarb, BPMC (2-(1-methylpropyl)-
phenylmethyl carbamate), butocarboxim,
butoxycarboxim, carbaryl, carbofuran, carbosulfan,
cloethocarb, isoprocarb, methomyl, oxamyl, primicarb[sic], promecarb, propoxur or thiodicarb.
3. from the carboxylic acid ester group
. 25 allethrin, alphamethrin, bioallethrin,
: bioresmethrin, cycloprothrin, cyfluthrin,
. cyhalothrin, cypermethrin, deltamethrin, alpha-
cyano-3-phenyl-2-methylbenzyl 2,2-dimethyl-3-(2-
chloro-2-trifluoromethylvinyl)-cyclopropanecarboxy-
late (FMC 54800), fenpropathrin, fenfluthrin, fen-
valerate, flucythrinate, flumethrin, fluvalinate,
permethrin, resmethrin or tralomethrin.
4. from the formamidine group
amitraz or chlordimeform
2 ~ 3 ~
- 15 -
5. from the tin compound group
azocyclotin, cyhexatin and fenbutatin oxide
6. Miscellaneous
abamektin, Bacillus thuringiensis, bensultap,
binapacryl, bromopropylate, buprofecin, camphechlor,
cartap, chlorobenzialate [sic], chlorfluazuron, 2-
(4-chlorophenyl)-4,5-diphenylthiophene (UBI-T 930),
chlofentezine, 2-naphthylmethyl cyclopropanecar-
boxylate (Ro 12-0470), cyromacin, DDT, dicofol, N-
(3,5-dichloro-4-(1,1,2,2-tetrafluoroethoxy)phenyl-
amino)carbonyl)-2,6-difluorobenzamide (XRD 473),
diflubenzuron, N-(2,3-dihydro-3-methyl-1,2-thiazol-
2-ylidene)-2,4-xylidine, dinobuton, dinocap, endo-
sulfan, fenoxycarb, fenthiocarb [sic], flubenzimine,
flufenoxuron, gamma-HCH, hexythiazox, hydramethylnon
(AC 217 300),ivermectin,2-nitromethyl-4,5-dihydro-
6H-thiazine (SD 52618), 2-nitromethyl-3,4-dihydro-
thiaz~le(SD 35651),2-nitromethylene-1,3-thiazinan-
3-yl-carbamaldehyde [sic] (WL 108 477), propargite,
teflubenzuron, tetradifon, tetrasul, thiocyclam,
triflumaron, core polyhedrosis and granulosis
viruses.
The active compound content of the application forms
prepared from the cornmercial formulations can vary within
wide ranges, and the active compound concentration of the
application forms can be from 0.0001 up to 100% by weight
of active compound, preferably between 0.001 and 1% by
weight. Application is carried out in one of the custom-
ary ways 6uited to the application forms.
The following examples serve to illustrate the invention.
A. Formulation example~
a) A dusting agent is obtained by mixing 10 parts by
weight of active compound and 90 parts by weight of
talc as the inert substance and comminuting the
2~g33~
- 16 -
mixture in a hammer mill.
b) A wettable powder which is e~sily dispersible in
water is obtained by mixing 25 part by weight of
active compound, 64 parts by weight of kaolin-
containing quartz as the inert sub~tance, 10 parts
by weight of potas~ium ligninsulfonate and 1 part by
weight of sodium oleoylmethyltaurate as the wetting
agent and dispersant and grinding the mixture in a
pinned disk mill.
c) A dispersion concentrate which is easily dispersible
in water is obtained by mixing 40 parts by weight of
active compound with 7 part~ by weight of a sul-
fosuccinic acid half-ester, 2 parts by weiyht of a
sodium ligninsulfonate and 51 parts by weight of
water and grinding the mixture in a friction ball
mill to a fineness o less than 5 microns.
d) An emulsifiable concentrate can be prepared from 15
parts by weight of active compound, 75 parts by
weight of cyclohexanone as the solvent and 10 parts
by weight of oxyethylated nonylphenol (10 E0) as the
- emulsifier.
e) Granules can be prepared from 2 to 15 parts by
weight of active compound and an inert granulate
support material such as attapulgite, pumice
; 25 granules and/or quartz sand. Expediently, a ~uspen-
sion of the wettable powder from Example b) having
a solid~ content of 30% is used and this is sprayed
onto the surface of attapulgite granules, dried and
mixed intimately. The weight content of the wettable
powder here i8 about 5% and that of the inert
support material is about 95% of the finished
granules.
2~33~
B. Chemical exa~ples
2-(6-Benzylpyridin-2-yl)-4-propylpyrimidine
(Example No.: 1.2)
0.2 g of 5% palladium/carbon is added to a solution of
3.24 g (0.01 mol) of 2-(6-benzylpyridin-2-yl)-6-chloro-
4-propylpyrimidine in 50 ml of ethanol. ~his mixture is
brought into contact with hydrogen under a pressure of 3
bar and at a temperature of 60C with vigorous stirring
for 2 h. The catalyst is then filtered off and the
filtrate is concentrated in vacuo. The residue is taken
up in water, saturated with sodium bicarbonate and
extracted with CH2Cl2. The organic phase is dried over
Na2S04 and concentrated. 2.85 g (98.6%) of a yellowish oil
are obtained.
2-(6-benzylpyridin-2-yl)-4-methoxy-6-phenylpyrimidine
(Example No.: 1.15)
A sodium methylate solution is prepared by dissolving
0.184 g (0.008 mol) of sodium in 40 ml of abs. methanol.
1.79 g (0.005 mol) of 2-(6-benzylpyridin-2-yl)-4~chloro-
6-phenylpyrimidine is added to this solution and the
mixture is boiled under reflux for 3 h. It is then
concentrated, water is added to the residue and the
mixture is extracted with methylene chloride. The organic
phase i5 dried using Na2S04 and concentrated. After
crystallization from diisopropyl ether, 1.49 g (84.3%) of
a colorless solid are obtained.
Melting point: 128 - 129C
2-(5-benzylpyridin-2-yl)-4,6-dimethyl-1,3,5-triazine
(Example No. 2.L)
2.47 g (0,01 mol) of 6-benzyl-2-picolinamidine hydrochlo-
ride are stirred together with 3048 g (0.04 mol) of ethyl
acekimidate at 60c for 2 h. The reacticn mixture is then
taken up in water and extracted with CHCl3. The organic
20~833~
~ 18 -
phase is washed with water, dried over Na2SO4 and con
centrated. The residue is subjected to column chromatog-
- raphy (eluent: methylene chloride). 1.62 g (58.7%) of a
colorless oil are obtained.
The compounds of Table A can be prepared analogously to
these examples.
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2~8338
- ~8 -
C. Biological Examples
Example 1
Rice plants of the "Ballila" type about 5 weeks old were
treated with the concentration of the claimed compounds
indicated below after prespraying with 0.05~ strength
gelatine solution. After the spray coating had dried on,
the plants were uniformly inoculated with a spore suspen-
sion of Piricularia oryzae and placed for 48 h in a
climatic chamber, which was kept dark, having a tempera-
ture of 25C and 100% relative atmospheric humidity. The
rice plants were then cultivated further in a greenhouse
having a temperature of 25C and 80~ relative atmospheric
humidity. Evaluation of attack was carried out after 5
days. The degree of attack was expressed in % of attacked
leaf surface in comparison to untreated infected controlplants. The results are collated in Table lo
T~ble 1
Compound Leaf surface attacked with Piricularia
according oryzae in % at mg of active compound/
to Bxample liter of spray liquor
500
. _
1.3 0
1.2
1.5 0
2.1 0
1.43 0
1.11 0
1.44 0
1.10 0
1.46 o
. _ _
untreated infected
plants 100
3 3 8
- 29 -
Exa~ple 2
Barley plants were heavily inoculated in the 2-leaf stage
with barley mildew conidia (Erysiphe graminis hordei) and
cultivated further in a greenhouse at 20C and a relative
atmospheric humidity of about 50%. 1 day after inocula-
tion, the plants were we~ted uniformly with the compounds
listed in Table 2 at the active compound concentration
indicated. After an incubation time of 7-9 days, the
plants were examined for attack by barley mildew. The
degree of attack is expressed in ~ of attacked leaf
surface, relative to untreated infected control plants (=
100% attack). The result is summarized in Table 2.
Table 2
Compound Leaf surface attacked with barley
according mildew in % at mg of active compound/
to Example liter of spray liquor
500
.. . ....
103
1.2 0
1.43 0
1.10 0
1.~6 0
.: -
untreated infected
plants 100
Example 3
Wheat of the "Jubilar" type was treated in the 2-leaf
stage with aqueous suspensions of the claimed compounds
until dripping wet. After the spray coating had dried on,
the plants were inoculated with an aqueous spore sus-
pension of Puccinia recondita. The plants were placed
dripping wet in a climatic chamber at 20C and about 100%
2~833~
- 30 -
relative atmospheric humidity for about 16 hours. The
infected plants were then cultivated further in a green~
house at a temperature of 22-25C and 50-70% relative
atmospheric humidity.
After an incubation time of about 2 weeks, the fungi
sporulates onto the entire leaf surface of the untreated
control plants such that an evaluation of attack of the
test plants can be carried out. The degree of attack was
expressed in % of attacked leaf surface in comparison to
untreated infected control plants and iY reproduced in
Table 3.
Table 3
Compound Leaf surface attacked with Puccinia re-
according condita in % at mg of active compound/
to Example liter of spray liquor
500
.
1.3 0
1.2 0
untreated infected
plants 100
~ample 4
Wheat plants of the "Jubilar" type were treated in the 2-
leaf stage with aqueous suspensions o~ the preparations
given in Table 4 until dripping wet.
After the spray coating had dried on, the plants were
inoculated with an aqueous pyknospore suspension of
Leptosphaeria nodorum and incubated at 100% relative
atmospheric humidity in a climatic chamber for several
hours. Until expression of symptoms, the plants were
further cultivated in a greenhouse at about 9Q% relative
atmospheric humidity.
- 31 - 2~83~
The degree of action is expressed as a percentage of the
untreated infected control and is reproduced in Table 4.
Table 4
Compound Leaf surface attacked with Leptosphaeria
according nodorum in % at mg of actlve compound~
to Example liter of spray liquor
500
1.43 0
1.11 0
1.44 0
1.46 o
1.14 0
1.5 0
1.4 0
1.3 0
1.2 0
untreated infected
plants 103
~xample 5
Broad beans of the "Herz Freya" or "Frank's Ackerperle"
type about 14 days old were treated with aqueous
suspensions of the claimed compounds until dropping wet.
After the spray coating had dried on, the plants were
inoculated with a spore suspension (1.5 million
spores/ml) of Botrytis cinerea. The plants were cul-
tivated further in a climatic chamber at 20-22C and
about 99% relative atmospheric humidity. The infection of
the plants is manifested by the formation of black spots
on the leaves ancl stalks. Evaluation of the tests was
carried out 1 week after inoculation.
The degree of action of the test substances was assessed
3 ~ ~
- 32 -
as a percentage of the untreated infected control and is
reproduced in Ta~le 5.
Table 5
Compound Leaf surface attacked with ~otrytis
according cinerea in % at mg of active compound/
to Example liter of spray liquor
500
2.1 0
untreated infected
plants 100
