Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
`^ -
The present invention relates to thiophosphoric acid phenyl esters
having pesticidal properties.
According to the present invention there are provided Compounds of
the formula (I)
R 0\10 ~ R2 (I)
wherein
R represents a~me~hyl or ethyl group, Rl represents a C3-C5-alkyl group,
R2 represents an alkylthiomethyl, alkylsulfinylmethyl or alkylsulfonylmethyl
group having at most 5 carbon atoms in toto or a group of the formula
-S(CH2)mCN~ -SO(CH2)mCN~ -S(CH2)mCl~ -SO(CH2)mCl, SCC13, SOCC13,
S(CH2)mCOOR3, -SO(CH2)mCOOR3, ~S(CH2)mCON(R4)R5 or -SO(CH2)mCON~R4)R5
wherein R3 represents an alkyl group having at most 4 carbon atoms, R4 and
R5 independently of one another represent~a hydrogen atom or an alkyl group
having at most 4 carbon atoms and m represents the integer 1 or 2; and Xl
~nd X2 independently of one another represent a hydrogen or halogen atom or
an alkyl group having at most 4 carbon atoms.
By halogen is meant fluorine, chlorine, bromine or iodine, in
particular chlorine or bromine.
The alkyl groups and moieties within the definitions of Rl to R5
may be straight-chain or branched. Examples of such groups or moieties are
as appropriate to the definitions: methyl, ethyl, propyl, isopropyl and n-~
i-, sec. and tert. butyl.
Rl in the compounds of formula I preferably represents an n-propyl,
i-propyl, i-butyl, sec.-butyl, or n-pentyl group. Most preferably R repre-
sents an ethyl group and ~ represents an n-propyl group.
- 1 -
Preferably R2 represents a group of the formula -SCH2CN3
-SOCH2C~ -SCH2Cl, SOCH2Cl, -SCC13, -SOCC13, -SCH2COOR3, -SOCH2COOR3,
-SCH2CON \ or -SOCH2CON \ (wherein R3 represents a methyl or ethyl group
and R4 and ~5 independently of one another represent a hydrogen atom or
methyl group); especially a group of the formula -SC}l2CN, -SCH2Cl,
-scH2cooc2Hs~ or -ScH2co 2
R2 may also suitably represent an alkylthiomethyl, alkylsulphinyl-
methyl or alkylsulphonylmethyl group containing at most 4 carbon atoms in the
said alkyl moiety; preferably a methylthiometh~l, methylsulphinylmethyl or
methylsulphonyl~et~yl group.
Preferably X, and X2 each represents a chlorine or bromine atom or
a methyl group.
The compounds of formula I can be manufactured by the following
processes which are analogous to those known in the art;
la) RO O R
> p _ Cl + HO ~ 2 acid binding
1 ~ ~1 agent
(II) X2 (III)
lb) R ~ O ~ ~eO ~ 1 -D
RlS X
(II~ (IV)
~8~7
2) \ P-Cl -~ H0 ~ acid binding \ ~ ~ R2
(V) x2 (VI) (X)n
R0 0 acid binding
\!1_o /9~R2 -~ HSR
/ ~\ ~ (VII) agent
Cl ~
(VI) X2 (VIII)
10R0 > S ~ ( 3)3 (X)
R30C~--SMe
S (XI)
~ ~Hal
or >
MeSR3 ~(XII) (XIV)
or
Me2S l(XIII)
In the formulae II to XIV, R, Rl, R2, Xl and ~2 have the meanings
given for the formula I, Me represents an alkali metal ( in particular sodium
or potassium~ or ammonium or alkyl-ammoniumion~ R3 represents hydrogen or
alkyl with 1 to 4 carbon atoms and Hal represents a halogen atom, such as
chlorine, bromine or iodine.
Suitable acid binding agents are: tertiary amines, e.g.
trialkylamines, pyridine, dialkylanilines; inorganic bases, such as hydrides,
hydroxides; carbonates and bicarbonates of alkali and alkaline earth metals.
During the reactions it is sometimes necessary to use a catalyst~ for
example copper or copper chloride. Processes 1~ 2, and 3 can be carried out
at normal pressure and in solvents or diluentsO
-- 3 --
~4~ L7
EXamples of suitable solvents or diluents are: ether and
ethereal compounds, such as diethyl ether, dipropyl ether, dioxan, tetra~
hydrofuran; amides, such as N,N-dialkylated carboxylic acid amides; aliphaticg
aromatic and halogenated hydrocarbons, in particular benæene, toluene,
xylenes, chloroform, chlorobenzene3 nitriles, such as acetonitrile; dimethyl
sulphoxide; alcohols, such as ethanol and ketones~ such as acetone, ethyl
methyl ketone, water.
The starting materials of the formulae, II~ III, IV, V and IX
are known or may be manufactured in analogous manner to known methods, e.g.
those described in German Auslegeschriften 1051863, 1063177, 1088980 or
i298990.
The active substances of the formula I are suitable for combatting
pests of the class Insecta or of the order Acarina. Thus the compounds of
formula I surprisingly have markedly better action against all development
stages, e.gO eggs~ larvae, pupae, nymphs and adults, of insects and repre-
sentatives of the order Acarina, such as mites andticks than e.g. analogous
compounds of German patent 1138041. Thus the compounds of the formula I can
be used against insects of the families:
Tetti~oniidae Tenebrionidae
5~ Chrysomel_ ae
E~ Bruchidae
BIattidae Tineidae
Reduviidae Noctindae
Pyrrhocoridae Lymatriida
Cimicidae Pyralidae
Delphacidae Culicidae
Aphididae ~
Diaspididae Stomoxydae
PseudocQccidae Trypetidae
81147
Scarabaeldae Muscidae
Dermestidae Calliphoridae and
Coccinellidae Pulicidae
Acarida of the families:
Ixodidae Argasidae
and Dermanyssidae.
The insecticidal a~d/or acaricidal action can be substantially
broadened and adapted to suit the particular circumstances by the addition of
other insecticides and/or acaricides.
The compounds of the formula I may be used as 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 convention-
ally used in formulation technique~such, for example, as solvents, dispersants,
wetting agents, adhesives, thickeners, binders and/or fertilisers.
For application~ the compounds of the formula I may be processed to
dusts, emulsion concentrates~ granules~ dispersions, sprays~ to solutions, or
suspensions inîthe conventional formulation which is commonly employed in
application technology. Mention may also be made of cattle dips and spray
races, in which aqueous preparations are used.
The agents according to the invention are manufactured in known
manner by intimately mixing and/or grinding active substances of the formula
I with the suitable carriers, optionally with the addition of dispersants or
solvents which are inert towards the active substances. 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 substances which are dispersible in water: wettable
8~
powders, pastes, emulsions;
b) solutions.
The active substances of the formula I can, for example, be
formulated as follows;
Dusts
The following substances are used to manufacture a) a 5% and b) a
2% dust:
a) 5 parts of active substance
parts of taleum
b) 2 parts of active substance
1 part of highly disperse silicic acid
97 parts of talcum.
The active substances are mixed with the carriers and ground.
Granules
The following substances are used to produce 5% granules:
5 parts of active substance,
0.25 parts of epichlorohydrin,
0.25 parts of cetyl polyglycol ether,
3.~0 parts of polyethylene glycol,
91 parts of kaolin (particle si~e 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 thus obtained solution is sprayed on kaolin, and the
acetone subsequently evaporated in vacuo.
~ettable powder:
The following constituents are used for the preparation of a) a
40%, b) and c) a 25%, and d3 a 10% wettable powder:
a) 40 parts of active substance,
5 parts of sodium lignin sulphonate,
~4~ 7
1 part of sodium dibutyl~naphthalene sulphonate,
54 parts of silicic acid.
b) 25 parts of active substance,
4.5 parts of calcium lignin sulphonate,
1.9 parts of Champagne chalk/hydroxyethyl cellulose mix~ure (1:1),
1.5 parts of sodium dibutyl naphthalene sulphonate,
19.5 parts of silicic acid,
19.5 parts of Champagne chalkg
28.1 parts of kaolin.
c) 25 parts of active substance,
2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol,
1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),
8.3 parts of sodium aluminium silicate,
16.5 parts of kieselguhr,
46 parts of kaolin.
d) 10 parts of active substance,
3 parts of a mixture of the sodi~ salts of saturated fatty
alcohol sulphates,
5 ~cparts of naphthalenesulphonic acid/formaldehyde condensate,
82 parts o~ kaolin.
The active substances are intimately mixed, in suitable mixers,
with the additives, the mixture being then ground in the appropriate mills
and rollers. Wettable powders are obtained which can be diluted with water
to give suspensions of an~ desired concentration.
~sifiable concentrates^
The following substances are used to produce a) a 10% and b) a
25% emulsifiable concentrate:
a) 10 parts of active substance,
3.4 parts of epoxidised vegetable oil,
-- 7 --
~L~4~7
3.4 parts of a combination emulsifier consisting of fatty alcohol
polyglycol ether and alkylarylsulphonate calcium saltg
parts of dimethylformamide,
43~2 parts of xylene.
b) 25 parts of active substance,
2.5 parts of epoxidised vegetable oil,
parts of an alkylarylsulphonate/fatty alcohol-polyglycol
ether mixture,
parts of dimethylformamide,
5?~5 parts of xylene.
From these concentrates it is possible to produce, by dilution
with water, emulsions of any desired concentration.
Spray:
~
The following constituents are used to prepare a 5% spray:
5 parts of active substance,
1 part of epichlorohydrin~
94 parts of benzine (boiling limits 160 - l90 C).
Example 1
0-ethyl-5-n-propyl-0-(4-methylmerca~to-phenyl~-thiophosph_te
12.2 g of triethylamine are added to a solution of 16.8 g of
4-methyl-mercapto-phenol in 150 ml of benzene. While stirring constantly,
24.4 g of thiophosphoric-0-ethyl-S-n-propyl-ester chloride are added drop-
wise at 10 - 15 C0 Stirring is then continued for 12 hours at room temper-
ature. The mixture is washed with water, 3% sodium carbonate solution, and
again with waterg then dried over anhydrous sodium sulphate. The benzene is
distilled off and the residu0 is purified by molecular distillation, to give
27 g of the compound of the formula
~48(~7
2 5\ ~
(n~c3H7s s~3
with a melting point of 125 C/O.OOl Torr; n D = 1.5501. The following
compounds are also manufactured in analogous manner:
2 3
R S >
6 5
~9L8~D~7
_ . .
~d u~
~1 ~1 ~1
~ 11 11 11
R c~
D p~ X ~
..
n
. . , _
~t V ~ ~
~ I ~ X
. _
r~
X 5
.
V ~Q V
~ C~ ~ C`~ ~`;i
.,
,~
r~
~:~ 3
.
U~
0:;
_ _ _ ~_
-- 10 --
-
~4~3~47
. ~ _ .. = .. ,..... ...
.
,~ o u~
U~
R C~f~ C`15 fl C`
. __ . _ _
~D ~
. ., . . , _ I
U~ ~ X ~ C
_ I
~ ~ 0 ~ ~
V
.
~ ~ ~T~ V ~ ~ ~
. . _ ..
C~ ~ ~ X ~q X P~
.
~; ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
~ V ~
,,,, ,.,,,,,,
. ~ . . _ _ . . ..
X :: ~ X
~; ~ ,~ V~ y~ V~ ,~ V~ y~ y~
3~41~47
., ___
R
. .__ ~ . . . . _ ,.
~9 ~ X ~: X
U~ ~ C X
. .. ... . , _____ .
~ c~ c~ c~ ~1 ~ C`l C~ ~ ~
I X ~ ~ ~ O
~ ~ a a ~ ~ ~
~ .
~ O
. . . . ... ..
~ I d
_I ~ ~ ~ ~ ~ ``~
~; ~ X ~ ~ !r ~ C ~ X~ ~-
2z ~ ~ ~ ol~ ~ o
-- 12 --
47
Example 2
Insecticidal ingest ~oison action
Tobacco and potato plants were sprayed with a 0.05% aqueous emwl-
sion (obtained from a 10% emulsifiable concentrate).
A~ter the coating had dried, the tobacco plants were populated
with Egyptian cotton leaf worms (Spodoptera literalis) and the potato plants
with Colorado potatO beetle larvae (~eptinotarsa decemlineata). The test
was carried out at 24 C and 60% relative humidity. In the above test, the
` compounds according tocExample I displayed ingest poison action against
Spodoptera literalis and Leptinotarsa decemlineata.
Example 3
Six rice plants at a time of the variety Caloro were transplanted
into plastic pots (diameter at the top = 17 cm) and reared to a height of
about 60 cm~ I~nfestation with Chilo suppressalis larvae (Ll: 3~4 mm long)
took place 2 days after the active substance had been applied in granule form
to the paddy water (rate of application: 8 kg of active substance per
hectare). Evaluation of the insectieidal action took plaee 10 days after
application of the granules.
The eompo~ds aceording to Example I were active in the above test
against Chilo suppressalis.
ExamF~e 4
Aetion a~ st Aulacophora femoralis, Paehmoda and Chortophila larvae
Sterilised eompost earth was homogeneously mixed with a wettable
powder containing 25% of aetive substance so that there resulted a rate of
application of ~ kg of active substance per hectar~.
Young zucchetti plants (Cucumis pepo) were put into plastic pots
with the treated soil ~3 plants per pot; diameter of pot = 7 cm). Each pot
was infeeted immediately after~ards with 5 Aulacophora femoralis and Pachmoda
- 13 -
i9iV47
or Chortophila larvae. The control was carried out 4, 8, 16 and 32 days
after depositing the larvae.
At 80 - 100% kill after the first control, a fresh infestation with
5 larvae each was carried out in the same soil sample with 3 new zucchetti
plants. If the activity was less than 80%, the remaining larvae remained in
the soil sample until the control immediately following. If an active sub-
stance at a rate of application of 8 kg/ha~still effected a 100% kill7 a
further control with 4 and 2 kg of active substance per hectare was carried
out.
In the above test, the compounds according to Example I displayed
action against Aulacophora femoralis, Pachmoda and Chortophila larvae.
Exam~e_5
ction ag_ nst ticks
-
~) Rhlcephalus burs
Five adult ticks and 50 tick larvae were counted into a glass tube
and immersed for l to 2 minutes in 2 ml of an aqueous emulsion from an
emulsion series each containing lOO~ lO, l and~O.l ppm of test substance.
The tube was then sealed with a standardised cotton wool plug and placed on
its head, so that the active substance emulsion could be adsorbed by the
cotton wool.
In the oase of the adults evaluation took place after 2 weeks, and
in that of the larvae after 2 days. Each test was repeated twice.
B) Boophilus microplus (larvae)
Tests were carried out in each case with 20 OP-sensitive larvae
using an an~logous dilution series as in the case of test A. (The resistance
refers to the tolerability of Diazinon).
The compounds according to Example I acted in these tests against
adults and larvae of Rhicephalus bursa and sensitive and OP-resistant larvae
of Boophilus microplus.
- 14 -
Example 6
Acaracidal action
Phaseolus vulgaris (dwarf beans) have an infested piece of leaf
from a mass culture of Tetranychus urticae placed onthem 12 hours before the
test for the acaricidal action. The mobile stages which have migrated are
sprayed with the e~ulsified tes~ preparations from a chromatography a~omiser
so that the spray broth does not run offO The number of living and dead
larvae, adults and eggs are evaluated after 2 to 7 days under a stereoscopic
microscope and the res~lt expressed in percentages. During the "interim",
the treated plants are kept in gr0enhouse compartments at 25 C.
The compounds according to ~xample 1 were ac~ive in the above test
against eggs, larvae and adults of Tetranychus urticae.
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