Pesticides

A compound of Formula I: ##STR1## wherein: Ar represents a polynuclear carboxyclic or heterocyclic fused ring system having at least one carbocylic or heterocyclic ring of aromatic character, the polynuclear ring system optionally carrying one or more of the substituents halogen, C.sub.1 -C.sub.6 alkyl --CF.sub.3, or --OCF.sub.y H.sub.3-y, wherein y is 0-3; PA0 n is 0 or 1 and m is 1-11 PA0 Z represents a group of Formula: ##STR2## wherein: R.sub.A and R.sub.B which may be identical or different each represent hydrogen or methyl; PA0 R.sub.C represents methyl; PA0 R.sub.D represents methyl, ethyl, n-propyl, isopropyl, t-butyl, or vinyl; and PA0 R.sub.E represents hydrogen or methyl or wherein: PA0 R.sub.C and R.sub.D together with C.sub..beta. form a cyclopropane or a cyclobutane ring or goether form a methylene group (.dbd.CH.sub.2) or wherein: PA0 R.sub.A and R.sub.B together with C.sub..alpha. and C.sub..beta. form a cyclobutane ring.

This invention relates to pesticidal compounds, compositions, the 
application and production thereof and in particular to pesticidal amides. 
Accordingly, the present invention comprises a compound of Formula I. 
##STR3## 
wherein Ar represents a polynuclear carboxyclic or heterocyclic fused ring 
system having at least one carbocylic or heterocyclic ring of aromatic 
character, the polynuclear ring system optionally carrying one or more of 
the substituents halogen, C.sub.1 -C.sub.6 alkyl, --CF.sub.3, or 
--OCF.sub.y H.sub.3-y, wherein y is 0-3; 
n is 0 or 1 and m is 1-11 
Z represents a group of Formula: 
##STR4## 
wherein: R.sub.A and R.sub.B which may be identical or different each 
represent hydrogen or methyl; 
R.sub.C represents methyl; 
R.sub.D represents methyl, ethyl, n-propyl, isopropyl, t-butyl, or vinyl; 
and 
R.sub.E represents hydrogen or methyl or wherein: 
R.sub.C and R.sub.D together with C.sub..beta. form a cyclopropane or a 
cyclobutane ring or toether form a methylene group (.dbd.CH.sub.2) or 
wherein: 
R.sub.A and R.sub.B together with C.sub..alpha. and C.sub..beta. form a 
cyclobutane ring. 
The ring attached to oxygen or carbon respectively of (O).sub.n or 
(CH.sub.2).sub.m in the chain is typically aromatic and preferably 
benzenoid. 
In preferred embodiments according to the present invention Ar is of 
Formula II. 
##STR5## 
wherein B represents a 5 or 6 membered carbocyclic or heterocyclic ring 
optionally fused to a further such ring C. Ar may contain only two rings 
as for example when Ar represents naphthyl or ring B may be fused to a 
further ring C in which case when ring B is 5-membered the ring system may 
be linear as for example in fluorenyl or dibenzofuranyl. When, however, 
ring B is 6-membered, for example A and B together represent naphthyl, any 
further ring C is usually fused to ring B across the 5, 6 or 7, 8 
positions so that the ring system is non-linear as for example in 
phenanthrenyl. 
At least when Ar comprises a naphthyl ring system it is preferably 
substituted by one or more halogen atoms (usually chlorine, bromine or 
fluorine) which may be identical or different, substitution in ring B for 
example at the 5, 6 and 7 positions, being of particular interest. Usually 
mono- or disubstitution is preferred and the 5-bromo 2 -naphthyl moiety is 
especially preferred. 
Although n may be 0 or 1 and m 1-11, when n is 0, m is preferably 1 or 7-9 
and especially 8 and when n is 1, m is preferably 6-8 and especially 7. 
In the group Z, it is generally preferably for R.sub.A and R.sub.B to both 
represent hydrogen or for one of R.sub.A and R.sub.B to represent hydrogen 
and the other to represent methyl. R.sub.C preferably represents methyl, 
R.sub.D methyl or vinyl, and R.sub.E hydrogen or methyl, the groups 
--CH.sub.2 CHMe.sub.2, --CH.sub.2 CMe.sub.3, --CH.sub.2 
CHMeEt--CHMeCHMe.sub.2 and --CH.sub.2 CMe.sub.2 CH.dbd.CH.sub.2 being of 
especial interest. 
In accordance with a further aspect of the present invention, a pesticidal 
composition comprises a compound of Formula I incorporated in an emulsion, 
emulsifiable concentrate, spray, aerosol, wettable powder, mosquito coil 
or vapour mat or is carried by a dust or dry granular solid. 
It will be appreciated that compositions of the present invention can be 
prepared, for example, by mixing one or more compounds of Formula I with 
an appropriate solid carrier, solvent or diluent which may contain a 
surface active agent. The compositions may also contain synergists, or 
pesticidally active compounds, for example synthetic pyrethroids, to 
improve kill or knock-down or both. 
Pesticidal compositions according to the present invention normally contain 
from 0.001 to 25% by weight of the compound of Formula I but the 
compositions can contain higher concentrations of active ingredient of 
Formula I e.g. up to 95% for compositions to be sold as concentrates for 
dilution before use by the ultimate user. 
The compositions of the invention may include diluents such as hydrocarbon 
oils, e.g. xylene or other petroleum fractions, water, anionic, cationic, 
or non-ionic surface-active agents, anti-oxidants and other stabilisers as 
well as perfumes and colouring matters. These inert ingredients may be of 
the type and in proportions such as are conventionally used in pesticidal 
compositions. 
Compositions according to the present invention and compounds of Formula I 
find application as insecticides for controlling weevils and aphids, for 
example, and are also of interest for the control of acarids (acarine 
species), e.g. mites and ticks. 
Accordingly, in a further aspect, the present invention comprises a method 
of pest control in which a pest or an environment which is susceptible to 
attack by pests is treated with a pesticidal compound of Formula I or a 
pesticidal composition as hereinbefore described. Control may be exerted 
in a domestic or agricultural scale. 
Compounds of Formula I may be produced by a Wittig reaction. 
According to a further aspect of the present invention, a process for the 
production of a compound of Formula I comprises treating a phosphorane of 
Formula III 
##STR6## 
with a carbonyl compound of Formula IV: 
EQU Ar(O).sub.n (CH.sub.2).sub.m CHO (IV) 
in which Formulae Ar, Z, n and m are as hereinbefore defined.

Aldehydes of Formula IV are preparable by the following routes or 
adaptations thereof. (All temperatures mentioned in this specification are 
in 0.degree. C.). 
ROUTE A 
(a) 5-Bromo-2-hydroxymethyl-naphthalene 
Methyl 5-bromo-2-naphthoate (6.0 g) in benzene (100 ml) was cooled at 
7.degree. and a 70% solution of Vitride (sodium dihydro 
bis-2-methoxyethoxy aluminate) (10 ml) in benzene (20 ml)) was added 
dropwise with stirring. The solution was stirred for 4 hours at this 
temperature and decomposed with water and dilute hydrochloric acid. The 
benzene solution was separated and washed successively with dilute acid, 
saturated sodium bicarbonate solution and saturated sodium chloride 
solution, dried over sodium sulphate and evaporated to give a solid (4.8 
g), m.p. 76.degree.-77.degree.. 
The following are similarly prepared. 
______________________________________ 
2-Hydroxymethyl-9,10-dihydrophenanthrene 
n.sub.D.sup.20 1.6530 
2-Hydroxymethylphenanthrene 
m.p. = 125-127.degree. 
5,8-Dibromo-2-hydroxymethylnaphthalene 
m.p. = 88-90.degree. 
9-Bromo-3-hydroxymethylphenanthrene 
m.p. = 136-142.degree. 
6-Bromo-2-hydroxymethylnaphthalene 
m.p. = 70-71.degree. 
______________________________________ 
(b) 5-Bromo-2-naphthaldehyde 
The 5-bromo-2-hydroxymethylnaphthalene alcohol (4.8 g) dissolved in 
methylene chloride (100 ml) was stirred at room temperature while 
pyridinium chlorochromate (7.6 g) was added in portions over 10 minutes. 
After stirring for a further 4 hours, ether (200 ml) was added and the 
mixture filtered through a pad of celite/charcoal. The filtrate was 
concentrated under reduced pressure and chromatographed on silica, eluting 
with ether. Evaporation yielded the aldehyde (3.8 g), m.p. 
73.degree.-74.degree.. 
The following are similarly prepared. 
______________________________________ 
9,10-Dihydrophenanthrene-2-carboxaldehyde 
n.sub.D.sup.20 1.6804 
Phenanthrene-2-carboxaldehyde 
m.p. = 54-55.degree. 
5,8-Dibromo-2-naphthaldehyde 
m.p. = 83-87.degree. 
9-Bromo-3-phenanthraldehyde 
m.p. = 130-32.degree. 
6-Bromo-2-naphthaldehyde 
m.p. = 50-52.degree. 
______________________________________ 
This method is of general applicability for the conversion of known esters 
ArCOOMe to aldehydes ArCHO. 
ROUTE B.sub.1 
(a) Methyl-5-bromo-2-naphthylvinyl ether 
A solution of phenyllithium (10.2 ml of a 2.7M solution in 
cyclohexane/ether) was added to a stirred suspension of 
methoxymethyltriphenylphosphonium chloride (6.4 g) in dry ether (100 ml) 
under nitrogen. After 30 minutes, a solution of 5-bromo-2-naphthaldehyde 
(2.8 g) in ether (20 ml) was added and stirring continued overnight. A few 
drops of water were added and the solution decanted, concentrated under 
reduced pressure and chromatographed on silica eluting with 50% 
ether/petrol. Evaporation yielded a gum (3.5 g), n.sub.D.sup.20 =1.6630. 
The following are similarly prepared. 
______________________________________ 
n.sub.D.sup.20 
______________________________________ 
Methyl 2-phenanthrenylvinyl ether 
Semi-solid 
Methyl 9,,10-dihydrophenanthrenylvinyl ether 
1.6650 
Methyl 2-dibenzofuranylvinyl ether 
1.6406 
______________________________________ 
(b) 5-Bromo-2-naphthaleneacetaldehyde 
The methyl 5-bromo-2-naphthylvinyl ether (2.8 g) dissolved in 
tetrahydrofuran (55 ml) was stirred with concentrated hydrochloric acid 
(10 ml) for 1 hour at room temperature. Ether and water were added and the 
organic solution separated and washed with water, saturated sodium 
bicarbonate and saturated sodium chloride solutions. Evaporation gave a 
liquid (2.8 g), n.sub.D.sup.20 =1.6444. 
The following are similarly prepared. 
______________________________________ 
n.sub.D.sup.20 
______________________________________ 
Phenanthrene-2-acetaldehyde 
1.6702 
9,10-Dihydrophenanthrene-2-acetaldehyde 
1.6372 
Dibenzofuran-2-acetaldehyde 
1.6304 
______________________________________ 
This method is of general applicability for the conversion of known 
aldehydes AfCHO to aldehydes of Formula IV: ArCH.sub.2 --CHO. 
ROUTE B.sub.2 
To the solution produced by reacting sodium (0.92 g) in dry ethanol (60 ml) 
was added methoxymethyltriphenylphosphonium chloride (15.2 g). After 
stirring at room temperature for 0.5 hours, 2-naphthaldehyde (5.5 g) was 
added and the mixture heated at reflux for 5 hours. The mixture was 
evaporated to dryness and extracted with boiling ether, cooled to 
precipitate triphenylphosphine oxide, filtered and evaporated. The residue 
in dichloromethane (5 ml) was passed through a column of alumina and 
eluted with hexane to give 2-(2-methoxyvinyl) naphthalene (3.6 g), 
n.sub.D.sup.20 1.6505, which was hydrolysed in dioxan (50 ml) containing 
2N sulphuric acid (5 ml) at 70.degree. for 5 hours. After adding water, 
the mixture was extracted with ether, and the extract washed, (saturated 
sodium chloride), dried, (sodium sulphate) and evaporated to give 
2-naphthylacetaldehyde (3.25 g) n.sub.D.sup.20 1.6232. 
ROUTE C 
2-Fluorenyl acetaldehyde 
A solution (2 ml) of 2-bromofluorene (4.6 g) in dry tetrahydrofuran (20 ml) 
was added to magnesium (0.46 g) covered with tetrahydrofuran and stirred 
under nitrogen. Reaction was initiated using iodine and after stirring for 
15 minutes the mixture was cooled to 0.degree. when the remainder of the 
bromide solution was added in one portion. 
A mixture of freshly distilled allyl bromide (3.0 g), dry tetrahydrofuran 
(30 ml) and cuprous bromide (0.3 g) was cooled in a cardice bath and 
stirred while the prepared Grignard solution was added. After stirring for 
1 hour, at room temperature, it was decomposed wih saturated ammonium 
chloride solution. The mixture was extracted with ether and the ethereal 
solution was washed with saturated sodium chloride solution, dried over 
sodium sulphate and evaporated to give the crude compound (2.1 g). 
The compound was dissolved in methanol/dichloromethane (50 ml) and ozonised 
at -20.degree.. Dimethyl sulphide (2.0 ml) was added and the solution 
stirred overnight at room temperature. Water was added and the solutions 
separated. The organic phase was dried, evaporated and chromatographed on 
neutral alumina (50 g). The fractions were collected after eluting with 
50% ether/petrol and yielded the ketal (0.9 g) n.sub.D.sup.20 =1.6024. 
The ketal (0.9 g) in tetrahydrofuran (30 ml) was treated with concentrated 
hydrochloric acid (6. ml) and after 30 minutes water was added. The 
organic material was extracted into ether and washed successively with 
water, saturated sodium bicarbonate, saturated sodium chloride, dried over 
sodium sulphate and evaporated to give the acetaldehyde (0.7 g), 
n.sub.D.sup.20 =1.6414. 
Table I summarises the route by which various carbonyl compounds of Formula 
IV may be prepared and gives characterising data on both the compounds of 
Formula IV and intermediate ethers of Formula Ar--CH.dbd.CHOMe. 
TABLE I 
______________________________________ 
ArCH.dbd.CHOMe 
ArCH.sub.2 --CHO 
n.sub.D.sup.20 
n.sub.D.sup.20 
Route 
______________________________________ 
6-bromo-2-naphthyl 
1.6510 1.6215 B1 
5,8-dibromo-2- 
1.6512 1.6350 B.sub.1 
naphthyl 
9-bromo-3- 1.6678 1.6678 B.sub.1 
phenanthyrenyl 
6-chloro-2- (Semi-solid) (Semi-solid) 
B.sub.1 
naphthyl 
______________________________________ 
It may be desirable to produce aldehydes from which compounds of Formula I 
in which n=0 and m=3-10 can be prepared by the following Route D: 
##STR7## 
In Route D, which is applicable, for example, to compounds in which m=3, 
and especially substituted naphthyl compounds (a) represents treatment of 
the product of reaction between the Grignard reagent and aldehyde with a 
mild acidifying agent e.g. ammonium chloride such that the 
tetrahydropyranyl group (THP) is retained. The step (b) represents 
treatment with a dehydrating agent such a phosphorus pentoxide, (c) 
hydrogenation, suitably catalysed and (d) oxidation, for example with 
pyridinium chlorochromate. 
Aldehydes in which n=1 and m is typically 6-8 may be produced if desired by 
following Route E which is particularly applicable to naphthoxy compounds. 
##STR8## 
In Route (E (a) represents reaction in the presence of 
N,N'-dicyclohexylcarbodiimide (DCC) and (b) acidification to produce an 
alcohol followed by oxidation to the aldehyde using for example pyridinium 
chlorochromate. 
The following procedure illustrates the use of Route E: 
8-(2-naphthyloxy octanol, tetrahydropyranyl derivative 
A mixture of 8-(2'-tetrahydropyranyloxy)-octanol (2.35 g), 
N,N'-dicyclohexyl-carbodiimide (2.5 g) and 2-naphthol (1.6 g) is stirred 
and heated at 100.degree. C. for 20 hours. After cooling, water and 
chloroform are added and the mixture separated. The organic solution is 
washed with dilute hydrochloric acid, saturated sodium hydrogencarbonate 
solution, dried over sodium sulphate and evaporated to yield the product 
(3.0 g), n.sub.D =1.5370. 
8-(2-naphthyloxy)-octanal 
A mixture of the above derivative (3.0 g) in methanol (50 ml) is stirred at 
50.degree. C. with amberlyst 15 (2.0 g) for 2 hours. Filtration followed 
by evaporation of the filtrate yields the crude alcohol which is dissolved 
in dichloromethane (150 ml) and stirred at room temperature with 
pyridinimum chlorochromate (4.0 g) for 3 hours. Ether (200 ml) is added 
and the mixture filtered through a pads of cellite/charcoal, evaporated 
and chromatographed on silica eluting with ether. Evaporation yields the 
title compound (1.4 g), n.sub.D =1.5148. 
The phosphorane of Formula III may be conveniently generated by treating 
the corresponding phosphonium salt of Formula V: 
##STR9## 
in which Formula Hal represents halogen, typically bromide, with a 
suitable base such as sodium ethoxide. The carbonyl compound of Formula IV 
may then be added to the reaction mixture and the product of Formula I 
isolated. 
The present invention also includes within its scope of phosphonium salt of 
Formula V where Z and Hal.sup.- are as hereinbefore defined, provided 
that Z is other than an isobutyl group. 
The phosphonium salt of Formula V may be produced by treatment of an amide 
of Formula VI. 
##STR10## 
with triphenyl phosphine, the amide VI being preferably generated by 
reaction of the corresponding acid or a derivative thereof with amine of 
Formula NH.sub.2 Z. 
In a further aspect of the present invention includes within its scope 
amides of Formula VI wherein Hal and Z are as hereinbefore defined, 
provided that Z is other than isobutyl. 
In some cases compounds of Formula I may be prepared by an alternative 
route (the Horner-Wittig route) with advantage in that the yield may be 
improved and/or the procedure simplified because of ease of product 
isolation. In particular the route generally gives rise to less cis 
product and the required product is typically isolated by simple column 
chromatography (e.g. on silica gel) followed by crystallisation from a 
suitable solvent. 
According to this further aspect of the present invention, a process for 
the production of a compound of Formula I comprises treating a phosphonate 
of Formula VII. 
##STR11## 
wherein Alk represents a lower alkyl group (say of 1 to 4 carbon atoms) 
and Z is as previously defined, with a base and reacting the product with 
a carbonyl compound of Formula IV. The base is suitably butyl lithium, 
sodium hydride or a sodium alkoxide e.g. sodium ethoxide. 
The present invention also includes within its scope a phosphonate of 
Formula VII useful as an intermediate in the production of a compound of 
Formula I. 
Phosphonates of Formula VII may be prepared from compounds of Formula VI by 
treatment with a trialkyl phosphite. It may be necessary or desirable to 
remove the compound AlkHal, typically ethyl bromide, from the reaction 
mixture prior to recovery of the desired product. 
Compounds of Formula I may be produced by adaptation of the Wittig reaction 
described particularly in Procedure 1: 
PROCEDURE 1 
A. N-isobutyl-4-bromocrotonamide 
4-bromocrotonic acid (27.1 g), thionyl chloride (54 ml) and petroleum ether 
(b.r. 40.degree.-60.degree., 267 ml) is mixed and refluxed for 2 hours, 
then evaporated first to a residue using a rotary evaporator, then 
distilled at 1.7 kPa (13 mm Hg). The fraction b.p. 86.degree.-90.degree. 
(24.1 g), n.sub.D.sup.20 1.5386) is collected as 4-bromocrotonic acid 
chloride. A stirred solution of the latter compound (24 g) in dry ether 
(120 ml) cooled continuously to less than -5.degree. is treated during 40 
minutes with isobutylamine (21. g) in dry ether (170 ml). After warming 
during 2 hours to 20.degree., dilute hydrochloric acid is added, and the 
clear ether layer is washed successively with sodium bicarbonate and 
sodium chloride solutions, then evaporated to leave as a residue (28.3 g) 
N-isobutyl 4-bromocrotonamide m.p. 94.degree.-95.degree.. 
B. N-isobutyl crotonamide-4-yl triphenyl phosphonium bromide 
The above amide (10.1 g) and triphenyl phosphine (13.5 g) in benzene (100 
ml) are kept at 20.degree. for 9 days, and the precipitated solid is 
triturated with warm ethyl acetate to leave a pale residue (19.8 g, m.p. 
202.degree.-204.degree.) of the required product. 
C. N-isobutyl 6-phenyl hexa-2(E), 4(E)-dienoic amide 
The above phosphonium bromide (3.05 g) is added under nitrogen to a stirred 
solution of sodium (0.14 g) in dry ethanol (18 ml) at 20.degree.. After 15 
minutes freshly distilled phenylacetaldehyde (0.7 g) is added and the 
mixture stirred, for 21 hours. The ethanol is removed by means of a rotary 
evaporator, and the residue extracted three times with ether. Evaporation 
of the ether gave an oil which is separated by preparative HPLC into the 
3(E), 5(E), (0.12 g), the 2(E), 4(Z) and the 2(E)4(E) isomers (0.7 g 
total) of the required product. The (2E) (4E) isomer has m.p. 
112.degree.-114.degree.. 
The present invention is illustrated by the following Examples: 
EXAMPLES 1-13 
The compounds of Formula 
##STR12## 
in Table II may be prepared by following Procedure 1A. 
TABLE II 
______________________________________ 
##STR13## 
m.p. (.degree.C.) or refractive 
Example NHZ index (n.sub.D.sup.20) 
______________________________________ 
1 NH.CH.sub.2 CMe.sub.3 
1.4980 
2 NH.CH.sub.2.CHMeEt 
52-53.degree. 
3 NH.CH.sub.2 CHMePr.sup.i 
1.5126 
4 NH.CHMe.CHMeEt 69.degree. 
##STR14## 104-107.degree. 
6 
##STR15## 1.5484 
(cis + trans) 
7 
##STR16## 119.degree. 
8 NH.CH.sub.2 CMe.sub.2.CHCH.sub.2 
1.5334 
9 
##STR17## 59-61.degree. 
10 NH.CHMe.CMe.sub.3 
94.degree. 
11 NH.CH.sub.2.CMeCH.sub.2 
56-58.degree. 
12 NH.CHMeCHMe.sub.2 
109-112.degree. 
13 NH.CMe.sub.2 CHMe.sub.2 
1.4750 
______________________________________ 
EXAMPLE 14 
The compound 
##STR18## 
is prepared from 
##STR19## 
by following Procedure 1B, the melting point being 211.degree.-3.degree.. 
EXAMPLES 15-28 
A compound of Formula 
##STR20## 
is made from the compound Br.CH.sub.2 CH=CHCONHCH.sub.2 CHMe.sub.2 by the 
following procedures: 
(N-isobutyl crotonoamide-4-yl) diethyl phosphonate 
The product of Procedure 1A (28.3 g) is added in portions to triethyl 
phosphite (31.1 ml) at 100.degree. with stirring, then the temperature is 
gradually raised to 150.degree., while ethyl bromide is distilled off. 
After 2 hours, the mixture is distilled, and the fraction b.p. 
168.degree.-170.degree./0.4 mm (25.9 g) n.sub.D.sup.20 1.4754 is removed 
and shown by NMR to be the required product. 
Compounds of Formula 
##STR21## 
which can be prepared from compounds of Formula 
##STR22## 
by following the latter procedure are set out in Table III with physical 
constants. 
TABLE III 
______________________________________ 
##STR23## 
Example 
NHZ Refractive index (n.sub.D.sup.20) 
______________________________________ 
15 NH.CH.sub.2 CH.sub.2 CHMe.sub.2 
1.4754 
16 NH.CH.sub.2 CHMeEt 
1.4770 
17 NH.CH.sub.2 CHMePr.sup.i 
1.4815 
18 NH.CHMeCHMeEt 1.4832 
19 
##STR24## 1.4812 
20 
##STR25## 1.4930 
21 
##STR26## 1.4914 
22 
##STR27## 1.4830 
23 NH.CHMe.CMe.sub.3 
1.4810 
24 NH.CH.sub.2 CMe(CH.sub.2) 
1.4753 
25 NH.CH.sub.2 CMe.sub.2 CHCH.sub.2 
1.4793 
26 NH.CMe.sub.2 CHMe.sub.2 
1.4777 
27 NH.CHMeCHMe.sub.2 
1.4754 
28 NH.CH.sub.2 CMe.sub.3 
1.4792 
______________________________________ 
EXAMPLES 29-65 
Compounds of Formula 
##STR28## 
which can be prepared from compounds of Formula 
##STR29## 
and compounds of Formula Ar(O).sub.n (CH).sub.m CHO by following Procedure 
2 are set out in Table IV with physical constants and bioassy data: 
PROCEDURE 2 
N-isobutyl-6-phenyl hexa (2E, 4E) dienoic amide 
The phosphonate of Example 15 (0.21 g) in dry benzene (2.3 ml) is treated 
at 20.degree. under nitrogen with a solution of butyl lithium in hexane 
(0.47 ml 1.6M), then 30 minutes later with freshly distilled 
phenylacetaldehyde (0.08 g) in benzene (1.2 ml), and stirred for 5 hours. 
After neutralising with glacial acetic acid water is added, and the whole 
extracted with ether. Purification by simple chromatography on silica gel 
eluting with 1:1 etherhexane gives the required product (35% yield). 
Illustrative compounds are set out in Table IV with physical constants and 
bioassy data. 
Compounds of Formula I are bioassayed by the following method: 
Acetone solutions (1 .mu.l) of compounds are applied topically by Arnold 
micro-applicator to the thorax of 4-day-old adult female houseflies (HF), 
anaethetised with ether, or to the ventral abdomen of approximately 
1-week-old adult male and female mustard beetles (MB), held by suction 
tube. For each concentration, and for a control, two replicates, each of 
15 insects, are dosed topically and the dead counted after 24 hours (HF) 
or 48 hours (MB); at these times end point mortalities are approached. 
The results are analysed by the method of probits, to give for each test 
LD.sub.50 values and standard errors for each compound, and for the 
standard (bioresmethrin). Comparisons between LD.sub.50 S and compound and 
standard give relative potencies (bioresmethrin=100). 
TABLE IV 
__________________________________________________________________________ 
Compounds I: ArCH.sub.2 --CHt.dbd.CH--CHt.dbd.CH CONHZ 
__________________________________________________________________________ 
Relative 
Potency 
Example No. 
Ar --NHZ m.p. (.degree.C.) or n.sub.D.sup.20 
HF MB 
__________________________________________________________________________ 
29 2-naphthyl --NHCH.sub.2 CHMe.sub.2 
146-8.degree. 
3.0 3.0 
30 2-naphthyl --NHCH.sub.2 CMe.sub.3 
68-69.degree. 
2.0 8.0 
31 2-fluorenyl --NHCH.sub.2 CHMe.sub.2 
174-176.degree. 
1.8 ca 
5.1 
32 2-naphthyl --NHCH.sub.2 CMe.sub.2 CH.dbd.CH.sub.2 
77-80.degree. 
0.8 3.7 
33 2-naphthyl --NHCH.sub.2 CHMeEt 
109-110.degree. 
0.6 7.6 
34 2-phenanthrenyl 
--NHCh.sub.2 CHMe.sub.2 
143-6.degree. 
-- 5.2 
35 5-bromo-2-naphthyl 
--NHCH.sub.2 CHMe.sub.2 
157.degree. 
4.7 25 
36 6-bromo-2-naphthyl 
--NHCH.sub.2 CHMe.sub.2 
123-6.degree. 
0.5 2 
37 2-dibenzofuranyl 
--NHCH.sub.2 CHMe.sub.2 
172.degree. 
-- 6 
38 2-naphthyl --NHCHMeCMe.sub.3 
125-7.degree. 
1 0.5 
39 2-naphthyl --NHCHMeCHMe.sub.2 
174-5.degree. 
2.8 0.7 
40 2-phenanthrenyl 
--NHCH.sub.2 CMe.sub.3 
137-8.degree. 
-- 3.3. 
41 2-phenanthrenyl 
--NHCHMeCHMe.sub.2 
62.degree. 
-- 1.0 
42 2-phenanthrenyl 
--NHCH.sub.2 CHMeEt 
123-5.degree. 
-- 2.6 
43 5-bromo-2-naphthyl 
--NHCH.sub.2 CMe.sub.3 
116-9.degree. 
6.3 17 
44 5-bromo-2-naphthyl 
--NHCH.sub.2 CHMeEt 
112-8.degree. 
3.0 17 
45 2-dibenzofuranyl 
--NHCH.sub.2 CMe.sub.3 
114.degree. 
1.4 9.0 
46 2-dibenzofuranyl 
--NHCH.sub.2 CMe.sub.2 CH.dbd.CH.sub.2 
119-20.degree. 
-- 2.4 
47 2-phenanthrenyl 
--NHCH.sub.2 CMe.sub.2 CH.dbd.CH.sub.2 
1.6158 0.2 2.7 
48 2-dibenzofuranyl 
--NHCHMeCHMe.sub.2 
172-173.degree. 
3.0 7.2 
49 2-dibenzofuranyl 
--NHCH.sub.2 CHMeEt 
138-139.degree. 
0.95 9.5 
50 5-bromo-2-naphthyl 
--NHCHMeCHMe.sub.2 
154.degree. 
10 22 
51 5-bromo-2-naphthyl 
--NHCH.sub.2 CMe.sub.2 CH.dbd.CH.sub.2 
88-90.degree. 
2.5 10 
53 9-bromo-3-phenanthrenyl 
--NHCH.sub.2 CMe.sub.3 
165-167.degree. 
N.T. 2.7 
54 6-chloro-2-naphthyl 
--NHCH.sub.2 CHMe.sub.3 
134-6.degree. 
2.4 57 
55 7-bromo-2-naphthyl 
--NHCH.sub.2 CMe.sub.3 
165.degree. 
2.9 11 
56 7-chloro-2-naphthyl 
--NHCH.sub.2 CMe.sub.3 
143-5.degree. 
2.4 14 
57 7-chloro-2-naphthyl 
--NHCH.sub.2 CHMe.sub.2 
158.degree. 
1.4 18 
58 7-fluro-2-naphthyl 
--NHCH.sub.2 CMe.sub.3 
110-1.degree. 
1.4 8.5 
59 9,10-dihydrophenanthrenyl 
--NHCH.sub.2 CMe.sub.2 CH.dbd.CH.sub.2 
1.6158 -- 2.7 
60 7-fluro-2-naphthyl 
--NHCMe--CHMe.sub.2 
168.degree. 
5.0 3.8 
61 5,8-dibromo-2-naphthyl 
--NHCH.sub.2 Me.sub.3 
115-6.degree. 
1.4 1.4 
__________________________________________________________________________ 
Relative 
Potency 
Example No. 
Ar n m Z m.p. (.degree.C.) or n.sub.D.sup.20 
HF MB 
__________________________________________________________________________ 
62 2-naphthyl 
1 7 --NHCH.sub.2 CHMe.sub.2 
83-6.degree. 
3 10 
63 2-naphthyl 
1 7 --NHCH.sub.2 CMe.sub.3 
1.5373 1 4 
64 2-naphthyl 
1 7 --NHCH.sub.2 CMeEt 
62-4.degree. 
0.4 4 
65 2-naphthyl 
1 7 --NHCMeCHMe.sub.2 
88-90.degree. 
4 3 
66 2-(4-bromonaphthyl 
1 7 --NHCH.sub.2 CHMe.sub.2 
107-9.degree. 
0.1 
ca 
3 
67 2-naphthyl 
0 8 --NHCH.sub.2 CHMe.sub.2 
101-2.degree. 
-- 2.0 
__________________________________________________________________________