Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
10743;~
The present invention provides derivatives of 1,2,4-
triazole, a process for the manufacture thereof, and a method
of controlling pests which comprises the use of these
derivatives.
` S The 1,2,4-triazole derivatives have the formula
:~ CH30C~I2 ~CH3
H
~ o-i~
wherein each of Rl, R2 and R3 represents a Cl-C6-alkyl group
and X represents an oxygen or sulphur atom.
The alkyl groups represented by Rl to R3 can be
straight-chain or branched. Examples of such groups include:
methyl, ethyl. propyl, iso-propyl, n-butyl, iso-butyl, sec.
butyl, tert. butyl, n-pentyl, n-hexyl and isomers thereof.
Preferred compounds on account of their action are
those of the formula I, wherein each of Rl, R2 and R3
represents a methyl or ethyl group and X represents a sulphur
atom.
The compounds of the formula I can be obtained by
methods which are known per se, for example as follows:
. ~
.
., . ~, , ~ . -.
.. . - . -
., ~ ~ ~ , . .. .
1(~7432~ .
~ 3 X
A) IN N + Hal-P ' 1 acid acceptor ~ I
(III)
(II)
30CH~ / CH3 X
,CH " / OR
B) N N ~ Hal-P
R 3S ~ N OMe ~ -
(IV) ~III)
In the formulae II, III and IV, the symbols Rl to R3
; and X are as defined for formula I and Hal represents a
halogen atomJ preferably a chlorine or bromine atom, and Me
represents an alkali metal, ammonium or trialkylammoniu~.
Suitable acid acceptors are for example the following
bases: tertiary amines, such as triethylamine, dimethyl
aniline, pyridine; inorganic bases, such as hydroxides and
carbonates of alkali metals and alkaline earth metals,
preferably sodium and potassium carbonate.
Processes A and B are carried out at a reaction
temperature of 0 to 120C, preferably at 20 to 80C, at
normal pressure and in solvents or diluents. Suitable solvents
10743Z~i
or diluents are for example: ethers and ethereal compounds,
such as diethyl ether, dipropyl ether, dioxan, dimethoxy-
ethane, tetrahydrofuranei amides, such as N,N-dialkylated
carboxamides; aliphatic, aromatic and halogenated hydrocarbons,
in particular benzene, toluene, xylenes, chloroform, chloro-
benzenei nitriles, such as acetonitrile; dimethyl sulphoxide;
ketones, such as acetone, methyl ethyl ketone,and water.
The starting materials of the formula III are known.
They can be prepared in analogy to known processes.
The starting materials of the formula II and IV are
new and can be prepared according to the following known
reaction scheme:
3 \C/ 3 hydrogen + 3 ~CH 3
" catalyst NH
N ~ ^ b
H~O ~ e.g. palladium-calcium NHCOOC2u5
N C OC2 5 carbonate or platinum~carbon
~V) (VI)
¦ ClCN
l NaHC03
3 ~2~ 3
NC-N
NHCCOC 2 H 5
(Vll)
. ~
7~3;~
NaSR3 3 2 ~CH CH30CH2 ~ 3
Vll (VIII) ~35 N QH ~35 OMe
CII) ~IV)
In the formulae II, IV to VIII, R3 is as defined in
formula I and Me represents an alkali metal. The reaction
of the compound VII with the compound VIII is carried out in
a solvent at 10 to 120C, preferably at 20 to 90C, and
lasts a few minutes to several hours, depending on the sub-
stituents and reaction conditions. Suitable solvents are for
example ketones, such as acetone or methyl ethyl ketone;
tetrahydrofurane, and water.
The active substances of the formula I are suitable
for controlling a variety of animal and plant pests. Thus they
possess nematocidal properties and can be used for example,
for controlling phytopathogenic nematodes. The active sub-
stances of the formula I are also partly suitable for use as herbi-
cides and plant regulators and for controlling viruses,
bacteria, and phytopathogenic fungi. Above all, however, they act
on all development stages, such as eggs, larvae, nymphs
pupae and adults, of insects and representatives of the order
Acarina, such as mites and ticks.
.
10743'~i
The compounds of the formula I have, for example, a
lethal or repellant action on the following insects or
representatives of the order Acarina:
Blattidae, Gryllidae, ~ryllotalpidae, Tettigoniidae, Cimicidae,
Pyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae,
Pseudococcidae, Chrysomilidae, Coccinellidae, Bruchidae,
Scarabaeidae, Dermestidae, Tenebrionidae, Tineidae, Noctuidae,
Lymantriidae, Pyralidae, Culicidae, Tipulidae, Stomoxydae,
Muscidae, Calliphoridae, Trypetidae, and Pulicidae, and of
the families: Txodidae, Argasidae, Tetranychidae and
Dermanyssidae .
The acaricidal and/or insecticidal action can be sub-
stantially broadened and adjusted to prevailing conditions by
adding other insecticides and/or acaricides.
Examples of suitable additives include: nitrophenols
and derivatives thereof; formamidinesi ureasi pyrethroids;
carbamates and chlorinated hydrocarbons.
The compounds of formula I can be used as pur~ active
substance or together with suitable carriers and/or additives.
Suitable additives can be solid or liquid and correspond to
the substances conventionally used in the art of formulation,
such as natural or regenerated substances, solvents, disper-
sants, wetting agents, tackifiers, thickeners, binding agents
and/or fertilizers. For application, the compounds of the
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~0~7~3Z6
formula I can be processed to dusts, emulsion concentrates,
granulates, dispersions, sprays, to solutions and suspensions
in the conventional formulations, which are co~monly employed
in application technology. Mention is also to be made of cattle
dips and spray races, in which aqueous preparations are used.
The compositions of the present invention are ob-
tained in known manner by intimately mixing and/or grinding
active substances of formula I with the suitable carriers,
with or without the addition of dispersants or so~vents which
are inert to the active substances.
The active substances can be in the form of and used
in the following application forms:
Solids: dusts, tracking agents, granulates
(coated granulates, impregnated
granulates and homogeneous granulates)
Liquids:
a) active substance concentrates
which are dispersible in water: wettable powders, pastes,
emulsionsi
b) solutions:
The content of active substances in the compositions describ-
ed above is between 0.1 and 95%.
The active substances of formula I can for example
be formulated as follows:
107432~i
Dust:
The following substances are used to prepare (a~ a 5% and
(b) a 25% dust:
a)5 parts of active substance,
95 parts of talcum.
b)2 parts of active substance,
1 part of highly dispersed silicic acid,
97 parts of talcum.
The active substance are mixed with the carriers and ground.
Granulate:
The following ingredients are used to prepare a 5% granulate:
5 parts of active substance,
0.25 part of epichlorohydrine,
0.25 part of cetyl polyglycol ether,
3.50 parts of polyethylene glycol,
91 parts of kaolin (particle size 0.3 to 0.8 mm).
The active substance is mixed with epichlorohydrin and
dissolved in 6 parts of acetone, then polyethylene glycol and
cetyl polyglycol ether are added. The resultant solution is
sprayed onto kaolin and the acetone is subsequently evaporated
in vacuo.
Wettable Powder:
The following ingredients are used to prepare
a) a 40%, b) and c) a 25% and d) a 10% ~ettable powder:
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.
107432~i
a) 40 parts of active substance,
5 parts of sodium lignin sulphona~e,
1 part of sodium dibu~yl-naphthalene sulphonate,
54 parts of silicic acid;
5 b) 25 parts of active substance~
4.5 parts of calcium lignin sulphonate,
1.9 parts of Champagne-chalk/hydroxyethylcellulose
mixture (1:1),
1.5 parts of sodium dibutyl-naphthalenesulphonate,
19.5 parts of silicic acid,
19.5 parts of Champagne-chalk,
28.1 parts of kaolini
c) 25 parts of active substance,
2.5 parts of isooctylphenoxy-polyethylene-ethanol,
1.7 parts of Champagne-chalk/hydroxyethylcellulose
mixture (1:1),
8.3 parts of sodium aluminium silicate,
16.5 parts of kieselguhr,
46 parts of kaolin;
20 d) 10 parts of active substance,
3 parts of a mixture of sodium salts of saturated
fatty alcohol sulphonates,
5 parts of naphthalenesulphonic acid/formaldehyde
condensate,
82 parts of kaolin.
- _ g _
,:,
1~)7432~
The active substances are intimately mixed with the additives
in suitable mixers and ground in appropriate mills and rollers
to yield wettable powders, which can be diluted with water to
give suspensions of the required concentration.
Emulsifiable concentrates
-
The following substances are used to prepare a) a 10%, b) a
25%, c) a 50% emulsifiable concentrate:
a) 10 parts of active substance,
3.4 parts of epoxidised vegetable oil,
3.4 parts of a combination emulsifier, composed of
fatty alcohol polyglycol ether and
calcium alkylarylsulphona~e,
40 parts of dimethyl formamide,
43.2 parts of xylene;
15 b) 25 parts of active substance,
2.5 parts of epoxidised vegetable oil,
10 parts of an alkylarylsulphonate/fatty alcohol
polyglycol ether mixture,
5 parts of dimethyl formamide
57.5 parts of xylenei
c) 50 parts of active substance,
4.2 parts of tributylphenol polyglycol ether,
~.5 parts of calcium dodecylbenzenesulfonate,
20 parts of cyclohexanone,
20 parts of xylene.
- ~O -
107432~ `
Emulsions of any required concentration can be prepared by
diluting the above described concentrates with water.
Spray
The following ingredients are used to prepare a) a 5% and b) a
95% spray
a) 5 parts of active substance,
1 part of epichlorohydrin,
94 parts of ligroin (boiling range 160-190C);
b) 95 parts of active substance,
5 parts of epichlorohydrin.
The following Examples will serve to illustrate the invention
in more detail.
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1~7432f~i
Example 1
a) Preparation of l-(l'-methyl-2'-methoxy-ethyl)-3-hydroxy-5-
methylthio-1,2,4-triazole
0.5 Mole of the compound of the formula
C~30C~l2~c~ C~13
N ~ ooC2~T5
CN
(n20 = l.47~.2)
is added dropwise at room temperature to a solution consisting
of 0.5 mole of sodium hydroxide in 100 ml of water and into
which 0.5 mole of CH3SH has been introduced. The reaction
proceeds exothermically (70C). The reaction mixture is keptforl
hour at 80C. After cooling, the product which crystallises
out is collected by filtration and recrystallised from ether/
hexane to yield the compound of the formula
3 `2CH C~13
N - N
CH3S ~N ~ 0ll
with a melting point of 102-104C. The compound of the formula
C~330C~2 ~ CH3
N-- N
2 5 ~N~ 011
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10743Zf~
(m.p. 94-96C) is obtained in analogous manner.
b) Preparation of 0,0-diethyl-0-~1-(1'-methyl-2'-methoxy-
ethyl)-5-methylthio-1,2,4-triazolyl-(3)-thiophosphoric acid
ester
_ .
0.1 mole of 1-(1'-methyl-2'-methoxy-ethyl)-3-hydroxy-5-
methylthio-1,2,4-triazole and 0.1 mole of potassium carbonate
in 200 ml of methyl ethyl ketone are refluxed for 2 hours.
After the dropwise addition of 0.1 mole of diethylthiophos-
phoric chloride at 40C, the mixture is refluxed once more
for 2 hours, then left to stand for 15 hours at 20C. The
salts are filtered off and the filtrate is concentrated in
vacuo. The oiiy residue is purified through a column of
silica gel with chloroform as eluant to yield the compound
of the formula
Cll30C~l2 / CH3
N - N
1 11 S
CH3S~ P(C2~l5)2
in the form of an oil with a refractive index of n20= 1.5033.
The following compounds are obtained in analogous manner:
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10-~3Z6i
CH30CH2~CH~ CH3
C2H5S~N ~P COC2H5) 2 n D = 1.5072
CH30CH2~CH~CH3
N--N S
(oc2H5)2 nD20 = 1.4970
3 2 \ ~CH3
--N
3 2 J~ ~L ,S, nD20 = 1.4935
3 2 \ / CH3
CH
~_ N S
2 5 J~NJI O-P(OC4Hg(n))2 nD20 = 1.4960
CH30CH2 CH3
,CH nD20 = 1.4770
C2H5S ~N/J O-P (C2H5) 2
CH30CH2 CH3
CH
C2H5S~ N~LO-P(OCH3)2 nD - 1.5025
-14-
1074~
Example 2
A) Insec~icidal stomach poison action
Cotton plants were sprayed with a 0.05% aqueous emulsion of
active substance (obtained from a 10% emulsifiable concentrace).
After the spray coating had dried, the cotton plants were
populated respectively with Spodoptera littoralis and Heliothis
virescens larvae in the L3 stage.
In this test, the compounds of Example lb exhibited a good
insecticidal stomach poison action on Spodoptera and Heliothis
larvae.
B) System insecticidal action
The systemic action was determined by immersing rooted bean
plants (Vicia faba) in a 0.01% aqueous solution of active
substance (obtained from a 10% emulsifiable concentrate).
After 24 hours the parts of the plants above the soil were
populated with aphids (Aphis fabae). The aphids were protected
from the contact and gas action by a special dev;ce. The test
was carried out at 24C and 70% relative humidity.
In this test, the compounds of Example lb exhibited systemic
insecticidal action on Aphis fabae.
Example 3
Action on Chilo suppressalis
Six rice plants of the variety Caloro were transplanted into
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10~3'~
each of a number of plastic pots having a diameter of 17 cm at
the top, and reared to a height of approx. 60 cm. Infestation
with larvae of Chilo suppressalis (Ll stage; 3 to 4 ~ in
length) took place 2 days after the active substance had been
added to the paddy water in granulate form (rate of application
8 kg of active substance/hectare). Evaluation of the insect-
icidal action took place 10 days after addition of the
granulate. The compounds of formula Ib acted in this test on
Chilo suppressalis.
Example 4
Acaricidal action
Phaseolus vulgaris (dwarf beans) had an infested piece of
leaf from a mass culture of tetranychus urticae placed on
them 12 hours before the test for the acaricidal action.
The mobile stages which had migrated to the plants were
sprayed with the emulsified test preparations from a chroma-
tography atomiser so that the sprayed preparation did not run
off. The number of living and dead larvae, adults and eggs
were evaluated after 2 to 7 days under a stereoscopic micro-
scope and the result expressed in percentages. During thecourse of the test, the treated plants were kept in green-
house compartments at 25C. The compounds of Example lb acted
in the above test on eggs, larvae and adults of Tetranychus
urticae.
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107432~i
Example 5
Action on soil nematodes
The action on soil nematodes was tested by applying the
active substances in the respe~tive concentration indicated
to and intimately mixing them with soil infected with root
gall nematodes (Meloidgyne arenaria). Im~ediately afterwards,
tomato cuttings were planted in the thus prepared soil in a
test run and after 8 days tomato seeds were sown in another
test run.
In order to assess the nematocidal action, the galls present
on the roots were counted 28 days after planting and sowing
respectively. In this test the compounds according to Example
lb exhibited good action on Meloidgyne arenaria.
EY.ample 6
Action on ticks
A) Rhipicephalus bursa
Five adult ticks and 50 tick larvae were counted into each of
a number of test tubes and imersed for l to 2 minutes in 2 ml
of an aqueous emulsion containing a concentration of lO0, lO,
l or O.l ppm of test substance. Each test tube was then
sealed with a cotton-wool plug and placed on its head to
enable the cotton wool to absorb the acti~e substance emulsion.
The adults were evaluated after 2 wee'~s and the larvae after
2 days. Each ~est was repeated twice.
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lOt7~3~
B) Boophilus_~icroDI~s (larvae)
Tests were carried out on 20 OP- sensitive and 20 OP-resistant
larvae with aqueous emulsions similar to those used in test A.
(The resistance refers to the tolerance towards diazinone).
The compounds of Example lb acted in these tests on adults and
larvae of Rhipicephalus bursa and OP-sensitive and of resistant
larvae of Boophilus microplus.
Example 7
Action of Erysiphe ~raminis on Hordeum vulgare
Barley plants (approx. 8 cm in height) were sprayed with a
spray broth (active subs~ance content: 0.05%) prepared from
a wettable powder of the active substance.
After 48 hours the trea~ed plants were dusted with conidia of
the fungus. The infec~ed barley plants were stood in a green-
house at approx. 22C and the fungus attack was evaluatedafter 10 days.
The compounds of Example lb acted in this test on Erysiphe
graminis.
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