GB2250022A - Pesticidal amides - Google Patents

Abstract

Pesticidally active amides of formula (I): Q Q<1> CR<2> = CR<3> CR<4> = CR<5>C (=X) NHR<1> and salts thereof, wherein Q is an monocyclic aromatic ring, or fused bicyclic ring system of which at least one ring is aromatic containing 9 or 10 atoms of which one to four may be nitrogen or sulphur and the rest carbon each optionally substituted, or Q is a dihalovinyl group or a group R<6>-C IDENTICAL C- where R<6> is C1-4 alkyl, tri C1-4 alkylsilyl, halogen or hydrogen; Q<1> is a 1,3 or 1,2 cyclobutyl ring optionally substituted by one or more groups selected from C1-4 alkyl, halo, C1-4 haloalkyl, alkynyl, or cyano; R<2>, R<3>, R<4> and R<5> are the same or different with at least one being hydrogen and the others being independently selected from hydrogen, halo, C1-4 alkyl or C1-4 haloakyl; X is oxygen or sulphur; and R<1> is selected from hydrogen and C1-8 hydrocarbyl optionally substituted by dioxalanyl, halo, cyano, trifluoromethyl, trifluoromethylthio or C1-6 alkoxy, are novel compounds. Novel intermediates have the formulae QQ<1>C<2>=CR<3>CR<4>=CR<5> (=X)2<1>, QQ<1)<CR<2>=CR<3>)COR<4>, QQ<1>COR<2> and QQ<1)<CR<2>=CR<3>)CR<4>Z<2>, where Z<1> is hydroxy, C1-6 alkoxy, halo or -P(O)(O-aryl)NH-aryl in which aryl is C6-10 aryl and Z<2> is (aryl)3P, (aryl)2P(O) or (alkyl-O)2P(O).

Description

PESTICIDES This invention relates to pesticidal compounds, processes for their preparation, compositions containing them and to their use in the treatment of pests.

Insecticidal unsaturated amides are known which have an alkylene chain of 1 to 11 carbon atoms optionally interspersed with at least one oxygen atom and terminating in various groups including optionally substituted phenyl (European Application Nos. 228222, 194764, 225011, Japanese Application No 57-212150, Meisters and Wailes: Aust. J. Chem.

1966, 19, 1215, Vig et al : J. Ind. Chem. Soc. 1974, 51(9), 817), pyridyl (European Application 269457), fused bicyclic ring systems (European Application Nos. 143593, 228853), dihalovinyl or optionally substituted ethynyl (European Application 228222).

H.O. Huisman et al, Rev. trav. chim. 77, 97-102, (1958) discloses a group of 5-(2,6,6-trimethyl cyclohexenyl)2,4-pentadienamides as insecticides.

A 1,2-disubstituted cyclopropane system linking the diene unit to a terminating group as described above has been disclosed as having interesting pesticidal properties (European application 39762).

It has now surprisingly been discovered that novel unsaturated amides having a cyclobutyl ring adjacent to the diene unit linking the latter to a terminal group selected from optionally substituted monocyclic aromatic or fused bicyclic ring system, dihalovinyl or optionally substituted ethynyl have interesting pesticidal properties.

Accordingly, the present invention provides a compound of formula (I): Q Q1 CR2 = CR3 CR4 - CR5C (-X) NHR or a salt thereof, wherein Q is an monocyclic aromatic ring, or fused bicyclic ring system of which at least one ring is aromatic containing 9 or 10 atoms of which one to four may be nitrogen or sulphur and the rest carbon each optionally substituted, or Q is a dihalovinyl group or a group R6-C=C- where R6 is C1-4 alkyl, tri C1-4 alkylsilyl, halogen or hydrogen; Q is a 1,3 or 1,2 cyclobutyl ring optionally substituted by one or more groups selected from C1-4 alkyl, halo, C1-4 haloalkyl, alkynyl, or cyano;R2, R3, R4 and R5 are the same or different with at least one being hydrogen and the others being independently selected from hydrogen, halo, C1-4 alkyl or C1-4 haloalkyl; X is oxygen or sulphur; and R1 is selected from hydrogen and C1-8 hydrocarbyl optionally substituted by dioxalanyl, halo, cyano, trifluoromethyl, trifluoromethylthio or C1-6 alkoxy.

When Q is a monocyclic aromatic ring, this is suitably phenyl, pyridyl or thienyl and preferably phenyl. When Q is a bicyclic ring system, this is preferably naphthyl.

When Q contains an aromatic system, suitable substituents include one to four groups selected from C1-6 hydrocarbyl, C1-6 alkoxy or methylenedioxy, each optionally substituted by one to three halos, or from halo, cyano or nitro, or the substituent is a group S(o)nR7 wherein n is O, 1 or 2 and R7 is C1-6 alkyl optionally substituted by one or more halos or R7 is amino optionally substituted by one or two C1-6 alkyl groups or the substituent is a group NR8R9 where R8 and are independently selected from hydrogen, C1-6 alkyl or a group COR where R10 is C1-6 alkyl.

The Q ring system normally contains up to three substituents and is suitably unsubstituted or substituted by one, two or three substituents such as halo or C1-4 haloalkyl such as trifluoromethyl.

The substitution of the Q ring system depends upon the nature of this ring system but is preferably at the 3, 4 or 5 positions when Q is a 6-membered ring.

Suitably R2, R3, R4 and R5 are chosen from hydrogen, methyl or fluoro.

Suitably the stereochemistry of the double bonds is (E). Suitably when R3 or R5 is fluoro then the stereochemistry of the double bond to which R3 or R5 is attached is (Z).

Preferably R2 is hydrogen, R3 is hydrogen or fluoro, R5 is hydrogen or fluoro and R is hydrogen or C14 alkyl, most preferably methyl.

Q1 is a 1,3-cyclobutyl group which may be optionally substituted.

Suitable substituents at the 1- and 3- positions of the cyclobutyl ring include hydrogen, fluoro, chloro, methyl or trifluoromethyl.

Preferably the 1- position is unsubstituted and the 3- position is unsubstituted or substituted by fluoro or chloro.

Preferably the stereometric configuration of Q1 is such that substituents (Q and CR2) are attached in a trans geometry.

Suitably R1 is alkyl optionally substituted by cycloalkyl, dioxalanyl, or R1 is C2-5 alkenyl. Most suitably R1 is a branched chain C4-6 alkyl group, such as isobutyl, 1,2-dimethylpropyl, 1,1,2-trimethyl propyl, 2,2-dimethylpropyl or R1 is 2-methylprop-2-enyl or (2-methyl-1,3- dioxalan-2-yl) methyl. Preferably R1 is isobutyl or 2-methyl-prop-2- enyl where R2 and R3 are hydrogen, R4 is methyl.

One suitable group of compounds of the formula (I) is that of the formula (II): QaQ1aCR2a-CR3aCR4a-CR5aC(-Xa)NHR1a (II) or a salt thereof, wherein Qa is an optionally substituted phenyl or pyridyl group or fused bicyclic ring system of which at least one ring is aromatic containing 9 or 10 atoms of which one may be nitrogen and the rest carbon or Qa is a dihalovinyl group or a group R6a-C#C- where R6 is C1-4 alkyl, trialkylsilyl or hydrogen;Q1a is a 1,3-cyclobutyl ring optionally substituted by one nr more groups qelected from C1-3 alkyl, halo, or C1-3 haloalkyl; R2a ,R3a ,R4a and R5a are the same or different with at least one being hydrogen and the others being independently selected from hydrogen, halo, C1-4 alkyl or C1-4 haloalkyl; Xa is oxygen or sulphur; and Rla is selected from hydrogen and C1-6 hydrocarbyl optionally substituted by dioxalanyl, halo, cyano, trifluoromethyl, trifluoromethylthio or C1-6 alkoxy.

When Qa contains an aromatic system, suitable substituents include one or more groups selected from halo, cyano, nitro, halo C1-6 alkyl, C1-6 alkoxy and methylenedioxy, each optionally substituted by one or more halos or the substituent is a group S(0)nR7a wherein n is 0, 1 or 2 and R7a is C1-6 optionally substituted by halo or R7a is amino.

Preferably Qa is substituted phenyl or naphthyl.

Suitably R2a, R3a, R4a and R5a are chosen from hydrogen, methyl, or fluoro.

Suitably R1a is C1-6 alkyl optionally substituted by dioxalanyl, or R1a is C2-5 alkenyl. Most suitably R1a is a branched chain C4-6 alkyl group, such as isobutyl, 1, 2-dimethylpropyl, 1,1,2-trimethylpropyl, 2,2-dimethylpropyl or Rla is 2-methyl-prop-2-enyl or (2-methyl-1,3-di- oxalan-2-yl) methyl. Preferably Rla is isobutyl or 2-methyl-prop-2en-yl where R2a and R3a are hydrogen and R4a is methyl. R5a is hydrogen or methyl.

One preferred group of compounds of the present invention includes those of formula (III).

Q Q1 CH-CR3CR4-CR5CONHR1 (III) wherein Q,Q1, R3, R4, R5 and R1 are as hereinbefore described.

Preferred compounds of the formula (III) include those wherein Q is substituted phenyl, Q1 is a trans or 1,3-cyclobutane ring, R4 is methyl or hydrogen, R2 is hydrogen, R3 and R5 are hydrogen or fluoro and R1 is isobutyl or 1,2-dimethylpropyl.

Thus, preferred compounds of the formula (I) include: 1. ()-(2E/Z,4E)-N-Isobutyl-3-methyl-5-(cis-3-phenylcyclobutyl) penta-2,4-dienamide (2E:2Z"2:1) and ()-(2E/Z,4E)-E-Isobutyl-3-methyl-5-(trans-3-phenylcyclobutyl) penta-2,4-dienamide (2E:2Z-2:l) (1:1).

2. (+)-(2Z,4E)-N-Isobutyl-5-[cis/trans-3-(3,4-dichlorophenyl, cyclobutyl]-3-methylpenta-2,4-dienamide (cis: trans 1:1).

3. (+)-(2E,4E)-N-Isobutyl-5-[trans-3-(3,4-dichlorophenyl) cyclobutyl]-3-methylpenta-2,4-dienamide.

4. (+)-(2E,4E)-N-Isobutyl-5-[gis/trans-3-(3,4-dichlorophenyl) cyclobutyl]-3-methylpenta-2,4-dienamide (cis: trans 6:1).

5. (+)-(2E,4E)-N-Isobutyl-5-[cisXtrans-3-(3,4-dichlorophenyl) cyclobutyl]-3-methylpenta-2,4-dienamide (cis:trans 1:1).

By the term halo is meant fluoro, chloro, bromo and iodo.

By the term hydrocarbyl group is meant, alkyl, alkenyl, alkynyl, aralkyl including a cyclic alkyl or alkenyl group optionally substituted by alkyl, alkenyl or alkynyl; and alkyl or alkenyl substituted by cyclic alkyl and alkenyl, and phenyl groups.

Salts of the compounds of the present invention will normally be acid addition salts. Such salts may be formed from mineral or organic or cycloalkyl acids. Preferred salts include those formed from hydrochloric, hydrobromic, sulphuric, citric, nitric, tartaric, phosphoric, lactic, benzoin, glutamic, aspartic, pyruvic, acetic, succinic, fumaric, maleic, oxaloacetic, hydroxynaphthoic, isethionic, stearic, methane- sulphonic, ethanesulphonic, benzenesulphonic, toluene-p-sulphonic, lactobionic, glucuronic, thiocyanic, propionic, embonic, naphthenoic and perchloric acids.

The compounds of formula (I) may exist in a number of stereoisomeric forms. The present invention encompasses both individual geometric and stereoisomers and mixtures thereof. The present invention also encompasses compounds of the formula (I) containing radioisotopes, particularly those in which one to three hydrogen atoms are replaced by tritium or one or more carbon atoms are replaced by 14C.

In a further aspect, the present invention provides a process for the preparation of a compound of the formula (I) as hereinbefore defined which comprises: (cf.Scheme 1) a) the reaction of the corresponding acid or acid derivative QQ1CR2=CR3CR4=CR5C(=X)Z1 with an amine H2NR1 wherein Q,Q1,R2, R3,R4,R5, X and R1 are as hereinbefore defined and Z1 is hydroxy, C1-6 alkoxy, halo or a phosphoroimidate ester (-P(O)(O-aryl)NH-aryl where aryl is C6-10 aryl).

CR2-CR3 4-CR5 1 b) the formation of the CR C(-X)NHR moiety through a Wittig type reaction.

c) the conversion of one compound of the formula (I) into another compound of the formula (I) by methods well known to those skilled in the art.

Process (a) is normally carried out at a non-extreme temperature, for example between -25 and 150 C in an anhydrous aprotic solvent, such as ether, dichloromethane, toluene or benzene. The precise conditions will be dependent on the nature of the group Z1, for example when Z1 is alkoxy the reaction is conveniently carried out at an elevated temperature, i.e. 50 to 1250C, and conveniently at reflux, preferably in the presence of a trialkylaluminium compound, such as trimethylaluminium, which forms a complex with the amine H2NR . When zl is halo or phosphoroimidate the reaction is conveniently carried out at 0 to 300C and suitably at room temperature preferably in the presence of a tertiary amine, such as triethylamine.

If the acid derivative is an acid halide, for example the 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 Z1 is a phosphoroimidate group then this is suitably formed from (PhO)P( O)NHPhC1 where Ph is phenyl. The acid, or the acid function in the compound QQ1CR2-CR3CR4-CR5COZ1, may be prepared by hydrolysis of the corresponding ester.

The esters may be prepared by a number of alternative routes, for example: (i) a conventional Wittig or Wadsworth-Emmons reaction, using for example an aldehyde and ethoxycarbonylmethylene triphenylphos phorane or an anion from triethylphosphonocrotonate or 3-methyl triethylphosphonocrotonate. This latter reaction may result in an isomeric mixture, for example a mixture of (Z) and (E) sub stituted 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: (1) (3) (CH3) 2C-CHCO2Et Z2CH2C(CH3)-CHC02Et Wittig/Wadsworth-Emmons (2) reagent wherein Z2= (aryl)3P, (aryl)2P(O) or (alkyl-0)2P(O) where aryl is preferably phenyl and alkyl is ethyl (1) N-bromo succinimide (2) e.g. (EtO)3P or (Ph)3P (3) This reaction is normally carried out in the presence of a base such as lithium diisopropylamide, butyllithium, sodium alkoxide or sodium hydride.

(ii) by rearrangement and elimination of HS( 0)Z3 from a compound of formula:

wherein Q,Q1,R2,R3 and R4 are as hereinbefore defined, Z3 is any suitable group, eg phenyl, 4-chlorophenyl or methyl, Z4 is C1-4 alkyl, e.g. methyl or ethyl.

The above compound may be obtained by reaction of a compound QQ1CHR2CHR3CR4O with a compound Z3 S(O)CH2CO2Z4.

(iii) By elimination on a compound QQ1CHR2CR3(OZ5)CR4=CR5CO2Z4 wherein Q,Q1,R2,R3,R4,R5 and Z4 are as defined above, and Z5 is hydrogen or C1-4 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-trimethylsilylacet amide.

The above compound may be obtained by the reaction of a suitable aldehyde with a suitable sulphenyl compound, followed by acylation.

(iv) reaction of a compound of formula QQ1CR2=CR3C(=O)R4 with one of formula Me3SiCHR5CO2Z4, wherein to Q,R2 to R5, Q1 and Z4 are as hereinbefore defined.

This process may be carried out in an anhydrous solvent, e.g.

tetrahydrofuran in the absence of oxygen, in the presence of a base, e.g. lithium cyclohexylisopropylamide.

(v) by reaction of a compound of formula QQ12-CR3C(OZ6 )-CR5 4 with a compound of formula R4M1 wherein Q,Q1,R2 ,R3 ,R4 ,R5 and Z4 are as hereinbefore defined, Z6 is a suitable group such as dialkylphosphate or trifluoromethanesulphonate and M is a metal such as copper (I) or copper (I) associated with lithium or magnesium.

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

(vi) by reaction of a compound of formula QQ1CR2=CR3M2 with one of halCR4=CR5CO2Z4, wherein Q,Q1,R2,R3 ,R4,R5 and Z4 are as hereinbefore defined, hal is halo and M2 is a silyl or metal containing group, such as trimethylsilyl or a group containing zirconium, aluminum or zinc, for example a bis(cyclopentadienyl) zirconium chloride group. This process is normally carried out at a non-extreme temperature i.e. between 0 and 100 C and conveniently at room temperature, in a non-aqueous 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.

(vii) by elimination of Z3S ( O)H from a compound of formula QQ1CR2-CR3 CHR45CO2Z4 S( O)Z wherein R2, R3, R4 and R5 Z3 and Z4 are as hereinbefore defined.

The above compound may be obtained by reaction of a compound QQ1CHR2CR3=CHR4 with Z3S(O)CH2Z4.

Process (b) may be carried out by having an aldehyde or ketone group attached either to the amide/thioamide terminus or to the QQ1 fragment of formula (I) and then reacting this with the appropriate phosphorous ylid.

i.e. QQ1(CR2=CR3)COR4 + Z2CR5.C(=X)NHR1 or QQ1CoR2 + Z2CR3.CR4=CR5.C(=X)NH.R1 QQl(CR2-CR3)CR5Z2 + (=X)NH.R1 wherein Q, Q1, R2, R3, R4, R5, R1, X and Z2 are as hereinbefore defined.

Process (b) 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 (-600C to 200C). The phosphorous ylid may be obtained from its precursor as described above by reaction with a base such as lithium diisopropylamide, butyllithium, sodium alkoxide or sodium hydride. Compounds of the formula (I) wherein X is sulphur are preferably prepared by process (b) when Z2 is a group (C1 4 alkoxy)2 P-O as hereinbefore defined.

The aldehyde intermediates QQ1CR2-O may be prepared by acid hydrolysis of a ketal, enol ether or acetal in a solvent such as acetone-water or by oxidation of the appropriate alcohols using for example pyridinium chlorochromate, pyridinium dichromate or oxalyl chloride-dimethyl sulphoxide in a solvent such ad dichloromethane. The aldehydes may also be prepared by reduction of the appropriate nitriles with a reagent such as diisobutylaluminium hydride in hexane.

1 8 where 28 The alcohols may be prepared by reduction of QQ CO2Z is hydrogen or lower alkyl (e.g. ethyl) with for instance lithium aluminium hydride in an inert solvent such as ether or tetrahydrofuran at moderate temperature (25-400C) or by for example sodium borohydride in a protic solvent such as ethanol at moderate temperature.

The intermediate esters may be prepared by esterification of the appropriate acids in a protic solvent such as ethanol in the presence of a strong acid like sulphuric acid at moderate/elevated temperatures (approximately 800C).

The acids QQ1CO2H may be prepared by decarboxylation of the diacids QQ1(CO2H)2 at elevated temperatures (approximately 180 C). The intermediate diacids may be prepared by saponification of the diesters QQ1(CO2Z8)2 using sodium or potassium hydroxide in alcohol-water solutions at moderate temperature.

The esters QQ1(CO2Z8)2 may be prepared by: (i) the reaction of malonate esters CH2(CO2Z8)2 with compounds of formula QCH(CH2X )2 in an inert solvent such as tetrahydrofuran or 1,4-dioxane at moderate to elevated temperatures (approximately 800C) in the presence of a strong base such as sodium hydride.

Where Q and Z are as described earlier and Z is a sulphur containing group such as p-toluenesulphonyl or methanesulphonyl, or where X1 is halo Wherein CH(CH2)2 and CH2 combine to form Q (Beard and Burger, J.Org.Chem., 27, 1647, 1962).

(ii) the cyclisation of QCHX2(CH2)2CH(CO2Z8)2 in the presence of sodium hydride in an inert solvent such as tetrahydrofuran or 1,4-dioxane.

Where Q and Z8 are as described earlier and X2 is halo, usually 8 bromine. Compounds such as QCHX2(CH2)2CH(CO2Z8)2 can be prepared according to Beard and Burger (J.Org.Chem., 26, 2335, 1961).

Compounds of formula QCH(CH2X )2 may be prepared for example by alkylation of the diol QCH(CH2OH)2 with a sulphonyl halide in the presence of a base, such as pyridine in a chlorinated solvent, such as dichloromethane, at moderate temperature.

The diols may be prepared by reduction of the substituted malonic esters with lithium aluminium hydride.

The substituted malonic esters may be prepared from the corresponding substituted phenyl acetic esters according to the procedure of Leuers and Meyer (Org.Syn.Coll. Vol II, p 288).

Compounds of formula QCH(X2 )(CH2)2CH(CO2Z8)2 may be prepared from the corresponding olefins QCH-CHCH2CH(CO2Z8)2 according to Beard & Burger.

The olefins may be prepared by alkylation of malonate esters by cinnamyl halides in the presence of a base such as sodium hydride according to Beard & Burger.

The following Examples illustrate, in a non-limiting manner, preferred aspects of the invention.

EXPERIMENTAL General Svnthetic Methods and Procedures: Various compounds were synthesised and characterised in accordance with the following experimental procedures.

111 n.m.r. spectra were obtained on a Bruker AM-250 spectrometer in deuterochloroform solutions with tetramethylsilane as internal standard and are expressed as ppm from mS, number of protons, number of peaks, coupling constant J Hz.

Progress of reactions could also be conveniently monitored on Aluminium sheets (40 x 80 mm) precoated with 0.25 mm layers of silica gel with fluorescent indicator and developed in appropriate solvent or solvent mixture. Temperatures are in degrees Celsius throughout.

Conventional work up was performed as follows: The reaction mixture was partitioned between an organic solvent and water. The phases were separated and the organic phase washed with at least an equivalent volume of dilute aqueous base as appropriate, and then with a saturated brine wash. The organic phase was then dried over a drying agent, suitably magnesium sulphate, and filtered.

The volatile solvents were removed and the resulting product subjected to the appropriate purification and used in the next stage of synthesis or analysed as the final product.

The cinnamyl alcohols, phenyl acetic acids and amine starting materials were obtained from Aldrich, BDH, Fluka or Lancaster synthesis with the exception of the following whose preparation is described below.

Example 1.

( (2ffiyZ,4E)-N-Isobutyl-3-methyl-5-(cis/trans-3-phenyl cyclobutyl)penta-2,4-dienamide. (2E:2Z 2:1 and cis:trans 1:1). (Compound 1).

(i) Cis,trans-3-phenyl cyclobutyl carboxylic acid (prepared according to Beard and Burger, J.Org.Chem., 27, 1647, 1962) (0.47g) in ethanol (25ml) was treated with concentrated sulphuric acid (ex BDH). After 5 hours at reflux the mixture was concentrated in vacuo and the residue worked up in the usual manner. Purification by chromatography on silica (20% ether in hexane) gave cis,trans-Ethyl-3-phenyl cyclobutyl formate (0.5g).

NNR 1H: 7.31 (5H,m), 4.21 (2H,2xq), 3.80 and 3.50 (lH,2xm), 3.11 (lH,m), 2.71 (2H,m), 2.48 (2H,m), 1.31 (3H,2xt).

(ii) Cis,trans-Ethyl-3-phenyl cyclobutyl formate (0.5g) in ether (5ml) was treated with lithium aluminium hydride (solution in ether, IM; 2.5ml) at room temperature under nitrogen. After 2 hours, sodium hydroxide (2M) was added and the resulting mixture filtered. Concentration of the organic phase in vacuo gave cis,trans-3-phenyl cyclobutyl methanol (0.39g).

NMR 1H: 7.24 (5H,m), 3.63 (3H,m), 2.70 (lH,bs), 2.36 (5H,m).

(iii) Oxalyl chloride (ex Aldrich) (0.22ml) was dissolved in dichloromethane (3ml) and cooled to -700C under nitrogen.

Dimethylsulphoxide (ex BDH) (0.36 ml) in dichloromethane (lml) was added dropwise. After five minutes, the above alcohol (0.39g) in dichloromethane (4ml) was added and the suspension stirred at -70 C for 30 minutes. Triethylamine (ex Aldrich) (1.6ml) was added and the mixture allowed to warm to O C over one hour. Work-up in the conventional manner gave cis,trans-3-phenylcyclobutylmethanol (0.37g) which was used directly.

NMR H: 9.91 and 9.70 (111,d), 7.25 (5H,m), 3.90 to 2.90 (2H,m), 2.90 to 2.10 (4H,m).

(iv) A solution of lithium diisopropylamide in dry tetrahydrofuran prepared from a n-butyl lithium (ex Aldrich) (1.6ml) and diisopropylamine (ex Aldrich) (0.4ml) was treated at -600C with triethyl 4-phosphonocrotonate (0.58g) in tetrahydrofuran under nitrogen. After 2 hours at -600C the above aldehyde (0.37g) was added. After 18 hours at 250C the mixture was partitioned between ether and water and the ethereal fraction worked up as above. Purification by chromatography (silica; ether/hexane) gave (+)-Ethyl-5-[cis/trans-3-phenylcyclobutyl]penta-2,4-dieno ate (0.56g).

NMR 1H: 7.28 (5H,m), 7.64 and 6.21 (2H,m), 5.70 (lH,m), 4.16 (2H,q), 3.80 to 3.00 (2H,m), 2.80-1.90 (4H,m), 2.36, 2.25, 2.04 and 1.96 (3H,4xd), 1.28 (3H,t).

(v)- The above ester (O.58g) in dry toluene, was added at -10 C to a complex prepared from trimethylaluminium (ex Aldrich) (1.5ml of a 2M solution in toluene) and isobutylamine (ex Aldrich) (0.22g in dry toluene). The whole was heated under reflux for three hours, treated with 2N-hydrochloric acid and the organic layer separated and worked up as above. Purification by chromatography (silica, ether/hexane) gave the title compound (0.51g). Tlc (silica, ethyl acetate:hexane, 2:3) RF 0.4.

Compounds were prepared in analogous manner, using the aldehyde, Wittig reagent and amine as specified.

Compound Aldehyde/R Dienamide Cyclobutyl Amine No. where R is Stereo- Stereo Chemistry Chemistry 2.3 4.5 2. 3,4-(C1)2Ph Z E c:t=l:1 Isobutylamine 3. 3,4-(Cl)2Ph E E t Isobutylamine 4. 3,4-(Cl)2Ph E E c:t-6:l Isobutylamine 5. 3,4-(C1)2Ph E E c:t-l:1 Isobutylamine Example 2.

()-(2E,4E)-N-Isobutyl-5-[t-3-(3,4-dichlorophenyl)-r-1-chlorocyclo- butyl]penta-2,4-dienamide. (Compound 6).

i) Cis,trans- Ethyl-3-(3,4- dichlorophenyl) cyclobutyl formate (0.55g) was added dropwise to a solution of lithium diisopropylamide (prepared at O C from diisopropylamine (0.34ml) and n-butyl lithium (1.4ml, 1.6M)] in tetrahydrofuran at -780C under nitrogen. After 3/4 hr, g-toluenesulphonyl chloride (0.57g) was added and the mixture stirred at room temperature for 18 hours.

A conventional work up was followed by chromatography on silica (10% ether in hexane) to give Ethyl-c,t-3-(3,4-dichlorophenyl-r- l-chlorocyclobutyl formate (0.52g).

NMR 1H: 7.40 & 7.38 (lH,d), 7.31 & 7.29 (lH,d), 7.08 (lH,m), 4.33 & 4.28 (2H,q), 3.94 & 3.36 (lH,m), 2.91 (4H,m), 1.39 & 1.35 (3H,t).

ii) The above esters (1.3g) in methylene chloride (20ml) at -20 C were treated with diisobutylaluminium hydride (8.8ml,1M). After 3.5 hours at 25 C conventional work up and chromatography on silica (20-40% ether in hexane) gave c-3-(3,4-dichlorophenyl)-r- l-chlorocyclobutyl methanol (0.4g).

NMR 1H: 7.39 (lH,d), 7.32 (lH,d), 7.07 (lH,dd), 3.89 (2H,s), 3.27 (lH,dddd), 2.92 (2H,m), 2.61 (2H,m), 2.12 (1H,sbroad) and t-3-(3,4-dichlorophenyl)-r-1-chlorocyclobutyl methanol (0.44g) NMR 1H: 7.39 (lH,d), 7.28 (lH,d), 7.03 (lH,dd), 4.94 (lH,dddd), 3.69 (2H,s > , 2.79 (2H,m), 2.55 (2H,m), 1.99 (1H, sbroad).

(iii) t-3-(3,4-Dichlorophenyl)-r-1-chlorocyclobutyl methanol (0.44g) was treated with oxalyl chloride (0.16ml), dimethyl sulphoxide (0.26ml) and triethlamine (1.14ml) in dichloromethane as described in Example 1, stage (iii) to give t-3-(3,4-dichloro phenyl)-r-l-chlorocyclobutyl methanol (0.4g).

NMR H: 9.61 (lH,s), 7.41 (lH,d), 7.32 (lH,d), 7.09 (lH,dd), 3.99 (lH,dddd), 2.92 (2H,m), 2.85 (2H,m).

(iv) A solution of lithium diisopropylamide in dry tetrahydrofuran prepared from- n-butyl lithium (1.35ml) and diisopropylamine (0.3ml) was treated at -600C with N-Isobutyl diethyl phosphono crotonamide (prepared according to Elliott M.et al, Pesticide Science 18, 1987, 191) (0.5g) in tetrahydrofuran under nitrogen.

After 2 hours at -60 C the above aldehyde (0.4g) was added.

After 18 hours at 250C the mixture was partitioned between ether and water and the ethereal fraction worked up in a conventional manner. Purification by chromatography on silica (60% ether in hexane) gave the title compound (0.04g). Tlc (silica, ethyl acetate: hexane, 2:3) Rf0.4.

Also prepared by an identical sequence from c-3-(3,4-dichloro phenyl)-r-l-chlorocyclobutyl methanol was (+)-(2E,4E)-N-Isobut yl-5- [c-3-(3,4-dichlorophenyl)-r-1-chlorocyclobutyl]penta-2,4- dienamide. (Compound 7).

NMR Data: Compound 1. 7.70, 7.60 & 6.10 (lH,d), 7.30 (5H,m), 6.38 & 6.10 (lH,dd), 5.65 & 6.04 (lH,d), 5.55 (1H, dbroad), 3.65 & 3.43 (lH,m), 3.15 (2H,m), 3.05 (lH,m), 2.60 (111,m), 2.42 & 2.03 (3H,m), 2.35, 2.29, 2.02 & 1.95 (3H,d), 1.81 (lH,m), 0.92 (6H,d).

2. 7.72 & 7.62 (lH,d), 7.30 (2H,m), 7.02 (lH,dd), 6.39 & 6.05 (lH,dd), 5.68 (1H, dbroad), 5.55 (lH,d), 3.57 & 3.47 (1H,m), 3.13 (2H,t), 3.04 (lH,m), 2.49 (lH,m), 2.38 (2H,m), 1.99 & 1.93 (3H,d), 1.80 (lH,m), 0.91 (6H,d).

3. 7.38 (lH,d), 7.33 (lH,d), 7.07 (lH,dd), 6.29 (lH,dd), 6.05 (lH,d), 5.68 (lH,s), 5.60 (1Htbroad), 3.57 (1H,m), 3.12 (2H,t), 3.07 (lH,m), 2.33 (4H,m), 2.31 (3H,d), 1.82 (lH,m), 0.93 (6H,d).

4. 7.33 (lH,d), 7.27 (lH,d), 7.02 (lH,dd), 6.07 (lH,dd), 6.04 (lH,d), 5.67 (lH,s), 5.67 (lH,m), 3.38 {lH,m), 3.12 (2H,t), 3.01 (lH,m), 2.59 (2H-,m), 2.27 (3H,d), 1.98 (2H,m), 1.80 (lH,m), 0.92 (6H,d).

5. 7.34 (lH,d), 7.34 (lH,d), 7.03 (lH,dd), 6.30 & 6.06 (lH,dd), 6.03 & 5.68 (1H,s),5.65 (lH,s), 5.65 (lH,m), 3.58 & 3.37 (lH,m), 3.11 (2H,m), 3.04(1H,m), 2.59, 2.35 & 1.95 (4H,m), 2.32 & 2.26 (3H,d), 1.81 (lH,m), 0.91 (6H,d).

6. 7.39 (lH,d), 7.28 (lH,d), 7.24 (1H,dd), 7.01 (lH,dd), 6.27 (lH,dd), 6.26 (lH,d), 5.94 (1H,d), 5.67 (lH,m), 4.04 (lH,m), 3.19 (2H,t), 2.91 (2H,m), 2.61 (2H,m), 1.82 (lH,m), 0.94 (6H,d).

7. 7.41 (lH,d), 7.33 (lH,d), 7.31 (lH,dd), 7.09 (lH,dd), 6.49 (lH,dd), 6.48 (lH,d), 5.98 (lH,d), 5.54 (1H,m), 3.24 (lH,m), 3.21 (2H,t), 3.02 (2H,m), 2.80 (2H,m), 1.84 (lH,m), 0.95 (6H,d).

The compounds of formula (I) may be used to control pests such as arthropods e.g. insect and acarine pests, and helminths, i.e.

nematodes. Thus, the present invention provides a method for the control of arthropods and/or helminths which comprises administering to the arthropod and/or helminth or to their environment an arthropodically effective amount of a compound of the formula (I).

The present invention also provides a method for the control and/or eradication of arthropod and/or helminth infestations of animals (including humans) and/or of plants,(including trees) and/or stored products which comprises administering to the animal or locus an effective amount of a compound of the formula (I). The present invention further provides for the compounds of the formula (I) for use in human and veterinary medicine, in public health control and in agriculture for the control of arthropod and/or helminth pests.

The compounds of formula (I) are of particular value in the protection of field, forage, plantation, glasshouse, orchard and vineyard crops, of ornamentals and of plantation and forest trees, for example, cereals (such as maize, wheat, rice, sorghum), cotton, tobacco, vegetables and salads (such as beans, cole crops, curcurbits, lettuce, onions, tomatoes and peppers), field crops (such as potato, sugar beet, ground nuts, soyabean, oil seed rape), sugar cane, grassland and forage (such as maize, sorghum, lucerne), plantations (such as of tea, coffee, cocoa, banana, oil palm, coconut, rubber, spices), orchards and groves (such as of stone and pip fruit, citrus, kiwifruit, avocado, mango, olives and walnuts), vineyards, ornamental plants, flowers and shrubs under glass and in gardens and parks, forest trees (both deciduous and evergreen) in forests, plantations and nurseries.

They are also valuable in the protection of timber (standing, felled, converted, stored or structural) from attack by sawflies (e.g.

Urocerus) or beetles (e.g. scolytids, platypodids, lyctids, bostrychids, cerambycids, anobiids).

They have applications in the protection of stored products such as grains, fruits, nuts, spices and tobacco, whether whole, milled or compounded into products, from moth, beetle and mite attack. Also protected are stored animal products such as skins, hair, wool and feathers in natural. or converted form (e.g. as carpets or textiles) from moth and beetle attack; also stored meat and fish from beetle, mite and fly attack.

The compounds of general formula (I) are of particular value in the control of arthropods or helminths which are injurious to, or spread or act as vectors of diseases in man and domestic animals, for example those hereinbefore mentioned, and more especially in the control of ticks, mites, lice, fleas, midges and biting, nuisance and myiasis flies.

The compounds of Formula (I) may be used for such purposes by application of the compounds themselves or in diluted form in known fashion as a dip, spray, fog, lacquer, foam, dust, powder, aqueous suspension, paste, gel, cream, shampoo, grease, combustible solid, vapourising mat, combustible coil, bait, -dietary supplement, wettable powder, granule, aerosol, emulsifiable concentrate, oil suspensions, oil solutions, pressure-pack, impregnated article, pour on formulation or other standard formulations well known to those skilled in the art.

Dip concentrates are not applied Der se, but diluted with water and the animals immersed 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, soil, plant or surface being treated may be saturated with the spray by means of high volume application or superficially coated with the spray by means of light or ultra low volume application.

Aqueous suspensions may be applied in the same manner as sprays or dips. Dusts may be distributed by means of a powder applicator or, in the case of animals, incorporated in perforated bags attached to trees or rubbing bars. Pastes, shampoos and greases may be applied manually or distributed over the surface of an inert material, such as that 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 (I) may be prepared either as formulations ready for use on the animals, plants or surface or as formulations requiring dilution prior to application, but both types of formulation comprise a compound of Formula (I) 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 (I) 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 and other solid formulations comprise the compound of Formula (I) in intimate admixture with a powdered solid inert carrier for example suitable clays, kaolin, bentonite, attapulgite, adsorbent carbon black, talc, mica, chalk, gypsum, tricalcium phosphate, powdered cork, magnesium siliate, vegetable carriers, starch and diatomaceous earths. Such solid formulations are generally prepared by impregnating the solid diluents with solutions of the compound of formula (I) in volatile solvents, evaporating the solvents and, if desired grinding the products so as to obtain powders and, if desired, granulating, compacting or encapsulating the products.

Sprays of a compound of Formula (I) may comprise a solution in an organic solvent (e.g. those listed below) or an emulsion in water (dip wash or spray wash) prepared in the field from an emulsifiable concentrate (otherwise known as a water miscible oil) which may also be used for dipping purposes. The concentrate preferably 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, aromatic 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 of 5 to 25% w/v and the emulsifiers are conveniently non-ionic surface active agents including polyoxyalkylene 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. Cationic emulsifiers include benzalkonium chloride and quaternary ammonium ethosuphates.

Amphoteric emulsifiers include carboxymethylated oleic imidazoline and alkyl dimethyl betain.

Vaporising mats normally comprise cotton and cellulose mix compressed into a board of approximately 35 x 22 x 3mm dimensions, treated with up to 0.3ml of concentrate comprising the active ingredient in an organic solvent and optionally an antioxidant, dye and perfume. The insecticide is vaporisedusing a heat source such as an electrically operated mat heater.

Combustible solids normally comprise of wood powder and binder mixed with the active ingredient and formed into shaped (usually coiled) strips. Dye and fungicide may also be added.

Wettable powders comprise an inert solid carrier, one 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.

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

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

Aqueous suspensions of a compound of Formula (I) may comprise a suspension in water together with suspending, stabilizing or other agents. The suspensions or solutions may be applied Der se or in a diluted form in known fashion.

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 (I) 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 (I) may be present as an 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 (I) 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 (I) in a liquid medium. 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 (I). Such articles include impregnated collars, tags, bands, sheets and strips suitably attached to appropriate parts of the body. Suitably the plastics material is a polyvinyl chloride (PVC).

The- concentration of the compound of Formula (I) to be applied to an animal, premises or outdoor areas 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 of from 0.0001% to 0.5% w/w except for undiluted 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%.The amount of compound to be applied to stored products in general will lie in the range of from O.-1-to 20ppm. Space sprays may be applied to give an average initial concentration of 0.001 to lmg of compound of formula (I) per cubic metre of treated space.

The compounds of formula (I) are also of use in the protection and treatment of plant species, in which case an effective insecticidal, acaricidal or nematocidal amount of the active ingredient is applied.

The application rate will vary according to the compound chosen, the nature of the formulation, the mode of application, the plant species, the planting density and likely infestation and other like factors but in general, a suitable use rate for agricultural crops is in the range 0.001 to 3kg/Ha and preferably between 0.01 and lkg/Ha. Typical formulations for agricultural use contain between 0.0001% and 50% of a compound of formula (I) and conveniently between 0.1 and 15% by weight of a compound of the formula (I).

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 (I) in the applied formulation may be used.

The compounds of formula (I) have been found to have activity against the common housefly (Musca domestica). In addition, certain compounds of formula (I) have activity against other arthropod pests including Myzus persicae, Tetranvchus urticae. Plutella xvlostella, Culex spp.

Tribolium castaneum, Sitophilus granarius, Periplaneta ameircana and Blattella germanic. The compounds of formula (I) are thus useful in the control of arthropods e.g. insects and acarines in any environment where these constitute pests, e.g. in agriculture, in animal husbandry, in public health control and in domestic situations.

Insect pests include members of the orders Coleoptera (e.g.

Anobium, Ceutorhynchus , Rhynchophorus. Cosmopolites, Lissorhoptrus.

Meligethes, Hypothenemus, Hvlesinus, Acalvmma, Lema, Psvlliodes, Leptinotarsa, Gonocenhalum, Agriotes, Dermolenida, Heteronychus, Phaedon, Tribolium, Sitophilus, Diabrotica, Anthonomus or Anthrenus spp.), Lepidoptera (e.g. Enhestia, Mamestra, Earias, Pectinophora, Ostrinia, Trichoplusia, Pieris, Laphygma. Agrotis, Amathes, Wiseana, Tryporysa, Diatraea, Sporganothis, Cydia, Archips, Plutella, Chilo, Heliothis, Snodontera or Tineola spp.), Diptera (e.g.Musca, Aedes, AnoDheles, Culex, Glossina, Simulium, Stomoxys, Haematobia, Tabanus, Hvdrotaea, Lucilia, Chrysomia, Callitroga, Dermatobia, Gasterophilus, Hvnoderma, Hvlemvia, Atherigona, Chlorops, Phytomvza, Ceratitis, Liriomvza and Melophagus spp.), Phthiraptera (Malophaga e.g.

Damalina spp. and Anoplura e.g. Linognathus and Haematoninus spp.), Hemiptera (e.g. Aphis, Bemisia,Phorodon, Aeneolamia, Empoasca, Parkinsiella, Pyrilla, Aonidiella, Coccus, Pseudococus. Heloneltis, Lygus, -Dvsdercus, Oxycarenus, Nezara, Aleurodes, Triatoma, Psvlla, Mvsus, Megoura, Phvlloxera, Adelves, Nilonarvata, Nephrotetix or Cimex spp.), Orthoptera (e.g. Locusta, Grvllus, Schistocerca or Acheta -spp.), Dictyoptera (e.g. Blattella, Periplaneta or Blatta spp.), Hymenoptera (e.g. Athalia, Cephus, Atta, Solenopsis or Monomorium spp.), Isoptera (e.g.Odontotermes and Reticulitermes spp.), Siphonaptera (e.g. Ctenocenhalides or Pulex spp.), Thysanura (e.-g. Lenisma spp.), Dermaptera (e.g. Forficula spp.), Pscoptera (e.g.

Peripsocus spp.) and Thysanoptera (e.g. Thrips tabaci),.

Acarine pests include ticks, e.g. members of the genera Boophilus,Ornithodorus, Rhipicephalus, Amblyomma, Hvalomma, Ixodes, Haemaphysalis, Dermacentor and Anocentor, and mites and manges such as Acarus, Tetranychus, Psoroptes, Notoednes, Sarcoptes, Psorergates, Choriontes, Eutrombicula, Demodex. Panonvchus, Brvobia, Eriophyes, Blaniulus, Polyphaotarsonemus, Scutigerella, and Oniscus spp.

Nematodes which attack plants and trees of importance to agriculture, forestry, horticulture either directly or by spreading bacterial, viral, mycoplasma or,.fungal diseases of the plants,- include root-knot nematodes such as Meloidogvne spp. (e.g. M. incognita); cyst nematodes such as Globodera spp. (e.g. . rostochiensis); Heterodera spp. (e.g.

hydrogen. avenae): RadoRholus spp. (e.g.R. similis); lesion nematodes such as Pratvlenchus spp. (e.g. P. pratensis); Belonolaimus spp. (e.g.

B. gracilis); Tvlenchulus spp. (e.g. T. seminenetrans); Rotvlenchulus spp. (e.g.R. reniformis); Rotylenchus spp. (e.g. R. robustus); Helicotvlenchus spp. (e.g. hvdrogen. multicinctus);Hemicycliophora spp. (e.g. hvdrogen. gracilis); Criconemoides spp. (e.g. C. similis); Trichodorus spp. (e.g. T nrimitivus): dagger nematodes such as Xiphinema spp. (e.g. X. diversicaudatum), Longidorus spp (e.g. L.

elongatus); Hoplolaimus spp. (e.g. hvdrogen. coronatus); Aphelenchoides spp. (e.g. A. ritzema-bosi, A. bessevi): stem and bulb eelworms such as Ditvlenchus spp. (e.g. D. dinsaci).

Compounds of the invention may be combined with one or more other pesticidally active ingredients (for example pyrethroids, carbamates and organophosphates) and/or with attractants, repellents, bacteriocides, fungicides, nematocides, anthelmintics 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 propyl 2-propynylphenylphosphonate; a second compound of the invention; or a pyrethroid pesticidal compound. When an oxidase inhibitor synergist is present in a formula of the invention, the ratio of synergist to compound of Formula (I) will be in the range 25:1-1:25 eg about 10:1.

Stabilisers for preventing any chemical degradation which may occur with the compounds of the invention include, for example, antioxidants (such as tocopherols, butylhydroxyanisole and butylhydroxytoluene) and scavengers (such as epichlorhydrin) and organic or inorganic bases e.g. trialkylamines such as triethylamine which can act as basic stabilises and as scavengers.

Industrial Apolicability Compounds of the present invention show activity as pesticides.

The following examples illustrate, in a non-limiting manner, preferred aspects of the invention.

Formulations 1. Emulsifiable Concentrate Compound of formula (I) 10.00 Alkyl phenol ethoxylate* 7.50 Alkyl aryl sulphonate* 2.50 C813 aromatic solvent 80,00 100.00 2. Emulsifiable Concentrate Compound of formula (I) 10.00 Alkyl phenol ethoxylate* 2.50 Alkyl aryl sulphonate* 2.50 Ketonic solvent 64.00 C8-13 aromatic solvent 18.00 Antioxidant 3 00 100 or 3. Wettable Powder Compound of formula (I) 5.00 C8 13 aromatic solvent 7.00 C18 aromatic solvent 28.00 China clay 10.00 Alkyl aryl sulphonate* 1.00 Napthalene sulphuric acid* 3.00 Diatomaceous earth 46.00 100.00 4. Dust Compound of formula (I) 0.50 Talc 99.50 100.00 5.Bait Compound of formula (I) 0.5 Sugar 79.5 Paraffin wax 20.0 100.00 6. Emulsion Concentrate Compound of formula (I) 5.00 C8 13 aromatic solvent 32.00 Cetyl alcohol 3.00 Polyoxyethylene glycerol monooleate* 0.75 Polyoxyethylene sorbitan esters* 0.25 Silicone solution 0.1 Water 58.9 100.00 7. Suspension Concentrate Compound of formula (I) 10.00 Alkyl aryl ethoxylate* 3.00 Silicone solution 0.1 Alkane diol 5.0 Fumed silica 0.50 Xanthan gum 0.20 Water 80.0 Buffering agent 1.2 100.00 8. Microemulsion Compound of formula (I) 10.00 Polyoxyethylene glycerol monooleate* 10.00 Alkane diol 4.00 Water 76.00 100.00 9. Water Dispersible Granules Compound of formula (I) 70.00 Polyvinyl pyrrolidine 2.50 Alkyl aryl ethoxylate 1.25 Alkyl aryl sulphonate 1.25 China clay 25.00 100.00 10.Granules Compound of formula (I) 2.00 Alkyl phenol ethoxylate* 5.00 Alkyl aryl sulphonate* 3.00 C8-13 aromatic solvent 20.00 Kieselguhr granules 70.00 100.00 11. Aerosol (pressure Dack) Compound of formula (I) 0.3 Piperonyl butoxide 1.5 C8 13 saturated hydrocarbon solvent 58.2 Butane 40.0 100.00 12. Aerosol (pressure pack) Compound of formula (I) 0.3 C8 13 saturated hydrocarbon solvent 10.0 Sorbitan monooleate* 1.0 Water 40.0 Butane 48.7 100.00 13. Aerosol (pressure pack) Compound of formula (I) 1.00 CO2 3.00 Polyoxyethylene glycerol monooleate* 1.40 Propanone 38.00 Water 56.60 100.00 14. Lacquer Compound of formula (I) 2.50 Resin 5.00 Antioxidant 0.50 High aromatic white spirit 92.0 100.00 15. Spray (ready to use) Compound of formula (I) 0.10 Antioxidant 0.10 Odourless kerosene 99.8 100.00 16. Potentiated Spray (ready to use) Compound of formula (I) 0.10 Piperonyl butoxide 0.50 Antioxidant 0.10 Odourless kerosene 99.30 100.00 17. Microencapsulated Compound of formula (I) 10.0 C813 aromatic solvent 10.0 Aromatic di-isocyanate&num; 4.5 Alkyl phenol ethoxylate* 6.0 Alkyl diamine&num; 1.0 Diethylene triamine 1.0 Concentrated hydrochloric acid 2.2 Xanthan gum 0.2 Fumed silica 0.5 Water 64.6 100.00 * = Surfactant # = react to form the polyurea walls of the microcapsule Antioxidant could be any of the following individually or combined Butylated hydroxytoluene Butyl ate hydroxyanisole Vitamin C (ascrobic acid)

Claims (8)

1. CLAIMS 1) A compound of formula (I): Q Q1 CR2=CR3 CR4 =CR5C(=X) NHR1 or a salt thereof, wherein Q is an monocyclic aromatic ring, or fused bicyclic ring system of which at least one ring is aromatic containing 9 or 10 atoms of which one to four may be nitrogen or sulphur and the rest carbon each optionally substituted, or Q is a dihalovinyl group or a group R6-C=C- where R6 is C1-4 alkyl, tri C1-4 alkylsilyl, halogen or hydrogen; Q is a 1,3 or 1,2 cyclobutyl ring optionally substituted by one or more groups selected from C1-4 alkyl, halo, C1-4 haloalkyl, alkynyl, or cyano; R2, R3, R and R5 are the same or different with at least one being hydrogen and the others being independently selected from hydrogen, halo, C1-4 alkyl or C1-4 haloalkyl;X is oxygen or sulphur; and R is selected from hydrogen and C1-8 hydrocarbyl optionally substituted by dioxalanyl, halo, cyano, trifluoromethyl, trifluoromethylthio or C16 alkoxy.
2. 2) A compound of the formula (I) according to claim 1 in which Q is phenyl, pyridyl, thienyl or naphthyl each optionally substituted by one to four groups selected from C1-6 hydrocarbyl, C1-6 alkoxy or methylenedioxy, each optionally substituted by one to three halos, or from halo, cyano or nitro, or the substituent is a group S(0) R7 wherein n is 0, 1 or 2 and R7 is C16 alkyl optionally substituted by one or more halos or R is amino optionally substituted by one or two C1-6 alkyl groups or the substituent is a group NR8R9 where R8 and R9 are independently selected from hydrogen, C1-6 alkyl or a group COR10 where R10 is C1-6 alkyl.
3. 3) A compound of the formula (I) according to either claim 1 or 2 in which R2, R3, R4 and R5 are chosen from hydrogen, methyl or fluoro.
4. 4) A compound of the formula (I) according to any one of claims 1 to 3 in which Q1 is a 1,3-cyclobutyl group which may be optionally substituted at the 1- and 3- positions of the cyclobutyl ring by hydrogen, fluoro, chloro, methyl or trifluoromethyl.
5. 5) A compound of the formula (I) according to any one of claims 1 to 4 in which R1 is isobutyl, 1,2-dimethylpropyl, 1,1,2-trimeth yl propyl, 2,2-dimethylpropyl or R1 is 2-methylprop-2-enyl or (2-methyl-1,3- dioxalan-2-yl) methyl.
6. 6) A compound of the formula (II): QaQ1aCR2a = CR3aCR4a = CR5aC(=Xa) NHR1a (II) or a salt thereof, wherein Qa is an optionally substituted phenyl or pyridyl group or fused bicyclic ring system of which at least one ring is aromatic containing 9 or 10 atoms of which one may be nitrogen and the rest carbon or Qa is a dihalovinyl group or a group R6a-C=C- where R6a is C1-4 alkyl, trialkylsilyl or hydrogen; Qla is a 1,3-cyclobutyl ring optionally substituted by one or more groups selected from C1 3 alkyl, halo, or C1-3 haloalkyl;R2a, R3a, R4a and R5a are the same or different with at least one being hydrogen and the others being independently a selected from hydrogen, halo, C14 alkyl or C14 haloalkyl; x is oxygen or sulphur; and R1a is selected from hydrogen and C1-6 hydrocarbyl optionally substituted by dioxalanyl, halo, cyano, trifluoromethyl, trifluoromethylthio or C1-6 alkoxy.
7. 7) A compound selected from: 1. ()-(2E/Z,4E)-N-Isobutyl-3-methyl-5-(cis-3-phenylcyclobutyl) penta-2,4-dienamide (2E:2Z=2:1) and (+)-(2ffi/Z,4E)-N-Isobutyl-3-methyl-5-(trans-3-phenylcyclo- butyl)penta-2,4-dienamide (2E:2Z=2:1) (1:1).

   2. (+)-(2Z,4E)-N-Isobutyl-5-[cis/trans-3-(3,4-dichlorophenyl) cyclobutyl]-3-methylpenta-2,4-dienamide (cis:trans 1:1).

   3. (+)-(2E,4E)-N-Isobutyl-5-[trans-3-(3,4-dichlorophenyl) cyclobutyl]-3-methylpenta-2,4-dienamide.

   4. (+)-(2E,4E)-~-Isobutyl-5-[cisXtrans-3-(3,4-dichlorophenyl) cyclobutyl]-3-methylpenta-2,4-dienamide (cis:trans 6:1).

   5. (+)-(2E,4E)-N-Isobutyl-5-[cis/trans-3-(3,4-dichlorophenyl) cyclobutyl]-3-methylpenta-2,4-dienamide (cis:trans 1:1).
8. 8. A process for the preparation of a compound according to any one of claims 1 to 7 which comprises: a) the reaction of the corresponding acid or acid derivative QQ1CR2=CR3CR4=CR5C(=X)Z1 with an amine H2NR1 wherein Q,Q1,R2,R3,R4,R5, X and R1 are as hereinbefore defined and Z1is hydroxy, C1-6 alkoxy, halo or a phosphoroimidate ester (-P(O)(O-aryl)NH-aryl where aryl is C6-10 aryl).

   b) the formation of the CR2=CR3 CR4=CR5C(=X)NHR1 moiety through a Wittig type reaction and thereafter optionally converting one compound of the formula (I) into another compound of the formula (I) by methods well known to those skilled in the art.

   9) A novel chemical intermediate of the formula QQ CR sCR CR =CR (=X)Z1, QQ1(CR2=CR3)COR4, QQ1COR2 or QQ1(CR2=CR3)CR4Z2 10) An insecticidal or acaricidal composition comprising a compound of formula (I) as defined in any one of claims 1-8 in admixture with carrier or diluent.

   11) A synergised pesticidal-composition comprising a compound of formula (I), as defined in any one of claims 1-8, a synergist for the formula I compound and a carrier of diluent.

   12) A mixture of a compound of formula (I) a-s defined in any one of claims 1-8 and another pesticidal compound.

   13) A method for the control of pests comprising application to the pest or to an environment susceptible to pest infestation of a compound according to any one of claims 1-8 or a composition or mixture according to any one of claims 10-12.

   14) A compound as defined in any one of claims 1-8 or composition according to any one of claims 10-12 for use in a method of surgery or therapy practised on the human or animal body or in a method of diagnosis practised on the human or animal body.