Note: Descriptions are shown in the official language in which they were submitted.
2~ S
Case 5-14473/+
Oxamic acid derivatives
The present invention relates to novel oxamic acid
esters substituted on the nitrogen atom, to the production
thereof, to their use for controlling pests, and to
pesticidal compositions containing these esters.
The compounds according to the invention correspond
to the formula I
(lco-o)(2-m) R2
, R10-CO-CO-~ R3 R4 .~ \-/X\-/ I. (I)
(CO-O) (m 1) ~:H-CH-O-!~ 11 '! +. R5
wherein
Rl is cl-clO-alkYl,
R2 i8 Cl~C4~alkyl
R3 and R4 are each hydrogen or methyl,
R5 is hydrogen, halogen, Cl-C4-alkyl, Cl-C4-alkoxy,
Cl-C4-alkylthio or Cl-C4-haloalkyl,
X is oxygen or sulfur, and
m is 1 or 2.
The Cl-C10-alkyl groups denoted by Rl can be branched-
chain or straight-chain. Examples of such alkyl groups
are, inter alia: methyl and ethyl as well as propyl, butyl,
,;, - '11
.:.,. ,' 3~;
pentyl, hexyl, octyl or decyl, and isomers thereof.
Preferred in this respect are Cl-C6-alkyl groups and
amongst these the Cl-C4-alkyl groups may in their turn
be given particular mention.
The Cl-C4-alkyl, -alkoxy, alkylthio- and -haloalkyl
groups denoted by R2 and R5 can be branched-chain or
straight-chain. Examples of such lower alkyl groups
to be mentioned are: methyl and ethyl as well as propyl
and butyl, and isomers thereof, methyl and ethyl being
preferred.
The halogen substituents mentioned for R5 are fluorine
and chlorine and also bromine and iodine, fluorine
and chlorine being preferred. This definition with regard
to halogen applies also to the Cl-C4-haloalkyl groups.
Examples of such haloalkyl groups are, inter alia: the
methyl group mono- to trisubstituted by fluorine, chlorine
and/or bromine; the ethyl group mono- to pentasubstituted
by fluorine, chlorine and/or bromine; or the propyl group
mono- to sevenfold-substituted by fluorine, chlorine
and/or bromine.
Preferred compounds of the formula I are those wherein
Rl is cl-C6-alkyl,
R2 i9 Cl-C4-alkyl,
R3 and R4 are each hydrogen or methyl,
R5 is hydrogen or halogèn,
X is oxygen or sulfur, and
m is 1 or 2.
Compounds of the formula I deserving special mention
are those wherein
Rl and R2 are each Cl-C4-alkyl,
R3 and R4 are each hydrogen or methyl,
-- 3 --
R5 is hydrogen or chlorine,
X is oxygen or sulfur, and
m is 1 or 2.
Of particular importance are above all the compounds
of the formula I wherein
Rl and R2 are each methyl or ethyl,
R3, R4 and R5 are each hydrogen,
X is oxygen, and
m is 2.
The compounds according to the present invention are
produced in a manner known per se by for example reaction
of a carbamic acid ester of the formula II
(~~~)(2-m) R2
, R3 R4 .~ \. ./ I- (II)
( ~~ ) (my H-~H-o- !~ . R5
with an oxalic acid ester chloride of the formula III
R10-CO-CO-Hal (III).
In the formulae II and III, the symbols Rl, R2, R3,
R4, R5, X and m have the meanings defined under the
formula I, and Hal is fluorine, chlorine or bromine. The
reaction is performed advantageously in the presence of an
inert diluent, preferably an organic solvent, and
optionally of a basic substance. In general, the reaction
is carried out between 0C and the boiling temperature of
the reaction mixture, preferably between room temperature
and the boiling temperature.
Suitable inert organic solvents are in particular:
a) ethers and ethereal compounds, such as diethyl ether,
,
24~6~5
1,2-dimethoxyethane, tert-butylmethyl ether, dioxane or
tetrahydrofuran; b) hydrocarbons, for example n-hexane,
benzene, toluene or xylenes; c) halogenated hydrocarbons,
for example methylene chloride, ethylene chloride,
chloroform or carbon tetrachloride; d) ketones, such as
acetone, 2-butanone or 3-pentanone; e) nitriles, for
example acetonitrile or propionitrile; and f) formamides,
such as dimethylformamide.
Suitable basic substances are inorganic or organic
acid binders, for example carbonates and bicarbonates of
alkali metals and alkaline-earth metals, especially
sodium or potassium carbonate or sodium bicarbonate,
lower tertiary alkylamines, particularly trimethylamine or
cycloalkylamine, especially pyridine or 1,4-diaza-
bicyclo(2,2,2)octane.
The compounds of the formulae II and III used as
starting materiaLs are known, or they can be produced
by known methods, for example from the corresponding
carboxylic acid halides and amines.
With favourable tolerance to warm-blooded animals and
to plants, the compounds according to the invention are
valuable active substances for controlling pests. The
compounds of the formula I are thus suitable for example
for controlling pests on animals and plants. Such pests
belong principally to the Arthropoda phylum, such as in
particular insects of the orders: Lepidoptera, Caleoptera,
Homoptera, Heteroptera, Diptera, Thysanoptera, Orthoptera,
Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera,
Psocoptera or Hymenoptera; and Arachnida of the order
Acarina, for example mites and ticks. Every development
stage of the pests can be controlled, that is to say,
the adults, pupae and nymphs and also in particular the
larvae and eggs. It is thus possible to effectively
control especially larvae and eggs of phytophagous insect
pests and mites in crops of ornamental plants and
productive plants, for example in cotton and vegetable
crops and particularly in fruit crops. When compounds of
the formula I are taken up with the feed by imagines,
the action of the compounds is shown by the immediate
destruction of the pests or by a reduced oviposition
and/or a lessened rate of hatching. The last-mentioned
effect can be observed especially in the case of Coleoptera.
In the control of zooparasitic pests, particularly on
domestic and productive animals, the pests concerned are
above all ectoparasites, for example mites and ticks
and ~iptera, such as Lucilia sericata.
The action of the compounds according to the invention,
or of compositions containing them, can be considerably
broadened and adapted to suit given circumstances by the
addition of other insecticides and/or acaricides. Suitable
additives are for example: organic phosphorus compounds,
nitrophenols and derivatives thereof, formamidines,
ureas, carbamates, pyrethroids, chlorinated hydrocarbons
and Bacillus thuringiensis preparations.
The compounds of the formula I can be combined with
particular advantage also with substances which intensify
pesticidal activity. Examples of compounds of this type
are, inter alia: piperonylbutoxide, propynyl ethers,
propynyl oximes, propynyl carbamates and propynyl
phosphonates, 2-(3,4-methylenedioxyphenoxy)-3,6,9-trioxa-
undecane or S,S,S-tributylphosphorotrithioates.
The compounds of the formula I are used either in an
unmodified form or preferably together with auxiliaries
customarily employed in formulation practice, and are
. . .
thus processed, in a known manner, for example into the
form of emulsion concentrates, directly sprayable or
dilutable solutions, diluted emulsions, wettable powders,
soluble powders, dusts or granulates, and also encapsu-
lations in for example polymeric substances. The
application processes, and likewise the type of compo-
sitions, are selected to suit the objectives to be
achieved and the given conditions.
The formulations, that is to say, the compositions
or preparations containing the active ingredient of the
formula I, or combinations of this active ingredient with
other insecticides or acaricides, and optionally a solid
or liquid additive, are produced in a known manner, for
example by the intimate mixing and/or grinding of the
active ingredients with extenders, such as with solvents,
solid carriers and optionally surface-active compounds
(tensides).
Suitable solvents are: aromatic hydrocarbons, prefer-
ably the fractions C8 to C12, such as xylene mixtures or
substituted naphthalenes, phthalic esters, such as dibutyl
or dioctylphthalate, aliphatic hydrocarbons, such as
cyclohexane or paraffins, alcohols and glycols, as well as
ethers and esters thereof, such as ethanol, ethylene
glycol, ethylene glycol monomethyl or -ethyl ethers,
ketones such as cyclohexanone, strongly polar solvents,
such as N-methyl-2-pyrrolidone, dimethylsulfoxide or
dimethylformamide, as well as optionally epoxidised
vegetable oils, such as epoxidised coconut oil or
soybean oil; or water.
The solid carriers used, for example for dusts and
dispersible powders, are as a rule natural mineral fillers,
such as calcite, talcum, kaolin, montmorillonite or
365
-- 7 --
attapulgite. In order to improve the physical properties,
it is also possible to add highly dispersed silicic acid
or highly dispersed absorbent polymers.
Suitable granulated adsorptive carriers are porous
types, for example: pumice, ground brick, sepiolite or
bentonite; and suitable nonsorbent carriers are materials
such as calcite or sand. A great number of pre-granulated
materials of inorganic or organic nature, such as in
particular dolomite or ground plant residues, can also
be used.
Depending on the nature of the active ingredient of
the formula I, or of the combination of this active
ingredient with other insecticides or acaricides, to be
formulated, suitable surface-active compounds are: nonionic
cationic and/or anionic tensides having good emulsifying,
dispersing and wetting properties. By 'tensides' are
also meant mixtures of tensides.
Suitable anionic tensides are both so-called water-
soluble soaps, as well as water-soluble, synthetic,
surface-active compounds.
Soaps which may be mentioned are the alkali metal,
alkaline-earth metal or optionally substituted ammonium
salts of higher fatty acids (C10-C22), for example the
sodium or potassium salts of oleic or stearic acid, or of
natural fatty acid mixtures, which can be obtained for
example from coconut oil or tallow oil. Also to be
mentioned as tensides are the fatty acid-methyl-taurine
salts.
So-called synthetic tensides are however more
frequently used, particularly fatty sulfonates, fatty
sulfates, sulfonated benzimidazole derivatives or
alkylarylsulfonates.
-- 8 --
The fatty sulfonates or sulfates are as a rule in
the form of alkali metal, alkaline-earth metal or
unsubstituted or substituted ammonium salts, and they
generally contain an alkyl group having 8 to 22 C atoms,
'alkyl' including also the alkyl moiety of acyl groups,
for example the Na or Ca salt of ligninsulfonic acid, of
dodecylsulfuric acid ester or of a fatty alcohol sulfate
mixture produced from natural fatty acids. Included among
these are the salts of sulfuric acid esters and sulfonic
acids of fatty alcohol ethylene oxide adducts. The
sulfonated benzimidazole derivatives preferably contain
2 sulfonic acid groups and a fatty acid group having
8 - 22 C atoms. Alkylarylsulfonates are for example the
Na, Ca or triethanolamine salts of dodecylbenzenesulfonic
acid, of dibutylnaphthalenesulfonic acid or of a
naphthalenesulfonic acid-formaldehyde condensation product.
Also suitable are corresponding phosphates, for example
salts of the phosphoric ester of a p-nonylphenol-(4-14)-
ethylene oxide adduct.
Suitable nonionic tensides are in particular polyglycol
ether derivatives of aliphatic or cycloaliphatic alcohols,
saturated or unsaturated fatty acids and alkylphenols,
which can contain 3 to 30 glycol ether groups and 8 to 20
carbon atoms in the (aliphatic) hydrocarbon radical and
6 to 18 carbon atoms in the alkyl moiety of the alkyl-
phenols. Further suitable nonionic tensides are the water-
soluble polyethylene oxide adducts, which contain 20 to
250 ethylene glycol ether groups and 10 to 100 propylene
glycol ether groups, with polypro W lene glycol, ethylene-
diaminopolypropylene glycol and alkylpolypropylene glycol
having 1 to 10 carbon atoms in the alkyl chain. The
compounds mentioned usually contain 1 to 5 ethylene
glycol units per polypropylene glycol unit.
Examples of nonionic tensides which may be mentioned
are: nonylphenol-polyethoxyethanols, castor oil polyglycol
ethers, polypropylene/polyethylene oxide adducts,
tributylphenoxy-polyethoxyethanol, polyethylene glycol
and octylphenoxy-polyethoxyethanol. Suitable also are
fatty acid esters of polyoxyethylenesorbitan, such as
polyoxyethylenesorbitan-trioleate.
In the case of the cationic tensides, they are in
particular quaternary ammonium salts which contain as
N-substituents at least one alkyl group having 8 to 22
C atoms and, as further substituents, lower, optionally
halogenated alkyl, benzyl or lower hydroxyalkyl groups.
The salts are preferably in the form of halides, methyl
sulfates or ethyl sulfates, for example stearyltrimethyl
ammonium chloride or benzyldi-(2-chloroethyl)-ethyl-
ammonium bromide.
The tensides customarily used in formulation practice
are described, inter alia, in the following publications:
"Mc Cutcheon's Detergents and Emulsifiers Annual",
MC Publishing Corp., Ridgewood, New Jersey, 1981;
Dr. Helmut Stache "Tensid-Taschenbuch" (Tenside Manual),
Carl Hanser Verlag, Munich/Vienna, 1981.
The pesticidal preparations contain as a rule 0.1 to
99%, particularly 0.1 to 95/0, of active ingredient of the
formula I, or of combinations of this active ingredient
with other insecticides or acaricides, 1 to 99.9~/0 of a
solid or liquid additive, and 0 to 25%, especially 0.1 to
20%, of a tenside. Whereas commercial products are
preferably in the form of concentrated compositions,
the products employed by the end-user are as a rule
preparations having considerably lower concentrations
of active ingredient.
- `
6~
- 10 -
The compositions can also contain further additives,
such as stabilisers, antifoaming agents, viscosity
regulators, binders and adhesives, as well as fertilisers
or other active ingredients for obtaining special effects.
Formulation examPles for liquid active ingredients of the
formula I or combinations of these active ingredients with
other insecticides or acaricides (% = per cent by weight)
1. Emulsion concentrates a) b) c)
active ingredient or active- 25% 40%50%
ingredient combination
calcium dodecylbenzenesulfonate 5% 8% 6~/o
castor-oil-polyethylene glycol5%
ether (36 mols of ethylene oxide)
tributylphenol-polyethylene glycol - 12% 4%
ether (30 mols of ethylene oxide)
cyclohexanone - 15% 20%
xylene mixture 65% 25% 20%
Emulsions of the concentration required can be produced
from such concentrates by dilution with water.
.
2. Solutions a) b) c) d)
active ingredient or active- 80% 10%5~/0 95%
ingredient combination
ethylene glycol monomethyl ether 20%
polyethylene glycol M.W. 400 - 70%
N-methyl-2-pyrrolidone - 20%
epoxidised coconut oil - - 1% 5%
ligroin (boiling limits 160-190C) - - 94%
The solutions are suitable for application in the
form of very fine drops.
,5
- 11 -
3. Granulates a) b)
active ingredient or active- 5% 10%
ingredient combination
kaolin 94%
highly dispersed silicic acid 1%
attapulgite 90%
The active ingredient or the active-ingredient
combination is dissolved in methylene chloride, the
solution is sprayed onto the carrier, and the solvent
is subsequently evaporated off in vacuo.
4. Dusts a) b)
active ingredient or active- 2% 5%
ingredient combination
highly dispersed silicic acid 1% 5%
talcum 97%
kaolin - 90%
Ready-for-use dusts are obtained by the intimate
mixing together of the carriers with the active ingredient
or active-ingredient combination.
Formulation examples for solid active ingredients of the
formula I or combinations of these active ingredients with
other insecticides or acaricides (% = per cent by weight)
5. Wettable powders a) b) c)
active ingredient or active-25% 50% 75%
ingredient combination
sodium lignin sulfonate 5% 5%
sodium lauryl sulfate 3% - 5%
sodium diisobutylnaphthalene - 6% 10%
sulfonate
octylphenolpolyethylene glycol ether - 2%
(7-8 mols of ethylene oxide)
highly dispersed silicic acid 5% 10% 10%
kaolin 62% 27%
S
- 12 -
The active ingredient or the active-ingredient
combination is well mixed with the additives, and the
mixture is thoroughly ground in a suitable mill. Wettable
powders which can be diluted with water to give suspensions
of the concentration required are obtained.
6. Emulsion concentrate
active ingredient or active- 10%
ingredient combination
octylphenol polyethylene glycol ether 3%
(4-5 mols of ethylene oxide)
calcium dodecylbenzene sulfonate 3%
castor oil polyglycol ether 4%
(36 mols of ethylene oxide)
cyclohexanone 30%
xylene mixture 50%
Emulsions of the concentration required can be
obtained from this concentrate by dilution with water.
7. Dusts a) b)
active ingredient or active- 5% 8%
ingredient combination
talcum 95%
kaolin - 92%
Dusts ready for use are obtained by mixing the active
ingredient or active-ingredient combination with the
carriers and grinding the mixture in a suitable mill.
8. Extruder granulate
active ingredient or active- 10%
ingredient combination
sodium lignin sulfonate 2%
carboxymethylcellulose 1%
kaolin 87%
~Z~365
- 13 -
The active ingredient is mixed and ground with the
additives, and the mixture is moistened with water.
The mixture is extruded, granulated, and subsequently
dried in a stream of air.
9. Coated granules
active ingredient or active- 3%
ingredient combination
polyethylene glycol (M.W. 200) 3%
kaolin 94%
The finely ground active ingredient or the active-
ingredient combination is evenly applied, in a mixer, to
the kaolin moistened with polyethylene glycol. Dustfree
coated granules are obtained in this manner.
10. Suspension concentrate
active ingredient or active- 40%
ingredient combination
ethylene glycol 10%
nonylphenol-polyethylene glycol 6%
(15 mols of ethylene oxide)
sodium lignin sulfonate 10%
carboxymethylcellulose 1%
37% aqueous formaldehyde solution 0.2%
silicone oiL in the form of a 0.8%
75% aqueous emulsion
water 32%
The finely ground active ingredient or the active-
ingredient combination is intimately mixed with the
additives. There is thus obtained a suspension
concentrate from which can be prepared, by dilution
with water, suspensions of the concentration required.
~L2~g~.~
- 14 -
Example 1: Production of N-ethoxycarbonyl-N-2-(4-phenoxy-
phenoxy~-ethyl-oxamic acid methyl ester
7.5 g of 2-(4-phenoxyphenoxy)-ethyl-carbamic acid
ethyl ester are dissolved in 80 ml of ethylene chloride.
To this solution are added 5.0 g of oxalic acid monomethyl
ester chloride, and the reaction mixture is stirred for
6 hours under mild refluxing conditions. The mixture is
subsequently concentrated by evaporation, and the residue
is taken up in dichloromethane. This so1ution is washed
with cold water, dried over sodium sulfate and finally
concentrated by evaporation to one fifth. Chromatography
on silica gel with dichloromethane as eluant thus yields
the compound of the formula
O-OC2H5
CH3O-CO-CO- I-\ /0\ /-~
H2CH2-0- 1 ll iI t compound No.l.l
as light-yellow oil having a refractive index of
n20 - 1.5419.
There are obtained by a procedure analogous to that
described above also the following compounds:
,CO-OR2
R10-CO-CO-~ R4 .~ \ A./ I.
R3-lH-CH-O-l~ UP I- R5
R2 R3 ¦ R4 Physical data
_ _
1. 2 CH3 CH3 H H H O nD : 1. 5486
1.3 CH3 C2H H H H S ` n20: 1.5694
1.4 C2H5 CzH~ U U U O nD: 1~5369
.~
$
- 15 -
Example 2: Production of N-ethYl-N-2-(4-phenoxyphenoxy)-
ethoxycarbonyl-oxamic acid ethyl ester
9.0 g of N-ethyl-carbamic acid-2-(4-phenoxyphenoxy)-
ethyl ester are dissolved in 90 ml of ethylene chloride.
To this solution are added 9.6 g of oxalic acid monoechyl
ester chloride, and stirring is maintained for 10 hours
under mild refluxing conditions. The cooled reaction
mixture is then poured into 200 ml of ice-water, and the
organic phase is separated. This is washed with cold
water, dried over sodium sulfate, concentrated by
evaporation and taken up in dichloromethane. Chromatography
on silica gel with dichloromethane as the eluant thus
yields the compound of the formula
H
C2H50-C0-C0- 2 5 \-/ \-/ I. compound No. 2.1
-ocH2-cH2-o-!~ ,Y
in the form of white crystals having a m.p. of 56-58C.
There are obtained by a procedure analogous to that
described above also the following compounds:
~2
R10-CO-Co-~ R3 R4 .
CO-O(~:H-CH-O- !~ l y 5
_6
Comp.No. Rl R2 R3 R4 R5 X Physical data
. . _ . .. _
2.2, CH3 CH3 H .~ H 0nD : 1.5508
2.3 CH3 C2H5 H H H 0m.p. 63-64C
2.4 CH3 C2Hs H H H Sm.p. 49-51C
2.5 C2H5 CH3 H H H 0m.p. 60-62C
2.6 C2H5 C2H5 H H H SnD : 1.5632
2.7 CH3 C2H5 H H 4-Cl 0nD : 1.5494
2.8 CH3 C2Hs CH3 H H 0nD : 1.5348
2.9 CH3 C2H5 H CH3 H 0nD : l.S376
2.10 CH3 C2H5 H CH3 H SnD : 1.5653
, 2.11 CU3 ~4U9-n U U U 0 nD : 1.5342
In the Biological Examples given in the following,
a good action signifies that the desired effect has been
obtained to the extent of at least 50 to 60%.
Example 3: Action against Laspeyresia pomonella (ergs)
Deposited Laspeyresia pomonella eggs, not more than
24 hours old, are immersed on filter paper for 1 minute in
acetonic/aqueous solutions containing 0.75, 12.5, 100
and 400 ppm, respectively, of the active ingredient to ye
tested. After the drying of the solution on the eggs,
these are laid out in Petri dishes and kept at a temperera-
ture of 28C. The percentage hatching rate from the
treated eggs is evaluated after 6 days.
- 17 -
The compounds Nos. 1.1, 1.2, 1.3, 1.4, 2.2, 2.4,
2.5 and 2.7 exhibit a 100% action (mortality) in the
above test at an active-ingredient concentration as
low as 0.75 ppm.
Example 4: Effect on reproduction of Anthonomus ~randis
Adult Anthonomus grandis, which have been hatched no
longer than 24 hours, are transferred, in groups each
of 25 beetles, to cages having lattice walls. The cages
containing the beetles are then immersed for 5 to 10
seconds in an acetonic solution containing 1.0% by weight
of the active ingredient to be tested.
After the beetles are again dry, they are placed, for
copulation and oviposition, into covered dishes containing
feed. Deposited eggs are flushed out with running water
two to three times weekly; they are counted, disinfected
by being placed for two to three hours into an aqueous
disinfectant, and then deposited into dishes containing
a suitable larval diet. An examination is made after 7
days to determine whether larvae have developed from
the deposited eggs.
In order to ascertain the duration of the reproduction-
influencing effect of the active ingredients tested, the
oviposition of the beetles is observed during a period
of about four weeks. The evaluation is on the basis of
the reduction in the number of eggs deposited and larvae
hatched in comparison with that in the case of untreated
control specimens.
Compounds according to Examples 1 and 2 exhibit a
good reproduction-influencing effect in the above test.
