IMIDAZOLINES PESTICIDES

PESTICIDAL IMIDAZOLINES

Abrégé anglais

A B S T R A C T
Pesticidal imidazolines are provided of
formula
<IMG>
wherein X is O or NH; and Y is Br, F, I, -NO2, -OR,
-CO2R, -CONR1R2 or -SO2NR1R2, ?, when X is NH, Y
may also be chosen from Cl, CN or alkyl of from 1 to
4 carbon atoms, in which R is an alkyl group of from
1 to 18 carbon atoms, and each of R1 and R2, which
may be the same or different, is hydrogen or an alkyl
group of from 1 to 18 carbon atoms. Pesticidal acid
additions salts of the imidazolines are also provided.
Methods are described for preparing the pesticides, together with
intermediates formed in the preparative methods. Pesticidal formulations
containing the pesticides and their use are also described.
The pesticides may be used against Arthropods,
e.g. against Acarina.

Revendications

- 23 - A 584 C
The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:
1. A compound of the formula (I)
(I)
<IMG>
or an acid addition salt thereof wherein X is
O or NH; and Y is Br, F, I, -NO2, -OR?-CO2R,
-CONR1R2 or -SO2NR1R2, or when X is NH, Y may
also be chosen from C1, CN or alkyl of from 1
to 4 carbon atoms, in which R is an alkyl group
or from 1 to 18 carbon atoms, and each of R1
and R2 which may be the same or different, is
hydrogen or an alkyl group of from 1 to 18
carbon atoms.
2. A compound according to claim 1 wherein Y is
-OR or CO2R wherein R is an alkyl group of from
1 to 4 or 12 to 18 carbon atoms.
3. A compound according to claim 1 wherein Y is
-CONR1R2 or SO2NR1R2 wherein each of R1 and R2,
which may be the same or different, is hydrogen
or alkyl group of from 1 to 4 or 12 to 18 carbon
atoms.
AS/22-5-79

- 24 - A584 C
4. A compound according to claim 3 wherein not more
than one of R1 and R2 is an alkyl group of from
12 to 18 carbon atoms.
5. A compound according to claim 1 of the formula
(Ia)
<IMG> (Ia)
or an acid addition salt thereof wherein X is
O or NH and Y1 is F, Br, -NO2, CH3O- or
-CO2C2H5, or X is NH and Y1 is Cl.
6. A compound selected from 1-(N-(4-methoxyphenyl)
carbamoyl-2-(2,3-dimethylphenoxymethyl)-2-
imidazoline, 1-(N-4-chlorophenyl)-carbamoyl)-
2-(2,3-dimethylanilinomethyl)-2-imidazoline,
1-(N-(4-bromophenyl)carbamoyl)-2-(2,3-dimethyl-
phenoxymethyl)-2-imidazoline, 1-(N-(4-nitro-
phenyl)carbamoyl)-2-(2,3-dimethylphenoxymethyl)
-2-imidazoline, 1-(N-(4-fluorophenyl)carbamoyl)
-2-(2,3-dimethylphenoxymethyl)-2-imidazoline,
AS/22-5-79

and 1-(N-(4-bromophenyl)carbamoyl)-2-(2,3-dimethylanilino-
methyl)-2-imidazoline, or an acid addition salt thereof.
7. 1-(N-4-chlorophenyl)carbamoyl)-2-(2,3-dimethyl-
anilino-methyl)-2-imidazoline or an acid addition salt
thereof.
8. 1-(N-(4-chlorophenyl)carbamoyl)-2-(2,3-dimethyl-
anilinomethyl)-2-imidazoline,
9. A process for the preparation of a compound of
formula (I) as defined in claim 1, or an acid addition
salt thereof, which comprises
(a) the reaction of a compound of the formula (II):
<IMG> (II)
or an acid addition salt thereof wherein X is as defined
in claim 1, with an isocyanate or with a compound of
the formula (III):-

wherein Y is as defined in claim 1 and X1 is a leaving
group;
(b) the reaction of a compound of formula (IV):
<IMG> (IV)
or a salt thereof wherein Y is as defined in claim 1 with
a compound of the formula (V):
<IMG> (V)
wherein X is as defined in claim 1 and Q is a carboxyl
group or a reactive derivative thereof, selected from
the group consisting of imidate, orthoester, thioimidate,
imidohalide, ester amidine, thioamide, nitrile, N-
alkoxycarbonylthioamide and thioester;
(c) the cyclisation of a compound of the formula
(VI):
26

- 27 - A584 C
<IMG> (VI)
wherein X and Y are as defined in claim 1 and
W is oxygen or sulphur;
(d) the reaction of a phenol or amine of the
formula (VII):
<IMG> (VII)
or an O-or N- metal compound thereof wherein
X is as defined in clalm 1 with a compound of
the formula (VIII):
(VIII)
<IMG>
or an acid addition salt thereof wherein Y is
AS/22-5-79
27

as defined in claim 1 and V is a leaving group selected
from the group consisting of chloro, iodo, bromo, alkyl-
sulphonyloxy and arylsulphonyloxy;
(e) the reaction of a compound of the formula (IX):
<IMG> (IX)
wherein X is as defined in claim 1 and P is a leaving
group selected from the group consisting of halo,
acyloxy, alkoxy, alkylthio, S-, SH sulphonyloxy and
carbalkoxy, with an amine of the formula (X):
<IMG>
wherein Y is as defined in claim 1; and thereafter if
desired converting a compound of the formula (I) to an
acid addition salt or converting an acid addition
salt of a compound of the formula (I) to the free base
or an alternative acid addition salt.
10. A method of controlling arthropod pests which
comprises applying to the pests or their environment a
compound of formula (I) as defined in claim 1.
28

11. A method according to claim 10, wherein the
compound applied to the pests or their environment is
at a concentration from 0.001 to 20% calculated by weight
of the free base.
12. A method according to claim 10 or 11, wherein
the pests are of the Order Acarina.
13. A method according to claim 10 or 11, wherein
the pests are ectoparasites of mammals or birds.
14. A method according to claim 10 or 11, wherein
the compound is applied by spraying, dusting or dipping.
15. A method according to claim 10 or 11, wherein
the compound is 1-(N-(4-chlorophenyl)-carbamoyl)-2-(2,3-
dimethylanilinomethyl)-2-imidazoline.
16. A method according to claim 10 or 11, wherein
said compound is selected from the group consisting of
1-(N-(4-methoxyphenyl)carbamoyl-2-(2,3-dimethylphenoxy-
methyl)-2-imidazoline, 1-(N-4-chlorophenyl)-carbamoyl)-2-
(2,3-dimethylanilinomethyl)-2-imidazoline, 1-(N-(4-
bromophenyl)carbamoyl)-2-(2,3-dimethylphenoxymethyl)-2-
imidazoline, 1-(N-(4-nitrophenyl)carbamoyl)-2-(2,3-
dimethylphenoxymethyl)-2-imidazoline, 1-(N-(4-fluoro-
phenyl)carbamoyl)-2-(2,3-dimethylphenoxymethyl)-2-
imidazoline, and 1-(N-(4-bromophenyl)carbamoyl)-2-(2,3-
dimethylanilinomethyl)-2-imidazoline and acid addition
salts thereof.
29

Description

~ ~ 86 2 1
_ ~ ~ A584
This învention relates to imidazolines, their
preparation and intermediates therefor, pesticidal
formulations containing the imidaæolines, and to their
use as pesticides.
We have discovered that the compounds of
formula (I) below and their acid addition salts have
activity against Arthropods, for. example against
members of the Order Acarina.
Compounds of formula ~I) are:-
'~X_C~
CO-NH ~ Y
, ~
wherein X is O or NH; and Y is Br, F, I, -NO2, -OR,
-CO2R, -CONRlR2 or -S02NRlR2, and, when X is NH, Y
may al~o be chosen from Cl, CN or alkyl of from 1 to
4 carbon atoms, in which R is an alkyl group of from ::
1 to 18 carbon atoms, preferably of from 1 to 4 or of
from 12 to 18 carbon atoms; and each of Rl and R2,
which may be the same or different, is hydrogen or

r
8621
- 2 - A584
an alkrl group .o rom l.to 18. ca~bon.atoms,
preferably of rom l.to 4' carbon.atoms-or o from
12 ~o 18 carbon a~oms, p.Te~er:ably onl~ one of Rl and
R being of from 12 ~o 18 carbon atoms.
Pre.ferred compounds o~.the ~o~mula C~ a~ be
represented by the formula (~a).
Me Me
X CH2 ~ N ~ ~Ia)
C0 _ NH ~ ~l
wherein X is as defined ab.o.ve and,~l is ~, Br, -N0
CH30-, or -C02C2H5, or X is NH and ~ is Cl.
Certain compounds o ormula ~I) mar exist in
' their solvated forms.
Pre~erred compounds o ~ormula CI) are:-
l-'(N-(4-methoxyphenyl)carbamo~ 2-~2~3~dimet,hyl-
phenoxymethyl)-2-imidazoline;
l-'~N-~4-chlorophenyl)carbamoyl)-2-(2,3-dimethyl- r
anilinomethyl)-2-imidazolîne;
1-'(N-~4-bromophenyl)carbamoyl)~2~C2~3~dimeth~1phenoxy~
methyl)-2-imidazoline;
l-'(N-(4-nitrophenyl)carbamorl)-2-(2,3-dlme.t,hrlphenox
methyl)-2-imidazolin'e;
:' ~
-, ., . .. , ,
~, . .

~J18621
A584
~ N-~4~1uorophenyl)carbamoyl)-2~(2,3-dimethylphenoxy-
meth~ 2~imidazoline-'and;
l-(N-~4-~r'omophe'n~I)carbamorl).~2~C2,3-d~me.t,hylanilino-
methyl)-2-imidazbline.'
The compounds of ormula CT) and.t~eir acid
' addition sal~s. have 'ac~i~ity ag~nst Arthropods. .The
compounds of formula Cl~ mar be used.to.control.pests
such as'Rhi'p'i'cep'hal'us a'p'p'e'nd~cu'la~us, ~'o'op'hl;lus
decolo'ratus J' Boophi'lus''ml'c'r~plus ?'.~h~p'~c'eP'~'al'us 'erert'si,
A~blyomma' ~e~'ra'e'um,''Ps'o`rop't'es'';vis and ~al'oma species
on animals and etranyc~'us spec.les on plants~
The compounds o~.t~e o'rmula C~) ater ~ave
improved stability in' aqueous media,.relati.re to known :
imidazolines.
The compounds o ormula ~I) mar be prepared by
any known method for the preparation o compounds of
an analogous structure.
.. ~ . . . . . .. . ~
.
. . , ~ .. .
- . :, . . .
. ., ,, :

L[3t862~
- 4 - A584
In particular the compounds of formula (I)
may be prepared from 2-substituted imidazolines of
formula ~II) or an acid addition salt thereof;
Me Me
~ X-CH2 ~ ~ (II)
wherein X is as defined above, either by a direct
addition reaction with an isocyanate (to give the
N~substituted carbamoyl compound) or by a substitution
reaction with a compound of formula (III):
Xl-CO.NI ~ Y (III~
wherein Y is as defined above and Xl is a leaving group
such as halo, acyl, alkoxy ~e.g. carbmates) or sulphonyloxy.
The reaction may be effected optionally in
water or an organic solvent, such as chloroform or
methylene chloride, preferably in the presence of a
base such as an alkali metal hydroxide, an alkali
metal carbonate, or a tertiary organic base, such as
triethylamine, pyridine or substituted pyridines or
piperidines, e.g. pentamethylpiperidine or tetramethyl-
piperidine; and generally at temperatures of -70C to
- ~ :, . .. , . ~ ~
,. ` ' ;' ,' . ~`' -; ~' , ~
. ~
- . ,,

2 1
A584
120C, preferably at temperatures of -10C to 40C.
Compounds of formula (I), in particular those
in which the group -CONH ~ Y~ is not strongly
electron withdrawing may be prepared by reacting an
ethylenediamine of formula (IV) or salt thereof;
H2N~CH2CH2NH C NH ~ Y (IV)
,
wherein Y is as defined hereinabove, with an appropriate
2,3-dimethylphenoxyalkyl or 2,3-dimethylanilinoalkyl
carboxylic acid or a reactive derivative thereof such as an :.-
imidate, thioimidate, imidohalide, ester, amidinej
thioamide, nitrile or carboxyalkylthioamide. These
reactants may be conveniently represented by formula (V):
e
` ~X--CH2--Q (V)
wherein X is as hereinbeforè defined and Q is a carboxyl
group or a reactive derivative thereof which produces
the imidazoline ring structure of formula (I) when
reacted with a compound of formula (IV).
Suitable derivatives include:-
. ~ . , ~, .
.
. - . ,
,

8621
- 6 - A584
~ Nll l~lk
-C \ (imidate), -C-OAlk (orthoester),
OAlk lAlk
,
~ H ~ NH
-C \ (thioimidate), -C (imido halide),
SAlk Hal
.
~ ~ NH
- \ (ester), -C (amidine),
OAlk NH2
-C ~ tthioamide), -C-N tnitrlle~, and
NH2
.
-C ~ h~-alkoxrca~onr~thio~ide) ~ A
\ ~ C Cthloes.ter)
NHCO2Alk ~ BAlk
- .whe.rein.'Alk' i~ an alkyl group ha~ing ~rom 1 to 6
carbon atoms, and one of ~ and B is S and the other ~s S or O . -
The conditions under which this reaction may be ca.rried
out of course depend.~ upon the nature of the starting materials
used, and a liquid medium may be present or absent; high and low . .
temperatures may be used, and various pressures employed.
.. ,_ .
. . , , , ., , ~
, .. , ,~ :
- . , .,j " . - ,. -.
,, :
;, ~ . . .
- .... . . . ..

~:~018621
_ 7 _ A584
When the carboxylic acid derivative is an imidate, this
is preferably in the form of an acid addition salt such as a
hydrogen halide salt, and may be prepared from the nitrile and a
suitable anhydrous alkanol such as ethanol or methanol in the
presence of dry diethyl ether or chloroform and hydrogen chloride
at a low temperature. The reaction may be carried out at a
temperature in the range of -20C to ambient temperature. The
reaction with an ethylenediamine of formula (IV) may be conducted in
an inert anhydrous medium,such as chloroform, methylene chloride
or ether. The reactants are preferably heated under reflux until
reaction is complete. ;
The thioimidate intermediates in the form of acid addition
salts may be prepared from the corresponding nitrile by reaction
with an alkyl mercaptan and a hydrogen halide gas at low tempera-
tures about 0C, in the presence of dry diethyl ether. The thio-
imidate may then be reacted with an ethylenediamine of formula ~IV)
the reaction being effected at the reflux temperature of the
reaction mixture.
The ester intermediates may be conveniently prepared from
the corresponding acid by known methods, and the acid itself may
- be prepared from the corresponding nitrile. They may then be
reacted with an ethylenediamine of formula (IV3, preferably in the
presence of a liquid medium which may be polar or non-polar. The
reaction is preferably carried out at an elevated temperature.
The compounds of formula (I) may be prepared from the
imidohalide intermediates by reaction with an ethylenediamine of
formula (IV), under anhydrous conditions in the presence or
absence of an acid acceptor and optionally at an elevated
: . ! .
,
. ~ '

~ ~86; :1
- 8 - A584
temperature. The reaction mixture may include a polar or non-
polar liquid medium such as a lower alkanol or an ether.
The amidine intermediate in the form of the base or acid
addition salts thereof, is preferably converted to a compound of
S formula (I) by heating under reflux with an ethylenediamine of
formula tIV) in the presence of a polar or non-polar liquid
medium, for example a lower alkanol, until ammonia ceases to be
evolved. The amidine intermediates themselves may be prepared
by any known method, but conveniently from the corresponding
dmidates by reaction with ammonia.
The thioamide and amide intermediates may be prepared from
the corresponding nitriles or by any other convenient method and
may be converted into compounds of formula (I) by heating with an
ethylenediamine of formula (IV), at a reflux or higher temperature,
in the presence or absence of a polar or non-polar solvent.
: Conveniently the reactions are partly effected under reduced
pressure to induce the removal of ammonia and/or hydrogen sulphide
from the reaction mixture.
The nitrile intermediates may be reacted in the presence-or
absence of a liquid medium with an ethylenediamine of formula (IV)
or a salt thereof; the reaction may be carried out in the presence
of hydrogen s,ulphide. A liquid medium such as a lower al~anol
may be included in the reaction mixture which may be heated to
reflux temperature, or to a higher temperature in a closed vessel,
optionally in the presence of an inert gas such as nitrogen.
.,
,..................................... .
. . . ~ - . ~ ". , .
. : . . .. . :
: . . . :-
- .

86Zl
~ 9 - - A584
.
It will of course be understood that where
the intermediate is the carboxylic acid, the ester
crthioamide, there may be isolated as an intermediate
the acylethylenediamines of formula (VI):
Me~_~le "W
X_SH2 _ C ~ (VI)
"N CH CH NH
IO NH ~ Y
wherein X and Y are as defined above and W is oxygen
or sulphur and these compounds may themselves be
converted in situ to a compound of formula (I), either
by separate treatment with a dehydrating agent such as
calcium oxide or by continuing the reaction to completion
under the original conditions giving rise to a compound
of formula (I).
The compounds of formula (I) may be prepared by
the reaction of a phenol or amine of formula -(VII), or
an 0- or N-metal compound thereof;
M~e ~e
~ X - H CV~I~
lS wherein X is as defined for fo~mula CI) ~ith a compound
of formula CVIIT):
_
~ ' :
, ~.
,

1iL6;1 86Z~
- 10 - A584
,~N\
V-CH2 ~ J (VIII)
CONH ~ y
wherein Y is as defined for formula (I), and V is
a leaving group derived from a suitable inorganic
or organic acid. Suitable derivatives are halo, suçh
as chloTo, iodo or bromo, alkylsulphonyloxy or aryl-
sulphonyloxy, such as ~-toluenesulphonyloxy.
The compounds of formula (VIII) may be in the
form of their bases or acid addition salts thereof.
The reaction may be carried out in an inert liquid medium
which is preferably a polar liquid such as acetonitrile
or isopropanol, or may be dimethylsulphoxide, sulpholane,
methyl ethyl ketone, dimethylformamide, acetone, dimethyl-
acetamide, N-methyl-2-pyrrolidone, or mixtures of the
foregoing. In the cases where V is chloro in a compound
of formula (VIII), then a small catalytic quantity of
an iodide salt, for example sodium iodide, or a phase
transfer catalyst, such as a quaternary ammonium salt,
such as benzyltrimethylammonium chloride, may advantageously
be included in the reaction mixture. The reactants may
be heated together under an inert atmosphere, such as
nitrogen, at the reflux temperature of the reaction
mixture.
. ~ ,................................. .
- .
, . , . ~ ,
.. .. ~ , . ,~. . . ~ -
- ., . ~.
- . .
- ~ .
~:

~ 6 21
- 11 - A584
The compounds of formula (I) may also be
preparedby reacting a compound of formula ~IX):
~ X-CHz ~ ~ ~IX)
f\P :~
in which X is as defined above and P is a leaving group
~such as halo, acyl, alkoxy, alkylthio, S , SH,
sulphonyloxy or carbalkoxy) with a suitably active
amine of formula (X):
y ~ NH2 (X)
wherein Y is as defined for formula (I).
The compounds of formula ~I) may be isolated
from the reaction mixtures as the free base or in the
form of an acid addition salt. The bases may be
converted into acid addition salts thereof by known
techniques with the aid of the appropriate acid, and
salts of the compound may also be conve`~ted into the
free bases or into other acid addition salts.
,, .
,, ~ . . . . .

~86Zl
- 12 - ~584
For use as a pesticide, the compounds of
formula (I) may be presented in the form of their
acid addition salts, or more preferahl~ as their ~ree bases.
Suitable salts of compounds of formula ~I) include
hydrohalide, sulphate, nitrate, phosphate, thiocyanate, .
acetate, propionate, stearate, naphthenate,
perchlorate, benzoate, methanesulphonate, ethane-
sulphonate, tosylate and benzenesulphonate acid -
addition salts thereof.
The compounds of formula ~I) may be used as pesticides
to combat insects, ticks, mites and other arthropods
including free living arthropods and those which are
ectoparasites of plants, mammals and birds and may be
used alone or in combination with an additive, which
may take the form of one or more of the carriers used
in the formulation art, such as: wetting, diluting,
stabilis~ng, thickening, emu~sifying, dispersing or
surface active agents or other standard carrier
ingredients.
A formulation ma~ be an aqueous solution of
an acid addition salt of a compound of formula (I),
or a suspension of a compound of formula (I) in water,
and may be used alone or in combination with suitable
surface active agents. The formulation ~ se may be
used alone or diluted in water for application to the
. ~
- ~ . . . . . .
- ~ - , : .: .: : : - ,

~8621
- 13 - A584
~,
pests or their immediate environment by way of
spraying or dipping.
A formulation may be in the form of a miscible
oil comprising a compound of formula ~I) in the form
of its free base or with equimolar quantity of a
suitable organic acid, such as oleic acid or naphthenic
acid, to provide a salt soluble in organic solvents,
and emulsifiers, and may be applied as an emulsion by
way of spraying or dipping~
A formulation may be a non-aqueous solution or
suspension of a compound of formula (I) in a suitable
organic solvent for the direct application by the ~pour-
on" method. A formulation may also take the form of a
wettable powder for dilution with water and application
by dipping or spraying. Other solîd formulations may
also be used for direct application without dilution,
such as-dusts, powders and granules.
A further formulation may be a paste, grease
or gel containing a compound of formula tI) and a
suitable carrier, and may be applied by spreading the
formulation over the infected area.
An acid addition salt or base of a compound of
formula (I) is preferably present in a pesticidal
formulation in an amount between 5 and 80~, calculated
by weight of the base, and particularly preferred
:. .
.
.- . . .

862~
- 14 - ~584
.
formulations containing about 20~, calculated by
weight of the base. The concentration of a compound
of formula ~I) applied to the pests or their immediate
environment may be in the range of 0.001%-20%,
calculated by weight of the base.
It will be appreciated from the foregoing that
what we will claim may comprise any novel feature
described herein, principally and not exclusive~ for
example:-
(a) A novel 2,3-dimethylphenoxyalkyl or 2,3-dimethyl-
anilinoalkyl imidazoline compound of formula (I) and
acid addition salts thereof;
(b) A method of preparation of a novel compound of
formula (I) and acid addition salts thereof;
(c) A method of controlling arthropod pests,
particularly members of the Order Acarina, by applying
to the pest or the pest's environment a compound of
formula (I);
(d) A pesticidal formulation comprising a compound
of formula (I) and a carrier thereof;
(e) A method of making a formulation comprising
admixture of a carrier and a compound of formula ~I)j and
(f) A novel intermediate formed in the preparation
of the imidazolines.
.
,. ' ' ' ~ '' ' ' '~ ' "'; ~ ', ,
', , . ~ '~ , ; '. ~ .

1~8621 ~
- 15 ~ A584
The following Examples are provided by way
of illustration of the present invention and should
not be construed as in any way constituting a
limitation thereof.
EXAMPLE 1
l-(N-~4-Chlorophenyl)carbamoyl)-2-(2~3-dimethylanilin
methyl)-2-imidazoline
2-~2,3-Dimethylanilinomethyl)-2-imidazoline
(4.20 g; 0.024 moles) was stirred in methylene chloride
(90 ml),cooled to 0C and a solution of 4-chlorophenyl
isocyanate (3.66 g; 0.024 moles) in methylene chloride
(10 ml) was then added dropwise. A white precipitate
formed rapidly. Stirring was continued for 2 to 3
hours after the addition at 0C, the reaction mixture
then allowed to reach ambient temperature and stirring
was cont;nued overnîght. The reaction mixture was then
evaporated to dryness under reduced pressure and the
solid residue so obtained recrystallised from propan-2-
ol to yield white crystals of l-(N-(4-chlorophenyl)-
2Q carbamoyl)-2-(2,3-dimethylanilinomethyl)-2-imidazoline
m.p. 153-155C.
.
.

~8621
.
- 16 - A584
EXAMPLES 2 T0 6
By methods analo~ous to that described in
Example 1 above the c ompounds of Examples 2 to 6
below were also prepared.
5 EXAMPLE 2
l-(N-~4-Bromophenyl~ ~a~banlo~ 2~c2?3--
dimethylphenoxymethyl)-2-imidazoline, monohydrate
m.p. 150-151C (white powder).
EXAMPLE 3
1-(N-(4-Methoxyphenyl)carbamoyl)-2-~2,3-dimethyl-
phenoxymethyl)-2-imidazoline, m.p. ï26-127C (white
powder).
. ,
EXAMPLE 4
l-(N-~4-Nitrophenyl)carbamoyl)-2-(2,3-dimethyl-
phenoxymethyl)-2-imidazoline~ monohydrate, m.p. 182-185C
(pale yellow powder).
- EXAMPLE S
l-(N-(4-Carbethoxyphenyl)carbamoyl)-2-(2,3-
dimethylphenoxymethyl)-2-imidazoline, m.p. 153C
20 (white powder).
,~, ,~ .

1~8621
- 17 - A584
BXAMPLB 6
l-(N-~4-Fluorophenyl)carbamoyl-2-(2,3-
dimethylphenoxymethyl)-2-imidazoline, m.p. ~about 5
impurity) 172-173C.
EXAMPLE 7
Preparation of l-(N-~-Bromopheny-l)carbamoy~-2-(2~3
dimethylphenoxymet~yl)-2-imidazoline
A. A solution of 2-(2,3-dimethylphenoxymethyl)-2-
imidazoline (20.4 g; 1.0 mol j in methylene chloride
t300 ml) was cooled to -65C and a solution of 4-bromo-
phenylisocyanate (19.8 g; 1.0 mol ~) in methylene
chloride (300 ml) added dropwîse during 30 minutes.
The reaction mixture was then allowed to warm to ambient
temperature and left to stand for 2 hours, when a
precipitate had formed. The reaction mixture was
evaporated under reduced pressure and the residue
recrystallised from acetone to give l-(N-(4-bromophenyl)-
carbamoyl)-2-(2,3-dimethylphenoxymethyl)-2-imidazoline
monohydrate, m.p. 150-151C.
B. ' via the N-Chlorocarbamoyl adduct 'of 2-(2,3-
dimethylphenoxymet~yl)-2-'imidaz'o'l'ine
A 17~ solution of phosgene in toluene (3.2 g
containing 0.5521 g; 0.00549 moles COC12) in dry
chloroform ~15 ml) was added slowly with stirring at
:

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0C to a solution of 2-(2,3~dimethrlp.henoxymethyl).2-
imidazoline (2~40 g, 0.0115 moles) in dry chloroform
~20 ml). When addi~ion was comple.te .the .reaction
mixture was .let at ambient .~emperature ~or 2 hours,
5. diluted with an equal volume o~ dry diethy.lether and
rapidly filtered. The filtrate, wh~ch contained the
N-chlorocarbamoyl adduct o 2-(2,3-dimethylphenoxy-
methyl)-2-imidazoline, was treated wi:th reshly
distilled dry 4-bromoaniline (1.22 g, 0.00714 moles)
10. and the mixture left at ambient .temperature o.~erni~ht
at which time tlc showed that the major compound was
the desired product. The mixture was. evaporated to
dryness in vacuo and .the residue taken up in a
_
mixture o aqueous sodium carbonate and dichloromethane.
15. The organic layer was washed with water, dried o~er
magnesium sulphate and evaporated to dryness to gi~e .
a residue which was purified as described in ~A)
above to give l-(N-~4-bromopehnyl)carbamoy1-2~2,3
dimethy~l-phenoxymethyl)-2-imidazoline, identical with
20. that obtained in ~A) above.
EXAMPLES 8 to 10
-
By methods analogous to that.described in ~xamp.le
1, the following compounds were prepared:
l-~N-(4-methylphenyl)carbamoyl)-2-~2,3~dimethyl~
25. anilinomethyl)-2-imidazoline (m.p. 154-155C);
l-(N-(4-cyanophenyl)caTbamoyl)~2~2,3~dime.thylanilino~
- .

621
~ 19 ~ ~5B4
me.thyl)~2~imldazoline; and
l-~N-(4~bromo~.henrl)carbamorl)~2~2~3~dimethyl~
anilinomethyl)~2-imidazoline (m.p. 161.6~162.2C)
~XAMPLE 11
~ngor.ged female ticks o the Biarra StTain of
Boo~hilus microPlus are immersed~ in gr~ups of 20
ticks, per concentration in washes o~ a range o
dilutions of the compound under test. The wash is
prepared immediately prior to the.test by dilution
(with water) of the compound under.test. The con-
stituents may be in the form o miscible oll or
wettable powder ormulations. The desi.red range o
concentrations for the ~test is obtained by urther
dilution of the master solution or wash.
lS The ticks are removed from the wash ater 1~
minutes, dried, and stuck dorsal side down on double-
sided adhesive tape. They remain ln this position
for 14 days when the numbers laying ~iable eggs are
determined. From this data a regression line is
plotted ~concentTation against ~ inhibition of egg-
production) and the IR99 (concentratlon a~ which 99
inhibition o egg-production occurs) is .deri.~ed.
The results obtained are .shown in Table 1 belo~.
.;
.
... .... . .
.. .. ; ~,~ , .. .

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. , . . .__ ..... _ ~
Compound Ex'ample
No '~R99
l-~N-~4-Chloro,phenyl.)carbamoyl- 1 0~029
. 2-~,3-dimeth~lanilinomet'hyl-)~
. 2-imid,azoline ¦ ,.,
. .l-(N-~4-Bromophenylcarbamoyl)~ . ~.0095
2-(2,3-dime~hylphenoxymethyl)- ,
. . 2-imidazoline
. l-~N-~4-Methoxyphenyl)carba- 3 0.0038
moy~)-2-(2,3-d'imethylphenoxy-
methyl)-2-imidazoline
1-(N-(4-Nitrophenyl~carbamoyl)- 4 0.010%
2-~,3-dimethylphenoxymethyl)-
2-imidazoline hydrate
l-(N-~4-Carbethoxyphenyl)carba- 5 0.019%
moyI)-2-(2,3-dimethylphenoxy-
methyl)-2-imidazoline. ,
The following formulations are given to
illustrate the way in which the pesticidal compounds
.of the i~vention can be applied to pests or envir,onments
susceptible to pest.attack.
FORMUL'A~ION 1
Dusting Powders
Active compound .1.0 20.0 parts by weight
Talc 99.0 80.0 " " "
'100 . O ' '1'00 . O
: .

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.
FORMULATION 2
Wettable Powder
Active compound 25.0 parts by weight
. Sodium dioctyl sulphosuccinate 1.0
5 Dispersol ACA 2.0 " " "
Kaolin 72.0 " " "
100.0
FORMULATION 3
Aqueous Dispersion
Active compound 20.0 parts by weight
10 Keltrol 0.4 " " "
Sodium dioctyl sulphosuccinate 0.5 " " "
Water 79.1 " " "
100.0
FORMULATION 4
Pour-On
15 Active compound 5.0 parts by weight
Dimethyl formamide 85.0 " " "
Castor oil 10.0 " " "
- ' '100. 0
, ,. ~ .-. ":, . . .

~ 8621
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FORMULATION 5
Grease
Active compound 6.0 parts by weight
Petroleum jelly 94.0 " " "
1'00 . O
.
FORMULATION 6
Miscible Oil
Compound from Example 3 10.0 parts by weight
Aromasol H 70.0 " " "
Nonyl phenol ethoxylate 20.0 " " "
100.0
STABILITY
10. The compound of Example 1 had a hal~1ie o g.reate~
than 6 months in an aqueous pH7 medium, ~hiie that
of 2-~2~3-dimethylphenoxy)~2-imidazoline ~as approx~
imately 2 weeks.
EXAMPLE 12
Using the procedure of Example 1, except that no re-
crystallization step was used, l-(N-(4-dimethylsulphon-
amidophenyl)carbamoyl)-2-(2,3-dimethylanilinomethyl)-
2-imidazoline, m.p. 151-153C was prepared.
.
~:
.- ~ . :: :: :- :: - ..
:. : . . :~ ~ : ,: