This invention relates to processes, intermediates in the processes and compounds obtainable by the processes. Many of the compounds have pesticidal, especially fungicidal, insecticidal and acaricidal, activity. in EP 299 694 there is described the preparation of pesticidal alkyl esters of aryl (methoxyimino) acetic acid. However, the preparation described therein cannot be used to obtain analogous compounds wherein the aryl group is connected to the acetic acid group through an oxygen or sulfur atom.

We have now found a route for preparing such compounds.

According to the invention, there is provided a process for preparing a compound of formula 1, which comprises reacting a compound of formula 11 R-X-H (11) under basic conditions, with a compound of formula 111, wherein; X is oxygen or sulfur; Y is alkyl, alkenyl, alkynyl or cycloalkyl, each of which may be substituted, or is hydrogen;

Z is as defined for Y or is an optionally substituted alkoxy or optionally substituted amino group; R is an organic group, preferably an optionally substituted aromatic carbo-or heterocyclyl group; and L is a leaving group, for example halogen,-OS02Q or-S (O) qQ where Q is an optionally substituted alkyl or optionally substituted carbocyclyi group and q is 1 or 2; preferably L is-S02Q where Q is Cl-C5 optionally substituted alkyl or optionally substituted phenyl, especially C1-Cs alkyl or phenyl.

A variety of basic conditions may be used with the process of the invention. We have found bases such as sodium hydride and potassium carbonate to be particularly effective.

Most compounds of formula III are novel, and therefore the invention includes compounds of formula III with the proviso that when Y is benzyl, L is not-S02Ph.

Many compounds of formula I are novel, and therefore the invention includes compounds of general formula la wherein X, Y and Z are as defined above; X preferably being oxygen; Y preferably being methyl, cyanomethyl, trifluoromethyl, difluoromethyl, monofluoromethyl (especially methyl); and Z preferably being methoxy or monomethylamino, especially monomethylamino; each R1, which may be the same or different to any other Rl, is alkyl, alkenyl, alkynyl, or cycloalkyl, each of which may be substituted, or is alkoxy,

haloalkoxy, halogen, nitro or cyano; R is preferably Cl-C5 alkyl (especially methyl) or halogen (especially chlorine or fluorine); m is 0 to 4, preferably 0 or 1; R2 is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted, or is hydrogen or Si (R3) 3, where R3 is alkyl, phenyl, alkoxy or haloalkoxy; R2 is preferably optionally substituted phenyl (preferred substituents are C 1-C5 alkyl, halogen, haloalkyl or haloalkoxy) or optionally substituted aromatic heterocyclyl (preferred substituents are C 1-C5 alkyl, halogen, haloalkyl, haloalkoxy, optionally substituted phenyl or optionally substituted phenoxy, especially unsubstituted phenyl or halophenyl); A is a direct bond, -O-, -S(O)n-, -CR4=CR4-, -C#C-, -A¹, -A¹-A¹-, -A4-, -A¹O-, -A¹S(O)n-, -OA¹-, -S(O)nA¹, -A¹-A4-, -A1-A4-C (R5) =N-N=CR5-,-A1-A4-C (R5) =N-X2-X3-, -A¹-A4-A³-, -A¹-A4-N(R6)-, -A¹-A4-X-CH2-, -A¹-A4-A¹-, -A1-A4-CH2X-,-A1-A4-C (R5) =N-X2-X3-X1-,-A1-X-C (R5) =N-, -A1-X-C (R5) =N-N=CR5-,-A1-X-C (R5) =N-N (R6)-,-Al-X-A2-X1-, -A1-o-A3-,-A1-0-C (R4) =C (R5)-,-Al-0-N (R6)-A2-N (R6)-, -A¹-O-N(R6)-A2-, -Al-N (R6)-A2-N (R6)-,-Al-N (R6)-A2-, -A¹-N(R6)-N=C(R5)-,(R6)-N=C(R5)-, -A³-A¹-, -A4-A³-, -A²-NR6-, -A²-O-, -A¹-A²-X¹-, -A¹-A¹-A²-X¹, -O-A³-N(R6)-A²-, <BR> <BR> <BR> <BR> <BR> -CR4=CR4-A²-X¹, -C#C-A²-X¹-, -N=C(R5)-A²-X¹-,<BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> -C (R5) =N-N=C (R5)-,-C (R5) =N-N (R6)-or-(CH2) 2-0-N = C (R5)-, where n is 0,1 or 2, A is-CHR4-, A2 is-C (=X)-, <BR> <BR> <BR> <BR> <BR> A3 (R5) =N-O-,<BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> A4 is-0-N=C (R5)-, X¹ is O, S, NR6 or a direct bond, X2 is 0, NR6 or a direct bond,

X3 is hydrogen,-C (=0)-,-S02-or a direct bond, R4, which may be the same or different to any other R4, is alkyl, cycloalkyl or phenyl, each of which may be substituted (preferably by alkyl, phenyl or halogen), or is hydrogen, halogen or cyano; R4 is preferably hydrogen or Cl-C5 alkyl (especially methyl); R5, which may be the same or different to any other R5, is alkyl, alkenyl, alkynyl, alkoxy, alkylthio, each of which may be substituted (preferably by halogen), carbo-or hetero-cyclyl which may be substituted (preferably by alkyl or halogen), or is hydrogen; R5 is preferably hydrogen or Cl-C5 alkyl (especially methyl); R6, which may be the same or different to any other R6 ; is optionally substituted alkyl (preferably by halogen) or optionally substituted carbo-or heterocyclyl (preferably by alkyl, phenyl or halogen), or is hydrogen, or two R6 groups on A, together with the connecting atoms, form a 5 to 7 membered ring; R6 is preferably Cl-C5 alkyl; where the moiety depicted on the right side of linkage A is attached to R2; or-A-R2 and Rl together with benzene ring M form an optionally substituted fused ring system.

Preferred linkages A are: a direct bond,-0-,-C=-C-,-A 1-,-A4-,-A 10-,-OA 1 -A1-A4-or-A1-A4-A3-. Particularly preferred linkages are: a direct bond,-0-, -C=-C-,-A 1-or-A 10-.

It is preferred that when m is 1, R1 is para to the-A-R2 group.

A preferred group of compounds are those where A is a direct bond,-0-,-C=C-, -A 1-or-A 10-, and R2 is phenyl or aromatic heterocycEyl, each of which may be substituted (preferably by C1-Cs alkyl, halogen, haloalkyl, haloalkoxy, optionally substituted phenyl or optionally substituted phenoxy). When A is a direct bond R2 is preferably phenyl optionally substituted by C1-C5 alkyl, halogen, haloalkyi or haloalkoxy, or R2 is aromatic heterocyclyl (preferably thiazol-2-yl or 1,2,4-

oxadiazol-3-yl) optionally substituted by Cl-C5 alkyl, halogen, haloalkyl, haloalkoxy or phenyl optionally substituted by halogen. When A is-O-,-C=C-, -A 1-or-A 10-, R2 is preferably phenyl optionally substituted by C 1-C5 alkyl, halogen, haloalkyl, haloalkoxy or optionally substituted phenoxy.

Any alkyl group present in the molecule may be straight or branched and is preferably of 1 to 10 carbon atoms, especially 1 to 7 and particularly 1 to 5 carbon atoms.

Any alkenyl or alkynyl group may be straight or branched and is preferably of 2 to 7 carbon atoms and up to 3 double or triple bonds which may be conjugated, for example vinyl, allyl, butadienyl or propargyl.

Any reference to the term carbocyclyl includes saturated carbocyclic groups; unsaturated carbocyclic groups having up to 3 double bonds, which may be conjugated; and aromatic carbocyclic groups, e. g. phenyl. Carbocyclic groups are typically 3 to 8 membered rings. In addition, the term carbocyclyl includes fused carbocyclyl groups, e. g. napthalene, phenanthrene, indane and indene.

Any reference to the term heterocyclyl includes both aromatic and non-aromatic heterocyclyl groups. Heterocyclyl groups are generally 5,6 or 7-membered rings containing up to 4 hetero-atoms selected from nitrogen, oxygen and sulfur.

Examples of heterocyclyl groups are furyl, thienyl, pyrrolyl, pyrrolinyl, pyrrolidinyl, <BR> <BR> imidazolyl, dioxolanyl, oxazolyl, thiazolyl, imidazolyl, imidazolinyl, imidazolidinyl,<BR> <BR> pyrazolyl, pyrazolinyl, pyrazolidinyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, pyranyl, pyridyl, piperidinyl, dioxanyl, morpholino, dithianyl, thiomorpholino, pyridazinyl, pyrimidinyl, pyrazinyl, piperazinyl, sulfolanyl, tetrazolyl, triazinyl, azepinyl, oxazepinyl, thiazepinyl, diazepinyl and thiazolinyl. In addition, the term heterocyclyl includes fused heterocyclyl groups, for example benzimidazolyl, benzoxazolyl, imidazopyridinyl, benzoxazinyl, benzothiazinyl, oxazolopyridinyl, benzofuranyl, quinolinyl, quinazolinyl, quinoxalinyl, dihydroquinazolinyl, benzothiazolyl, phthalimido, benzofuranyl, benzodiazepinyl, indolyl and isoindolyl.

Any alkyl, alkenyl, alkynyl, carbocyciyl, heterocyclyl group, alkoxy or alkylthio group when substituted, may be substituted by at least one group, which may be the same or different, and may be selected from the group: nitro, halogen, cyano, acyl,-0-acyl,-S-acyl, optionally substituted amino, optionally substituted carbocyclyl, optionally substituted heterocyclyl,-SFS, trialkylsilyl,-ORa and-SRa, where Ra is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl and optionally substituted heterocyclyl. Any carbocyclyl or heterocyclyl groups may also be substituted by optionally substituted alkyl, optionally substituted alkenyl and optionally substituted alkynyl.

Any amino group when substituted, may be substituted by one or two optionally substituted aikyl or acyl groups, or two substituents together with the nitrogen to which they are attached may form a heterocyclyl group, preferably a 5 to 7- membered heterocyclyl group, which may be substituted and may contain other hetero atoms, for example morpholino, thiomorpholino or piperidinyl.

The term acyl includes the residue of sulfur and phosphorus-containing acids as well as carboxylic acids. Examples of acyl groups are:-C =O) Rb,-C (=0) ORb, -C (= E) NRbRC,-CF = O) N (Rb) ORC,-C (= O) ONRbRC,-CS = O) N (Rb) NRCRd, -C (=0) SRb,-C (=S) SRb,-S (O pRb,-S (0) 20Rb,-S (O) pNRbRC,-Pf = E) (ORb) (ORC), <BR> <BR> <BR> <BR> and-C (=0)-C (=0) OR; where p is 1 or 2; E is 0, S or, where appropriate, NRa or NORD; and where Rb, Rc and Rd, which may be the same or different, are as defined for Ra hereinabove, or Rb and RC, or Rc and Rd, together with the atom (s) to which they are attached may form a ring, preferably a 5 to 7- membered heterocyclyl group which may be substituted and may contain other hetero atoms.

In cases where the compounds of the invention exist as the E and Z isomers, the invention includes individual isomers as well as mixtures thereof.

In cases where compounds of the invention exist as tautomeric isomers, the invention includes individual tautomers as well as mixtures thereof.

The compounds of the invention have activity as fungicides, especially against fungal diseases of plants, e. g. mildews and particularly barley powdery mildew (Erysiphe graminis) and vine downy mildew (Plasmopara viticola), rice blast (Pyricularia oryzae), cereal eyespot (Pseudocercosporella herpotrichoides), rice sheath blight (Pellicularia sasakii, grey mould (Botrytis cinerea), damping off (Rhizoctonia solanlD, wheat brown rust (Puccinia recondita), late tomato or potato blight (Phytophthora infestans), apple scab (Venturia inaequalis), glume blotch (Leptosphaeria nodorum). Other fungi against which the compounds may be active include other powdery mildews, other rusts, and general pathogens of Deuteromycete, Ascomycete, Phycomycete and Basidomycete origin.

The compounds of the invention also have insecticidal, acaricidal and nematicidal activity and are particularly useful in combating a variety of economically important insects, acarids and plant nematodes, including animal ectoparasites and especially Diptera, such as sheep blow-fly, Lucilia sericata, and house-flies, Musca domestica; Lepidoptera, including Plutella xylostella, Spodoptera littoralis, Heliothis armigera and Pieris brassicae; Homoptera, including aphids such as Megoura viciae; Coleoptera, including corn rootworms (Diabrotica spp., e. g.

Diabrotica undecimpunctata); and spider mites, such as Tetranychus spp..

The invention thus also provides a method of combating pests (i. e. fungi, insects, nematodes, acarids and weeds) at a locus infested or liable to be infested therewith, which comprises applying to the locus a compound of formula I.

The invention also provides an agricultural composition comprising a compound of formula I in admixture with an agriculturally acceptable diluent or carrier.

The composition of the invention may of course include more than one compound of the invention.

In addition the composition can comprise one or more additional active ingredients, for example compounds known to possess plant-growth regulant, herbicidal,. fungicidal, insecticidal or acaricidal properties. Alternatively the

compound of the invention can be used in sequence with the other active ingredient.

The diluent or carrier in the composition of the invention can be a solid or a liquid optionally in association with a surface-active agent, for example a dispersing agent, emulsifying agent or wetting agent. Suitable surface-active agents include anionic compounds such as a carboxylate, for example a metal carboxylate of a long chain fatty acid; an N-acylsarcosinate; mono-or di-esters of phosphoric acid with fatty alcohol ethoxylates or salts of such esters; fatty alcohol sulfates such as sodium dodecyl sulfate, sodium octadecyl sulfate or sodium cetyl sulfate; ethoxylated fatty alcohol sulfates; ethoxylated alkylphenol sulfates; lignin sulfonates; petroleum sulfonates; alkyl-aryl sulfonates such as alkyl-benzene sulfonates or lower alkyinaphthalene sulfonates, e. g. butyl-naphthalene sulfonate; salts of sulfonated naphthalene-formaldehyde condensates; salts of sulfonated phenol-formaldehyde condensates; or more complex sulfonates such as the amide sulfonates, e. g. the sulfonated condensation product of oleic acid and N-methyl taurine or the dialkyl sulfosuccinates, e. g. the sodium sulfonate of dioctyl succinate. Nonionic agents include condensation products of fatty acid esters, fatty alcools, fatty acid amides or fatty-alkyl-or alkenyl-substituted phenols with ethylene oxide, fatty esters of polyhydric alcohol ethers, e. g. sorbitan fatty acid esters, condensation products of such esters with ethylene oxide, e. g. polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylenic glycols such as 2,4,7,9-tetramethyl-5-decyne- 4,7-diol, or ethoxylated acetylenic glycols.

Examples of a cationic surface-active agent include, for instance, an aliphatic mono-, di-, or polyamine as an acetate, naphthenate or oleate; an oxygen-containing amine such as an amine oxide or polyoxyethylene alkylamine; an amide-linked amine prepared by the condensation of a carboxylic acid with a di-or polyamine; or a quaternary ammonium salt.

The compositions of the invention can take any form known in the art for the formulation of agrochemicals, for example, a solution, a dispersion, an aqueous mulsion, a dusting powder, a seed dressing, a fumigant, a smoke, a dispersible

powder, an emulsifiable concentrate or granules. Moreover it can be in a suitable form for direct application or as a concentrate or primary composition which requires dilution with a suitable quantity of water or other diluent before application.

An emulsifiable concentrate comprises a compound of the invention dissolved in a water-immiscible solvent which is formed into an mulsion with water in the presence of an emulsifying agent.

A dusting powder comprises a compound of the invention intimately mixed and ground with a solid pulverulent diluent, for example, kaolin.

A granular solid comprises a compound of the invention associated with similar diluents to those which may be employed in dusting powders, but the mixture is granulated by known methods. Alternatively it comprises the active ingredient absorbed or adsorbed on a pre-granular diluent, for example, Fuller's earth, attapulgite or limestone grit.

Wettable powders, granules or grains usually comprise the active ingredient in admixture with a suitable surfactant and an inert powder diluent such as china clay.

Another suitable concentrate is a flowable suspension concentrate which is formed by grinding the compound with water or other liquid, a wetting agent and a suspending agent.

The concentration of the active ingredient in the composition of the present invention, as applied to plants is preferably within the range of 0.0001 to 1.0 per cent by weight, especially 0.0001 to 0.01 per cent by weight. In a primary composition, the amount of active ingredient can vary widely and can be, for example, from 5 to 95 per cent by weight of the composition.

In the method of the invention the compound is generally applied to seeds, plants or their habitat. Thus, the compound can be appiied directly to the soil before, at

or after drilling so that the presence of active compound in the soil can control the growth of fungi which may attack seeds. When the soil is treated directly the active compound can be applied in any manner which allows it to be intimately mixed with the soil such as by spraying, by broadcasting a solid form of granules, or by applying the active ingredient at the same time as drilling by inserting it in the same drill as the seeds. A suitable application rate is within the range of from 5 to 1000 g per hectare, more preferably from 10 to 500 g per hectare.

Alternatively the active compound can be applied directly to the plant by, for example, spraying or dusting either at the time when the fungus has begun to appear on the plant or before the appearance of fungus as a protective measure.

In both such cases the preferred mode of application is by foliar spraying. It is generally important to obtain good control of fungi in the early stages of plant growth as this is the time when the plant can be most severely damaged. The spray or dust can conveniently contain a pre-or post-emergence herbicide if this is thought necessary. Sometimes, it is practicable to treat the roots of a plant before or during planting, for example, by dipping the roots in a suitable liquid or solid composition. When the active compound is applied directly to the plant a suitable rate of application is from 0.025 to 5 kg per hectare, preferably from 0.05 to 1 kg per hectare.

In addition, the compounds of the invention can be applied to plants or parts thereof which have been genetically modified to exhibit a trait such as fungal, insect and/or herbicidal resistance.

Compounds of the invention may be prepared, in known manner, in a variety of ways.

Compounds of formula III where Z is not an amino group containing a free NH, may be prepared according to reaction Scheme 1, where QSM is a preferably an alkali metal thioalkoxide, and the oxidation is preferably performed using meta- chloroperbenzoic acid or the like.

5 10 Scheme 1 o o phosphorus ci + Y-O-NH2. HCI- YzOsNtfZ oxvchlori e O O CI Q S02Q QSM oxidation , O/ZO/Z Y N (Y N O O (111) Alternatively, compounds of formula III where Z is not an amino group containing a free NH may be prepared from iminoyl chlorides according to Scheme 2. Where L is a leaving group such as halogen or sulfonate.

Scheme 2 ci 1) base 2) Y-L iW Q H N HON Z o t! 0 0 Q S S02Q oxidation oxydation YN YN O O o o (111) In the preferred case where Z is alkoxy, especially methoxy or ethoxy, the iminoyl sulfones III may be prepared according to Scheme 3.

5 10 15 Scheme 3 o o 1)ROH/NH20H. HCI/H2SO4 1) NaNO2/HCI OCOH 2) 0, 0 2) 00 i O/XC02H <F </V\OR OR CI cl HOX l QSM fl'Q 1) base then Y-L 02Q s 2) oxidation HOCCO910 YO-- C02R Compounds of formula la may be prepared by reacting compounds of formula IV under basic condition with compounds of formula III according to Scheme 4.

Preferred basic conditions comprise an alkali metal hydride in a suitable solvent, such as tetrahydrofuran, or a weak base such as sodium carbonate in a suitable solvent, such as methylethyl ketone.

Scheme 4 (R1) m (R) m 1) Basic conditions nô A XH YO/Z , O/Z Y N -5' (IV) (la) Compounds of formula lb, i. e. compounds of formula la where A comprises a -CHR4X-group wherein the carbon is attached to benzene ring M, may be prepared according to Scheme 5. Compounds of formula Ic are reacted under basic conditions, with R2XH, where R2XH includes alcools, phenols, thiophenols, mercaptans, oximes, amides, thioamides etc. Preferred basic conditions comprise an alkali metal hydride in a suitable solvent, e. g. tetrahydrofuran.

5 10 15 Scheme 5 (R'),,, m (R1) m benzylic R4 halogenationI MU YOwN Z R4 YiOwN Z O O o 8 (Ic) (R1) m R2XH/RX M basicconditions wX 4 YN 0 (lb) The groups R1, R2 and A may be introduced either before or after reaction of IV with III in Scheme 4.

Compounds of formula Id, i. e. compounds of formula la where Z is optionally substituted amino, may be prepared by a number of routes. A preferred route is shown in Scheme 6 and involves reacting compounds of formula le, where Z is optionally substituted alkoxy, with an amine other than a tertiary amine.

Scheme 6 (Rm m (R1) m R2 R2 p2 1 ! iR2 M) \A/X amination \AXX A-p, X O/alkoxy, p/amino Y N Ny O O (le) (Id) Compounds of formula If, i. e. compounds of formula la where A is a direct bond and R2 is optionally substituted carbocyclyl or optionally substituted heterocyclyl,

may be prepared by a variety of routes. A preferred route is shown in Scheme 7 and involves reacting compounds of formula 19 (Q1 is a displaceable group such as iodine, bromine or triflate) with a boronic acid or boronate ester of formula R2- B (ORe) 2 (Re is hydrogen or alkyl, or the two groups together form a ring, for example-CH2C (Me) 2CH2-) in the presence of a palladium catalyst according to the well known method of Suzuki. Preferred conditions involve treating Ig, where Q1 is iodine, with a boronic acid R2-B (OH) 2, sodium carbonate, a catalytic amount of palladium catalyst such as tetrakis (triphenylphosphine) palladium (0) in a two phase system such as toluene, methanol and water at conditions between room temperature and reflux. For compounds If where Z is alkoxy, reactions are preferably performed at room temperature. Where Z is amino, rections are preferably carried out at reflux.

Scheme 7 () m () m < R2-B (ORe) 2/Pd (cat) < (Suzukicoupling) Q1 X R X /0/Z O.Z Y N Y N 0 O (Ig) (If) Compounds of formula If may also be prepared according to Scheme 4, whereby the carbocyclic or heterocyclic ring R2, linked by a direct bond A to the benzene ring M are assembled first and then coupled with compound 111.

Compounds of formula Ih, i. e. compounds of formula la where A is a direct bond and R2 is polyfluoroalkyl, may be prepared by reacting compounds of formula Ig with a polyfluoroalkyl iodide in the presence of a copper catalyst according to Scheme 8. Preferred conditions involve reacting Ig, where Q2 is iodide, with polyfuororalkyl iodide and copper-bronze in dry dimethyl sulfoxide solvent at 130 °C.

Scheme 8 () m () m M iodide/ Cu-IronzelDMSO Yz Z YiON Z O p ( ! g) (ih) Compounds of formula Ij, i. e. compounds of formula la where A is-C_C-, may be prepared by a variety of routes. A preferred route involves reacting a compound of formula lg with a terminal acetylene V in the presence of palladium catalyst, a tertiary amine, a tertiary phosphine and a copper salt in an aprotic solvent. Typical conditions are shown in Scheme 9.

Scheme 9 Other methods will be apparent to the chemist skilled in the art as will be the methods for preparing starting materials and intermediates.

The following Examples also make apparent various methods of preparing compounds of the invention as well as processes, starting materials and intermediates of the invention. Structures of isolated novel compounds were confirmed by elemental and/or other appropriate analyses. Where 1 H N. M. R. spectra were used to confirm chemical structure, these were performed in CDC13.

Example 1 <BR> <BR> <BR> <BR> Methyl 2- (2-chloro-5-methylphenoxy)-2- (methoxyimino) acetate (Compound 22)<BR> <BR> <BR> <BR> <BR> <BR> Sodium hydride (8.4 g of a 60% suspension in mineral oil) was added in small portions to a solution containing 2-chloro-5-methyl-phenol (27.3 g) in dry THF (300 ml) keeping the temperature below 20 °C. After stirring for 10 mins, a solution containing the product from stage d) below (37.37 g) in dry tetrahydrofuran (200 ml) was added slowly over 30 mins whilst keeping the temperature below 10 °C. When addition was complete, the reaction was allowed to warm to room temperature and stirred for 5 days. The solvent was removed in vacuo and the residue partitioned between water and dichloromethane. The aqueous phase was extracted with dichloromethane (x3) and the combined organic phases were dried (MgSO4) and evaporated to give an oily solid which was triturated with di-isopropyl ether to give the title product, m. p. 1 18-20 °C.

Preparation of starting materials a) Methyl methoxyaminoglyoxylate Methoxyl amine hydrochloride (20 g) was suspended in dichloromethane (150 ml). Triethylamine (25 g) was added and the mixture stirred for 20 mins at room temperature. Methyl oxalyl chloride (30 g) was then added dropwise whilst maintaining the temperature between 20-25 °C. The mixture was stirred for 2 hours at room temperature. Triethylamine (25 g) was then added dropwise over 20 mins, and the solution stirred for a further 20 mins. The solvent was removed in vacuo, and the residue triturated with ether. The mixture was filtered to remove the solid triethylamine hydrochloride and the filtrate was evaporated to give the title product, 1 H N. M. R. 3.78 (3H, s, OMe) and 3.85 (3H, s, OMe). b) Methyl 2-chloro-2- (methoxyimino) acetate.

A solution containing the product from stage a) (5.8 g) and phosphorus oxychloride (20 ml) were heated under reflux for 18 hours. The solution was cooled and excess phosphorus oxychloride was removed in vacuo.

Water was added and the reaction mixture was extracted with

dichloromethane. The combined organic extracts were dried (MgSO4), filtered and the filtrate evaporated to give the title product, m. p. 44-5 °C. c) Methyl 2- (methoxyimino)-2- (methylthio) acetate.

Sodium thiomethoxide (2.5 g) was suspended in dry tetrahydrofuran (20 ml) and a solution containing the product from stage b) below (5.0 g) in dry tetrahydrofuran (10 ml) was added dropwise. The mixture was heated under reflux for 3 hours. On cooling the reaction mixture was poured into water. The reaction mixture was extracted with diethyl ether to give the title product, 1 H N. M. R. 2.38 (3H, s, SMe), 3.88 (3H, s, OMe) and 4.04 (3H, s, OMe). d) Methyl 2-(methoxyimino)-2-(methylsulfonyl) acetate.

To a solution containing the product from stage c) below (4.0 g) in dry dichloromethane (40 ml) was added dropwise, a solution containing 55% meta-chloroperbenzoic acid (8.5 g) in dry dichloromethane (40 ml). The solution was allowed to stir at room temperature overnight. The reaction mixture was filtered and the filtrate washed sequentially with saturated sodium bicarbonate solution, sodium bisulfite solution and brine, and then dried (MgSO4). The solvent was evaporated to give the title product, m. p.

57-8 °C.

Example 2 <BR> <BR> <BR> <BR> Methyl 2-(5-bromomethyl-2-chlorophenoxy)-2-(methoxyimino) acetate (Compound 48) A solution containing the product from Example 1 (2.6 g), 1,3-dibromo-5,5- dimethyl hydantoin (2.9 g) and benzoyl peroxide (0.1 g) in isopropyl acetate (50 ml) was slowly heated to 85 °C. During heating, the reaction mixture darkened and then turned clear as the reaction began. The reaction mixture was heated for 30 mins at 85 °C. On cooling the solvent was removed in vacuo and the residue dissolved in diisopropyl ether. The mixture was filtered to remove the insoluble dimethyl hydantoin, and the filtrate was purified by silica gel chromatography, gradient eluting with hexane/ethyl acetate to give the title product, m. p. 65-7 °C.

Example 3 <BR> <BR> <BR> <BR> Methyl 2-[2-chloro-5-(4-chlorophenoxymethyl) phenoxy]-2-(methoxyimino) acetate (Compound 5) To a solution of the product from Example 2 (1.0 g) and 4-chlorophenol (0.38 g) in acetone was added potassium carbonate (0.3 g) and the mixture was stirred at room temperature for 48 hours. Water was added and the mixture was extracted with ethyl acetate. The combined organic extracts were dried (MgS04), filtered and evaporated to give a residue which was purified using silica gel chromatography gradient eluting with hexane/ethyl acetate to give the title product, m. p. 117-9 °C.

Example 4 N-Methyi 2- [2-chloro-5- (4-chlorophenoxymethyf) phenoxyl-2- (methoxyimino) acetamide (Compound 9) To a solution of the product from Example 3 (0.24 g) in tetrahydrofuran (2 ml) was added 33% w/v methylamine in ethanol (2 ml), and the solution was stirred at room temperature for 18 hours. The solvent was removed in-vacuo to give the title product, m. p. 126-7 °C.

Example 5 Methyl 2- [5- (3-biphenylyl)-2-methylphenoxy)-2- (methoxyimino) acetate (Compound 157) To a solution containing the starting material (see below, 1.0 g) and 3- biphenylylboronic acid (0.57 g) in toluene (9 ml) and methanol (3 ml) was added sodium carbonate (0.86 g) in water (4 mi ? followed by tetrakis (triphenylphosphine) palladium (0) (0.17 g). The mixture was heated to 60°C for 2 hours. The mixture was cooled, filtered through kieselguhr and the filtrate poured into brine. The mixture was extracted with toluene (x3) and the combined extracts were dried (MgS04) and evaporated to give a residue which was purified by silica gel chromatography eluting with 8% ethyl acetate in light petroleum (b. p. 40-60 °C) to give the title product, m. p. 104-10°C.

Preparation of starting materials Methyl 2- (5-iodo-2-methylphenoxy)-2- (methoxyimino) acetate A mixture containing 5-iodo-2-methylphenol (W096 32399), methyl 2- (methoxyimino)-2-(methylsulfonyl) acetate (0.82 g, see Example 1, stage d) and ground potassium carbonate (0.6 g) in dry methylethyl ketone (28 ml) was heated under gentle reflux with stirring for 3.5 hours. The reaction mixture was cooled, filtered to remove inorganic solids and the filtrate evaporated to dryness in vacuo.

The product was dissolved in dichloromethane, washed with brine and dried (MgSO4). Work-up gave the title product as a solid, m. p. 88-91 °C.

Example 6 Methyl 2- (methoxyimino)-2- (2-methyl-5-perfluorobutylphenoxy) acetate (Compound 161) A mixture containing methyl-2- (5-iodo-2-methylphenoxy)-2- (methoxyimino) acetate (0.5 g, starting material from Example 5), perfluorobutyl iodide (0.36 ml), and copper-bronze powder (0.51 g) in dry dimethyl sulfoxide (2 ml) was heated to 130 °C under nitrogen for one hour. On cooling, the reaction mixture was poured onto water and then filtered through kieselguhr, washing through with diethyl ether. The filtrate was extracted with diethyl ether (x3) and the combined ether extracts were washed with brine and dried (MgSO4). Work-up gave a crude product which was purified by silica gel chromatograph eluting with 6% ethyl acetate in light petroleum (b. p. 40-60°C) to give the title product, 1 H N. M. R. d (ppm) 2.40 (3H, s, CH3-Ar), 3.82 (3H, s, CH30), 4.02 (3H, s, CH30N), 6.86 (1H, s, Ar-H), 7.25 (1H, d, Ar-H), 7.34 (1H, d, Ar-H).

Example 7 N-Methyl2-S5-(3-formylphenyl)-2-methylphenoxy]-2-(methoxyimi no) acetamide (Compound 166) To a solution containing the starting material (0.5 g, see below), 3-formylphenyl boronic acid (0.22 g) in toluene (45 mi) and methanol (3 ml) was added sodium carbonate (0.43 g) in water (3 ml) and tetrakis (triphenylphosphine) palladium (0) (0. 085 g). The reaction mixture was heated to a gentle reflux for 4.5 hours. The reaction mixture was cooled, filtered, and the filtrate extracted ethyl acetate (x3).

The combined organic extracts were washed with brine and dried (MgS04).

Work-up gave a crude product which was purified by silica gel chromatogrphay eluting with 30% ethyl acetate in light petroleum (b. p. 40-60°C) to give the title product as a solid, m. p. 128-130°C (with decomposition) Preparation of starting materials N-Methyl 2-(5-iodo-2-methylphenoxy]-2-(methoxviminoNacetamide The compound was prepared from methyl 2-(5-iodo-2-methylphenoxy]-2- (methoxyimino) acetate (see Example 5) using conditions analogous to Example 4.

Example 8 Methyl 2-(methoxyimino)-2-[2-methyl-5-(3, 4-xylyloxy) phenoxy] acetate (Compound 168) To a solution containing 2-methyl-5- (3, 4-xylyloxy) phenol (0.36 g) in dimethylformamide (4 ml) was added sodium hydride (0.068 g, 60% in mineral oil). When the effervescence had ceased methyl 2- (methoxyimino)-2- (methylsulphonyl) acetate (0.42 g, the product from Example 1 stage a)) was added and the solution stirred at room temperature for 3.5 hours. The reaction mixture was poured onto water and extracted with diethyl ether (x2). The combined ether extracts were washed with brine and dried (MgSO4). Work-up gave a crude product which was purified by silica gel chromatography eluting with dichloromethane; light petroleum (b. p. 40-60°C) (2: 1) to give the title product, m. p. 66-9°C.

Example 9 Methyl 2-(methoxyimino)-2-[2-methyl-5-(phenylethynyl) phenoxy] acetate (Compound 143) To a mixture of methyl 2- (5-iodo-2-methylphenoxy)-2- (methoxyimino) acetate (1.0 g) in triethylamine (50 ml) was added phenylacetylene (0.33 ml), copper (i) iodide 30 mg), triphenylphosphine (15 mg) and PdC12 (PPh3) 2 (15 mg). The reaction was heated to reflux for 2 hours. On cooling, the reaction was filtered through kieselguhr, washing through with toluene. Evaporation of the filtrate in vacuo gave the title compound, m. p. 135-8°C.

Example 10 Methyl 2-(methoxyimino)-2-82-methyl-5-[1-(3-trifluoromethylphenyl) ethylidene aminooxymethyl] phenoxy} acetate (Compound 150) To a solution containing 3-trifluoromethylphenylacetophenone oxime (0.32 g) was dissolved in methyl ethyl ketone (14 ml). To this was added potassium carbonate (0.23 g) followed by the product from stage d (see below) (0.5 g). The mixture was heated under gentle reflux for 18 hours. On cooling, the mixture was filtered and evaporated to dryness to give a crude product which was purified by silica gel chromatography gradient eluting with ethyl acetate/light petroleum (b. p. 40-60°C) (5- 20%) to give the title product as a solid, m. p. 62-4°C.

Preparation of Startinq Materials a) 3-Hydroxy-4-methylbenzyl acetate A suspension containing 5- (hydroxymethyl)-2-methylphenol (0.5 g) and Candida Rugosa Lipase Type VII (0.70 g, ex-Sigma) in vinyl acetate (14 ml) and hexane (28 ml) was stirred for 4 hours. Removal of the enzyme by filtration followed by evaporation in-vacuo gave the title compound which was used without further purification. b) Methyl 2- 5-acetoxymethyl-2-methylphenoxy]-2- (methoxyimino) acetate To a solution containing the product from stage a) (10 g) in dry tetrahydrofuran (275 mi) was added sodium hydride (60% in mineral oil; 2.4 g) portionwise over 10 minutes. When the effervescence had ceased, methyl 2-(methoxyimino)-2-(methylsulphonyl)(methoxyimino)-2-(methyl sulphonyl) acetate (11.9 g, the product from Example 1 stage a) was added portionwise and stirred at room temperature for 18 hours. The reaction was quenched with methanol (5 ml), poured onto ice water (1 litre) and extracted with diethyl ether. The combined organic extracts were washed with brine and dried (MgSO4).

Work-up gave a crude product which was purified by silica gel chromatography gradient eluting with ethyl acetate: light petroleum (b. p.

40-60°C (1-10%) to give the title product.

c) Methyl 2- [5- (hydroxymethyl)-2-methylphenoxy]-2- (methoxyimino) acetate A mixture containing the product from stage b) (7. 69 g) and potassium carbonate (3.59 g) in dry methanol (152 ml) was stirred at room temperature for 25 minutes. The mixture was poured into a vigorously stirred solution of water (500 ml) and dichloromethane (500 ml). The layers were separated and the aqueous phase extracted with dichloromethane (x2). The combined organic extracts were washed with brine and dried (MgS04). Work-up gave the title compound as a solid. d) Methyl 2- (5-bromomethyl-2-methylphenoxy)-2- (methoxyimino) acetate To a solution containing the product from stage c) (3.55 g) in dry dichloromethane (66 ml) was added triphenylphosphine (4.04 g). The solution was stirred at room temperature and carbon tetrabromide (5.11 g) was added in one portion. The reaction mixture was stirred at room temperature for 18 hours. The mixture was then washed with saturated aqueous sodium bicarbonate solution and the layers separated. The aqueous phase was extracted with dichloromethane (x2) and all organic phases were combined, washed with brine and dried (MgS04). Work up followed by silica gel chromatography gradient eluting with ethyl acetate in petrol (b. p. 40-60°C) (10-15%) gave the title compound as a solid, m. p.

84-7°C.

The following compounds of formula If, i. e. compounds of general formula la where X is oxygen, Y is methyl, m is 1 and R1 is para to-A-R2, were prepared by methods analogous to those of the previous Examples. The moiety depicted on the right side of linkage A is attached to R2. Cmp Z R 1 A R2 m. p./°C MeO Me direct bond 87-8 2 NHMe Me direct bond H 51-3 3 MeO Me direct bond Cl 83-5 4NHMe Medirect bondC) 112-4 5 MeO Cl-CH2O-4-CI-phenyl 117-9 6 NHMe Cl-CH2O-4-F-phenyi 96-8 7 NHMe Cl-CH20-3, 5-diCl-phenyl 103-5 8 MeO Cl-CH20-2, 5-diMe-phenyl 96-7 9 NHMe Cl -CH2O- 4-Cl-phenyl 126-7 10 MeO CI-CH20-2-tolyi 89-90 11 MeO Cl -CH2SC(SMe)=N-N=CH- 4-F-phenyl oil 12 NHMe CI-CH20-2-tolyl 105-6 13 NHMe Cl -CH2O- 2,5-xylyl 97-8 14 NHMe Cl -CH2SC(SMe)=N-N=CH- 4-F-phenyl foam 15 MeO Cl -CH2O- 4-PhO-phenyl 100-1 16 NHMe Ci-CH2O-4-PhO-phenyl 80-1 17 MeO Cl-CH2O-3-PhO-phenyl 91-2 18 MeO Cl -CH2SC(SMe)=N- 4-tolyl oil 19 MeO Cl -CH2O- 4-F-phenyl 102-4 20 MeO Cl -CH2O- 2-napthyl 126-8 21 MeO Cl-CH20-4- (2, 4-diCl-benzyloxy)- 125-7 phenyl 22 MeO Cl direct bond Me 118-20 23 NHMe Ci-CH2O-2-napthyl 164-6 24 NHMe CI direct bond Me 108-10 Cmp Z R1 A R2 m. p./°C 25 NHMe Cl -CH2O- 4-(2,4-diCl-benzyloxy)- 131-3 phenyl 26 MeO Cl -CH2SC (SMe)=N-N=CH- tert-butyl 108-10 27 MeNH Cl-CH2SC (SMe) = N-N = CH-tert-butyl 103-5 28 MeO Cl -CH2SC (SMe)=N-N=C(Me)- tert-butyl 117-9 29 MeNH Cl-CH2SC (SMe) = N-N = C (Me)- tert-butyl 124-6 30 MeO Cl -CH2ON=C(Me)- 3,5-diCl-phenyl 112-4 31 MeNH Cl-CH20N=CH-3, 5-diCl-phenyl 106-8 32 MeO Cl -CH2ON=CH- 4-MeO-phenyl 103-5 33 MeNH Cl-CH2ON = CH-4-MeO-phenyl 98-100 34 MeNH Cl -CH2SC(SMe)=N-(SMe)=N- 4-tolyl oil 35 MeO Cl -CH2O- 3-CF3-phenyl 90-1 36 MeNH Cl-CH2O-3-CF3-phenyl 81-2 37 MeO Ci-CH2ON = CH-2-tolyl 63-4 38 NHMe CI-CH20N=CH-4-CI-phenyl 133-4 39 MeO Cl -CH2O- 3-Cl-5-CF3-2-pyridyl 133-5 40 MeO Cl -CH2ON=C(Me)- 4-Cl-phenyl 67-70 41 MeO Ci-CH2ON = C (Me) C (Me) N-0-methyl 64-67 42 MeO Ci-CH2O-4-biphenylyl 85-8 43 MeO Cl -CH2O- 4-CF3-phenyl 110-2 44 MeNH CI-CH20-3-PhO-phenyl 66-8 45 MeNH Ci-CH20-3-biphenylyl 116-8 46 MeNH Ci-CH20-4-CF3-phenyl 103-5 47 MeNH Ci-CH20-N=CH-2-tolyl 74-6 48 MeO Cl -CH2- Br 65-7 49 NHMe CI-CH20-3-CI-5-CF3-2-pyridyl 172-4 50 NHMe Cl -CH2ON=C(Me)- 3-CF3-phenyl oil 51 NHMe Cl-CH2ON = C (Me)-4-CI-phenyl oil 52 NHMe Cl -CH2ON=C(Me)-C(Me)=N-(Me)-C(Me)=N- methyl oil 53 NHMe Ci-CH2ON = C (Me)-3, 5-CI2-phenyl 95-6 Cmp Z R¹ A R² m.p./°C 54 NHMe CI-CH20N = C (Me)-C (= NOMe)-phenyl oil 55 NHMe Cl -CH2O- 4-[(MeO)N=C(Me)]-phenyl oil 56 NHMe H-0-phenyl 88-90 57 NHMe Cl-CH20-4-í-phenyl 143-4 58 NHMe Cl -CH2ON=C(Me)- 4-MeO-phenyl 121-3 59 NHMe Cl -CH2ON=C(Me)- 4-PhO-phenyl 60 NHMe Me direct bond 3- (4-CI-phenyl)-1,2,4-162-4 oxadiazol-5-yl 61 NHMe Me direct bond 3-(3-CF3-phenyl)-1, 2, 4-148-50 oxadiazol-5-yl 62 NHMe Cl -CH2ON=C(Me)- 4-PhO-phenyl oil 63 NHMe Cl-CH2SC (SMe) = N-2-MeO-5-pyridyl oil 64 NHMe H-OCH2-4-CI-phenyl 65 NHMe Me direct bond 4-F-pheny ! 79-80 66 NHMe H-CH20-4-CI-phenyl 65-8 67 NHMe H-CH20-3-PhO-phenyl 102-3 68 NHMe H -CH2O-N=CH- 4-Cl-phenyl 90-1 69 NHMe H-CH20-N = C (Me)-3-CF3-phenyl oil 70 NHMe H-CH2SC (SMe) = N-N = CH-4-F-phenyl 114-5 71 NHMe Cl -CH2SC (SMe)=N-N=C(Me)- 4-F-pheny ! 114-5 72 NHMe Me direct bond 4-CF3-phenyl 126-7 73 NHMe Me direct bond 3-Pri-phenyl 111-3 74 NHMe Me direct bond 4-But-phenyl 139-42 75 NHMe Cl-0-phenyl oii 76 NHMe Me direct bond 4-CI-phenyl 138-40 77 NHMe Me direct bond 4-benzyloxyphenyl 159-62 78 NHMe Me direct bond 2-naphthyl 132-4 79 NHMe Me-C_C-phenyl 112-6 80 NHMe Me direct bond 3CF3-phenyl 135-7 81 NHMe Me direct bond 4-biphenylyl 169-70 82 NHMe Me-C=C-tert-butyl 130-1 83 NHMe Me-CH2SC (SMe) = N-N = CH-3-CF3-phenyl 63-7 Cmp Z R¹ A R² m.p./°C 84 NHMe Me-CH2SC (SMe) = N-N=CH-4-F-phenyl 119-22 85 NHMe Me -CH2SC (SMe)=N- 4-tolyl oil 86 NHMe Me-CH20-3-PhO-phenyi 93-5 87 NHMe Me-CH20-4PhO-phenyl 90-3 88 NHMe Me-CH20-3-biphenylyl 105-9 89 NHMe Me -CH2ON=C(Me)- 4-Cl-phenyl oil 90 NHMe Me-CH20N=C (Me)- 4-CI-phenyl 107-11 91 NHMe Me direct bond 4-CF3-phenyl 135-6 92NHMe Medirect bond3-F-phenyi114-5 93 NHMe Me direct bond 3-Cl-phenyl 110-3 94 NHMe Me -C#C- MeOC(Me)2- 94-8 95 NHMe MeMe-CH20N=C (Me)- 3-CF3-phenyl oil 96 NHMe Me-CH20-4-biphenylyl 152-4 97 NHMe Me direct bond 2-F-phenyl 129-30 98 NHMe Me direct bond 2-CI-phenyl 93-4 99 NHMe Me direct bond 2-CF3-phenyl 130-1 100 NHMe Me direct bond 2-biphenylyl 147-8 101 NHMe Me direct bond 4-PhO-phenyl 124-6 102 NHMe t Me | direct bond 3-biphenylyl 122-4 103 NHMe Me direct bond 4-CF3-phenyl 123-4 104 NHMe Me direct bond 3-PhO-phenyl 102-4 105 NHMe Me direct bond CF3 (CF2) 3-oii 106 NHMe H direct bond 4-(4-CI-phenyl)-2-thiazolyl(4-CI-phenyl)-2-thiazolyl 170-2 107 MeO Cl-CH20-3-biphenylyl 85-8 108 MeO Cl -CH2O- 4-l-phenyl 131-32 109 MeO Cl -CH2O- 4-biphenylyl 150-3 110 MeO Cl-CH20N = C (Me)-Cf = NOMe)-phenyl 111 MeO Cl -CH2O- 4-[(MeO)N=C(Me)]-phenyl 76-83 112 MeO I-CH20N = CH-3, 5-CI2-phenyl 112-4 113 MeO H-O-phenyl oil 114 MeO Cl -CH2ON=C(Me)- 4-PhO-phenyl 88-9 Cmp Z R¹ A R² m.p./°C 115 MeO Cl -CH2ON=C(Me)- 3-PhO-phenyl 91-3 116 MeO H-0-H oil 117 MeO Me direct bond 3-(4-Cl-phenyl)-1,2,4- 109-11 oxadiazol-5-yl 118 MeO Me direct bond 3- (3-CF3-phenyl)-1,2,4-102-4 oxadiazol-5-yl 119 MeO H-OCH2-4-CI-phenyl 80-1 120 MeO H-CH20-4-CI-phenyl 64-8 121 MeO H-CH20-3-PhO-phenyi oil 122 MeO H-CH20N = CH-4-CI-phenyl 103-5 123 MeO H-CH20N = C (Me)-3-CF3-phenyl 49-51 124 MeO H-CH2SC (SMe) = N-N = CH-4-CI-phenyl oil 125 Me0 Cl -CH2SC(SMe)=N-N=C(Me)- 4-F-phenyl 114-5 126 MeO Cl -O- phenyl oil 127 MeO Me direct bond 3-Pri-phenyl 84-5 128 MeO Me direct bond 4-But-phenyl 115-7 129 MeO Me direct bond 4-Cl-phenyl 129-30 130 MeO Me direct bond 4-benzyioxyphenyl 155-7 131 MeO Me direct bond 2-naphthyl 123-4 132 MeO Me direct bond 3-CF3-phenyl 104-7 133 MeO Me direct bond 4-biphenylyl 179-80 134 MeO H-OCH2-phenyl oil 135 MeO Me-CH2SC (SMe) N-N = CH-3-CF3-phenyl oil 136 MeO MeO-CH2SC (SMe) N-N =CH-4-F-phenyl oil 137 MeO Me CH2SC (SMe) = N-4-tolyl oil 138 MeO Me-CH20-3-PhO-phenyl 67-9 139 MeO Me-CH20-4-PhO-phenyl 81-4 140 MeO Me-CH20-3-biphenylyl 153.1 141 MeO Me-CH20N = C (Me)-4-CI-phenyl oil 142 MeO Me-CH20N = CH-4-CI-phenyl 75-9 143 MeO Me-C=-C-phenyl 135-8 144 MeO Me-C-C-tert-butyl 123-4 Cmp Z R¹ A R² m.p./°C 145 MeO Me-C=C-MeOC (Me) 2- 101-2 146 MeO Me -C#C- trimethylsilyl 136-9 147 MeO Me direct bond 3-F-phenyl 106-7 148 MeO Me direct bond 4-CF3-phenyl 140-2 149 MeO Me direct bond 3-CI-phenyl 105-9 150 MeO Me-CH20N=C (Me)-3-CF3-phenyl 62-4 151 MeO Me-CH20-4-biphenylyl 128-32 152 MeO Me direct bond 2-F-phenyl 73-4 153 MeO Me direct bond 2-Cl-phenyl 88-9 154 MeO Me direct bond 2-CF3-phenyl 106-7 155 MeO Me direct bond 2-biphenylyl 89-90 156 MeO Me direct bond 3-PhO-phenyl 103-5 157 MeO Me direct bond 3-biphenylyl 107-9 158 MeO Me direct bond 4-(4-Cl-phenyl)-2-thiazolyl 95-7 159 MeO Me direct bond 4-CF30-phenyl 96-7 160 MeO Me direct bond 3-PhO-phenyl 115-7 161 MeO Me direct bond CF3(CF2)3- oil 162 MeO Me-0-3, 4-xylyl 66-9 163 NHMe Me-CH2-0-4-biphenylyl 163-5 164 NHMe Me-C-C-trimethylsilyl 132-4 165 MeO Me-CH2SC 166 NHMe Me direct bond 3-formylphenyl 128-30 167 NHMe Me-0-3, 4-xylyl 66-9 168 MeO Me-0-3, 4-xylyl 111-3 169 NHMe H direct bond 4-biphenylyl 143-8 170 NHMe H direct bond 5-(CF3CF2)-1,2,4- 62-3.5 oxadiazol-3-yi 171 NHMe Me direct bond 2-F-phenyl 108-10 172 NHMe Me direct bond 2-PhO-phenyl 90-2 173 NHMe Me-0-3-PhO-phenyl oil 174 NHMe Me-0-4-PhO-phenyl 118-9 175 NHMe Me-0-4-biphenylyl 112-4 176 NHMe Me-O-4-F-phenyl 82-4 Cmp Z R1 A R2 m. p./°C 177 NHMe Me-0-3-CF3-phenyl oil 178 NHMe Me-0-4-CF30-phenyl 96-8 179 NHMe Me-0-3-biphenylyl 153-5 180 NHMe Me direct bond 4-MeO-phenyl 146-8 181 NHMe Me direct bond 5-Me-1,2,4-oxadiazol-3-yl 123-5 182 NHMe Me direct bond 4-Me-thiazol-2-yl 119-21 183 MeO H direct bond 5-(CF3CF2)-1,(CF3CF2)-1, 2,4-56-8 oxadiazol-3-yl 184 MeO Me-0-3-PhO-phenyl oil 185 MeO Me -O- 4-PhO-phenyl oil 186 MeO Me-0-4-biphenylyl oil 187 MeO Me-0-4-F-phenyl oil 188 MeO Me direct bond 2-PhO-phenyl 80-2 189 MeO Me-0-3-CF3-phenyl oil 190 MeO Me-O-4-CF30-phenyl oil 191 MeO H direct bond 4-But-thiazol-2-yl oil 192 MeO Me-0-3-biphenylyl oil 193 MeO H direct bond 4-Me-thiazol-2-yl 68-70 194 MeO Me direct bond 5-Me-1,2,4-oxadiazol-3-yl 133-5 195 MeO Me direct bond 4-MeO-Ph 145-7 196 MeO Me -C(=O)-O- -CH (Me)Ph oil 197 MeO Me -C(=O)-O- t-butyl oil 198 MeO H direct bond 6-CI-benzothiazol-2-yl 136-7 199 MeO Me -C(=O)-O- -CH(Me)CH2CH(Me)2 oil 200 MeO Me direct bond 2-Me-1,3,4-oxadiazol-5-yl 115-7 201 MeO Me-C (=O)-0-4-CI-phenyl-CH (Me)-oil 202 MeO Me direct bond 3-(4-CI-phenyl) thiazol-2-yl(4-CI-phenyl) thiazol-2-yl 113-4 203 MeO Me direct bond 5-C2F5-1,2,4-oxadiazol-3-yl 81-3 204 MeO H direct bond 5-(4-Cl-phenyl)-1,2,4- 127-8 oxadiazol-3-yl 205 MeO H direct bond 4-(4-F-phenyl)-thiazol-2-yl(4-F-phenyl)-thiazol-2-yl 94-5 206 MeO H direct bond 4-phenylthiazol-2-yl oil 207 MeO H direct bond 5- (4-CF3-phenyl)-1,2,4-132-3 Cmp Z R¹ A R² m.p./°C oxadiazol-3-yl 208 MeO H direct bond 5-phenyl-1,2,4-oxadiazol-3- 106-7 yl 209 MeO H direct bond 2- (4-CF3-phenyl)-1, 3,4-130-1 oxadiazol-5-yl 210 MeNH Me direct bond 3-MeO-phenyl 120-2 211 MeNH Me direct bond 4-CN-phenyl 170-1 212 MeNH H direct bond 4-CF30-phenyl 95-6 213 MeNH H direct bond 4-tbutylthiazol-2-yl oil 214 MeNH H direct bond 3-PhO-phenyl oil 215 MeNH Me direct bond 3-CF30-phenyl 129-31 216 MeNH Me-C =O)-0-PhCH (Me)- oil 217 MeNH Me -C(=O)-O- tert-butyl 112-4 218 MeNH Me direct bond 6-Cl-benzothiazol-2-yl 137-8 219 MeNH Me -C(=O)-O- -CH(Me)CH2CH(Me)2 oil 220 MeNH Me direct bond 3-CN-phenyl 152-5 221 MeNH H direct bond 3-CF3-phenyl 100-2 222 MeNH Me direct bond 4-(4-CI-phenyl)-thiazol-2-yl 151-153 223 MeNH Me direct bond--5-C2Fs-1, 2, 4-oxadiazol-3-yl 91-2 224 MeNH Me direct bond 5- (4-CI-phenyl)-1, 2,4-167-8 oxadiazol-3-yi 225 MeNH H direct bond 4-(4-F-phenyl) thiazol-2-yl 149-50 226 MeNH H direct bond 4-phenylthiazol-2-yl 118-119 227 MeNH Me-C (= 4-CI-phenyl-CH (Me)- oil 228 MeNH Me direct bond 5- (4-CF3-phenyl)-1,2,4-165-7 oxadiazol-3-yl 229 MeNH Me direct bond 5-phenyl-1,2,4-oxadiazol-3- 138-9 Xi 230 MeNH Me direct bond 4- (3-CF3-phenyl)-thiazol-2- 154-6 il 231 MeNH Me direct bond 4- (3-CF3SO20-phenyl)- oil thiazol-2-yl 232 MeO F direct bond 4-MeO-phenyl Cmp Z R 1 A R2 m. p./°C 233 NHMe F direct bond 4-MeO-phenyl 234 MeO Br direct bond 4-MeO-phenyl 235 MeNH Br direct bond 4-MeO-phenyi 236 MeO I direct bond 4-MeO-phenyl 237 MeNH I direct bond 4-MeO-phenyl

Those compounds in the above table which do not have discrete melting points have the following characteristic 1 H N. M. R. data in CDC13.

Compound 11 1 H N. M. R. 6 (ppm) (mixture of E/Z isomers) 2.48 and 2.56 (3H, 2xs, CH3S), 3.79 and 3.82 (3H, 2xs, CH30), 3.98 and 4.02 (3H, 2xs, CH30), 4.20 and 4.32 (2H, 2xs, CH2-Ar), 6.94-7.80 (7H, m, 7xAr-H) and 8.30 (1H, s, Ar-CH).

Compound 14 ¹H N.M.R. #(ppm) (mixture of E/Z isomers) 2.48 and 2.58 (3H, 2xs, CH3S), 2.78 and 2.82 (3H, 2xd, NHCH3), 3.90 (3H, 2xs, CH30), 4.21 and 4.33 (2H, 2 x s, CH2-Ar), 6.60 (1H, br. s, NH), 7.00-7.80 (7H, m, 7xAr-H) and 8.28 (1H, s, Ar- CH).

Compound 18 1H N. M. R. 8 (ppm) 2.28 (3H, s, CH3-Ar), 2.44 (3H, s, CH3S), 3.80 (3H, s, CH30), 3.98 (3H, s, CH30), 4.22 (2H, s, CH2-Ar) and 6.74-7.34 (7H, m, 7xAr-H).

Compound 34 1H N. M. R. 8 (ppm) 2.30 (3H, s, CH3-Ar), 2.44 (3H, s, CH3S), 2.84 (3H, d, CH3NH), 3.90 (3H, s, CH30), 4.20 (2H, s, CH2-Ar), 6.60 (1H, d, CH3NH) and 6.74-7.32 (7H, m, 7xAr-H).

Compound 50 1 H N. M. R. 8ppm) 2.25 (3H, s, CH3), 2.80 (3H, d, CH3NH), 3.90 (3H, s, CH30N), 5.15 (2H, s, CH20), 6.65 (1H, br. s, CH3NH), 7.00-7.90 (7H, m, 7 x Ar-H).

Compound 51 1 H N. M. R. 6 (ppm) 2.25 (3H, s, CH3), 2.85 (3H, d, CH3NH), 3.90 (3H, s, CH30N), 5.15 (2H, s, CH20), 6.60 (1H, br. s, CH3NH), 7.00-7.60 (7H, m, 7 x Ar-H).

Compound 52 1 H N. M. R. 8 (ppm) (mixture of E/Z isomers) 1.90-2.00 (3H, 3 x s, CH3), 2.05- <BR> <BR> <BR> <BR> 2.10 (3H, 3 x s, CH3), 2.85 (3H, d, CH3NH), 3.90-3.95 (6H, 4 x s, CH30N), 5.10 (2H, s, CH2O), 6.65-6.75 (1H, 2 x br. s, CH3NH), 6.85-7.35 (3H, m, 3 x Ar-H).

Compound 54 1 H N. M. R. 8 (ppm) 2.20 (3H, s, CH3), 2.85 (3H, d, CH3NH), 3.95 (3H, s, CH30N), 5.00 (2H, s, CH2O), 6.70 (1 H, br. s, CH3NH), 6.85-6.95 (2H, m, 2 x Ar-H), 7.20-7.40 (6H, m, Ar-H).

Compound 55 1 H N. M. R. 8 (ppm) (mixture of E/Z isomers) 2.20-2.25 (3H, 2 x s, CH3), 2.85 (3H, d, CH3NH), 3.90-4.00 (6H, 4 x s, CH30N), 5.00-5.10 (2H, 2 x s, CH20), 6.70 (1H, br. s., CH3NH), 6.90-7.45 (7H, m, 7 x Ar-H).

Compound 69 1H N. M. R. 8 (ppm) 2.27 (3H, s, CH3), 2.83 (3H, d, CH3NH), 3.90 (3H, s, CH30N), 4.98 (2H, s, CH20), 6.62 (1H, br. s, CH3NH), 6.84-7.90 (8H, m, 8 x Ar-H).

Compound 89 1 H N. M. R. 8 (ppm) (mixture of E/Z isomers) 2.20 (3H, 2 x s, N=C-CH3), 2.35 (3H, s, CH3), 2.80-2.90 (3H, 2 x d, CH3N), 3.95 (3H, 2 x s, CH30), 5.10 (2H, s, CH20), 6.60 (1 H, br. s., NH), 6.75-7.60 (7H, m, 7 x Ar-H).

Compound 95 1H N. M. R. 6 (ppm) 2.25 (3H, s, N=C-CH3), 2.35 (3H, s, CH3), 2.80 0 (3H, d, CH3N), 3.90 (3H, s, CH30), 5.15 (2H, s, CH2O), 6.60 (1H, br. s., NH), 6.75- 7.90 (7H, m, 7 x Ar-H).

Compound 105 1 H N. M. R. 8 (ppm) 2.41 (3H, s, CH3-Ar), 2.89 (3H, d, CH3NH) 3.93 (3H, s, CH30N), 6.64 (1H, br. s, CH3NH), 6.85 (1H, s, Ar-H), 7.22 (1H, d, Ar-H), 7.32 (1H, d, Ar-H).

Compound 121 1 H N. M. R. 8 (ppm) 3.80 (3H, s, CH30), 4.01 (3H, s, CH30N), 4.98 (2H, s, CH2O), 6.58-7.36 (8H, m, 8 x Ar-H).

Compound 124 1 H N. M. R. 8 (ppm) (mixture of E/Z isomers) 2.50 and 2.59 (3H, 2 x s, CH3S), 3.83 and 3.84 (3H, 2 x s, CH30), 4.04 and 4.05 (3H, 2 x s, CH30N), 4.28 and 4.38 (2H, 2 x s, CH2-Ar), 6.86-7.85 (8H, m, 8 x Ar-H), 8.34 and 8.36 (1H, 2 x s, CH=N).

Compound 135 1H N. M. R. 8 (ppm) (mixture of E/Z isomers) 2.35 (3H, s, Ar-CH3), 2.50-2.60 (3H, 2 x s, CH3S), 3.90 (3H, 2 x s, CH30), 4.00 (3H, 2 x s, CH30), 4.25-4.35 (2H, 2 x s, CH2S), (7H, m, 7 x Ar-H), 8.40 (1H, 2 x s, N=CH).

Compound 136 1 H N. M. R. 8 (ppm) (mixture of E/Z isomers) 2.35 (3H, s, Ar-CH3), 2.50-2.60 (3H, 2 x s, CH3S), 3.80 (3H, 2 x s, CH30), 4.00 (3H, 2 x s, CH30), 4.20-4.30 (2H, 2 x s, CH2S), 6.75-7.85 (7H, m, 7 x Ar-H), 8.35 (1H, 2 x s, N=CH).

Compound 137 1 H N. M. R. 5 (ppm) (mixture of E/Z isomers) 2.35 (6H, s, Ar-CH3), 2.45 (3H, br. s, CH3S), 3.75-3.85 (3H, 2 x s, CH30), 4.00-4.10 (3H, 2 x s, CH30), 4.25 (2H, br. s, CH2S), 6.75-7.20 (7H, m, 7 x Ar-H).

Compound 141 1H N. M. R. 8 (ppm) 2.20 (3H, s, N=C-CH3), 2.30 (3H, s, CH3), 3.70 (3H, s, CH30), 4.00 (3H, s, CH30), 5.10 (2H, s, CH2O), 6.70-7.60 (7H, m, 7 x Ar-H).

Compound 161 1 H N. M. R. 5 (ppm) 2.40 (3H, s, CH3-Ar), 3.82 (3H, s, CH30), 4.02 (3H, s, CH30N), 6.86 (1H, s, Ar-H), 7.25 (1H, d, Ar-H), 7.34 (1H, d, Ar-H).

Compound 177 1H N. M. R. 6 (ppm) 2.35 (3H, s, CH3-Ar), 2.9 (3H, d, NHCH3), 3.9 (3H, s, OCH3), 6.4 (1H, d), 6.6 (1 H, broad, NH), 6.7 (1H, dd, Ar-H), 7.05-7.4 (5H, m).

Compound 184 1H N. M. R. 8 (ppm) 2.35 (3H, s, CH3-Ar), 3.8 (3H, s, OCH3), 4.0 (3H, s, OCH3), 6.45 (1H, d), 6.6-6.75 (4H, m), 6.95-7.4 (7H, m).

Compound 185 1 H N. M. R. 8 (ppm) 2.35 (3H, s, CH3-Ar), 3.8 (3H, s, OCH3), 4.0 (3H, s, OCH3), 6.4 (1H, d), 6.65 (1H, dd), 6.9-7.4 (10H, m).

Compound 186 <BR> <BR> <BR> <BR> 1 H N. M. R. b (ppm) 2.35 (3H, s, CH3-Ar), 3.8 (3H, s, OCH3), 4.0 (3H, s, OCH3), 6.5 (1H, d), 6.7 (1H, dd), 7.0 (2H, d), 7.19 (1H, d), 7.35 (1H, m), 7.45 (2H, m) 7.55 (4H, m).

Compound 187 1 H N. M. R. 8 (ppm) 2.35 (3H, s, CH3-Ar), 3.8 (3H, s, OCH3), 4.0 (3H, s, OCH3), 6.4 (1H, d), 6.6 (1H, dd), 6.85-7. 05 (4H, m), 7.15 (1H, d).

Compound189 <BR> <BR> <BR> <BR> 1H N. M. R. 5 (ppm) 2.35 (3H, s, CH3-Ar), 3.8 (3H, s, OCH3), 4.0 (3H, s, OCH3),<BR> <BR> <BR> <BR> <BR> 6.4 (1H, d), 6.7 (1H, dd), (5H, m).

Compound 190 <BR> <BR> <BR> <BR> ¹H N.M.R. #(ppm) 2.35 (3H, s, CH3-Ar), 3.8 (3H, s, OCH3), 4.0 (3H, s, OCH3), 6.4 (1H, d), 6.7 (1H, dd), 6.9-7.2 (5H, m).

Compound192 1H N. M. R. 8 (ppm) 2.35 (3H, s, CH3-Ar), 3.8 (3H, s, OCH3), 4.0 (3H, s, OCH3), 6.5 (1H, d), 6.75 (1H, dd), 6.9 (1H, m), 7.15-7.6 (9H, m).

Compound196 <BR> <BR> <BR> <BR> ¹H N.M.R. #(ppm) 1.62 (3H, d, Me), 2.38 (3H, s, CH3-Ar), 3.8 (3H, s, OCH3), 4.02 (3H, s, OCH3), 6.08 (1H, q, CHMe), 7.20-7.45 (7H, m, Ar-H) and 7.75 (1H, <BR> <BR> <BR> <BR> d, Ar-H).<BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> <P>Compound1 97 1H N. M. R. 8 (ppm) 1.55 (9H, s, (Me) 3C), 2.38 (3H, s, CH3-Ar), 3.8 (3H, s, OCH3), 4.00 (3H, s, OCH3) and 7.15-7.62 (3H, m, Ar-H).

Compound 199 ¹H N.M.R. #(ppm) 0.90 (6H, d, (Me) 2CH), 1.28 (3H, d, MeCH), 1.37 (1H, m, CH (Me) 2), 1.67 (2H, m,-CH2-), 2.40 (3H, s, CH3-Ar), 3.82 (3H, s, OCH3), 4.03 (3H, s, OCH3), 5.18 (1H, m,-CHO-), 7.20-7.37 (2H, m, Ar-H) and 7.69 (1H, d, Ar-H).

Compound 201 1 H N. M. R. ppm) 1.59 (3H, d, MeCH), 2.38 (3H, s, CH3-Ar), 3.77 (3H, s, OCH3), 3.98 (3H, s, OCH3), 6.00 (1H, q,-CHMe), 7.20-7.39 (2H, m, Ar-H) and 7.71 (1H, d, Ar-H).

Compound 206 1 H N. M. R. 6 (ppm) 3.86 (3H, s, CH30CO), 4.06 (3H, s, CH30N) and 7.03-7.97 (10H, m, Ar-H).

Compound 213 ¹H N.M.R. #(ppm) 1.36 (9H, s, Me3C), 2.89 (3H, d, MeNH), 3.95 (3H, s, CH30N), 6.66 (1H, b, NH) and 6.86-7.66 (5H, m, Ar-H).

Compound 214 1H N. M. R. 5 (ppm) 2.86 (3H, d, MeNH), 3.97 (3H, s, CH30N) and 6.66-7.20 (13H, m, Ar-H).

Compound 215 1H N. M. R. 8 (ppm) 2.18 (3H, s, Me-ring), 2.86 (3H, d, MeNH), 3.96 (3H, s, CH30N) and 6.58-7.24 (7H, m, Ar-H).

Compound 216 ¹H N.M.R. #(ppm) 1.63 (3H, d, MeCH), 2.40 (3H, s, CH3-Ar), 2.80 (3H, d, NHMe), 3.91 (3H, s, OCH3), 6.05 (1H, q, CHMe), 6.63 (1H, br q, NH), 7.16- 7.42 (7H, m, Ar-H) and 7.72 (1H, d, Ar-H).

Compound 219 1H N. M. R. S (ppm) 0.88 (6H, d, Me2CH-), 1.25 (3H, d, MeCH), 1.32 (1H, m, CHMe2), 1.63 (2H, m,-CH2-), 2.38 (3H, s, CH3-Ar), 2.78 (3H, d, NHMe), 3.86 (3H, s, OCH3), 5.14 (1H, m,-CHO-), 6.78 (1H, br q, NH), 7.19 (1H, d, Ar-H), 7.32 (1H, s, Ar-H) and 7.63 (1H, d, Ar-H).

Compound 230 ¹H N.M.R. #(ppm) 1.62 (3H, d, MeCH), 2.39 (3H, s, CH3-Ar), 2.83 (3H, d, NHMe), 3.92 (3H, s, OCH3), 6.02 (1H, q,-CHMe), 6.66 (1H, brq, NH), 7.22- 7.42 (6H, m, Ar-H) and 7.71 11 H, d, Ar-H).

Compound 231 1 H N. M. R. 8 (ppm) 2.86 (3H, d, MeNH), 3.97 (3H, s, CH30N), 6.69 (1H, b, NH) and 7.03-8.00 (9H, m, Ar-H).

The following compounds of formula Im, i. e. compounds of general formula la where R2 is 4-methoxylphenyl, A is a direct bond, m is 1, R1 is methyl para to -A-R2, were prepared by methods analogous to those of the previous Examples. Cmp X Y Z m.p./°C 301 S Me MeO 302 S Me NHMe 303 0 CF3 MeO 304 O CF3 NHMe 305 O CF2H MeO 306 O CF2H NHMe 307 O CFH2 MeO 308 O CFH2 NHMe

Test Examples Compounds were assessed for activity against one or more of the following: Phytophthora infestans: late tomato blight Plasmopara viticola: vine downy mildew Erysiphe graminis f. sp. tritici: wheat powdery mildew Pyricularia oryzae: rice blast Leptosphaeria nodorum: glume blotch Aqueous solutions or dispersions of the compounds at the desired concentration, including a wetting agent, were applied by spray or by drenching the stem base of the test plants, as appropriate. After a given time, plants or plant parts were inoculated with appropriate test pathogens before or after application of the compounds as appropriate, and kept under controlled environmental conditions suitable for maintaining plant growth and development of the disease. After an appropriate time, the degree of infection of the affected part of the plant was visually estimated. Compounds are assessed on a score of 1 to 3 where 1 is little or no control, 2 is moderate control and 3 is good to total control. At a concentration of 500 ppm (w/v) or less, the following compounds scored 2 or more against the fungi specified.

Phytophthora infestans 15,25,43,57,72,73,104,106,129,132,158,173,174,180,197,202 and 222.

Plasmopara viticola: 64,66-72,78,82,88,94,104,114,120-125,127,145,146,158,164,165 , 184,186,188,217 and 222.

Erysiphe graminis f. sp. tritici: 7,35,53,55,61,65,72,73,76,80,81,91-94,96,98,101,103,104,106, 127,129,149,150,152-154,159,164,169,176,180,187,190,211,215, 217,218,220-223 and 225-231.

Pyricularia oryzae 16-21,23,25,36-40,47,62,65-67,72-74,76,78-82,88,96, 98,103,105-107,120,127,129,132,140,142,143,157,159,160,161, 167,169,173-175,179,180,191,194,195,199 and 231.

Leptosphaeria nodorum 12,23,31-33,37,38,47,54,58,61,65,72,76,78,80-82,90-94,101, 132,137-139,141,147,148,156, 220-222 and 225-229.