AU595030B2 - Pesticidal compositions - Google Patents

Description

Li COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION FOR OFFICE USE Form Short Title: Int. Cl: Application Number: Lodged: Complete Specification-Lodged: Accepted: Lapsed: Published: Priority: Related Art: 7 t P7 5950 a.

0* o I: Is the u~rrr--r~ nrl, ir i :;i!is unr ct forr -C it o TO BE COMPLETED BY APPLICANT Name of Applicant: Address of Applicant: Actual Inventor: Address for Service: THE WELLCOME FOUNDATION LIMITED 183-193 Euston Road, LONDON NW1 2BP,

ENGLAND

Robert John Blade John Edward Robinson; Norman Frank Janes and Bhupinder Pall Singh Khambay GRIFFITH HASSEL FRAZER 71 YORK STREET SYDNEY NSW 2000

AUSTRALIA

Complete Specification for the invention entitled: PESTICIDAL COMPOUNDS The following statement is a full description of this invention, including the best method of performing it known to me/us:- 7302A:rk -1A- PESTICIDAL COMPOUNDS This invention relates to pesticidal compounds.

EP-A-164 187 (The Wellcome Foundation Limited) discloses pesticidal w-aryl lipid amide compounds having zero, one or two alkenyl links adjacent the carbonyl of the amide function, such links being optionally substituted by halo. It is stated that unsubstituted linking is preferred. It has now been found that surprisingly good activity is found when the unsaturated link is substituted by at least one optionally substituted alkyl group or nitrile group.

Miyakado et, al Pesticide Sci. 10, 25030, 1985) disclose various naturally-occurring and synthetic lipid amides, including two having a 3-methyl group, in other words a methyl group on the diene linking unit referred to above. However, except in the case of a compound having a 3,4-methylenedioxy substituent on the terminal aromatic group, they found that such a group did not increase insecticidal activity.

The present invention provides compounds of Formula

(I)

M Ar(CH2 xO(CH2 mA(CH)n(CE=CE 2 )(CE3=CE 4

)CONR

1

Z

wherein Ar is phenyl or naphthyl, in either case unsubstituted or substituted by one or more of alkyl, halogen, alkoxy, optionally substituted alkyl, or optionally substituted alkoxy x 0 or 1 m 1 to 7 n 1 to 7 A CH 2 or oxygen a 0 or 1 R is independently selected from hydrogen, -2- C -6 alkyl and C3- 6 cycloalkyl (either of which may be substituted by one or more of halo, C1-6 alkyl, C2-6 alkoxy, C2- 6 alkynyl, dioxalanyl and C36 z-6 2~b 3-2 cycloalkyl Z represents hydrogen or a group:

-C

1

(R

A

(RB)-C (RC )(R

D

(R

E

wherein R and R which may be identical or different, each represent hydrogen or methyl;

R

C represents methyl; R D represents methyl, ethyl, n-propyl, isopropyl, t-butyl or vinyl; and R E represents hydrogen or methyl; or wherein R and R form a methylene group S2 D 2 S. (=CH or together with C form a cyclopropane or l cyclobutane ring, RA, RB and R E representing hydrogen or methyl; or wherein RA and R C together with Cl and C 2 form a cyclobutane ring, R RD and R

E

independently representing hydrogen or methyl: E, E 2 E and E are independently selected from hydrogen, C alkyl optionally substituted by halo, 1-4o o 3 or nitrile, provided that at least one of E E 4 and E is optionally substituted alkyl or nitrile.

except that the compound (2E, 4E) N-isobutyl 3-methyl-7-(3-chlorophenoxy)-dodeca-2, 4-dienamide is excluded.

Preferably Ar is phenyl substituted by one or more halogen or trifluoromethyl groups. Conveniently, there are no more than three, preferably no more than two, such substituents. For the avoidance of doubt, it is hereby stated that 3,4-methylenedioxy is not to be regarded as being covered by the list of possible substituents given above.

V -3- Prefera.bly a is 1. Suitably A is -CH 2 and the sum of m and n is equal to an odd number, preferably 3 or or is equal to 6.

Preferably R1is hyoi.z-,en and Z is C 1 5 alkyl, most preferably isobutyl, l,2-dimeti.ylpropyl or 2,2-dimethylpropyl.

Preferably the stereochemistry of the or each double bond conjugated to the carbonyl is trans. Stereochemically pure compounds MI are preferred. Although the presence of Z isomers maybe tolerated for reasons of economy, the content of such isomers is kept as low as 0990 possible, for example not exceeding 33%, 25%, 10% or Suitably at least one of E 1 E 3and E 4is hydrogen and Qne other is methyl, f luoromethyl or 1 2 *trifluoromethyl. Preferably E I E 2 and E are hydrogen OE 3 and E is methyl, f luoromethyl or trifluoromethyl, particularly methyl. N-isobutyl methyl ben zyloxy -methyl undeca-2, 4 -di enami de, N-isobutyl 12-(2-naphthylcoxy)-3-methyldodeca-2,4-dienamide, N-isobutyl1 ll-(2,4-dichlorobenzyloxy)-3-methylundeca- -2,4-dienamide and N-isobutyl 12-(3,5-bistrifluoromethylphenoxy)-3-methyldodeca-2,4-dienamide (in each case 2E, 4E) are particularly preferred compounds.

Thus, a particularly preferred class of compounds may be represented by Formula (IA): U)Ar(C 2 xO(CH 2 )m CH2 (H2 )n C=CH-C 4 3=CH-CONHZ where: Ar is phenyl optionally substituted by fluoromethyl or 2,4-dichloro or 2,3,4,5,6-pentafluoro or Ar is l-naphthyl or 2-naphthyl; x is 0 or 1; m n 3, or 6; E 1and E 3are independently hydrogen or methyl but not both hydrogen; Z is isobutyl, 1,2-dimethyl, 2,2-dimethylpropyl or 1,l,2-trimethylpropyl; and the two double bonds are both E trans), although the -4presence of some Z material may be tolerated for reasons of economy of manufacture.

Preferably, in Formula E is hydrogen.

Compounds of Formula may be prepared inany of the following ways: by amidation of the corresponding acid or acid derivative, i.e. by reaction of a compound of Formula (II) with a compound of Formula (III): (II) Ar(CH 2 x

O

(CH

m

A(CH

2 n (CE =CE2 (CE =CE 4

)COZ

(III), HNR z wherein is hydroxyl, halo, a phosphoroimidate ester (-P(--0)(OAryl)NH.aryl) or alkoxy and the other variables are as defined above, t f by reaction of a compound of Formula (IV) with a compound of Formula V 1 2 (IV) Ar(CH 2 x(C 2 )mA(C H 2 )(CE =CE Z

Z"CONRI^

where one of Z' and Z" is -C(O)E 5 and the other is (Z2 3 P=CE6 (CE =CE 4 or (Z 2) 2 P(O)=CE6(CE3=CE 4)q wherein 2 is C1-4 alkyl, C 4 alkoxy (preferably ethoxy) or aryl (preferably phenyl), p and q are each 0 or 1 and p+q is 0 5 1 3 6 2 4 or 1, E is E or E and E is E or E as appropriate; by an elimination reaction on a compound of Formula (VI) or (VII (VI) Ar(CH 2 )O(CH 2

)A(CH

2 (CE=CECE 3 (X)CE 4 (Y)CONR1Z (VII) Ar(CH 2 xO(CH2)A(CH2 CE (X)CE2 (Y)(CE =CE4 )CONR where one of X and Y is hydrogen and the other is a group in which Q is sulphur or selenium and L is a suitable group such as C,-4 alkyl (preferably methyl) or aryl (preferably phenyl); by reacting a compound of Formula (VIII) with a compound of Formula (IX): (VIII) Ar(CH 2 )xO(CH 2 )mA(CH)n CE CE -M (IX) Hal-(CE 3

=CE

4

)CONRZ

i *L wherein Hal is halide e.g. bromide or iodide and M is a silicon or a metal atom or metal-containing group, for example comprising zirconium, aluminium, zinc, tin, tellurium or copper, such as a bis-(cyclopentadienyl) zirconium chloride group, zirconium and zirconiumcontaining groups being generally preferred; by reaction of a compound of Formula with a compound of Formula (XI): Ar(CH 2)Z3 4 4 (XI) Z -(C 2

A(CH

2 n (CE=CE2)a (CE =CE 4 CONR Z wherein one of Z and Z 4 is -OH and the other is -OH or a suitable leaving group such as halo; when A is oxygen, by reaction of a compound of Formula (XII) with a compound of formula (XIII): (XII) Ar(CH 2 )xO(CH 2

Z

A1 -6- (XIII) Z 6 (CH 2)n(CE 1=CE a CE 3 =CE )CONR 1

Z

where one of 5 and 6 is -OH and the other is a suitable leaving group such as halo; by reacting a compound of Formula (XIV) with one of Formula (XV) or (XVI) (XIV) Ar(C 2 xO(CU2 )mA(CH 2

)CE

1

=CE

2 -Bal 3- 4 1 4 1 (XV) BCE =CE CONR1 Z (XVI) HC CE CONR1 Z where Bal is halogen, e.g. iodine dr bromine, followed by semihydrogenation of the triple bond, if present; by semi-hydrogenation of the triple bond in a compound of Formula (XVII) or (XVIII): 99 9 3 4 1 u4 9 (XVII) Ar(C 2 OC,(C 2

MCH

2 )nC(C C-(CE =CE) bCONR Z 1 2 1 (XVIII) Ar(CH )xO(CH )ACC )n (CE1 CE2 )-CC-CONR Z 2 x 2 m 2 n a o wherein a and b are both 1.

by conversion of one compound of Formula (1) prepared as above into another compound of Formula by any suitable process.

0 *ItProcess is normally carried out at 0 C to room temperature about 0o 25 or 00 20 0 C) in an aprotic solvent, such as ether, dichloromethane or 4 benzene, optionally in the presence of a tertiary amine, such as triethylamine, but in the absence of water. If it 414 the compound of Formula (11) is an acid halide, for example acid chloride, then it may be formed from the corresponding acid by reaction with a suitable reagent such as oxalyl chloride or thionyl chloride. When Z is a -7phOsphoroimidate group then this is suitably formed from (PhO)P(-O)NHPh Cl. The acid, or the acid function in the compound of Formula may be prepared by hydrolysis of an ester, the ester being prepared by a conventional Wittig or Wadsworth-Emmons reaction, using for e.xample an aldehyde and ethoxycarbonylmethylene triphenylphosphorane or an anion from triethylphosphonocrotonate. This latter reaction may result in an isomeric mixture, for example a mixture of and substituted dienoates; such a mixture may be reacted as above, and the resulting mixture of amides separated by chromatography or other convenient techniques. The Wittig-type reagent may be produced for example by the following route or a modification thereof: N-bromo succinimide

(C

3 2 C=CHCOEt (Et)POCH 2

C(CH=CHCO

2 Et (EtO) P (E+Z) Aldehydes may be produced, if desired, by one of the following routes which are particularly applicable to naphthoxy compounds.

ArOH HO(CH n+IOTHP ArO(CH 2

OTHP

ArOH Br(CH 2 n+ OTHP ArO(CH 2 )n+1OTHP ArO(CH 2 )n+IOTHP ArO(C 2 )nCH 2

CH

ArONa Br(CH OH ArO(CH 2 )nCH 2

OH

ArO(CH 2 )nCH 2 OH ArO(CH 2 )nCHO (THP tetrahydropyran-2-yl) In the above route represents reaction in the presence of N,N'-dicyclohexylcarbodiimide (DCC), (B) reaction under phase-transfer conditions, for example using 50% aqueous sodium hydroxide and tetrabutylammonium bromide at 90°, acidification to produce an alcohol, reaction of for example the sodium naphthoxide with

NPPP

the bromo alcohol in refluxing benzene and dimethyl forimamide, and oxidation to the aldehyde using, for example, pyridinium chlorochromate.

The present invention also includes within its scope intermediates for the production, inter alia of compounds such as those of Formula (II) ArO(CH)n CHE=CHCE 3 =CHCO H and E 3 ArO(CH 2 nCH CHCE =CHCO 2 Alk).

When Z is alkoxy, the compound of Formula (II) is treated with a complex of the compound of Formula (III) and trialkyl (preferably trimethyl) aluminium in an aprotic solvent such as benzene or toluene, under reflux.

Alternatively, the ester referred to above may be derived by rearrangement and elimination on a compound of Formula (XIX) 3 S )R 3 2s 3 (XIX) Ar(CH 2 xO(CH )mA(CHn+CE =C CO2R 3 4 Swherein R 3 is any suitable group, such as phenyl, and R S* is C1-4 alkyl, e.g. methyl or ethyl.

The compound of Formula (XIX) may be obtained by reaction of a compound of Formula (XX) with a compound of Formula (XXI):

A

(XX) Ar(CH2 )xO(C 2 )mA(CH 2 n+ 2

COH

(XXI) PhS(-PO)CB 2

CO

2

R

4 A further route is for the ester above to be prepared by elimination on a compound of Formula (XXII): (XXII) Ar(CH 2 )xO(CH 2 m

A(CH

2 )n-A -A (CE =CE 4

)COOR

4 -9wherein R is as defined above, A 1 is -CHE and A is CE2 (OR5), R 5 being H or acyl such as acetyl. The reaction is preferably carried out in an aromatic solvent, conveniently in the presence of a molybdenum catalyst and a base, such as bis-trimethylsilylacetamide.

A further route for the above ester is by reaction of a compound of Formula (XXIII) with one of Formula (XXiV (XXIII))Ar(CH)xO(CH 2 mA(CH 2 (CE1= CE2)C(=0)E 3 (XXIV) Me 3 SiCHE COOR where R is as above. This process may be carried out in a dry solvent, e.g. tetrahydrofuran in the absence of So a oxygen, in the presence of a base, e.g. lithium cyclohexylisopropylamide.

e A further route for the above ester is by reaction of compound of Formula (XXV) with compound of Formula

(XXVI)

o 2(XXV) Ar(CH2)xO(CH 2 )mA(CH 2 )n(CE =CE2)BCO 2

R

4 (XXVI) E 3

-M

where B is a group -C(OD)CE in which D is a suitable group such as dialkylphosphate or trifluoromethane- 044o Q sulphonate, M is a metal such as copper or copper (I) 4 4 o associated with lithium o'r magnesium, and R is as above.

0 This process can be performed at low temperature in a dry ethereal solvent such as diethyl ether, dimethyl sulphide or tetrahydrofuran in the absence of oxygen.

A still further route is for the ester to be formed by reaction of a compound of Formula (IX) above with one of Formula (XXVII): (XXVII) Hal-(CE =CE )CO 2

R

Process is carried out in an anhydrous inert solvent, for example an ether such as tetrahydrofuran, optionally in the presence of a base, and preferably in the absence of oxygen, e.g. under a nitrogen atmosphere, at a low temperature (-40 to 0 0 The Wittig-type reagent may be obtained from compounds of Formula by reaction with a base such as lithium diisopropylamide, butyllithium, sodium alkoxide or sodium hydride.

Process may be effected by refluxing in a suitable non-polar solvent, such as benzene, toluene or xylerie. The compound of Formula (VI) or (VII) may be prepared by oxidation, for example with periodate, of the corresponding compound having a QL group. This latter compound, in turn, may be prepared by reaction of a compound of Formula (XXVIII) with a compound of Formula 44 (XXIX): (XXVII Ar(CH., 'x(CH

C

I

y (CH) nCHE CE 2

=CE

3

G

(XXIX) CHE CONR Z where G is an alkyl or aryl group. Preferably, the compound of Formula (XXIX) is reacted with trifluoroacetic anhydride in trifluoroacetic acid and then the compound of Formula (XXVIII) is added, at 0-20 0

C.

t8 Process is normally carried out at room Stemperature, in a dry ethereal solvent such as tetrahydrofuran, in the presence of a palladium (0) catalyst, (such as bis(triphenylphosphine) palladium) and under an inert atmosphere of nitrogen or argon.

When processes and comprise the reaction of two alcohols, this is preferably in the presence of a dehydrating agent, such as concentrated sulphuric acid or -11diethyl diazo carboxylate, in a non-polar solvent at about 80-110 C. When Z is halo, a base is preferably present. Other standard methods for the formation of ethers and thioethers, such as those described in "Compendium of Organic Synthetic Methods", Harrison and Harrison, Wiley Interscience, (New York) 1971, may be used.

Process may be conducted at room temperature to reflux in the presence of a base, e.g. triethylamine and a palladium catalyst in the absence of oxygen.

The alkyne compound of Formula (XVII) or (XVIII) may, when E or E is hydrogen, be prepared by reaction of a compound of Formula (XXX) with a compound of Formula (XXI) or (XXXII); 1, (XXX) Ar (CH 2) O (CH 2)mA (CH2) n-Hal SF(XXXI) EC C(CE=CE 4

)CONRI

(XXXII) E 3

CC-CONRI

at room temperature or lower, in the presence of a base (such as butyl lithium) and in an etheral solvent (such as THF) or by any process analogous to processes to above, resulting in the formation of a compound having a triple bond.

The intermediates of Formulae (III)-(XXXII) may be prepared by standard methods. For example, the compounds of Formula may be prepared by the reaction of an appropriate phosphine, phosphonate or phosphite with an w-halo amid.

Compounds of Formula (IV) may be prepared by j hydrolysis of a ketal ring or oxidation of the corresponding alcohol, for example using pyridinium chlorochromate or oxalyl chioride/DMSO.

-12- Compounds of Formula (I may be used to control arthropod pests such as insects and acarines. Acaricidal activity has been found to be enhanced when R1is hydrogen and R2has an alkyl substituent alpha to the nitrogen, for example when R 2is 'i,2-dimethylpropyl.

The compounds of Formula may be used for such purposes by application of the compounds themselves or in diluted form in known fashion as a dip, spray, lacquer, foam, dust, powder, aqueous suspension, paste, gel, shampoo, grease, combustible solid, vapour emanator (e.g.

coil, mat or the like), granule, aerosol, oil suspensions, oil solutions, pressure-pack, impregnated article (such as a plastics ear tag or collar or a strip to treat the air of an enclosed space) or pour-on formulation. Dip conqentrates are not applied per se, but diluted with water and the animals irnnersed in a dipping bath containing the dip wash. Sprays may be applied by hand or by means of a spray race or arch. The animal, plant or surface may be saturated with the spray by means of. high volume application or superficially coated with the spray by means ot light or ultra low volume application. Aqueous suspensions may be applied to the animal in the same manner as sprays or dips. Dusts may be distributed over the animals by means of a powder applicator or incorporated in perforated bags attached to trees or rubbing bars. Pastes, s8hampoos and greases may be applied manually or distributed over the surface of an inert material against which animals rub and transfer the material to their skins. Pour-on formulations are dispensed as a unit of liquid of small volume on to the backs of animals such that all or most of the liquid is retained on the animals.

The compounds of Formula may be formulated either as formulations ready for use on the animals or as formulations requiring dilution prior to application, but -13both types of formulation comprise a compound of Formula in intimate admixture with one or more carriers or diluents. The carriers may be liquid, solid or gaseous or comprise mixtures of such substances, and the compound of Formula may be present in a concentration of from 0.025 to 99% w/v depending upon whether the formulation requires further dilution.

Dusts, powders and granules comprise the compound of Formula in intimate admixture with a powdered solid inert carrier for example suitable clays, kaolin, talc, mica, chalk, gypsum, vegetable carriers, starch and diatomaceous earths.

Sprays of compound of Formula may comprise a solution in an organic solvent those listed below) 0 00 or an emulsion in water (dip wash or spray wash) prepared in the field from an emulsifiable concentrate (otherwise o known as a water miscible oil), a wettable powder or a controlled release formulation, such as a microencapsulated formulation. The concentrate preferably a comprises a mixture of the active ingredient, with or without an organic solvent and one or more emulsifiers.

Solvents may be present within wide limits but preferably in an amount of from 0 to 90% w/v of the composition and may be selected from kerosene, ketones, alcohols, xylene, Saromatic naphtha, and other solvents known in the formulating art. The concentration of emulsifiers may be varied within wide limits but is preferably in the range o .of 5 to 25% w/v and the emulsifiers are conveniently nonionic surface active agents including polyoxyalkylene S*0 esters of alkyl phenols and polyoxyethylene derivatives of hexitol anhydrides and anionic surface active agents including Na lauryl sulphate, fatty alcohol ether sulphates, Na and Ca salts of alkyl aryl sulphonates and alkyl sulphosuccinates.

Wettable powders comprise an inert solid carrier,

-I

14one or more surface active agents, and optionally stabilisers and/or anti-oxidants.

Emulsifiable concentrates comprise emulsifying agents, and often an organic solvent, such as kerosene, ketones, alcohols, xylenes, aromatic naphtha, and other solvents known in the art.

Wettable powders and emulsifiable concentrates will normally contain from 5 to 95% by weight of the active ingredient, and are diluted, for example with water, before use. Microencapsulated formulations may be made by any known technique, for example coacervation or interfacial polymerisation.

Lacquers comprise a solution of the active ingredient in an organic solvent, together with a resin, t an optionally a plasticiser.

I Dip washes may be prepared not only from emulsifiable concentrates but also from wettable powde-a,, soap based dips and aqueous suspensions comprising a compound of Formula in intimate admixture with a dispersing agent and one or more surface active agents.

Aqueous suspensions of a compound of Formula may comprise a suspension in water together with suspending, stabilizing or other agents. Aqueous solutions may also be formed from acid addition salts of a compound of Formula The suspensions or solutions may be applied per se or in a diluted form in known fashion. Electrostatic spraying techniques may be used with suitable formulations.

Greases (or ointments) may be prepared from vegetable oils, synthetic esters of fatty acids or wool fat together with an inert base such as soft paraffin. A compound of Formula is preferably distributed uniformly through the mixture in solution or suspension.

Greases may also be made from emulsifiable concentrates by diluting them with an ointment base.

Pastes and shampoos are also semi-solid preparations in which a compound of Formula may be present as a uniform dispersion in a suitable base such as soft or liquid paraffin or made on a non-greasy basis with glycerin, mucilage or a suitable soap. As greases, shampoos and pastes are usually applied without further dilution they should contain the appropriate percentage of the compound of Formula required for treatment.

Aerosol sprays may be prepared as a simple solution of the active ingredient in the aerosol propellant and co-solvent such as halogenated alkanes and the solvents referred to above, respectively. Pour-on formulations may be made as a solution or suspension of a compound of Formula in a liquid medium which also contains a 1 viscous oil to minimise spreading of the formulation on the surface of the animals. An avian or mammal host may also be protected against infestation of acarine ectoparasites by means of carrying a suitably-moulded, shaped plastics article impregnated with a compound of Formula Such articles include impregnated collars, tags, bands, sheets and strips suitably attached to appropriate parts of the body.

The concentration of the compound of Formula to be applied to a locus animal, grain, crop, soil, building etc.) will vary according to the compound chosen, the interval between treatments, the nature of the formulation and the likely infestation, but in general 0.001 to 20.0% w/v and preferably 0.01 to 10% of the compound should be present in the applied formulation. The amount of the compound deposited on an animal will vary according to the method of application, size of the animal, concentration of the compound in the applied formulation, factor by which the formulation is diluted and the nature of the formulation, but in general will lie in the range from 0.0001% to 0.5% except for r: -16undiluted formulations such as pour-on formulations which in general will be deposited at a concentration in the range from 0.1 to 20.0% and preferably 0.1 to 10%. For public health usage, a deposited concentration of up to about 5% may be needed. The concentrate may contain up to active ingredient.

Dusts, greases, pastes and aerosol formulations are usually applied in a random fashion as described above and concentrations of 0.001 to 20% w/v of a compound of Formula in the applied formulation may be used.

Bait formulations for, for example, cockroaches will include suitable attractants and/or foodstuffs. The compounds of the invention can be formulated specifically for use on grain or on the exposed surfaces of buildings, or for space spraying.

"f The compounds may be administered in an animal's .feed to combat insect larvae infesting the animal's dung.

Any suitable formulation, including microencapsulated material, may be used. The amount of the compound which is administered will vary according to the type and size of animal, and is chosen to provide a suitable concentration of the compounds in the animal's dung.

Typically, 0.001 to 100 mg/kg bodyweight, preferably 0.1 to 10 mg/kg, are administered daily, to give concentrations of 0.001 to preferably 0.01 to 0.1% compound in the dung. The compound will usually be formulated as a concentrate or premix for mixing with a feed supplement, feed concentrate, roughage or the like.

Alternatively, the compound may be added to the supply of drinking water. Suitable animals include cattle, pigs, horses, sheep, goats and poultry.

Insect pests include members of the orders Coleoptera Anobium, Tribolium, Sitophilus, Diabrotica, Anthonomus, Hylotrupes or Anthrenus spp.), Lepidoptera Ephestia, Plutella, Chilo, Heliothis, -17- Spodoptera, Tinea or Tineola spp.), Diptera (e.g.

Anopheles, Simulium, Musca, Aedes, Culex, Glossina, Stomoxys, Haematobia, Tabanus, Hydrotaea, Lucilia, Chrysomia, Callitroga, Dermatobia, Hypoderma, Liriomyza, and Melophagus spp.), Phthiraptera (Malophaga e.g.

Damalina spp. and Anoplura e.g. Linognathus and Haematopinus spp.) Hemiptera Triatoma, Rhodnius, Aphis, Bemisia, Aleurodes, Nilopavata, Nephrotetix or Cimex spp.), Orthoptera Schistocerca or Acheta spp.), Dictyoptera Blattella, Periplaneta or Blatta spp.), Hymenoptera Solenopsis or Monomorium spp.), Isoptera Reticulitermes spp.), Siphonaptera (e.g.

Ctenocephalides or Pulex spp.), Thysanura Lepisma spp.), Dermaptera Forficula spp.) and Psocoptera Peripsocus spp.). Acarine pests include ticks, e.g.

members of the genera Boophilus, Rhipicephalus, Amblyomma, Hyalomma, Ixodes, Haemaphysalis, Dermocentor and Anocentor, and mites and manges such as Tetranychus, Psoroptes, Psorergates, Chorioptes, Demodex, Dermatophagoides, Acarus, Tyrophagus and Glycyphagus Spp.

The compounds exhibit killing and/or knockdown activity against adult and/or larval arthropod pests.

Compounds of the invention may be combined with one or more other active inc nts (for example pyrethroids, carbamates and org4, ,hosphates) and/or with attractants and the like. Furthermore, it has been found that the activity of the compounds of the invention may be enhanced by the addition of a synergist or potentiator, for example one of the oxidase inhibitor class of synergists, such as piperonyl butoxide or NIA 16388. When an oxidase inhibitor synergist is present in a formula of the invention, the ratio of synergist to compound of Formula will be in the range 25:1-1:25 e.g. about 10:1.

Stabilisers for preventing any chemical degradation -18which may occur with the compounds of the invention include, for example, antioxidants (such as tocopherols, butylhydroxyanisole and butylhydroxytoluene) and scavengers (such as epichlorhydrin).

It will be understood that what we will claim may comprise: compounds of Formula processes for the preparation of compounds of Formula insecticidal and acaricidal compositions comprising a compound of Formula in admixture with a carrier; processes for the preparation of such pesticidal compositions; methods for the control of insect or acarine pests S, comprising the application to the pest or its S <*environment of a compound of Formula a 9 o synergised pesticidal compositions comprising a compound of Formula S(g) potentiating or non-potentiating mixtures of a compound of Formula and another pesticidal compound; and :o novel intermediates of the preparation of compounds a. of Formula particularly compounds of Formula

S(II).

The following Examples illustrate, in a non-limiting manner, preferred aspects of the invention. All temperatures are in degrees Celsius.

Example 1 Triethyl-4-phosphono-3-methylcrotonate A mixture of ethyl 3,3-dimethylacrylate (12.8g, 100 mmol), N-bromosuccinimide (11.8g, 66 mmol), dry benzene ml) and benzoyl peroxide (20 mg) was heated under reflux for 0.5h. After cooling, filtration, concentration and distillation, ethyl 4-bromo-3-methyl- 4 .4 o 4 44 44 44 C 4 .4 0 4 4 *0 4, 4* 4. 1 4 44 4 @4~ £4

S

4~.

.t~ 4 4 II it r 445 1 Is -It It' Sit -19crotonate was obtained. The latter (33.8 mmol) wais added dropwise tu trietihylphosphite (47.17 mmol) at 1000. The mixture was warmed to 150 0 and the residue purified by distillation to give triethyl 4-phosphono-3-methylcrotonate(b.p.120* at 0.5 mxn.Hg) as a cis/trans mixture.

Example 2 N-Isobutyl 11- 5-bi strifluoromethylbenzyloxy )-3-methylundeca-2, 4-dienaiuiide 7-(3,5-bistrifluoromethylbuenzyloxy)-heptan-l-al (4.7g, 13.27 mmcl) (prepared according to methods described in EP-A-l64 187) was reacted with the anion derived from the compound of Example 1 (13.27 mmol) and lithium diisopropylamide (13.27 mmcl) in dry tetrahydrofuran in the absence of moisture from -40 0 to room temperature.

After standard work-up and purif ication on column chromatography (silica/85:15 hexane: ether), ethyl 11-C 3, 5-bi strif luoromethylbenzyloxy )-3-methyl-undeca-2, 4 -dienoate was obtained.

The above ester (10.2 mmcl) was hydrolysed by potassium hydroxide (41.2 mmol) in aqueous ethanol at room temperature over 24 hours. After standard work-up, the residue was triturated with hexane to give (2E,4E) ll-(3,5-bistrifluorornethylbenzyloxy)-3-methylundeca-2,4- -dienoic acid.

The above acid (0.5 mmol) was treated sequentially with triethylamine (0 .5 mmcl) and phenyl N-phenylphosphorami dochiori date (0.5 mmol) in dichioromethane in the absence of moisture. After 30 mins, triethylamine (0.5 mmol) and isobutylamine (0.5 mmcl) were added sequentially and after 16 hours at room temperature the reaction was worked up in standard fashion. The crude material was purified by flash column chromatography (silica/80:20 ether:hexane) to give (2E,4E) N-isobutyl- 11l- (3,S5-bi strif 1uoromethyl ben zyloxy) -3 -methylundeca-2 r4 -dienamide as a pale yellow oil. Glc, 3% 0V210 at 2500, retention time 2.9 min; tic, R f (silica-ether) 0.58; NMR; 7.61 ppm S, aromatic; 5.81, (3H1), 4,H5,NH;5.49, ClH),S,H2; 4.42,(2H), S, benzylic CH 2 3.44,(2H1), t,Hll; 2. 20, (3H1), S(bd), Me; 2. 22,C(3H) H6,Bu 1.37, H7, 8 9, 10; 3. 20,C(2H )d of d; 0. 94, (6H) Id, Bu The following compounds, all (2E, 4E) unless otherwise stated, were prepared similarly: Example 3 N-2, 2-Dirnethyipropyl methylbenzyloxy -3-methylundeca-2, 4-dienataide.

tic; R f silica-ether) 0.52 Example 4 N-l--methylpropyl benz-yoxy )-3-methyl-2, 4-dienamide tlc, R f (silica-ether) 0.43.

Example 5 N-1, 2-dimethylpropyl methylbenzyloxy)-3-methlylundeca-2, 4-dienamide.

Trimethylaluminium (4.2 mrnol) in dry toluene was treated with 1lr2 -dime thylpropylami ne (4.2 mmol) at After 30 mins (00 room temp) the ester of Example 1 (3.82 minol) in toluene Was added. The mixture was heated under reflux for 6h in the absence of moisture and oxygen, treated wit.h aqueous hydrochloric acid and worked in standard fashion. The crude material was purified (silica/l:l ether:hexane) by column chromatography to give (2E/Z,4EB) N-l,2--dimethylpropy. methylbenzyloxy)-3-methylundeca-2,4-dienamide as a pale yellow oil. (85:15 2E,4E:2Z,4E). Gic; 0V210 at 250 0, Rt 2.2,1.5 mins; tic, silica-ether, R f 0.60.

Example 6 N-isobutyl -5-methyl-und(,Aca-2,4-dienamide.

-21- 7-(3,5)--iBistrifluoromethylbenzyloxy)-heptan-l-al (26.5 mmjol) was reacted in dry ether with methyl magnesium iodide (26.5 mmol) and worked up in conventional fashion.

The crude material was purified by column chromatography to give 8-C3,5-bistrifluoromethylbenzyloxy)-octan-2-ol.

The above alcohol (16.17 mmol) was oxidised using methods described in EP-A-164 187 (Swern oxidation, DMSO, oxalyl chloride, triethylamine) to give 8-(3,5-bistrif luorometbylbenzyloxy) -octan-2-one. The ketone was reacted with triethyl-4-phosphonocrotonate/lithium diisopropylamide to give ethyl methyl )benzyloxy-5-methylundeca-2, 4-dienoate. The ester was converted into the amide as in Example The product was purified by preparative reverse 900 phase HPLC (85% methanol 15% water) 'to give (2E,4E)N- 9 isobutyl ll-(3,5,bistrifluoromethylbenzyloxy)-5-methylundeca-2,4-dienamide as a yellow oil. Gl1c; OV210 at 270 0 :Rt 6.2 mins; tlc, silica-ether, Rf 0.48, NMR; 7.75,(3H), 9s,aryl; 7. 5 2 (1H),d of d, H3; 5. 95, (lH),d,H4; Nfl; 5.75, (lH),d,H2; 4.56, S, benzylic; 3,52, (211),t,Hh1; 2.12, (2H),t,H6; l.65-1.3,(8H),H7,8f9, 1.85, (3Hz),S,Me;- 3.16,(2H),d of d, l.8,C1H),m,0.91, (6H-),d,isobutyl.

Example 7 (2E, 4E) N-1,2-dimethylpropyl fluoromethylbenzyloxy) 5-methy*,L-undeca-2,4-dienamide, The compound was prepaired as in Example 6. tlc, silica-etheXR 0.52.

at f Example .8 (2E, 4E) N-isobutyl methylbenzyloxy 5-dimethylundeca-2, 4-dienamide, 5-bistriflutoromethylbenzyloxy)octan-2-one was reacted with triethyl 4-phosphono-3-methylcrotonate/ -22lithium diisopropylamide to give an ester which was converted as in Exanmple 5 into (2E,4E) N-isobutyl l1-( 3, 5-bistrifluoromethylbenzyloxy)-3,5-dimethylundeca-2,4-dienamide. Pale yellow oil, tic (silica-ether) R f 0 .59; NMR; 7,80,(3H),S,aryl; 5. 69, ClH),S,H4; 5. 54, (lH),S,112; 4.60, S, benzylic, 3.54, t,Hll; 2. 24, S, 3Me; 2.08, (2H),t,H6; 1.83, 1.75-1.3, H7,8,910; 3.15, (2H),d of d, 1.8, (lH), m, 0.92, d,isobutyl.

The following compounds were prepared similarly: Example 9 (2E,4E) N-isobutyl 9-Cl-naphthyloxy).-3-methylnona-2,4-dienarnide (yellow oil), starting from a reaction of l-naphthol and bromopentanol in dimethylformamide in the presence of sodium hydride, the bromopentanol having been prepared from pentanediol and hydrobromic acid.

*Example 10 (33% 2E,4E,67%2Z,4E) N-l,2-dimethylpropyl 0 60 9-(l-naphthyloxy)-3-methylnona-2,4-dienamide (yellow oil) 00 *0Example 11 (67% 2E,4E; 4E)N-, 2-diiterhy2propyl 0 11 9-(l-naphthyloxy)-3-methylnona-2,4-dienamide (yellow oil) Exa-mple 12 N-I1sobutyl .0 benzyloxy)-3-ethyl-undeca-2, 4-dienamide 7-(3,5-bistrifluoromethylbenzyloxy)heptan-l-al (See 0 Example 2, 4 .97g, 13.96 minol) was reacted with carboethoxymethylene triphenylphosphorane (4 .8 6g, 13. 96 mmol, Lancaster Synthesis Ltd., in dry dichloroomethane to give ethyl 9-(3,5-bistrifluoromethyl- "oo -20n at 5 benzyloxy)nona--eot The ester (5g, 13.55 mxnol) was reacted with diisobutylaluminium hydride (27 mmol) in toluene-dichioromethane at -30O After conviantional work-up, benzyJloxy)nona-2-en-1-ol (4.43g) was obtained. The alcohol was converted into 9-(3,5-bistrifluoromethyl- P -23benzyloxy)nona-2-en-al by Swern oxidation (oxalyl chioride-dimethylsuiphoxide, see EP-A-164 187).

The above aldehyde (4.47g, 15.13 minol) was reacted in dry ether with ethyl magnesium bromide prepared from magnesium (0.36g, 15.13 mmol) and bromoethane (1.65g, 13 mmol) After conventional work-up with ammonium chloride, the crude product was purified by chromatography (silica, ether:hexane) to give l1-(3,5-bistrif luoromethylbenzyloxy)undeca-4-ene-3-ol which was converted by Swern oxidation into methylbenzyloxy )undeca-4-ene-3-one.

n-Butyl lithium (4.99 mrnol) in hexane was added to N-isopropyl cyclohexylamine (0.69 g, 4.88 mnol, Aldrich Chem. Co.) in dry tetrahydrofuran (20 ml) at -78O0 under nitrogen. After 15 mi ns, ethyl trimethylsilylacetate (0.78 g, 4.88 mmol, Fluka Chem. Co. was added. After a further l0mins, undeca-4-ene-3-one (1 g, 2.44 mrnol) was added and the temperature was allowed to reach room temperature. After conventional work-up and chromatography on silica, ethyl 11- 5-bi strif luoromethylbenzyloxy) -3-ethyl -udca-2, 4 dienoate was obtained as a mixture of two isomers.

The above esters (0.8 g, 1.67 mmol) were treated, with a complex prepared from isobutylamine (0.18 ml, 1.84 minol) and trimethyl aluminium (1.84 mxnol) in toluene (see Example After chromatography, (2E, 4E) K-isobutyl 11- 5-bi strl;f luoromethyl benzyloxy) -3 -ethyl -Undeca- 2,4 dienamide was obtained as a yellow oil. Gic, 3% 0V210 at 2500, retention time 1,6 min; tlc, R f (silica-ether) 0.64; NMR: 7.81 (3Hi), aromatic; 6.03 (lH)tm,HS5; 5.92 (lH),d,H4; 5.52 (lH),s,112; 5.45 NHl; 4.62 (2H),s,benzylic;- 3.52 (2H),t,flll; 2.81 (211), q, 1.11 3-Et; 2.18 (2H),m,H6; 1.3-1.7 M8), satd.chain;- 3.23 (21i)t, 1.80 0.94 (6H),d,isobutyl.

-24- Example 13 N-Isobutyl benzyloxy )-3-fluoromethylundeca-2, 4-dienamide l-Chloro-3-fluoro-prop-2-one (16.1 g, 146 minol, Bergmiann Cohen, J Am. Chem Soc., 1958, 2259) in dichioromethane was treated with carboethoxy-methylenetriphenyiphosphorane (50.5 g, 146 mmol). After 48hours at room temperature, the reaction was worked up in conventional fashion and purified by column chromatography (silica-ether hexane) to give ethyl 4-chloro-3fluoro-inethyicrotonate. The latter (18 g, lO0mmol) was added at 100 0 to triethylphcsphite (23.3 g, 140 minol).

The mixture was warmed to 150 0, maintained at that temperature for 6 hours and subjected to distillation to give triethyl 3-fluoromethyl-4-phosphonocrotonate (21 g) (bp (1 nmn) 140 500) The above phosphonate (3 g, 1123 mnol Was reacted with lithium di isopropylamide (11.23 minol) and the resultant anion reacted with 7-(3,5-bistrifluoromethylben zyloxy) -heptan-l-al (4 9, 11.23 mmQl) in dry TUF (as in Example After work-up and purification, ethyl 1l--(3,5-bistrifluoromethylbenzyllexy)-3-fluoromethylundeca-2,4-dienoate, (3.95 g) was obtained. The ester was converted to the dienoic acid and then as in Example 1 to give (2E,4E) N-isobutyl benzyloxy)-3-fluoromethylundeca-2,4-dlenamide as a yellow Oil. (Rff silica/ether, 0.64). NMR: 7.81 O3N), s, aromatic; 6.22 (lH),mn,H; 6.05 (11-)td,H; 5.72 (lH),S,112; 5.64 (2Ei),d,CH 2 F; 5.68 0il; 4.62 M2),stbenzylic; 3.56 chain; 3.26 (2H),t,l.80 (UH)Om, 0.95 M6),d,isobutyl.

Exam~ple 14 N-1,2-Dimethylpropyl, l,1-(3,5-bistrifluoromethylbenzyloxy)-3-fluoromnethyl-undeca-,2,4-dienamide prepared as in Example 13.

Rf (silica/ether) 0.66.

Example 15 N-isobutyl 12-(2-naphthyloxy)-3-methyldodeca- 2, 4-dienaride Prepared as in Example 5, starting from 2-naphthol and bromooctanol, the latter being prepared from octanediol and hydrobromic acid mp 84-60 An alternative synthesis is given in more detail below: A mixture of ethyl 3-methylbut-2-enoate (10.19), N-bromasuoonimide (14g) and benzoyl peroxide (Q0.g) in dry carbon tetrachloride (150 m) was stirred under reflux for 3ht filtered, solvent e .tporated under reduced pro ssnure and residue distilled to yield ethyl (E ,'/Z-4-bromo- 3-ne thylbut-2-enoate (9.49, b.pt" 100-10(0 l'rnmmIcj. nl. 4 63. Ewhich was then added dropwise to trityl paipht, (3.

1 at 1000, 'The temperature was flxowlv ralrled to ISOC and the ethyl bromide formed allw k1 to distil ov er after 2h, the residue was hdilled ol qi.w ethyl UYZ-4-diethylphosphono)-3nphyl!It-2-enoat C2.1g, bpt. L6-120 C at Q.Zmmig. n 0 l44%1 An ari ter fraction (1,2g) from the d(istillatin also (cntan(d mainly the required products.

A mixture of 2-naphthol (2.89)t 0-bromo-tetra- Ir o, y ran l otan-1- o 1 50% aqueous sodium iydr~oxile and tetrabtitylammonium bromide (0.69) was s;tirtere at 9O for 2h. ThO reaction mixture was cooled to reo i t -'ratute, diluted with watery extracted with ethf~ Cx38, wLshhd with water, then dte UC, dried EInd n,~t eva-Qra~ted undr reduced pressure to give -26- 2(8-CTetrahydropyran-2-y'I (octyloxy) naphthalene 72- Naphthyl )OTHiP) (6.81g, n 0 1.5380) which was then (6.89) mixed with Amberlyst (Regd. T.M. A15 (1.9g) and methanol (120 mi) and stirred at 65 0 C for l6hf filtered, diluted with water, extracted with dichiorometha-ie, (x3) washed with dilute HCl, and the solvent evaporated under reduced pressire to give 2 (8-ijydroxyoctyloxy) naphthalene (2-Naphthyl-O-

(CH

2 CH OH) (3.8g) rn.pt 67-68 0 C. Pyridinium chlorochromate (0.6g) was added to a solution of the 2 (8-hydroxyoctyloxy) napDhthalene 5g) in dichioromethane ml) and the mix--ture stirred at 20 0

C.

Petroleum ether b.D. 60-80 0 C Was added and after stirring for a further 10 min. filtered through a pad of charcoal/ceJlite. The solvent was evaporated under reduced pressure and 2(8 -Oxooctyloxy naphthalene (2-Naphthyl-O-(CH 2 7 CHO.) purified by thin layer chromatography on silica eluted with 20% diethyl ether in petroleum ether b.pt 60-80 0 C. Yield 0.2g., nD 1.5570.

Sodium methoxide was prepared by reacting sodium 195 mg) with dry methanol (1.5 ml). The solvent was removed under reduced pressure and replaced by dry DM.F (8 ml). A solution of the ethyl 4-(diethylphosphono)-3methylbut-2-(E/Z)-enoate (0.96g) frozi step in dry DM.F ml) was then added over 2 min. After 5 min, a solution of the aldehyde from step (OQ,9g) in dry DMF ml) was added dropwise. The, mixture was st-*rred at 0 C for 3h, poured onto RdI, extracted with diethyl ether washed with water, dried and the, solvent removed under reduced pressure to give ll-methoxycarboflyluliCiec-8(E) ,l0(E/Z4) -dienyloxy) naphthalene (2-Naphthyl-0-(CH 2 7

-CMC-C(CRE

3 )=CRCO 2 Me).

Yield 0.42g n. 1.5740.

A mixture of the latter (0.46g), ethanol (ZD ml) and 7% aqueous sodium hydroxide (2 ml) was stirred under -27reflux for 1 hour and poured onto water. The precipitate was filtered off, shaken with dilute HC1, extracted with diethyl ether dried and the solvent removed under reduced pressure to give the product as pure E isomer (0.14g, m.pt. 84-850C). The filtrate was acidified with dilute HCl and extracted with diethyl ether The combined extracts were dried and the solvent evaporated to give 2(10-Methyl-ll-carboxylundeca-8(E) 10(E/Z) -dienyloxy naphthalene (2-Naphthyl-O-(CH 2 7 -CH=CH-C(CH3)=CHCO 2

H).

The residue was recrystallised from diethyl ether/petroleum ether b.pt. 60-80°c to give a further quantity of the E-isomer (80 mg) and the Z isomer removed in the mother liquor as a semi-so .d which was used without further purification.

Finally, 2(10-methyl-ll-carboxy undeca-8(E), Sdienyloxy) naphthalene mg) was stirred with oxaly chloride (1 ml) and dry benzene (5 ml) for 3h. The o solvents were removed under reduced pressure and the acid Schloride redissolved in dry diethyl ether (3 ml). A solution of isobutylamine (0.5 ml) in dry diethyl ether S: (5 ml) was then added dropwise. The mixture was stirred at 20 0 C for 2h, poured onto dilute HCl, extracted with diethyl ether dried and the solvent evaporated.

The product was recrystallised from diethyl ether and petroleum ether b.pt. 60-80°c to give the title product m.pt. 83-85 0

C.

Alternatively the 2(8-tetrahydropyran-2-yl) (octyloxy)naphthalene 2-Naphthyl-O-(CH2) 8 -OTHP) may be produced as follows. A mixture of 8-(2'tetrahydropyranyloxy)-octanol (2.35g), N,N' -dicyclohexyl-carbodiimide (2.5g) and 2--naphthol (1.6g) is stirred and heated at !0 0 °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 hydrogen carbonate solution, dried over 'J L,

I

-28sodium sulphate and, evaporated to yield the product, n D 1. 5370.

Examole 16 N-1-methylpropvl 12-(2-naphthvloxv)-3-methyldodeca-2, 4-dienamide Prepared as in Example 5 m.p. 65-8 0 Examnole 17 N-isobutyl ll-(2,3,4,5,6-pentafluorobenzvloxy )-3-methvlundeca-2, 4-dienamide Prepared as in Example 5, starting from pentaf luorobenzyl bromide Rf (silica/ether) 0.57 (2E,4E) 30% (2Z,4Z) Examole 18 N-1, l,2-trimethvlaropvl ll-(3, methvlbenzvloxv)-.3-methvlundeca-2, 4-dienamide Prepared as in Example 1, starting from fluorometnyl )phenol R f (silica/ether) 0.70 1:1 (2E:4E): (2Z,4Z) Examule 19 N-Isobutvl 1l-(2,4-dichloroberizvloxv)-3methylundeca-2, 4-dienamide Prepared as in Example R f (silica/ether) 0.60 (2E, 4E) 25% (2Z, 4E) 4 1.

14 4 '4 t~' 4 0* 'I F S ~I1 -29- Example 21 N-Isobutyl ll-(3,5-bist7 fluoromethylbenzvloxy)-3-trifluoromethyl-undeca-2,4-dienamide Cis -CE) 3-trifluoromethyl triethyiphosphonocrotonate was prepar:i according to Liu et al (J.kAm. Chem. Soc., 1982, 104,4979) and reacted with 7-(3,5-bistri'fluoromethylbenzyloxy)-heptan-l-al as in Example 2 to give an ester which was reacted with trimethyl aluminium and isobutylamine as in Example 5 to give the title compound as a yellow oil. Rf (silica/l:l ether:hexane) 0.54 98% 2-cis, 4-trans (2E, 4E) 'H NNR Colefinics): 7.19,(d,lB),H4; 6.26,(MlB),H5; 00 aP 6.16, (slH),H2.

*c s Examole 22 2-(L0-methyl-12(2,2-dimethylpropv\lamino)-12oxo-dodec8(E), 1Q(E/Z)-dienyloxynaphthalene m.pt. 93-6 C err The above compound was prepared by a procedure similar to that described in Example wt4I Examole 23 23:(10-methyl-12(2-methylbutylamino)-12-oo 9 4R dodec-S(-P.), (E/Zdd-ienyloxynaphthalenen The above compound was prepared by a procedure similar to that described in Example Example 24 2-(0-methyl -12(,2-dimettylamino)-12oxdodec-8), 10(E/Z)dienloxynaphthalen e The compound was prepared by a procedure similar to that described in Example Example 25 6-Bromo-2'-( 1-me thyl-l2 2-di me thylpropylarino-12-oxo-dodec-8(E), 10 (E/Z)-dienyloxynaphthalene This compound was prepared as in Example 15, via the following intermediates: 6-Bromo-2-( 8- (Tetrahydropyran-2y1 )-octyloxy naphthalene (n Dl. 5432).

6-Bromo-2-(B-hydroxyoctyloxy) naphthalene 59-61 0C) 6-Bromo-2-( 8-oxooctyloxy) naphthalene 49-51 0 C 6-Bromo-2-( lO-methyl-11-methoxycarbonyl dec-B 10(E/Z dienyloxy)naphthalene n D 1.5433.

in the final steps, trimethylaluminium (2M, 1 ml) in *hexane was added dropwise to a stirred solution of isobutylamine (0.2 ml) in dry benzene (2 ml) at 20 0 under an atmosphere of nitrogen. After 15 min, a solution of the above ester (0.1g) from D in dry benzene (1 ml) was added and the mixture stirred under reflux, for 16h, cooled to 20 0 Cand dilute hydrochloric acid (10 ml) added cautiously. The mixture was stirred f'or 30 min. extracted with dichloromethane, dried and the solvent evaporated.

The residue was purified by thin layer chromatography on silica eluted with 60% ether/petroleum ether to give the title product m.p. 79-81l C Biological Activity A.Topical application versus house flies Compounds of the invention were administered topically in Cellosolve solution, with or without 6p~g -31piperonyl butoxide,to adult female Musca domestica (WRL strain). The results, in terms of kill, are given in Table 1.

In addition, the compounds of Examples 9-14 showed activity at 3 pg ug PB).

B.Activity versus grain pests Approximately 20 each of Sitophilus granarius and Tribolium castaneum adults are placed in a tube of 15 g grain onto which 1.5 ml of a 0.2% w/v solution of the compound has been pipetted and left to dry. Mortality at 7 days is given in Table 1.

Table 1 Compound of Example No.

2 3 4 6 7 8 M.domestica Dose (pg) -PB 0.6 77.5 0.6 53 0.6 24 0.12 0.6 5 1.5 19 0.3 0.3 3 0 S. g. T. C.

+PB

100 100 84 100 52 0 4 12 *721 C.ctivity versus blowfly The compounds of Examples 2 and 5 had an effective dose of <cl0 ppm against Lucilia cuprina.

~II

1 -32- D.Activity versus mosquito o 44 4.

4O 4 I. P SP 44 P. 4I 4., 4I i4 Against Culex fatigans in a wind tunnel, the compounds of Examples 2 and 5 each had an LC 50 of in OPD/dichloromethane solution.

E.Trackspray When sprayed as an acetone:water:wetters emulsion (5:94.5:0) the following examples showed activity at <1000 ppm sprayed against: M. domestica: 2, 9, 11, 12, 15, 16, 17, 19, C. quinquefasciatus: 9, 11 A. aegypti: 9 P. xylostella: 2, 4, 9, 11, 12, 15, 16, 17, 19, M. persicae: 2, 3, 4, 11, 12 T. urticae: 2, 3, 4, 15, 16, 17, 18, 19, F.Spodoptera littoralis The compound of Example 2 showed activity against larvae of S. littoralis when topically applied at Examples 15, 16, 17, 19, 20 showed activity against larvae of S.littoralis when injected at G.Comparative example The compound of Example 2 was compared with the compound of Example 4 of EP-A-164 187,A namely the analogue lacking the 3-methyl group. When applied as deposits on glass, the following results were obtained.

i -33- Compound Ex.2 prior art analogue -2

LC

50 (mg.m A. aegypti c40 >200 C.quinquefasciens >200 09 i9 o 9 9; *9*

I

9r

J

9i 0 0$ 0lr 0* a w When applied as acetone solutions to Spodoptera littoralis larvae, Ex. 2 had LD 50 2 ug and the analogue had LD 50 >10 ug.

Illustrative compounds of Examples 15 and 22 to are set out in Table 2 with physcial constants and bioassay date.

Compounds of Formula are bioassayed by the following method: Acetone solutions (lul) of compounds are applied topically by Arnold micro-applicator to the thorax of 4-day adult female houseflies (HF) (not the same strain as in Example A above), anaesthetised with ether, or to the ventral abdomen of approximately 1-week- old adult male and female mustard beetles 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 at these times end point mortalities are approached.

The results are analysed by the method of probits, to give for each test LD 50 values and standard errors for each compound, and for the standard (bioresmethrin).

Comparisons between LD 5 0S and compound and standard give relative potencies (bioresmethrin 100).

wwwwm_ -34- TABLE 2 Ar(H2 m C 2 (H 2 )n CH-CH CE -CHCONHZ Compound of Configuration ExNo Ar m+n E3 Z at C-C-CO M ML 2-naphthyl 6 CH 3 CH 2 CH(CH 3 2 E 83-5 0 C 0.4 37 22 2-naphthyl 6 CH 3 CH 2 CCH 3 3 E/Z 93-6 0 C NT 5.8 23 2-naphthyl 6 CH 3 CH CH CB )C H 5 E/Z Semi 1.0 11 3 2 2 5 Solid 24 2-naphthyl 6 CH 3 CH(CH 3 )CH(CH 3 2 E/Z Semi ca.0.2 6.4 Solid- 6-bromo-2naphthyl 6 CH CH H(H3),Imil E 64-670 NT (NT :non-toxic or concentrations used) Formulations 1. Emulsifiable Concentrate Compound of Example 2 10.00 Ethylan KEO 20.00 Xylene 67.50 Butylated Hydroxyanisole 2.50 100.00 2. Wettable Powder Compound of Example 2 25.00 Attapulgi te 69.50 Sodium i sopropyl benzene sulphonate 0.50 Sodium salt of condensed naphthalene suiphonic acid 2.50 Butylated hydroxytoluene 2.50 100.00 3. Dust Compound of Example 2 0.50 Butylated Hydroxyanisole 0.10 Talc 99.40 100.00 4. Bait Compound of Example 2 40.25 Icing Sugar 59.65 Butylated hydroxy toluene 0.10 100.00 Lacquer Compound of Example 2 2.50 Resin 5.00 Butylated Hydroxy anisole 0.50 High aromatic white spirit 92.00 100.00 6. Aerosol Compound of Example 2 0.30 Butylated Hydroxy anisole 0.10 1,,1-Trichloroethane 4.00 Odourless Kerosene 15.60 Arcton 11/12. 50:50 mix 80.00 100.00 7. Spray Compound of Example 2 0.10 Butylated Hydroxy anisole 0.10 -36- Xyl1e ne 10.00 Odourless Kerosene 89.80 100. 00 8. Potentiated Spray Compound of Example 2 0.10 Permethrin 0.50 Butylated Hydroxyanisole 0.10 Xylene 10.10 Odourless Kerosene 89.20 100.00

Claims (6)

1. A compound of Formula (I A(C )0C H)c 1 2 3= 4 1 AT(CH2 )x(CH )mA(CH 2 n(CE1=CE )a CE=CE )CONR wherein Ar is phenyl or naphthyl, in either case unsubstituted or substituted by one or more of C 1 alkyl, halogen, C alkoxy, C, alkyl substituted by 1-6 16 halo, or C alkoxy substituted by halo 1-6 x 0 or 1 1 to 7 n 1 to 7 A CB 2 or oxygen Sa 0 o 1 l is independently selected from hydrogen, C alkyl and C 3-6 cycloalkyl (either of which may be substituted by one or more of halo, C1-6 alkyl, C 2 6 alkenyl, C2-6 alkoxy, C 2 6 alkynyl, dioxalanyl and C3i cycloalkyl z represents a hydrogen or a group: -C (RA -C (RC) (RD)(RE wherein RA and which may be identical or diZferent, each represent hydrocen or methyl; Rc represents methyl; represents methyl, ethyl, n-propyl, isopropyl, t-butyl tr vinyl; and RE represents hydrogen or 00 E methyl; or wherein Rc and RD form a methylene group (=CH2) or together with C2 form a cycloptopane or cyclobutane ring, RA' RB and R representing hydrogen or methyl; or wherein RA and R. together with C 1 and C 2 form a cyclobutae ring, RB, RD and RE independently representing hydrogen or methyl: -38- El E 2 E a rd E 4are indeperidentiY selected f ram hydrogen, C I-ral -yl, op~nl substituted by halo, or hitrL'e., provided that at least one of E 1 E 2, E 3and E+ ,s optionally! ubsltituted alkyl. or nitrile except that 2E, 4E) fl-Isobutyi 3-methvl-7-(]-chlorophenox<y)-dodeca-

4-dieniaide is excluded and X is zero only Mien Ar is optionally substituted naphithyl and one of RI and Z, but not both, is hydrogen. 2. A compound according to Claim I wherein Ar is phenyl. substituted by one or more halogen or trifluoromethyl groups. 1. A compound according to Claim 1. or 2. wherein a is 1. 4. A compound aczcording to any one of the preceding claims wherein Ax i s -CH 2 and the sum of m and n is equal to an odd number, A compou~nd according to aniy one of the preceding clalna Wherein RpI is hydrogen and z is C 1 alkyl.

6. A compou4nd according to any one o4 the precedin cIlims wherein the stereoichemistry off the or each double bond conjugated to the amide carbonyl is trans.

7. A qompouind according to any one oe the preceding clis weria E E~ and E are hydrogen and E 3 is men~lyl, fuoromethyl. Or trifluoromethyl. ~udca~,4-dienamide, 'N-isobutyd. l2-(2-onaphthyl- )x 0- a-2,4-dinamide, N-i*sobutyl 2d-(2,4- i .4hro be n zy Ioxy -3 -me thy 1undeca 4 -dioenarnide and ,J~d,-a-f4-dienatnide (in each case 4V). I A proCeS.$ for preparing a comnpound according to Claim (a y aidation of the corresponding aaid or acid dovA e by reaction oe a compound otf F'ormul~a 11 with a, compound oe Formiula (IZ1). AC)X11O(Cql (CI (CtlmCt-2 )C~Z 4 )CO (C bcV)O -39- (III) HNR I wherein Z is hydroxyl, halo, a phosphoroimidate ester (-P(---~0(OAryl)NH.aryl) or alkoxy and the other variables are as defined in Claim 1; by reaction of a compound of Formula (IV) with a compound of Formula (IV) Ar(C 2 xO(C 2 )mACH 2 )n(CE =CE 2 )DZ' Z"CONR Z where one of Z' and Z" is -C(O)E 5 and the other is 2 6 3 4 2 6 3 4 (Z 2 =CE (CE =CE4) q or (Z2) 2 P(O)=CE(CE=CE wherein Z is C1-4 alkyl, C1-4 alkoxy (preferably ethoxy) or aryl (preferably phenyl), p and q are each 0 or 1 and p+q is 0 or 1, E s E or E 3 and E 6 is E 2 or E 4 a s appropriate; by an elimination reaction on a compound of Formula (VI) or (VII): (VI) Ar(CH 2 xO (C 2 mA(CH 2 nE 1 =CE 2 )CE 3 )CE 4 (Y)CONR Z V) 21 2 34 1 (VII) Ar(C2 x O(CH 2 A(C 2 n CE (X)CE (Y)(CE 3 CE 4 )CONR 1 where one of X and Y is hydrogen and the other is a group Q in which Q is sulphur or s.lenium and L is a suitable group. by reacting a compound of Formula (VIII) with a compound of Formula (IX) 1 2 (VIII) Ar(CH 2 xO(CH 2 m 2 n CE =CE 2-M (IX) Hal-(CE =CE )CONR Z wherein Hal is halide and M is a silicon or a metal atom I,' I V 'I ~f I I II el I~ as al a I a a ~I II It ft d or metal-containing group); by reaction of a compound of Formula MX with a compound of Formula (XI): Ar (CH 2 Z 3 (XI z 4 (CH 2 A (CH 2 )n (CE 1=CE 2)a (CE 4)CONR 1Z wherein one of Z3and Z4is -OR and the other is -OE or a suitable leaving group; when A is oxygen, by reaction of a compound of Formula CXII) with a compound of Formula CXIII): (XII) ArCCH 2 X 0C(E 2mz CXIII) Z6 (CH n(CE =CE 2) a(CE 3=CE 4)CONR 1Z where one of Z5and Z 6 is -OH and the other is a suitable leaving group; Cg) by reacting a compound of Formula CXIV) with ono of Formula CXV) or CXVI): CXIV) Ar(C 2 X.OC 2 MACSl 2 VCE =CE 2_Hal MX) HC =CE 4CONR 1z CXVI) HACaCE 4CONR 1z where Hal is halogen, followed by semi hydrocjenation of the triple bond, if present; by semi -hydrogenation of the triple bo~nd in a compound of Formula CXVII) or CXVIII): CXVII) Ar(CI 2 X OCCH 2 mACCH 2 n C-(CE 3 CE )bCONR Z CXVIII1) Ar(CH 2 x OCH 2 )MA(CC 2 )n(CE ICE 2 )a-C5CCONR 1 z -41- wherein a and b are both 1. by conversion of one ccmpound of Formula (I) J prepared as above into another compound of Formula by any suitable process. A pesticidal composition comprising a compound according to Claim 1 and one or more diluents or carriers.

11. A method of combatting pests by applying to the pest S0 or its locus a compound according to Claim 1 or a composition according to Claim

12. A locus when treated with a composition according to S* Claim S* 13. Any compound of Formula or process of production thereof substantially as disclosed in any one of the Examples, (excluding Comparative Examples) e Dated this 30th day of November 1989 THE WELLCOME .FOUNDATION LIMITED By their Patent Attorney GRIFFITH HACK CO. L-