AU527770B2 - Benzyloxime ethers - Google Patents

Description

Ii

fFORM 4 COMMONWEALTH OF AUSTRAL4 PATENTS ACT 1952-73 z

K R

Convention Applicationfo a In sup] SHELL f'or a SHELL SELINTERNATIONAL 4855 6179 1 E RESEARCH MAATSCHAPPIJ B.,V.

I, Adr: the Ne, of Carel van Bylantlaan 30, The Hague, the Netherlands

th de

2. Th hereby apply for the grant of a Patent for an invention entitled

"BENZYLOXIME ETHERS 2 M THEIR USE AS PESTICIDES" 0

a e

0 0 0 which is described in the accompanyig complete specification. This application is a Convention Application and is based on the 3. N Q application numbered 28599/78 Er Hi for a patent or similar protection made in Great Britain

0

t~

0 h.Th on -3rd July, 1978 00

Cc Our addres for service is: aa t

Care: SPRUSON FERGUSON -a dat CC a Hague PATENT ATTORNEYS ESSO HOUSE, 127 KENT STREET SYDINTY. NEW SOUTH WALES. AUSTRALIA.

Dated this TWENTY-SECOSJ day of MIAY i1979 SHELL INTERNATIONALEE RESEARC~H iM4ATS PPIJ B. V.

By: To: TI Cc Registered Patent Attorney

Form

CO IMONWEALTH OF AUS9RALIA Patents Act 1952-55

DECLARATION IN SUPPORT OF A CONVENTIOWl APPLICATION FOR A PATENT OR PATENT OF ADDITION

4855 6/79 In support of the Convention Appiication made by SHELL INTERNATIONALE RT5SEARCH MAATSCHAPPIJ B.V. for a patent Gt-ea4&4iofi for an invention entitled:

,"Benzyloxime ethers and their use as pesticides"

I, Adrianus Pieter Pieroen, of Carel van Bylandtlaan 30, The Hague, the Netherlands, do solemnly and sincerely declare as follows:

1. I agi authorized by SHELL INTERNATIONALE RESEARCH MAA'TSCHAPPIUJ B.V., tho applicant for the patent of- addein, to make this declaration on its behalf.

2. The basic application(s) as defined by Section 141 of the Act was/wee made in Great Britain on the 3rd day of July, 1978 by SHELL INTERNA'IONALE RESEARCH AATSCEAPPIJ B.V.

3. Michael John BULL of 19, Burntwick Drive, Lower Haistow, Kent, England, and Robert John Griffith SEARLE of Highworth, Stockers Hill, Rodmersham Green, Sittingbourne, Kent, England, both British subjects -/are the actual inventor(s) of the invention and the facts upon which the Applicant Company is entitled to make 0), application are as follows: as Assignees of the inventors.

4, The basic application(=s) referred to in paragraph 2 of this Declaratiorn was/wem the first application(s) made in a Convention Country in respect of the invention the subject of the application.

at Hague Dated this lltb- day of May, 1979

f

7PIJ I gnature of Declarant Adrianus Pieter Pieroen

To: The Commissioner of Patents, Commonwealth of Australia :orney

(12) AUSTRALIAN PAT'cNT ABRIDGMENT (19) AU (11) AU-B -48556/79

(54) BENZYLOXIME ETHERS (71) SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V. 21) 48556/79 527M7 (22) 2,9,6.79 A 3,7.78 Application Mum 1) 3( 7828599 (32) 3.7.78 Lodj (43) 10. 1.80 3.833 (51)2 C07C 131/02 C07C 131/08 C07C 131/00 (72) MICHAEL JOHN BULL AND ROBERT JOHN GRIFFITH SEARLI. Complete Specifi (74) SF (56) 37269/68 09. Priority: (57) The compounds exhibit pesticidal activity. Claim 1. A benzyloxime ether derivative of formula: aelated Art

*1

of Applicc

Address of Appl

wherein R1 is an optionally substituted aryl or alkyl group, R2is an optionally substituted cycl oal kyl al kyl or al kenyl group ,Actual Inventor wherein the substituents are one or more of the same or different! substituents selected from halogen, alkyl, alkenyl, haloalkenyl, alkylene, alkoxy and aryl, and X1 arid X are independently kdress for Sei

sciected from fluorine, chlorine and bromine; in the form of its E-jsomer, its Z-isoler or i mixture thereof. Complete Speci

The following it known to ,i ND 10 4

11(3183v~/12

To:

V COMMONWEALTH OF A\\JSTRALI)A PATENTS ACT 15 Form

COMPLET PEalIdAT litP, (ORIGINAL)

FOR 0O.FFICE USE

4855 6/79 Class Int. Class Application Number Lodged 4I 49

Complete Specification Lodged Accepted Published Priority:

0-' a 4geolated Art 3S4~

r a

0.. of Applicant SHELL INTEE NATIONALt RESEARCH MAATSCHAPPIJ B.V.

Address of Applicant Carel van BylandtlaF-n 30, The Hague, the Nether:lands 10 z o 30) 0 a

,Actual lnventors MICHAEL JOHN BULL and. ROBERT JOHN GRIFFITH SEARLE ,'ent a a

4'dress for Service Spruson Ferguson, Patent Attorneys, Eso-u +4 -Kem-Street, Sydney, New South Wales, 2000 Australia,

0 V

Complete Specification for the invention ev-tled V a a "1BENZYLOXIME ETHERS AND THEIR USE AS PESTICIDES" Va

The following statement is a full description of this invention including the 'est method of performing it known towF/us: 20 c1-l

To; Thi By: Col To: Registered Patent Attorney

Form 10 7w

by one g~;NYT.XIME ET14ERS AND THEFiR USE As PESTICiDES select Int. Class The invention relates to benzyloxime ethers, to groups their preparation, and to their use as pesticides. atoiris The invention provides a compound of t,'e general 5 prefer formula:4 Cc 21 K-1 ~kgroup

R C= N 0 -CH 2 (I) u~~stituE 00 alkyl 0-' 2) 0 2 '0 group 0 0 5 wherein RI represents an optionally substituted aryl Co st;'tul 22) 0 or alkyl group, R2 represents an optionally substituted alkox, 0 o 0

0 0 cycloalkyl, alkcyl or alkenyl group, and XI and X are 00 group 0 0

0 independently selected from fluorine, chlorine and 00 stitu bromine; in the form of either its E isomer or its 15 4-pos erlands 10 Z isomer or a mixture thereof. 0 )02~ 16- 0) An aryl group represented by R s rreferably a -2) 0 00 ?ARLE C naphthyl group or a phenyl group which may be un- 4-me 0 00 0 2) ~0 02) 0 substituted or substituted by one or more of the same or different substituents 4%elected from halogen atoms 00 20 alky' 2)

04 125 and alkyl or alkoxy groups preferably having from to 6 0 0 03 0

0 0 I to 4{ carbon atoms, for example fluorine, chlorine be s' *0

and bromine at4-oms and methyl, ethyl, t-butyl and be s" t~elthoxy groups. brom

An alkyl group represented by RI may be straight- 25 R2 m cI_-in or branched and may, for example, be substituted espe by one or more of the same or different substituents selected from halogen atoms, alkoxy groups and aryl groups, for example chlorine, fluwori'e pnd bromine atoms and methoxy and phenyl groups. The alkyl moiety preferably contains from 1 to 10 carbon atoms.

S Conveniently R1 is a naphthyl group, a phenyl

Sgroup optionally substituted by one or more sub-

stituents independently su ,elected from halogen, C1 -4 00 Salkyl and Ci_4 alkoxy moieties, or a C1_10 alkyl

group optionally substituted by one or more sub-

stituents independently selected from halogen, Ci_4

alkoxy and phenyl moieties. Preferably R1 is a phenyl

°on group optionally -abstituted by one or two sub- oO

stituents, preferably a single substituent in the

4-position, selected from fluorine, chlorine, bromine,

C1 4 alkyl, and methoxy moieties. Advantageously R1

is 4-fluorophenyl, 4-chlorophenyl, 4-t-butylphenyl or

a 4-methoxyphenyl. o 2 oe If R represents an unsubstituted or substituted

alkyl or alkenyl group, this group preferably has up

to 6, more preferably 3 to 6, carbon atoms, and may

Sbe straight-chain or branched. It may, for example,

be substituted by one or more fluorine, chlorine or

bromine atoms, but is preferably unsubstituted. Thus,

R 2 may, for example, represent a methyl, ethyl or,

especially, isopropyl group.

R conveniently represents a C 3 branched alkyl

group, or a C3-6 cycloalkyl group optionally sub-

stituted by one or more substituents selected from

halogen, C 1 -6 alkyl, C2-6 alkenyl and C2_ 6 halo-

alkenyl. When R 2 is C3_ 6 branche. alkyl,it is prefer-

ably an isopropyl group.

The group R preferably represents a cyclopropyl

group having the following general formula: C0 R R a b

R H C R d

wherein Ra and Rb both represent hydrogen atoms, alkyl

groups having from 1 to 6 carbon atoms, especially

methyl groups, or halogen atoms, especially chlorine

o. or bromine atoms; or R and Rb together represent an c o*a b Salkylene group having from 2 to 6, especially 3, carbon atoms; or Ra represents a hydrogen atom and 15 Rb represents an a'ltkinyl group having from 2 to 6

carbon atoms, especially an isobutenyl group, or a

haloalkenyl group having from 2 to 6 carbon atoms and

from 1 to 3 chlorine or bromine atoms, especially a

mono- or dichlorovinyl group; Rc and R d both represent

hydrogen atoms or alkyl groups having 1 to 6 carbon or kl6!og<e cA-o"S atom, especially methyl groups, or R is hydrogen and R d is an alkenyl group having from 2 to 6 carbon atoms, especially an isobutenyl group or a halo- alkenyl group having from 2 to 6 carbon atoms and from 1 to 3 chlorine or bromine atoms, especially a mono- or dichlorovinyl group; or Rc and Rd together represent an alkan-1 group having from 2 to 6,

U- especially 3, carbon atoms. 0 111 Most preferably, R represents an unsubstituted cyclopropyl group.

Especially preferred compounds of the general formula I are those in which R 1 represents a phenyl 0 o0 group, mono-substituted in the 4-position by a

0o fluorine, chlorine or bromine atom or an alkyl or

alkoxy group having up to 4 carbon atoms, and R 2

represents an unsubstituted cyclopropyl group.

o The compounds of the general formula I exhibit

pesticidal, especially acaricidal, activity. As

o 0stated above a compound of the general formula I may

exist in the form of the E- or the Z-isomer or a

mixture thereof. The isomer in the form: X1

R2 O CH 2

S N' X1

II

nay be referred to as the R 2 cis-isomer while the isomer

in the form:

SR 2 X1

SC N H H/ R I 0 CH 2

may be referred to as the R 1 cis-isomer. In the pre-

ferred compounds of the general formula I, wherein R 2

S 5 is a cyclopropyl group and R is an aryl group, the

R 2 cis-isomer is the E-isomer. Depending on the S1 2 Smeanings of R and R other possibilities for

geometric and/or optical isomerism may exist, and

the present invention should be understood to include

all possible isomers of a compound of the general 9 formula I and mixtures thereof.

The invention also provides a process for the

oe3° preparation of a compound of the general formula I,

which comprises reacting an alkali metal salt of a

15 compound of the general formula:

2

R1 C N OH (IT)

wherein R 1 and R 2 have the meanings given above, with

a compound of the general formula:

4kI

X

Hal CH 2 (III)

I4 1 2 wherein X and X have the meanings given above, and SHal represents a chlorine, bromine or iodine atom,

especially a chlorine or bromine atom. .e r-.bly, the reaction is carried out in a two-

phase ic-inoiganic system in the presence of a

So phase-transfer catalyst. The phase-transfer catalyst

may be any compound which will accelerate interphase

t A°°o reactions in organic-inorganic two-phase systems.

oe rTetrabutylammonium bromide is an example. Thus, the 0 10 compounds of the general formulae II and III may be ooo

0 mixed in the presence of aqueous potassium hydroxide,

a suitable organic solvent, for example methylene chloride, and a catalytic amount of a phase-transfer

0, catalyst. The reaction is suitably carried out under

So 15 reflux. If the compound of the general formula II used

as starting material is in substantially pure E-isomeric

form, usually little or no isomerism takes place 0 0

S ~cduring the reaction and the resulting compound of the

general formula I contains a high proportion of E-

isomer. Preferably, a small excess of the compound of

the general formula II is used, since some of this

starting material may be hydrolyzed under the re- action conditions.

The reaction may also be carried out by reacting

the compound of the general formula II with sodium

hydride in a suitable aprotic solvent, for example

acetonitrile, tetrahydrofuran, or dimethylformamide

in toluene, at a temperature in the range of from

to 100°C. The compound of the general formula III,

u preferably in the form of a solution in the same O Ssolvent, may then be added to the resulting solution,

and1 a reaction temperature of from 60 to 150°C,

p f'rably f'c, i100 to 110°C, is suitably maintained.

The presence of the strong base sodium hydride in the

resulting reaction mixture may cause some degree of

o isomerization if substantially pure E-isomeric start-

15 ing material is used, although the resulting compound

of the general formula I usually contains a higher

0,0 proportion of E-isomer than Z-isomer.

-j The invention also provides: a pesticidal com-

position which comprises as active ingredient, a

D 20 benzyloxiwe ether derivative of the general formula I,

o in association with an inert carrier. The invention

o also provides a method of combating pests at a locus,

o which comprises applying to that locus a benzyloxime

ether derivative of the general formula I or a

pesticidal composition according to the invention. The

invention further provides the ute of a benzyloxime ether derivative of the general formula I as a pesticide.

A carrier in a composition of the invention may

be a solid or a liquid, including a material which is

normally gaseous but which has been compressed to

<4 form a liquid, inorganic or organic, and of synthetic

Sor nF'ural origin. The active ingredient is suitably

formulated with ac least one carrier to facilitate

d, its application to the locus, for example plants,

seeds or soil, to be treated, or to facilitate stor-

age, transport or handling.

Preferably, a composition of the invention contains

at least two carriers, at least one of which is a

surface-active agent. The surface-active agent may be

an emulsifier, a dispersing agent or a wetting agent;it

may be non-ionic or ionic. Pesticidal compositions

are generally formulated and transported in a con-

Scentrated form which is subsequently diluted by the

farmer or other user before application. A surface-

active agent facilitates this process of dilution.

Any of the carriers commonly used in the form-

ulation of pesticides may be used in the compositions

of the invention, and suitable examples of these are

to be found, for example, in British Patent Speci-

fication No. 1,232,930.

c-

The composition of the invention may, for example,

be formulated as a wettable powder, microcapsules, a

dust, granules, a solution, an emulsifiable con-

centrate, an emulsion, a suspension concentrate or an

aerosol. The composition may have controlled release

r properties, or may be suitable for use as a bait.

Wettable powders usually contain 25, 50 or

of active ingredient and may contain, in addition to 00 inert solid material, 3-10%w of a dispersing agent

and, where necessary, 0-10%w of a stabilizer, a

penetrant and/or a sticker. A dust is usually form-

ulated as a dust concentrate having a composition

0 similar to that of a wettable powder but without a Sdispersant, and is diluted in the field with further

15 solid carrier to give a composition usually con-

taining 1-10%w of active ingredient.

6 Granules usually have ze in the range of from

V" 10 to 100 BS mesh (1.676-0.152 mm) and may be manu-

factured by agglomeration or impregnation techniques.

Generally, granules will contain -25%w active in-

gredient and 0-10%w of additives, for example a

stabilizer, slow-release modifier and/or a binding

agent.

Emulsifiable concentrates usually contain, in

addition to a solvent, and, when necessary, co-solvent,

10-50% w/v active ingredient, 2-20% w/v emulsifier and

0-20%0 w/v of other additives, for example a stabilizer, a penetrant and/or a corrosion inhibitor. A sus- E pension concentrate is stable, non-sedimenting, flow- able product and usually contains 10-75%w active in-

gredient, 0.5-15%w of dispersing agent, 0.1-10%w of suspending agent, for example protective colloid and/or ~2 a thixotropic agent, and 0-101'0w of other additivesC- including, for example, a defoamer, a corrosion in-LOt 00hib itor., a stabilizer, a penetrant and/or a sticker, 0 and as dispersant, water or an organic liquid in which w or 7 the active ingredient is substantially insoluble; ov certain organic additives and/or inorganic salts may a be dissolved in the dispersant to assist in preventing c Q o, sedimentation or as anti-freeze for water. CO

0 C) "Ico The aqueous dispersions and emulsions formed by S diluting a wettable powder or an emulsifiable con- C) cent-rate of the invention with water, also lie within 0CC 000

C, the scope of the present invention. Such dispersions

and emulsions may be of the water-in-o-il or of the

oil-in-water type, and may have a thick "mayonaise"- 200E Q like consistency.

A coomposition of the invention may also contain other ingredients, for example, one or more other o compounds possessing pesticidal, herbicidal or d fungicidal properties, or attractants for example251 pheromones or food ingredients, fc~r use in baits and 0 trap formulations.

The following Examples illustrate the invantion.

EXAMPLE 1 Preparation of cyclopropyl-4-flucrophenyl

ketoxime 2-chloro-6-fluorobenzyl ether (1)

A reaction mixture consisting of 1.9 g (10.5 mmol.)

of the E-isomer of cyclopropyl-4-fluorophenyl ketoxime, a S2.3 g (10 mmol.) 2-chloro-6-fluorobenzyl bromi.de, 12 ml (12 mnol.) aqueous potassium hydroxide 0."5 g tetrabutylammonium bromide and 15 ml methylene 00lori OO s was stirred under gentle -eflux for five hours. The organic layer was separate, washed with 2N NaGH, dr-ed

over MgSO4 and stripped of solvent to give 3.9 g of

an orange oil. This oil was eluted from an SiO- 2a

column with 1:1 toluene/hexane to give 2.3 g of 1,

corresponding to a yield of 72". This sample of 1 was

substantially all E-isomer.

Refractive index n23 =1.5657 D Analysis: C H N

Calculated for C 1 7 H14NClFCO 63.5 4.4 4.4 7 14 Found 63.9 11.4 4.3 EXAMPLE 2 Preparation of cyclopropyl-4-t-butylphenyl

ketoxime 2,6-dichlorobenzyl ether (2) A solution of 2.17 g (10 mmol.) of the E-isomer

of cyclopropyl-4-t-butylphenyl krztoxime in 15 ml

dimethylformamide in toluene was added dropwise or 25 25 r 10 minutes to 1.0 g (40 mmol.) of sodium hydride in

ml of the same solvent. A solution of 2.15 g

(11 mmol.) of 2,6-dichlorobenzy, chloride ir. 15 ml of the same solvent was ther addled d~ropwise over -5minutes, and the mixture was then stirred 3 hours at 100 to 110 0C. After cooling tneP reaction mixture, 5 in! methanol were add:od there~to to inactivate untreated Ssodium hydrid-, i.,nd the mixture was poured onto a mixt- ure of ice and concentrated hydrochloric acid. 1ml1 SThe product wa, extracted with diethyl ether and washed f irst with saturated sodium cvrbonate scoluti on and then with weo:until the washings,, wre neutral.. The solu~ti o de ove mage.um sulphate and evapor- ated to gri'; 2.7 of a dark brown oil. This was lut ed If:rom an SiO.,-column using tcluene to give a u'priduct whi'ch after recrystallization from hexane gave 1.2 g of 2, corresponding to a yield of 3211). This sample of 2 was substantially all E-iLsomer. Melting point: 78-7900c

Analysis: a H N Calcu'l.ted for, 0 E2 Nol 0 67.0 6.2 3.7 Found 67.7 6.5 BXAMFLE 3 Preparation of ,'yc--Iopropyl-4L-fluorophely-L Xi:-tczime 2,6-dichl,)robenzyl ether The procedure of Exatip"Le 2 was folloxred usiLng cyclopropyl-L1-flhoophe. l ketoxime as stoirt ing material, with the exception that dry acetoniitrile was used as solvent. g of 3 ats a whi1te ,:olid were ( C) obtained, corresponding to a yield of 58%. This sample of 3 contained 85% E-isomer.

Melting point: 46-48°C

Analysis: C H N

Calculated for C 1 7 H 1 4 FC1 2 NO 60.3 4.1 4.1

Found 60.7 4.1 3.6

EXAMPLES 4-8

The following compounds were prepared using the u' -O -ocedure of Example 2.

S 10 Cyclopropyl-4-methoxyphenyl ketoxime 2,6-dichloro-

benzyl ether (50% E-isomer)

Analysis: C H N

Calculated for C 1 8 H 1 7 NO 2 C1 2 61.7 4.9

Found 60.8 4.7 3.9

S 15 Melting point: 55-62°C

Cyclopropyl-4-chlorophenyl ketoxime 2,6-dichloro-

benzyl ether (75% E-isomer)

U Melting point: 80-81 0 C

Analysis: C H N

Calculated for C17H14NOC1 3 57.6 4.0

Found 57.5 3.9 3.7 4-Fluorophenyl-isopropyl ketoxime 2-chloro-6-fluoro-

benzyl ether (E-isomer) 18 nD8 1.5473

Analysis: C H N

Calculated for C1 7 H1 6NOF 2 Cl 63.1 5.0 4.3

Found 63.6 5.3 4.3

4-E uorobenzyl-isopropyl ketoxime 2-chloro-6-

fluorobenzyl ether (50% E-isomer)

nD18 1.5442 Analysis: C H N

Calculated for C 1 7 H 1 6 NOF 2 Cl 63.1 5.0 4.3 Foune 63.5 5.3. 4-Fluorobenzyl-isopropyl ketoxime 2-chloro-6-

uD fluiobenzyl ether (Z-isomer) 00 my Melting point: 50-520 C

Analysis: C H N

Calculated for C 1 7 H 1 6 NOF 2 C1 3.1 5.0 4.3 Found 63.3 5.0 4.2

EXAMPLE 9 Pesticidal activity of compounds of the

Sinvention

The activities cf the compounds prepared in

Examples 1 to 8 were tested against the glasshouse

red 6oider mite, tetranychus urticae, as follows:

The compounds were formulated as solutions or

suspensions in water containing 20% by weight of

acetone and 0.05% by weight of Triton X-100 ctrde

mark) as wetting agent. The formulations contained

0.4% by weight of the compound to be tested. Leaf

discs cut from French beea plants were held on moist

filter paper placed on a lid inside a waxed carton.

The discs were then sprayed using a logarithmic

spraying machine, allowed to dry, and then infested with 10 adult mites. The discs were held under glass- house conditions and, after 24 hours, the percentage of dead and moribund mites were assessed.

The concentration of material expected to kill

50% of the test species was calculated (LC 50 and the

toxicity of the compound was compared with that of the

standard (parathion) and expressed as a Toxicity

Index

0O S Toxicity Index =100LC50 of standard x 100 S Toxicity Index LC of test compound

10 The LC 5 0 used for the standard in this calculation

was the mean value based on 20 determinations. The

results are given in the following Table.

:6

o

o f

f, 1

o L -16--

C- C C 4 000 C- C C- c c C C C ~CC 0 'C O~

48556/76 TABLE

com- Structure of compound with reference Percent- Toxicity index pound to general formula I age of against No. tetranychus R 1 ~2 X 1T x2 E-isomer in test urticae compound I~ 4- .4-l

4-fluorophenyl cyclopropyl Cl 2 4-t-butylphenyl cyclopropyl Cl 4-fluorophenyJ. cyclopropyl Cl 4-methoxyphenyl cyclopropyl Cl 4-chlorophenyl cyclopropyl Cl 4-fluorophenyl isopropyl Cl 7 ~4-fluorophenyl is opropyl CiJ 8 L-fluorophenyl is opropyl Cl

A

9 SS 9 S SO S 99 too so,9 00, 06 *09 64 9 9 9 S 9 99 9 9 U 9 6 0.. 99* 99 4 *9

TABLE

Corn- Structure of compound with reference pound to general formula I No. 1 2x 2

1 2 -fluorophenyl cyclopropyl Cl 2 4-t-butylphenyl cyclopropyl Cl Cl 3 4-ffluorophen7 1 cyclopropyl Cl Cl 4-methoxyphen,, cyclopropyl Cl Cl 4.I-chlorophenyl cyclopropyl Cl Cl 6 4-fluorophenyl isopropyl F Cl

7 0 4-fluoropheny 1 isopropyl F Cl 8 4-fluorophenyl isopropyl F Cl

485 5 6/79 rcent- Toxicity index ;e of against isomer tetranychus test urticae mpound

33 6)4 33 12 12 18 32

Claims (1)

The claims defining the invention are as follows:

1. A benzyloxime ether derivative of formula:

R2 X1 X\

R- C N- 0 CH

X2

2 group, R is an optionally substituted cycloalkyl, alkyl or

alkenyl group wherein the substituents are one or more of the

same or different substituents selected from haloge, alkoxy

and aryl, and X 1 and X 2 are independently selected from

fluorine, chlorine and bromine; in the form of its E-isomer,

its Z-isomer or a mixture thereof.

2. A benzyloxime ether derivative according to

claim 1, wherein R is a naphthyl group, a phenyl group

optionally substituted by one or more substituents

independently selected from halogen, C 1 4 alkyl and C-_ 4 alkoxy moieties, or a C1-10 alkyl group optionally

substituted by one or more substituents independently

selected from halogen, Cl_ 4 alkoxy and phenyl moieties.

3. A benzyloxime ether derivative according to

claim 2, wherein R is a phenyl group optionally

substituted by one or two substituents selected from

fluorine, chlorine, bromine, C-_ 4 alkyl, and methoxy

I moieties.

17 48556/79

4. A benzyloxime ether derivative according to claim chl r 15, wherein R is a phenyl group bearing a single sub- atc r3 stituent in the 4-position. )0 hy, C 5. A benzyloxire ether derivative according to claim zi hai 4, wherein RI is 4-fluorophenyl, 4-chlorophenyl, 4-t-

butylphenyl or 4-methoxyphenyl. 5 to

9. 6. A benayloxime derivative according to any one of 8, claims 1 to 5, wherein R 2 represents a C3-6 branched

alkyl group, or a C3- 6 cycloalkyl group optionally 1, substituted by one or more stibstituents selected from or 10 1 halogen, C 1-6 alkyl, C 2 6 alkenyl ard C2-6 halo- the 11 alkenyl. ,oxy de 7. A benzyloxime ether derivative according to claim 6, wherein RB represents isopropyl. ME 8. A benzyloxime ether derivative according to claim 6, wherein RB represents a cyclopropyl group of

formula:

RaB W* 0

Rc

d

wherein Ba and Bb are both hydrogen atoms, C1-6 alkyl

groups o halogen atoms, or Ba and Bb together re-

present a C 2 6 alkylene group or Ba is hydrogen and

Bb is C2-6 alkenyl or C2-6 haloalkenyl having 1 to 3

6/79

Schlorine or bromine atoms; R. and R d are both hydrogen

u@ atoms, C1-6 alkyl groups or halogen atoms, or R c is

OO hydrogen and Rd is C2- 6 alkenyl or C2_6 haloalkenyl

having 1 to 3 chlorine or bromine atoms, or R c and Rd

together represent a C2_ 6 alkenyl group.

9. A benzyloxime ether derivative according to claim

8, wherein R 2 is an unsubstituted cyclopropyl group.

A benzyloxime ether derivative according to claim

1, as hereinbefore described in any one of Examples

1 to 8.

11. A process for preparing a benzyloxime ether

derivative of formula I, as defined in any one of

claims 1 to 10 wnich comprises reacting an alkali

metal salt of a compound of formula:

R 1 1 R C =N OH (II)

1 2 where R 1 and R are as defined in claim 1, with a

compound of formula:

X1

Hal CH

1 2 where X 1 and X 2 are a, defined in claim 1, and Hal

represents a chlorine, bromine or iodine atom.

10-507%w/v active ingredient, 2-2UP w/v emulsirler ana

o, 0 12. A process according claim 11, substantially as

hereinbefore described in any one of Examples 1 to 8.

13. A benzyloxime ether prepared by a process ac- OO Scording to claim 11 or 12.

14. A pesticidal composition which comprises a benzyl-

oxime ether derivative according to any one of claims

1 to 10 and 13 in association with an inert carrier

therefor.

A method of combating pests at a locus which

comprises applying to the locus a benzyloxime ether

derivative according to any one of claims 1 to

and 13 or a composition according to claim 14.

DATED this TWENTY-SECOND day of MAY, 1979

o SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.

Patent Attorneys for the Applicant SPRUSON FERGUSON 3 c/ o- pheromones or food. ingredients, vuse in roaJi6 u trap formulations.