Note: Descriptions are shown in the official language in which they were submitted.
1053Z3tj
The present invention relates to thiolphosphoric acid esters, to
processes for their production, and to their use in the control of pests.
The thiolphosphoric acid esters have the formula
R10 \ ¦¦
R2S ~ P-O-R3 (I)
wherein
Rl represents a methyl or ethyl group,
R2 represents an n-propyl, n-butyl or iso-butyl group,
X represents an oxygen or sulphur atom and
R3 represents a group of the formula A, B or C
~ R4 (A)
W
O (B)
8 :~
~ (C) ~
: wherein
: R4 represents an allyl, methallyl, cyanomethyl or O-ethyl-S-n-propyl-
phosphorothiolyl group,
R5 represents a hydrogen or halogen atom or a Cl-C5-alkyl, nitro, cyano,
methylmercapto or methoxycarbonyl group,
R6 represents a hydrogen or halogen atom,
R7 represents a hydrogen or halogen atom or a Cl-C5-alkyl group,
~A~
,.. , ~ .~. .,- .,.. ,.-.... . . ` ~ . .. . . .. .
lOS3~3~
R8 represents a hydrogen atom or an allyl or methylcarbonyl group and
n represents the integer 1 or 2.
By halogen are meant fluorine, chlorine, bromine and/or iodine,
particularly however chlorine.
The alkyl groups applicable for formula I can be branched or
straight-chain. Examples of such groups are: methyl, ethyl, propyl, iso-
propyl, n-, i-, sec.-, tert.-butyl, n-pentyl, and isomers thereof.
Compounds of formula I preferred because of their effectiveness
are compounds of the formula
RIO ~ I O ~ (la)
wherein ( 5)n
Rl represents a methyl or ethyl group,
R2 represents an n-propyl, n-butyl or iso-butyl group,
R4 represents an allyl, methallyl, cyanomethyl or O-ethyl-S-n-propyl-
phosphorothiolyl group,
R5 represents a hydrogen or halogen atom or a Cl-C5-alkyl, nitro, cyano,
methylmercapto or methoxycarbonyl group,
n represents the integer 1 or 2 and
X represents an oxygen or sulphur atom.
Preferably, R4 in formula (Ia) represents allyl or methallyl,
especially the former, particularly in the ortho-position. However, in
formula Ia, R4 may alternatively represent, according to a preferred aspect
of the invention, an 3-ethyl-S-n-propyl-phosphorothiolyl group. In such a
case it is preferred that R5 represents hydrogen.
Another group of compounds of formula I preferred because of their
effectiveness are compounds of the formula -~
R17 ~,
X ~ (Ib)
p_ o ~ O ,L
~ ~ - 2 -
~()53Z3~i
wherein
Rl represents a methyl or ethyl group,
R2 represents an n-propyl, n-butyl or iso-butyl group,
X represents an oxygen or sulphur atom and
wherein
R6 represents a hydrogen atom while
R7 represents a hydrogen atom or methyl group, or
wherein
R6 represents a halogen atom while
R7 represents a hydrogen atom.
Yet another group of preferred compounds of formula I are com-
pounds of the formula
R10 11o ~R8
~ (Ic)
:,
,
wherein
Rl represents a methyl or ethyl group,
R2~ represents an n-propyl, n-butyl or iso-butyl group,
R8~ represents a hydrogen atom or methylcarbonyl group, and
X represents an oxygen or sulphur atom.
~ In all cases, it is particularly preferred in the above formulae
`~ 20 ~ that Rl represents an ethyl group and R2 an n-propyl group.
The compounds of formula I can be produced according to the in-
vention by the following methods known per se:
R10
; la) P - Cl I H0-R3 acid-binding
_
1(~53Z3~;
R O 11
lb) 1 \ P - Cl + MeOR.................................... I
(II) (IV)
The symbols Rl, R2, R3 and X in formulae II, III and IV have
the meanings given in the case of formula I, and Me stands for an alkali
metal, particularly for sodium or potassium, or for an ammonium group
such as, e. g. the group (R4)3 NH ~ wherein R4 represents hydrogen
or alkyl.
X ~ ~:
2) 1 P - Cl + HO-R3 acid-binding X
~ ..... . . .
(V) (III) (VI)
R10 11
P - OR3 + HSR2 acid-binding
(VI) (IIIa)
X :
R10
Cl ,,-' P - OR3 + MeSR2
. .
(VI) (IIIb)
.:
The symbols Rl, R2, R3 and X in formulae II, IIIa, IIIb, V and VI :-
have the meanings given in the case of formula I, and Me stands for an ..
alkali metal, particularly sodium or potassium, or for the group R ) NH '
wheTein R4 represents hydrogen or alkyl.
; ~Al
~ 4
.~ , : . .
1053Z3~
R O S
3a)1 \p O + (R4)3N
,
(VII) (XI) .
Rl
(R4)3N ~ 9 0 \ S
/ P - OR3 + R2Hal
R10
- (VIII) (XII)
1,.
R10 0
.. R S ~ 3
.
3b3 \P O R
., . R10
(VII) . :
.. . . . .
R 0 0
OR3 ~ R2Hal
KS (IX) 1 (XII)
R O O
P - OR3 (X)
2 :.-.
;~ The symbols Rl, R2 and R3 in formulae VII to XII
have the meanings given in the case of formula I, R4
stands for an alkyl radical, and Hal or a halogen
a~om euch as chlorine, bromine or iodine.
- 5 -
'A~``
~()5323~;
Suitable acid-binding agents are: tertiary amines,
e.g. trialkylamines, pyridine, pyridine ~ases, dialkyl
anilines; inorganic bases such as hydrides, hydroxides;
carbonates and bicarbonates of alkali metals and
alkaline-earth metals.
It is sometimes necessary in performing the reactions
to use catalysts,such as, e.g. copper or copper chloride.
The processes la and lb, 2 and 3a and 3b are carried
out at a reaction temperature of between 0 and 130C,
at normal pressure and in solvents or diluents.
Suitable solvents or diluents àre, e.g. ethers
and ethereaL compounds, such as diethyl ether, dipropyl
ether, dioxane, tetrahydrofuran; amides such as N,N-
dialkylated carboxylic acid amides; aliphatic, aromatic
as well as halogenated hydrocarbons, especially benzene,
toluene, xylenes, chloroform, chlorobenzene; nitriles
such as acetonitriles; DMS0, ketones such as acetone,
methyl ethyl ketone, and waterO A further suitable
solvent in the case of processes 3a and 3b is ethanol.
The starting materials oE formulae II, V and VII
can be produced by methods analogous to known methods,
e.g. those described in "Organic Reactions II", pp. 1 to 48.
The compounds of formula I have a broad biocidal
action, and can be used for the control of diverse
; 25 plant and animal pests. Surprisîngly, they have a better
~ action against, for example, larvae of Spodoptera littoralis
.-
6 ~
r~.
1~)53Z36
than-analogous compounds from the German Patent 1,164,408
have. Furthermore, the compounds of formula I are
suitable also for the control of all development stages,
such as, e.g. eggs, larva~, pupae, nymphs and adults of insects
of the families: Acrididae, Blattidae, Gryllidae,
Gryllotalpidae, Te~tigoniidae, Cimicidae, Phyrrhocoridae,
Reduviidae, Aphididae, Delphacidae, Diaspidae,
Pseudococcidae, Chrysomelidae, Coccinellidae, Bruchidae,
Scarabaeidae, Dermestidae, Tenebrionidae, Curculionidae,
Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleridae,
Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae,
Trypetidae, Pulicidae, as well as acarids of the
families: Ixodidae, Argasidae, Tetranychidae,
Dermanysidae.
The insecticidal or acaricidal action can be substantially
broadened and adapted to suit the given circumstances by the addition
of other insecticides and/or acaricides.
According to another aspect of the invention, there is pro-
vided a pesticidal composition comprising (i) a compound of formula (I)
as defined above in intlmate admixture with at least one of the
following:
tii) a solid extender;
(iii) a surfactant; or
(iv) an aerosol propellant.
According to yet a further aspect of the invention, there is
provided a method of combatting pests at a locus, which method comprises
applying to the locus a compound of formula (I), as defined above.
Pests particularly envisaged are insects or representations of the class
Acarina.
' :
.. . . .
.
~5;~Z3~
The compounds of formula I can be used on their
own or together with suitable carriers and/or additives.
Suitable carriers and addi~ives may be solid or liquid,
and correspond to the substances co~mon in formulation
practice, such as, e.g. natural and regenerated substances,
solvents, dispersing agents, wetting agen~s~ adhesives,
thickeners, binders and/or fertilisers.
For application, the compounds of formula I can
be processed into the form of dusts, emulsion concentrates,
granulates, dispersions, sprays, or solutions, the formul-
ation of these preparations being effected in a manner
commonly known in practice. Also to be mentioned are
cattle dips and spray races, in which aqueous prepar--
ations are used.
The agents according to the invention are pro-
duced in a manner known per se by the intimate mixing and/or
grinding of active substances of formula I with the suitable
carriers, optionally with the addition of dispersing agents
or solvents which are inert to the active substances. The
actire substances can be obtained and used in the ~ollow-
ing preparation forms;
solid preparations: dhsts~ scattering agents~ granulates
coated granulates, impregnated granulates
and homogeneous granulates;
li~uid preparations:
a) water dispersible activç substance concentrates;
wettable powders, pastes3 emulsions;
b) solutions
., . : . . ...
l~S32~
The solid preparations (dusts, scattering agents~
are produced by the mixing of the active substances with
solid carriers. Suitable carriers are, e.g. kaolin5 tal-
cum~ bole, loess~ chalk~ limestone, ground limestone, at-
tapulgite, dolomite, diatomaceous earth, precipitated
silicic acid, alkaline-earth silicates, sodium and pot-
assium aluminium silicates (feldspar and mica~, calcium
and magnesium sulphates, magnesium oxide~ ground syn-
thetic materials, fertilisers such as ammonium sulphate,
ammonium phosphate, ammonium nitrate, urea, ground veg-
etable products such as bran, bark dust, sawdust~ ground
nutshells~ cellulose powder, residues of plant extractions
active charcoal, etc., alone or in admixture with each
other.
Granulates can be very easily prepared by a
process in which an active substance of formula I is dis-
solved in an organic solvent7 the thus obtained solution
applied to a granulated mineral, e.g. attapulgite, SiO2,
granicalcium, bentonite, etc., and the organic solvent then
evaporated off.
It is possible also to produce polymer granulates;
in this case the active substances of formula I are mixed with
polymerisable compounds (urea/formaldehyde; dicyandiamide/
formaldehyde; melamine/formaldehyde, or others); polymerisation
is then carefully carried oRt in a ~anner which leaves the active
.ubstances unaffected, and granulation performed actually,
during the gel forming process. It is more favourable, however,
~05;~Z3~
to impregnate finished porous polymer granules (urea/
formaldehyde, polyacrylonitrile, polyester and others~,
having a specific surface area and a favourable predeterminable
adsorption/desorption ratio, with the active substances,
e.g. in the form ot` their solutions (inna low-boiling
solvent), and to then remove the solvent. Polymer granulates
of this kind can be also sprayed in the form of microgranulates
having bulk weights of preferably 300 g/litre to 600 g/litre~
with the aid of spray apparatus. Spraying can be carried
out over extensive areas of useful plant crops by the use
of ae~hanes.
Granulates can also be obtained by the compac$ing of
the carrier material with the active substances and additives,
and a subsequent reducing operation.
Moreover, it is possible to add to these mixtures,
additives stabilising the active substance and/or nonionic,
anion-active and cation-active substances which improve, e.g.
the adhesiveness of the active substances on plants and
parts of plants (adhesives and agglutinants)~ and/or ensure
a better wettability (wetting agents) as well as dispersibility
(dispersing agents).
The following substances are~ for example~ suitable:
-10- '
. ~ :
1~53Z;~i
olein/lime mixture~ cellulose derivatives (methyl cellulose,
carboxymethyl cellulose~, hydroxyethylene g~ycdlethers of
monoalkyl and dialkyl phenols having 5 to 15 ethylene oxide
radicals per molecule and 8 to 9 carbon atoms in the alkyl
radical, lignin-sulphonic acid, the alkali metal and alkaline-
earth metal salts thereof, polyethylene glycol ethers (carbo-
waxes3~ fatty alcohol polyglycol ethers having 5 to 20
ethylene oxide radicals per molecule and 8 to 18 carbon
atoms in the fatty alcohol moiety condensation products
of ethylene oxide, propylene oxide, polyvinyl-pyrrolidones,
polyvinyl alcohols, condensation products of urea and
formaldehyde, as well as latex products.
~ater dispersible concentrates of active sub-
stances, i.e. wettable powders, pastes and emulsion con-
centrates are agents which can be diluted with water to
obtain any desired concentration. They consist of active
substance, carrier~ optionally additives which stablise the
active substance, surface-active substances, and anti-foa~m
agents and, optionally, solvents
The wettable powders and pastes are obtained by
the mixing and grinding of the active substances with dis-
persing agents and pulverulent carriers, in suitable devices
until homogeneity is obtainedO 5uitable carriers are, e.g.
those previously mentioned in the case of solid preparations.
It is advantageous in some cases to use mixtures of different
carriers. As dispersing agents it is possible to
,.
- , . . .
~l~53Z3~
use, e.g.: condensation products of sulphonated naphthalene
and sulphonated naphthalene derivatives with formaldehyde,
condensation products of naphthalene or of naphthalene-
sulphonic acids with phenol and formaldehydeJ as well as
alkali, ammonium and aIkaline-earth metal salts of lignin-
sulphonic acid~ also alkylarylsulphonates, alkali metal salts
and alkaline-earth metal salts of dibutyl naphthalenesul-
phonic acid, fatty alcohol sulphates such as salts of sul-
phated hexadec~nols~ heptadecanols, octadecanols, and salts
of sulphated fatty alcohol glycol ethers, the sodium salt
of oleyl methyl tauride, ditertiary ethylene glycols,
dialkyl dilauryl ammoni~ chloride, and fatty acid alkali-metal
and alkaline-earth metal salts.
Suitable anti-foam agents are, e.g. silicones.
The active substances are so mixed, ground~ sieved
and strained with the above mentioned additives that the
solid constituent in the case of wettable powders has a
particle size not exceeding 0.02 to 0.04 mm, and in the
case of pastes not exceeding 0.03 mm. For the preparation
of emulsion concentrates and pastes, dispersing agents are
used such as those mentioned in the preceding paragraphs,
organic solvents and water. Suitable solvents are~ e.g.
alcohols, benzene, xylene, toluene~ dimethylsulphoxide~
and mineral oil fractions boiling in the range of 120 to
350 C. The solvents must be practically odourless non-
phytotoxic, and inert to the active substances.
. ... ..
l~S3Z3~
Furthermore, the agents according to the invention
can be used in the form of solutions. For this purpose, the
active substance or several active substances, of the general
formula I is dissolved in suitable organic solvents, solvent
mixtures, or water. As organic solvents it is possible to
use aliphatic and aromatic hydrocarbons, their chlorinated
derivatives, al4ylnaphthalenes, mineral oils on their own
or in admixture with each other.
The content of active substance in the above de-
scribed agents is between 0.1 and 95~0; it is to be mentioned
in this connection that in the case of application of the
agents from an aeroplane~ or by means of some other suit-
able application devices, concentrations of up to 99.5%
can be used~ or even the pure active substance.
The active substances of formula I can be pre-
pared, e.g. as ~ollows:
~usts:
The following substances are used for the prep-
aration of a) 5% dust, and b) a 2% dust:
a)5 parts of active substance
95 parts of talcum
b)2 parts of active substance
1 part o~ highly dispersed silicic acid
97 parts of talcum~ -
The active substances are mixed and ground with the
carriers.
13
1/~53Z36
Granulate:
_ .
The following substances are used to produce a
5 % granulate:
5 parts of active substance,
0.25 parts of epichlorhydrin,
0.25 parts of cetyl polyglycol ether,
3.50 parts of polyethylene glycol,
91 parts of kaolin (particle size 0.3 - o.8 mm).
The active substance is mixed with epichlorhydrin
and dissolved with 6 parts of acetone; the polyethylene
glycol and cetyl polyglycol ether are then added. The
thus obtained solution is sprayed on to kaolin~ and
the acetone subsequently evaporated in vacuo.
Wettable powder:
The following constituents are used for the prep-
aration of a) a 40%, b~ and c) a 25%, and d) a 10% wettable
PWder:
a) 4 parts of active substance,
5 parts of sodium lignin sulphonate,
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 cell~lose
mixture (1~
105 parts of sodium dibutyl naphthalene sulphonate,
1905 parts of silicic acid
14
'. . . ' ' . ~ ::',. '
1~53Z3~
19.5 parts of Champagne chalk,
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 aluminiu~ silicate,
16.5 parts of kieselguhr~
46 parts of kaolin.
d) 10 parts of active substance,
3 parts of a mixture of the sodium salts of
saturated fatty alcohol sulphates~
5 parts of naphthalenesulphonic acid/formaldehyde
condensate,
82 parts of 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 pow-
ders are obtained which can be diluted with water to give
suspensions of any desired concentration.
Emulsifiable 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,
~ '
.,
.
. - . ~ : ~ . . . . .
105;~;236
3.4 parts of a combination emulsifier consisting
of fatty alcohol polyglycol ether and alkylaryl-
sulphonate calcium salt,
40 parts of dimethylformamide,
43.2 parts of xylene.
b) 25 parts of active substance
2~5 parts of epoxidised vegetakle oil~
10 parts of an alkylarylsulphonate/fatty alcohol-
polyglycol ether mixture
5 parts of dimethylformamide~
57~5 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 epichlorhydrin~
94 parts of ligroin (boiling limits 160-190C)
16
- - . - ~ - ~, . .. . . . :
~s~z;~;
Example 1
0-Eth~ S-n-propyl-0-(2-al~yl-4-~hlorophenyl)-thiol-
phosphate
An amount of 10.12 g of triethylamine is added to a
solution of 16.86 g of 2-allyl-4-chlorophenol (B.P
133C/16 Torr) in 100 ml of benzene. An addition is then
made dropwise at 10 - 15C, with continuous stirring,
of 20.3 g of 0-ethyl-S-n-propylthiolphosphoric acid
chloride; stirring is subsequently continued for 12
hours at room temperature. The mixture is washed with
water, with a 3% Na2C03 solution, -and again with water,
and dried over anhydrous sodium sulphake. The benzene
is distilled off and the residue purified by means of
molecular distillation. There is thus obtained the
compound of the formula
Cll-CH -CH
C2115\ ~1 ~ 2 2 ;
P - 0~ /~-Cl
(n)C3H7S . ~-
having a refraction of n20 = 1.5306 and a B.P. of
124C/0.1 Torr.
The following compounds too are obtained in an
analogous manner:
"
:
~ /7
. . - ~ . ......... . . . .. .
lQS3Z36
C H 0 0
2 5 \l~
(n)c3~17s ~ n~2~ 1.5765
C H 0` 0
2 5 \ ~
P - 0--~\,~ CH2CN n~20 1 . S262 ~:;
(njC H 5/ ~r~ n3 : 1,5213
CH2 - CH=CH2
, '
2 5\ ;I g ~C2H5 ~ 1,5205
( ) 3 7S SC3H7
CH3
2 5 ~ ,l ~
P - O ~J~0,~- nD2~ 1. 5694
(n ) C3H7 S
.
.
~', ' , '. ' -' .,
1 8
-d~--' .
s~
CH2 - CH=CH2
C2H5\ !~
(n)C3H7s/ ~^~ . nV20 . 1 . 5~4
.
CH2 ~ CH-CH
P - 0 ~ C l nI~20: 1. 5415
(n)C3H7S Cl~
Cl
2 5 \ jj ,'~ 23
~ p _ o ~ Cl nD : 1. 5413
(n) C3H7 S j~ ~
CH2 - CH=CH2
CH2-CH=CH2
C2H50 ~ O >~ , . . .
(n~C3H7S ~ _ Br
Br
1 3
CH2 - C=CH
/P -0--~--Cl nD23: 1~5330 ~:.
(n)C3H7S
CH2 - CH=CH2
~2H50 01 ~
P _0 _~ nD23: 1. 5395
(n ) C3EI 7 S i-~
~2
~ ' ' , ' tq
_ ~ _
- . - .
.,
~5323~; -
CH2 CH=C~12
P - ~ 2 1
(n ) C3117 S
CH2CH=CH2
( ) 3 7S --COOCH3 nD23~269
CH2CH=CH2
C2H50~ 0 ~ -
(n)C3H7S/
C2H5\
/ P ~ O ~ nD23:1. 52û4
~) 3 7 ~ ~:
(n)
C2H5
5(n)C3H7S /C2H5 nD23:1~5196
3 7 (n)
~l. ' ' .
.. ,.. ~ ,~o
lg~S;~Z36
.. . . . . ...
2 5/~ C 2H5 2
(n)c3H7~> V <~C3H (~) nD L~ ~342
3 7 nD3: l, 5707
.
0 CH2CH=CH2 :
C~ 0\ 11 >=~
(n)C3H7S~P~ nD~: 1.5417
0 CH --CH=CH
3>CH-CH2~ nD: 1.5270
.: :-
.. . . .. . . . .. . .. . . . .
... . . . ..
lC~S~23~
C112C~-I=C112
C2~-150~ 0 `,
~P -O~_ Cl n20: 1~5265
CH2 - CH=C}12
n-C3H7S 5 ~3-- Cl nD3: 1.5542
CH2 -CH=CH
~P - ~t-- 3r nD3: 1.5640
CH CH C~l
- O~ Cl nD: 1.5587
C2H5` _~ / OC2~15
Sn-c3H7s/ S SC3H7
C2H5\ OU3
P - O~ ~0 n20: 1.5776 -
n-C3H7S S
, .
r,~..
1~?53Z~6
n C H S/ S ~ 3 n20: 1. 5890
C2H5\ ~Y-~
n~C H S ~ ~
3 7 CH CH-CH
/ 1 \J~ cH2cN
n-C3H7S ~ . ~
I H3
CH2 - C-CH
P - O_~ CI
.
2 S \ ~ ~ ~OC2H5
/P ~ ~\-- P~\ -
n C3H7S ~ ` 1 S SC3 7(n)
: ' - ',
C2H5 f~`' ~
/p o~ o n23 c 1, s780
,
' ~ '- '
, ,- . .
- ~
.. ... .. . . . ..
, . . . ~ , . ~ ,.. .
~5;123~i
(n)c3H S >ll ~ n23~ 6~6
C2H50 >p_O ~ CO~
(n)~3H7S ll ~ 3 n23~ 812
. ' '' ~ '
.. . .
; (n)C H S>ll ~ SCH3 n : 1.5525
O CH -CH=CH D
:
,
2X5> _<~aN
(n)C3H7S 11 22
O CH2-CH=CH2 nD : 1.5349
o ~cH~\cH
2H5 ~ ~ O/c=o M.P. : 56 C
Br
i~
,
.:
lQ53Z36
... . .. ... . . . .. . . ... . .. .. .. . . . . . . .
. . o
(n)C3~7S\ 11 /:~\
C2H O ~ ~ Cl nD3: 1.5330
CH2-CI-CH
3 ~
':
O CH -CH=CH . ~:-
( 3 ; ~ P- ~ H3 2 nD3: 1.5215 ~
.. ..
`
,
( ) 3 7 ~ ~ 23
C H O> ~ nD: 1,5335
2 5 CH2-CE=CH
: . .
O C~l ' ,
(n)C3H7S\ 11 ~ ' . ,',:
P- ~\ /~ CH2-CH=CH2 23, 1 2
2 5 Cl ~ nD ~541
CH --CH CH
(n)C3H7S\ 11 ~al 2 :- .
`; C2H 0~ ~ nD3: lts4la
o aH3
; ~ 2 5 ~ -O D
., :. ~ .
.
. ~ - ~ . ...
.. .. .
:
1 ~ ~ 3~ 3
Example 2
.
A) Insecticidal stomach poison ac_ion
Cotton and potato plants were sprayed with a 0.05%
aqueous active-substance emulsion (obtained from a 10%
emulsifiable concentrate).
After the drying of the obtained coating, Spodoptera
litoralis or Heliothis virescens larvae L3 were placed
onto the cotton plants, and Colorada beetle larvae
(Leptinotarsa decemlineata) onto the potato plants. The
test was carried out at 24C with 60% relative humldity.
The compounds according to Example 1 exhibited in the
above test a good insecticidal stomach poison action
against Spodoptera litoralis, Heliothis and Leptinotarsa
decemlineata larvae.
B) Systemic insecticidal action
In order to determine the systemic action, rooted bean
,
plants (Vicia faba) were placed into a 0.01% aqueous active-
substance solution (obtained from a 10% emulsifiable
concentrate). After a period of 24 hours, bean aphids (Aphis -
fabae)~ were placed onto the parts of the; plants above the
2a ~ soil.~ The~insects were protected by a special device from
the~e~ffects of contact and~of gas. The test was carriet
out~at~;24~C with 7070 relative humidity.
In~the~above tests, the compounds according to Example 1
~c~ exhlbited a systemLc action ag-inst Aphis fabae.
aG
.
l~)S;~Z3~
Example 3
ActLon_a ~ lnst Chilo suppressalis
Rice plants o~ the type Caloro were planted, 6 plants
per pot, in plastic pots having a top diameter of 17 cm,
and grown to a height of ca. 60 cm. Infestation with -
Chilo suppressalis larvae (Ll; 3-4 mm long) was carried
out 2 days after application of the active substance in
granular form (amount applied = 8 kg of active substance
per hectare) to the paddy water. The evaluation of the
insecticidal action was made 10 days after application ~-
of the granules. ~;
The compo~mds according to Example 1 were effective
against Chilo suppressalis in the above test.
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Example 4
Action_a~ainst ticks
A) Rhipicephalus bursa
In each case, S adult ticks or 50 tick larvae were
placed into a small glass test tube, and the test tubes
then immersed for 1 to 2 minutes ;n 2 ml of an aqueous
emulsion from a dilution series of 100, 10, 1 and 0.1 ppm
of test substance. The tubes were then sealed with a
standardised cotton plug, and inverted so that the
active substance emulsion could be absorbed by the
cotton wool.
An evaluation in the case of the adults was made after
2 weeks, and in the case of the larvae after 2 days.
There were two repeats for each test.
B) Boophilus micro~lus (larvae)
With a dilution series analogous to that in Test A,
tests were carried out with 20 sensitive larvae and
OP-resistant larvae, respectively (resistance is with
respect to diazinon compatibility).
The compounds according to Example 1 were effective
~-20 ; in these tests against adults and larvae of Rhipicephalus
bursa and against sensitive and OP-resistant larvae,
respecti~vely, of Boophilus microplus.
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1~3Z36
Example S
Acaricidal action
Phaseolus vulgaris (plants) were infested, 12 hours
before the test for acaricidal action, with an infested
piece of leaf from a mass culture of Tetranychus urticae.
The transferred mobile stages were sprayed with the
emulsified test preparations from a chromatography-sprayer
in a manner ensuring no running off of the spray liquor.
An assessment was made after 2 to 7 days, by examination
under a binocular, of the living and of the dead larvae,
adults and eggs, and the results expressed in percentages.
The treated plants were kept during the "holding time"
in greenhouse compartments at 25C.
The compounds according to Example 1 were effec~ive
in the above test against adults, larvae and eggs of
Tetranychus urticae.
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