Compounds of formula (I) are pesticides active against arthropods. ##STR1## wherein R.sup.1, R.sup.2, and R.sup.3 are H, alkyl, alkoxy, halo, CN or CF.sub.3 or two are linked to form a 3 or 4 carbon atom group; PA1 X is O or NA where A is H or alkyl; PA1 R is H or alkyl; PA1 R.sup.4 is H or optionally substituted alkyl, aryl, aralkyl, alkenyl or alkynyl; and PA1 R.sup.5 is --CB. R.sup.6 where B is O, S or NR.sup.7 where R.sup.7 is H, alkyl, alkoxy, or optionally substituted aryl or aralkyl; PA1 R.sup.6 is H, R.sup.8, OR.sup.8, SR.sup.8 or NR.sup.9 R.sup.10 where R.sup.8 is alkyl, alkenyl or optionally substituted aryl, aralkyl or aryloxyalkyl; and R.sup.9 and R.sup.10 are H, alkyl or optionally substituted aryl or aralkyl; The invention also comprises processes for the preparation of compounds (I), formulations containing them, and their use as pesticides.

This invention relates to novel amides, processes for their preparation, 
intermediates useful in those processes, pesticidal formulations 
containing the amides, and their use as pesticides. 
Compounds of formula (I) below have activity against Arthropods, in 
particular against members of the Order Acarina. 
##STR2## 
In formula (I), R.sup.1, R.sup.2 and R.sup.3 are the same or different and 
are selected from hydrogen, alkyl, alkoxy, halo, cyano and trifluoromethyl 
or two of R.sup.1, R.sup.2 and R.sup.3 are linked to form a 3 or 4 carbon 
atom group; 
X is O or NA where A is hydrogen or alkyl; 
R is hydrogen or alkyl; 
R.sup.4 is hydrogen; alkyl; substituted alkyl wherein the substituent(s) 
are selected from halo, hydroxy, cyano, alkoxy, aryloxy, alkylthio, 
arylthio and substituted amino; alkynyl; alkenyl; haloalkenyl; aralkyl; 
aryl; or a substituted aryl or aralkyl group where the substituents are 
selected from alkyl, alkoxy, halo, cyano and trifluoromethyl; and 
R.sup.5 is a group 
##STR3## 
where B is O, S or NR.sup.7 where R.sup.7 is hydrogen, CN, alkoxy, alkyl, 
aralkyl, aryl or a substituted aryl or aralkyl group where the 
substituents are selected from alkyl, alkoxy, halo, cyano and 
trifluoromethyl; and R.sup.6 is hydrogen or a group R.sup.8, OR.sup.8, 
SR.sup.8 or NR.sup.9 R.sup.10 where R.sup.8 is alkyl, aryloxyalkyl, 
alkenyl, aralkyl, aryl or a substituted aryl, aralkyl or aryloxyalkyl 
group where the substituents are selected from alkyl, alkoxy, halo, cyano 
and trifluoromethyl, and R.sup.9 and R.sup.10 are the same or different 
and are selected from hydrogen, alkyl, aralkyl, aryl or substituted aryl 
or aralkyl where the substituents are selected from alkyl, alkoxy, halo, 
cyano and trifluoromethyl. 
Certain compounds of formula (I) where X is NA or B is NR.sup.7 and 
intermediates as hereinafter defined are able to form acid addition salts, 
and references to such compounds include references to acid addition salts 
unless the conext clearly indicates otherwise. 
When used herein, `alkyl` and `alkoxy` mean a straight or branched alkyl or 
alkoxy group, respectively, having from 1 to 20 such as 1 to 5 carbon 
atoms, such as methyl and methoxy; `halo` means fluoro, chloro, bromo or 
iodo; `alkenyl` means an alkenyl group having from 2 to 20 carbon atoms, 
and having one or more double bonds, such as prop-2-enyl; `aryl` means 
phenyl or naphthyl; and `aralkyl` means alkyl substituted by an aryl 
group, such as benzyl. When R.sup.4 is alkenyl, it is an alkenyl group 
which is saturated in the 1-position. 
One preferred sub-group or compounds of formula (I) are those of formula 
(II): 
##STR4## 
wherein R.sup.1, R.sup.2, R.sup.3, R and X are as defined above and Y is 
alkyl, alkenyl aryl or aralkyl. 
Preferred compounds of formulae (I) and (II) are those having one or more 
of the following features: 
X is O or NH; 
R is hydrogen or methyl; 
R.sup.1 is in the 2-position and R.sup.2 is in the 3-position, particularly 
those where R.sup.3 is hydrogen and at least one of R.sup.1 and R.sup.2 is 
halo or alkyl; 
R.sup.4 is hydrogen; 
Y is alkyl aryl or aralkyl, such as ethyl; phenyl or benzyl 
B is S; and 
R.sup.6 is optionally substituted phenylamino. 
The compound of formula (I) may be made by any method known for making 
compounds having analogous functional groups. These methods include: 
(a) the reaction of a compound of formula (III): 
##STR5## 
wherein R.sup.1, R.sup.2, R.sup.3, X and R are as defined in formula (I) 
and Z is a leaving group such as alkoxy, alkylthio, aralkoxy, aralkylthio 
or mercapto with a compound of formula (IV): 
##STR6## 
or a salt thereof wherein R.sup.4 and R.sup.5 are as defined in formula 
(I): 
(b) the reaction of a phenol or aniline of formula (V): 
##STR7## 
or an O- or N- metal derivative thereof (such as an alkali metal 
derivative) wherein X, R.sup.1, R.sup.2 and R.sup.3 are as defined in 
formula (I) with a compound of formula (VI): 
##STR8## 
wherein R, R.sup.4 and R.sup.5 are as defined in formula (I) and V is a 
leaving group derived from a suitable organic or inorganic acid, such as 
halo (e.g. chloro, bromo or iodo), alkylsulphonyloxy or arylsulphonyloxy 
(e.g. p-toluenesulphonyloxy); 
(c) the reaction of a compound of formula (VII): 
##STR9## 
wherein R.sup.1, R.sup.2, R.sup.3, X, R and R.sup.4 are as defined in 
formula (I) with a compound of formula (VIII): 
EQU W-R.sup.5 
wherein R.sup.5 is as defined in formula (I) and W is a leaving group such 
as halo; 
(d) the reaction of a compound of formula (IX): 
##STR10## 
wherein R.sup.1, R.sup.2, R.sup.3, X and R are defined in formula (I) and 
M.sup..sym. is one equivalent of a metal ion, such as K.sup.+ or Na.sup.+ 
with a compound of formula (X): 
##STR11## 
wherein R.sup.4 and R.sup.5 are as defined in formula (I) and V is as 
defined in relation to formula (VI); 
(e) for those compounds where B is S, the reaction of a compound of formula 
(XI): 
##STR12## 
wherein R.sup.1, R.sup.2, R.sup.3, X, R, R.sup.4 and R.sup.5 are as 
defined in formula (I) with P.sub.2 S.sub.5 or other suitable inorganic 
sulphides; 
(f) for those compounds where R.sup.4 is hydrogen, the reaction of a 
compound of formula (XII): 
##STR13## 
wherein R.sup.1, R.sup.2, R.sup.3, X and R are as defined in formula (I) 
or a compound of formula IX as hereinbefore defined with a compound of 
formula (XIII): 
##STR14## 
wherein R.sup.5 is as defined in formula (I); and 
(g) for those compounds where B is O or S and R.sup.6 is NR.sup.9 R.sup.10 
where R.sup.9 is hydrogen, the reaction of a compound of formula (XIV): 
##STR15## 
wherein R.sup.1, R.sup.2, R.sup.3, X, R and R.sup.4 are as defined in 
formula (I) with a compound of formula (XV): 
EQU R.sup.10 --N.dbd.C.dbd.B 
wherein R.sup.10 is as defined in formula (I) and B is O or S. 
Process (a) will normally be effected in a dry aprotic solvent, such as 
ether, chloroform or dichloromethane, at a moderate temperature, such as 
-30.degree. to 50.degree. C., e.g. at ambient temperature. 
Processes (b) and (d) will normally be effected in a dry polar solvent, 
such as a ketone, e.g. butanone, preferably at an elevated temperature, 
e.g. at reflux. 
Process (c) will normally be effected in a dry polar solvent, such as ether 
or dichloromethane, at ambient or depressed temperature, e.g. -20.degree. 
C. to room temperature. 
Process (e) will normally be effected in a dry aprotic solvent, such as 
benzene or pyridine, at ambient or elevated temperature, e.g. at reflux. 
Process (f) will normally be effected in an anhydrous solvent at an 
elevated temperature, such as refluxing tetralin or diphenyl, in the 
presence of aluminium trichloride. 
Process (g) will normally be effected in a dry aprotic solvent, such as 
ether, at ambient or depressed temperature, such as -20.degree. C. to room 
temperature, e.g. about 0.degree. C. 
The anilino compounds of formula (I) may be isolated from the reaction 
mixture 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 
compounds may also be converted into the free bases or into other acid 
addition salts. 
For use as a pesticide, the anilino compounds of formula (I) may be 
presented in the form of their free bases, or as acid addition salts 
thereof. Suitable salts of formula (I) include hyrohalide, sulphate, 
nitrate, phosphate, thiocyanate, acetate, propionate, stearate, 
naphthenate, perchlorate, benzoate, methanesulphonate, ethanesulphonate, 
tosylate and benzenesulphonate acid addition salts thereof. 
The compounds of formula (I) may be used to combat insects, ticks, mites, 
and other arthropods including free living arthropods and those which are 
ectoparasites of plants, mammals and birds. They are especially useful for 
the control of acarine ectoparasites of animals, particularly those ticks 
of the genera Boophilus, Rhipicephalus, Amblyomma, Hyalomma, Ixodes, 
Haemaphysalis, Dermacentor, and Anocentor; mites of veterinary importance, 
such as Psoroptes spp., Psorergates, spp., Sarcoptes spp., Chorioptes spp. 
and Demodex spp., e.g. the sheep scab mite Psoroptes ovis; and other 
ectoparasites of the sub-Orders Ixodoidea and Sarcoptiformes; and 
Tetranychus species on plants. Such ectoparasites infest stock and 
domestic animals and fowls, depending upon the location of the host and 
the particular ectoparasites. Common hosts are cattle, pigs, sheep, goats, 
horses, camels, chickens, dogs and cats. 
The compounds of formula (I) 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, stabilising, thickening, 
emulsifying, dispersing or surface active agents or other standard carrier 
ingredients. 
A formulation may 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 per se may be used alone or diluted in 
water for application to the pests or their immediate environment by way 
of spraying, dipping, or other known means of application. 
A formulation may be in the form of a water-miscible oil comprising a 
compound of formula (I) per se or, when X is NA, or B is NR.sup.7, with an 
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 is applied as an emulsion by way of spraying or dipping. 
A formulation may be a non-aqueous solution or suspension of compound (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 solid 
formulations may also be used for direct application without dilution such 
as dusts, powders and granules. 
Formulations may also be in the form of an aerosol, a foam or an 
impregnated article, such as a tag or collar. These may be prepared using 
conventional techniques. 
A further formulation may be a paste, grease or gel containing a compound 
of formula (I) and a suitable carrier, and may be applied by spreading the 
formulation over the infested area. 
A compound of formula (I) is preferably present in a pesticidal formulation 
in an amount between 1 and 80%, particularly preferred formulations 
containing about 20%, calculated by weight of the compound (I) per se. The 
concentration of a compound of formula (I) applied to the pests or their 
immediate invironment may be in the range of 0.001%-20%, calculated by 
weight of the compound (I) per se. 
It will be appreciated from the foregoing that what we will claim may 
comprise any novel feature described herein, principally and not 
exclusively, for example: 
(a) A compound of formula (I); 
(b) A method of preparation of a compound of formula (I) 
(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 therefor. 
(e) A method of making a formulation comprising admixture of a carrier and 
a compound of formula (I). 
(f) A compound of formula (I) for use as a pesticide. 
(g) Novel intermediates used in processes (a)-(g).

EXAMPLE 1 
N-[(2,3-Dimethylphenoxy)thioacetyl]-N'-ethoxycarbonylethane-1,2-diamine 
(i) A stirred suspension of ethyl (2,3-dimethylphenoxy)acetimidate 
hydrochloride (13 g) in dry ether (100 ml) was treated with dry 
triethylamine (5.39 g). The resultant mixture was treated with dry gaseous 
hydrogen sulphide for 2 hours at 0.degree. and set aside at 
0.degree.-5.degree. overnight. The resulting solids were removed by 
filtration and the filtrate evaporated to dryness to yield ethyl thiono 
(2,3-dimethylphenoxy)acetate as a colourless solid, m.p. 
39.degree.-40.degree.. 
(ii) A solution of N-ethoxycarbonylethane-1,2-diamine (2 g) in dry 
chloroform (10 ml) was added dropwise to a stirred solution of ethyl 
thiono (2,3-dimethylphenoxy) acetate (3.4 g) in dry chloroform (30 ml) at 
ambient temperature. After stirring overnight the solvent was removed 
under reduced pressure and the resulting solid recrystallised from 
isopropanol to yield the title product, 104.degree.-105.degree. C. 
EXAMPLE 2 
N-[(2,3-dimethylphenoxy)thioacetyl]-N'-phenylthiocarbamoyl-1,2-diaminoethan 
e. 
(i) A solution of ethyl thiono-(2,3-dimethylphenoxy)-acetate (2.85 g, 5% 
molar excess) in dry ether (10 ml) was added dropwise to a stirred 
ethereal solution (30 ml) of dry 1,2-diaminoethane (0.69 g) at 0.degree. 
C. After 1-2 hours tlc analysis indicated completion of reaction. 
(ii) The ethereal solution resulting from the previous reaction was treated 
with an equimolar solution of phenyl isothiocyanate (1.55 g) in dry ether 
(10 ml) at 0.degree. C. and the stirred reaction mixture allowed to rise 
to ambient temperature overnight. The title compound was recovered by 
filtration and subsequent vacuum desiccation; mp 112.degree.-113.degree. 
C. 
EXAMPLES 3 TO 10 
By methods analogous to those described in Examples 1 and 2 above, the 
compounds of examples 3 to 10 below were prepared. 
EXAMPLE 3 
N-[(2,3-dimethylphenoxy)-thioacetyl]-N'-(benzyloxycarbonyl)-ethane-1,2-diam 
ine; mp 91.degree.-92.degree. C. 
EXAMPLE 4 
N-[(2,3-dimethylphenoxy)-thioacetyl]-N'-(4-chlorophenyl 
carbamoyl)ethane-1,2-diamine; mp 110.degree. C. 
EXAMPLE 5 
N-[(2,3-dimethylphenoxy)-thioacetyl]-N'-(methylthiocarbamoyl)ethane-1,2-dia 
mine; mp 120.degree. C. 
EXAMPLE 6 
N,N'-Bis[(2,3-dimethylphenoxy)-thioacetyl]-ethane-1,2-diamine; mp 
168.degree. C. 
EXAMPLE 7 
N-[(2,3-dimethylphenoxy)thioacetyl]-N'-acetyl-ethane-1,2-diamine; mp 
119.degree.-121.degree. C. 
EXAMPLE 8 
N-[(2,3-dimethylphenoxy)-thioacetyl]-N'-[3-phenoxybenzyloxycarbonyl]-ethane 
-1,2-diamine; mp 76.degree. C. 
EXAMPLE 9 
N-[(2,3-dimethylphenoxy)-thioacetyl]-N'-(4-methoxybenzoyl)-ethane-1,2-diami 
ne; mp 148.degree.-149.degree. C. 
EXAMPLE 10 
N-[(2,3-dimethylphenoxy)-thioacetyl]-N'-(N"-methyl-N"-phenylcarbamoyl) 
ethane-1,2-diamine; mp 111.degree.-113.degree. C. 
EXAMPLE 11 
Engorged female ticks of the Biarra Strain of Boophilus microplus are 
immersed in groups of 20 ticks per concentration in a range of 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 constituents 
may be in the form of miscible oil or wettable powder formulation. 
The desired range of concentrations for the test is obtained by further 
dilution of the master solution or wash. 
The ticks are removed from the wash after 10 minutes, dried, and stuck 
dorsal side down on double-sided adhesive tape. 
They remain in this position for 14 days when the proportions of viable 
eggs laid are determined. From this data a regression line is plotted 
(concentration against % inhibition of viable egg production) and the IR50 
and IR99 (concentrations at which 50% and 99% inhibition respectively of 
viable egg production occurs). 
TABLE I 
______________________________________ 
Compound IR50 IR99 
______________________________________ 
Urethane product of Example I 
0.018 0.10 
______________________________________ 
In a similar manner the IR50 of other compounds of the invention against 
Boophilus microplus Biarra was determined. The results are shown in Table 
1a. 
TABLE 1a. 
______________________________________ 
Compound IR50 
Example No. (%) 
______________________________________ 
2 0.00061 
3 0.004 
4 (42% inhibition at 0.01%) 
5 (85% inhibition at 0.03%) 
6 0.03 
7 (100% inhibition at 0.03%) 
______________________________________ 
In a further test using the compound of Example 1, the IR50 and IR99 were 
determined as 0.0054% and 0.029%, respectively. 
EXAMPLE 12 
Test compounds were formulated in polyethyleneglycol and 0.622 .mu.l was 
injected into ticks at a site just ventral to the mouth parts. After 14 
days the percentage inhibition of viable egg production (IR) was 
determined. The results are shown in Table 2 below. 
TABLE 2 
______________________________________ 
Compound % IR 
______________________________________ 
Urethane Product of Example I 
80% at 10 mg/ml. 
50% at 1.0 mg/ml. 
100% at 0.1 mg/ml. 
______________________________________ 
In a similar manner, other compounds of the invention were tested against 
ticks. The results are shown in Table 2a. 
TABLE 2a 
______________________________________ 
Compound of % IR 
Example No. at 1 mg-ml 
______________________________________ 
2 80 
3 30 
4 30 
______________________________________ 
EXAMPLE 13--WETTABLE POWDER 
______________________________________ 
Active compound 25.0 parts by weight 
Kaolin 69.5 parts by weight 
Sodium Alkyl Naphthalenesulphonate 
2.5 parts by weight 
Sodium Salt of condensed Naphthalene 
Sulphonic acid 3.0 parts by weight 
100.0 
______________________________________ 
EXAMPLE 14--AQUEOUS SUSPENSION 
______________________________________ 
Active compound 50.0 parts by weight 
Sodium carboxy methyl Cellulose 
0.5 parts by weight 
Calcium lignosulphonate 
5.0 parts by weight 
para-Chloro-meta-cresol 
0.2 parts by weight 
Water 44.3 parts by weight 
100.0 
______________________________________ 
EXAMPLE 15--AQUEOUS SOLUTION. 
______________________________________ 
Active compound 10.0 parts by weight 
Ethylan KEO 0.5 parts by weight 
Deionised water 89.5 parts by weight 
100.0 
______________________________________ 
EXAMPLE 16--WATER-MISCIBLE OIL 
______________________________________ 
Active compound 10.0 parts by weight 
Ethylan KEO 20.0 parts by weight 
"Esso 200" 70.0 parts by weight 
100.0 
______________________________________ 
EXAMPLE 17--PASTE 
______________________________________ 
Active compound 45.0 parts by weight 
Glycerol 5.0 parts by weight 
Xanthan Gum 2.5 parts by weight 
Methyl para-Hydroxy-Benzoic Acid 
0.2 parts by weight 
Fine Silica 5.0 parts by weight 
Water 42.3 parts by weight 
100.0 
______________________________________ 
EXAMPLE 18--POUR-ON 
______________________________________ 
Active compound 2.0 parts by weight 
Corn oil 83.0 parts by weight 
Iso-propanol 15.0 parts by weight 
100.0 
______________________________________ 
EXAMPLE 19--DUST 
______________________________________ 
Active compound 1.0 parts by weight 
Talc 99.0 parts by weight 
100.0 
______________________________________ 
EXAMPLE 20--GREASE 
______________________________________ 
Active compound 1.5 parts by weight 
White petroleum jelly 
8.5 parts by weight 
100.0 
______________________________________