Note: Descriptions are shown in the official language in which they were submitted.
rhe Present invention provides a method of controlling insects,
whicll comprises the ~Ise of a 3-N-phenylcarbamoyl-4-hydroxy-coumarin
derivative, and pesticidal compositions which contain this derivative as
active component.
The 3-N-phenylcarbamoyl-4-hydroxy-coumarin derivatives have the
formula I
f~ ~ o NH ~ Cl (I)
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According to the invention, there is provided a method of
controlling insect pests at a locus, which method comprises applying to the
locus an insecticidally effective amount of the compound of the formula I
OH /~=~\
= O - NH ~ Cl (I)
The compound of formula I is known ~cf. Chem. Abst. 67 (1967)
90676j; J. Org; Chem. 39 ~1974) 1008 - 1009; J. Heterocycl. Chem. 9 (1972)
495-499; Anschutz Ann.]
,. , - - . . - . - , . .
367 (1909) 186, Monatsheft 101 (1970~ 88 and the published United States ~-
patent application B 587 786~ and is obtained by methods which are kno~rn
per se by reacting for example (a) an ester of the formula I
0
(II)
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with p-chloroaniline, (b) a compound of the formula IV
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qH
~o (1~) ~
with p-chlorophenyl isocyanate or treating (c) a compound of the above
formula IV with p-chlorobenzoic-acidazide in which ~ represents an a].kyl
group of 1 to 4 carban atoms.
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Preferably the processes (a~ and (c) are carried out at a
reaction temperature between 100 and 200 C and process (b) at a reaction
temperature between 0 a~d 200 C. The reactions can be carried out at nor~
mal or elevated pressure, optionally in a solvent or diluent which is
inert to the reactants and~ if appropriate~ in the presence of a base.
Solvents and diluents which are suitab~e for these reactions
are for example: ethers and ethereal compounds, such as dipropyl ether,
dioxan~ dimethoxyethane and tetrahydrofurane; amides, such as N~N-di-
alkylated carboxamides, aliphatic, aromatic and halogenated hydrocarbons~
in particular benzene, toluene, xylenes, chloro~orm and chlorobenzene; ~ ~
nitriles, such as acetonitrile; dimethyl sulphoxide; and ketones, such as ;~ -
acetone and methyl ethyl ketone.
: Suitable bases are tertiary amines, such as triethylamine, :~
dimethyl aniline, pyridine~ picolines and lutidines,
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hydroxides, oxidesg carbonates and bicarbonates of alkali metaIs and
aIkaline earth metals~ for example potassium tert. butylate and sodium
methylate.
The compound of the formula I is already known as a bactericide,
fungicide and anthelminthic from the above mentioned published United ~ -
States pa~ent application B 587~786 and from the particulars in Chem.
Abst, 67 (1~67) 90 676 j. The present invention, however, is based on the
surprising observation that the compound of the formula I possesses an~i ;
exceptionally good activity ~r controlling insects. ~;
In particular~ the compound of the formula I is highly effective
against insects which are harmful to plants and animals. However, the ~
compound of the formula I is chiefly suitable for controlling plant- ~;
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injurious insects~ especially those of ~
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the order Coleoptera, for example Leptinotarsa decemlineata
and Anthonomous grandis, for example in vegetable crops and
cotton plantations~ In addition, the compound of the
for~nula I is outstandingly effectire against ectoparasitic
insects, for example Lucilia sericata, and against insects
which are harmful in the spheres of hygiene and storago, for
example Musca domestica, and Aëdes aegyp-ti.
The insecticidal or acaricidal action can be sub -
stantially broadened and adapted to prevailing circumstances
by the addition of other insecticides and/or acaricides.
Examples of suitable additives are: organic phosphorus com-
pounds, nitrophenols and derivatives thereof, formamidiries,
ureas, pyethroids, carbamates, and chlorinated hydrocarbons.
The compound of the formula I is used as the pure
active substance or together with suitable carriers and/or
additives. Suitable carriers and additives can be solid or
liquid and correspond to the substances conventionally used
in the art of formulationg for example natural or regenerated
subst~nces, solvents, dispersants, wetting agents, tackifiers,
thickeners, binders and/or fertilisers.
For application, t,he compounds of the ~ormula I can
be processed to dusts, emulsion concentrates3 granules, dis-
. : : . : :~
persions, sprays, to solutions or suspensions, in the con-
ventional formulation which is commonly emplo~ed in appli-
cation technology.
The compositions according to the invention are
obtained in known manner by intimately mixing and/or grind
ing the active substance of the formula I with the suitable
carriers, with or without the addition of dispersants or
solvents which are inert to the active substance.
The active substances may take, and be used in,
the following forms:
Solid forms: ;
Dusts, tracking agents, granules, coated granules,
impregnated granules and homogeneous granules.
Liquid forms:
a) active substance concentrates which are dispers-
ible in water: wettable powders, pastes, emulsions;
b) solutions.
The content of active substance in the above described
compositions is between 0.1% and 95%, in which connection it
must be mentioned that higher concentrations can also be used i~
the compositions are applied from an aircraft or other appropriate
application devices. ~;
The active substance of the formula I can, for ~
~ 8
example, be formulated as follows:
Dusts
The following subs~ances are used to obtain ~ -
a) a 5% and b) a 2% dust:
a) 5 parts of active substance~
95 parts of talcum;
b) 2 parts of active substance,
1 part of highly disperse silicic acid,
97 parts of talcum.
s~,b5t~R~c e J~
The active ~R~r~ e mixed with the carriers
and ground.
Granules
The following substances are used to produce 5/~
granules:
parts of active substance,
0.25 parts of epichlorohydrin,
0.25 parts of cetyl polyglgcol ether,
3 50 parts of polyethyle.le glycol,
91 parts of kaolin (particle size 0.3 - 0.8 mm~.
The active substance is mixed with epichlorohydrin ~.
and dissolved with 6 parts of acetone, the polyethylene
glycol and cetyl polyglycol ether are then added. The re-
sultant solutio~n is sprayed on kaolin, and tke acetone is
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subsequently evaporated in vacuo.
Wettable powder:
The following constituents are used for the pre-
paration of a) a 40%~ b) and c) a 25%, and d) a lO~o wettable
powder:
a) 40 parts of active substance,
5 parts of sodium lignin sulphonate,
1 part o~ sodium dibutyl-naphthalene sulphonate.
b) 54 parts of silicic acid,
25 parts of active substance,
4 5 parts of calcium lignin sulphonate,
1.9 parts of Champagne chalk/hydroxyethyl cellulose
mixture ~1:1),
l.S parts o~ sodium dibutyl naphthalene sulphonate,
19.5 parts of silicic acid, ~;
19.5 parts of Champagne chalk,
28.1 par~s of kaolin. ~:
c3 25 parts of active substance, ~ .
2.5 parts o~ isooctylphenoxy-polyoxye~hylene- :
ethanol,
1.7 parts of Champagen chalk/hydroxyethyl cellulose
mixture (1:1),
8~3 parts of sodium aluminium silicate,
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16.5 parts of kieselgur,
46 parts of lcaolin.
d) 10 parts of active substance,
3 parts of a mlxture of the sodium salts of
saturated fatty alcohol sulphates,
parts of naphthalenesulphonic acid/formaldehyde
condensate,
82 parts of kaolin.
s6~bs~,.
The active ~Y~e~ intimately mixed, in suit-
able mixers, with the addLtives, the mixture being then
ground in appropriate mills and rollers to yield wettable
powders, which can be diluted with water to give suspensions
of the desired concentration.
Emulsifiable concentrate: ;
The following substances are used to produce a 10% ~ i
emulsifiable concentrate:
~ .
a) 10 parts~of ac~ive substance,
3.4 parts of epoxidised vegetable oil~
- 3.4 parts o~ a combination emulsiier consisting
o fatty alcohol polyglycol ether and alkyl
~ryl sulphonate calcium salt,
parts of dimethylformamide,
~3.2;parts of xylene. ~ ~-
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By dlluting s~lch a concentrate with water it is
possi~le ~o man~.lfacture emulsions of the desired concen-
tration,
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The following constituents are used ~o prepare a)
a 5% and b~ a 95% spray:
a)5 parts of active suhstance,
1 part of epichlorohydrin, ~-.
94 parts of ben~ene (boiling limits 160C - 190C,
b)95 parts o~ active substance,
5 parts of epichlorohydrin.
The following Examples illustrate the invention in
ore detail.
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Example I
Prep~ration of 3-N-C3-trifluoromethylphenyl)-carbamoyl~ _hy~ y-coumarin
With stirring, 10.1 g of ~riethylamine and then 18.6 g o 3-
triEluoromethylphenylisocyanate are added dropwise at room temperature to a
solution of 16.2 g of 4-hydroxycoumarin in 150 ml of dimethyl sulphoxide.
The reaction mixture is stirred for a further 4 hours at room temperature
and then poured into a solution of 15 ml of concentrated hydrochloric acid
in 300 ml of water. The precipitate which has formed is collected by suction
filtration Recrystallisation from dioxane gives the product of the formula
OH ~ CF3
~ C0-NH ~ ~compound 1)
O O ';
with a melting point of 198 - 201C.
3-N-(4-Chlorophenyl)-carbamoyl-4-hydroxycoumarin (compound 2)~ mp.
208-210C, was also obtained in an analogous manner using 4-chlorophenyl-
isocyanate and 4-hydroxycoumarin as starting materials.
OH
~ CO-NH - ~ R2 (la)
Com- R _ Physical
pound l2 3 data _
2 H _ Cl H m.p. 208-210C
Example 2
Action on Leptinotarsa decemlineata I
,
Potato plants were sprayed with a 0.05% aqueous emulsion of active
substance ~obtained from a 10% emulsifiable concentrate).
After the spray coating had dried, the plants were populated with
larvae of the potato beetle (Leptinotarsa decemlineata in the L3-stage).
Evaluation of the mortality achieved took place after 2, 4, 8, 24 and 48
hours. The test was carried out at 24C and 60% relative humidity.
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In thc above test, compound 2 exhlbited particularly good
insecticidal stomach poison action on Leptinotarsa decemlineata larvae.
Exam~le 3
Action on Le~tinotarsa decemlineata ~
Two potato plants with a height of 15 cm were sprayed with 25 ml
of an acetone/water mixture (1:1) containing 0.05% of test substance.
After the spray coating had dried, each of the potato plants was
populated with 10 larvae of the species Leptinotarsa decemlineata (L3 -
stage). A plas~ic cylinder was then slipped over each plant to prevent the
larvae from migrating. A copper gauze top was used to seal the cylinder.
The damage caused by eating was determined 2 days later.
In the above test, compound 2 effectively inhibited damage from
eating (only minor damage was observed). ~,
Exam~le 4
Action on Spodoptera littoralis
Two cotton plants with a height of 15 cm were sprayed with 25 ml
of a solution of acetone/water ~1:1) containing 0.1% of test substance.
After the spray coating had dried, each plant was populated with 5 larvae of
the species Spodop~era littoralis (L3-stage). A plastic cylinder was
slipped over each plant and sealed with a copper gauze top. The damage
caused by eating was determined 2 days la~er.
In the above test, compound 2 effectively inhibited damage caused
by eating (only minor damage was observed).
Example 5
Action on Lucilia sericata
_~ .
An a~ueous solution containing 0.1% of test substance (2 ml) was
added tG 2 ml of a culture medium. Approx. 30 freshly hatched-out larvae of
Lucilia sericata were then added to the culture medium and the insecticidal
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action was determincd a~'ter 96 hours by evaluating the mortality rate.
In this test, compound of Example 1 was particularly effective
against larvae of Lucilia sericata.
Example 6
Action on Musca domestica
50 g of freshly prepared CSMA nutrient substrate for maggots
were charged into beakers. A specific amount of a 1% acetonic solution of
the active substance was pipetted onto the nutrient substrate pres2nt in the
beakers. ~he substrate was then thoroughly mixed and the acetone subsequent-
ly allowed to evaporate over a period of at least 20 hours.
Then 25 one daY-old maggots of Musca domestica were put into each
of the beakers containing the treated nutrient substrate for testing with
each active substance at one of its given concentrations. After the maggots
had pupated, the pupae were separated from the substrate by flushing them
out with water and then deposited in containers closed with a perforated top.
Each batch of flushed out pupae was counted to determine the toxic
effect of the active substance on the maggot development. The number of
flies which had hatched out of the pupae was then counted after lO days and
any in~luence on the metamorphosis thereby determined.
In the above ~est, compound 2 was very effective against Musca
domestica.
Exam~le 7
Action on the larvae of Aedes aegypti
Approx. 20 two day-old larvae of the yellow f'ever fly (Aëdes
aegypti) were put into a beaker containing a solution of the active substance
(concentration = 5 ppm). The beaker was then covered with a perforated top.
After the controls had shed and emerged fully to the adult stage, the test
subjects were examined and the percentage of normal adults in comparison
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with the controls was dete~mined. In this test, compounds 2, 4, 6, 8, 11,
12 and 13 of Example 1 were very effective against larvae of Aedes aeg~pti.
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