Note: Descriptions are shown in the official language in which they were submitted.
1~48929
O, O-dialkyl dithiophosphoryl methyl halo-6- benzoxazolones
have been proposed as insecticides and miticides or acaricides in Fren.ch
patent No. 1, 277, 401 and British patent No. 1, 005, 372 to Rhone-Poulenc.
Certain of these compounds also are indicated as possessing parasiticidal
properties, in British patent No. 1,164, 028 and French patent No. 1, 482, 025
to Rhc-ne-Poulellc. It has nc,t howe-ver been suggested that mixtures of these
compounds with other phosphate esters be employed or ha~e advantageous
properties .
Phosphate esters such as S-(1, 2-dicarba~oxyalkyl) O, O-
dia kyl dithiophosphates ha~Je also been known as insecticidal. Such
compounds were develo~ed in Germany during World War II, and became
available following the war upon release of previously secret German
technology in this field. However, these have not been proposed for
comblnation with other phosphate esters.
In accordance with the invention, it has been determined
that a mixture of these two types of phosphate esters is synergistically
more effecti~e than either ester taken alone, and that the mixture is
particularly effective aga.inst arthropods, such as insects and mites.
These two types of compounds are sufficiently similar in structure, since
both have a phosphate or thiophosphate nucleus witll two homologous alkoxy
substituents al:tached thereto, that it is surprising tha'c one has a synergistic
- or activity-enhancing effect on the other, when used in combination.
The O, O-dialkyl diphosphoryl methyl halo-6-benzoxazolones
employed in the ~ynergistic mixtures of the invention have the structure:
~ '
1~)48929
X ~ ~= o ~ ~
J_ N--CH~--X2--~ I
Y ~1
wherein X represents a hydrogen or halogen atom, such as fluorine, chlorine,
bromine, or iodine; R and Rl represent alkyl groups containing from one to
about four carbon atoms, Xland X2 represent an oxygen or sulphur atom, and
Y represents an oxygen or sulphur atom. Xl X2 and Y can be the same or
different.
Preferably, Xl is oxygen, X2 is sulfur and R and Rl are ethyl,
in which case the compound is phosalone, O, O-diethyl dithiophosphoryl
methyl-3-chloro-6-benæoxazolone. This compound has the structure:
- Cl ~ ~_ O
~1~ CH2--S--ll(OC2Hs)2
S
Also useful is 0, O-diethyl-dithiophosphoryl methyl-3-
benzothiazolone .
Additional compounds which can be used include:
~0~8~Z9
N--CH2--S--11 --(OC2H~)2
S
Cl ~N--CH2S--P -- (OC H )
Cl ~56`~ =o
~ N--CH2--S--11 --(OCH3)2
Cl f ~ ~--
~N ' CH2--S--11 --(OC3H7)2
Cl ~O~=o
N--CH2--S--11 --(OC.4Hg)2
1~)489Z9
CL ~ H2--S--11 --(OC2Hs)2
C1 ~ r . CHZS--~ OC2H5)2
C1 _~ S ~ O
~.N--CH2--S--~ CH3)2
- - S
1~ Cl ~S ~=o
~N--CH2--S--11 --(OC3~7)2
'
C1 ~S~_O
N--C~I2--S ~ (0~4H9)2
3a
1~)4~929
Cl ~~
b~ N - CH2--O--11 --(OC2H5~2
o
' ~~=o
Cl ~N--CH2-O-II --(OC2H5)2
O . .
Cl _~0 ~=o
~ N--CHz----11 --(C~3)2
Cl ~ ~--
N--CH2--O--11 --(OC3~I7)2
C~ .
Cl--'~0~ o
~ N--CH2--O--11 --(OC4Hg)2
0
~ 4
1~89Z9
Cl ~S ~=o
~_ N--CH2--O~ (OC2EIs)2
O
~S~_o
Cl --:~,~N--CH2-O~ (OC2Hs)2
O
Cl r~S~=O
.N--CH2--O--11 --(OCH3)2
O
Cl ~=
~, N--CH2--O--11 --(OC3H7)2
Cl--~S~=o
1~ N--CH2--O--11 --(CgH9)2
0
1~)48929
Cl ~~0
1~ N--CH2--S--11--(C2H5)2
Cl ~X CH S--P--(OCzHs)2
o
Cl ~s~~_o
1~~ N--CH2-- S--11 --(OCH3)2
o
Cl ~jl'~=
N--CH2--S ~ (OC3H7)2
o
Cl--~0~_ o
~ N--CH2--S--îl --~oc~H9~a
1~ 0
~,CP 5 .
1~)489Z9
Cl ~`~S~=o
~ ~--CH2--S-- I--(OC2H5)2
~S~=o
Cl ~,L-_N--CH2S ~ (OC2H5)2
O
Cl ~S~ S~_o
~N--CH2--S--11 --(OCH3)2
O
Cl ~S~=o ' '
~N--C~I2--S--11 --(OC3~I7)2
Cl ~S ~_ O
N--CH2--S--11 --(Oc4~s)2
5a
1~413929
Cl ~/ ~_o
l~ N--CH2--O--11--(OC2H6)2
Cl ~N--CHA-O-P--(OC,Hs¦
Cl _~O~=o
~ __N--CH2--O--P--(OCH3):2
Cl ~~
~ N--CH2--O--11 --(OC3H7)2
Cl--~0~= o
N--CH~--O--11 --(OC4Hg)2
~ 6
1048~29
Cl ~S ~=O
N--CH2--O~ (OC2~I5)2
, ~S~_o
Cl ~ T
Cl _~S~=o
N--CH2--O--11 --(OCH3)2
. ~
Cl ~S~=o
I~N--C~2--O--11 --(0C3H7)2
.
Cl ~S~--O
~ N--CH2--O--11 --(OC4Hg)2
S
6a
1(~48929
The O, O-dialkyl-(1, 2-dicarbalkoxy alkyl) diphosphates
have the structure:
R2--O X O
\ 113 11
P--X4--CH--C--O--R4 II
. 5 R3--O/ ¦ e
CH2--O--OR5
wherein X3 and X4 are oxygen or sul~ur, and can be the same or di~erent;
and R2, R3, R4 and R5 are alkyl groups having from one to about four
carbon atoms, and can be the same or different.
Preferably, X3 and X4 are sulfur, R2 and R3 are methyl,
11) and R4 and R5 are ethyl, in which case the compound is malathion.
Other compounds in this class include:
1~48929
CH3--o ~ S O
P--S--CH--C--O--C2H5
CH3--O / ¦ O
CH2 --C--O--CH3
C2H2--O~ S Oj
P--S--CH--C--O--CH3
CH3--O / ¦ O
Il
CH2--C--O--CH3
C3H7--O~SI 1l
10P--S--CH--C--O--C2H5
C3H7 --O/ ¦ O
. CH2--C--O--C2H5
C4H~3--O~SI l
P--S--CH--C--O--CgHg
15C4Hg--O/ ¦ O
CH2--C--O--C4H9
CH3--~) S 1l
P--S--CH--C--O--CH3
CH3--O I I .
CH2--C--O--CH3
1~)489Z9
CH3--O 1
P--O--CH--C--O--C2H~
CH3--O/ ¦ O
CH2--C--O--CH3
C2H2--O~ O lî
P--O--CH--C--O--OE13
CH3--O / I O
l 11
CH2--C--O--CH3
C3H7--O~ O O
P--O--CH--C--O--C2H,
C3H7--O/ ¦ O
CH2--C----C2~5
C4Hg--\ l
- P--O--CH--C--O--C4H9
C~H9--o/ ¦ O
- CH2--C--O--C4H9
CH3--o~ 11 1
P--O--CH--C--O--CH3
CH3--O/ ¦ l
CH2--C--O--CH3
1048929
CH3--O ~ S O
P--O--CH--C O--C2H,
CH3--O ¦ O
CH2--C--O--CH3
C2~2 - \ 11 8
P--O--CH--C--O--CH3
CH3--O/ ¦ ¦
CH2--C--O--CH3
C3H7--O~ 1 1
P--O--CH--C----C2H5
C3H7--O/ ¦ O
CH2--C--O--C2H5
C~Hg--O~S
P--O--CH--C--O--C4Hg
C~H5--O/ ¦ 1l
CH2--C--O--C4Hg
CH3--O~ 11 1
~ P--O--CH--C--O--CH3
CH3--O/ ¦¦ .
C~2--C--O--CH3
1~48929
CH3--O~O
~P--S--CH--C--O--C2HD
CH3--O ¦ O
CH2--C--O--CH3
C2H2--~ O
P--S--CH--C--O--CH3
CH3--O/ - ¦ 1l
CH2--C--O--CH3
C3H7--O~ O 1
P--S--CH--C--O--C2H5
C3H7 --O ¦ O
CH2--C--O--C2H5
C,~Hg--O~ f 11 ~
P--S--CH--C--O--C4Hg
CgHg--O ¦ O
CHz--C--O--C,~H~
CH3--O~O I -
P--S--CH--C--O--CH3
CH3--O/
CHz-- C--O--CH3
1~)48~29
The proportions of each phosphate ester can be widely varied, but
in general a synergistically enhanced arthropodicidal, i. e., insecticidal
and miticidal, effect is obtained at ratios of 0, O-dialkyl-diphosphoryl
methyl-halo-6-benzothiazolone to 0, O-dia~kyl~ 2-dicarba~koxyalkyl)
diphosphate within the range from 0.225:1 to 50:1; and preferably from 10:1
to 20:1.
The compositions of the invention show excellent pesticidal
activity against all orders of harmful insects, and suborders of harmful
mites and ticks.
Exemplary insects are Thysanura such as the silverfish
Lepisma saccharina; Orthoptera such as the German cockroach Blattela
germanica; Isoptera such as the termite Reticulitermes santoninsis;
Dermaptera such as the earwig Forficula auricularia; Anoplura such as
the hog louse Haematopinus suis; Mallophaga such as the chicken body louse
Menacantl us stramineus; Thysanoptera such as the citrus thrip
Scirtothrips citri: Hemiptera such as the tarnished plant bug Lygus
lineolaris; Homoptera such as the rosy apple aphid Dysaphis plantaginea
and the pear psylla Psylla pyricola, Coleoptera such as the plum curculio
Conotrachelus nenuphar and the striped cucumber beetle Acalymma vittata;
Lepidoptera such as the southern armywormSpodoptera eridania and the
codling moth Laspeyresia pomonella; Diptera such as the apple maggot
Rhagoletis pomonella and the cherry fruit fly Rhagoie~is cingulata;
Siphonaptera such as the dog flea Ctenocephalides canis; Hymenoptera
such as the rose sawfly Caliroa aethiops and springtails (Collernbola).
The compositions according to the present invention are
especlally effective when combating representatives of the order Acarina.
Exemplary suborders of mites and ticks are Mesostigmata such as the
~048929
chicken mite, Dermallyssus gallinae; Ixodides such as the ~merican dog
tick, Dermacentor variabilis; Sarcoptiformes such as the itch mite Sarcoptes
scabiei; Trombidiformes such as the maple bladdergall mite Vasates
quadripedes, the twospotted spider mite Tetranychus urticae, and the
-
European red mite Panonychus ulmi.
The compositions of the invention are also very effective
against member-s of the class Diplopoda (millipedes)and the orders
Isopoda (sowbugs) and Araneida (spiders).
These compositions can include the two insecticides-
acaracides and also if desired inert carriers and/or other additives known
to be useful in insecticidal-acaricidal compositions.
These compositions can include the two arthropodicides
and also if desired inert carriers and/or other additives known to be
useful in insecticidal acaricidal compositions. The inert carriers and
additives can be solid or liquid, and include mineral salts, solvents,
diluents, dispersing agents, emulsifiers, wetting agents, adhesives,
thickeners, binders and fertilizers. Biocidal compounds can also be
added, such as the ureas, the saturated or unsaturate~ h~logen-fatty acids,
halogenobenzonitriies, halogenobenzoic acids, phenoxyalkyl-carboxylic
acids, triazines, nitroaLkylphenols, organic phosphoric acid compounds,
quaternary ammonium salts, sulphamic acids, arsenatqs, arsenites,
borates or chlorates.
The compositions can be in the form o~ solutions,
emulsions, suspensions, granules or dusting agents, The forms of
application depend on the end uses and ensure that the active substances
are finely distr-ibuted.
1~8~29
The content of active arthropodicides according to the
invention is withill the range from û. 1 and 95~C- For application from
a.ircraft or other sultable forms, concentrations of up to 99. 50`/G or even
pure active substance combinations can be employed.
Solutions are prepared using solvents for the arthropodicides
such as aliphatic alcohols~ for example ethyl alcohol or isopropyl
alcohol, aliphatic ketones, such as acetone or cyclohexanone, a.liphatic
hydrocarbons, such as kerosene, and cyclic hydrocarbons, such as
benzene, toluene, xylene, tetrahydronaphthalene, alkylated naphthalenes,
chlorinated hydrocarbons, such as tetrachlorethane and ethylene chloride,
and mineral a.nd vegetable oils or mixtures of the abo~e mentioned
substances .
Aqueous preparations in the form of emulsions and
dispersions are especially useful. The active arthropodicides according to
the invention, suitably in solution in a solvent, are homogenized in water,
preferably by means of wetting agents or dispersing agents; quaternary
ammonium compounds may be mentioned as examples of cationic emulsifiers
or dispersing agents; soaps, aliphatic long-chain sulphuric acid monoesters,
aliphatic-aromatic sulphonic acids and lone-chain alkoxyacetic acids may
be mentioned as examples of anionic agents; any polyglycol ethers of
fatty alcohols or ethylene oxide condensation products with p-tert--
alkylphenols may be mentioned annongst non-ionic agants.
It is also possible to formulate concentra$es of the
active substance, emulsifier or dispersing agent, and optionally
solvents. Such concentrates can be diluted before use, for example,
with water.
1~)48929
Dusting ~gents can be made by mixing or grindin~ the
active arthropodicides according to the invention with a solid carrier.
Solid carriers are, for example: talc, diaton~aceous earth, kaolin,
bentonite, calcium carbonate, boric acid and tricalcium phosphate,
5 wood flour, cork powder, charcoal and other materials of vegetable
origin. Alternatively, the substarlces can be absorbed on the carriers,
using a volatile solvent. Pulverulent preparations and pastes can be
made capable of suspension in water, and used as spraying agents, by
adding wetting agents and protective colloids.
In many cases the use of granules for gradual release
of the active substance combination over a prolonged period of time
is of advantage. These can be manufactured by dissolving the active
substances in an organic solvent, absorbing this solution by a granular
material, for example attapulgite or SiO2, and removing the solvent.
15 They can also be manufactured by mixing the active substance
combination with polymerisable compounds, after which polymerisation
is carried out which leaves the active substances unaffected, the
granulation being carried out whilst the polymerisation is still proceeding.
The following Examples in the opinion of the inventors
20 represent preferred embodiments of the invention.
.
1~489Z9
EXAMPLE 1
The toxicity response from Tetranychus urticae Koch
treated with (1) Zolone 34. 8~c EC (phosalone), (2) Malathion 95~Zc Tech,
and(3) combinations of Zolone EC and Malathion Tech, was studied
in the following experiments:
Mites used in this study were obtained from a
University of Kentucky greenhouse culture maintained free from
phosphate ester acaricide contact (phosphate-susceptible strain),
and a New Jersey culture maintained in contact with phosphate ester
acaricide (phosphate-resistant strain).
Thirty 8 day old T. urticae ~ mites were dipped into the
solutions noted in Table I below. Mortality data were ta~en 48 hours
after treatment. The test was repeated providing about 300 mites
per treatment.
A lO,Q00 PPM stock solution of Malathion in acetone
was used, and all formulations were mixed with tap water containing
1 drop of TritonX-207 ~Registered Trademark) per 500 ml of water.
The synergism of Zolone and Malathion as compared
with either alone is shown in Tables I and II against both phosphate-
susceptible and phosphate-resistant mites:
16
.. . .
1~48929
TABLE I
Mortality of T. urticae (Ky.--strain) at various
concentrations oE Zolone and Malathion and the
__ _
synergistic activity of Zolone-Malathion mixture.
_ _
5 Example No. Arthrvpodicide Conc. lbs ai/100 gal ~/cmortalitya;
Control A Zolone EC 0.188 (0. 5 pt) 23.9
(phosalone) 0.375 (1. 0 pt) 47.1
Q. 750 (1. 0 qt) 60.6
Control B Malathion 0.00835 (10 PPM) 1. 6
0.0835 (100 PPM) 5. 1
0.835 (1000 PPM) 62. 7
Example 1 ~olone EC+ 0.188: 0. 00835 65.4
Malathion 0.188: 0. 0835 79. 5
0. 188: 0. 835 100. 0
0.375: 0. 00835 98.3
0.375: 0. 0835 99. 6
0.375: 0. 835 100. 0
a Control corrected mortality by Abbot's Formula
b A phosphate-susceptible strain of predacious mites commonly found
in apple orchards.
~048929
TABLE II
_
~ortality of T. urticaeNJb strain) at various
concentrations of Zolone, Malathion, and Zolone-
.. ..
Malathion mixture.
. _
5Example No. Test material Conc. lbs. ai/100 gal. ~cmortality-
Control A Zolone EC 0. 188 (O. 5 pt 18.9
(phosalone)
0.375 (l.Opt) 32.5
O. 750 (1. 0 qt) 63. 6
Control B Malathion 0.û0835 (10 PPM) O
O. 0835 (100 PP~) 2. 1
0.835 (lûOO PPM) 25.4
Example 1 Zolone EC ~ O. 188:0. 00835 32.2
Malathion 0.188: O. 0835 77.9
0.188: 0.835 100
0.375:0.00835 64.2
0.375: O. 0835 84.3
0.375: 0.835 100
a Control corrected mortality by ~bbot's formula
-- A phosphate-resistant strain of predacious mites commonly found
in apple orchards.
1-~
1~1489Z9
It is apparent from the above data that the mixture of
malathion and phosalone in accordance with the invention is synergistically
more effective than either alone against both phosphate-susceptible and
phosphate-resistant mites. The degree of enhancement of miticidal
activity is in fact remarkable, since it is several times that of either
alone, in the same concentration, and is clearly far more than merely
additive.
EXAMPLE 2
In these experiments, the relative toxicity of zolone EC,
malathion,and Zolone EC plus malathion is measured by induced 72-hour
mortality of southern armyworm larvae.
Zolone EC was diluted to desired concentrations
in deionized water. Malathion (95~) was dissolved in 10% acetone
emulsion base, and then diluted to desired concentrations in deionized
water.
Individually potted horticultural bean (Phaeseolus vulgaris),
Dwarf French cultivar, plants in fir~t true leaf growth stage, were used
as host plants. Upper and lower surfaces of foliar portions were
alternately sprayed at 20 psi to incipient run-oEf, allowed to air dry
under laboratory conditions, and then removed to greenhouse holding
racks provided with subterranean water source. Five third-instar
larvae were caged on each plant for 72 hours. Ten test plants
(replicates) were used for each test unit.
At the end of the 72-hour holding period, observations
were made for insect mortality, any abnormal physiological responses
and plant injury. Phytotoxicity is rated on a zero (no injury) to ten
(death of the test plant) scale.
19
1048929
The to~icity data obtained appear in Table III below:
TABL E III
Toxicity of Zolone EC, Malathion and Zolone EC plus
Malathion as measured by induced 72-hour mortality
of Southern Armyworm larvae.
Spodoptera eridania, 3rd instar
Example No. Treatment Applied Test Concentration AYe C/cMorta
Lbs a. i. /100 gal72 hours
Control A Zolone EC 0. 188 40
0.37~ 64
0. 750 90
Control B Malathion 0.00835 4
- 0. 0835 34
0.835 90
Example 2 Zolone EC ~ 0.188 + 0. 00835 92
Malathion
0.188 + 0.083596
0.188 + 0.835 100
0.375 + 0. 00835 94
0.375 + 0. 0835 88
0.375 + 0.8351002
0.375 + 0.08 80
Untreated controls 4
2 100~C mortality all replicates in 24 hours
The data in Table III indicate quite clearly t~hat Zolone EC
in com~ination with malathion is more toxic to southern armyworm
larvae as a stomach poison than either 2~lone EC or malathion alone.
N is significant to note that Zolone EC plus malathion
(0.375 + 0. 835 lbs a. i./100 gal) induced 100~C mortality in 24 hours.
."~
~v
1048929
Zolone EC plus malathion (0.188 ~ 0.835 l~s a.i./100 gal) induced
1O0~G control but was slower acting, requiring 72 hours to induce
complete control.
The reason for the potentiation of malathion by phosalone
and of phosalone by malathion is not understood, and has not been
established. It is however suggested that one of the possible reasons for
malathion resistance is some insects and mites is a high carboxylesterase
level, which detoxifies malathion before it can kill them. Phosalone
inhibits carboxylesterase, and it is therefore possible that the
phosalone blocks carboxylesterase, and thereby makes it possible to
kill certàin arthropods with malathion that were previously malathion-
resistant. The result is a mixture which is capable of killing phosphate-
resistant arthropods, i.e., insects and mites.
EXAMPLE 3
The toxicity response from Tetranychus urticae Koch
treated with (1) Parathion - O, O- diethy~-o-p-nitrophenyl phosphorothioate
(2) Phosdrin - dimethyl phosphate of methyl-3-hydroxy-cis-crotonate
and (3) cornbinations of Parathion and Phosdrin is studied.
Thirty 8 day old T urticae + mites are dipped into
solutions of the abo~e arthropodicides as noted in Tahle IV below.
Mortality data are taken 48 hours after treatment. The tests provide
about 300 mïtes per treatment. . -
All formulations are mixed with tap water containing
1 drop of Triton ~-207 per 500 ml of water.
~0489Z9
TABLE IV
Example No. Arthropodicide Conc. lbs ai/100 gal
. _
Control C Parathion 0.188 (0.5 pt)
0.375 (1.0 pt)
0.750 (1.0 qt)
5Control D Phosdrin 0.00835 (10 PPM3
0.0835 (100 PPM)
0.835 (1000 PPM)
Example 3 Parathion ~ 0.188:0.00835
Phosdrin 0.188:0.0835
0.188:0.835
0.375:0.00835
0.375:~.0835
0.375: 0.835
The mixture of parathion and phosdrin in accordance
with the invention is synergistically more effective than either alone
against both phosphate-susceptible and phosphate-resistant mites.
EXAMPLE 4
15 The toxicity response from Tet_nychus urticae Koch
treated with (l) Ethion - (2- chloroethyl) phosphonic acid, (2) Malathion
95% Tech, and (3) combinations of Ethion and Malathion Tech, is studied.
Thirty 8 day old T. urticae ~ mites are dipped into the
solutions noted in Table V below. Mortality data ar.e taken 48 hours
20 after treatment. The tests provide about 30~ mitesper treatment.
All formulations are mixed with tap water containing
1 drop of Triton X-207 per 500 rnl of water.
22
1~48~29
TABLE V
Example No. Arthropodicide Conc. lbs ai/100 gal
Control E Ethion 0.188 (0.5 pt)
0.375 (1.0 pt)
0.750 (1. ~ qt)
Control F Malathion 0.00835 (10 PPM)
0.0835 (100 PPM)
0.835 (1000 PPM)
Example 4 - Ethion + 0.188:0.00835
Malathion 0.188:0.0835
0.188:0.835
0.375: 0.00835
0.375:0.0835
0.375: 0.835
The mixture of Ethion and Malathion in accordance with
the invention is synergistically more effective than either alone against
both phosphate-susceptible and phosphate-resistant mites.
E~AMPLE 5
The toxicity response from Tetranychus urticae Koch
treated with (1) Trithion - S-( (p-chlorophenylthio) methyl) O,O-diethyl
phosphorodithioate, (2) Phenthoate - O, O- dimethyl-S- ( a -ethoxycarbonyl-
benzyl)-phosphorodithioate and (3) combinations of Trithion and Phenthoate
is studied.
Thirty 8 day old T. urtlcae +o mites are dipped into the
solutions noted in Table VI below. Mortality data are taken 48 hours
after treatment. The tests provide about 300 mites per treatment.
All formulations are mixed with tap water containing
1 drop of Triton X-207 per 500 ml of water.
23
~)48929
TABLE VI
Example No. Arthrop i_de Conc. lbs ai/100 gal
Control G Trithion 0.188 (0.5 pt)
0.375 (1.0 pt)
0.750 (1.0 qt)
Control H Phenthoate 0.00835 (10 PPM)
O,0835 (100 PPM)
0,835 (lOOOPPM)
Example 5 Trithion ~ 0.188: 0.00835
Phenthoate 0~ 188:0.0835
0.188:0.835
0.375: 0.00835
0.375:0.0835
0.375: 0.835
The mixture of trithion and phenthoate in accordance with
the in~ention is synergistically more effective than either alone against
both phosphate-susceptible and phosphate-resistant mites.
EXAMPLE 6
The toxicity response from Tetranychus urticae Koch
treated with (1) Guthion - O, O-Diethyl-S-(4-oxo-1,2,3-benzotriazin-3
(4H)-ylmethyl)-phosphorodithioate, (2) Malathion 95% Tech, and (3)
combinations of Guthion and Malathion Tech, is studied.
Thirty 8 day old T. urticae t mites are dipped into the
solutions noted in Table VII below. Mortality data are taken 48 hours
after treatment. The tests provide about 300 mites per treatment.
All formulations are mixed with tap water containing
1 drop of Triton X-207 per 500 ml of water.
24
~)489Z9
TAE3LE VII
Example No. Arthropodicide Conc. lbs ai/10û gal
Control I Guthion 0.188 (0.5 pt)
0.375 (1.0 pt)
0.750 (1.0 qt)
Control J Malathion 0.00835 (10 PPM)
0.0835 (100 PPM)
0.835 (1000 PP~)
Example 6 Guthion+ 0.188:0.00835
Malathion 0.188: 0.0835
0.188:0.835
0.375:0.00835
0.375:0.0835
0.375: 0.835
The mixture of Guthion and Malathion in accordance with
the invention is synergistically more effective than either alone against
both phosphate~susceptible and phosphate-resistant mites.
EXAMPLE 7
The toxicity response from Tetranychus urticae Koch
treated with (1) DDVP - 2t 2- dichlorovinyl dimethyl phosphate (2)
Phosdrin - dimethyl phosphate of methyl -3-hydroxy-cis-crotonate and
(3) combinations of DDVP and Phosdrin is studied.
Thirty 8 day old T. urticae + mites are dipped into the
solutions noted in Table VIII below. Mortality data are taken 48 hours
after treatment. The tests provide about 300 miteæ per treatment.
All formations are rnixed with tap water containing 1 drop
of Triton X-207 per 500 ml of water.
2~
1~3489Z9
TABLE VIII
Example No. Arthropodicide Conc. lbs ai/100 gal
Control K DDVP 0.188 (0.5 pt~
0.375 (1.0 pt)
0.750 (1.0 qt)
Control L Phosdrin 0.00835 (10 PPM)
0.0835 (100 PPM)
0.835 (1000 PPM)
Example 7 DDVP ~ 0.188:0.00835
Phosdrin 0.188: 0.0835
0.188: 0.835
0.375:0.00835
0.375: 0.0835
0.375:0.835
The mixture of DDVP and Phosdrin in accordance with
the invention is synergistically more effective than either alone against
both phosphate-susceptible and phosphate-resistant mites.
EXAMPLE 8
The toxicity response from Tetranychus urticae Koch
treated with (1) Dimethoate -O, O - dimethyl S-(N-methylcarbamoyl-methyl)
phosphorodithioate, (2) F~enthoate - O,O-dimethyl S-(~-etho~carbonyl-
benzyl)-phosphorodithioate, and (3) combinations of I)imethoate and
Phenthoate is studied.
Thirty 8 day old T. urticae + mites are dipped into the
solutions noted in Table ~ below. Mortality data are-taken 48 hours
after treatment. The tests provide about 300 mites per treatment.
All formulations are mixed with tap water containing
1 drop of Triton X-20~ per 500 ml of water.
26
1~489~:9
TABLE IX
Example No. Arthropodicide Conc. lbs ai/100 gal
Control M Dimethoate 0.188 (0.5 pt)
0.375 (1.0 pt)
0.75~ (1.0 qt)
Control N Phenthoate 0.00835 (10 PPM~
0.0835 (100 PPM)
0.835 (1000 PPM)
Example 8 Dimethoate + 0.188:0.00835
Phenthoate 0.188: 0.0835
0.188:0.835
0.375: 0.00835
0.375:0.0835
0.375:0.835
The mixture of dimethoa.te and phenthoate in accordance
with the invention is synergistically more effective than either alone
against both phosphate-susceptible and phosphate-resistant mites.
27
