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Title:
DITHIOCARBAZONIC ACID DERIVATIVES AS PESTICIDES
Document Type and Number:
WIPO Patent Application WO/1998/050352
Kind Code:
A1
Abstract:
The invention relates to compounds of general formula (I), wherein X is O or NH; Y is CH or N; W is methyl or methoxy; R?1� and R?2�, which may be the same or different, are optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted phenyl or optionally substituted heterocyclyl; R?3� has the same meaning as R?2� or can be hydrogen; or R?2� and R?3� together with the carbon to which they are attached form a 5- to 7-membered heterocyclyl, cycloalkyl or cycloalkenyl group which is optionally substituted; R?7� is alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, halogen, cyano, alkoxy, alkylthio, haloalkoxy, and optionally substituted phenyl; and q is 0 to 4.

Inventors:
Briggs, Geoffrey Gower (Chesterford Park, Saffron Walden, Essex CB10 1XL, GB)
Cornell, Clive Leonard (Chesterford Park, Saffron Walden, Essex CB10 1XL, GB)
Thomas, Peter Stanley (Chesterford Park, Saffron Walden, Essex CB10 1XL, GB)
Application Number:
PCT/GB1998/001234
Publication Date:
November 12, 1998
Filing Date:
April 28, 1998
Export Citation:
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Assignee:
AGREVO UK LIMITED (Hauxton, Cambridge CB2 5HU, GB)
Briggs, Geoffrey Gower (Chesterford Park, Saffron Walden, Essex CB10 1XL, GB)
Cornell, Clive Leonard (Chesterford Park, Saffron Walden, Essex CB10 1XL, GB)
Thomas, Peter Stanley (Chesterford Park, Saffron Walden, Essex CB10 1XL, GB)
International Classes:
A01N47/42; C07C337/08; C07D207/335; C07D209/14; C07D213/53; C07D213/61; C07D213/89; C07D215/12; C07D239/34; C07D277/28; C07D307/52; C07D307/74; C07D307/81; C07D333/22; C07D207/32; (IPC1-7): C07C337/04; C07D213/53; C07D333/22; C07D307/52; C07D213/61; C07D333/28; C07D207/32; C07D215/12; C07D271/06; A01N47/42
Foreign References:
EP0299694A21989-01-18
DE4439334A11996-05-09
Attorney, Agent or Firm:
Sewell, Richard Charles (AgrEvo UK Limited, Patent Dept. Chesterford Par, Saffron Walden Essex CB10 1XL, GB)
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Claims:
CLAIMS
1. The invention provides a compound of general formula I wherein X is O or NH; Y is CH or N; W is methyl or methoxy; R1 and R2, which may be the same or different, are optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted phenyl or optionally substituted heterocyclyl; R3 has the same meaning as R2 or can be hydrogen; or R2 and R3 together with the carbon to which they are attached form a 5 to 7 membered heterocyclyl, cycloalkyl or cycloalkenyl group which is optionally substituted; R7 is alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, halogen, cyano, alkoxy, alkylthio, haloalkoxy, and optionally substituted phenyl; and q is 0 to 4.
2. A compound according to claim 1 wherein the double bond attached to Y is of E geometry.
3. A compound according to claim 1 or 2 wherein R1 is optionally substituted alkyl.
4. A compound according to claim 3 where R1 is methyl.
5. A compound according to any preceding claim wherein R3 is hydrogen.
6. A compound according to any preceding claim wherein q is 0.
7. A compound according to any preceding claim wherein R2 is optionally substituted alkyl, optionally substituted phenyl or optionally substituted heterocyclyl.
8. A compound according to claims 7 wherein when R2 is optionally substituted branched alkyl.
9. A compound according to claim 8 wherein R2 is optionally substituted tertiary butyl.
10. A compound according to claim 7 wherein when R2 is a phenyl group substituted by one or more electronwithdrawing groups.
11. A compound according to claim 10 wherein the electron with drawing group or groups are halogen.
12. A compound according to claim 7 wherein when R2 is optionally substituted heterocyclyl, the heterocyclyl group is aromatic and deactivating.
13. 3 A compound according to claim 1 2 wherein the heterocyclyl group is optionally substituted pyridine or pyrimidine.
14. 14 A compound according to any preceding claim wherein X is NH, Y is N and W is methoxy.
15. 1 5 A pesticidal composition comprising compounds as claimed in any preceding claim in admixture with an agriculturally acceptable diluent or carrier.
Description:
DIEIOCARBAZONIC ACID DERIVATIVES AS PESTICIDES This invention relates to compounds having pesticidal, especially fungicidal, insecticidal and acaricidal, activity.

The invention provides a compound of general formula I wherein X is O or NH; Y is CH or N; W is methyl or methoxy; R1 and R2, which may be the same or different, are optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted phenyl or optionally substituted heterocyclyl; R3 has the same meaning as R2 or can be hydrogen; or R2 and R3 together with the carbon to which they are attached form a 5- to 7- membered heterocyciyl, cycloalkyl or cycloalkenyl group which is optionally substituted; R7 is alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, halogen, cyano, alkoxy, alkylthio, haloalkoxy, and optionally substituted phenyl; and q is 0 to 4, preferably 0.

Any alkyl group may be straight or branched and is preferably of 1 to 10 carbon atoms, especially 1 to 7 and particularly 1 to 5. Alkenyl and alkynyl groups are generally of 3 to 6 carbon atoms. Cycloalkyl or cycloalkenyl groups are preferably of 3 to 8 carbon atoms.

Substituents, when present on any alkyl, cycloalkyl, cycloalkenyl, alkenyl or alkynyl moiety include trialkylsilyl, halogen, cyano, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted haloalkyl, hydroxy, nitro, optionally substituted amino, acyl, acyloxy, optionally substituted phenyl, optionally substituted heterocyclyl, optionally substituted phenoxy, optionally substituted phenylthio, optionally substituted hetercyciyloxy, or optionally substituted heterocyclylthio.

Any cycloalkyl or cycloalkenyl groups may also be substituted by alkyl, alkenyl or alkynyl, all of which may be substituted as described above.

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, imidazolyl, dioxolanyl, oxazolyl, thiazolyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, pyranyl, pyridyl, piperidinyl, dioxanyl, morpholino, dithianyl, thiomorpholino, pyridazinyl, pyrimidinyl, pyrazinyl, piperazinyl, triazinyl, thiazolinyl, benzimidazolyl, tetrazolyl, benzoxazolyl, imidazopyridinyl, benzoxazinyl, benzothiazinyl, oxazolopyridinyl, benzofuranyl, quinolinyl, quinazolinyl, quinoxalinyl, sulfolanyl, dihydroquinazolinyl, benzothiazolyl, phthalimido, benzofuranyl, azepinyl, oxazepinyl, thiazepinyl, diazepinyl and benzodiazepinyl.

Heterocyclyl groups may themselves be substituted.

Substituents when present on any phenyl or heterocyclyl group may for example be halogen, trialkylsilyl, CN, NO2, acyl, O-acyl, SF5 or a group E1, OE1, -S(O)nE or -(E1)=NOE2, where n is O, 1 or 2, E1 and E2, which may be the same or different, are hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted acyl, optionally substituted phenyl or optionally substituted heterocyclyl. E1 can also be optionally substituted amino. Alternatively two adjacent groups on the phenyl or heterocyclyl group together with the atoms to which they are attached form a carbocyclic or heterocyclic ring, which may be similarly substituted.

Any amino group may be substituted for example by one or two optionally substituted alkyl or acyl groups, or two substituents can form a ring, preferably a 5 to 7- membered ring, which may be substituted and may contain other hetero atoms, for example morpholine, or piperidine.

The term acyl includes the residue of sulfur and phosphorus-containing acids as well as carboxylic acids. Examples of acyl groups are thus -C(=O)R4, -C(=o)oR4, <BR> <BR> <BR> <BR> <BR> -C(=Z)NR4R5, -C(=O)N(R4)0R5, -C(=O)ONR4R5, -C(=O)N(R4)NR5R6, -C(=o)SR4, -C(=S)SR4, -S(o)pR4, -S(0)20R4, S(O)pR4R5, -P(=Z)(OR4)(0R5), -C(=O)-C(=O)ORS, where R4, R5 and R6 which may be the same or different, are hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted phenyl or optionally substituted heterocyclyl or R5 and R6 together with the atom(s) to which they are attached can form a ring; p is 1 or 2; and Z isQorS.

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 addition, each crossed bond depicted in general formula I represents a double bond having either Z or E stereochemistry.

We have found that compounds where the double bond attached to Y is of E geometry generally provide the highest activity for combating fungi. in addition, we have found that R1 is preferably optionally substituted alkyl, especially methyl.

Further we have found that R3 is preferably hydrogen.

R2 is preferably optionally substituted alkyl, optionally substituted phenyl or optionally substituted heterocyclyl.

When R2 is an optionally substituted alkyl group, preferred groups are optionally substituted branched alkyl, particularly optionally substituted tertiary butyl. When substituted, the substituents are preferably halogen, alkyl or optionally substituted phenyl, which when substituted is substituted by alkyl.

When R2 is an optionally substituted phenyl group or an optionally substituted phenylalkyl group, preferred substituents are alkyl, haloalkyl, halogen, cyano, nitro, haloalkoxy, alkoxy, aryloxy or acyl. Particularly preferred substituents are electron withdrawing groups, especially halogen.

When R2 is an optionally substituted heterocyclyl group, preferred groups are deactivating aromatic heterocyclyl groups, especially pyridine or pyrimidine. When the heterocyclyl group is substituted, preferred substituents are alkyl, haloalkyl, alkoxy, haloalkoxy, halogen or aryloxy.

Although good activity has been found for all combinations of X, Y and W, we have found particularly good activity when X is NH, Y is N and W is methoxy.

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 sasakill, grey mould (Botrytis cinerea), damping off (Rhizoctonia solaml, 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, acaricidai 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-fiy, 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.

Diabrntica 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. Suitabie 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 alkylnaphthalene 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 alcohols, 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, biock 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 emulsion, 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 emulsion 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 applied 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 and/or herbicidal resistance.

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

Compounds of general formula I can be prepared by reacting a benzyl bromide of general formula 11 with a dithiocarbazate of general formula Ill, in the presence of a suitable base eg sodium hydride, according to the following reaction scheme.

Scheme 1 3 H R3 (R7)q N 41\ 2 ;q Base BEl5e XX W\ O XMe SR1 W\ XMe SR 0 (Il) (III) Intermediates of formula Ill can be prepared in turn by reacting aldehydes and ketones V with compounds of formula IV. Preferred reaction conditions comprise heating a methanolic solution of IV and V in the presence of a small amount of glacial acetic acid.

Scheme 2 Alkyl dithiocarbazates of formula IV can be prepared by reacting a basic solution of hydrazine hydrate with carbon disulphide followed by addition of a compound of general formula R1Q where Q is a leaving group, eg halogen, alkyl or aryl sulfonate, alkyl sulfate etc. When R1 is methyl, Q is preferably methyl sulfate.

Preferred bases include metal hydroxides [M+(OH)-], such as potassium hydroxide. Alkyl dithiocarbazates IV can either be prepared in one step by addition of R1 Q to the crude reaction mixture or alternatively in two steps by firstly isolating the metallated dithiocarbazate VI as a crystalline solid. When the base is potassium hydroxide the crystalline solid is the mono-potassium salt of dithiocarbazate VI.

Scheme 3 Compounds of formula la, i.e. compounds of general formula I where X is 0 and Y is CH, may be prepared from compounds of formula Ila according to Scheme 5.

Compounds of formula lla may be prepared by methods described in EP 0 299 694.

Scheme 4 (R7) (R7) N Br q N R3 According to SN\ w OMe Scheme 1 N R2 w OMe Scheme 1 SR1 0 0 (Ila) (la) Similarly compounds of formula Ib, i.e. compounds of general formula I where X is O and Y is N, may be prepared according to Scheme 6. Compounds of formula llb may be prepared by methods described in EP 0299694.

Scheme 5 (R7)q (R7)q N N R3 w According N 2 OMe Scheme 1 Br According to N O O (lib) Compounds of formula Ic, i.e. compounds of general formula I where X is NH and Y is N can be prepared by treating compounds of formula lb with a solution of methylamine in a suitable solvent according to Scheme 7. Preferred reaction conditions comprise stirring with 20% methylamine in methanol at room temperature.

Scheme 6 (R7) (R7)q q WS.u: > Xf \nix R2 solution NdnNHMe R2 N - 0 Me SR1 w NHMe N 0 (Ib) (Ic) Alternatively to preparing compounds of general formula I by reacting compounds of formula II with compounds of formula Ill according to Scheme 1, compounds of general formula I can be prepared according to reaction Scheme 8. Preferred reaction conditions for reacting compound Il with compound Ill comprise sodium hydride in tetrahydrofuran. Preferred reaction conditions for reacting compound VII with carbonyl V comprise stirring a methanolic or tetrahydrofuran solution of VII in the presence of a small amount of glacial acetic acid.

Scheme 7 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 starting materials and intermediates of the invention. Structures of isolated novel compounds were confirmed by elemental and/or other appropriate analyses.

Example 1 Methyl 3-methoxy-2-(2-[[1 -(3-methylphenyl)ethylidenehydrnzonoj(methylthio) methylthiomethyliphenyl)acrylate (Compound 1) Sodium hydride (165 mg of a 60% oil dispersion) was added to a solution of methyl [1 -(3-methylphenyl)ethylidene]dithiocarbazate (0.67 g) in dry tetrahydrofuran (20 ml) under an atmosphere of nitrogen. After stirring for 30 minutes, the solution was purged with nitrogen and methyl 3-methoxy-2-[2- (bromomethyl)phenyl]acrylate (see EP 0 299 694 for preparative method) (0.8 g) added. The resulting mixture was stirred for 1 8 hours, quenched with methanol (0.2 ml) and evaporated under reduced pressure. The residue was taken up in diethyl ether, washed with brine, dried (MgS04) and concentrated to give an oil.

Trituration with diethyl ether/hexane gave the titled product as a mixture of geometric isomers, m.p. 102-5 OC.

Preparation of starting materials a) Methyl [1 -(3-methylphenyl)ethylideneidithiocarbazate To a solution of methyl dithiocarbazate (1.22 g) in methanol (10 ml) containing glacial acetic acid (2 drops) was added 3'-methylacetophenone (1.34 g) and the mixture was heated at reflux for 2 hours. The reaction was cooled to room temperature and diluted with diisopropyl ether/hexane 1:1 (8 ml). The resulting solid was filtered and washed with further diisopropyl ether/hexane 1:1 to give the title compound, m.p. 128-130 "C. b) Methyl dithiocarbazate Hydrazine hydrate (48.5 ml) was added to a solution of potassium hydroxide (59 g, 85% purity) cooled to 10 °C. The resultant solution was cooled to 5 "C and carbon disulfide (63.5 ml) was added dropwise using efficient stirring and cooiing. The resultant mixture was stirred at O "C for 1 hour prior to the dropwise addition of dimethyl sulfate (100 ml). The

mixture was stirred at 10 OC for 30 minutes then water (100 ml) was added dropwise followed by further water (250 ml) as a steady stream. The resultant mixture was chilled for 30 minutes and the resulting solid filtered.

The solid was washed with water followed by diethyl ether/hexane 1:1 to give the title product, m.p. 80-81 OC.

Example 2 Methyl 3-methoxy-2-82-[(benzylidenehydrazono)(methylthio)methylthio methyll phenylwacryiate (Compound 6).

To a solution of methyl 3-methoxy-2-f2-[(hydrazono)(methylthio)methylthiomethylj phenyl}acrylate (0.5 g of major isomer) in dry tetrahydrofuran (10 ml) was added benzaldehyde (0.16 ml), followed by glacial acetic acid (2 drops). The reaction mixture was stirred at room temperature for 1 hour. The solvent was removed and the residue purified by silica gel chromatography using petrol (40-60)/ether as eluents to give the title compound as a 1.38:1 mixture of geometric isomers).

Preparation of starting materials Methyl 3-methoxy-2-( 2-[(hydrazono) (methylthio)methylthiomethyll phenyl } acrylate To a solution of methyl dithiocarbazate (1.22 g, starting material from step b) in Example 1) in dry tetrahydrofuran (20 ml) was added, portionwise, sodium hydride (60% dispersion in oil) (400 mg). The solution was stirred at room temperature for 30 minutes before adding dropwise a solution of methyl 3-methoxy-2-[2-(bromomethyl)phenyllacrylate (EP 0 299 694) (2.86 g) in dry tetrahydrofuran (15 ml). The solution was stirred at room temperature for 56 hours and quenched with a few drops of glacial acetic acid. The reaction mixture was poured onto brine (100 ml) and extracted with diethyl ether (3x50 ml). Organic extracts were combined, washed with water, dried over magnesium sulphate, filtered and evaporated to give a crude product. The crude product was purified by silica gel chromatography using diethyl ether and petrol (b.p. 40-60 "C) as eluents to give title compound as an isomeric mixture; 1 H N.M.R. 5(pom, major isomer) 2.34 (3H, s, CH3S), 3.74 (3H, s, CH3O), 3.82 (3H, s, CH300C), 3.98 (2H, s, CH2Ar), 5.60 (2H, s, NNH2), 7.08 (1H, m, ArH), 7.22 (2H, m,

2xArH), 7.30 (1H, m, Ar-H) and 7.60 (1H, s, MeOCH=), 1H N.M.R. #(ppm, minor isomer) 2.36 (3H, s, CH3S), 3.68 (3H, S, CH30), 3.80 (3H, s, CH300C), 4.04 (2H, s, CH2Ar), 5.55 (2H, s N-NH2), 7.08 (1H, m, Ar-H), 7.24 (2H, m, 2xAr-H) and 7.56 (1H, s, MeOCH=).

Example 3 Methyl (E)-2-(methoxyimino)-2-{2-[(3-methylbenzylidenehydrazono)(me thylthio) methylthiomethyli phenyl }acetate (C om pound 1 65) Sodium hydride (150 mg of a 60% oil dispersion) was added to a solution of methyl [1 -(3-methylphenyl)ethylideneidithiocarbazate (0.78 g, starting material from step a) in Example 1) in dry tetrahydrofuran (15 ml). After stirring at room temperature for 15 minutes, a solution containing methyl (E)-2-(methoxyimino)-2- [[2-(bromomethyl)phenyllacetate EP 0299694 (1.0 g) in dry tetrahydrofuran (5 ml) was added. The solution was stirred at room temperature for 24 hours. The solvent was removed and the residue quenched with water. The mixture was extracted (x3) with ether. The ether extracts were combined, washed with brine, dried over magnesium sulphate, filtered and evaporated to give a crude product which was purified by silica gel chromatography (1:4 ethyl acetate: petrol 40-60) to give the title product, m.p. 108-1 1O0C.

Example 4 (E)-2-(Methoxyimino)-N-methyl-2-t 2-[(3-methyl benzylidenehydrazono) (methylthio)methylthiomethyll phenyl }acetamide (C om pound 147) To a solution containing methyl (E) 2-(methoxyimino)-2-[[2-[1-(3-methylphenyl) ethylidinehydroazono] (methylthiomethyl)phenyl] acetate (1.5 g, Compound 165 from Example 3) in tetrahydrofuran (5 ml) and methanol (5 ml) was added 27% w/v solution of methyiamine in methanol (3 ml). The solution was allowed to stir at room temperature for 24 hours. Removal of the solvent followed by trituration of the resultant solid with 1:1 petrol 40-60: diethyl ether gave the title product, m.p. 121-1250 C.

The following compounds of formula Id, i.e. compounds of general formula where R1 is methyl and W is methoxy, q is 0, may be prepared by methods analogous to those of Examples 1 to 4. All isolated compounds exist as a mixture of two or more geometric isomers which may equilibrate in solution. It is possible in some cases to separate the mixture into individual geometric isomers. Those instances where this was attempted have been indicated by an asterisk in the Table. Table Cmp R2 R3 X Y m.p./°C 2 Me 4-tolyl O CH 117-119 3 H 3-CF3-phenyl O CH 92.5-94.5 4 H 2,6-diCI-phenyl O CH 103-106 5 H 2-CF3-phenyl O CH 113-114.5 6 H phenyl 0 CH 105-107.5 7 H 4-iPr-phenyl O CH 116-118 8 H 4-Me2N-phenyl O CH 162-163.5 9 H 4-MeO-phenyl O CH 112-115 10 H 2-CN-phenyl 0 @ CH 104-106.5 11 H 4-CI-phenyl O CH 119-121 12 H 4-NO2-phenyl O CH 159-160 13 H 2-furyl O CH 109.5-111 14 H 2-pyridyl O CH 89.5-92 15 H 3-pyridyl O CH 110-112 16 H 4-pyridyl O CH 99.5-101.5 17 H 4-CF30-phenyl O CH 98.5-100 18 H 3,4-diMeO-phenyl O CH 102-106 19 H 4-tBu-phenyl O CH 123-126 Cmp R2 R3 X Y m.p./°C 20 H 3-Br-phenyl O CH 115.5-117.5 21 H pentaF-phenyl 0 CH 113-115 22 H 3-N02-phenyl O CH 134-136 23 H 3,5-xylyl O CH 121-123 24 H 3,4-diCI-phenyl O CH 100-102 25 H 2,3-diCI-phenyl O CH 118-120 26 H 2,5-xylyl O CH 106-108 27 H 1-napthyl O CH 96.5-98.5 28 H N-Me-3-indolyl O CH 183-187 29 H 5-Me-2-pyridyl O CH 123-124.5 30 ¼ 0 CH 101-103 A 11 v 31 O 0 CH 137-140 X 32 Me 2-pyridyl O CH 96-97.5 33 Me 3-pyridyl O O CH 99-102 34 Me 4-pyridyl O CH 149-150.5 35 OF3 2-thienyl O CH 101-102.5 36 Me 2,4-diMe-5-thiazolyl O CH 146-147 37 Me N-Me-2-pyrrolyl O CH 102.5-105.5 38 H 4-PhO-phenyl O CH oil 39 H 3-PhO-phenyl O CH oil 40 Me 2-thienyl O CH 78-86 41 Ph phenyl 0 CH 132-136.5 42 Me phenyl 0 CH 102-104 43 H 2-thienyl O CH oil (isomeric with 44) 44 * H 2-thienyl O CH oil (isomeric with 43) 45 H N-Me-2-pyrrolyl O CH oil Cmp R2 R3 X Y m.p./°C 46 Me propyl 0 CH oil 47 CF3 phenyl 0 CH oil 48 Me iso-propyl 0 CH oil 49 Me tert-butyl 0 CH oil 50 Me cyclopropyl 0 CH oil 51 -(CH2)4- O CH oil 52 Et phenyl O CH oil 53 Pr phenyl 0 CH oil 54 Bu phenyl 0 CH oil 55 Me 2-Ph-ethyl O CH oil 56 H 2-Ph-ethyl O CH oil 57 H methyl 0 CH oil 58 Me methyl 0 CH oil 59 Me 2-furyl O CH oil 60 H ethyl 0 CH oil 61 H propyl 0 CH oil 62 H tert-butyl 0 CH oil 63 Me ethyl 0 CH oil 64 Me benzyl O CH oil 65 H 2-MeO-5-pyridyl O CH oil 66 Me -C(Me)=NOMe O CH oil 67* H phenyl O CH oil 68 H 3-CF3-phenyl NH N 55-70 69* H 2-thienyl NH N oil (isomeric with 70) 70* H 2-thienyl NH N oil (isomeric with 69) 71 * H 2-thienyl O N oil (isomeric with 72) 72* H 2-thienyl O N oil (isomeric with 71) 73 H 2-CF3-phenyl O N 131-132 74 H 3-CF3-phenyl O N oil 75 H phenyl 0 N oil Cmp R2 R3 X y m.p./°C 76 H 4-CI-phenyl O N 138-140 77 H 3,4-diCI-phenyl O N oil 78 H 2-CF3-phenyl NH N 78-85 79 H phenyl NH N 113-114.5 80 H 4-CI-phenyl NH N 126.5-129 81 H 3,4-diCI-phenyl NH N 127-129 82 H 3,4-diMeO-phenyl O N 108-113 83 H 3-PhO-phenyl O N oil 84 H pentaF-phenyl 0 N 105-109 85 H 2-pyridyl O N 85-89 86 H 3-pyridyl O N oil 87 H 4-pyridyl O N oil 88 Me 3,4-diMeO-phenyl NH N 124-128 89 H 3-PhO-phenyl NH N oil 90 H pentaF-phenyl NH N 134-137 91 H tert-butyl 0 N 80-81 92 H 2-MeO-5-pyridyl O N 165-170 93 Me -C(Me)= NOMe O N 93-94 94 H 3-pyridyl NH N oil 95 H 2-pyridyl NH N 51-56 96 Me -C(Me) = NOMe NH N 102-105 97 H 4-pyridyl NH N 59-65 98 H tert-butyl NH N 87-90 99 H 2-MeO-5-pyridyl NH N 57-60 100 H 2-quinolinyl O N 128-130 101 H 4-iPr-phenyl O N oil 102 H 4-MeO-phenyl O N 133-135 103 Ph phenyl 0 N 142-144 104 H 4-CF30-phenyl O N oil 105 H 3,5-xylyl O N oil 106 H 2,3-diC1-phenyl O N 130-132 Cmp R2 R3 X y m.p./°C 107 H 2,5-xylyl O N oil 108 H 1-napthyl 0 N oil 109 Et phenyl 0 N oil 110 Pr phenyl 0 N oil 111 Me 2-Ph-ethyl O N oil 112 H 2-quinolinyl NH N 136-138 113 H 4-iPr-phenyl NH N 128-136 114 H 4-MeO-phenyl NH N 130-132 115 H 4-CF30-phenyl NH N 98-100 116 H 3,5-xylyl NH N 94-96 117 H 2,5-xylyl NH N 108-110 118 H 2,6-diCI-phenyl O N 133-135 119 H 3-Br-phenyi O N 83-86 120 H 4-Br-phenyl O N 133-135 121 Et 4-CI-phenyl O N 86-89 122 H 2-F-phenyl O N 87-89 123 H 4-F-phenyl O N 100-103 124 H 2,4-diF-phenyl O N 103-105 125 Me 4-F-phenyl O N 106-107 126 H 3-Br-phenyl NH N 133-135 127 H 4-Br-phenyl NH N 121-123 128 Et phenyl NH N 104-108 129 H 2-F-phenyl NH N 107-110 130 H 4-F-phenyl NH N 128-130 131 H 2,4-diF-phenyl NH N 131-133 132 Me 4-F-phenyl NH N 100-103 133 Me 3-pyridyl O @ N 99-100 134 H 1-napthyl NH N 96-99 135 H 2,3-diCI-phenyl NH N 125-128 136 Et phenyl NH N 106-108 137 Pr phenyl NH N 121-124 138 Me 3-pyridyl NH N 105-108 Omp R2 R3 x y m.p./°C 139 H 2,6-diCI-phenyl NH N 109-112 140 H 3-F-phenyl NH N 100-102 141 H 3,4-diF-phenyl NH N 103-106 142 H 2,6-diF-phenyl NH N 77-79 143 Me 2,4-diF-phenyl NH N 75-79 144 H 2,4,5-triF-phenyl NH N 123-126 145 H 2-tolyl NH N 118-120 146 Me 4-CI-phenyl NH N 118-120 147 H 3-tolyl NH N 79-84 148 Me 2-Ph-ethyl NH N 104-107 149 Me N-Me-2-pyrrolyl NH N 127-130 150 H 4-tolyl NH N 121-125 151 Me 4-tolyl NH N 140-142 152 H 4-MeS02-phenyl NH N 143-145 153 Me 4-MeSO2-phenyl NH N oil 154 Me 4-tolyl O N 100-104 155 H 4-tolyl O N 111-113 156 H 3-F-phenyl O N 111-113 157 H 3,4-diF-phenyl O N 11 7-119 158 H 4-MeS02-phenyl O N oil 159 H 2,6-diF-phenyl O N 109-110 160 Me 4-MeS02-phenyl O N 126-128 161 Me 2,4-diF-phenyl O N 91-92 162 H 2,4,5-triF-phenyl O N 109-110 163 H 2-tolyl O N 102-104 164 Me 4-CI-phenyl O N 102-103 165 H 3-tolyl O N 108-110 166 H 4-Me2N-phenyl NH N 138-140 167 H 2-CN-phenyl NH N 132-134 168 Me methyl NH N oil 169 Me phenyl NH N 118-119 Cmp R2 R3 X Y m.p./°C 170 Me tert-butyl NH N oil 171 Me 2-pyridyl NH N 87-89 172 Me 4-pyridyl NH N 189-191 173 H 1,3-thiazol-2-yl NH N 166-169 174 H 3-quinolinyl NH N 145-147 175 H 2-Me-prop-1-enyl NH N oil 176 H 5-Me-2-thienyl NH N oil 177 H 4-Br-2-thienyl NH N oil 178 H 5-Br-2-thienyl NH N oil 1 79 Me 3-Me-2-thienyl NH N oil 180 Me 5-CI-2-thienyl NH N oil 181 Et 2-thienyl NH N 112-115 182 H 4-tBu-phenyl NH N 135-139 183 H 4-PhO-phenyl NH N 102-105 184 H 3-thienyl NH N oil 185 H N-Me-2-pyrrolyl NH N 11 8-1 21 186 -(CH2)2-S-CH2-- NH N oil 187 -(CH2)2-S-(CH2)2- NH N oil 188 H 5-Me-2-furyl NH N oil 189 H 2-benzo[b]furyl NH N 11 6-1 20 190 H 5-Et-2-furyl NH N oil 191 H 4,5-diMe-2-furyl NH N oil 192 H 5-Br-2-furyl NH N oil 193 H cyclohexyl NH N oil 194 H cyclohex-3-enyl NH N oil 195 H 1-Me-2-Ph-vinyl NH N 121-124 196 H 4-Me2N-phenyl O N oil 197 H 2-CN-phenyl O N oil 198 Me methyl 0 N oil 199 Me phenyl 0 N oil 200 Me tert-butyl 0 N oil Omp R2 R3 X Y m.p./°C 201 Me 2-pyridyl O N oil 202 Me 4-pyridyl O N oil 203 H 1,3-thiazol-2-yl 0 N oil 204 H 3-quinolinyl 0 N oil 205 H 3-CI-5-CF3-2-pyridyl O N 121-123 206 H i) O O N 163.5-165 N 0 207 H 2-Me-prop-1 -enyl O N oil 208 Me a,a-diMe-4-CI-benzyl NH N 138-139 209 Me 3-tolyl NH N 98-100 210 H 3-furyl NH N 112-114 211 Me 2,5-diMe-3-furyl NH N 120-121 212 H 5-CI-2-thienyl NH N 121-123 213 H a-Me-benzyl NH N oil 214 H 1-CF3-ethyl NH N oil 215 H 2-(4-MeO-phenyl)vinyl NH N oil 216 -(CH2)2-O-(CH2)2- NH N oil 217 H 1-Et-propyl NH N oil 218 H NH N oil 219 H 1,1-diMe-allyl NH N oil 220 H 1 -Me-3-Ph-butyl NH N oil 221 Me 5-Me-2-thienyl O N oil 222 H 5-Me-2-thienyl O N oil 223 H 3-thienyl O N oil 224 H 4-Br-2-thienyl 0 N oil 225 H 5-Br-2-thienyl O N oil 226 H 4-tBu-phenyl O N oil 227 Me 5-CI-2-thienyl O N oil 228 -(CH2)2-S-CH2-- O N oil Cmp R2 R3 X Y m.p./°C 2291 -(CH2)2-S-(CH2)2-- O N oil 230 H 3-furyl O N oil 231 H 5-Me-2-furyl O N oil 232 H 2-benzo[blfuryl O N oil 233 H 5-Et-2-furyl O N oil 234 H 2,5-diMe-3-furyl O N oil 235 H 4,5-diMe-2-furyl O N oil 236 H 5-Br-2-furyl O N oil 237 H cyclohexyl 0 N oil 238 H cyclohex-3-enyl 0 N oil 239 H isopropyl NH N oil 240 H 3-(4-tBu-phenoxy)phenyl NH N 126-130 241 H 3-(3-CF3-phenoxy)phenyl NH N 108-110 242 H 3-hexyloxyphenyl NH N oil 243 H 3-(1,1,2,2-tetraF- NH N oil ethoxy)phenyl 244 H 3-(3,4-diCI- NH N oil phenoxy)phenyl 245 H 2-Ph-vinyl NH N oil 246 Me N-Me-2-pyrrolyl O N 102-104 247 H iso-propyl 0 N oil 248 H 3-(4-tBu-phenoxy)phenyl O N oil 249 H 3-(3-CF3-phenoxy) phenyl 0 N oil 250 H 3-Hexyloxy-phenyl O N oil 251 H 3-(3,4-diCI- O N oil phenoxy) phenyl 252 H 2-Ph-vinyl O N 118-121 253 H 3-(1,1,2,2-tetraF- O O N oil ethoxy)phenyl 254 H 1-Ph-ethyl O N oil 255 H 1-CF3-ethyl O N oil Cmp R2 R3 X Y m.p./°C 256 H 2-(4-MeO-phenyl)vinyl O N oil 257 -(CH2)2-O-(CH2)2-- O N oil 258 H 1 -Et-propyl 0 N oil 259 H O O N oil X 260 Me a,a-diMe-4-CI-benzyl 0 N oil 261 H 1,1-diMe-ally O N oil 262 H 1-Me-4-Ph-butyl O N oil 263 Me 3-tolyl O N oil 264 H 4-PhO-phenyl O N oil 265 H N-Me-2-pyrrolyl O N oil 266 H 6-Me-2-pyridyl O N oil 267 Me 2-thienyl O N oil 268 H 5-N02-2-furyl O N 120-123 269 H 5-N02-2-furyl NH N 133-136 270 H 4-CF3-phenyl O N 111-112 271 H 4-MeOC( = O)-phenyl O N 125-127 272 H 3-CF3-4-F-phenyl O N oil 273 H 2-MeO-pyrimidin-5-yl O N 86-89 274 H 4-CF3-phenyl NH N 104-106 275 H 3-CF3-4-F-phenyl NH N 80-84 276 H 4-CN-phenyl O N 173-175 277 H 4-CN-phenyl NH N 124-128 278 H 3-N02-phenyl O N 133.5-135.5 279 H 3-NO2-phenyl NH N 141-144 280 H 4-N02-phenyl O N 174-176 281 H 4-N02-phenyl NH N 177-178 282 H 3-CI-4-N02-phenyl NH N 283 H 2-N02-6-CI-phenyl NH N Cmp R2 R3 X y m.p./°C 284 H 2-CF3O-phenyl NH N 285 H 4-F-3-N02-phenyl NH N 286 H 2-C02Me-phenyl NH N 287 H 2-CONMe2-phenyl NH N 288 H 2-NO2-phenyl NH N 289 H 3-CN-phenyl NH N 290 H 2-F-5-N02-phenyl NH N 291 H 4-CI-3-N02-phenyl NH N 292 H 3-CI-6-N02-phenyl NH N 293 H 4-(1 ,2,4-triazolyl)-phenyl NH N 294 H 4-(1 -imidazolyl)-phenyl NH N 295 H 3-(1,2,4-oxadiazol-3-yl)- NH N phenyl 296 H 3-(5-Me-1 2,4-oxadiazol- NH N 3-yl)phenyl 297 H 4-(1 ,2,4-oxadiazol-3- NH N yl)phenyl 298 H 4-(5-Me-1 ,2,4-oxa-diazol- NH N 3-yl)phenyl 299 H 3-F-4-MeO-phenyl NH N 300 H 4-CHF2O-phenyl NH N 301 H 4-CHF2CF20-phenyl NH N 302 H 4-MeON = C-phenyl NH N 303 H 3-MeON = C-phenyl NH N 304 H 4-Me2NSO2-phenyl NH N 305 H 2-CI-3-pyridyl NH N 306 H 6-CI-2-pyridyl NH N 307 H 6-CI-3-pyridyl NH N 308 H 6-F-3-pyridyl NH N 309 H 6-Me-3-pyridyl NH N

Cmp R2 R3 X y m.p./°C 310 H 2-Me-3-pyridyl NH N 311 H 5,6-diCI-3-pyridyl NH N 312 H 2,6-diCI-3-pyridyl NH N 313 H 3-CI-5-CF3-2-pyridyl NH N 314 H 6-CHF20-3-pyridyl NH N 315 H 5-CI-pyrimidin-2-yl NH N 316 H 2-MeO-pyrimidin-5-yl NH N 317 H 2-F-pyrimidin-5-yl NH N 318 H 2-Cl-primidin-5-yl NH N 319 H 2-Me-pyrimidin-5-yl NH N 320 H 2-Ph-pyrimidin-5-yl NH N 321 H 2-NMe2-pyrimidin-5-yl NH N 322 H 2-MeNH-pyrimidin-5-yl NH N The 1 H N.M.R. data of those compounds in Table I which did not possess discrete melting points at room temperature are presented below.

Compound 38 1H N.M.R. 6(pom) 2.42 (3H, s, CH3S), 2.55 (3H, s, CH3S), 3.68 (3H, s, CH30), 3.70 (3H, s, CH30), 3.83 (3H, s, CH300C), 3.85 (3H, s, CH300C), 4.18 (2H, s, CH2Ar), 4.35 (2H, s, CH2Ar), 6.95-7.78 (26H, m, 2x13 Ar-H), 7.60 (2H, m, 2x=CHOCH3), 8.25 (1H, s, ArCH=N) and (1H, s, ArCH=N).

Compound 39 1H N.M.R. #(ppm) 2.42 (3H, s, CH3), 2.55 (3H, s, CH3S), 3,66 (3H, s, CH30), 3.70 (3H, s, CH3O), 3.80 (3H, s, CH300C), 3.84 (3H, s, CH300C), 4.15 (2H, s, CH2Ar, 4.32 (2H, S, CH2Ar), 6.96-7.55 (26h, m, 2 x 13 Ar-H), 7.6 (2H, m, 2x=CHOCH3), 8.26 (1H, s, ArCH=N) and 8.32 (1H, s, ArCH=N).

Compound 43 1H N.M.R. 6(ppm) 2.44 (3H, s, CH3S), 2.54 (3H, s, CH3S), 3.66 (6H, m, 2xCH30), 3.82 (6H, m, 2xCH300C), 4.20 (2H, s, CH2Ar), 4,36 (2H, s, CH2Ar), 7.02-7.5 (14H, m, 2x7Ar-H/Het-H), 7.6 (2H, m, 2x-CHOCH3), 8.42 (1H, s, ArCH = N) and 8.48 (1H, s, ArCH = N).

Compound 44 1H N.M.R.6(ppm) 2.46 (3H, s, CH3S), 2.74 (3H, s, CH3S), 3.64 (6H, m, 2xCH30), 3.78 (3H, s, CH300C), 3.82 (3H, s, CH300C), 4.20 (2H, s, CH20 Ar), 4.58 (2H, s, CH2Ar), 7.06-7.56 (14H, m, 2x7Ar-H/Het-H), 7.6 (2H, m, 2x=CHOCH3), 8.00 (1H, s, ArCH=N) and 8.04 (1H, s, ArCH=N).

Compound 45 1H N.M.R. #(ppm) 2.42 (3H, s, CH3S), 2.55 (3H, s, CH3S), 3.62 (3H, s, CH30), 3.64 (3H, s, CH30), 3.80 (3H, s, CH3N), 3.82 (3H, s, CH3N), 3.82 (3H, s, CH3N), 3.9 (3H, s CH300C), 3.98 (3H, s, CH300C), 4.16 (2H, s, CH2Ar), 4.34 (2H, s, CH2Ar), 6.14 (2H, m, 2xHet-H), 6.54 (2H, m, 2xHet-H), 6.76 (2H, m, 2xHet-H), 7.14 (2H, m, 2xAr-H), 7.28 (4H, m, 2xAr-H), 7.56 (2H, m, 2xAr-H), 7.6 (2H, m, 2x=CHOCH3), 8.24 (1H, s, ArCH=N) and 8.30 (1H, s, ArCH=N).

Compound 46 1H N.M.R.6(ppm) 0.92 (9H, m, CH3CH2), 1.56 (6H, m, 3xCH2CH3), 1.94 (6H, m, 2xCH3C=), 2.04 (3H, s, CH3C=), 2.16 (6H, m, 3 x CH2CH2), 2.40 (6H, m, 2 x CH3S), 2.48 (3H, s, CH3C), 3.68 (9H, s, 3xCH30), 3.82 (9H, m, 3xCH300C), 4.14 (2H, s, CH2Ar), 4.26 (4H, m, 2xCH2Ar), 7.12 (3H, m, 3xAr- H), 7.24 (6H, m, 3x2Ar-H), 7.46 (3H, m, 3xAr-H) and 7.58 (3H, m, 3x = CH30CH3).

Compound 47 <BR> <BR> <BR> <BR> <BR> 1H N.M.R. G(ppm) 2.06 (3H, s, CH3S), 2.44 (3H, s, CH3S), 3.62 (3H, s, CH30), <BR> <BR> <BR> <BR> <BR> <BR> <BR> 3.68 (3H, s, CH30), 3.70 (3H, s, CH300C), 3.82 (3H, s, CH300C), 4.04 (2H, s, CH2Ar), 4.38 (2H, s, CH2Ar), 7.02-7.5 (18H, m, 2x9Ar-H) and 7.62 (2H, m, 2xCHOCH3).

Compound 48 <BR> <BR> <BR> <BR> 1H N.M.R. G(ppm) 1.10 (12H, m, 2xCH(CH3)2), 1.90 (6H, m, 2xH3-C =), 2.38 <BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> (3H, s, CH3S), 2.46 (3H, s, CH3S), 2.56 (2H, m, 2xCH(CH3)2), 3.68 (6H, s, 2xCH3O), 3.80 (6H, m, 2xCH3OOC), 4.14 (2H, s, CH2Ar), 4.24 (2H, s, CH2Ar), 7.10 (2H, m, 2 x Ar-H), 7.26 (4H, m, 2xAr-H), 7.48 (2H, m, 2xAr-H) and 7.60 (2H, m, 2x=CHOCH3).

Compound 49 1H N.M.R. #(ppm) 1.12 (9H, s, C(CH3)3), 1.92 (6H, m, 2xCH3-C=), 2.38 (3H, s, <BR> <BR> <BR> <BR> <BR> <BR> CH3S), 2.50 (3H, s, CH3S), 2.66 (6H, s, 2x30), 2.82 (6H, s, CH300C), 4.14 (2H, s, CH2Ar), 4.26 (2H, s, CH2Ar), 7.10 (2H, m, 2xAr-H), 7,28 (4H, m, 2x2Ar- H), 7.5 (2H, m, 2xAr-H) and 7.58 (2H, m, 2x=CHOCH3).

Compound 50 1H N.M.R. #(ppm) 0.90 (16H, m, 4xCH2CH2), 1.66 (4H, m, 4xCHCH2), 1.84 (12H, m, 4xCH3C=), 2.38 (6H m, 2xCH3S), 2.50 (6H, m, CH3S), 3.66 (12H, m, 4xCH3O), 3.82 (12H, m, 4xCH3OOC), 4.14 (4H, m, 2xCH2Ar), 4.26 (4H, m, 2xCH2Ar), 7.10 (4H, m, 4xAr-H), 7.28 (8H, m, 4x2Ar-H), 7.46 (4H, m, 4xAr-H) and 7.58 (4H, m, 4x=CHOCH3).

Compound 51 1H N.M.R. #(ppm) 1.76 (8H, m, 2xCH2CH2), 2.40 (3H, s, CH3S), 2.44 (3H, s, CH3S), 2.46 (8H, m, 4x=CCH2), 3.66 (6H, s, 2xCH3O), 3.82 (6H, s, 2xCH3OOC), 4.15 (2H, s, CH2Ar), 4.26 (2H, CH2Ar), 7.10 (2H, m, 2xAr-H), 7.24 (4H, m, 2x2Ar-H), 7.50 (2H, m, 2xAr-H) and 7.60 (2H m, 2xCHOOCH3).

Compound 52 1H N.M.R. #(ppm) 1.14 (6H, m, 2xCH3CH2), 2.44 (3H, s, CH3S), 2.58 (3H, s, CH3S), 2.94 (4H, m, 2x2CH2CH3), 3.68 (3H, s, CH3O), 3.70 (3H, s, CH3O), <BR> <BR> <BR> <BR> <BR> 3.80 (3H, s, CH300C), 3.82 (3H, s, CH300C), 4.18 (2H, s, CH2Ar), 4.38 (2H, s, CH2Ar), 7.14 (2H, m, 2xAr-H), 7.32 (10H, m, 2x5Ar-H), 7.54 (2H, m, 2xAr-H), 7.60 (2H, m, 2x=CHOCH3) and 7.84 (4H, m, 2x2Ar-H).

Compound 53 1H N.M.R. 5(ppm) 0.94 (6H, m, 2xCH3CH2), 1.58 (4H, m, 2xCH2CH3), 2.44 <BR> <BR> <BR> <BR> <BR> <BR> (3H, s, CH3S), 2.58 (3H, s, CH3S), 2.90 (4H, m, 2x=CCH2), 3.64 (3H, s, <BR> <BR> <BR> <BR> <BR> <BR> <BR> CH30), 3.68 (3H, s, CH30), 3.80 (3H, s, CH300C), 3.84 (3H, s, CH300C), 4.18 <BR> <BR> <BR> <BR> <BR> <BR> <BR> (2H, s CH2Ar), 4.35 (2H s, CH2Ar), 7.14 (2H, m, 2xAr-H), 7.34 (1 OH, m, 2x5Ar-H), 7.54 (2H, m, 2xAr-H), 7.62 (2H, m, 2x=CHOCH3) and 7.84 (4H, m, 2x2Ar-H).

Compound 54 1H N.M.R. #(ppm) 0.9 (6H, m, 2xCH3CH2), 1.34 (4H, m, 2xCH2CH3), 1.52 (4H, <BR> <BR> <BR> <BR> <BR> <BR> m, 2xCH2CH2CH3), 2.44 (3H, s, CH3S), 2.56 (3H, s, CH3O) 2.92 (4H, m, <BR> <BR> <BR> <BR> <BR> <BR> <BR> 2x = CCH3), 3.66 (3H, s, CH30), 3.68 (3H, s, CH30), 3.80 (3H, s, CH300C), 3.84 (3H, s, CH3OOC). 4.18 (2H, s, CH2Ar), 4.35 (2H, s, CH2Ar), 7.14 (2H, m, 2 x Ar-H), 7.34 (1 OH, m, 2x4Ar-H), 7.60 (2H, m, 2x=CHOCH3) and 7.84 (4H, m, 2x2Ar-H).

Compound 55 1H N.M.R. #(ppm) 1.98 (9H, m, 3x=CHCH3), 2.40 (6H, m, 2xCH3S), 2.50 (3H, s, CH3S), 2.55-2.94 (12H, m, 3x2CH2), 3.62 (3H, s, CH30), 3.68 (6H, m, <BR> <BR> <BR> <BR> 2CH30), 3.72 (3H, s, CH300C), 3.84 (6H, m, 2xCH300C), 4. 18(2H, s, CH2Ar), 4.25 (4H, m, 2xCH2Ar), 7.68-7.34 (24H, m, 3x8Ar-H), 7.50 (3H, m, 3xAr-H) and 7.58 (3H, m, 3x=CHOCH3).

Compound 56 1H N.M.R. #(ppm) 2.40 (6H, m, 2xCH3S), 2.46 (3H, s, CH3S), 2.62-2.90 (12H, <BR> <BR> <BR> <BR> <BR> m, 3x2CH2), 3.64 (3H, s CH3O), 3.68 (6H, m, 2xCH3O), 3.76 (3H, s, <BR> <BR> <BR> <BR> <BR> CH300C), 4.02 (6H, m, 2xCH300C), 4.16 (2H, s, CH2Ar), 4.26 (4H, m, <BR> <BR> <BR> <BR> <BR> 2xCH2Ar), 7.10-7.34 (24H, m, 3x8Ar-H), 7.50 (3H, m, 3xAr-H), 7.58 (3H, m, 3x=CHOCH3) and 7.76 (3H, m, 3xN=CHCH2).

Compound 57 1H N.M.R #(ppm) 1.98 (6H, m, 2x=CCH3), 2.04 (6H, m, 2x=CCH3), 2.40 (6H, <BR> <BR> <BR> <BR> <BR> m, 2xCH3S), 2.48 (6H, m, 2xCH3S), 3.68 (12H, s, 4xCH3O), 4.02 (12H, m, <BR> <BR> <BR> <BR> <BR> 4xCH3OOC), 4.15 (2H, s, CH2Ar), 4.24 (2H, s, CH2Ar), 4.30 (2H, s, CH2Ar), <BR> <BR> <BR> <BR> <BR> 4.44 (2H, s, CH2Ar), 7.12(4H, m, 4xAr-H), 7.16(8H, m, 2x2Ar-H), 7.48 (2H, m, 4xAr-H), 7.58 (4H, m, 4x=CHOCH3) and 7.75 (4H, m, 4xN=CHCH3).

Compound 58 1H N.M.R. 5(ppm) 1.98 (9H, m, 3x=CCH3), 2.06 (3H, s, =CCH3), 2.40 (3H, s <BR> <BR> <BR> <BR> CH3S), 3.80 (3H, s, CH3S), 3.68 (6H, s, 2xCH30), 3.80 (6H, m, 2xCH300C), <BR> <BR> <BR> <BR> <BR> 4.15 (2H, s, CH2Ar), 4.28 (2H, s, CH2Ar), 7.14 (2H, m, 2xAr-H), 7.26 (4H, m, 2x2Ar-H), 7.48 (2H, m, 2xAr-H) and 7.58 (2H, m, 2x=CHOCH3),

Compound 59 1H N.M.R. #(ppm) 2.28 (3H, s, CH3C =), 2,36 (3H, s, CH3C =), 2.42 (6H, m, CH3C = and CH3S), 2.55 (3H, s, CH3S), 2.60 (3H, s, CH3S), 3.68 (9H, m, 3xCH30), 3.76 (3H, s, CH300C), 4.02 (6H, m, 2xCH300C), 4.16 (2H, s, CH2Ar), 4.34 (4H, m, 2xCH2Ar), 6.42 (3H, m, 3xHet-H), 6.82 (3H, m, 3xHet-H), 7.13 (3H, m, 3xAr-H), 7.26 (6H, m, 3x2 Ar-H), 7.48 (6H, m, 3xArH/3xHet-H) and 7.60 (3H, m, 3x=CHOCH3).

Compound 60 1H N.M.R. 6(ppm) 1.12 (9H, m, 3xCH3CH2), 2.28-2.50 (6H, m, 3xCH2CH3), 2.38 (3H, s, CH3S), 2.42 (3H, s, CH3S), 2.45 (3H, s, CH3S), 3.66 (9H, s, 3xCH30), 3.82 (9H, m, 3xCH300C), 7.10 (3H, m, 3xAr-H), 7.26 (6H, m, 3x2Ar H), 7.46 (3H, m, 3xAr-H), 7.58 (3H, m, 3xCHOCH3) and 7.72 (3H, m, N =CHCH2).

Compound 61 1H N.M.R. #(ppm) 0.96 (9H, m, 3xCH3CH2), 1.60 (6H, m, 3xCH3CH2), 2.35 (6H, m, 3xCH2CH2CH3), 2.40 (3H, s, CH3S), 2.44 (3H, s, CH3S), 2.46 (3H, s, CH3S), 3.70 (9H, m, 3xCH30), 3.82 (9H, m, 3xCH300C), 4.14 (2H, s, CH2Ar), 4.24 (4H, m, 2xCH2Ar), 7.10 (3H, m, 3xAr-H), 7.24 (6H, m, 3x2Ar-H), 7.46 (3H, m, 3xAr-H) and 7.58 (3H, m, 3x=CHCH2).

Compound 62 1H N.M.R. ô(ppm) 1.08 (9H, s, C(CH3)3), 1.15 (9H, s, C(CH3)3), 2.38 (3H, s, CH3S), 2.48 (3H, s, CH3S), 3.66 (6H, s, 2xCH30), 3.82 (6H, m, 2xCH300C), 4.14 (2H, s, CH2Ar), 4.26 (2H, s, CH2Ar), 7.10 (2H, m, 2xAr-H), 7.26 (4H, m, 2x2Ar-H), 7.44 (2H, m, 2xAr-H) and 7.56 (4H, m, 2x=CHOCH3 and 2xN = CHC(CH3)3).

Compound 63 1H N.M.R. #(ppm) 1.00-1.18 (12H, m, 4xCH3CH), 1.90 (3H, s, CH3C=), 1.94 <BR> <BR> <BR> <BR> <BR> (3H, s, CH3S=), 1.98 (3H, s, CH3C=), 2.05 (3H, s, CH3C), 2.24-2.50 (8H, m, <BR> <BR> <BR> <BR> <BR> <BR> 4xCH2CH3), 2.38 (6H, m, 2xCH3S), 2.46 (6H, m, 2xCH3S), 3.68 (1 2H, s, 4xCH3O), 3.82 (12H, m, 4xCH3OOC), 4.14 (4H, m, 2xCH2Ar), 4.26 (4H, m, 2xCH2Ar), 7.10 (4H, m, 4xAr-H), 7.26 (8H, m, 4x-2Ar-H), 7.48 (4H, m, 4xAr-H) and 7.60 (4H, m, 4x=CHCH3).

Compound 64 1H N.M.R. 5(ppm) 1.84 (6H, m, 2xCH3C =), 1.92 (3H, s, CH3C =), 1.98 (3H, s, CH3C=), 2.40 (6H, m, 2xCH3S), 2.46 (6H, m, 2xCH3S), 3.59-3.88 (32H, 4xCH3O, 4xCH3OOC and 4x-CCH2), 4.18 (4H, s, 2xCH2Ar), 4.24 (2H, s, <BR> <BR> <BR> <BR> CH2Ar), 4.30 (2H, s, CH2Ar), 7.10(8H, m, 4x2Ar-H), 7.24 (24H, m, 4x6Ar-H), 7.48 (4H, m, 4xAr-H) and 7.56 (4H, m, 4x=CHOCH3).

Compound 65 <BR> <BR> <BR> 1 H N.M.R. (ppm) 2.54 (6H, s, 2xCH3S), 3.66 (6H, m, 2xCH30C), 3.82 (6H, m, <BR> <BR> <BR> <BR> <BR> <BR> 2xCH300C), 3.96 (6H, m, 2xCH30Py), 4. 18(4H, s, 2xCH2Ar), 6.72 (2H, m, <BR> <BR> <BR> <BR> <BR> 2xPy-H), 7.14 (2H m, 2xAr-H), 7.26 (4H, m, 2x2 Ar-H), 7.48 (2H, m, 2xPy-H), 7.60 (2H, m, 2x=CHOCH3), 8.08 (2H, m, 2xPy-H) and 8.28 (4H, m, 2xPy-H, 2xN = CHPy).

Compound 66 1H N.M.R. 6(ppm) 2.04 (3H, s, CH3C=), 2.10 (3H, s, CH3C=), 2.16 (3H, s, <BR> <BR> <BR> <BR> <BR> CH3C=), 2.18 (3H, s, CH3C=), 2.42 (3H, s, CH3S), 2.35 (3H, s, CH3S), 3.66 <BR> <BR> <BR> <BR> <BR> (3H, s, CH30), 3.68 (3H, s. CH30), 3.80 (6H, m, 2xCH300C), 3.96 (3H, <BR> <BR> <BR> <BR> <BR> s.CH30N), 3.98 (3H, s, CH30N), 4.16 (2H, s, CH2Ar), 4.35 (2H, s, CH2Ar), 7.12 (2H, m, 2xAr-H), 7.26 (4H, m, 2x2Ar-H), 7.46 (2H, m, 2xAr-H) and 7.58 (2H, m, 2x = CHOCH3).

Compound 67 1H N.M.R. ô(ppm) 2.44 (3H, s, CH3S), 2.56 (3H, s, CH3S), 3.64 (3H, s, CH30), 3.66 (3H, s, CH30), 3.80 (3H, s, CH300C), 3.82 (3H, s, CH300C), 4.22 (2H, s, CH2Ar), 4.38 (2H, s, CH2Ar), 7.12 (2H, m, 2xAr-H), 7.26 (4H, m, 2x2Ar-H), 7.38 (6H, m, 3x2Ar-H), 7.50 (2H, m, 2xAr-H), 7.60 (2H, m, 2x-CHOCH3), 7.78 (4H, m, 2xAr-H), 8.32 (1H, s, N=CHAr) and 8.36 (1H, s, N=CHAr).

Compound 69 1H N.M.R. #(ppm) 2.44 (3H, s CH3S), 2.52 (3H, s, CH3S), 2.88 (6H, m, 2xCH3NH), 3.96 (6H, m, 2xCH30N), 4.1 6 (2H, s, CH2Ar), 4.28 (2H, s, CH2Ar), 6.74 (2H, s, 2xNH), 7.06 (2H, m, 2xHet-H), 7.17 (2H, m, 2xAr-H), 7.40 (8H, m, 2x2Het-H and 2Ar-H), 7.50 (2H, m, 2xAr-H) and4 (2H, m, 2xN=CH-Het).

Compound 70 1H N.M.R. #(ppm) 2.46 (3H, s, CH3S), 2.74 (3H, s, CH3S), 2.88 (6H, m, 2xCH3NH), 3.90 (3H, s, CH30N), 3.97 (3H, s, CH30N), 4.18 (2H s, CH2Ar), 4.55 (2H, s, CH2Ar), 6.76 (2H, s, 2xNH), 7.06 (2H, m, 2xHet-H), 7.16 (2H m, 2xAr-H), 7.34 (6H, m, 2x2xHet-H, 2x2Ar-H), 7.52 (4H, m, 2xHet-H and 2xAr-H), 7.98 (1H, s, N=CH-Het) and 8.04 (1H, s, N=CH-Het).

Compound 71 1H N.M.R. 5(pom) 2.42 (3H, s, CH3S), 2.52 (3H, s, CH3S), 3.80 (3H, s, CH30N), 3.82 (3H, s, CH30N), 4.08 (6H, s, 2xCH300C), 4.15 (2H, s, CH2Ar), 4.28 (2H, s, CH2Ar), 7.05 (2H, m, 2xHet-H), 7.14 (2H, m, 2xAr-H), 7.32 (8H, m, 2x2Het- H), 7.54 (2H, m, 2xAr-H), 8.42 (1H, s, N=CH-Het) and 8.44 (N=CH-Het).

Compound 72 1H N.M.R. #(ppm) 2.46 (3H, s, CH3S), 2.54 (3H, s, CH3S), 3.83 (6H, s, CH30N), 4.02 (3H, s, CH3OOC), 4.06 (3H, s, CH300C), 4.17 (2H, s, CH2Ar), 4.54 (2H, s, CH2Ar), 7.06 (2H, m, 2xHet-H), 7.14 (2H, m, 2xAr-H), 7.36 (6H, m, 2xHet-H and 2x2Ar-H), 7.56 (4H, m, 2xHet-H and 2xAr-H), 8.00 (1H, s, N=CH-Het) and 8.04 (lH, s N=CH-Het).

Compound 74 1H N.M.R. 5(pom) 2.44 (3H, s, CH3S), 2.56 (3H, s, CH3S), 3.82 (3H, s, CH30N), 3.86 (3H, s, CH30N), 4.06 (3H, s, CH300C), 4.07 (3H, s, CH300C), 4.16 (2H, s, CH2Ar), 4.30 (2H, s, CH2Ar), 7.14 (2H, m, 2xAr-H), 7.36 (4H, m, 2x2Ar-H), 7.52 (4H, m, 2x2Ar-H), 7.64 (2H, m, 2xAr-H), 7.94 (4H, m, 2x2Ar-H), 8.34 (1H, s, N=CH-Ar) and 8.36 (1H, s, N=CHAr).

Compound 75 1H N.M.R. #(ppm) 2.44 (3H, s, CH3S), 2.56 (3H, s, CH3S), 3.81 (3H, s, CH30N), 3.85 (3H, s, CH30N), 4.07 (3H, s, CH300C), 4.09 (3H, s, CH300C), 4.14 (2H, s, CH2Ar), 4.28 (2H, s, CH2Ar), 7.14 (2H m, 2xAr-H), 7.36 (10H, m, 5x2Ar-H), 7.55 (2H, m, 2xAr-H), 7.75 (4H, 2x2Ar-H), 8.30 (1H, s, N=CHAr) and 8.32 (1H, s, N=CHAr).

Compound 77 1H N.M.R. ô(ppm) 2.44 (3H, s, CH3S), 2.56 (3H, s, CH3S), 3.82 (3H, s, CH30N), 3.84 (3H, s, CH30N), 4.05 (6H, s, 2 x CH300C), (4.15 (2H, s, CH2Ar), 4.28 (2H, s, CH2Ar), 7.14 (2H, m, 2xAr-H), 7.28-7-67 (10H, m, 2x5Ar-H), 7.84 (2H, m, 2Ar-H), 8.20 (2H, s, N=CHAr) and 8.22 (1H, s, N=CHAr).

Compound 83 1H N.M.R. #(ppm) 2.42 (3H, s, CH3S), 2.55 (3H, s, CH3S), 3.80 (3H, s, CH30), 3.84 (3H, s, CH30), 4.08 (3H, s, CH300C), 4.10 (3H, s, CH300C), 4.14 (2H, s, CH2Ar), 4.30 (2H, s, CH2Ar), 6.99-7.56 (26H, m, 2x13Ar-H), 8.26 (1H, s, ArCH=N) and 8.28 (1H, s, ArCH=N).

Compound 86 1H N.M.R. 5(pom) 2.48 (3H, s, CH3S), 2.55 (3H, s, CH3S), 3.84 (3H, s, CH30), 3.90 (3H, s, CH30), 4.08 (3H, s, CH300C), 4.10 (3H, s, CH300C), 4.18 (2H, s, CH2Ar), 4.31 (2H, s, CH2-Ar), 7.05-8.95 (16H, m, 2x8Ar-H), 8.35 (1H, s, ArCH=N) and 8.37 (1H, s, ArCH=N).

Compound 87 1H N.M.R.8(ppm) 2.48 (3H, s, CH3S), 2.56 (3H, s, CH3S), 2.56 (3H, s, CH3S), 3.81 (3H, s, CH30), 3.84 (3H, s, CH30), 4.09 (6H, s, 2xCH300C), 4.19 (2H, s, CH2Ar), 4.30 (2H, s, CH2Ar), 7.14-8.64 (16H, m, 2x8Ar-H), 8.25 (1H, s, Ar- CH=N) and 8.26 (1H, s, Ar-CH=N).

Compound 89 1H N.M.R. #(ppm) 2.46 (3H, s, CH3S), 2.59 (3H, s, CH3S), 2.94 (6H, m, 2xNHCH3), 3.97 (3H, s, CH30), 3.99 (3H, s, CH30), 4.13 (2H, s, CH2Ar), 4.32 (2H, s CH2Ar), 6.78 (2H, m, 2x13Ar-H) and 8.27 (1H, s, Ar-CH=N).

Compound 94 1H N.M.R. #(ppm) 2.46 (3H, s, CH3S), 2.58 (3H, s, CH3S), 2.4-2.94 (6H, m, 2xNHCH3), 3.99 (6H, m, s, 2xCH30), 4.20 (2H, s, CH2Ar), 4.33 (2H, s, CH2Ar), 6.80 (2H, m, 2xCH3NH), 7.14-8.64 (16H, m, 2x4Ar-H, 2x4Het-H), 8.37 (1H, s, Ar-CH=N) and 8.38 (1H, s, Ar-CH=N).

Compound 101 1H N.M.R. 8(ppm) 1.24 (12H, m, (CH3)2Cx2), 2.44 (3H, a CH3S), 2.55 (3H, a, <BR> <BR> <BR> <BR> <BR> <BR> CH3S), 2.94 (2H, m, (CH3)2CHx2), 3.81 (3H, s, CH30), 3.85 (3H, s, CHQO), <BR> <BR> <BR> <BR> <BR> <BR> <BR> 4.06 (3H, s, CH302C), 4.10 (3H, s, CH302C), 4.17 (2H, s, CH2Ar), 4.32 (2H, s, CH2Ar), 7.15-7.77 (16H, m, 2x8Ar-H), 8.32 (1H, s, CH=N) and 8.35 (1H, s, CH=N).

Compound 104 1H N.M.R. #(ppm) 2.43 (3H, s, CH3O), 2.57 (2H, s, CH3S), 3.09 (6H, s, CH3Sx2), 3.83 6H, s, 2xOCH3), 4.06 (6H, s, 2xCH3O2C), 4.1 (6H, s, 2xCH3O2C), 4.16 (4H, s, 2xCH2Ar), 4.30 (4H, s, 2xCH2Ar) and 7.0-7.9 (32H, m, 4x8Ar-H), Compound 105 1H N.M.R. 5(ppm) 2.30 (6H, a, Ar-CH3x2), 2.42 (6H s, Ar-CH3x2), 2.56 (3H, a, CH30), 2.64 (3H, s, CH3S), 3.82 (3H, s, CH30), 3.86 (3H, s, CH302C), 4.07 (3H, s, CH3O2C), 4.14 (2H, s, CH2Ar), 4.30 (2H, s, CH2Ar), 7.0-7.8 (14H, m, 2x7Ar-H), 8.30 (1H, s, CH=N) and 8.33 (1H, s, CH=N).

Compound 107 1H N.M.R. #(ppm) 2.35 (3H, s, CH3Ar), 2.38 (3H, s, CH3Ar), 2.42 (3H, s, <BR> <BR> <BR> <BR> <BR> <BR> CH3Ar), 2.48 (3H, s, CH3Ar), 2.58 (3H, s, CH3S), 2.70 (3H, s, CH3S), 3.82 (3H, <BR> <BR> <BR> <BR> <BR> <BR> <BR> s, CH30), 3.90 (3H, s, CH30), 4.08 (3H, s, CH302C), 4.10 (3H, s, CH302C), <BR> <BR> <BR> <BR> <BR> <BR> <BR> 4. 18(2H, s, CH2Ar), 4.38 (2H, s, CH2Ar), 7.1-7.78 (14H, m, 2x7Ar-H), 8.59 (1H, a, CH=N) and 8.60 (1H, s, CH=N).

Compound 108 1H N.M.R. G(ppm) 2.52 (3H, s, CH3S), 2.62 (3H, s, CH3S), 3.8 (3H, s, CH30), <BR> <BR> <BR> <BR> <BR> 3.88 (3H, s, CH30), 4.08 (3H, s, CH302C), 4.10 (3H, s, CH302C), 4.2 (2H, s, <BR> <BR> <BR> <BR> <BR> <BR> <BR> CH2Ar), 4.4 (2H, s, CH2Ar), 7.14-8.0 (22H, m, 2x11Ar-H), 8.98), (1H, s, CH=N) and 9.04 (1H, s, CH=N).

Compound 109 1H N.M.R. o(ppm) 1.14 (6H, m, CH3CH2x2), 2.48 (3H, s, CH3S), 2.58 (3H, s, CH3S), 2.90 (4H, m, CH2CH3x2), 3.80 (3H, s, CH30), 3.86 (3H, s, CH30), 4.08 (3H, s, CH302C), 4.09 (3H, s, CH302C), 4.16 (2H, s, CH2Ar), 4.34 (2H, s, CH2Ar) and 7.06-7.98 (18H, m, 2x9Ar-H).

Compound 110 1H N.M.R. #(ppm) 0.94 (6H, m, CH3CH2x2), 1.58 (4H, m, CH2CH3x2), 2.44 (3H, s, CH30), 2.59 (3H, s, CH3S), 2.90 (4H, m, CH2CH2x2), 3.82 (3H, s, CH30), 3.88 (3H, s, CH30), 4.08 (3H, s, CH302C), 4.09 (3H, s, CH302C), 4.1 5 (2H, s, CH2Ar), 4.34 (2H, s, CH2Ar) and 7.04-7.94 (18H, m, 2x9Ar-H).

Compound 111 1 H N.M.R. 6(ppm) 1.96-2.0 (3H, s, CH30x4), 2.40 (3H, s, CH3S), 2.46 (3H, s, CH30), 2.47 (3H, s, CH30), 2.64 (8H, m, CH2CH2x4), 2.96 (8H, m, CH2CH2x4), 3.86 (12H, m, CH30x4), 4.08 (12H, m, CH302Cx4), 4.12 (4H br.s, CH2Arx2), 4.20 (4H, br.s, CH2Arx2) and 7.08-7.6 (36H, m, 4x9Ar-H).

Compound 153 1H N.M.R. #(ppm) 2.39 (3H, s, N=CCH3), 2.41 (3H, s, N=CCH3), 2.50 (3H, s, CH3S), 2.59 (3H, s, CH3S), 2.90-2.95 (6H, m, 2xNHCH3), 3.02 (6H, m, 2xCH3S02), 3.99 (6H, 2xs, 2xCH30), 4.20 (2H, s, CH2Ar), 4.38 (2H, s, CH2Ar), 6.80 (2H, m, 2xCH3NH) and 7.14-8.10 (16H, m, 2x8Ar-H).

Compound 158 1H N.M.R. ô(ppm) 2.50 (3H, s, CH3S), 2.60 (3H, s, CH3S), 3.10 (6H, 2xs, 2xCH3S02), 3.86 (3H, s, CH30), 3.91 (3H, s, CH30), 4.07 (6H, 2xs, 2xCH300C), 4.19 (2H, s, CH2Ar), 4.34 (2H, s, CH2Ar), 7.14-7.56 (8H, m, 2x4Ar-H), 7.95 (8H, m, 2x4Ar-H), 8.37 (1H, s, Ar-CH=N) and 8.39 (1H, s, Ar- CH=N).

Compound 168 1H N.M.R. ô(ppm) 1.95-2.05 (4x3H, 4s, CH3C), 2.41 (3H, s, CH3S), 2.92 (2x3H, 2xd, CH3N), 3.95 (3H, s, CH30), 3.99 (3H, s, CH2Ar), 4.22 (2H, s, CH2Ar), 6.76 (2H, s, 2xNH) and 7.12-7.54 (8H, m, 2x4Ar-H).

Compound 170 1H N.M.R. #(ppm) 1.15 (9H, s, (CH3)3C), 1,83 (3H, s, CH3C=N), 1.92 (6H, s, 2xCH3C=N), 2.39 (3H, s, CH3S), 2.50 (3H, s, CH3S), 2.93 (3x3H, 2xd, CH3N), 3.95 (3H, s, CH30), 3.95 (3H, s, CH30), 4.09 (2H, s, CH2Ar), 4.22 (2H, s, CH2Ar), 6.77 (2H, s, 2xNH) and 7.12-7.54 (8H, m, 2x4Ar-H).

Compound 175 1H N.M.R. ô(ppm) 1.89-1.95 (4x3H, s, CH3S), 2.41 (3H, s, CH3S), 2.45 (3H, s, CH3S), 2.90 (6H, d, 2xCH3N), 3.95 (2x3H, 2xs, CH30), 4.14 (2H, s, CH2Ar), 4.27 (2H, s, CH2Ar), 6, (1H, d, =CHCH=), 6.77 (2H, s, 2xNH), 7.13-7.53 (8H, m, 2x4Ar-H) and 8.14 (2H, m, 2xN=CH).

Compound 176 1H N.M.R. #(ppm) 2.35-2.50 (18H, m, SCH3 and =CCH3), 2.85-2.95 (9H, m, CONHCH3), 3.90 (3H, s, NCCH3), 3.95 (3H, s, NCCH3), 4.00 (3H, s, NCCH3), 4.15 (2H, s, CH2Ar), 4.25 (2H, s, CH2Ar), 4.50 (2H, s, CH2Ar). 6.75 (3H, m, 3xCH3NH), 6.80-7.60 (18H, m, 3x4Ar-H and 3x2Het-H), 7.95 (1H, s, N=CH), 8.30 (lH, s, N=CH) and 8.35 (1H, s, N=CH).

Compound 177 1H N.M.R. #(ppm) 2.45 (3H, s, SCH3), 2.50 (3H, s, SCH3), 2.55 (3H, s, SCH3), 2.65 (3H, s, SCH3), 2.90-2.95 (12H, m, CONHCH3), 3.95 (3H, s, NCCH3), 4.00 (9H, m, NCCH3), 4.15 (2H, s, Ar-CH2), 4.20 (2H, s, Ar-CH2), 4.35 (2H, s, Arm CH2), 4.50 (2H, s, ArCH2), 6.95 (4H, m, 4xCH3NH), 7.20-7.60 (24H, m, 4xAr- H), 4x2Het-H), 7.95 (1H, s, N=CH), 8.00 (1H, s, N=CH) and 8.40 (2H, m, N=CH).

Compound 178 1H N.M.R. #(ppm) 2.45 (3H, s, SCH3), 2.50 (3H, s, SCH3), 2.55 (3H, s, SCH3), 2.75 (3H, s, SCH3), 3.90 (12H, m, CONHCH3), 3.95 (6H, s, NOCH3), 4.00 (6H, s, NOCH3), 4.15-4.20 (4H, m, Ar-CH2), 4.25 (2H, s, Ar-CH2), 4.50 (2H, s, Ar- CH2), 6.80-6.90 (4H, m, 4xCH3NH), 7.04-7.55 (24H, m, 4x4Ar-H and 4x2Het-H) and 7.90 (2H, m, N=CH).

Compound 179 1H N.M.R. ô(ppm) 2.40 (12H, s, N=CCH3 and =CCH3), 2.50 (3H, s, S-CH3), 2.55 (3H, s, SCH3), 3.90 (6H, m, CONHCH3), 3.95 (6H, s, NOCH3), 4.15 (2H, Ar-CH2), 4.25 (2H, s, Ar-CH2), 4.25 (2H, s, Ar-CH2), 6.80 (2H, m, 2xCH3NH) and 6.90-7.55 (12H, m, 2x4Ar-H and 2x2Het-H).

Compound 180 1H N.M.R. 6(ppm) 2.25-2.50 (21H, m, N=CCH3 and SCH3), 2.75 (3H, s, S-CH3), (12H, m, CONHCH3), 3.95-4.05 (12H, m, NOCH3), 4.15 (4H, m, Ar-CH2), 4.25 (2H, m, Ar-CH2), 4.50 (2H, s, Ar-CH2), 6.78 (4H, m, 4xCH3NH), 6.90 (4H, m, 4xHet-H), 7.14-7.60 (20H, m, 4x4Ar-H and 4xHet-H).

Compound 184) 1H N.M.R. #(ppm) 2.40 (3H, s, SCH3), 2.55 (3H, s, SCH3) 2.95 (6H, m, CONHCH3), 4.00 (6H, s, NOCH3), 4.20 (2H, s, Ar-CH2), 4.30 (2H, s, Ar-CH2), 6.85 (2H, m, 2xCH3NH), 7.15-7.66 (14H, m, 2x4Ar-H and 2x3Het-H) and 8.35 (2H, m, N=CH).

Compound 186 1H N.M.R. #(ppm) 2.42 (3H, s, CH3S), 2.43 (3H, s, CH3S), 2.44 (3H, s CH3S), 2.82-3.00 (12H, m, 3xSCH2CH2), 2.96 (9H, m, 3xNHCH3), 3.61 (6H, m, 3xNCCH2S), 3.98 (9H, m, 3xCH30N), 4.16 (2H, s, CH2Ar), 4.23 (4H, m, 2xCH2Ar), 6.80 (3H, m, 3xNHCH3) and 7.10-7.56 (12H, m, 3x4Ar-H).

Compound 187 1H N.M.R. #(ppm) 2.42 (3H, s, CH3S), 2.44 (3H, s, CH3S), 2.61-2.79 (8H, m, 2xCH2SCH2), 2.81-2.90 (8H, m, 2x=CH2)2), 2.93 (6H, m, 2xCH3NH), 3.97 (3H, s, CH30N), 3.99 (3H, s, CH30N), 3.99 (3H, s, CH30N), 4.10 (2H, s, CH2Ar), 4.20 (2H, s, CH2Ar), 6.80 (2H, m, 2xCH3NH), 7.13-7.55 (8H, m, 2x4ArH).

Compound 188 1H N.M.R. G(ppm) 2.35-2.62 (18H, m, 3xCH3S and 3xCH3C=), 2.96 (9H, m, 3xCH3NH), 3.94 (3H, s, CH3ON), 3.96 (3H, s, CH3ON), 3.97 (3H, s, CH3ON), 4.18 (2H, s, CH2Ar), 4.30 (2H, s, CH2Ar), 4.40 (2H, s, CH2Ar), 6.10 (3H, m, 3x=CH), 6.72 (3H, m, 3x=CH), 6.82 (3H, m, 3xCH3NH), 7.17-7.58 (12H, m, 3x4Ar-H) and 8.10 (3H, m, 3xN=CH).

Compound 190 1H, N.M.R. #(ppm) 1.14 (9H, m, 3xCH3CH2), 2.42 (3H, s, CH3S), 2.43 (3H, s, <BR> <BR> <BR> <BR> <BR> <BR> CH3S), 2.50 (3H, s, CH3S), 2.72 (6H, m, 3xCH2CH3), 2.90 (9H, m, 3xCH3NH), 3.90 (3H, s, CH3S), 3.85 (3H, s CH30N), 3.87 (3H, s, CH30N), 4.15 (2H, <BR> <BR> <BR> <BR> <BR> CH2Ar), 4.28 (2H, S CH2Ar), 4.38 (2H, s, CH2Ar), 6.10 (3H, m, 3x=CH), 6.74 (3H m, 3x=OH), 6.80 (3H, m, CH3NH) 7.18-7.58 (12H, m, 3x4Ar-H) and 8.08 (3H, m, 3xN=CH).

Compound 191 1H N.M.R. #(ppm) 1.95 (9H, m, 3xCH3C=), 2.24 (9H, m, CH3C=), 2.40 (3H, s, <BR> <BR> <BR> <BR> <BR> CH3S), 2.41 (3H, s, CH3S), 2.48 (3H, m, CH3S), 2.94 (9H, m, 3xCH3NH), 3.95 <BR> <BR> <BR> <BR> <BR> <BR> (9H, m, 3xCH30N), 4.16 (2H, s, CH2Ar), 4.26 (4H, m, 2xCH2Ar), 6.60 (3H, m, 3x=CH), 6.75 (3H, m , 3xCH3NH), 7.08-7.55 (12H, m, 3x4Ar-H) and 8.02 (3H, m, 3xN=CH).

Compound 192 1H N.M.R. G(ppm) 2.42 (3H, s, CH3S), 2.44 (3H, s, CH3S), 2.50 (3H, s, CH3S), 2.90 (9H, m, 3xCH3NH), 3.95 (9H, m, 3xCH30N), 4.17 (2H, s, CH2Ar), 4.28 (2H, s CH2Ar), 4.35 (2H, s, CH2Ar), 6.40 (3H, m, 3x=CH), 6.74 (3H, m, 3x=CH), 6.80 (3H, m, 3xCH3NH), 7.10-7.55 (12H, m, 3x4Ar-H) and 8.06 (3H, m, 3xN=CH).

Compound 193 1H N.M.R. #(ppm) 1.10-1.42 (24H, m, 4xCH2CH2CH2), 1.60-1.90 (16H, m, 4xCH(CH2)2), 2.28-2.50 (16H, m, 4x=CH3S), 2.92 (12H, m, 4xCH3NH), 3.98 (12H, m, 4xCH3ON), 4.15 (2H, s, CH2Ar), 4.23 (4H, m, 2xCH2Ar), 4.40 (2H, m, CH2Ar), 6.97 (4H, m, 4xCH3NH), 7.10-7.55 (16H, m, 4x4Ar-H) and 7.62 (4H, m, 4xN=CH).

Compound 194 1H N.M.R. #(ppm) 1.10-2.75 (28H, m, 4x3CH2 and 4xCH(CH2)2, 2.40-2.52 (12H, m, 4xCH3S), 2.94 (12H, m, 4xCH3NH), 3.98 (12H, m, 4xCH3ON), 4.15 <BR> <BR> <BR> <BR> (2H, s, OH2Ar), 4.22 (6H, m, 3xCH2Ar), 5.70 (8H, m, 4xCH=CH), 6.78 (4H m, 4xCH3NH), 7.14-7.58 (16H, m, 4x4Ar-H) and 7.68 (4H, m, 4xCH=N).

Compound 196 1H N.M.R. #(ppm) 2.47 (3H, s, CH3S), 2.57 (3H, s, CH3S), 3.04 (6H, s, (CH3)2N), 3.07 (6H, s, (CH3)2N), 3.86 (3H, s, CH30N), 3.89 (3H, s, CH30N), 4.10 (2x3H, 2xs, CH3O2C), 4.15? (2H, s, CH2Ar), 4.32 (2H, s, CH2Ar), 6.73 (2H, d, 2xAr-H), 7.15-7.65 (6H, 2x3Ar-H), 8.25 (1H, s, CH=N) and 8.27 (1H, s, CH=N).

Compound 197 1H N.M.R. #(ppm) 2.47 (3H, s, CH3S), 2.61 (3H, s, CH3S), 2.70 (3H, s, CH3S), 3.85 (3H, s, CH30N), 3.91 (6H, s, 2xCH30N), 4.10 (3H, s, CH300C), 4.13 (6H, s, 2 x CH300C), 4.19 (2H, s, CH2Ar), 4.36 (4H, m, 2xCH2Ar), 7.17-7.75 (21H, m, 3x7Ar-H), 8.22 (5H, m, 3xAr-H and 2xN=CH) and 8.73 (1H, s, N=CH).

Compound 198 1H N.M.R. #(ppm) 1.97 (3H, s, CH3C=N), 1.99 (3H, s, CH3C=N), 2.07 (3H, s, CH3C=N), 2.04 (3H, s, CH3C=N), 2.42 (3H, s, CH3C), 2.5 (3H, s, CH3S), 3.89 (6H, s, 2xCH30N), 4.06 (3H, s, CH302C), 4.08 (3H, s, CH302C), 4.13 (2H, s, CH2Ar), 4.23 (2H, s, CH2Ar) and 7.13-7.59 (8H, m, 2x4ArH).

Compound 199 1H N.M.R. #(ppm) 2.39 (3H, s, CH3C=N), 2.42 (3H, s, CH3C=N), 2.46 (3H, s, CH3S), 2.59 (3H, s, CH3S), 3.83 (3H, s, CH30N), 3.90 (3H, s, CH30N), 4.09 (3H, s, CH3S02C), 4.11 (3H, s, CH302C), 4.18 (2H, s, CH2Ar), 4.36 (2H, s, CH2Ar) and 7.16-7.93 (18H, m, 2x9ArH).

Compound 200 1H N.M.R. #(ppm) 1.16 (9H, s, (CH3)3C), 1.2 (9H, s, (CH3)3C), 1.88 (3H, s, CH3O=N), 1.93 (3H, s, CH3OC=N), 2.42 (3H, s, CH3S), 2.52 (3H, s, CH3S), 3.87 (3H, s, CH30N), 3.88 (3H, s, CH3ON), 4.08 (3H, s, CH3S), 4.09 (3H, s, CH302C), 4.13 (2H, s, CH2Ar), 4.23 (2H, s, CH2Ar) and 7.14-7.58 (8H, m, 2x4ArH).

Compound 201 1H N.M.R. #(ppm) 2.48 (12H, m, 4x=CCH3), 2.60-2.70 (12H, m, 4xCH3S), 3.83 (3H, s, CH30N), 3.90 (9H, m, 4xCH30N), 4.04-4.16 (18H, 4xCH300C and 3xCH2Ar), 4.35 (2H, s, CH2Ar), 7.18-7.76 (24H, m, 4x4Ar-H), 8.23 (4H, m, 4xHet-H) and 8.62 (4H, m, 4xHet-H).

Compound 202 1H N.M.R. #(ppm) 2.32 (3H, s, =CCH3), 2.36 (3H, s, =CCH3), 2.40 (3H, s, =CCH3), 2.48 (6H, m, CH3S and =CCH3), 2.60 (6H, m, 2xCH3S), 2.72 (3H, s, CH3S), 3.82 (3H, s, CH30N), 3.90 (9H, m, 3xCH30N), 4.10 (12H, m, 4xCH300C), 4.18 (4H, m, 2xCH2Ar), 4.35 (4H, s, 2xCH2Ar), 7.18-7.76 (24H, m, 4x4Ar-H and 4x2Het-H) and 8.66 (8H, m, 4x2Het-H).

Compound 203 1H N.M.R. G(ppm) 2.49 (3H, s, CH3S), 2.59 (3H, s, CH3S), 3.86 (3H, s, CH30N), <BR> <BR> <BR> <BR> <BR> <BR> 3.91 (3H, s, CH30N), 4.09 (3H, s, CH302C), 4.10 (3H, s, CH302C), 4.34 (2H, s, CH2Ar), 4.37 (2H, s, CH2Ar), 7.14-7.95 (12H, m, 2x6ArH), 8.49 (1H, s, CHC=N) and 8.54 (1H, s, CHC=N).

Compound 204 1H N.M.R. #(ppm) 2.50 (3H, s, CH3S), 2.61 (3H, s, CH3S), 3.86 (3H, s, CH3ON), <BR> <BR> <BR> <BR> <BR> <BR> 3.90 (3h, s, CH30N), 4. 10(3H, s, CH302C), 4.22 (2H, s, CH2Ar), 4.34 (2M, s, CH2Ar), 8.46 (18H, m, 2 x 9, Ar-H), 8.53 (1H, s, CHC=N), 8.56 (1H, s, CHC=N), 9.35 (1H, d, Ar-H) and 9.41 (1H, d, ArH).

Compound 207 1H N.M.R. 6(ppm) 1.94 (3H, s, CH3C), 1.95 (3H, s, CH3C=C) 1.97 (3H, s, CH3C=C), 2.42 (3H, s, CH3S), 3.51 (3H, s, CH3S), 3.89 (3H, s, CH3ON), 3.40 (3H, s, CH30N), 4.08 (6H, s, 2xCH302C), 4.14 (2H, s, CH2Ar), 4.26 (2H, s, CH2Ar), 6.14 (1H, d, C=CHC=), 7.13-7.57 (8H, m, 2x4 Ar-H), 8.08-8.12 (1H, d, CHC=N) and 8.10-8.15 (1H, d, CHO=N).

Compound 213 1H N.M.R. a(ppm) 1.48 (6H, m, 2xCH3C), 2.20 (3H, s, CH3S), 2.23 (3H, s, CH3S), 2.84 (3H, m, CH3NH), 2.86 (3H, m, CH3NH), 3.78 (2H, m, 2x=CHCHMe), 3.94 (3H, s, CH30N), 3.98 (3H, s, CH30N), 4.13 (2H, s, CH2Ar), 4.19 (2H, s, CH2Ar), 6.73 (2H, s, 2xNHMe), 7.10-7.55 (18H, m, 2x9ArH) and 7.62 (2H, m, 2x=CHCHMe).

Compound 214 1H N.M.R. #(ppm) 1.34 (6H, m, 2xCH3CHCF3), 2.40 (3H, s, CH3S), 2.46 (3H, s, CH3S), 2.90 (6H, m, 2xCH3NH), 3.24 (2H, m, 2xCH3CHCF3), 3.94 (6H, s, 2xCH30N), 4.12 (2H, s, CH2Ar), 4.22 (2H, s, CH2Ar), 6.75 (2H, s, 2xNHMe), 7.14 (2H, m, 2xAr-H), 7.30 (4H, m, 2x2 Ar-H), 7.44 (2H , m, 2xAr-H) and 7.64 (2H, m, 2xN=CHCH).

Compound 215 1H N.M.R. 5(pom) 2.43 (6H, m, 2xCH3S), 2.52 (3H, s, CH3S), 2.70 (9H, m, 3xCH3NH), 3.81 (9H, m, 3xCH30Ar), 3.96 (9H, s, 3xCH30N), 4.16 (2H, s, CH2Ar), 4.28 (4H, m, 2xCH2Ar), 6.76 (3H, m, 3xCH3NH), 6.82-6.95 (12H, m, 3x2ArH and 3xCH=CH), 7.14 (3H, m, 3xArH), 7.23-7.54 (15H, m, 3x5ArH) and 8.10 (3H, m, N=CH).

Compound 216 1 H N.M.R. #(ppm) 2.40 (3H, s, CH3S), 2.44 (3H, s, CH3S), 2.40-2.75 (8H, m, 2x2CH2CH2C), 2.98 (6H, m, 2xCH3NH), 3.66-3.86 (8H, m, 2x2CH2CH2C), 3.90 (3H, s, CH30N), 3.92 (3H, s, CH30N), 4.10 (2H, s, CH2Ar), 4.19 (2H, s, CH2Ar), 6.76 (2H, m, 2xCH3NH), 7.14 (2H, m, 2xAr-H), 7.30 (4H, m, 2x2ArH) and 7.48 (2H, m, 2xArH).

Compound 217 1H N.M.R. 6(pom) 0.92 (18H, m, 3xCH(CH2CH3)2), 1.50 (12H, m, 3xCH(CH2CH3)2), 2.18 (3H, m, 3xCH(CH2CH3)2), 2,38 (6H, m, 2xCH3S), 2.44 (3H, s, CH3S), 2.90 (9H, m, 3xCH3NH), 3.94 (9H, s, 3xCH30N), 4.10 (2H, s, CH2Ar), 4.22 (4H, m, 2xCH2Ar), 6.76 (3H, m, CH3NH), 7.14 (3H, m, 3xArH), 7.30 (6H, m, 2x2ArH) and 7.45 (6H, m, 3xNCH and 3xArH).

Compound 218 1H N.M.R. #(ppm) 1.07-2.10 (20H, m, 4x3CH and 4xCH2), 2.20-2.25 (12H, m, 4xCH3S), 2.92 (12H, m, 4xCH3NH), 3.04 (8H, m, 4xCH2 bridging), 3.96 (12H, m, 4xCH30N), 4.14 (2H, s, CH2Ar), 4.22 (6H, m, 3xCH2Ar), 6.00-6.23 (8H, m, 4xCH = CH), 6.75 (4H, m, 4 x CH3NH), 7.15 (4H, m, 3 x Ar-H), 7.34 (8H, m, 4 x2ArH), 7.48 (4H, m, 4xArH) and 7.72 (4H, m, 4xN=CH).

Compound 219 1H N.M.R. â(ppm) 1.08 (3H, s, CH3C), 1.15 (3H, s, CH3C), 2.02 (4H, m, 2xCH2CH), 2.38 (3H, s, CH3S), 2.46 (3H, s, CH3S), 2.95 (6H, m, 2xCH3NH), 3.95 (6H, m, 2xCH30N), 4.12 (2H, s, CH2Ar), 4.22 (2H, s, CH2Ar), 5.02 (4H, m, 2xHC=CH2), 5.80 (2H, m, 2xCH=CH2), 6.75 (2H, s, 2xCH3NH), 7.14 (2H, m, 2xArH), 7.30 (4H, m, 2x2ArH), 7.48 (2H, m, 2xArH), 7.55 (1H, s, N=CH) and 7.57 (1H, s, N=CH).

Compound 220 1H N.M.R. â(ppm) 1.08 (12H, m, 4xCH3), 1.54-2.00 (8H, m, 4xCH2), 2.35 (4H, m, 4xCHMe), 2.42 (6H, m, 2xCH3S), 2.48 (6H, m, 2xCH3S), 2.82 (4H, m, 4xCHMe), 2.88 (12H, m, 4xCH30N), 4.14 (4H, m, 2xCH2Ar), 4.22 (4H, m, 2xCH2Ar), 6.76 (4H, m, 4xCH3NH), 7.08-7.42 (32H, m, 4x8ArH) and 7.52 (8H, m, 4xN =CH and 4xArH).

Compound 221 1H N.M.R. #(ppm) 2.35-2.70 (36H, m, =CCH3, N=CCH3 and S CH3), 3.85 (3H, s, CH30N), 3.90 (9H, m, CH30N), 4.10 (12H, m, COOCH3), 4.15-4.20 (4H, m, ArCH2), 4.35 (4H, m, ArCH2), 6.75 (4H, m, Het-H), 7.10-7.60 (20H, m, Ar-H), 7.90 (1H, s, N=CH), 7.95 (1H, s, N=CH) and 8.40 (2H, m, N=CH).

Compound 222 1H N.M.R. #(ppm) 2.40-2.50 (18H, m, =CCH3 and SCH3) 2.65 (3H, s, SCH3), 2.75 (3H, s, SCH3), 3.90 (12H, m, CH30N), 4.10 (12H, m, COOCH3), 4.15 (4H, m, ArCH2), 4.30 (2H, s, ArCH2), 4.60 (2H, s, ArCH2), 6.75 (4H, m, Het-H), 7.10-7.60 (20H, m, Ar-H), 7.90 (1H, s, N=CH), 7.95 (1H, s, N=CH) and 8.40 (2H, m, N=CH).

Compound 223 1H N.M.R. #(ppm) 2.45 (3H, s, SCH3) 2.55 (3H, s, SCH3), 3.85 (3H, s, CH30N), 3.90 (3H, s, CH30N), 4.10 (6H, m, COOCH3), 4.15 (2H, m, ArCH2), 4.30 (2H, s, ArCH2), 7.15 (2H, m, ArH), 7.30-7.45 (6H, m, ArH), 7.50-7.70 (6H, m, ArH) and 8.35 (2H, m, N=CH).

Compound 224 1H N.M.R. #(ppm) 2.40 (3H, s, SCH3), 2.50 (3H, s, SCH3) 2.55 (3H, s, SCH3), 2.75 (3H, s, SCH3), 3.90 (12H, m, CH30N), 4.05-4.20 (12H, m, COOCH3), 4.30 (4H, s, ArCH2), 4.35 (2H, s, ArCH2), 4.50 (2H, s, ArCH2), 7.10-7.60 (30H, m, Ar-H), 7.95 (1H, s, N=CH), 8.00 (1H, s, N=CH) and 8.35 (2H, m, N=CH).

Compound 225 1H N.M.R. #(ppm) 2.45 (3, s, CH3S), 2.50 (3H, s, CH3S), 2.55 (3H, s, CH3S), 2.75 (3H, s, CH3S), 3.90 (12H, m, 4xCH30N), 4.12 (12H, m, 4xCH300C), 4.15 (2H, s, CH2Ar), 4.26 (2H, s, CH2Ar), 4.38 (2H, s, CH2Ar), 4.50 (2H, s, CH2Ar), 7.00-7.60 (24H, m, 4x4Ar-H and 4x2Het-H), 7.85 (1H, s, NCH), 7.90 (1H, s, N=CH) and 8.30 (2H, m, 2xN=CH).

Compound 226 1 H N.M.R. â(ppm) 1.35 (27H, m, C(CH3i3), 2.45 (3H, s, SCH3), 2.55 (3H, s, SCH2), 2.70 (3H, s, SCH3), 3.85-3.90 (9H, m, CH30N), 4.10 (9H, CH300C), 4.20 (2H, s, ArCH2), 4.30 (2H, s, ArCH2), 4.35 (2H, s, ArCH2), 7.15-7.20 (3H, m, ArH), 7.30-7.50 (12H, m, ArH), 7.55-7.60 (3H, m, ArH), 7.65-7.80 (6H, m ArH), 7.85 (1H, s, N=CH) and 8.35 (2H, m, N=CH).

Compound 227 1H N.M.R.6(ppm) 2.30 (3H, s, N=CCH3), 2.35 (3H, s, N=CCH3), 2.45 (9H, m, N=CCH3SCH3), 2.50 (3H, s, SCH3), 2.55 (3H, s, SCH3), 2.75 (3H, s, SCH3), 3.95 (12H, m, CH30N), 4.05 (12H, m, CH300C), 4.10 (4H, m, ArCH2), 4.30 (2H, s, ArCH2), 4.50 (2H, s, ArCH2), 6.85 (2H, m, Het-H), 7.10-7.20 (8H, m, ArH), 7.30-7.45 (8H, m, ArH) and 7.55-7.60 (4H, m, Ar-H).

Compound 228 1H N.M.R. #(ppm) 2.04 (12H, m, 4xCH3S), 2.78-3.00 (16H, m, 4xCH2CH2S), 2.92 (12H, m, 4xCH3NH), 3.58-3.68 (8H, m, 4xN=CCH2S), 3.86 (12H, m, 4xCH30N), 4.06 (12H, m, 4xCH300C), 4.10-4.21 (8H, m, 4xCH2Ar) and 7.14- 7.58 (16H, m, 4x4Ar-H).

Compound 229 1H N.M.R. #(ppm) 2.42 (3H, s, CH3S), 2.44 (3H, s, CH3S), 2.72 (8H, m, 2xCH2SCH2), 2.86 (8H, m, 2x=C(CH2)2), 3.84 (6H, s, 2xCH30N), 4.04-4.10 (10H, m, 2xCH300C and 2xCH2Ar) and 7.14-7.58 (8H, m, 2x4Ar-H).

Compound 230 1H N.M.R. #(ppm) 2.44 (3H, s, CH3S), 2.52 (3H, s, CH3S), 3.84 (3H, s, CH30N), 3.86 (3H, s, CH30N), 4.06 (6H, m, 2xCH300C), 4.25 (2H, s, CH2Ar), 4.34 (2H, s, CH2Ar), 6.80-7.78 (14H, m, 2x4ArH and 2x3Het-H), 8.26 (1H, s, N=CH) and 8.30 (1H, s, N=CH).

Compound 231 1H N.M.R. a(ppm) 2.35-2.55 (12H, m, 2xCH3S and 2xCH3C=), 3.84 (6H, m, 2xCH3ON), 4.06 (6H, s, CH300C), 4.15 (2H, s, CH2Ar), 4.30 (2H, s, CH2Ar), 6.10 (2H, m, 2x=CH), 6.74 (2H, m, 2x=CH), 7.12-7.60 (8H, m, 2xArH), 8.10 (1H, s, N=CH) and 8.14 (1H, s, N=CH).

Compound 232 1H N.M.R. #(ppm) 2.46 (3H, s, CH3S), 2.55 (3H, s, CH3S), 3.84 (3H, s, CH30N), 3.86 (3H, s, CH30N), 4.08 (6H, s, 2xCH300C), 4.21 (2H, s, CH2Ar), 4.32 (2H, s, CH2Ar) and 7.14-7.66 (18H, m, 2x8ArH and 2xHet-H).

Compound 233 1H N.M.R. a(ppm) 1.25 (9H, m, 3xCH3CH2), 2.48 (3H, s, CH3S), 2.50 (3H, s, CH3S), 2.54 (3H, s, CH3S), 2.68-2.78 (6H, m, 3xCH2CH3), 3.86 (9H, m, 3xCH30N), 4.06 (9H, m, 3xCH300C), 4.15 (2H, s, CH2Ar), 4.28 (2H, s, CH2Ar), 4.35 (2H, s, CH2Ar), 6.10 (3H, m, 3x=CH), 6.74 (3H, m, 3x=CH), 7.15-7.60 (12H, m, 3x4Ar-H) and 8.14 (3H, m, 3xN=CH).

Compound 234 1H N.M.R. 5(ppm) 2.42-2.66 (18H, m, 2OH3-O= and 2xCH3S), 3.83 (3H, s, CH3ON), 3.88 (3H, s, CH3ON), 4.06 (6H, m, 2xCH3OOC), 4.15 (2H, s, CH2Ar), 4.30 (2H, s, CH2Ar), 7.16-7.60 (8H, m, 2x4Ar-H) and 8.08 (2H, m, 2xN=CH).

Compound 235 1H N.M.R. G(ppm) 2.08-2.66 (36H, m, 4x3CH3C = and 4xCH3S), 3.86 (12H, m, 4xCH30N), 4.03 (3H, s, CH300C), 4.08-44.18 (11H, m, 3xCH300C and <BR> <BR> <BR> <BR> 1xCH2Ar), 4.28 (2H, s, CH2Ar), 4.35 (4H, m, 2xCH2Ar), 6.63 (4H, m, 4xHC=), 7.1-7.62 (16H, m, 4x4Ar-H) and 8.00 (4H, s, 4xN=CH).

Compound 236 1H N.M.R. #(ppm) 2.24-2.68 (12H, m, 4xCH3S), 3.86 (12H, m, 4xCH3ON), 4.04- 4. 18 (14H, m, 4xCH300C and1xCH2Ar), 4.34 (6H, m, 3xCH2Ar), 6.38-6.55 (4H, m, 4x=OH), 6.75-6.86 (4H, m, 4x=OH), 7.14-7.58 (16H, m, 4x4ArH) and 8.08 (4H, m, 4xN=CH).

Compound 237 1H N.M.R. #(ppm) 1.08-1.40 (24H, m, 4xCH2CH2CH2), 1.62-1.94 (16H, m, 4xCH(CH2)2), 2.28-2.54 (16H, m, 4x=CH and 4xCH3S), 3.88 (12H, m, 4xCH30N), 4.10-4.18 (14H, m, 4xCH300C and 1xCH2Ar), 4.24 (2H, s, CH2Ar).

4.36 (2H, s, CH2Ar), 4.38 (2H, s, CH2Ar), 7.10-7.56 (16H, m, 4x4ArH) and 7.62 (4H m, 4xN=CH).

Compound 238 1H N.M.R. #(ppm) 1.44-2.70 (28H, m, 4x3CH2and 4xCH(CH2)2), 2.42-2.55 (12H, m, 4xCH3S), 3.90 (12H, m, 4xOH30N), 4.04-4.17 (14H, m, 4xCH300C and 1xCH2Ar), 4.24 (4H, m, 2xCH2Ar), 4.35 (2H, s, CH2Ar), 5.70 (8H, m, 4xHC=CH), 7.14-7.58 (16H, m ,4x4ArH) and 7.72 (4H, m, 4xN=CH).

Compound 239 1H N.M.R.6(ppm) 1.14 (12H, m CH3CHCH3x2), 2.40 (3H, s, CH3S), 2.48 (3H, s, CH3S), 2.60 (2H, CH3CHCH3x2), 2.94 (6H, m, CH3NHx2), 3.98 (6H, m, CH30x2), 4.18 (2H, s, CH2Ar), 4.21 (2H, s, CH2Ar), 6.80 (2H, br.t, NHCH3x2), 7.1-7.9 (10H, m, 2x4ArH and CH=Nx2).

Compound 242 1H N.M.R. #(ppm) 0.90 (6H, m, CH3CH2x2), 1.34 (8H, m, CH3CH2CH2x2), 1.48 (8H, m, CH2CH2CH2CH2x2), 1.80 (4H, m, OCH2CH2x2), 2.46 (3H, s, CH3S), 2.55 (3H, s, CH3S), 2.90 (6H, m, CH3NHx2), 3.98 (6H, m, CH30x2), 4.17 (2H, s, CH2Ar), 4.30 (2H, s, CH2Ar), 6.80 (2H, br.t, NH CH3 x2), 6.90-7.60 (16H, m, 2x8 ArH), 8.30 (2H, s, CH=N) and 8.33 (1H, s, CH=N).

Compound 243 1H N.M.R. #(ppm) 2.44 (3H, s, CH3S), 2.58 (3H, s, CH3S), 2.98 (6H, m, CH3NHx2), 3.99 (6H, m, CH30x2), 4.18 (2H, s, CH2Ar), 4.26 (2H, s, CH2Ar), 5.7-6.18 (2H, t, CHF2x2), 6.79 (2H, br.s, NHCH3x2), 7.38-7.78 (16H, m, 2x8ArH), 8.30 (1H, s, CH=N) and 8.32 (1H, s, CH=N).

Compound 244 1H N.M.R. #(ppm) 2.46 (3H, s, CH3S), 2.60 (3H, s, CH3S), 2.88 (3H, d, CH3NH), 2.90 (3H, d, CH3NH), 3.98 (3H, s, CH30), 4.00 (3H, s, CH30), 4.22 (2H, s, CH2Ar), 4.38 (2H, s, CH2Ar), 6.82 (2H, br.d, NHCH3x2), 7.00-8.3 (22H, m, 2x11ArH), 8.35 (1H, s, CH=N) and 8.40 (1 H, s, CH=N).

Compound 245 1H N.M.R. G(ppm) 2.42 (3H, s, CH3S), 2.56 (3H, s, CH3S), 2.94 (6H, d, <BR> <BR> <BR> <BR> <BR> <BR> CH3NHx2), 3.98 (6H, s, CH30x2), 4.18 (2H, s, CH2Ar), 4.3 (2H, s, CH2Ar), 6.8 <BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> (2H, br.m, NHCH3x2), 6.94-7.18 (4H, m, CH= CHx2), 7.20-7.60 (18H, m, 2x9ArH), 8.18 (1H, s, CH=N) and 8.20 (1H, s, CH=N).

Compound 247 1H N.M.R. #(ppm) 1.1 (6H, d, CH3CHCH3), 1.15 (6H, d, CH3CHCH3), 2.41 (3H, <BR> <BR> <BR> <BR> <BR> <BR> s, CH3S), 2.48 (3H, s, CH3S), 2.60 (2H, m, CH(CH3)2x2), 3.85 (6H, s, <BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> CH30x2), 4.05 (6H, s, 2xCH302C), 4. 10 2H, s, CH2Ar), 4.20 (2H, s, CH2Ar), 7.0-7.5 (8H, m, 2x4ArH) and 7.52-7.61 (2H, m, CH=Nx2).

Compound 248 1H N.M.R. G(ppm)1.28 (18H, s, (CH3)3Cx2), 2.44 (3H, s, CH3S), 2.56 (3H, s, <BR> <BR> <BR> <BR> <BR> <BR> CH3S), 3.80 (3H, s, CH30), 3.85 (3H, s, CH30), 4.05 (3H, s, CH302C), 4. 10 <BR> <BR> <BR> <BR> <BR> <BR> <BR> (3H, s, CH302C), 4. 15(2H, s, CH2Ar), 4.24 (2H, s, CH2Ar), 6.9-7.6 (24H, m, 2x12 ArH), 8.21 (1H, s, CH=N) and 4.23 (1H, s, CH=N).

Compound 249 1H N.M.R. G(ppm) 2.42 (3H, s, CH3S), 2.56 (3H, s, CH3S), 3.78 (3H, s, CH30), 3.82 (3H, s, CH3O), 4.05 (3H, s, CH3O2C). 4.10 (3H, s, CH3O2C), 4.25 (2H, s, <BR> <BR> <BR> <BR> <BR> CH2Ar), 4.30 (2H, s, CH2Ar), 6.9-7.6 (24H, m, 2x12ArH), 8.24 (1H, s, CH =N) and 8.28 (1H, s, CH=N).

Compound 250 1H N.M.R. G(ppm) 0.90 (6H, m, CH3CH2x2), 1.36 (12H, m. CH3CH2CH2CH2x2), <BR> <BR> <BR> <BR> <BR> <BR> 1.45 (8H, m, CH2CH20x2), 2.44 (3H, s, CH3S), 2.56 (3H, s, CH3S), 3.84 (3H, <BR> <BR> <BR> <BR> <BR> <BR> <BR> s, CH30), 3.86 (3H, s, CH30), 4.0 (3H, s, CH302C), 4.16 (2H, s, CH2Ar), 4.28 (2H, S CH2Ar), 6.8-7.6 (16H, m, 2x8ArH), 8.22 (1H, s, CH=N) and 8.24 (1H, s, CH=N).

Compound 251 1H N.M.R. #(ppm) 2.40 (3H, s, CH3S), 2.50 (3H, s, CH3S), 3.78 (3H, s, CH30), <BR> <BR> <BR> <BR> <BR> <BR> 3.84 (3H, s, CH30), 4.08 (3H, s, CH302C), 4. 16(3H, s, CH302C), 4. 18(2H, s, CH2Ar), 4.30 (2H, s, CH2Ar), 6.78-7.6 (22H, m, 2x11ArH), 8.26 (1H, s, CH=N) and 8.30 (1H, s, CH=N).

Compound 253 1H N.M.R. #(ppm) 2.44 (3H, s, CH3S), 2.56 (3H, s, CH3S), 3.80 (3H, s, CH30), <BR> <BR> <BR> <BR> <BR> <BR> 3.82 (3H, s, CH30), 4.02 (3H, s, CH302C), 4.04 (3H, s, CH302C), 4. 18(2H, s, OH2Ar), 4.28 (2H, s CH2Ar), 5.7-6.1 (2H, t, CHF2x2), 7.1-7.8 (16H, m, 2x8ArH), 8.32 (1H, s CH=N) and 8.34 (1H, s, CH=N).

Compound 254 1H N.M.R. #(ppm) 1.38 (3H, m, CH3CH), 1.55 (6H, m, 2xCH3CH), 2.42 (3H, s, CH3S), 2.46 (3H, s, CH3S), 2.50 (3H, s, CH3S), 3.73 (3H, m, 3xCHCH3), 3.80 (6H, m, 2xCH30N), 3.82 (3H, s, CH30N), 4.02 (6H, m, 2xCH3OOC), 4.06 (3H, s, CH3OOC), 4.10 (2H, s, CH2Ar), 4.18 (2H, s, CH2Ar), 4.24 (2H, s, CH2Ar), 7.1 (3H, m, 3xArH), 7.26 (21H, m, 3x7ArH), 7.50 (3H, s, 3xArH) and 7.74 (3H, m, 3xN=CH).

Compound 255 1H N.M.R. #(ppm) 1.14-1.20 (24H, m, 4xCH(CH3)2), 2.38 (6H, s, 2xCH3S), 2.42 (3H, s, CH3S), 2.46 (3H, s, CH3S), 3.22 (4H, m, 4xCH(CH3)2), 3.83 (12H, m, 4xCH3ON), 4.02 (12H, m, 4xCH3OOC), 4.08 (4H, m, 2xCH2Ar), 4.22 (4H, m, 2xCH2Ar), 7.12 (4H, m, 2xCH2Ar), 7.12 (4H, m, 4xArH), 7.34 (8H, m, 4x2ArH), 7.48 (4H, m, 4xArH) and 7.65 (4H, m, 4xN=CH).

Compound 256 1H N.M.R. 5(pom) 2.42 (3H, s, CH3S), 2.50 (3H, s, CH3S), 3.80 (6H, m, 2xArOCH3), 3.84 (6H, m, 2xCH30N), 4.04 (6H, m, 2xCH300C), 4.14 (2H, s, CH2Ar), 4.26 (2H, s, CH2Ar), 6.88 (8H, m, 2xHC=CH and 2x2ArH), 7.14-7.58 (12H, m, 2x6ArH) and 8.14 (3H, m, 3xN=CH).

Compound 257 1H N.M.R. #(ppm) 2.40 (3H, s, CH3S), 2.44 (3H, s, CH3S), 2.44-2.76 (8H, m, 2x2CH2), 3.66 (4H, m, 2xCH2), 3.82 (4H, m, 2xCH2), 3.82 (6H, m, 2xCH30N), 4.02 (3H, s, CH300C), 4.04 (3H, s, CH300C), 4.08 (2H, s, CH2Ar), 4.18 (2H, s, CH2Ar), 7.10 (2H, m, 2xArH), 7.34 (4H, m, 2x2ArH) and 7.50 (2H, m, 2xArH).

Compound 258 1H N.M.R. #(ppm) 0.88 (18H, m, 3x(CH2CH3)2), 1.52 (12H, m, 3xCH(CH2CH3)2, 2.18 (3H, m, 3xCH(CH2CH3)2), 2.37 (3H, s, CH3S), 2.40 (3H, s, CH3S), 2.44 (3H, s, CH3S), 3.84 (9H, m, 3xCH30N), 4.05 (9H, s, 3xCH300C), 4.10 (2H, s, CH2Ar), 4.20 (4H, m, 2xCH2Ar), 7.12 (3H, m, Ar-H), 7.34 (6H, m, 3xArH), 7.48 (6H, m, 2xArH and 2xN=CH).

Compound 259 1H N.M.R. #(ppm) 1.06-2.06 (20H, m, 4x3CH and 4xCH2), 2.40 (12H, m, 4xCH3S), 2.83-3.10 (8H, m, 4xCH2 bridging), 3.83 (12H, s, 4xCH30N), 4.02 (12H, m, 4xCH300C), 4.18 (2H, s, CH2Ar), 4.20 (6H, m, 3xCH2Ar), 5.95-6.22 (8H, m, 4xCH=CH), 7.10 (4H, m, 4xArH), 7.36 (8H, m, 4x2ArH), 7.44 (4H, m, 4xArH) and 7.75 (4H, m, 4xN=CH).

Compound 260 1H N.M.R. a(ppm) 1.44 (6H, s, =C-C(CH3)2), 1.60 (3H, N=CCH3), 1.64 (3H, s, N=CCH3), 2.42 (3H, s, CH3S), 2.48 (3H, s, CH3S), 3.83 (6H, s, 2xCH30N), 4.02 (3H, s, CH300C), 4.06 (3H, s, CH300C), 4.14 (2H, s, CH2Ar), 4.20 (2H, s, CH2Ar) and 7.08-7.56 (16H, m, 2x8Ar-H).

Compound 261 1H N.M.R. G(ppm)1.06 (6H, s, =CHC(CH?)2), 1.12(6H, s, =CHC(CH3)2), 2.20 <BR> <BR> <BR> <BR> <BR> <BR> (4H, m, 2xOH2), 2.38 (3H, s, CH3S), 2.46 (3H, s CH3S), 3.84 (6H, m, <BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> 2xCH30N), 4.04 (6H, m, 2xCH300C), 4.10 (2H, s, CH2Ar), 4.18 (2H, s, CH2Ar), <BR> <BR> <BR> <BR> <BR> <BR> <BR> 5.02 (4H m, 2xC=CH2), 5.60 (2H, m, 2xCHCH2), 7.10 (2H, m, 2xAr-H), 7.32 (4H, m, 2x2ArH), 7.48 (2H, m, 2xArH), 7.55 (2H, m, 2xN=CH).

Compound 262 1H N.M.R. #(ppm) 1.06 (12H, m, 4xCH3CH), 1.14 (12H, 4xCH3CH), 1.50-1.98 <BR> <BR> <BR> <BR> <BR> <BR> (8H, m, 4xCH2), 2.34 (4H, m, 4xCHCH3), 2.40 (6H, m, 2xCH3S), 2.44 (6H, m, <BR> <BR> <BR> <BR> <BR> <BR> <BR> 2xCH3S), 2.84 (4H, m, 4xOHCH3), 3.84 (12H, m, 4xCH3ON), 4.02 (12H, m, <BR> <BR> <BR> <BR> <BR> <BR> <BR> 4xOH3O0C), 4.08 (4H, m, CH2Ar), 4.20 (4H, m, 2xOH2Ar), 7.06-7.40 (32H 4x8 Ar-H) and 7.54 (4H, m, 2xArH and 2xN=CH).

Compound 263 1H N.M.R. G(ppm) 2.34 (12H, m, 2xN =CCH3 and 2xN=CCH3), 2.44 (3H, s, <BR> <BR> <BR> <BR> <BR> CH3S), 2.58 (3H, s, CH3S), 3.80 (3H, s, CH30N), 3.88 (3H, s, CH30N), 4.04 <BR> <BR> <BR> <BR> <BR> <BR> <BR> (6H, m, 2xOH3OOC), 4.15 (2H, s, CH2Ar), 4.30 (2H, S CH2Ar), 7.10-7.40 (10H, m, 2x5ArH), 7.55 (2H, m, 2xArH) and 7.66 (4H, m, 2x2ArH).

Compound 264 1H N.M.R. G(ppm) 2.45 (3H, s, SCH3), 2.55 (3H, s, SCH3), 3.85 (3H, s, CH30N), <BR> <BR> <BR> <BR> <BR> <BR> 3.90 (3H, s, CH30N), 4. 10(6H, m, CH300C), 4. 15(2H, m, Ar-CH2), 4.30 (2H, <BR> <BR> <BR> <BR> <BR> <BR> <BR> s, Ar-CH2), 6.95-7.10 (8H, m, Ar-H), 7.15-7.20 (4H, m, Ar-H), 7.35-7.40 (8H, m, Ar-H), 7.55 (2H, m, Ar-H), 7.70-7.80 (4H, m, Ar-H), 8.30 (1H, s, N= CH) and 8.35 (1H, s, N=CH).

Compound 265 1H N.M.R. #(ppm) 2.45 (3H, s, SCH3), 2.55 (3H, s, SCH3), 2.65 (3H, s, SCH3), 3.85 (3H, s, CH30N), 3.90 (6H, s, CH30N), 4.00 (9H, m, NCH3), 4.10 (9H m, CH300C), 4.30 (6H, m, ArCH2), 6.20 (3H, m, Het-H), 6.60 (3H, m, Het-H), 6.80 (3H, m, Het-H), 7.25 (3H, m, Ar-H), 7.30-7.45 (6H, m, Ar-H), 7.60 (3H, m, Ar-H) and 8.30 (3H, m, N=CH).

Compound 266 1H N.M.R. #(ppm) 2.45 (3H, s, =CCH3), 2.55-2.70 (9H, m, =CCH3and 2xCH3S), 3.85 (3H, s, CH30N), 3.90 (3H, s, CH30N), 4.08 (6H, m, 2xCH300C), 4.15 (2H, s, CH2Ar), 4.34 (2H, s, CH2Ar), 7.12-8.00 (14H, m, 2x4ArH and 2x3Het-H), 8.35 (1H, s, N=CH) and 8.40 (1H, s, N=CH).

Compound 267 1H N.M.R. #(ppm) 2.44 (9H, s, 3xCCH3), 2.54 (3H, s, CH3S), 2.66 (3H, s, CH3S), 2.76 (3H, s, CH3S), 3.96 (9H, m, 3xCH30N), 4.08 (9H, m, 3xCH300C), 4.30 (2H, s, CH2Ar), 4.34 (2H, s, CH2Ar), 4.55 (2H, s, CH2Ar) and 7.00-7.62 (21 H, m, 3x4Ar-H and 3x3Het-H).

Compound 272 1H N.M.R. #(ppm) 2.44 (3H, s, CH3S), 2.56 (3H, s, CH3S), 3.82 (3H, s, CH30N), 3.86 (3H, s, CH30N), 4.06 (6H, m, 2xCH300C), 4.18 (2H, s, CH2Ar), 4.30 (2H, s, CH2Ar), 7.15-8.04 (14H, m, 2x7Ar-H), 8.28 (1H, s, N=CH) and 8.30 (1H, s, N = CH).

Test Example Compounds were assessed for activity against one or more of the following: Erysiphe graminis f sp. tritici: wheat powdery mildew Pyricularia oryzae: rice blast Leptosphaeria nodorum: glume blotch Phytophthora infestans: late blight of potatoes Plasmopara viticola: downy mildew of vines 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 and kept under controlied 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.

Erysiphe graminis f sp. tritici <BR> <BR> <BR> 1,3,5,11,14,17,18, 18,19, 20, 21, 22, 23, 24, 25, 26, 27, 32, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 62, 69, 70, 74, 76, 77, 78, 79, 80, 81, 89, 91,94,95, <BR> <BR> <BR> 96, 97, 98, 99, 103, 104, 112, 113, 114, 115, 116, 117, 123, 126, 127, 129, 130, 131, 132, 134, 135, 139, 140, 141, 142, 143, 144, 145, 146, 147, 150, 151, 167, 176, 177, 178, 183, 184, 189, 190, 212, 214, 215, 217, 219, 220, 243, 245, 249, 255, 260 and 261.

Pyricularia oryzae 1, 2, 3, 4, 5, 6, 9, 11, 12, 17, 18, 20, 21, 22, 23, 24, 25, 27, 30, 32, 38, 39, 42, 44, 45, 46, 48, 49, 52, 62, 63, 64, 65, 66, 67, 69, 70, 71, 72, 73, 74, 75, 76,77,78,79,80,81,91, 92, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 155, 156, 157, 158, 159, 161, 163, 164,

165, 167, 169, 170, 171, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 186, 188, 189, 191, 192, 193, 194, 195, 197, 199, 200, 202, 203, 218, 219, 220, 221, 222, 224, 225, 243, 245, 249, 254, 255, 258, 260 and 261.

Leptosphaeria nodorum 1, 3, 4, 5, 6, 11, 17, 18, 19, 20, 22, 23, 24, 25, 29, 32, 38, 39, 42, 43, 44, 49, 62, 64, 65, 66, 67, 68, 69, 70,71,72,73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 101, 102, 104, 105, 107, 108, 112, 113, 114, 115, 116, 117, 119, 120, 122, 123, 124, 125, 126, 127, 129, 130, 131, 132, 139, 140, 141, 142, 143, 144, 145, 146, 147, 150, 151, 176, 177, 178, 183, 184, 188, 189, 192, 194, 200, 203, 218, 219, 220, 221, 222, 224, 225, 243, 245, 249, 254, 255, 258, 260 and 261.

Phytophthora infestans 6, 9, 10, 11, 14, 15, 16, 22, 28, 69, 70, 71, 72, 74, 76, 77, 78, 79, 80, 81, 88, 91, 95, 96, 97, 98, 99, 113, 114, 115, 116, 117, 119, 123, 124, 127, 129, 130, 131, 132, 134, 135, 139, 140, 141, 142, 143, 144, 145, 147, 150, 151, 155, 156, 157, 159, 163, 165, 166, 169, 170, 174, 176, 177, 178, 184, 214, 219, 223, 236, 237, 238, 245, 247, 254, 255, 258, 259, 261, 265 and 266.

PlasmoPara viticola 2, 4, 6, 8, 9, 10, 11, 12, 14, 16, 18, 21, 22, 29,31,33,34, 35, 36, 43, 44, 45, 48, 49, 50, 52, 62, 64, 66, 67, 68, 69, 70, 72, 74, 76, 77, 78, 79, 80, 81, 84, 85, 86, 87,90,91,91, 92, 93, 94, 95, 96, 98, 99, 101, 102, 104, 105, 106, 107, 108, 109, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 124, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 182, 183, 184, 185, 202, 206, 211, 212, 213, 214, 215, 216, 220, 235, 236, 237, 238, 240, 241, 246, 247, 249, 252, 259, 261 and 265.