Note: Descriptions are shown in the official language in which they were submitted.
-1- 21489-6921D
This application is a divisional application for
application no. 505,550 filed on April 1, 1986. This
divisional application relates to 2,2-difluoro-4-amino-1,3-
benzodioxole and to a process for its preparation.
The invention of the parent application relates to
the novel anilinobenzodioxole compound of the ,formula I helow.
The invention further relates to the preparation of this
compound and to compositions which contain said compound as
active ingredient, as well as to the use of the novel compound
or said compositions for controlling pests, in particular
phytopathogenic fungi or bacteria, and also insects and acarids.
The compound of the parent invention has the formula
I.
~N02
2N ~ ~ - NH ~
~ ~ \ (I)
In accordance with this invention, said compound is
prepared by reacting the compound of formula II
:: '
,
-la- 21489-6921D
H2N \ ~ (II)
~ F
with the compound of formula III
/N2
02N - ~ CF3 (III)
in the presence of an acid acceptor in an inert solvent
or diluent.
-2- 21~89-6921~
Examples of suitable inert solvents or diluents are:
aliphatic and aromatic hydrocarbons such as benzene, toluene,
xylenes, petroleum ether; halogenated hydrocarbons such as
chlorobenzene, methylene chloride, ethylene chloride, chloro~orm,
carbon tetrachloride, tetrachloroethylene; ethers and ethereal
compounds such as dialkyl ethers (diethyl ether, diisopropyl
ether, tert-butylmethyl ether etc.), dioxane, tetrahydrofurane;
nitriles such as acetonitrile, propionitrile; N,N-diaikylated
amides such as dimethylEormamide; dimethyl sulfoxide; ketonessuch
as acetone, diethyl ketone, methyl e-thyl ke-tone; and mixtures
of such solvents with each other. Dimethylformamide, tetrahydro-
furan and dioxane are preferred. In some cases it is advantageous
to carry out the reaction in aqueous suspension.
Examples of suitable acid acceptors are inorganic
bases, e.g. oxides, hydroxides, carbona-tes or bicarbonates of
alkali metals or alkaline earth metals, as well as alkali metal
hydrides or alkali metal acetates, and also or~anic bases, e.g.
tertiary amines such as trialkylamines (trimethylamine,
triethylamine etc.), pyridine or pyridine bases (~-dimethylamino-
pyridine, ~-pyrrolidylaminopyridine). Preferred acid acceptors
are alkali metal hydroxides, alkali metal bicarbonates and alkali
metal hydrides.
The xeaction temperature iq variable depending on
the reaction conditions. It is in general in the range ~rom -25
to 150C, preferably from ~10 to 120C.
The reac-tion partners are normally employed in
equimolar amoun-ts,.
J~
-2a- 21489-6921D
The compound of formula ~I employed for the preparation
of the compound of formula I of this invention is novel. Said
novel compound of formula II is a valuable intermediate for the
synthesis of biocidal compounds and constitutes a subject of the
divisional application. It is prepared e.g. by Hofmann degradation,
i.e. by reacting 2,2-difluoro-4-carbamoyl-1,3-benzodioxole with
bromine, in the presence of aqueous alkali metal hydroxide, which
is also the subject of the divisional application.
~ONH2 ~H2
~ / \O X allall m~ta~ ~ \1/ X (II)
This process i6 carried out in accordance wlth the method of L.M.
Yagupol6kil ~t al., Zhur. Obshch. Khym. 31, 628 (1981).
The precursors for the preparation of the compound of formula II are
syntheslsed as follows starting from 4-carboxy~1,3-benzodioxole (in
accordance with W.H. Perkin ~nd V.M. Triko~us, J. Chem. Soc. 1926,
2925): -
1~
~00~2 ~OCl
~ \ PCl,s __~ T~,~X
~OCl ~OF
oXc~ X
3~
~OF ICONH2
~-~ /O\ /F ~ O
~ \o~ ~ N~3 ~
Diaryla~ine~ are known which have been proposed for u~e as fungi-
cides, insectlcides and acaricides (q.v. German Offenlegungsschrift
28 23 168). Howev~r, the activity of ~ald diarylsmlnes ls not
-- 4 --
entirely satisfgctory to the dssired degree. The followlng com-
pound A for example is known from the aforHmentloned German OfEen-
legungsschrift:
~NO2
02N~ -N~ (A).
~CF3 \~ ~ F
Surprislngly, it has been found that th~ compound of formula I of
this lnvention has a very useful biocidal activity spsctrum against
fungi, bacteria, ln6ects and representatives of tho order Acarina,
in particular against phytopathogenic fun~l and bacteria, which
activity spectrum satisfies practical requirements well. The
compound of formula I has very advantageous curative, systemic and,
in partlcular, preventive properties, and can be used for protecting
numerous cultivated plants. With the compound of formula I it ls
possible to inhlbit or destroy the pests which occur in plant6 or
parts of plants (fruit, blossoms, leaves, stems, tubers, roots~ in
different crops of useful plants, while at the same tlme the part6
of plants which grow later are also protected from attack by
phytopathogenic microorganisms and lnsects. Acarina can also be
succQssfully controlled with the compouna of fo~mula I.
As microbicide6, the compound of formula I ls effectlve e.g. again6t
the phytopathogenic fungi balonging to the following cla6ses: Fungl
imperfecti ~e.g. Botrytis, Helmintho6porium, Fu6arium, Septoria,
Cerco~pora and Alternaria); ~asidiomycotes (e.g. of tho genera
Hemileia, Rhizocotonia, Puccinia); as woll as a~ainst Oomycetes
(Q . g. Plasmopar~ viticola) belonglng to tho class of the Phyco-
mycetes; and, in partlcular, agalnst the class of the Ascomycet~6
(s.g. Venturla, Podospllaera, Erysipho, Monllinia, Uncinula). In
addition, the compound of formula I ha a systemic action. It can
also be usHd as drQsslng agent for protscting soeds (fruit, tuber6,
gralns) and plant cuttlngs against fungus infections es wHll as
against phytopsthogenic fungi which occur in th~ soil~
- 5 -
A6 insectlclde, the compound of formula I can also be used for
controlling lnsects of the orders: Lepidoptera, Coleoptera, Homop-
tera, Heteroptera, Diptora, Thysanoptera, Orthoptera, ~lattaria,
Anoplura, Siphonaptera, Mallophaga, Thy6anura, Isoptera, Psocoptera
and Hymenoptera.
The compound of formula I is also suitable for controlling represen-
tatives uf the order Acarins, e.g. of the families Ioxididae,
Argasidae, Tetranychidae and Dermanyssldae. The compound of for-
mula I can be successfully used for controlllng phytopathogenic
mites, e.g. of the famili06 Tetranychidae and Phytoptipalpidae
(spider mite6), Tarsonemidae and Eriophydiae (gall mites).
In addition to its action against flies, e.g. Aëdes aegyti and
Musca domestica, the compound of formula I is also suitable for
controlling plant-destructive feeding insects in ornamentals and
crops of useful plants, especially in cotton (e.g. against Spodop-
tera littoralis and }leliothis virQficens~ and in crops of ceraals,
fruit and vegetables (e.g. agains~ Laspeyresia pomonelia, Leptlno-
tarsa decemllneata and Epilachna varivestis)~ The compound of
formula I has a good actlon against larval developmant stages and
nymphs, ~specially of noxious feeding insects.
The compound of for~ula I can also 'oe ussd for controlllng ecto-
parasitic lnsects and acarids in domestic animals and productivs
livestoc~, e.g. by treating animals, cowsheds, barns, stables etc.,
and pa6tures.
Ths actlvity of the compound of formula I and of the composlt~on6
containing it can be substantlally broad~ned and adapted to pre-
vailing circumstances by addition of other insecticides andlor
acaricides.
Accordlngly, ~he invention also relates to pestlcidal compositlons
(microbicideL, insectlcidesl acarlcldes) and to the use th~reof ln
agriculture or related fields .
The invention Eurther embraces the preparatlon of the6e co~po61-
tlons, which comprises homogeneously mlxing the actlve lngredient
with one or more compounds or groups of compounds described hereln.
The invention furthermore relates to a method of treating plants,
which comprlses applying thereto the compound of formula I or the
novel composltions.
Target crops to be protected withln the scope of the pre6ent
inventlon comprlse e.g. the followlng specles of plant6:
cereals (wheat, barley, rye, oat6, rice, sorghum and ralated crop6),
beet (sugar beet and fodder beet), pomes, drupes and soft frult
(apples, pears, plums, peaches, almonds, cherri~s, strawberrles,
rasberrl~s and blac~berrles), legumlnous plants (beans, 10ntll6,
peas, ~oybeans), oll plant6 (rape, mu6tard~ poppy, ollves, sun-
flowers, coconuts, castor oil plants, cocoa beans, groundnuts),
cucumber plants (cucumber, marrows, melons), fibre plants (cotton,
flax, hemp, ~ute), cltrus frult (orange6, lemons, grapefrult,
mandarins), vagetables (spinach, lettuce, asparagus, cabbages,
carrots, onlons, tomatoe6, potatoes, paprika)j lauraceae (avocados,
cinnamon, camphor), or plants 6uch as malze, tobacco, nut6, coffee,
sugar cane, tea, vine6~ hops, banana~ and nntural rubber plants, as
well a6 ornamental6 (composite6).
The compound of formula I is normally applied ln the form of
composition6 contalning ad~uvants such as carriers ~nd diluent6 and
can be applied to the crop area or plant to be treated, slmulta-
neously or ln succ~6sion, with further compounds. These further
compounds can be both fsrtlllsers or micronutrlent donor6 or other
preparatlons that ~nfluence plant growth. They can also be selective
herblcides, ins~cticldes, fungicides, bactericides, nematlcides,
mollu6clcide6 or mixtures of several of the6e preparatlon6, lf
de61red together with further carrlers, sur~actant6 or application
~$~
promoting adjuvants customarlly employed ln the art of forMulatlon.
Suitable carriers and ad~uvants can be solid or liquid and corres-
pond to the substances ordlnarily employed in formulation tech-
nology, e.g. natural or regenerated mineral substances, solvents,
dispersants, wetting agents, tackifiers, thickeners, binders or
fertilisers.
A preferred method of applying the compound of formula I or an
agrochemical composition which contains said compound, ls foliar
application. The number of applications and the rate of application
depend on the risk of infestation by the corresponding parasite
(e.g. type of fungus). However~ the compound of formula I can also
penotrate the plant through the roots via the soil (systemic action)
by drenching the locus of the plant wlth a llquld co~posltlon, or by
applying the compound in solid orm to the soil, e.g. in granular
form (soil appllcation). The compound of formula I may also be
applied to seeds (coatlng) by impregnating the saeds either with a
liquld formulatlon containlng sald compound, or coating
them with a solid formulation. In special casas, further types of
appllcation are also possible, e.g. seloctivo treatment of the plant
stems or buds.
The compound of formula I is used ln unmodifled form or, preferably,
together with ths ad~uvants conventionally employed in the art of
formulation, and is therofore formulat0d in known manner e.g. to
emulslflabla concentrates, coatable pastes, directly 6prayable or
dilutable solutions, dilute emulsions, wettablo powders, soluble
powders, dusts, granulates, and also encapsulations ln e.g. polymer
substances. As with the nature of the compositions, tho methods of
appllcatlon, such as 6praying, atomlsing, du~tlng, scatterlng,
coatlng or pouring, are chosen in accordance with the lntonded
ob~ectivos and the prevailing circumstances. Advantageous rates of
application are normally from 50 g to 5 ~g of active lngredient
(a.i.) por hecta~e, preferably fro~ 100 g to 2 ~g a.l.lha~ most
preferably from 200 g to 600 g a.i./ha.
: '
-- 8 --
The formulations, l.e. the compositions or preparations containlng
the compound (actlve ingredient) of formula I and, wher~
appropriate 7 a solid or liquid ad~uvant, are prepared in known
manner, e.g. by homogeneously mixing and/or grindlng the active
ingredient with extenders, e.g. solvents, solid carrier& and, where
appropriate, surEace-active compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, preferably the
fractions containlng 8 to 12 carbon atoms, e.g. ~ylene mixturss or
substituted naphthalenes, phthalates such as dibutyl phthalate or
dioctyl phthalate, aliphatlc hydrocarbons such as cyclohexane or
paraffins, alcohols and glycols and their ethers and esters, such as
ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl
ether, ketone6 such as cyclohexanone, strongly polar solvents such
as ~-methyl-2-pyrrolldone, dimethyl sulfoxide or dimethylformamlde,
as well as vegetable oils or epoxidised vegetable oils 6uch as
epoxidised coconut oil or soybean oll; or water.
The 601id carrlers used e.g. for du6ts and dlsper61ble powders, are
normally natural mlneral flller6 such as calcite, talcum, kaolin,
~ontmorillonite or attspulgite. In order to improve the physical
properties it ls also posslble to add highly dispersed silicic acld
or hlghly dl6persed absorbent polymers. Sultable granulated adsorp-
tive carriers are porous types9 for example pumice, broken brick,
sepiollte or bentonlte; and su~tabl0 nonsorbent carrlers are
materlals such as calclte or sand. In addltlon, a great number of
pregranulated materlals of inorganic or organic nature can be used,
e.g. especially dolomlte or pulverisad plant residues. Particularly
advantageous appllcatlon promotlng ad~uvants whlch are able to
reduce ~ubstantially the rate of appllcatlon ara slso natural
(anl~al or vagetable) or synthatlc phosphollplds of the serles of
the cephalins and leclthin6, e.g. phosphatidyl ethanolamlne,
pho6phatidyl serine, pho8phatidyl chollne, sphlngomyallne, phosphat-
ldyl lnosltol, phosphatldyl glycerol~ lysolacithln, plasmalogenes or
cardlolipln, wh:Lch can be obtained e.g. from animal or plant c0116,
36~
ln partlcular from the brain, heart, liver, egg yokes or soybeAns.
Examples of useful physlcal forms are phosphatldyl choline mixtures.
Examples of synthetic phospholipids are dioctanoylphosphatidyl
chollne and dipalmitoylphosphatidyl choline.
Dependlng on the nature of th0 compound of formula I to be formu-
lated, 3uitable surface-active compound6 are nonlonlc, cationic
and/or anionic sllEactants havlng good emulsifying, dispersing and
wetting properties. The term "surfactants" will also be understood
as comprising mixtures of surfactants.
Suitable anlonic 6urfactants can be both water-601uble soaps and
water-soluble synthetic surface-actlve compounds.
Suitable soaps are the alkali metal salts, alkallne earth metal
saltB or unsubstituted or substituted ammonium salts of higher fatty
acid6 (C1O-C22), e.g. the sodium or potassium salts of olelc or
stearlc acld, or of natural fatty acid mlxtures which can oe
obtalned e.g. from coconut oil or tallow oil. Mention may also ba
made of fatty acid methyllaurin salts~
More frequeDtly, however, so-called synthotic surfactants are used,
especially fatty sulEonates, fatty sulfates, sulfonated benzlmid-
azole derivatives or alkylarylsulfonates.
ThP fatty sulfonates or sulfates are usually in the form of alkall
metal salts, alkaline earth metal salt6 or un~ubstltuted or sub-
stituted a~monium salts and contain a C8-C22alkyl radical which also
lncludes the alkyl moiety of acyl radlcal~, e.g. the sodium or
calcium salt of lignosulfonic acid, of dodecylsulfate or of a
mixture of fatty alcohol sulfates obtained from natural fatty acids.
These compounds also comprise the salts of sulfuric acid esters and
6ulEonic acids of fatty alcohol/ethylene oxide adduct6. The sulfona-
ted benzimidazole derivatlves preferably contain 2 sulfonic acid
groups and one fatty acld radical containing 8 to 22 carbon atoms.
Examples of alkylarylsulfonates are the sodium, calcium or tri-
- 10 -
ethanolamlne salts of dodecylbenzenesulfonic acid, dibutylnsphtha-
lenesulfonic acid, or of a naphthalenesulfonlc acid~formaldehyde
condensation product. Also suitable are corre~ponding phosphates,
e.g. salts of the phosphoric acid ester of an adduct of p-nonyl-
phenol wi~h 4 to 14 moles of othylene oxide.
Non-ionic surfactants are preferably polyglycol ether derivatives of
aliphatlc or cycloaliphatic alcohols, or saturated or unsaturated
~atty acids and alkylphenols, said derivative6 containing 3 to 30
glycol ether groups and 8 to 20 carbon atoms ln the (aliphatic)
hydrocarbon moiety and 6 to 18 carbon atoms ln the alkyl molety of
the alkylphenols.
Further suitable non-ionic surfactant6 are the water-601uble adducts
of polyethylene oxlde wlth polypropylene glycol, ethylenediamino-
polypropylene glycol and alkylpolypropylene glycol contalning 1 to
10 carbon atoms in the alkyl chain, which adducts contain 20 to 250
ethylene glycol ether groups and 10 to 100 propylene glycol ether
groups. These compounds u6ually contaln 1 to 5 ethyl~ne glycol units
per propylene glycol unit.
Representative axamples of non-lonlc surfactants are nonylphenol-
polyethoxyethanols, castor oil polyglycol ethers, polypropyleneJ
polyethylene oxide adducts, trlbutylphenoxypolyethoxy~thanol,
polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid
esters o~ polyoxyethylene sorbitan, e~g. polyoxyethylene sorbitan
trioleate, are also suitable non-ionic surfactants.
Cationic surfactants are pre~erably quaternary a~nonium salts which
contaln, as N-substituent, at 18a6t one C8-C22alkyl radical and, a~
f~rther substituents, unsubstituted or haloganated lower alkyl,
benzyl or hydro~y-lower alkyl radicals. The salts are prefsrably in
the form of halide6, methylfiulfates o~ ethylsulfates, e.g. stearyl-
trimethylammonium chlorlde or benzyldi(2-chloroethyl)ethylammonium
bromida.
.:
f~
The 6urfactants customarily amployed ln the art of formulatlon are
described e.G. ln
"McCutcheon's Detergents and Emulsifier6 Annual",
MC Publishing Corp., Ridgewood, New Jersey, 1~81;
Slsley and ~ood, "Encyclopedia of Surface Active
Agent6", Chemical Publishing Co. Inc., New York, 1980;
Helmut Stache, "Tensld-Taschenbuch" (Handbook of Sur-
factants~, Carl Hanser Verlag, Munich/Vienna, 1981.
The agrochemical compo6itions usually contain 0.1 tD 99 %, prefer-
ably 0.1 to 95 Y0, of the compound of formula I, 99.9 to 1 %,
preferably 99.8 to 5 %, of 8 solid or liquid ad~uvant, and 0 to
25 %, preferably 0.1 to 25 %, of a surfactant.
Whereas commercial products are preferably formulated as concen-
trates, the end user will normally employ dilute formulations.
The compofiitions may also contaln further ingredients such a6
stabilisers, antifoams, vlscosity regulators, binders, tackifiers a6
well as fertiliser6 or other actlve ingredient6 in order to obtain
special effects.
Such agrochemical compositions also constitute an ob~ect of the
present lnvention.
The invention is illu~trated in more detall by the followlng
Examples, without implying any restrlction to what is described
therein.
, ,
: : ,
.
- 12 - 2148~-6921D
1. rr~paratory Examples (Example 1.2 is the ~ject o~ the divisional
applicatlon)
xa~el~ 1.1 Prcparatlon of 2,2-dlfluoro-4-¦2'14'~dlnltro-6'~(trl-
fluorometllYl~anll~
/Dx~ I O~N~ Cl L1011~11,0 _
~2
02N~ Nll ~ /
CF ~ of ~0
\/
- F/~F
20.8 g of Ll0ll~ll20 are addud at O~C to a 601utlon of 24.5 g of
2,2-dlfluoro-4-amlno-1,3-banzodloxolo in 70 ml of dlmathyl sulf-
oxlde. Tha mixture ls thon stlrrud for 20 minutus. Subsuguantly, ~
6nlutlon of 38.3 ~ of 2,4-dlnltro-6-trlfluoromethylchlorobenzona in
70 ml of dlmethyl 6ulfoxldu i5 addud, and the ruGultant resctlon
mlxturu i8 stlrred at O~C for 20 minutafi and thun heatad to room
temperatur~. After 5 hours~ thu mixturu 1~ pourod into 350 ml o~
uatar, acldlflud ulth dilute hydrochlorlc acid and extracted saveral
tlmes wlth die~hyl ather. Ths comblnud etllor pha6e6 ara washud tll~0a
tlmes ulth a 5 X solution of sodlum carbonate and tllen wltll 5 X
hydrochlor c acld and drlud oYa~ sodlum fiulEata, an~ tha Gol~ont 16
uYaporated off ln vacuo. Tho resldue comprlse6 51.6 e of oranga-
brown crystals which ara rocry6talll6ud ln toluenu.
Ylel~: 41.6 g; meltlng polni: 14b-146C.
Exampla 1.2: Preparntlon of 2,2-difluo~n-4-fimlno-l,3-benzodloxolu
~ONI12 ~i~l2
.SSS \,f \~ Dr2lKOII ,;~
~ !\o~ o/~F
- 13 -
52.5 g of bromlne are added dropwl6e at 0C to a solutlon of 120 g
of pota~slum hydro~ide ln 780 ml of water. Sub6equently, so.a g of
2,2-difluoro-4-carbamoyl-1,3-benzodioxole are added, and the
reactlon mi~ture is stir~ed for 30 minute6 at room temperature and
then heated for 45 mlnutes to 80C. The reaction solution ls then
diluted ln 400 ml of water and distilled with steam. Thc distlllate
is e~tracted with diethyl ether and dried over sodium sulfate. The
solvent ls evaporated off, affording 38.1 g of the title co~pound as
a yellowish oil with a refrac~ive lndex nDlof 1.4955.
xample 1.3: Preparation of 2,2-dichloro-4-carbonyl chloride
1,3-benæodioxole
ICOOH ICOCl
E~ \ PCls~ D~oXcl
40 g of 4-carboxy-1,3-benzodioxole are mixed with 150 g of phos-
phorus pentachloride, and the mixture is heated to 70C. After 3.5
hours, the temperature i8 incrsased to 90C and then held at thls
level for 12 hour6. Sub6equently, the volatile components are
dlstilled off at 110C and 2000 Pa, and the re6idue i6 di~tilled off
under high va~uum, affordlng 45 g of the tltle compound as a
sllghtly yellowish solld.
Example 1.4: Preparatlon of 2,2-difluoro-4-carkonyl fluoride
1,3-benzodioxole
ICOCl ICOF
i~ \ti~ X SbF3
~ O Cl ~- ~
In a dlstillation apparatus, 5S.7 g of SbE3 are added to 59.4 g of
2,2-dichloro-4-carbonyl chloride 1,3-benzodioxole, whereupon a
reactlon take6 place immediately. In order to maintain the reaction,
~L2~
~ 14 -
the tempera~ure ls 610wly increased, while simul~aneously gradually
evacuating. 59.5 g of a red oil distill over at 105-117~C and
66S6 Pa. The distillate is taken up in 100 ml of dlethyl ether and
washed with two 150 ml portlons of semiconcentrated hydrochloric
acld and then with water. The ether solution is dried over sodium
sulfate and the solvent i6 evaporated off, affording 42.0 g of the
title compound.
xample_1.5: Preparation of 2,2-difluoro-4~carbamoyl-1,3-b~nzo-
dioxole
~OF ~ONh~
E~ ~i' X ~ NH3 ~ X
With ice cooling and stirrlng, 63,6 g of 2,2-difluoro-4-carbonyl
fluoride 1,3-benzodioxole are added dropwi6e to 120 ml of a concen-
trated 25 % solution of ammonia. In the coUrsQ of several hours a
cry6talline slurry i6 formed which is then i601ated by filtration
and ~ashed in 6ucces610n with a dilute solution of am~onia and then
with water, affording Sl g of 2,2-difluoro-4-carbamoyl-1,3-benzo-
dioxole with a melting point of 129.5-131C.
2. Formulation Example~ for the active in~redisnt of formula I
(throughout, percentages are by weight)
2.1. Emulsiflable concentrates a) b) c)
the compound of formul~ I2S % 40 % 50 %
calcium dodecylbQnzene6ulfonats 5 % 8 ~0 6 %
castor oll polyethylene glycol ether
(36 moles of ethylene oxide)5 % - -
tributylphenol polyethylena glycol ether
(30 mole6 of ethylene oxide)12 % 4 %
cyclohexanone - 15 % 20 %
xylene mlxture 65 % 25 % 20 %
'
~ .
36~
Emulslons of any required concentration can be produced from such
concentrates by dilutlon wlth watsr.
2.2. Solutlons a) b) c) d)
the compound of formula I 80 % 10 % 5 % 9S %
ethylene glycol monomethyl etber 20 % - - -
polyethylene glycol (mol.wt.400) - 70 %
N-methyl-2-pyrrolidone - 20 % - -
epoxldised coconut oll - - 1 % 5 %
petroleum distlllate (bolling range
160-190C) ~ ~ 94 %
These solutlons are sultable for application in the form of mlcro-
drops.
2.3. Cranulates a) b)
the compound of formula I 5 % 10 %
kaolln 94 %
highly dlspersed silicic acld 1 %
attapulgite - 90 %
The active lngredient i8 dissolved in methylene chloride, the
solution i5 sprayed onto the carrler, and the solvent is subse-
quently evaporated off in vacuo.
2.4. Dusts a) b)
.. ..
the compound of formula I 2 % 5 %
highly dispers2d silicic acld 1 % 5 %
talcum 97 %
kaolin 90 %
Ready-for-use dusts are obtained by intimately mixing the carriers
with the active ingrsdient.
~L2~ 4
- 16 -
2.5. Wettable powders a) b) c)
the compound of formula 1 25 % 50 % 75 %
sodlum llgnosulfonate 5 % 5 %
sodium lauryl sulfate 3 % - 5 %
sodlum dllsobutylnaphthalenesulfonate - 6 % 10 %
octylphenol polyethylene glycol ether
(7-8 moles of ethylene oxide) - 2 %
hlghly dlspersed &iliclc acid S % 10 % 10 %
kaolin 62 % 27 %
The actlve ingredlent is thoroughly mlxed wlth the ad~uvants and the
mixture 1B thoroughly ground ln a suitable mill, affordinK wettable
powders which can be diluted with water to give 6u6pensions of the
desired concentration.
2.6. Emulsifiable concentrate
the compound of formula I 10 %
octylphenol polyethlene glycol ether
(4-5 moles of ethylene oxlde) 3 %
calcium dodecylbenzenesulfonate 3 %
castor oll polyglycol ether
(35 moles of ethylene oxlde) 4 %
cyclohexanone 30 %
xylene mixture 50 %
Emulsions of any required concentration can be obtained from this
concentrate by dilutio~ with water.
2.7. Dusts a) b)
the compound of formula I 5 % 8 %
talcum 95 %
kaolin - 92 %
Ready-for-use dusts are obtalned by mixing the actl~e ingredient
with the carriar, and grinding the mixture in a 6uitable ~111.
'~ .
~;241~
- ~7 -
2.8. Extruder ~ranulata
the compound of formula I10 %
sodlum llgnosulfonate 2 %
carboxymethylcellulo6e 1 %
kaolln 87 %
The active ingredient is mixed and grclund with the adjuvants, and
the m1xture ls subsequently moistened wlth water. The mlxture 1
extruded and then dried in a stream of air.
2.9. Coated granulate
the compound of formula I 3 %
polyethylene glycol (mol.wt.200) 3 %
kaolln 94 %
The finely ground active ingredient ls unlformly applled, in a
mlxer, to the kaolin moistened with polyethlene glycol. Non-dusty
coated granulates are obtalned in thls manner.
2.10. Su6pension conce trate
the compound of formula I 40 %
ethylens glycol 10 %
nonylphenol polyethylene glycol
(15 moles of ethylene oxide) 6 %
sodium llgnosulfonate 10 %
carboxymethylcallulose 1 %
37 % aqueous formaldahyde 601utlon0.2 %
silicone oil in the fcrm of a 75 %
aqueous emulsion 0.8 %
water 32 %
The finely ground active ingredient is intlmately mixed with tha
adJuvant6, givlng a ~uspension concentrate from which suspensions of
any desired concentration can be obtained by dilutlon with wat~r.
96a~
- 18 -
3. niolo~ical Examples
In the following tests (Examples 3.1 to 3.5) tha compound of
formula I of the present invention
/NO2
02N~ NH - ~
\C~3 O~ ~O
and the compound of Example 1 of Cerman OffenlegungsschriPt
28 26 168
~NOz
02N~ -NH-~ \ (A)
C~3 ~ F
are subJected to a co~parison of thelr fungicidal actlvity.
Example 3.1: Actlon a~alnst Plasmopara vltlcola on vlnes
Residual protective actlon
Yine seedling6 in the 4-5 leaf stage are sprayed with a spray
mixture (0.006 % a.i.) prepared from a wettable powdcr formulation
of the test compound. After 24 hours the treated plants are infected
with a sporangia suspension of the fungus. Fungus attac~ is evalua-
ted after incubation for 6 days at 95-lOOX relative humidity and
20C.
Example 3.2: Action a~ainst Pyricularia oryzae on rice plants
Residual protectlve action
After a cultlvation period of 2 weaks, rlce plants are sprayed with
a spray misture (0.006 % a.i.) prepared from a wettable powder
for~ulatlon of the test compound. After 48 hour6 the treated plants
.
-- 19 --
are lnfectPd wlth 8 conldia suspen6ion of the fungu6. ~valuation oE
fungus sttack ls made after incubation for 5 days at ~5-100%
relatlve humldlty and 24C.
Example 3.3: Action a~ainst Cercos~ora arachidicola on ~oundnut
plants
Resldual protective actlo_
Groundnut plsnts 10-15 cm in height are sprayed wlth a spray mlxture
(0.006 % a.l.) prepared from a wettab]Le powder formulation of the
test compound, and infected 48 hours later with a conidia suspension
of the fungus. The lnfected plants are incubated for 72 hours at
abou~ 21C and high humidity and then stood ln a greenhouse until
the typical leaf specks occur. Evaluation of the fungicldal actlon
i6 made 12 days after infectlon and is based on the number and si~e
of the 6peCkS.
Example 3.4: Actlon a~alnst Venturla in~g~ rple shoot6
Resldual protective action
Apple cuttlngs wlth 10-20 cm long fresh shoot6 are sprayed with a
spray mlxture (o.006 æ a.l.~ prepared from a wettable powder
formulatlon of the test çompound. The plants are lnfected 74 hours
later with a conldla suspension of the fungus. The plants are then
incubated for 5 days at 90-100 % relatlve humldity and stood in a
greenhouse for a further 10 dayR st 20-24C. Scab infe6tation ls
svaluated 15 day6 after lnfectlon.
Example 3.5: Action a~sinst ~otrrtls clnerea o~ ples
Resldual protectlve action
Artlficlally da~aged apples are treated by dropping a spray mixture
(0.006 % a.i.) prepared from a wcttable powder formulatlon of the
test compound onto the ln~ury sites. The treated frult6 are then
infected wlth a conidia suspen6ion of the fungu& and lncubated for
:' '`` .
::
~.248~6~
- 20 -
1 week at high humidity and about 20C. Evaluatlon i5 made by
counting tlle number of in~ury sites attacked by rot and deducing the
fungicidal actlon of the test compound therofrom.
Results:
Com- Test organisms (FUNGI)
pound
. . .
Plasmo- Pyricu- Cercospora Venturia ~otrytl~
para larla arachidlcola inae- clnerea
I viticola oryzae quali
A _ ~ _
Evaluation:
-
The rating is bAsed on the percentage fungus attack in comparisonwith untreated and lnfected controls.
Rating % attack
O O - S
1 5 - 20
2 20 - 50
3 ~ 50 (inactlve)
Example 3.6: Action a~ainst OP-re61stant s~ider mites
(Tetranychus clnnabarlnus)
24 hours before treatment~ bean plant6 ln the priMary leaf stage are
populated with a mixed group of Tetranychus. The plants are then
treated with the test solution containing 200 ppm of the test
compound. Evaluation is made after 7 days to dstermine the mortality
of the vsrious stages. In this test, the compound of the inventlon
exhib~ts full activity (no llving indlvlduals).
