Note: Descriptions are shown in the official language in which they were submitted.
~3~6~
This invention relates to cyclopropyl carboxylates
to a method for their preparation and to pesticidal compositions
containing them.
The present invention provides cyclopropyl carboxylates
having the follo~ing general formula:-
H X
R2 / ~ R3 (I)
wherein X is a halogen atom;
R is a hydrogen atom or an alkyl group;
R is an alkyl groupj or R and R together represent
an alkylene chain;
R3 is a hydrogen atom, a cya~no, ethynyl or thioamido
group; and
R is a phenoxyphenyl, benzylphenyl, phenyl-thiophenyl,
benzylfuryl, halophenyl, ph-thalimido, tetrahydrophthalimido,
or halophenoxyphenyl group.
Preferred compounds according to the invention are those
having general formula I wherein
X is a halogen atom;
R is a hydrogen atom or an alkyl group of 1 to 6 carbon
atoms;
R is an alkyl group of 1 to 6 carbon atoms or
R and R together represent an alkylene chain of up to
5 carbon atoms;
R is a hydrogen atom or a cyano or ethynyl groupj and
R is a phenoxyphenyl, benzylfuryl, phthalimido, or tetra-
hydrophthalimido group.
¢`~ 3
!
The substituent X is a halogen atom in the compounds
according to the invention and it is preferably a chlorine,
bromine or fluorine a-tom; e~fective results in terms of the
resulting pesticidal activity have been obtained when X ~ -
is a chlorine atom.
The substituen-ts Rl and R2 are preferably both methyl
groups or one of them is a methyl group and -the other a hydrogen
atom.
The cyclopropyl carboxylates according to the invention
0 may be prepared by conventional methods e.g. the esterification
of the appropriate acid by -the appropriate alcohol. ~o
generally preferred methods involve either reaction of the acid
chloride with the alcohol in -the presence of base (e.g. an
amine such as triethylamine), or, the reaction of the acid
with the appropriate alkyl halide in the presence of a base
te.g. an alkali metal salt such as potassium carbonate).
Thus a process ~or preparing the compounds according to the
invention comprises reacting a cyclopropyl compound of ~-
formula II:-
H X
Rl f \ COZ (II)
R H
with a substituted alkyl compound of formula III:-
X3
Y - CH - R (III)
6~
(wherein one of the substituents Y and Z represent an -OH group and the other
represents a halide (suitably a chloride), and X, R , R , R3 and R have the
meanings hereinbefore specified) in the presence of a hydrogen halide accep-
tor, for example a base such as an organic or inorganic base. The reaction
is suitably carried out in an inert solvent and may be effected at ambient
temperature, e.g. a temperature in the range 5 to 50 C.
In the preparation of the cyclopropyl carboxylates according to the
invention the starting materials are essentially a substituted cyclopropyl
carboxylic acid or a simple derivative thereof (e.g. a compound of formula
II) and an alkyl alcohol or a simple deriva-tive thereof (e.g. a compound of
formula III). The alcohols and simple derivatives thereof are known com-
pounds but the cyclopropyl acid and derivatives are novel compounds; the nov-
el compounds and a process for their preparation are disclosed in copending
Canadian application Serial No. 294,304; this process essentially consists of
dehalogenating the corresponding di-halo-cyclopropyl carboxylic acid in the
presence of a dehalogenating agent, e.g. zinc and a lower alkanoic acid such
as acetic or propionic acid.
The cyclopropyl carboxylates according to the invention are of
interest as pesticides, in particular as insecticides ana acaricides for
agricultural and domestic outlets. Moreover they have shown surprising
activity as knockdown agents for flying pests such as Musca domestica and
thus are potentially useful for domestic insecticidal uses. The invention
therefore includes within its scope a pesticidal composition comprising a
carrier and/or a surface-active agent together with, as active ingredient,
a cyclopropyl carboxylate of forml~a I. The invention also includes a method
of combating insect and/or acarid pests at a locus which comprises applying
to -the locus a pesticidally effective amount of a cyclopropyl carboxylate
according to the invention or composition containing such a compound.
The term 'carrier' as used herein means a material, which may be
inorganic or organic and of synthetic or natural origin~ with which the
63
active compound is mixed or formulated to facilitate its applicati.on t~ the
plarlt, seed, soil or other obJect to ~e treated, or its storage, transport
or handling. The carrier may be a solid or a liquid. Any of the materials
usually applied in formulating pesticides, herbicides, or fungicides may be
used as the carrier.
Suitable solid carriers are natural and synthetic clays and sili-
cates, for example natural silicas such as diatomaceous earths; magnesium
silicates, for example, talcs; magnesium aluminium silicates, for example~
attapulgites and vermiculites; aluminium silicates, for example, kaolinites,
montmorillinites and micas; calcium carbonates; calcium sulphate; synthetic
hydrated silicon oxides and synthetic calcium or aluminium silicates; ele-
ments for example, carbon and sulphur; natural and synthetic resins such as,
for example coumarone resins, polyvinyl chloride and styrene polymers and
copolymers; solid polychlorophenols; bitumen; waxes such as for example,
beeswax, paraffin wax, and chlorinated minera] waxes; and solid fertilisers,
for example superphosphates.
Suitable liquid carriers are water, alcohols, for example, iso-
propanol and glycols 7 ketones for example, acetone, met~yl ethyl ketone,
and cyclohexanone; e~hers; aromatic hydrocarbons, for example, benzene,
toluene and xylene; petroleum fractions, for example, kerosine and light
mineral oils; chlorinated hydrocarbons, for example, carbon tetrachloride,
perchloroethylene, trichloroethane; and liquefied normally vaporous, gaseous
compounds. Mixtures of different liquids are often suitable.
The surface-active agent may be an emulsifying agent or a dispers-
ing agent or a wetting agent, it may be nonionic or ionic. Any of the sur- ~ Y
face-active agents usually applied in formulating pesticides, herbicides or
fungicides, may be used. Examples of suitable surface-active agents are the
sodium or calcium salts of polyacrylic acids and lignin sulphonic acids; the
condensation products of fatty acids or aliphatic amines or amides containing
at least 12 carbon atoms in the molecule wi-th ethylene oxide and/or propylene
3~
oxide; fatty acid esters of glycerol, sorbitan, sucrose or pentaery-
thritolg condensates of these with ethylene oxide and/or propylene oxide;
condensation products of fatty alcoho]s or alkyl phenols for example
~-octylphenol or ~-octylcresol, with ethylene oxide and/or propylene oxide;
sulphates or sulphonates of these condensation products; alkali or alkaline
earth metal salts, preferabl~ sodium salts, or sulphuric or s~phonic acid
esters containing at least 10 carbon atoms in the molecule, for example,
sodium lauryl sulphate, sodium secondary alkyl sulphates, sodium salts of
sulphonated castor oil, and sodium alkylaryl sulphonates such as sodium
dodecylbenzene sulphate; and polymers of ethylene oxide and copolymers of
ethylene oxide and propylene oxide.
The compositions of the invention may be formulated as wettable
powders, dusts, granules, solutions, emulsifiable concentrates, emulsions,
suspension concentrates and aerosols. Wettable powders are usually com-
pounded to contain 25, 50 and 75~ of toxicant and usually contain, in addi-
tion, to solid carrier, 31-0% w of a dispersing agent and, where necessary,
0-10% w of stabiliser(s) and/or other additives such as penetrants or
stickers. Dusts are usually ~ormulated as a dus-t concentrate having a sim-
ilar composition to that of wettable powder but without a dispersant, and
are diluted in the field with further solid carrier to give a composition
usually containing 1~2-10% w of -toxicant. Granules are usually prepared to
have a size between 10 and 100 BS mesh (1.676-0.152 mm), and may be manu-fac-
tured by agglomeration or impregnation techniques. Generally, granules will
contain 1/2-25% w toxicant and 0-10% w o~ additives such as stabilisers,
slow release modifiers and binding agent. Emulsifiable concentrates usually
contain, in addi-tion to the solvent and, when necessary, co-solvent, 10-50%
w toxicant, 2-20% w/v emulsifiers and 0-20% w/v of appropriate additives
such as stabilisers, penetrants and corrosion inhibitors. Suspension con-
centrates are compounded so as to obtain a stable, non-sedimen-ting flowable
product and usually contain 10-75% w toxicant, 0.5-15~ w of dispersing
- 6 -
3r~
agents, 0.1-10% w of suspending agents such as protec-tive colloids and
thixotropic agents, 0-10% w of appropriate additives such as defoamers,
corrosion inhibitors, stabilisers, penetrants and stickers, and as carrier,
water or an organic liquid in wbich the toxicant is ~ubstantially insoluble;
certain organic solids or inorganic salts may be dissolved in the carrier to
assist in preventing sedimentation or as antifreeze agents for water.
Aqueous dispersions and emulsions, for example, compositions ob-
-tained by diluting a wettable powder or a concentrate according to the inven- ;~
tion with water, also lie within the scope of the present invention. The
said emulsions may be of the water-in-oil or of the oil-in-water type, and
may have a thick 'mayonnaise' like consistency. `
The compositions of -the invention may also contain other ingred-
ients, for example, other compounds possessing pesticidal, herbicidal or
fungicidal properties.
The invention is further illustrated in the following examples.
Example 1 Preparation of alpha-cyano-3-phenoxybenzyl ;~;
3-chloro-2,2 dimethylcyclopropyl carboxylate
3-Chloro-2,2-dimethylcyclopropanecarboxylic acid (0.75 g, 5.0 mm)
and alpha-cyano-3-phenoxybenzyl bromide (1.45 g, 5.0 mm) were stirred to- ~;
gether in acetone (30 ml) at room temperature for 4 hours. The reaction
mixture was diluted with wa-ter and extracted with ether. The ether extracts d
were washed with sodium bicarbonate (x4) and dried over magnesium sulphate.
Removal of solvent gave a yellow oil which was purified by eluting from a
silica gel column using 3% acetone/hexane R.I. nD 1.5623.
Analysis Calculated for C20H18N03Cl : C 67.6; H 5.1; N 3.9%
Found : C 67.7; H 5.1; N 3.8%
Example 2 Preparation of 5-benzyl-3-furylmethyl 3-chloro-
2,2-dimethylcyclo~propyl carboxylate
3-Chloro-2,2-dimethylcyclopropanecarboxylic acid (0.7 g, 4.7 mm)
in toluene (20 ml) was refluxed with excess thionyl chloride for 45 minutes.
-- 7 --
The solvent was removed and the crude 3-chloro-2,2-dimethylcyclopropane
acid chloride in toluene (20 ml) added to 5-benzyl-3-hydroxymethylfuran
(1.1 g, 5.8 mm) and triethylamine (1.0 g) in toluene (20 ml) at room temper-
ature. The mixture was stirred overnight, diluted with water and extracted
with diethyl ether. The ether extracts were washed with sodium bicarbonate
(x2) and dried over magnesium sulphate. Removal of solvent gave an orange
oil whicb was purified by eluting from a silica gel column using toluene
R.I. nD 11.5414.
Analysis Calculated for C18H1903Cl : C 67-8; H 6-o%
Found : C 67.8, H 6.1%
Examples 3-5
Further examples of the compounds according to the invention were
prepared by methods similar to those described in the preceding Examples.
These compounds and their physical data are presented in Table I.
~ 3S~3
, . ~ u~ N .
~iX ~ ~ '' ;,"
~ 0~ ~ U~ - `
L(~ U~ U~ U~ U~
~P~ ~ ~ :'`
co C~ cr~ O ~ ~ : `' :~
u~ ~ ~ c~ a\ ~i ~ . ~,
~ L~ ~ ~ ~ ~ :-.
~ O ~ ,~ V :~ ~
X,~ ~, V ~: .
~ ~ 1 t :~
O _ N ~O _ _ ~ ~ ~ t
' '
_ ~, ___. ___ -~
~ ~ ~ _. ,
_ 9 _
..
5~3
Example 6
The insecticidal activity of the compounds according to the present
invention was assessed employing the following pests:- -
Insects: Musca domestica (M.d.)
Phaedon cochleariae (P.c.)
Spodoptera littoralis (S.l.)
Aphis fabae (A.f.)
The test methods employed for each species appear below:-
(i) Musca domestica (M.d.). A 0.4% by weight solution in
acetone of the compound to be tested was prepared and taken up in a micro-
meter syringe. Two to three day old adult female houseflies (Musca
domestica) were anaesthetised with carbon dioxide, and 1 ~1 of the test solu-
tion was applied to the ventral side of the abdomen of each fly, 20 flies
being tested. The treated flies were held in glass dars covered with paper
tissue held by an elastic band. Cotton-wool pads soaked in dilute sugar
solution were placed on top of the tissue as food. After 24 hours the per-
centage of dead and moribund flies were recorded.
(ii) Phaedon cochleariae.(P.c.). The compounds were formulated
as solutions or suspensions in water containing 20% by weight of acetone and
0.05% by weight of Triton X-100 as wetting agent. The formulations contained
0.4% by weight of the compound to be tested. Turnip and broad bean plants,
trimmed to one leaf each, were sprayed on the undersurface of the leaf with
the above formulation. Spraying was effected with a spraying machine, de- ~ `livering 340 litres per hectare, the plants passing under the spray on a
moving belt. After spraying, the plants were left for 1/2-1 hour drying
period and then each plant was enclosed within a ~50 ml bottle from which ~-
the bottom had been removed. Ten adult 2-3 week old mustard beetles
(Phaedon cochleariae) were placed on the sprayed leaf of each turnip plant.
The open ends of the bottle were then closed with squares o~ paper -tissue
held with elastic bands. Mortality counts were made after 24 hours.
-- 10 --
~35~
(iii) Spodoptera littoralis (S.l.). Pairs of leaves were removed
from broad bean plants and placed on filter paper inside plastic petri
dishes. The leaves were sprayed as in (ii), using the same concentrations.
After spraying the leaves were left for 1/2-1 hour drying period and then
each leaf pair was infested with ten larvae of the Egyptian cot-ton leafworm ~
(Spodo~tera littoralis). After 24 hours the percentage of dead and moribund ~-
larvae were recorded. -
(iv) Aphis fabae (A.f.). Pairs of leaves are removed from broad
bean plants and placed ventral side uppermost on filter paper inside a 9 cm
petri dish. Ten to twenty 5-7 day old adult aphids were transferred onto a
filter paper inside a 5 cm petri dish and covered with a wire-mesh lid. The ~;
leaves and aphids were sprayed in parallel with a 0.2% solution or suspension
of the compound in 20% ace-tone in water con-taining 0.05% Triton X-100.
After spraying the aphids are transferred to the sprayed leaves and the per-
centage dead and moribund individuals recorded a~ter 2~ hours.
The results of those -tests are shown in Table II in which the test
species are identified by the initials noted above and A denotes complete
kill, B some kill and C no kill of the test species.
TABLE II
2Q INSECTIDICAI. ACTIVITY
Compound of M.d. P.c. S.1 A.F.
Example No.
1 A A A B
3 C A B A
4 A A A A
A A A A
2 A B A A
Example 7
The acaricidal activity of the compounds according to the invention
was assessed employing the following pest:-
33~ 3
Tetranychus urticae (T.u.)
The test method employed was as follows. Leaf discs cut fromFrench bean plants were inoculated with 10 red spider mites in the manner
described in Example 6 for the insects Phaedon cochlear ae 1 hour after dry-
ing. Mortality counts were made 21l hours after inoculation. The results of
these tests are shown in Table III employing the same notation as used in the
previous example.
TABLE III
ACARICI A _ CTIVITY
__,.,. . ~
Compound of T u
Example ~o. . .
. 1, ~
Example 8
The knockdown activity of the compounds according to the invention
was assessed employing the common housefly (Musca domestica) by means of the
Kearns-March chamber test.
The Kearns-March chamber consists of a 2 foot x 1 foot transparent
glass cylinder into which flies can be introduced through a sliding panel at
one end. 0.2 ml of a 20% MeC12/80% Shellsol K solution containing active
material was sprayed for 1 1/2 seconds into the chamber at 10 psi and the ;~
air supply kept on for a further two seconds to facilitate even distribution
of the spray. About 70 flies were used in each treatment and knockdown -
counts made at 1, 2, 3, ~, 5, 7 and 10 minutes after spraying.
Compounds are graded into six classes according to the concentra- ~;
tion of toxicant required to achieve 90% knockdown after ten minutes, that is
to say
Class 0 90% at 10 minutes = concentration 0.025%
Class 1 90% at 10 minutes = concentration 0.05%
Class 2 90% at 10 minutes = concentration 0.1%
Class 3 90~ at 10 minutes = concentration 0.2%
- 12 -
Class 4 90% at lO minutes = concentration 0.4%
Class 5 90% at lO minutes = concentra-tion 0.4%
Class 6 No knockdown at 0.4%
The results of these tests are shown in Table IV.
TABLE IV
KNOCKDOWN ACTIVITY
___ .... . . . ~
Compound of Knockdown Grading
____ .
l Class O :~
2 Class O
3 Class l
4 Class O ~.
Class O
_~ ___ .~ .. ._ .
