Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
5-15531/~
Benzoylphenylureas
The present invention relates to novel substituted N-benzoyl-N'-3,5-
dichloro-4-hexafluoropropyloxyphenylureas, to processeG and to
intermediates for the preparation thereof, and to the u~e of the
novel compounds in pest control.
The invention relates to compounds of formula I
-C0-NH-C0-NH~ 0-CF2-CHF-CF3 (I)
~2 ~1
whereln R1 is hydrogen or fluorine and R2 i5 fluorine or chlorine,
and to salts thereof.
Compounds of formula I meriting particular interest are those
wherein Rl i9 fluorine and R2 is fluortne or chlorine.
Further preferred compound~ of formula I are those wherein R1 i8
hydrogen and R2 is fluorine or chlorine.
The compounds of formula I can be prepared by msthod~ analogous to
ones known per se ~q.v. e.g. German Offenlegungs~chrift specifi-
cat~on~ 2 123 236, 2 601 780 and 3 240 975).
Thus, for example, a compound of ~ormula I can be obtained by
reactlng
, . ~
a) the compound of formula II
lCl
CF3-CHF-CF2-O~ --NHz (II)
~1
with a compound of formula III
~1
CO-N=C=O (III)
A2
or
b) the compound of formula IV
CF3-CHF-CFz-O-~ N=C=O (IV)
Cl
with a compound of formula V
lLl
--CO-NH2 (V),
~2
or
c) thc compound of formula II with a compound of formula VI
, ~Ll
~ ~--CO-NH-COOR (VI).
~2
In formulae III, V and VI above, the radicals R1 and R2 are a8
dcfined for formula I, and R i~ a Cl-Cnalkyl radical which is
unsubstituted or substituted by halogen, preferably chlorine.
- 3 -
The above proces~es a), b) and c) can preferably be carried out
under normal pressure and in the presence of an organic solvent or
diluent. Examples of suitable solvents or diluents are: ethers and
ethereal compounds such as diethyl ether, dipropyl ether, dibutyl
ether, dioxane, dimethoxyethane and tetrahydrofuran; N,N-dialkylated
carboxamides; aliphatic, aromatic and halogenated hydrocarbons,
especially benzene, toluene, xylene, chloroform, methylene chloride,
carbon tetrachloride and chlorobenzene; nitrlles such as aceto-
nitrile or propionitrile; dimethyl sulfoxide; and ketones, e.g.
acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl
isobutyl ketone. Process a) is normally carried out in the tempera-
ture range from -10 to +200C, preferably from 0 to 100C, e.g at
room temperature, and, if desired in the presence of an organic
base, e.g. triethylamine. Process b) is carried out in the tempera-
ture range from 0 to 150C, preferably at the boiling point of the
solvent employed and, if desired, in the presence of an organic base
such as pyridine1 and/or with the addition of an alkali metal or
alkaline earth metal, prefersbly sodium. For proces~ c), i.e. for
the reaction of the urethane of formula YI with an aniline of
formula II, a temperature range from about 60 to the boiling point
of the reaction mixture i8 preferred, and the solvent amployed is
preferably an aromatic hydrocarbon such a3 toluene, xylene, chloro-
benzene and the like.
The starting materials of formulae III and V are known and can be
prepared by methods analogous to known ones. The starting sniline of
formula II is a novel compound which likewise constitutes an object
of the present invention. The compound of formula II can be prepared
in a mannar known per se by hydrogenating the suitably substituted
nitrobenzene o~ formula VII
~1
CF3-CHF-CF2-O~ -N0~ (VII)
~1
.. . .
-- 4 --
by a proces~ analogous to that described ln J. Org. Chem. 29 ~1964),
1, (q.v. al~o the literat~re cited therein). However, the aniline of
formula II can also be obtained by chemical reduction le.g. with
Sn(II) chloride/HCl) of the nitro compound of formula VII (q.v.
Houben-Weyl, "Methoden d. org. Chemie" 11/1, ll22). The nitro
compound of formula VII itself can be prepared by fluoroalkylating
3,5-dichloro-4-nitrophenol. A further process for the preparation of
the aniline of formula II comprises fluoroalkylating in
corresponding manner the acylated 2,6-dichloro-4-hydroxyaniline and
then removing the acyl group9 s.g. by acid hydroly~is, or effecting
the fluoroalkylation with a salt of 3,5-dichloro-4-hydroxyaniline,
e.g. ~he chlorohydrate.
Benzoylisocyanates of formula III can be obtained, in~er alia, as
follows (q.v. J. Agr. Food Chem. 21, 348 and 993; 1973):
C ~ N H?SO4~120~ -CO-NH2
~2 ~2
1~1
ClOC-COCl ~ -CO-N~C~O (III) .
The 4-(hexafluoropropyloxy)phenylisocyanate of formula IV (b.p.
95C/0.01 torr), which is novel per se, can be prepared a.g. by
phosgenat~ng the aniline of formula II by methods which are commonly
employed in the art and also comprise~ an ob~ect of this invention.
The benazmides of formula V which are furtber used as starting
materials are known (q.v. for example Beil~tein "Handbuch der
organischen Chemie", Vol. 9, p. 336~.
Urethanes of for~ula VI can be obtained in a manner known per se by
reacting a benzoylisocyanate of formula III with a suitable alcohol
or by reacting a benzamide of formula V, in the presence of a base,
with a corresponding ester of chloroformic acid Cl-COOR.
- 5 ~
In accordance with the present invention, the novel compounds of
formula I also comprise the salts thereof which not only exhibit
high insecticidal activity, but are also readily soluble in solvents
and diluents, in particular in organic solvents, and can also be
formulated more easily.
To be singled out for special mention are the metal salts of the
compounds of formula I of the invention, in particular the alkali
metal and alkaline earth metal salts thereof, preferably the sodium
salts and potassium salts. These salts are prepared in a manner
known per Qe, e.g. by reacting a compound of formula I with a metal
alkanolate such as 30dium ethylate or potassium methylate. A given
salt can be converted into a deslred ~alt of another metal by
salt-interchange, e.g. wi~h another alkanolate.
Of particular importance are the salts of compounds of formula I
with organic bases, an essential feature of which is the presence of
a quaternary nitrogen atom. Such salt6 are of formula Ia
[ ~ o-~CO~N~CO~NH~~ o--0-CF2-CHF-CF3 ¦ X (Ia)
wherein Rl and R2 are as defined above and X~ is the cation of an
organic ba3e. X0 is preferably one of the following organic
catioDs:
- 6 -
(CH3)4 N , (C2Hs)4 N , (n-C3H7)4 N , (i-C3H7)4 N ,
(n-C4Hg)4 N , (~ CH2) (CH3)3 N '
~ CH3)3 N , i~il ~ (C4Hg)3 NH
H
'~ \'/ ~' and [ CH3-(CH2)n--] N-CH3
H
whereby n i8 an integer from 8 ~o 12. The aalts of forrnula Ia al~o
comprise mixtures of these salts with different cations. The salts
of formula Ia can be prepared in a ~anner known per se by reacting a
compound of formula I with corresponding ammonium hydroxides of the
formula X~(OH)~, wherein X~ iB as defined above.
N-Ben20yl-N'-2,5-dichlorophenylureas with a haloalkoxy substituent
in the 4-position of the phenyl rlng are already known as
insecticldes (q.v. US patent speciflcation 4 518 804 and German
Offenlegungsschrift 2 848 794). In3ecticidal N-halobenzoyl-N'-(3,5-
dichloro-4-haloalkenyloxyphenyl)ureas are de~cribed in VS patent
specification 4 162 330. Insectic~dal N-halobenzoyl-N'-(3,5-di-
chloro-4-haloalkoxyphenyl)ureas are the sub~ect matter of US patent
~pecification 4 468 405. Furthermore, compounds of similar ~ructure
are known from US patent specification 4 529 819 and British patent
applications 2 106 499, 2 106 500, 2 106 501 and 2 113 679. The
feature which essentially distinguishes the noval benzoylphenyl-
ureas of formula I according to the present invention from the
compounds described ln th0se references is that the novel compound~
of this invention carry in the 4-position of the ph~nyl ring a
1,1,2,3,3,3-hexafluoropropyloxy group.
_ 7 ~ 5~
Surprisingly, it has been found that the compounds of ~his inven-
tion and the salts thereof have excellent yroperties as pesticides
while being well tolerated by plants and having low toxlcity to
warm-blooded animals. They are particularly suitable for controlling
insects and representatives of the order Acarina that attack plants
and animals.
In particular, the compounds of formula I are suitable for control-
ling insects o~ the orders: Lepidoptera, Coleoptera, Homoptera,
Heteroptera~ Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera,
Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera, as well
as representatlves of the order AcariDa of the families: Ixodidae,
Argasidae, Tetranychldae and Dermanys3idae.
In addition to their action against flies, e.g. Musca domestica, and
mo3quito larvae, the compounds of formula I are also suitable for
controlling plant-destructive feeding insects in ornamentals and
crops of useful plants, especially in cotton (e.g. against Spodoptera
littoralis and ~ellothls virescens) and in fruit and veg~table~
~e.g. against Laspeyresia pomonolla, Ieptlnotarsa decemlineata and
Epilachna varivestis). The compounds of formula I have a pronounced
ovicidal and, in particular, larvicidal action against insects,
especially against larvae of noxious feeding insect~. If compounds
of formula I are ingested by adult insect stages with the feed, then
a diminished oviposition and~or reduced hatching rate is observed in
many insect3, especially in Coleopterae, e.g. Anthonomus grandis.
The compound3 of formula I can also be used for controlling ecto-
parasite3 such as Lucilia sericata, in domestic animals and produc-
tive livestock, e.g. by treating animals, cowsheds, barns, stables
etc., and pa~tures.
The compounds of formula I are also suitable for controlling the
following specie3 of mites which attack crops of fruit and veget~bles:
Tetranychu~ urticae, Tetranychus cinnabarinus, Panonychus ul~i,
- 8 - ~2~
Broybla ~ubrioculus, Panonychu~ citri, Eriophyes piri, E~iophyes
ribis, Eriophyes vitis, Ta~sonemus pallidus, Phyllocoptes vitis and
Phyllocoptruta oleivora.
~oreover, the benzoylureas of formula I have properties enabling
them to be used for conerolling slugs and snails. The repellant and
feed inhibiting action of these compounds is frequently very
difficult to ascertain in laboratory tests. However, in field trials
even at very low concentrations good activity is observed in
agricultural and horticultural crops. In particular, sensitive crops
of lettuce, vegetables and fruit (such as strawberries) and
ornamentals and flowers are af~orded protection agalnst feeding
damage caused by slugs and snails. The compound~ of formula I of
this invention are effective against all slugs and snails, most of
which occur as polyphagic pests in agricultural and horticultural
crops. In addition to exhibiting feed inhiblting action, the
compounds of formula I can also effect mortality. Numbering among
terrestrial 91ugs are aeveral pests which cau~e damage of great
economic significance, for example the slugs Arion rufus (red slug),
Arion ater and other Arionida~, Limax species and field slugs, e.g.
Deroceras reticulatum snd D. agreste of the family Limacidae, and
also species of the family Milacidae. Damage is also caused by
snails, inee~ alia, of the genera Bradybaena, Cepea, Cochlodina,
Discus, Euomphalia, Galba, Helicigona, Helix, Helicella, Helico-
discus, Lymnaea, Opeas, Vallonia and Zonitoides.
The good pesticidal activity of the compounds of formula I of the
invention corresponds to a mortality of at least 50-60 % of the
above pests.
The activity of the compounds of formula I and of the compositions
containing them can be substsntially broadened and adapted to
prevailing circum~tances by addition of other insecticides and~or
acaricides. Examples of suitable additive~ include: organophosphorus
- 9 ~
compounds, nitrophenols and derivatives thereof, formamidines,
ureas, carbamates, pyrethroids, chlorina~ed hydrocarbona, and
Bacillus thurlngiensis preparations.
The compounds of formula I are used in unmodlfied form, or preferably
together with the adjuvants conventionally employed in the art of
formulation, and are therefore formulated in known manner to
emulsifiable concentrates, directly sprayable or dilutable solutions,
dilute emulsions, wettable powders, soluble powders, dusts, granulates,
and also encapsulations in e.g. polymer substances. As with the
nature of the compositions, the methods of application such as
spraying, atomising, dusting, scattering or pouring, are chosen in
accordance with the intended objectives and the prevailing circumstances.
The formulations, i.e. the compositions, preparations or mixtures
containing the compound (activ~ ingredient) of formula I or
combinations thereof with other insecticides or acaricides, and,
where appropriate, a solid or liquid ad~uvant, are prepared in known
manner, e.g. by homogeneously mixlng and~or grinding the active
ingredients with extenders, e.g. solvents, 301id carriers and, in
some cases, surface-active compounds (surfactants).
Suitabls solvents are: aromatic hydrocarbons, preferably the
fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or
substituted naphthalenes, phthalates such as dibutyl phthalate or
dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or
pars~fins, alcohol~ and glycols and their ethers and esters, such as
ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl
ether, ketones ~uch as cyclohexanone, strongly polar solvents such
as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide,
as well as vegetable oils or epoxidised vegetable olls such as
epoxidised coconut oil or soybean oil; or water.
The solid carriers used e.g. ~or dusts and dispersible powders are
nor~ally natural mineral fillers such as calcite, talcum, kaolin,
montmorillonlte or attapulgite. In order to improve the physical
-- 10 --
properties it is also pos6ible to add highly dispersed silicic acids
or highly dispersed absorbent polyme~s. Su1table granula~ed adsorp-
tive carriers are porous types, for e~ample pumice, broken brick,
sepiolite or bentonite; and suitable nonsorben~ carriers are
materlals such as calcite or aand. In addition, a great number of
pregranulated materials of inorganic or organic nature can be used,
e.g. especially dolomite or pulverised plant residues.
Depending on the nature of the compound of formula I to be formulated,
or of combinations thereof with other insecticides or acaricides,
suitable surface-active compounds are non-ionic, cationic and/or
anionic surfactants having good emulsifylng, dispersing and wetting
properties. The term "surfactants" will also be understood as
comprising mixtures o$ surfactants~
Suitable anionic surfactants can be both water-soluble soaps and
water-soluble synthetic surface-active compounds.
Suitable soaps are the alkali metal salts, alkaline earth metal
salts or unsubstituted or substituted ammonium salts of higher fatty
acids (C1O-C22), e.g. the sodium or potassium salts of oleic or
stearic acid, or of natural fatty acid mixtures which can be
obtained, e.g. from coconut oil or tallow oil. Further suitable
surfactants are also the fatty acid methyltaurin salts a5 well aB
modified and unmodified phospholipids.
More frequently, however, so-called synthetic surfactants are uaed,
especially fatty sulfonates, fatty sulfates, sulfonated benzimida-
zole derivatives or alkylarylsulfonates.
The fatty sulfonatas or sulfates are usually in the form of alkali
metal salts, alkaline earth metal salts or unsubstituted or substi-
tuted ammonium salts and contain a Cg-C22alkyl radical which also
includes the alkyl moiety of acyl radicals, e.g. the sodium or
calcium salt of lignosulPonic acid, of dodecylsulfate, or of a
mixture of fatty alcohol sulfates obtained from natural fatty acids.
::
These compoundæ also comprise the salts of sulfurlc acid esters and
sulfonic acids of fatty alcohol/e~hylene oxide adducts. The sulfona-
ted benzimidazole deriva~ives preferably contain 2 sulfonic acid
groups and on~ fatty acid radical contalning 8 to 22 carbon atoms.
Examples of alkylarylsulfonates are the sodium, calcium or tri-
ethanolamine ~alts of dodecylbenzenesulfonic acid, dibutylnaphtha-
lenesulfonic ~cid, or of a naphthalenesulfonic acid/formaldehyde
condensation produet. ~lso suitable are corresponding phosphates,
e.g. salts of the phosphoric acid ester of an adduct of p-nonyl-
phenol with ~ to 14 moles of ethylene oxide.
Non-ionic surfactants are preferably polyglycol ether derivatives of
aliphatic or cycloaliphatic alcohols, or saturated or unsaturated
fatty aclds and alkylphenols, said derivatives containing 3 to 30
glycol ether groups and 8 to 20 carbon atoms in the (allphatic)
hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of
the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts
of polyethylene oxide with polypropylene glycol, ethylenediamino-
polypropylene glycol and alkylpolypropylene glycol containing 1 to
10 csrbon 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 usually contain 1 to 5 ethylene glycol units
per propylene glycol unit.
Representative examples of non-ionic surfactants are nonylphenol-
polyethoxyethanols, castor oil polyglycol ethers, polypropylene/-
polyethylene oxide adducts, tributylphenoxypolyethoxyethanol,
polyethyl~ne glycol and octylphenoxypolyethoxyethanol. Patty acid
esters of polyoxyethylene ~orbitan, e.g. polyoxyethylene sorbitan
trioleate, are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary a~monium salts which
contain, a~ N-substituent, at least one Cg-C22alkyl radical and, as
$urther substituents, unæubstituted or halogenated lower alkyl,
- 12 ~
benzyl or hydroxy-lower alkyl radicals. The salts are preferably in
the form of halidesl methylsulfates or ethyl~ulfates, e.g. stearyl-
trimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonlum
bromide.
The surfactants customarily employed in ~he art of formulation are
described e.g. in "McCutcheon's Detergents and Emulsifiers Annual",
MC Publishing Corp., Ridgewood, New JerDey, 1979; Dr. Helmut Stache,
"Tensid Taschenbuch" (Handbook of Surfactants), Carl Hanser Verlag,
Munich/Vienna 1981.
The pesticidal compo~itions usually contain 0.1 to 99 %, preferably
0.1 to 95 %, of a compound of formula I or combination thereof
with other lnsecticldes or acariclde~, 1 to 99.9 % of a eolid or
liquid ad~uvant, and 0 to 25 %, preferably 0.1 to 20 %, uf a
surfactant.
Whereas commercial products are preferably formulated as concen-
trates, the end user will normally employ diluted formulations of
substantially lower concentration.
The compositions may also contain further ingredisnts, such as
stabilisers, antifoams, viscosity regulators, binders, tackifiers as
well as fertilisers or other active ingredients in order to obtain
special effects.
Exam~la 1:
a) Preparation o~ 3~5-dichloro-4-(1,1,2,313,3-hexafluoropropyl-
o~y~aniline
47 g of 4-acetylamino-3,5-dichlorophenol tugether with 154 g of 90 %
potassium hydroxide solution and 130 ml of dimethylformamide are
stirred in an au~oclave. 75.8 g of hexafluoropropylene are then
pressed into the closed autoclave. The mixture is stirred for
20 hours at 70C under the pressure developing in the autoclave.
After cooling, the mixture i8 concentrated by rotary evaporation and
- 13 ~
the resldue is dissolved in methylene chloride. The resultant
solution is washed with water, dried over Na~S04 and concentrated.
The crude product obtainsd as residue i9 chromatographed through a
column of silica gel (length: 1 m; dlameter: 10 cm) eluted with an
11:1 mixture of toluene and acetone, affording 4-acetylamino-3,5-di-
chloro-1-(1,1,2,3,3,3-hexafluoropropyloxy~benzene in the form of
pale yellow crystals (m.p.: 113-115C), 26 g of which a~e kept for
10 hours under reflux with 110 ml of ethanol and 35.6 ml of 37 %
hydrochloric acid. The reaction mixture is then concentrated,
diluted with ice/water and made weakly alkaline. The product is
extracted from the mixture with methylene chloride. The organic
extract phase i3 washed with water, dried over NazSO4 and
concentrated. The residue is purified by distillation, thus
affording the title compound of the formula
~1
H2N~ OCFz-CHF-CF3
~1
as a colourlesfi liquid with a boiling point of 91-96C/0.001 torr.
b~ Preparation of N~(2,6-difluorobenzoyl~-N'-~3~5-dichlor_-4-
~1,1?2,3,3,3-hexafluoropropyloxy)phenyl~urea
4.3 g of 3,5-dichloro-4-~1,1,2,3,3,3-hexafluoropropyloxy)aniline are
dissolved with stirring in 50 ml of dry toluene and, with exclusion
of moisture, a solution of 2.41 g of 2,6-difluorobenzoylisocyanate
in 10 ml of dry toluene is added at room temperature. ~he batch i3
stirred for a further 12 hours at room temperature. About 75 % of
the solvent i9 then removed by rotary evaporation, the precipitated
residue is filtered with suction, wa~hed with a ~mall amount of cold
toluene and hexane and then dried in vacuo, affording the title
compound of the formula
- 14
Cl
C0-NH-C0-NH~~ OCF2-CHF-CF3
F Cl
in the form of a crystalline white powder with a melting polnt of
171-172C (compound l).
The following compounds of formula I have been prepared in a manner
corresponding to that described above:
Compound m.p.
2 ~/ /Cl
2 ~ ~--C0-NH-C0-NH-~ -0-CFzCHFCF3 178-180C
Cl
Cl /Cl
. , ~s~
3 ~ C0-NH-C0-NH~ -0-CFzCHFCF3 177-17~C
~Cl \Cl
,2,/F /Cl
4 ~ -C0-NH-C0-NH-~ -0-CF2CHFCF3 156-158C
Cl
c) Prepara_ion of the sodium salt of compound 1
9.58 g of N-(2,6-difluorobenzoyl)-N'-[3,5-d1chloro-4-(1,1,2,3,3,3-
hexafluoropropyloxy3phenyl3urea are ~uspended in 20 ml of ab~olute
methanol. A oolution of 0.43 g of sodium in 30 ml of absolute
methanol i8 added dropwise with stirring to this suspen610n. A clear
solutioD forms which i8 then concentrated. The residual product is
dried in vacuo at room temperature, a~fording the title compound of
the formula
-- 15 --
~ ~ -CO-~-CO-NH-~ O-CFzCllPCF3
as colourless crystals.
The following salt of compound 2 of the formula below can also be
prepared by proceeding as described above:
Cl /Cl
~ CO-~-CO-NH--~ ~ -O-CF2CHFCF3
d) Preparation o~ the tetrabutyla~monium_salt of compound 1
2.56 8 of N-(2,6-difluorobenzoyl)-N'-[3,5-dichloro 4-(1,1,2,3,3,3-
hexafluoropropyloxy)phenyl~urea are suspended ln 30 ml of methanol.
With stirring, 5.2 g of a methanolic solution containing 1.3 g of
tetra-n-butylammonium hydroxide are added to this suspension,
whereupon 8 clear solution forms. This solution iB concentrated and
the residual crude product is suspended in hexane. The suspension is
$iltered with suctlon and the ~ilter residue is washed with hexane
and then dried, affording the title compound of the formula
[ ~ ~ -C0-~-C0-N~ -0-CF2CHFCF3 ¦ [~n~C4H9)4N ]
as coIourless crystals.
The following salts of formula la can also be prepared in accordance
with this procedure:
- 16 -
CO-N-CO-NH-^~ ~-OCFzCHFCF3 ] [(CH3)4 N J
\F \Cl
~F ~Cl
CO-N-CO-NH-~ -OCF2CHFCF3 ~(C2H5)4N ]
\Cl
-CO-N-CO-NH~ OCF2CIIFCFI ] [ ~ _ s ]
~F ~Cl
-CO-N-CO-NH-~ -OCF2CHFCF3 C(n-c3H7)4N ]0
\Cl \Cl
\~ CO-N-CO-NH-~ -OCF2CHFCF3 ] ~ ]
~CI ~Cl
.`'`. :
~ 8 ~ /
CO-N-CO-NH~ -OCFzCHFCF3 [(t~C4Hs)3NH
\Cl
Example 2:
Formulation3 for active in~redients of formula I according to
Example 1 or combinations thereof with other insecticides or
acaricides (throughout, percentages are by weight)
1. Wettable powders a) b) c)
compound of formula I or combination 25 % 50 % 75 %
sodium lignosulfonate 5 % 5 %
sodium laurylsulfate 3 % - 5 %
sodium diisobutylnaphthalenesulfonate - 6 % 10 %
octylphenol polyethylene glycol ethar
(7-8 moles of ethylene oxide) - 2 %
highly disparsed silicic acid5 % 10 % 10 %
kaolin 62 % 27 %
The active ingredient or combination i~ thoroughly mixed with the
ad~uvants and the mixture is thoroughly ground in a suitable mill,
affording wettable powders which can be diluted with watsr to give
suspension~ of the deslred concentratlon.
2. Emulslfiable_concentrata
compound of formula I or combination 10 %
octylphenol polyethylene glycol ether
(4-5 moles of ethylene oxide) 3 %
calcium dodecylbenzen2sulfonate 3 %
castor oil polygycol ether
(36 moles of ethylene oxide) 4 %
cyclohaxanone 30 %
xylene mlxture 50 %
.
5~
- 18 -
~mulsions of any required concentration can be obtained from this
concentrate by dilution with water.
3. Dusts a) b)
compound of formula I or combination 5 % 8 %
talcum 95 %
kaolin - 92 %
Ready for use dusts are obtained by mixing the active ingredi0nt
with the carrier, and grinding the mixture in a suitable mill.
4. Extruder_~ranulate
compound of formula I or combination10 %
sodium lignosulfonate 2 %
carboxymethylcellulose 1 %
kaolin 87 %
The active ingredient or combination is mixed and ground with the
ad~uvants, and the mixture is sub3equéntly moistened with water. The
mixture is extruded and then dried in a stream of air.
5. Coated granulate
compound of formula I or combination 3 %
polyethylene glycol (mol.wt.200) 3 %
kaolin 94 %
The finely ground active ingredient or combination is uniformly
applied, in a mixer, to the kaolin moistened with polyethylene
glycol. Non-dusty coated granulates are obtained in this manner.
19 -
6. Suspension concentrate
compound of formula I or combination 40 %
ethylene glycol 10 %
nonylphenol polyethylene glycol ether
(15 moles of ethylene oxide) 6 %
sodium lignosulfonate 10 %
carboxymethylcellulose 1 %
37 % aqueous formaldehyde solution 0.2 %
silicone oil in the form of a 7S %
aqueous emulsion 0.8 %
water 32 %
Ths finely ground active ingredient or combination is lntimately
mixed with the adjuvants, giving a suspension concentrate from which
suspensions o~ any desired concentration can be obtainsd by dilution
with water.
Exampl _3 Action again t Musca domestica
50 g of freshly prepared nutrient substrate fo~ maggots are charged
into each of a number of beakers. A specific amount of a 1 %
acetonic solution of the respective test compound is pipetted onto
the nutrient substrate present in the beakers to give an active
ingredient concentration of 800 ppm. The substrate is then thoroughly
mixed and the acetone sub3equently allowed to evaporate over a
period of at least 20 hours.
Then 25 one-day-old maggots of Musca domestica are put into each of
the beakers containing the treated nutrient substrate for testing
wlth each active ingredient at the given concentration. After the
maggots have pupated, the pupae are separa~ed from the substrate by
flushing them out with water and then deposited in containers closed
with a perforated top.
- 20 ~
Each batch of flushed out pupae i~ counted to determine the toxic
effect of the test compound on the MaggO~ development. A count i8
then made after 10 days of the number of flies which have hatched
out of the pupae.
The compounds of formula I according to Example 1 exhibit good
activity in this test.
Example 4. Action against Lucllia sericata
-
l ml of an aqueous solution containlng 0.5 % of test compound is
added at 50C to 9 ml of a culture medium. Then about 30 freshly
hatched Lucilia ~ericata larvae are added to the culture medium, and
the lnsectlcldal action i9 determlned after 48 and 96 hours by
evaluatlng the mortality rate.
In this test, compounds of formula I according to Example 1 exhiblt
good activity again~t Lucilia sericata.
Example 5 Action a~ es aegypti
A concentration of 800 ppm is obtained by pipetting a specific
amount of a 0.1 % solution of the test compound in acetone onto the
surface of 150 ml of water in a beaker. After the acetone has
evaporQted, 30 to 40 two-day-old larvae of Aëdes aegyp-ti Qre put
into the beaker cGntaining the test compound. Mortality counts are
made after 1, 2 and 5 days.
In this test, compounds of formula I according to Example 1 exhibit
good activity against A8des aegypti.
Example 6: Insecticidal action against feeding insects
a) Cotton plants about 25 cm high, in pots, are spr~yed with aqueous
emulsions which contain the respective test compound in concentra-
tions of 3, 12.5 and 50 pp~. After the spray coating has dried, the
cotton plants are populated with Spodoptera littoralis and Heliothis
5~
- 21 -
virescens larvae in the L3-stage. The test is carried out at 24C
and 60 % relative humidity. The percentage mortallty of the test
insects is determined after 2 day~.
Compounds l, 2, 3 and 4 according to Example 1 effect 80-100 %
mortality against Spodoptera larvae at 3 ppm. 80-100 % mortality is
effected agalnst Heliothis larvae by compound 1 at 12.5 ppm and by
compounds 2 and 3 at 50 ppm.
b) Comparative test
The above test a) is repeated using compound 1 of this invention and
two prior art compounds. In distinction to test a), the percentage
mortality of the larvae is not determined until after 7 days. The
active ingredient concentrations, the compounds employed and the
results obtained are indicated in the following Table:
~1 r. O
~ ~ ~ ---~ - --
o ~ ~ ~
o a~ ~ O
: -
~ ~ ~ o o o
~ o ~
~ -- - -------- ~ ---~-
~ ~. ~o ~o
. _ .. _ - .. .. _. _ ___ . .. ,. _ _
N _I q N
5~ P~ 0_ 0~ 0
~ ~.~ V-./ ~.~ ~ ~a .~;\ ~ #, ¢~
~, ~ ~ 0~ f ~ ~
~ Z o o ~ ~ ~ ~ ~ o~
~o b ~ ~ o P~ oo o ~ o
q o o ~ C~ ~o ~
~ ~ '.... .
- 23 -
Example 7~ Action against Epilachna varivesti~
Phaseolus vulgaris plants (dwarf beans) about 15-20 cm i~ height are
sprayed with aqueous emulsion formulatlons of the test compound in a
concentration of 800 ppm. After the spray coating has dried, each
plant is populated with 5 larvae of Epilachna varivsstis (Mexican
bean beetle) in the L~-stage. A plastic cylinder is slipped over the
treated plants and covered with a copper gauze top. The test is
carried out at 28C and 60 % relative humidity. The percentage
mortality is determined after 2 snd 3 days. Evaluation of feeding
damage (anti-feeding effect), and of inhibition of development and
shedding, is made by observing the test insects for a further
3 days.
The compounds of formula I according to E~ample l exhibit good
activity in this test.
Exsmple 8: Ovicidal action against Heliothis virescens
Corresponding amounts of a wettable powder formulation containing
25 % by weight of the test compound are mlxed with sufficient water
to produce an aqueous emulsion with an active ingredient concentration
of 800 ppm. One-day-old egg deposits of Heliothis on cellophane are
immersed in these emulsions for 3 minutes and then collected by
suction on round filters. The treated deposits are placed in petri
dishes and kept in the dark. The hatching rate in comparison with
untreated controls is determined after 6 to 8 days.
The compounds of formula I according to Example l exhibit good
activity in this test.
Example 9 Action against Laspeyresia pomonella (eggs):
Egg deposits of Laspeyresia pomonella not more than 24 hours old are
immersed on filter paper for 1 minute in an aqueous acetonic
solutlon containing 800 ppm of the test compound.
- 24 -
After the solution has dried, the eggs are placed in petri diahes
and kept at a temperature of 28C. The percentage of larvae hatched
from the treated eggs and the percentage mortality is evaluated
after 6 days.
The compound3 of formula I according to Example 1 exhibit good
activity in this te3t.
Example 10: Influence on the reproduction of Anthonomous grandi3
Anthonomou~ grandi3 adults which are not more than 24 hour3 old
after hatching are transferred in groups of 25 to barred cages. The
cages are then immersed for 5 to 10 second3 in an acetonic solution
containing 400 pm of the test compound. After the beetle3 have
dried, they sre placed in covered dishes containing feed and left
for copulation and oviposition. Egg deposits are flushed out with
running water twice to three times weekly, counted, disinfected by
putting them for 2 to 3 hours into an aqueous disinfectant, and then
placed in dishes containing a suitable larval feed. A count is made
after 7 days to determine the percentage mortality of the eggs, i.e.
the number of larvae which have developed from the eggs.
The duration of the reproduction irlhibiting effect of the test
compounds i~ determined by monitoring the egg deposits further, i.e.
over a period of about 4 weeks. Evaluation is made by assessing
the reduction in the number of deposited eggs and hatched larvae in
comparison with un~reated controls.
Compounds of formula I according to Example 1 exhibit good activity
in this test.
Example 11: Action against Anthonomu~ ~randis (adults)
Two cotton plants in the 6-leaf stage, in pot3, are each ~prayed
with a wettable aqueous emulsion formulatlon containing 400 ppm of
the test compound. After the ~pray coating has dried (about
l.S hours), each plant is populated with 10 adult beetles
(Anthonomus grandis). Plastic cylinders, covered at the top with
- 25 -
gauze, are then sllpped over the treated plants populated wlth the
test insects to prevent the beetles from Migrating from the plants.
The treated plants are then kept at 25C and about 60 % relative
humidity. Evaluation is made after 2, 3, 4 and 5 days to determine
the percentage mortality of the beetles (percentage in dorsal
position) as well as the anti-feeding action as compared with
untreated controls.
Compounds of formula I according to Example 1 exhibit good activity
in this test.
xample 12~. Insecticidal stomach ~osion action against Plutella
xylostella
Potted Chinese cabbage plants (pot size: 10 cm diameter~ in the
4-leaf stage are sprayed with aqueous emulsions which contain the
test compound in a concentration of 0.8 ppm and which dry on the
plants.
After 2 days, each of the treated Chinese cabbage plants i8 pOpU-
lated with 10 Plutella xylostella larvae in the L2-stage. The test
is carried out at 24C and at 60 % relative humidity in dim llght.
Evaluation of the percentage mortality of the larvae is made after
2 and 5 days.
Compound 1 according to Example 1 effect~ 100 % mortality in this
test.
Example 13: Feed inhibiting action against ~lu~8
5 red slugs (Arion rufus) are left for 17 hours under controlled
~est conditions in each of a number of cages containing 4 fresh
lettuce leaves. In these tests, each cage either only contains
untreated leaves or only contalns leaves which have been trea~ed by
spray application. The concentration of the test compound in the
aqueous formulation applied i8 0.5 % by weight. The extent of the
feeding damage i8 determined on tha basis of weight differences,
- 26 ~ 5~
photocopies of pictures of the feeding damage and on the basis of
any evident assessable criteria in comparison with untreated
controls.
The mortality of the te~t animals is also determlned.
Compounds of formula I according to claim 1 exhibit good activity in
this tèst.
