WO1998050352A1

WO1998050352A1 - Dithiocarbazonic acid derivatives as pesticides

Info

Publication number: WO1998050352A1
Application number: PCT/GB1998/001234
Authority: WO
Inventors: Geoffrey Gower Briggs; Clive Leonard Cornell; Peter Stanley Thomas
Original assignee: Agrevo Uk Limited
Priority date: 1997-05-02
Filing date: 1998-04-28
Publication date: 1998-11-12
Also published as: AU7220498A; GB9708903D0

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 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 R?2 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.

Description

DITHIOCARBAZONIC 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

(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, haloalkyi, 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 haloalkyi, hydroxy, nitro, optionally substituted amino, acyl, acyloxy, optionally substituted phenyl, optionally substituted heterocyclyl, optionally substituted phenoxy, optionally substituted phenylthio, optionally substituted hetercyclyloxy, or optionally substituted heterocyclylthio.

Any cycloalkyl or cycloalkenyl groups may also be substituted by alkyl, alkenyl or alkynyl, ail 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, pyrrolidinyi, 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(0)_nE¹ or -(E^ ) = NOE², where n is 0, 1 or 2, E^ 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. E^"* 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(=0)R⁴, -C(=0)OR⁴, -C(=Z)NR R⁵, -C(=0)N(R⁴)OR⁵, -C(=0)ONR⁴R⁵, -C(=0)N(R⁴)NR5R6_| -C(=0)SR⁴, -C(=S)SR⁴, -S(0)_pR⁴, -S(0)₂OR⁴, -S(0)_pR⁴R⁵, -P(=Z)(OR )(OR⁵), -C(=0)-C(=0)OR⁵, 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 R^ and R⁶ together with the atom(s) to which they are attached can form a ring; p is 1 or 2; and Z is O or S.

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 R^ 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, haloalkyi, 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, haloalkyi, 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 (Pseudocercospore/la herpotrichoides) , rice sheath blight (Pellicularia sasakii), grey mould (Botrytis cinerea), damping off (Rhizoctonia solani), 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, Mυsca domestica; Lepidoptera, including Plutella xylostelia, Spodoptera Httoralis, Heiiothis 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 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, 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 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 II with a dithiocarbazate of general formula III, in the presence of a suitable base eg sodium hydride, according to the following reaction scheme.

Scheme 1

Intermediates of formula III 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

(IV) (V) (III)

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 R ¹ Q where Q is a leaving group, eg halogen, alkyl or aryl sulfonate, alkyl sulfate etc. When R ^ 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

(VI) (III)

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 lla according to Scheme 5. Compounds of formula lla may be prepared by methods described in EP 0 299 694.

Scheme 4

(lla) (la)

Similarly compounds of formula lb, i.e. compounds of general formula I where X is 0 and Y is N, may be prepared according to Scheme 6. Compounds of formula lib may be prepared by methods described in EP 0299694. Scheme 5

(lib) (lb)

Compounds of formula lc, 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

(lb) (10

Alternatively to preparing compounds of general formula I by reacting compounds of formula II with compounds of formula III according to Scheme 1 , compounds of general formula I can be prepared according to reaction Scheme 8. Preferred reaction conditions for reacting compound II with compound III 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)ethylidenehydrazono](methylthio) methylthiomethyl]phenyl)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 18 hours, quenched with methanol (0.2 ml) and evaporated under reduced pressure. The residue was taken up in diethyl ether, washed with brine, dried (MgSθ4) 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 °C.

Preparation of starting materials a) Methyl [1 -(3-methylphenyl)ethylidene]dithiocarbazate

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. 1 28-130 °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 cooling. The resultant mixture was stirred at 0 °C for 1 hour prior to the dropwise addition of dimethyl sulfate (100 ml). The mixture was stirred at 10 °C 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 °C.

Example 2

Methyl 3-methoxy-2-(2-[(benzylidenehydrazono)(methylthio)methylthiomethyl] phenyl)acrylate (Compound 6). To a solution of methyl 3-methoxy-2-{2-[(hydrazono)(methylthio)methylthiomethyl] phenyl}acrylate (0.5 g of major isomer) in dry tetrahydrofuran (10 ml) was added benzaldehyde (0.1 6 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)methylthiomethyl]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)phenyl]acrylate (EP 0 299 694) (2.86 g) in dry tetrahydrofuran (1 5 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; ^"Η N.M.R. δ(ppm, major isomer) 2.34 (3H, s, CH₃S), 3.74 (3H, s, CH₃0), 3.82 (3H, s, CH3OOC), 3.98 (2H, s, CH₂Ar), 5.60 (2H, s, NNH?), 7.08 (1 H, m, ArH), 7.22 (2H, m, 2xArH), 7.30 (1 H, m, ArXI) and 7.60 ( 1 H, s, MeOCH = ), ¹ H N.M.R. δ(ppm, minor isomer) 2.36 (3H, s, CH3S), 3.68 (3H, S, CH3O), 3.80 (3H, s,

CH3OOC), 4.04 (2H, s, CH₂Ar), 5.55 (2H, s N-NH₂>< ⁷-⁰⁸ <^{1 H}' ^m< ^Ar:Hh 7.24 (2H, m, 2xArXI) and 7.56 (1 H, s, MeOCH = ).

Example 3

Methyl (E)-2-(methoxyimino)-2-(2-[(3-methylbenzylidenehydrazono)(methylthio) methylthiomethyl]phenyl)acetate (Compound 165)

Sodium hydride (1 50 mg of a 60% oil dispersion) was added to a solution of methyl [1 -(3-methylphenyl)ethylidene]dithiocarbazate (0.78 g, starting material from step a) in Example 1 ) in dry tetrahydrofuran (1 5 ml). After stirring at room temperature for 1 5 minutes, a solution containing methyl (E)-2-(methoxyimino)-2- [[2-(bromomethyl)phenyl]acetate 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 10°C.

Example 4

(E)-2-(Methoxyimino)-/V-methyl-2-{2-[(3-methylbenzylidenehydrazono)

(methylthio)methylthiomethyl]phenyl)acetamide (Compound 147)

To a solution containing methyl (E) 2-(methoxyimino)-2-[[2-[1 -(3-methylphenyl) ethylidinehydroazono] (methylthiomethyl)phenyl] acetate (1 .5 g, Compound 1 65 from Example 3) in tetrahydrofuran (5 ml) and methanol (5 ml) was added 27% w/v solution of methylamine 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. 1 21 -1 25 °C. The following compounds of formula Id, i.e. compounds of general formula I 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.

(Id) Table

The ^ 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

¹ H N.M.R. δ(ppm) 2.42 (3H, s, CH₃S), 2.55 (3H, s, CH₃S), 3.68 (3H, s, CH3O), 3.70 (3H, s, CH3O), 3.83 (3H, s, CH3OOC), 3.85 (3H, s, CH3OOC), 4.1 8 (2H, s, CH₂Ar), 4.35 (2H, s, CH₂Ar), 6.95-7.78 (26H, m, 2x1 3 Ar l), 7.60 (2H, m, 2x = CHOCH₃), 8.25 ( 1 H, s, ArCH = N) and (1 H, s, ArCH_ = N).

Compound 39

^"> H N.M.R. δ(ppm) 2.42 (3H, s, CH3), 2.55 (3H, s, CH3S), 3,66 (3H, s, CH3O), 3.70 (3H, s, CjH₃0), 3.80 (3H, s, CH3OOC), 3.84 (3H, s, CH3OOC), 4.1 5 (2H, s, CH₂Ar, 4.32 (2H, S, CH₂Ar), 6.96-7.55 (26h, m, 2 x 1 3 ArJH), 7.6 (2H, m, 2x = CH_OCH₃), 8.26 (1 H, s, ArCH = N) and 8.32 (1 H, s, ArCH = N). Compound 43 H N.M.R. δ(ppm) 2.44 (3H, s, CH₃S), 2.54 (3H, s, CH₃S), 3.66 (6H, m, 2xCH₃0), 3.82 (6H, m, 2xCH OOC), 4.20 (2H, s, CH₂Ar), 4,36 (2H, s, CH₂Ar), 7.02-7.5 ( 1 4H, m, 2x7Ar-H/Het-JH), 7.6 (2H, m, 2x-CHOCH₃), 8.42 ( 1 H, s, ArCH = N) and 8.48 (1 H, s, ArCH = N).

Compound 44

¹ H N.M.R. δ(ppm) 2.46 (3H, s, CH₃S), 2.74 (3H, s, CH₃S), 3.64 (6H, m, 2xCH₃0), 3.78 (3H, s, C_H₃OOC), 3.82 (3H, s, CH3OOC), 4.20 (2H, s, CH₂0 Ar), 4.58 (2H, s, CH₂Ar), 7.06-7.56 ( 1 4H, m, 2x7Ar_:HJHet;H), 7.6 (2H, m, 2x = CH0CH₃), 8.00 ( 1 H, s, ArCH = N) and 8.04 ( 1 H, s, ArCH = N).

Compound 45

¹ H N.M.R. δ(ppm) 2.42 (3H, s, CH3S), 2.55 (3H, s, CH3S), 3.62 (3H, s, CH Q), 3.64 (3H, s, CH3O), 3.80 (3H, s, CH3N), 3.82 (3H, s, CH3N), 3.82 (3H, s,

CH3N), 3.9 (3H, s, CH3OOC), 3.98 (3H, s, CH3OOC), 4.1 6 (2H, s, CH₂Ar), 4.34

(2H, s, Cϋ₂Ar), 6.14 (2H, m, 2xHet;H), 6.54 (2H, m, 2xHet;H), 6.76 (2H, m,

2xHetX1), 7.14 (2H, m, 2xArXI), 7.28 (4H, m, 2xArXI), 7.56 (2H, m, 2xAH-j), 7.6 (2H, m, 2x = CHOCH₃), 8.24 (1 H, s, ArCH = N) and 8.30 ( 1 H, s, ArCH = N).

Compound 46

¹ H N.M.R. δ(ppm) 0.92 (9H, m, CH₃CH₂), 1 .56 (6H, m, 3xCH₂CH₃), 1 .94 (6H, m, 2xCH₃C = ), 2.04 (3H, s, CH₃C = ), 2.1 6 (6H, m, 3 x CjH₂CH₂), 2.40 (6H, m,

2 x CH₃S), 2.48 (3H, s, C_H₃C), 3.68 (9H, s, 3xCϋ₃0), 3.82 (9H, m, 3xCH₃OOC), 4.1 4 (2H, s, CH₂Ar), 4.26 (4H, m, 2xCH₂Ar), 7.1 2 (3H, m, 3xAr;

H), 7.24 (6H, m, 3x2Ar-H), 7.46 (3H, m, 3xAr-H) and 7.58 (3H, m, 3x = CH₃OCH₃). Compound 47

¹ H N.M.R. δ(ppm) 2.06 (3H, s, CH₃S), 2.44 (3H, s, CH₃S), 3.62 (3H, s, CH₃0), 3.68 (3H, s, CH3O), 3.70 (3H, s, CH3OOC), 3.82 (3H, s, CH3OOC), 4.04 (2H, s, CH_?Ar), 4.38 (2H, s, CH₂Ar), 7.02-7.5 (1 8H, m, 2x9ArJH) and 7.62 (2H, m, 2xCHOCH₃).

Compound 48

¹ H N.M.R. δ(ppm) 1 .10 (1 2H, m, 2xCH(CH₃)₂), 1 .90 (6H, m, 2xH₃-C = ), 2.38

(3H, s, CH3S), 2.46 (3H, s, CH3S), 2.56 (2H, m, 2xCH(CH₃)₂), 3.68 (6H, s, 2xCH₃0), 3.80 (6H, m, 2xCH₃OOC), 4.14 (2H, s, CH₂Ar), 4.24 (2H, s, CH₂Ar),

7.10 (2H, m, 2 x ArXI), 7.26 (4H, m, 2xAr-IH), 7.48 (2H, m, 2xAr H) and 7.60 (2H, m, 2x = CHOCH₃).

Compound 49 ¹ H N.M.R. δ(ppm) 1 .1 2 (9H, s, C(CH₃)₃), 1 .92 (6H, m, 2xCH₃-C = ), 2.38 (3H, s, CH3S), 2.50 (3H, s, CjH₃S), 2.66 (6H, s, 2xCH₃0), 2.82 (6H, s, CH3OOC), 4.14 (2H, s, CH₂Ar), 4.26 (2H, s, CH₂Ar), 7.1 0 (2H, m, 2xArXi), 7,28 (4H, m, 2x2Ar- H), 7.5 (2H, m, 2xAr-H) and 7.58 (2H, m, 2x = CjHOCH₃).

Compound 50

^"Η N.M.R. δ(ppm) 0.90 ( 1 6H, m, 4xCH₂CH₂), 1 .66 (4H, m, 4xCHCH₂), 1 .84 (1 2H, m, 4xCH₃C = ), 2.38 (6H, m, 2xCH₃S), 2.50 (6H, m, CjH₃S), 3.66 (1 2H, m, 4xCH₃0), 3.82 (1 2H, m, 4xCH₃OOC), 4.1 4 (4H, m, 2xCH₂Ar), 4.26 (4H, m, 2xCH_?Ar), 7.10 (4H, m, 4xAr-JH), 7.28 (8H, m, 4x2Ar_:H), 7.46 (4H, m, 4xAr^H) and 7.58 (4H, m, 4x = CH0CH_?). Compound 51

1 H N.M.R. δ(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, 2xCH₃0), 3.82 (6H, s, 2xCH₃OOC), 4.1 5 (2H, s, CH₂Ar), 4.26 (2H, CH₂Ar), 7.10 (2H, m, 2xAr H), 7.24 (4H, m, 2x2Ar;H), 7.50 (2H, m, 2xAr-JH) and 7.60 (2H, m, 2xCHOOCH₃).

Compound 52

¹ H N.M.R. δ(ppm) 1 .14 (6H, m, 2xCH_₃CH₂), 2.44 (3H, s, CjH₃S), 2.58 (3H, s, CH₃S), 2.94 (4H, m, 2x2CH₂CH₃), 3.68 (3H, s, CH₃0), 3.70 (3H, s, CH3O), 3.80 (3H, s, CjH₃OOC), 3.82 (3H, s, CH3OOC), 4.1 8 (2H, s, CH₂Ar), 4.38 (2H, s, CH₂Ar), 7.1 4 (2H, m, 2xArXI), 7.32 ( 10H, m, 2x5Ar H), 7.54 (2H, m, 2xArXI), 7.60 (2H, m, 2x = CHOCH₃) and 7.84 (4H, m, 2x2ArXI).

Compound 53 ¹ H N.M.R. δ(ppm) 0.94 (6H, m, 2xCH₃CH₂), 1 .58 (4H, m, 2xCH₂CH₃), 2.44 (3H, s, CH3S), 2.58 (3H, s, CH3S), 2.90 (4H, m, 2x = CCIH₂), 3.64 (3H, s, CH3O), 3.68 (3H, s, CH3O), 3.80 (3H, s, CH3OOC), 3.84 (3H, s, CH3OOC), 4.1 8 (2H, s, CH₂Ar), 4.35 (2H, s, CH₂Ar), 7.1 4 (2H, m, 2xAr;H), 7.34 (1 0H, m, 2x5Ar-H), 7.54 (2H, m, 2xAr-H), 7.62 (2H, m, 2x = CHOCH_?) and 7.84 (4H, m, 2x2Ar-H).

Compound 54 H N.M.R. δ(ppm) 0.9 (6H, m, 2xCH₃CH₂), 1 .34 (4H, m, 2xCH₂CH₃), 1 .52 (4H, m, 2xCj ₂CH₂CH₃), 2.44 (3H, s, CH3S), 2.56 (3H, s, CH3O), 2.92 (4H, m, 2x = CCH₃), 3.66 (3H, s, CH3O), 3.68 (3H, s, CH3O), 3.80 (3H, s, CH3OOC),

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 0H, m, 2x4Ar-H), 7.60 (2H, m, 2x = CHOCH₃) and 7.84 (4H, m, 2x2Ar-H). Compound 55

¹ H N.M.R. δ(ppm) 1 .98 (9H, m, 3x = CHCH₃), 2.40 (6H, m, 2xCH_₃S), 2.50 (3H, s, CH3S), 2.55-2.94 ( 1 2H, , 3x2CH₂), 3.62 (3H, s, CH3O), 3.68 (6H, m, 2CH₃0), 3.72 (3H, s, CH3OOC), 3.84 (6H, m, 2xCH₃OOC), 4.1 8 (2H, s, CH₂Ar), 4.25 (4H, m, 2xCH₂Ar), 7.68-7.34 (24H, m, 3x8Ar H), 7.50 (3H, m, 3xArXI) and 7.58 (3H, m, 3x = CHOCH₃).

Compound 56

¹ H N.M.R. δ(ppm) 2.40 (6H, m, 2xCϋ₃S), 2.46 (3H, s, CH3S), 2.62-2.90 ( 1 2H, m, 3x2CH₂), 3.64 (3H, s, CH3O), 3.68 (6H, m, 2xCJH₃0), 3.76 (3H, s, CH3OOC), 4.02 (6H, m, 2xCH₃OOC), 4.1 6 (2H, s, CH_?Ar), 4.26 (4H, m, 2xCH₂Ar), 7.1 0-7.34 (24H, m, 3x8ArXI), 7.50 (3H, m, 3xAr;H), 7.58 (3H, m, 3x = CHOCH₃) and 7.76 (3H, m, 3xN = CHCH₂).

Compound 57

¹ H N.M.R. δ(ppm) 1 .98 (6H, m, 2x = CCH_?), 2.04 (6H, m, 2x = CCH₃), 2.40 (6H, m, 2xCH₃S), 2.48 (6H, m, 2xCH₃S), 3.68 (1 2H, s, 4xCH₃0), 4.02 (1 2H, m, 4xCH₃OOC), 4.1 5 (2H, s, CH₂Ar), 4.24 (2H, s, CH₂Ar), 4.30 (2H, s, CH₂Ar), 4.44 (2H, s, CH₂Ar), 7.1 2 (4H, m, 4xAr±- \), 7.1 6 (8H, m, 2x2Ar±\), 7.48 (2H, m, 4xArϋ), 7.58 (4H, m, 4x = CHOCH₃) and 7.75 (4H, m, 4xN = Cj CH₃).

Compound 58

¹ H N.M.R. δ(ppm) 1 .98 (9H, m, 3x = CCH₃), 2.06 (3H, s, = CCH₃), 2.40 (3H, s, CH3S), 3.80 (3H, s, CH₃S), 3.68 (6H, s, 2xCH₃0), 3.80 (6H, m, 2xCH₃OOC), 4.1 5 (2H, s, CH_₂Ar), 4.28 (2H, s, CH₂Ar), 7.14 (2H, m, 2xArX(), 7.26 (4H, m, 2x2ArXI), 7.48 (2H, m, 2xAr H) and 7.58 (2H, m, 2x = CHOCH₃). Compound 59

¹ H N.M.R. δ(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, CH3OOC), 4.02 (6H, m, 2xCH₃OOC), 4.1 6 (2H, s, CH₂Ar), 4.34 (4H, m, 2xC_H₂Ar), 6.42 (3H, m, 3xHet-IH), 6.82 (3H, m, 3xHet-H),

7.1 3 (3H, m, 3xAMH), 7.26 (6H, m, 3x2 Ar-H), 7.48 (6H, m, 3xArH/3xHet-H) and 7.60 (3H, m, 3x = CHOCH₃).

Compound 60 ¹ H N.M.R. δ(ppm) 1 .1 2 (9H, m, 3xCjH₃CH₂), 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, 3xCjH₃OOC), 7.1 0 (3H, m, 3xAr^H), 7.26 (6H, m, 3x2Ar_:

H), 7.46 (3H, m, 3xArXl), 7.58 (3H, m, 3xCHOCH₃) and 7.72 (3H, m,

N = CHCH₂).

Compound 61

¹ H N.M.R. δ(ppm) 0.96 (9H, m, 3xC_H₃CH₂), 1 .60 (6H, m, 3xCH₃CH₂), 2.35

(6H, m, 3xCH₂CH₂CH₃), 2.40 (3H, s, CΗ3S), 2.44 (3H, s, CJ3S), 2.46 (3H, s,

CH3S), 3.70 (9H, m, 3xCH₃0), 3.82 (9H, m, 3xCH₃OOC), 4.14 (2H, s, CH₂Ar), 4.24 (4H, m, 2xCH₂Ar), 7.1 0 (3H, m, 3xArXI), 7.24 (6H, m, 3x2Ar-H), 7.46 (3H, m, 3xArXI) and 7.58 (3H, m, 3x = CHCH_?).

Compound 62

¹ H N.M.R. δ(ppm) 1 .08 (9H, s, C(CH₃)₃), 1 .1 5 (9H, s, C(CH₃)₃), 2.38 (3H, s, CH3S), 2.48 (3H, s, CH3S), 3.66 (6H, s, 2xCH₃0), 3.82 (6H, m, 2xCH₃OOC),

4.14 (2H, s, CH₂Ar), 4.26 (2H, s, CH₂Ar), 7.1 0 (2H, m, 2xArXI), 7.26 (4H, m, 2x2Ar;H), 7.44 (2H, m, 2xAr H) and 7.56 (4H, m, 2x = CH0CH₃ and

2xN = CHC(CH₃)₃). Compound 63

¹H N.M.R. δ(ppm) 1.00-1.18 (12H, m, 4xCH₃CH), 1.90 (3H, s, CH₃C = ), 1.94 (3H, S, CH₃S = ), 1.98 (3H, s, CH₃C = ), 2.05 (3H, s, CH3C), 2.24-2.50 (8H, m, 4xCH₂CH₃), 2.38 (6H, m, 2xCH₃S), 2.46 (6H, m, 2xCH₃S), 3.68 (12H, s, 4xCH₃0), 3.82 (12H, m, 4xCH 00C), 4.14 (4H, m, 2xCH₂Ar), 4.26 (4H, m, 2xCH₂Ar), 7.10 (4H, m, 4xAr₁H), 7.26 (8H, m, 4x2AMH), 7.48 (4H, m, 4xAr j) and 7.60 (4H, m, 4x = CHCH₃).

Compound 64 ¹H N.M.R. δ(ppm) 1.84 (6H, m, 2xCH₃C = ), 1.92 (3H, s, CH₃C = ), 1.98 (3H, s,

CJ-j₃C = ), 2.40 (6H, m, 2xCH₃S), 2.46 (6H, m, 2xCH₃S), 3.59-3.88 (32H,

4xCH₃0, 4xCH₃QOC and 4x-CCH ), 4.18 (4H, s, 2xCH₂Ar), 4.24 (2H, s,

CH₂Ar), 4.30 (2H, s, CH₂Ar), 7.10 (8H, m, 4x2AMH), 7.24 (24H, m, 4x6Ar^H),

7.48 (4H, m, 4xArXl) and 7.56 (4H, m, 4x = CHOCH₃).

Compound 65

^"Η N.M.R. δ(ppm) 2.54 (6H, s, 2xCH₃S), 3.66 (6H, m, 2xCH₃OC), 3.82 (6H, m,

2xCH₃OOC), 3.96 (6H, m, 2xCH₃OPy), 4.18 (4H, s, 2xCH₂Ar), 6.72 (2H, m,

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, 2xPyXI) and 8.28 (4H, m, 2xPy-H,

2xN = CHPy).

Compound 66

^">H N.M.R. δ(ppm) 2.04 (3H, s, CH₃C = ), 2.10 (3H, s, CH₃C = ), 2.16 (3H, s, CH₃C = ), 2.18 (3H, s, CH₃C = ), 2.42 (3H, s, CH3S), 2.35 (3H, s, CH3S), 3.66

(3H, s, CH3O), 3.68 (3H, s, CH3O), 3.80 (6H, m, 2xCH₃OOC), 3.96 (3H,

S.CH3ON), 3.98 (3H, s, CH3ON), 4.16 (2H, s, CH₂Ar), 4.35 (2H, s, CjH₂Ar), 7.12

(2H, m, 2XAXH), 7.26 (4H, m, 2x2ArXI), 7.46 (2H, m, 2xArXI) and 7.58 (2H, m, 2x = CHOCH₃). Compound 67

¹ H N.M.R. δ(ppm) 2.44 (3H , s, CH₃S), 2.56 (3H, s, CH₃S), 3.64 (3H, s, CH₃0), 3.66 (3H, s, CH3O), 3.80 (3H, s, CH3OOC), 3.82 (3H, s, CH3OOC), 4.22 (2H, s, CH₂Ar), 4.38 (2H, s, Oi₂Ar), 7.1 2 (2H, m, 2xAr^H), 7.26 (4H, m, 2x2Ar±\), 7.38 (6H, m, 3x2Ar;H_), 7.50 (2H, m, 2xAr₁H), 7.60 (2H, m, 2x-CHOCH₃), 7.78 (4H, m, 2xAr;H), 8.32 (1 H, s, N = CHAr) and 8.36 (1 H, s, N = CHAr).

Compound 69

¹ H N.M.R. δ(ppm) 2.44 (3H, s CH3S), 2.52 (3H, s, CH3S), 2.88 (6H, m, 2xCH₃NH), 3.96 (6H, m, 2xCH₃ON), 4.1 6 (2H, s, CH₂Ar), 4.28 (2H, s, CH₂Ar),

6.74 (2H, s, 2xNH), 7.06 (2H, m, 2xHet-H), 7.1 7 (2H, m, 2xAr-H), 7.40 (8H, m, 2x2HetXi and 2Aτ_±), 7.50 (2H, m, 2xAMH) and4 (2H, m, 2xN = CH-Het).

Compound 70 ¹ H N.M.R. δ(ppm) 2.46 (3H, s, CH3S), 2.74 (3H, s, CH3S), 2.88 (6H, m,

2xCH₃NH), 3.90 (3H, s, CH3ON), 3.97 (3H, s, CH3ON), 4.1 8 (2H, s, CH₂Ar),

4.55 (2H, s, CH₂Ar), 6.76 (2H, s, 2xNH), 7.06 (2H, m, 2xHet-H), 7.1 6 (2H, m,

2xAr-H), 7.34 (6H, m, 2x2xHet;H. 2x2Ar ), 7.52 (4H, m, 2xHet H and 2xAr H), 7.98 (1 H, s, N = CH-Het) and 8.04 (1 H, s, N = CH-Het).

Compound 71

¹ H N.M.R. δ(ppm) 2.42 (3H, s, CH3S), 2.52 (3H, s, CI^S), 3.80 (3H, s, CH3ON),

3.82 (3H, s, CH3ON), 4.08 (6H, s, 2xCH₃OOC), 4.1 5 (2H, s, CH₂Ar), 4.28 (2H, s, CH₂Ar), 7.05 (2H, m, 2xHetXI), 7.1 4 (2H, m, 2xAr j), 7.32 (8H, m, 2x2Het_: H), 7.54 (2H, m, 2xAr-H), 8.42 ( 1 H, s, N = CH-Het) and 8.44 (N = CH-Het). Compound 72

¹ H N.M.R. δ(ppm) 2.46 (3H, s, CH_₃S), 2.54 (3H, s, CH₃S), 3.83 (6H, s, CH₃ON),

4.02 (3H, s, CH3OOC), 4.06 (3H, s, CH3OOC), 4.1 7 (2H, s, CH₂Ar), 4.54 (2H, s,

CH₂Ar), 7.06 (2H, m, 2xHet-H), 7.14 (2H, m, 2xArXI), 7.36 (6H, m, 2xHetXI and 2x2ArX(), 7.56 (4H, m, 2xHet-H and 2xAr^H), 8.00 ( 1 H, s, N = CIH-Het) and 8.04 (1 H, s, N = CH-Het).

Compound 74

^"Η N.M.R. δ(ppm) 2.44 (3H, s, CH3S), 2.56 (3H, s, CH3S), 3.82 (3H, s, CH3ON), 3.86 (3H, s, CH3ON), 4.06 (3H, s, CH3OOC), 4.07 (3H, s, CH3OOC), 4.1 6 (2H, s, CH₂Ar), 4.30 (2H, s, CH_₂Ar), 7.14 (2H, m, 2xArXi), 7.36 (4H, m, 2x2Ar±\),

7.52 (4H, m, 2x2Ar;HJ, 7.64 (2H, m, 2xAr^H), 7.94 (4H, m, 2x2Ar^H), 8.34 ( 1 H, s, N = CH-Ar) and 8.36 (1 H, s, N = CHAr).

Compound 75

¹ H N.M.R. δ(ppm) 2.44 (3H, s, CH3S), 2.56 (3H, s, CH3S), 3.81 (3H, s, CH3ON),

3.85 (3H, s, CH3ON), 4.07 (3H, s, CH3OOC), 4.09 (3H, s, CH3OOC), 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, 2x2ArMH), 8.30 ( 1 H, s, N = CHAr) and 8.32 (1 H, s, N = CHAr).

Compound 77

¹ H N.M.R. δ(ppm) 2.44 (3H, s, CH3S), 2.56 (3H, s, CH3S), 3.82 (3H, s, CH3ON), 3.84 (3H, s, CH3ON), 4.05 (6H, s, 2 x CH3OOC), (4.1 5 (2H, s, CH₂Ar), 4.28 (2H, s, CH₂Ar), 7.1 4 (2H, m, 2xArXI), 7.28-7-67 (1 0H, m, 2x5Ar i), 7.84 (2H, m, 2Ar-H), 8.20 (2H, s, N = CHAr) and 8.22 (1 H, s, N = CHAr). Compound 83

¹H N.M.R. δ(ppm) 2.42 (3H, s, CH₃S), 2.55 (3H, s, CH₃S), 3.80 (3H, s, CH₃0), 3.84 (3H, s, CH_₃0), 4.08 (3H, s, CH3OOC), 4.10 (3H, s, CH3OOC), 4.14 (2H, s, CH₂Ar), 4.30 (2H, s, CH₂Ar), 6.99-7.56 (26H, m, 2x13Ar^H), 8.26 (1H, s, 5 ArCH = N) and 8.28 (1H, s, ArCH = N).

Compound 86

TH N.M.R. δ(ppm) 2.48 (3H, s, CH3S), 2.55 (3H, s, CH3S), 3.84 (3H, s, CH3O), 3.90 (3H, s, CH3O), 4.08 (3H, s, CjH₃OOC), 4.10 (3H, s, CH3OOC), 4.18 (2H, s, ° CH₂Ar), 4.31 (2H, s, CH₂-Ar), 7.05-8.95 (16H, m, 2x8ArXl), 8.35 (1H, s, ArCH = N) and 8.37 (1H, s, ArCH = N).

Compound 87

¹H N.M.R. δ(ppm) 2.48 (3H, s, CH3S), 2.56 (3H, s, CH3S), 2.56 (3H, s, CH3S), 5 3.81 (3H, s, CH3O), 3.84 (3H, s, CH3O), 4.09 (6H, s, 2xCjH₃OOC), 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 0 ¹ H N.M.R. δ(ppm) 2.46 (3H, s, CH3S), 2.59 (3H, s, CH3S), 2.94 (6H, m,

2xNHCH₃), 3.97 (3H, s, CH3O), 3.99 (3H, s, CH3O), 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 5 ¹ H N.M.R. δ(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, CjH₂Ar), 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

¹ H N.M.R. δ(ppm) 1.24 (12H, m, (CH₃)₂Cx2), 2.44 (3H, s, CH3S), 2.55 (3H, s, CH3S), 2.94 (2H, m, (CH₃)₂CHx2), 3.81 (3H, s, CH3O), 3.85 (3H, s, CH3O), 4.06 (3H, s, CH₃0₂C), 4.10 (3H, s, CH₃0₂C), 4.17 (2H, s, CH₂Ar), 4.32 (2H, s, 5 CH₂Ar), 7.15-7.77 (16H, m, 2x8ArXI), 8.32 (1H, s, C_H = N) and 8.35 (1H, s, CH = N).

Compound 104

^"•H N.M.R. δ(ppm) 2.43 (3H, s, CH3O), 2.57 (2H, s, CH3S), 3.09 (6H, s, 10 CH₃Sx2), 3.836H, s, 2xOCH₃), 4.06 (6H, s, 2xCH₃0₂C), 4.1 (6H, s,

2xCH₃0 C), 4.16 (4H, s, 2xCH₂Ar), 4.30 (4H, s, 2xCH₂Ar) and 7.0-7.9 (32H, m, 4x8ArX().

Compound 105 15 ¹ H N.M.R. δ(ppm) 2.30 (6H, s, Ar-CH₃x2), 2.42 (6H, s, Ar-CH x2), 2.56 (3H, s, CH₃Q), 2.64 (3H, s, CH3S), 3.82 (3H, s, CH3O), 3.86 (3H, s, CH₃0₂C), 4.07 (3H, s, CH₃0₂C), 4.14 (2H, s, CH₂Ar), 4.30 (2H, s, CH_?Ar), 7.0-7.8 (14H, m, 2x7ArXI), 8.30 (1H, s, CJH = N) and 8.33 (1H, s, CH = N).

20. Compound 107

¹H N.M.R. δ(ppm) 2.35 (3H, s, CH₃Ar), 2.38 (3H, s, CH₃Ar), 2.42 (3H, s, CH Ar), 2.48 (3H, s, CH_3Ar), 2.58 (3H, s, CH3S), 2.70 (3H, s, CH3S), 3.82 (3H, s, CH3O), 3.90 (3H, s, CH3O), 4.08 (3H, s, CH3O2C), 4.10 (3H, s, CH3O2C), 4.18 (2H, s, CIH₂Ar), 4.38 (2H, s, CH₂Ar), 7.1-7.78 (14H, m, 2x7Ar-JH), 8.59

25 (1H, s, CH = N) and 8.60 (1H, s, CH = N).

Compound 108

¹H N.M.R. δ(ppm) 2.52 (3H, s, CH3S), 2.62 (3H, s, CH3S), 3.8 (3H, s, CH3O), 3.88 (3H, s, CH3O), 4.08 (3H, s, CH₃0₂C), 4.10 (3H, s, CH₃0₂C), 4.2 (2H, s, 30 CH Ar), 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

1 H N.M.R. δ(ppm) 1 .1 4 (6H, m, CH₃CH₂x2), 2.48 (3H, s, CH₃S), 2.58 (3H, s, CH3S), 2.90 (4H, m, CH₂CH₃x2), 3.80 (3H, s, CH3O), 3.86 (3H, s, CH3O), 4.08 (3H, s, CH₃0₂C), 4.09 (3H, s, CH₃0₂C), 4.1 6 (2H, s, CH₂Ar), 4.34 (2H, s, CH₂Ar) and 7.06-7.98 ( 1 8H, m, 2x9Ar_;H_).

Compound 1 10 H N.M.R. δ(ppm) 0.94 (6H, m, CH₃CH₂x2), 1 .58 (4H, m, CΗ₂CH₃x2), 2.44 (3H, s, CH3O), 2.59 (3H, s, CH3S), 2.90 (4H, m, CH₂CH₂x2), 3.82 (3H, s, CH3O), 3.88 (3H, s, CH3O), 4.08 (3H, s, CH3θ₂C), 4.09 (3H, s, CH_₃0₂C), 4.1 5 (2H, s, CH₂Ar), 4.34 (2H, s, CH₂Ar) and 7.04-7.94 (1 8H, m, 2x9Ar;H).

Compound 1 1 1

¹ H N.M.R. δ(ppm) 1 .96-2.0 (3H, s, CH₃0x4), 2.40 (3H, s, CH3S), 2.46 (3H, s, CH3O), 2.47 (3H, s, CH3O), 2.64 (8H, m, CH₂CH₂x4), 2.96 (8H, m,

CH₂CH₂x4), 3.86 ( 1 2H, m, CH₃0x4), 4.08 ( 1 2H, m, CH₃0₂Cx4), 4.1 2 (4H, br.s, CH₂Arx2), 4.20 (4H, br.s, CH₂Arx2) and 7.08-7.6 (36H, m, 4x9Ar₁H).

Compound 1 53 ¹ H N.M.R. δ(ppm) 2.39 (3H, s, N = CCH₃), 2.41 (3H, s, N = CCH₃), 2.50 (3H, s, CH3S), 2.59 (3H, s, CI-I3S), 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 7.1 4-8.10 ( 1 6H, m, 2x8AMH).

Compound 1 58

^"Η N.M.R. δ(ppm) 2.50 (3H, s, CH3S), 2.60 (3H, s, CH3S), 3.10 (6H, 2xs, 2xCH₃S0₂), 3.86 (3H, s, CH3O), 3.91 (3H, s, CH3O), 4.07 (6H, 2xs, 2xCH₃OOC), 4.1 9 (2H, s, CH₂Ar), 4.34 (2H, s, CH₂Ar), 7.14-7.56 (8H, m, 2x4ArX(), 7.95 (8H, m, 2x4Ar H), 8.37 ( 1 H, s, Ar^H = N) and 8.39 ( 1 H, s, Ar- CH = N). Compound 168

¹ H N.M.R. δ(ppm) 1.95-2.05 (4x3H, 4s, CH₃C), 2.41 (3H, s, CH₃S), 2.92 (2x3H,

2xd, CH₃N), 3.95 (3H, s, CH3O), 3.99 (3H, s, CH₂Ar), 4.22 (2H, s, CH₂Ar), 6.76

(2H, s, 2xNH) and 7.12-7.54 (8H, m, 2x4AM-]).

Compound 170

¹H N.M.R. δ(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, CH3O), 3.95 (3H, s, CH3O), 4.09 (2H, s, CH₂Ar), 4.22 (2H, s, CH₂Ar), 6.77 (2H, s, 2xNIH) and 7.12-7.54 (8H, m, 2x4Ar;H).

Compound 175

¹ H N.M.R. δ(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, CH3O), 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, 2X4AMH) and 8.14 (2H, m, 2xN = CH).

Compound 176

¹H N.M.R. δ(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 i and 3x2Het-H), 7.95 (1H, s, N = CH), 8.30 (1H, s, N = CH) and 8.35 (1H, s, N = CH).

Compound 177

¹H N.M.R. δ(ppm) 2.45 (3H, s, SCH3), 2.50 (3H, s, SCjH₃), 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, NCCJH₃), 4.15 (2H, s, Ar-CH_?), 4.20 (2H, s, Ar-CH_?), 4.35 (2H, s, Ar_:

CH?), 4.50 (2H, s, Ar-CH₂), 6.95 (4H, m, 4xCH₃NH), 7.20-7.60 (24H, m, 4xAr- H), 4x2Het-H), 7.95 (1 H, s, N = CJH), 8.00 (1 H, s, N = CH) and 8.40 (2H, m, N = CH). Compound 178

¹H N.M.R. δ(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), -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 4x2HetX() and 7.90 (2H, m, N = CH).

Compound 179

¹H N.M.R. δ(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, NOCH_₃), 4.15 (2H, Ar-CH₂), 4.25 (2H, s, Ar-CH₂), 4.25 (2H, s, Ar-CH₂), 6.80 (2H, m, 2xCH₃ JH) and 6.90-7.55 (12H, m, 2x4ArXI and 2x2HetMH).

Compound 180 ¹H N.M.R. δ(ppm) 2.25-2.50 (21 H, m, N = CC_H₃ 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, 4xHetXI), 7.14-7.60 (20H, m, 4x4ArXI and 4xHet H).

Compound 184

¹H N.M.R. δ(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. δ(ppm) 2.42 (3H, s, CH3S), 2.43 (3H, s, CH3S), 2.44 (3H, s CH3S),

2.82-3.00 (12H, m, 3xSCjH₂CH_2), 2.96 (9H, m, 3xNHCy₃), 3.61 (6H, m,

3xNCCH_?S), 3.98 (9H, m, 3xCH₃ON), 4.16 (2H, s, CH₂Ar), 4.23 (4H, m, 2xCH₂Ar), 6.80 (3H, m, 3xNHCH₃) and 7.10-7.56 (12H, m, 3x4ArXI). Compound 187

¹H N.M.R. δ(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, CH3ON), 3.99 (3H, s, C_H₃ON), 3.99 (3H, s, CH3ON), 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. δ(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, 3xCH_?NH), 7.17-7.58 (12H, m, 3x4Ar-JH) and 8.10 (3H, m, 3xN = CH).

Compound 190

^"Η N.M.R. δ(ppm) 1.14(9H, m, 3xCH₃CH₂), 2.42 (3H, s, CH_₃S), 2.43 (3H, s, 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, CΗ3ON), 3.87 (3H, s, CH3ON), 4.15 (2H, CH₂Ar), 4.28 (2H, s, CH₂Ar), 4.38 (2H, s, CH₂Ar), 6.10 (3H, m, 3x = CH), 6.74 (3H, m, 3x = CH), 6.80 (3H, m, CH3NH), 7.18-7.58 (12H, m, 3x4ArXI) and 8.08 (3H, m, 3xN = CH).

Compound 191 H N.M.R. δ(ppm) 1.95 (9H, m, 3xCϋ₃C = ), 2.24 (9H, m, C_H₃C = ), 2.40 (3H, s, CH3S), 2.41 (3H, s, CH3S), 2.48 (3H, m, CH3S), 2.94 (9H, m, 3xCH₃NH), 3.95 (9H, m, 3xCH_₃ON), 4.16 (2H, s, CH Ar), 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. δ(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, 3xCH₃ON), 4.17 (2H, s, CH_₂Ar), 4.28 (2H, s, CH_?Ar), 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. δ(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, 4xCH₃0N), 4.15 (2H, s, CH₂Ar), 4.23 (4H, m, 2xCH₂Ar), 4.40 (2H, m, CH_?Ar), 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. δ(ppm) 1.10-2.75 (28H, m, 4x3CH₂ and 4xCH(CH₂)₂)_> 2.40-2.52

(12H, m, 4xCH₃S), 2.94 (12H, m, 4xCH NH), 3.98 (12H, m, 4xCH₃0N), 4.15

(2H, s, CH_₂Ar), 4.22 (6H, m, 3xCH₂Ar), 5.70 (8H, m, 4xCH = CH), 6.78 (4H, ,

4xCH₃NH_), 7.14-7.58 (16H, m, 4x4ArXI) and 7.68 (4H, m, 4xCH = N).

Compound 196

¹H N.M.R. δ(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, CH3ON), 3.89 (3H, s, CH3ON),

4.10 (2x3H, 2xs, CH_₃0₂C), 4.15? (2H, s, C_H₂Ar), 4.32 (2H, s, CH Ar), 6.73 (2H, d, 2xAr;H), 7.15-7.65 (6H, 2x3ArXi), 8.25 (1H, s, CH = N) and 8.27 (1H, s, CH = N). Compound 197

1H N.M.R. δ(ppm) 2.47 (3H, s, CH₃S), 2.61 (3H, s, CH₃S), 2.70 (3H, s, CH3S), 3.85 (3H, s, CH3ON), 3.91 (6H, s, 2xCH₃ON), 4.10 (3H, s, CH3OOC), 4.13 (6H, s, 2 x CH3OOC), 4.19 (2H, s, CH₂Ar), 4.36 (4H, m, 2xChl₂Ar), 7.17-7.75 (21 H, m, 3x7Ar:H), 8.22 (5H, m, 3xAr;H and 2xN = CH) and 8.73 (1 H, s, N = CH).

Compound 198

¹H N.M.R. δ(ppm) 1.97 (3H, s, CH₃C = N), 1.99 (3H, s, CH₃C = N), 2.07 (3H, s, C_H₃C = N), 2.04 (3H, s, CH₃C = N), 2.42 (3H, s, CjH₃C), 2.5 (3H, s, CH3S), 3.89 (6H, s, 2xCH₃ON), 4.06 (3H, s, CH₃0₂C), 4.08 (3H, s, CH3θ₂C), 4.13 (2H, s, CH₂Ar), 4.23 (2H, s, CH₂Ar) and 7.13-7.59 (8H, m, 2x4ArH).

Compound 199

¹H N.M.R. δ(ppm) 2.39 (3H, s, C_H₃C = N), 2.42 (3H, s, CH₃C = N), 2.46 (3H, s, CU3S), 2.59 (3H, s, CH3S), 3.83 (3H, s, CH3ON), 3.90 (3H, s, CH3ON), 4.09 (3H, s, CH₃S0₂C), 4.11 (3H, s, CH3O2C), 4.18 (2H, s, CH₂Ar), 4.36 (2H, s, CH₂Ar) and 7.16-7.93 (18H, m, 2x9ArH).

Compound 200 ¹H N.M.R. δ(ppm) 1.16 (9H, s, (CH₃)₃C), 1.2 (9H, s, (CH₃)₃C), 1.88 (3H, s, CH₃C = N), 1.93 (3H, s, Cj ₃0C = N), 2.42 (3H, s, CH3S), 2.52 (3H, s, CH3S), 3.87 (3H, s, CH3ON), 3.88 (3H, s, CH3ON), 4.08 (3H, s, Cy₃S), 4.09 (3H, s, CU3O2C), 4.13 (2H, s, CH₂Ar), 4.23 (2H, s, CH_?Ar) and 7.14-7.58 (8H, m, 2x4ArH).

Compound 201

¹H N.M.R. δ(ppm) 2.48 (12H, m, 4x = CCH₃), 2.60-2.70 (12H, m, 4xCjH₃S), 3.83

(3H, s, CH3ON), 3.90 (9H, m, 4xCH₃ON), 4.04-4.16 (18H, 4xCH₃OOC and

3xCH₂Ar), 4.35 (2H, s, CH₂Ar), 7.18-7.76 (24H, m, 4x4ArXi), 8.23 (4H, m, 4xHet-H) and 8.62 (4H, m, 4xHet-H). Compound 202

¹H N.M.R. δ(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, CH₃ON), 3.90 (9H, m, 3xCH₃ON), 4.10 (12H, m, 4xCH₃OOC), 4.18 (4H, m, 2xCH₂Ar), 4.35 (4H, s, 2xCH₂Ar), 7.18-7.76 (24H, _m, 4x4Ar^H and 4x2HetXl) and 8.66 (8H, m, 4x2Het^l).

Compound 203

¹H N.M.R. δ(ppm) 2.49 (3H, s, CH_₃S), 2.59 (3H, s, CH3S), 3.86 (3H, s, CH3ON), 3.91 (3H, s, CH3ON), 4.09 (3H, s, CH₃0₂C), 4.10 (3H, s, CH₃0₂C), 4.34 (2H, s, CH₂Ar), 4.37 (2H, s, CH2^Ar>' 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. δ(ppm) 2.50 (3H, s, CH3S), 2.61 (3H, s, CH3S), 3.86 (3H, s, CH3ON), 3.90 (3h, s, CH3ON), 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, ArXI) and 9.41 (1H, d, ArH).

Compound 207

¹H N.M.R. δ(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, CH3ON), 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 ArXI), 8.08-8.12 (1H, d, CHC = N) and 8.10-8.15 (1H, d, CHC = N). Compound 21 3

¹ H N.M.R. δ(ppm) 1 .48 (6H, m, 2xCjH₃C), 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, CH3ON), 3.98 (3H, s, CH.3ON), 4.1 3 (2H, s, CH₂Ar), 4.1 9 (2H, s, CH₂Ar), 6.73 (2H, s, 2xNHMe), 7.10-7.55 (1 8H, m, 2x9ArH) and 7.62 (2H, m, 2x = CHCHMe).

Compound 214

¹ H N.M.R. δ(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,

2xCH₃ON), 4.1 2 (2H, s, CH₂Ar), 4.22 (2H, s, CH₂Ar), 6.75 (2H, s, 2xNHMe),

7.1 4 (2H, m, 2xAr H), 7.30 (4H, m, 2x2 Ar- ), 7.44 (2H , m, 2xAr i) and 7.64 (2H, m, 2xN = CHCH).

Compound 21 5

¹ H N.M.R. δ(ppm) 2.43 (6H, m, 2xCH₃S), 2.52 (3H, s, CH3S), 2.70 (9H, m,

3xCH₃NH), 3.81 (9H, , 3xCH₃OAr), 3.96 (9H, s, 3xCH.₃ON), 4.1 6 (2H, s,

CH₂Ar), 4.28 (4H, m, 2xCH₂Ar), 6.76 (3H, m, 3xCH₃NH), 6.82-6.95 ( 1 2H, m,

3x2ArH and 3xCH = CH), 7.14 (3H, m, 3xArH), 7.23-7.54 ( 1 5H, m, 3x5ArlH) and 8.10 (3H, m, N = CH).

Compound 21 6

¹ H N.M.R. δ(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, 2x2CH_?CH?C), 3.90 (3H, s, CH3ON), 3.92 (3H, s, CH3ON), 4.1 0 (2H, s, CH₂Ar), 4.1 9 (2H, s,

CH₂Ar), 6.76 (2H, m, 2xCH₃NH), 7.14 (2H, m, 2xAτ__), 7.30 (4H, m, 2x2ArH) and 7.48 (2H, m, 2xArH). Compound 217

¹H N.M.R. δ(ppm) 0.92 (18H, m, 3xCH(CH₂CJH₃)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, 3xCH₃ON), 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. δ(ppm) 1.07-2.10 (20H, m, 4x3CH and 4xCH₂), 2.20-2.25 (12H, m, 4xCH₃S), 2.92 (12H, m, 4xCH_₃NH), 3.04 (8H, m, 4xCH₂ bridging), 3.96 (12H, m, 4xCH₃ON), 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 AHH), 7.34 (8H, m, 4 x2ArH), 7.48 (4H, m, 4xArH) and 7.72 (4H, m, 4xN = CH).

Compound 219

¹H N.M.R. δ(ppm) 1.08 (3H, s, CH₃C), 1.15 (3H, s, CJH3C), 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 (1 H, s, N =CH) and 7.57 (1H, s, N = CH).

Compound 220

1H N.M.R. δ(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, 4xCH₃ON), 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. δ(ppm) 2.35-2.70 (36H, m, =CCH₃, N = CCH₃ and S CH₃), 3.85 (3H, s, CH₃ON), 3.90 (9H, m, CH3ON), 4.10 (12H, m, COOCH3), 4.15-4.20 (4H, m, ArCH₂), 4.35 (4H, m, ArCH₂), 6.75 (4H, m, HetXO, 7.10-7.60 (20H, m, ArXI), 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. δ(ppm) 2.40-2.50 (18H, m, =CCH₃ and SCH3), 2.65 (3H, s, SCH3),

2.75 (3H, s, SCH3), 3.90 (12H, m, CU3ON), 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, ArXI), 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. δ(ppm) 2.45 (3H, s, SCH3), 2.55 (3H, s, SCH3), 3.85 (3H, s, CjH₃ON),

3.90 (3H, s, CH3ON), 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. δ(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, CH3ON), 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

•Η N.M.R. δ(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, 4xCH₃ON), 4.12 (12H, m, 4xCH₃OOC), 4.15 (2H, s, CH₂Ar), 4.26 (2H, s, CH₂Ar), 4.38 (2H, s, CH_?Ar), 4.50 (2H, s, CIH Ar),

7.00-7.60 (24H, m, 4x4ArXI and 4x2Het-JH), 7.85 (1 H, s, NCH), 7.90 (1 H, s, N = CH) and 8.30 (2H, m, 2xN = CH).

Compound 226 ¹ H N.M.R. δ(ppm) 1.35 (27H, m, C.CH3.3), 2.45 (3H, s, SCH3), 2.55 (3H, s,

SCH₂), 2.70 (3H, s, SCH3), 3.85-3.90 (9H, m, CH3ON), 4.10 (9H, CH3OOC),

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. δ(ppm) 2.30 (3H, s, N = CCH₃₎, 2.35 (3H, s, N = CCH₃), 2.45 (9H, m,

N = CCH₃SC_H₃), 2.50 (3H, s, SCH₃), 2.55 (3H, s, SCH3), 2.75 (3H, s, SCH3),

3.95 (12H, m, CH3ON), 4.05 (12H, m, CH3OOC), 4.10 (4H, m, ArCH₂), 4.30 (2H, s, ArCH₂), 4.50 (2H, s, ArCH₂), 6.85 (2H, m, Het±l), 7.10-7.20 (8H, m,

ArH), 7.30-7.45 (8H, m, ArH) and 7.55-7.60 (4H, m, Ar ).

Compound 228

¹H N.M.R. δ(ppm) 2.04 (12H, m, 4xCH₃S), 2.78-3.00 (16H, m, 4xCH_₂CH₂S), 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. δ(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, 2xCH₃ON), 4.04-4.10

(10H, m, 2xCH₃OOC and 2xCH₂Ar) and 7.14-7.58 (8H, m, 2x4Ar j).

Compound 230

¹H N.M.R. δ(ppm) 2.44 (3H, s, CH₃S), 2.52 (3H, s, CH₃S), 3.84 (3H, s, CH3ON),

3.86 (3H, s, CH3ON), 4.06 (6H, m, 2xCH₃OOC), 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. δ(ppm) 2.35-2.55 (12H, m, 2xCH₃S and 2xCH₃C = ), 3.84 (6H, m,

2xCH₃ON), 4.06 (6H, s, CJ-J3OOC), 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. δ(ppm) 2.46 (3H, s, C_H₃S), 2.55 (3H, s, CH3S), 3.84 (3H, s, CH3ON), 3.86 (3H, s, CH3ON), 4.08 (6H, s, 2xCH₃OOC), 4.21 (2H, s, CH₂Ar), 4.32 (2H, s, CH₂Ar) and 7.14-7.66 (18H, m, 2x8ArH and 2xHet-JH).

Compound 233

¹H N.M.R. δ(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,

3xCjH₃ON), 4.06 (9H, m, 3xCH₃OOC), 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 = CIH), 7.15-7.60 (12H, m, 3x4Ar-H) and 8.14 (3H, m, 3xN = CH). Compound 234

¹H N.M.R. δ(ppm) 2.42-2.66 (18H, m, 2CH₃-C = and 2xCH₃S), 3.83 (3H, s, CH₃0N), 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-JH) and 8.08 (2H, m, 2xN = CH).

Compound 235

^"Η N.M.R. δ(ppm) 2.08-2.66 (36H, m, 4x3CH₃C= and 4xCH₃S), 3.86 (12H, m, 4xCH₃0N), 4.03 (3H, s, CH.3OOC), 4.08-44.18 (11H, m, 3xCH₃OOC and 1xCH₂Ar), 4.28 (2H, s, CH₂Ar), 4.35 (4H, m, 2xCH₂Ar), 6.63 (4H, m, 4xH_C = ), 7.1-7.62 (16H, m, 4x4ArXI) and 8.00 (4H, s, 4xN = CH).

Compound 236

¹H N.M.R. δ(ppm) 2.24-2.68 (12H, m, 4xCH₃S), 3.86 (12H, m, 4xCH₃0N), 4.04-

4.18 (14H, m, 4xCH₃00C and1xCH₂Ar), 4.34 (6H, m, 3xCH₂Ar), 6.38-6.55 (4H, m, 4x = CH), 6.75-6.86 (4H, m, 4x = CH), 7.14-7.58 (16H, m, 4x4ArH) and 8.18 (4H, m, 4xN = CH).

Compound 237

¹H N.M.R. δ(ppm) 1.08-1.40 (24H, m, 4xCH_?CH?CH_?), 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. δ(ppm) 1.44-2.70 (28H, m, 4x3CH₂and 4xCH(CH₂)₂), 2.42-2.55 (12H, m, 4xCH₃S), 3.90 (12H, m, 4xCH₃ON), 4.04-4.17 (14H, m, 4xCH OOC 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. δ(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, C_H₂Ar), 4.21 (2H, s, CH₂Ar), 6.80 (2H, br.t, NHCH₃x2), 7.1-7.9 (10H, m, 2x4ArH and CH = Nx2).

Compound 242 H N.M.R. δ(ppm) 0.90 (6H, m, CH₃CH₂x2), 1.34 (8H, m, CH₃CH₂CH₂x2), 1.48 (8H, m, CH₂CH₂CH₂CH x2), 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. δ(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. δ(ppm) 2.46 (3H, s, CH3S), 2.60 (3H, s, CjH₃S), 2.88 (3H, d, CH3NH),

2.90 (3H, d, CH3NH), 3.98 (3H, s, CH3O), 4.00 (3H, s, CH3O), 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 (1H, s, CH = N). Compound 245

¹H N.M.R. δ(ppm) 2.42 (3H, s, CH₃S), 2.56 (3H, s, CH₃S), 2.94 (6H, d, CH₃NHx2), 3.98 (6H, s, CH₃0x2), 4.18 (2H, s, CH₂Ar), 4.3 (2H, s, CI ₂Ar), 6.8 (2H, br.m, NjHCH₃x2), 6.94-7.18 (4H, m, CH = CHx2), 7.20-7.60 (18H, m, 2x9ArlH), 8.18 (1H, s, CH = N) and 8.20 (1H, s, CH = N).

Compound 247

¹H N.M.R. δ(ppm) 1.1 (6H, d, CH3CHCH3), 1.15 (6H, d, CH3CHCH3), 2.41 (3H, s, CH3S), 2.48 (3H, s, CH3S), 2.60 (2H, m, CH(CH₃)₂x2), 3.85 (6H, s, CH₃0x2), 4.05 (6H, s, 2xCH₃0₂C), 4.102H, 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. δ(ppm) 1.28 (18H, s, (CH_?)₃Cx2), 2.44 (3H, s, CH3S), 2.56 (3H, s, CJH₃S), 3.80 (3H, s, CH3O), 3.85 (3H, s, CH3O), 4.05 (3H, s, CH₃0₂C), 4.10 (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. δ(ppm) 2.42 (3H, s, CH3S), 2.56 (3H, s, CH3S), 3.78 (3H, s, CH3O), 3.82 (3H, s, CH3O), 4.05 (3H, s, CH₃0₂C), 4.10 (3H, s, CH₃0₂C), 4.25 (2H, s, 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. δ(ppm) 0.90 (6H, m, CH₃CH₂x2), 1.36 (12H, m, CH₃CH₂CH₂CH₂x2), 1.45 (8H, m, CH₂CH₂0x2), 2.44 (3H, s, Cj±₃S), 2.56 (3H, s, CH3S), 3.84 (3H, s, Cj ₃0), 3.86 (3H, s, CH3O), 4.0 (3H, s, CH₃0₂C), 4.16 (2H, s, CH₂Ar), 4.28 (2H, s, CH₂Ar), 6.8-7.6 (16H, m, 2x8ArlH), 8.22 (1H, s, CH = N) and 8.24 (1H, s, CH = N). Compound 251

¹ H N.M.R. δ(ppm) 2.40 (3H, s, CjH₃S), 2.50 (3H, s, CH₃S), 3.78 (3H, s, CH3O), 3.84 (3H, s, CH3O), 4.08 (3H, s, CH3O2C), 4.1 6 (3H, s, CH₃0₂C), 4.1 8 (2H, s, CH₂Ar), 4.30 (2H, s, CH₂Ar), 6.78-7.6 (22H, m, 2x1 1 ArH), 8.26 (1 H, s, CH = N) and 8.30 (1 H, s, CH = N).

Compound 253

¹ H N.M.R. δ(ppm) 2.44 (3H, s, CH3S), 2.56 (3H, s, CH3S), 3.80 (3H, s, CH3O), 3.82 (3H, s, CjH₃0), 4.02 (3H, s, CH₃0₂C), 4.04 (3H, s, CH₃0₂C), 4.1 8 (2H, s, CH₂Ar), 4.28 (2H, s, CH₂Ar), 5.7-6.1 (2H, t, CHF₂x2), 7.1 -7.8 (1 6H, m, 2x8ArH), 8.32 (1 H, s CH = N) and 8.34 ( 1 H, s, CH = N).

Compound 254

¹ H N.M.R. δ(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, C_H₃S), 3.73 (3H, m, 3xCHCH_?), 3.80

(6H, m, 2xCH₃ON), 3.82 (3H, s, CH3ON), 4.02 (6H, m, 2xCH₃OOC), 4.06 (3H, s, CH3OOC), 4.10 (2H, s, CH₂Ar), 4.18 (2H, s, CIH₂Ar), 4.24 (2H, s, CIH₂Ar), 7.1

(3H, m, 3xArH), 7.26 (21 H, m, 3x7ArH), 7.50 (3H, s, 3xArH) and 7.74 (3H, m, 3xN = CH).

Compound 255

¹ H N.M.R. δ(ppm) 1 .1 4-1 .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 (1 2H, m,

4xCH₃ON), 4.02 ( 1 2H, m, 4xCϋ₃OOC), 4.08 (4H, m, 2xCH₂Ar), 4.22 (4H, m, 2xCH₂Ar), 7.1 2 (4H, m, 2xCH₂Ar), 7.1 2 (4H, m, 4xArH), 7.34 (8H, m, 4x2ArH),

7.48 (4H, m, 4xArH) and 7.65 (4H, m, 4xN = CH). Compound 256

^"Η N.M.R. δ(ppm) 2.42 (3H, s, CH₃S), 2.50 (3H, s, CH₃S), 3.80 (6H, m, 2xArOCH₃), 3.84 (6H, m, 2xCH₃ON), 4.04 (6H, m, 2xCH₃OOC), 4.14 (2H, s, CH Ar), 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

T H N.M.R. δ(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, 2xCH₃ON), 4.02 (3H, s, CH3OOC), 4.04 (3H, s, CH3OOC), 4.08 (2H, s, CH₂Ar), 4.1 8 (2H, s, CH₂Ar), 7.10 (2H, m, 2xArH), 7.34 (4H, m, 2x2ArH) and 7.50 (2H, m, 2xArH).

Compound 258

¹ H N.M.R. δ(ppm) 0.88 ( 1 8H, m, 3x(CH₂CH₃)₂), 1 .52 (1 2H, m, 3xCH(CH₂CH₃)₂, 2.1 8 (3H, m, 3xCH(CH₂CH₃)₂), 2.37 (3H, s, CH3S), 2.40 (3H, s, CH3S), 2.44 (3H, s, CH3S), 3.84 (9H, m, 3xCH₃ON), 4.05 (9H, s, 3xCH₃OOC), 4.10 (2H, s, CH₂Ar), 4.20 (4H, m, 2xCH₂Ar), 7.1 2 (3H, m, Ar l), 7.34 (6H, m, 3xArlH), 7.48 (6H, m, 2xArH and 2xN = CH).

Compound 259

¹ H N.M.R. δ(ppm) 1 .06-2.06 (20H, m, 4x3CH and 4xCH₂), 2.40 (1 2H, m,

4xCH₃S), 2.83-3.10 (8H, m, 4xCH₂ bridging), 3.83 (1 2H, s, 4xCH₃0N), 4.02

(1 2H, m, 4xCH₃00C), 4.1 8 (2H, s, CH₂Ar), 4.20 (6H, m, 3xCH₂Ar), 5.95-6.22

(8H, m, 4xC_H = CH), 7.1 0 (4H, m, 4xArH), 7.36 (8H, m, 4x2ArH), 7.44 (4H, m, 4xArH) and 7.75 (4H, m, 4xN = CH).

Compound 260

¹ H N.M.R. δ(ppm) 1 .44 (6H, s, = C-C(CH₃)_?), 1 .60 (3H, N = CCH₃), 1 .64 (3H, s, N = CCH₃), 2.42 (3H, s, CI^S), 2.48 (3H, s, CH3S), 3.83 (6H, s, 2xCH₃0N), 4.02 (3H, s, CH3OOC), 4.06 (3H, s, CH3OOC), 4.14 (2H, s, CH_₂Ar), 4.20 (2H, s, CH₂Ar) and 7.08-7.56 ( 1 6H, m, 2x8Ar H). Compound 261

¹H N.M.R. δ(ppm) 1.06 (6H, s, =CHC.Cϋ₃)₂), 1.12 (6H, s, =CHC(CH₃)₂), 2.20 (4H, m, 2xCH₂), 2.38 (3H, s, CH₃S), 2.46 (3H, s, CH₃S), 3.84 (6H, m, 2xCH₃ON), 4.04 (6H, m, 2xCH₃OOC), 4.10 (2H, s, CH₂Ar), 4.18 (2H, s, CH₂Ar), 5.02 <4H, m, 2xC = CH₂), 5.60 (2H, m, 2xCH_CH₂), 7.10 (2H, m, 2xAr_IH), 7.32 (4H, m, 2x2ArH), 7.48 (2H, m, 2xArH), 7.55 (2H, m, 2xN = CH).

Compound 262

¹H N.M.R. δ(ppm) 1.06 (12H, m, 4xCH₃CH), 1.14 (12H, 4xCH₃CH), 1.50-1.98 (8H, m, 4xCH₂), 2.34 (4H, m, 4xCHCH₃), 2.40 (6H, m, 2xCH₃S), 2.44 (6H, m, 2xCH₃S), 2.84 (4H, m, 4xCHCH₃), 3.84 (12H, m, 4xCH₃ON), 4.02 (12H, m, 4xCH₃OOC), 4.08 (4H, m, CH₂Ar), 4.20 (4H, m, 2xCH₂Ar), 7.06-7.40 (32H, 4x8 AMH) and 7.54 (4H, m, 2xArH and 2xN = CH).

Compound 263

¹H N.M.R. δ(ppm) 2.34 (12H, m, 2xN = CCH₃ and 2xN = CCH₃), 2.44 (3H, s,

CH₃S), 2.58 (3H, s, CH₃S), 3.80 (3H, s, CH3ON), 3.88 (3H, s, CH3ON), 4.04

(6H, m, 2xCH₃OOC), 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. δ(ppm) 2.45 (3H, s, SCH3), 2.55 (3H, s, SCH3), 3.85 (3H, s, CH3ON),

3.90 (3H, s, CH₃ON), 4.10 (6H, , CI^OC), 4.15 (2H, m, Ar-CH₂), 4.30 (2H, s, Ar-CH₂), 6.95-7.10 (8H, m, Ar l), 7.15-7.20 (4H, m, Ar l), 7.35-7.40 (8H, m, AMH), 7.55 (2H, m, Ar ), 7.70-7.80 (4H, m, AMH), 8.30 (1 H, s, N = CH) and 8.35 (1H, s, N = CH). Compound 265

¹ H N.M.R. δ(ppm) 2.45 (3H, s, SCH₃), 2.55 (3H, s, SCH₃), 2.65 (3H, s, SCH₃),

3.85 (3H, s, CH₃ON), 3.90 (6H, s, CH3ON), 4.00 (9H, m, NCH3), 4.10 (9H, m,

CJH₃OOC), 4.30 (6H, m, ArCH₂), 6.20 (3H, m, Het±l), 6.60 (3H, m, Het-H), 6.80 (3H, m, Het±l), 7.25 (3H, m, Ar±l), 7.30-7.45 (6H, m, Ar±l), 7.60 (3H, m, Ar±l) and 8.30 (3H, m, N = CH).

Compound 266

^"> H N.M.R. δ(ppm) 2.45 (3H, s, = CCH₃), 2.55-2.70 (9H, m, = CCH₃and 2xCH_₃S), 3.85 (3H, s, CH3ON), 3.90 (3H, s, CH3ON), 4.08 (6H, m, 2xCH₃OOC), 4.1 5 (2H, s, CIH₂Ar), 4.34 (2H, s, CH₂Ar), 7.1 2-8.00 (14H, m, 2x4ArH and 2x3Het±i), 8.35 (1 H, s, N = CH) and 8.40 (1 H, s, N = CH).

Compound 267 ¹ H N.M.R. δ(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, 3xCH₃ON), 4.08 (9H, m, 3xCH₃OOC), 4.30 (2H, s, Cj-j₂Ar), 4.34 (2H, s, CH₂Ar), 4.55 (2H, s, CH₂Ar) and 7.00-7.62 (21 H, m, 3x4Ar±i and 3x3Het±l).

Compound 272

^"Η N.M.R. δ(ppm) 2.44 (3H, s, CH3S), 2.56 (3H, s, CH3S), 3.82 (3H, s, CH3ON),

3.86 (3H, s, CH3ON), 4.06 (6H, m, 2xCH₃OOC), 4.1 8 (2H, s, CH_₂Ar), 4.30 (2H, s, CH₂Ar), 7.1 5-8.04 ( 1 4H, m, 2x7Ar±l), 8.28 (1 H, s, N = CH) and 8.30 (1 H, 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 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.

Erysiphe graminis f sp. tritici

1,3, 5, 11, 14, 17, 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, 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.

Claims

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;

R " 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

R⁷ is alkyl, haloalkyi, alkenyl, alkynyl, cycloalkyl, halogen, cyano, alkoxy, alkylthio, haloalkoxy, and optionally substituted phenyl; and q is 0 to 4.

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 R ^ is optionally substituted alkyl.

4 A compound according to claim 3 where R¹ is methyl. A compound according to any preceding claim wherein R³ is hydrogen.

A compound according to any preceding claim wherein q is 0.

A compound according to any preceding claim wherein R2 js optionally substituted alkyl, optionally substituted phenyl or optionally substituted heterocyclyl.

A compound according to claims 7 wherein when R² is optionally substituted branched alkyl.

A compound according to claim 8 wherein R² is optionally substituted tertiary butyl.

A compound according to claim 7 wherein when R² is a phenyl group substituted by one or more electron-withdrawing groups.

A compound according to claim 10 wherein the electron with drawing group or groups are halogen.

A compound according to claim 7 wherein when R2 is optionally substituted heterocyclyl, the heterocyclyl group is aromatic and deactivating.

A compound according to claim 1 2 wherein the heterocyclyl group is optionally substituted pyridine or pyrimidine.

A compound according to any preceding claim wherein X is NH, Y is N and W is methoxy.

A pesticidal composition comprising compounds as claimed in any preceding claim in admixture with an agriculturally acceptable diluent or carrier.