Note: Descriptions are shown in the official language in which they were submitted.
~)6~740'~
Pe V
The present invention relate~ to new preparations,
having a depot gas action, based on dimethyl-2,2-dichloro-
vinyl thiophosphate as a gassing agent which acts automatic-
ally via the gas phase, and on solid carriers.
~he use of dimethyl-2,2-dichlorovinyl phosphate (D~VP)
in ~ormulatio~s which automatically aot as gassing agents, in
combating pests, has been known ~or a long time. Very
diverse materials have been proposed as carriers for the
above-mentioned active compound: macromolecular thermoplastic,
thermosetting and elastomeric plastics or natural materials,
such as wood, cardboard, asbestos, lime~ gypsum, beeswax and
montan wax. Further examples o~ suitable carriers are natural
and synthetic rubber, polyolefins such as polyethylene,
polypropylene and copolymers of ethylene and propylene,
polyacrylates and copolyacrylates of methyl acrylate~ ethyl
acrylate and methyl metacrylate, polyvinyl compounds such as
polystyrene, polyvinyltoluene and poly~inyl acetate, poly-
vinyl halides and polyvinylidene halides such as polyvinyl
chloride, polyvinyl fluoride and polyvinylidene chloride,
polyvinyl acetals such as polyvinyl butyral, linear and
branched polyesters and polyethers, and cellulose plastics
such as cellulose acetate, cellulose propionate~ cellulose
butyrate and cellulose nitrate. ~xamples of further suitable
carriers are unsaturated polyesters, epoxides, polyurethanes,
phenol-~ormaldehyde, urea-~ormaldehyde and melamine-~ormalde-
hyde resins~
The polymers and copolymers o~ vinyl chloride (see
DT-AS (German Published $pecification) 1,230,259~ as well as
unsaturated polyester systems (see D~_QS (German Published
Specification) 1,694,240 and DT-OS (German PublishecL
Le A 15 971 - 2 -
~067402
Specification) 2,231,099~ have ~een de~cribed as particularly
pre~erred carriers, as have al90 polymerlo aorylates and
polymeric ~inyl compounds such a~ polystyrene.
In addition to the ac~ive compound, the formulations
frequently also contain auxiliaries such a~ plastl cisers,
sta~iliser~, vaporisatlon regulators and fillers, depending
on the nature of the carrier. Example~ o~ possible
plasticisers are dioctyl phthalate, alkanesulphonic acid aryl
esters, trioctyl phosphate, triphenyl phosphate; dibutyl
adipate, chlorinated para~fin, diisono~yl phthalate, di-2-
ethylhe~yl adipate, di-2-ethylhexyl phthalate and di-2-ethyl-
hexyI sebacate D Examples of suitable stabilisers are phenols,
amines or lower nitrogen-oontaining heterocyclic co~pounds,
as well as azo and hydrazo compound~, acid anhydrides,
epo~ides and elementary sulphur (DT-OS (German Published
i
Specification) 2,145,718), and also compounds which are
usually employed for stabilising macromolecular substances 7
such as, for example, organic cadmium compounds and lead
compounds as heat ætabilisers for poly~ingl chloride~
~xamples of suitable vapori~ation rçgulators are palmitic
acid ethyl e~terS myristic acid isopropyl e~ter, di-n-butyl
phthalate, 2-chloronaphthalene, camphor, benzoic acid,
biphenyl, isobutyl benzoa~e and others, such a~ are described,
for e~ample, in Ea~t Gorman Patent Speci~ication 91,898 and also
in DT-OS's (German Publishsd Speci~ication3) 1,954,501, 2,026,119
and 2,028~226.
Fillers may be, for e~ample, ~ibres o~ glass, si3al,
hemp, nettle, coir and flax, ~s well as titanium dio~ide, iron
oxides9 kaolin, quartz and other inert materials.
The ~ormulations in question are in ~ost case~ employed
; le A 15 971 - 3 ~
~106'740'~
a~ moulding~ such as slab~, ~heet~, tapes t bar~, ~pheres,
foams, strip~, films, tablets or granule~. Xf, in the
course o~ use, such a mouldlng ~ or e~ample, brou~ht ~nto
the living room or bedroom o~ a hou~e, or placed, in the form
of a n?ckband, round the neck of a domest;ic animal, the DDV~
contained in the preparation i~ gradually released into the
surrounding air7 as a result of the vapour pressure o~ the
DDVP or with the aid o~ heat sources, ~or e~ample electrical
energy, and thus automatically kills, via the ga~ phase,
the pests pr~sent in the room and on domestic anima}s (see
DT-AS (German Published Specification) 1,2~0,259; ~riti~h
Patent Specification 1,015,933; South ~frican Patent
; Specification 62/~71; DT-AS (German Published Specification) 1,694,240; DT-OS's (German Publlshed Specification~
1,941,046 and 2,2~1,099; and DT-AS (German Published
Specification~ 1,802,684).
The mouldings can either be employed for use directly
or be surrounded by casings (qui~ers~ which can be opened
or closed completely or partially in order thereby
periodically to interrupt the release o~ the DDVP or to
regulate the amount of active compound releasedO
~ow the problem of using DDVP in these automatic gassing
mouldings is that the rele~se o~ the active compound must be
so controlled that suf~icient active compou~d i~ released
into the air o~ the room to kill the pests relia~ly whilst
the humans and domestic animal~ present in the room are not
harmed. Active compound~ having a lower toxioity to mammals
than has DDVP would there~ore represent a great tec~ical
advance ~or this end use.
Though, in addition to DDVP~ South A~rican Patent
Specification 62/~71 describe~ combinations with a :Large
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106~4~:)2
number o~ other phosphoric acid esters and the corresponding
thiophosphates, hitherto no other compound than DD~P has
attained practical importance in this re~pect. With regard
to the thiophosph~tes7 DT-AS tGerman Published Specification)
1,230,259 discloses that they are less compatible with
macromolecular substances than are the phosphoric acid
esters in question. Furthermore, it is generally known that
thiophosphoric acid esters have a lower insecticidal power
;- than the corresponding pho~phates. The poorer insecticidalaction of dimethyl-2,2-dichlorovinyl thiophosphate, (here-
after re~erred to ~or brevity as thio-D~VP) compared to
DDVP is shown by the ~ollowing comparison e~periment:
Aerosol test
Test animals: Musca ~@L~
Solvent: Acetone
To produce a suitable preparation of active compound,
the active compound w&s mixed, at a range o~ concentrations,
with the stated solvent.
A wire cage which contained about 25 test animals was
suspended in the centre o~ a gas-tight glass chamber of size
1 m3. After the chamber had been closed again, 2 ml of the
preparation of active compound were atomised in the chamberO
The condition of the test animals was constantly checked
from outside, through the glass walls, and the time re-
quired for a knock-down ef~ect on 50~ o~ the animals was
determined.
The active compounds, amounts used and time a~ter which
50~ of the animals were lying on their backs (~T50) can be
seen ~rom the table which ~ollows:
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~0674~
T a b 1 e
Aerosol test
Active compoundm /m3 LTso
g
DDVP 1 10'37"
Thio-DDVP 1 19'15"
13'37"
3 11'~0"
4 9'20"
It is therefore not surprising that the above-mentioned publica-
tions do not contain an example of the use of thio-DDVP, or that this
active compound is not mentioned anywhere, even cursorily, as an example
in a list.
It has now been found that, surprisingly, thio-DDVP can advan-
tageously be employed in place of DDVP as an active compound in preparation
having a depot gas action if it is employed, in combination with solid
carriers, as a gassing agent, acting automatically via the gas phase, for
combating pests.
According to the invention, there is provided an insecticidal pre-
paration having a depot gas action and comprising an insecticidally effective
amount of dimethyl-2,2-dichlorovinyl thiophosphate in admixture with an un-
saturated polyester resin as carrier.
The invention also provides a method of excluding insects from a
predetermined area which comprises placing in such area an insecticidal pre-
paration as defined above.
In addition to the active compound, the preparations in question
can, depending on the nature of carrier, also contain the above-mentioned
auxiliaries such as, for example, plasticisers, stabilisers, vaporisation
regulators, vaporisation inhibitors or vaporisation promoters~ and fillers.
Thus, materials such as asbestos, gyps~mm, cardboard and montan wax may be
included. The preparations may be used in the form of shaped articles such
as slabs, sheets, tapes, bars, spheres, foams, strips,
- 6 -
~06740~
films, tablets, neckband~ or granules. ~hey oan be surrounded
by ca`~ings which permlt ~ oontrollable ~`ull or reduoed
release of active compound, A factor which proves
partioularly advantageous in the use, aocording to the
invention9 of thio-DDVP i~ bhat compared to DDVP the active
compound, and it~ degradation products, decomposition
products and possible by-products have a lower toxici-ty to
warm-blooded animals, as can be seen from the table which
; follows:
D50 male rat~
Acute oral
toxicity DDVP62 mg/kg
Thio-D~VP773 mg/kg
50 ma~s rats
Aoute inhala-
tion toxioity DDVP340 mg/m'
- (4 hours'
exposure) ?hio-DDvp~ 477 mg/m~ *
*This concentration, which is the maximum possible in the
experiment, wa~ tolerated without ~ymptoms by the ani~als.
The preparations acoording to the invention, ba~ed on
thio-DDVP as an automatically acting ga~sing agent~ and solid
carriers, can be used to co~bat a great diversity of species
o~ pests. The thio-DDVP to be used as the active compound
according to the in~ention i9 known from the literature and
can be prepared, for e~ample, in accordance with the process
described in DT-OS ~German Published Specificatio~) 2,238,921 D
The following examples explain the invention in more
detail9 with "parts" denotin~ parts by weight.
~e A 15 971 - 7 -
~0674~)2
For ~xample~ 1 and 2, the carrier used wae in each ca~e
a mixture of 440 parts of an unsaturat~d polyester (propared
by polycondensation of 205~8 parts o~ maleic anhy~ride,
725.2 parts of phthalic anhydride, 546.4 parts o~ 1,2-propane-
diol and 0.265 parts of hydroquinone, and having an acid number
of 42) and 240 parts of styrene (po}yester mi~ture 1).
For Examples 3 and 4, the carrier used was in each case
a mixture of 730 parts of an urlsaturated pol~ester (prepared
by polycondensation of 262.8 parts of maleic anhgdride,
926.8 parts of phthalic anhydride, 612 parts of 1,2-propane-
diol, 359.6 parts of dipropylene glycol and 0.214 parts of
hydroquinone, and having an acid number of 3.9) and 350 parts
of styrene ~polyester mixture 2).
A homogeneous premix wa~ prepared from 680 parts o~
polyester mixture 1,~90 parts of thio-DDVP, 2~0 parts o~
alkanesulphonic acid aryl e~qter and 27 parts of maleic
anhydride. After adding 41 parts of a 10% strength solution
of dimethylaniline in toluene, a cast sheet having a glass
fibre content of 26% was produced by heating the mixture for
about 30 minutes to 800100C in a closed mould in which a
gla~qs fibre mat (600 g/m2) had been lald The sheet was
subsequently cut into shaped pieces o~ size 8 ~ 25 cm. The
active compound content wa~ 20 g.
E~xamPle 1a
; (Comparison e~ample)
Shaped pieces of siæe 8 ~ 25 cm and having an acti~e
; compound content of 20 g were produced in the same manner asdescribed in E~ample 1, bu~ using DDVP a~ the active compound.
E~3~
A homoganeous premix was prepared ~rom 6~0 parts of
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~6~40Z
polyester mixture 1 and 450 parts o~ thlo-DDVP. A~ter
adding 36 parts of benzoyl peroxide in phthalate plastloiser
~50% stren~th), a oast sheet havine an a~bestos oontant o~
3.5 per cent by weight was produced by heating for about 30
minutes to 80-100C in a closed mould, into which granul~r
asbestos particles had been introduced. ~he sheet was
subsequently cut into shaped pieces o~ size 8 x 25 cm, h~ving
an active compound content of 38%.
A homogeneous premix was prepared from 665 parts of
polyester mixture 2 and 475 parts of thio-DDVP. After adding
~8 parts of benzoyl peroxide in phthalate plasticiser ~50~o
strength), a cast sheet with a fabric content of 26 per cent
by weight was produced by heating for about 30 minutes to
80-100C in a closed mould, into which a fabric o~ poly-
acrylonitrile fibres (280 g/m2) had been laid~ The sheet
was subsequently cut into shaped piece~ of size 8 x 25 cm,
having an active compound content of 24 g each.
Exam~le 3a
(Comp~rison e~ample)
A homogeneous premix, and shaped pieces of the same
sizes and of the same active compound content, were prepared
in the same manner as in Example 3, but using DDVP as the
active compound.
E~
A homogeneous premix was prepared from 438 parts o~
polyester mixture 2 and 299 parts of thio-DDVP. A~ter adding
26 parts of benzoyl pero~ide in phthalate plasticiser (50~o
strength), a cast sheet with a weight content of 26 per cent
by weight was produced by heating for about 30 minutes to
Le A 15 971 - 9 ~-
~L~67402
80-100C in a closed mould, into which a ~ute ~abric (1,150 g/
m2) had been laid. ~he shee~ was subsequently out into
shaped pieces of si~e 8 x 25 cm, ha~ing E~n acti~e compound
content of 25 g each.
Example 4a
(Comparison e~ample)
A homogeneous premix, and shaped pieces of the same
si~es and of the same active compound content, were prepared
in the same manner as in ~ample 4, but using DDVP as the
active compound.
Shaped pieces of size 8 x 25 cm were cut from 3 mm
thick cardboard and impregnated with thio DDVP. The active
compound content in the cardboard was 30 g.
The pesticidal activlty o~ the present ~ormulations is
illustrated in the following biotest Examples.
~xample A
One shaped piece produced according to E~ample 1 and
one shaped piece produced according to E~ample 1a were each
; 20 pushed into a casing of fine wire me~h and suspended from the
ceiling in the centre o~ identical rooms of 50 m3 cubic
capacity. ~our weeks later, 200 ~lies of the species Musca
domestica were released in the rooms. In the room in which
the shaped piece according to ~xample 1 was suspended, the
flies dropped a~ter 2 hours. In the room in which the shaped
piece according to Example 1a was suspended, it required
3 hours ~or 100~o o~ the ~lies to lie on their backs.
~BBa~
One shaped piece produced according to Example 3 and
one shaped piece produced according to E~ample ~a were each
pushed into a net-like qui~er and suspended from the ceiling
~e A 15 971 _ 10 -
)2
in the centre o~ identical rooms of 40 m~ cubic capaclty.
Immediately thereaftar (O), and after 4, 8 and 12 week~, 200
~lies of the species Mu~ca domes-tica were in each ca~e exposed
~n the rooms. The flie~ did not come into direct contact
with the shaped piece~ In each case, the percentage o~
animals which had fallen on their backs was determined 1 hour
after exposing the ~lies. The results obtained can be seen
from the table which follows:
T a b l e _~
Age of the shaped percentage of animals lying on
pieces, in weeks their backs after one hour
.
DDVP Thio-DD~P
0 80 100
4 70 95
, 8 60 90
-i 15 12 20 50
~ One shaped piece pr~d~ced according to E~ample 4 and
,~
one shaped piece produced according to Example 4a were each
pushed into an open-pore quiver and suspended open in a room.
After 2 weeks, the shaped piece according to Example 4 was
first brought into a room o~ 43 m3 cubic capacity and 300 flies
of the species Musca domeetica were released. The time after
which 100~o of the ~lie~ had fallen on their backs was
; determined. Thereafter the room was thoroughly aired and the
~ame experiment was carried out with the shaped piece
according to ~xample 4al The results obtained are shown in
the ~ollowing table:
. ~
Shaped piece according Time elap~ed before 100~ of
to Example the animal~ were lying on
4a 5
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