DD291467A5 - AGRICULTURAL COMPOSITION - Google Patents

Abstract

The invention relates to agricultural compositions with a content of acrylate fungicides for the control of Pflanzenschaedlingen, in particular of fungi. They also have insecticidal and acaricidal effects. According to the invention, compounds of the formula (I) in which Q, X, Me, m, n have the meaning given in the description and in the claims are used as active ingredient in the novel agricultural compositions. Formula (I) {new agricultural compositions; Akrylfungizide; Fighting plant pests; fungicidal, insecticidal, acaricidal action}

Description

Q is R ² -N = C-

R is ¹ ,

R ^{1 is} alkyl, alkoxy or alkylthio and R ^{2 is} heteroaryl, non-aromatic heterocyclyl, optionally substituted cycloalkyl or optionally substituted alkyl of at least 5 carbon atoms, phenyl substituted by one or more groups selected from halogen, optionally substituted Alkyl, alkoxy, haloalkoxy, aryloxy, alkylthio and alkoxycarbonyl, and when R ¹ is alkyl or an alkoxy group or when W is nitrogen, R ^{2 may} also be unsubstituted phenyl, and acid addition salts of any of the compounds which are basic and base addition salts of any of the compounds which are acidic in admixture with an agriculturally acceptable diluent or carrier material.

2. Composition according to claim 1, characterized in that R ^{1 is} a methylthio group or methyl.

3. Composition according to claim 1 or 2, characterized in that η is 1, m is 0 and X is equal to S.

A method of controlling pests, and in particular fungi, at a site infected therewith or susceptible to such infection, characterized in that a composition according to claim 1, 2 or 3 is applied to the site.

Field of application of the invention

The invention relates to an agricultural composition containing Akiylatfungiziden. The compositions according to the invention are used for controlling plant pests, in particular Piizen.

Characteristic of the known state of the art

n, especially in

EP-PS 178826 and 203608.

The aim of the invention is the provision of new agricultural compositions having a strong fungicidal and also insecticidal and acaricidal action.

Explanation of the essence of the invention

The invention has for its object to find new compounds which are suitable as active ingredient in agricultural compositions having the desired properties.

According to the invention, compounds of the formula I as active ingredient in the novel agricultural compositions

Q- (CH ₂ ) _m -X- (CH ₂ ) _n _ ^

applied, in which

X is oxygen or sulfur,

W is CH or N,

m is 0 or 1 and either

a) is 1 and

Q is a non-aromatic heterocyclic ring of from 3 to 10 carbon atoms containing one to three heteroatoms selected from oxygen, sulfur and nitrogen, which may be substituted and fused to another ring, provided that a) Q, if Thiazole-2-yn-2-yl is substituted but not by methylene, and b) Q is not a six-membered ring having only two nitrogen atoms, or

b) η is 0 or 1 and

Q is R ² -N = C-

R 'is,

R ¹ is alkyl, alkoxy or alkylthio and

R ^{2 is} a heteroaryl, non-aromatic heterocyclyl, optionally substituted cycloalkyl or optionally substituted alkyl of at least 5 carbon atoms, phenyl substituted by one or more groups selected from halogen, optionally substituted alkyl, alkoxy, haloalkoxy, aryloxy, alkylthio and alkoxycarbonyl and R ^{2 may} also be an unsubstituted phenyl when R ^{1 is} an alkyl or an alkoxy group or when W is nitrogen,

and the acid addition salts of all basic compounds and the base added salts of all acidic compounds. When Q is a ring, it is preferably a five- to seven-membered ring. Examples include a) the group

wherein A is CH ₂ , S, O, NMe, NPh or CHMe, ρ is 0 or 1 and

R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁷ and R ^{8 are the} same or different and are selected from hydrogen, alkyl, substituted alkyl (ζ, Tr trifluoromethyl), alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, alkoxy , Haloalkoxy, alkylthio, haloalkylthio, halo, alkoxycarbonyl, oxoalkyl, aryl or optionally substituted amino or

i) R ³ and R ⁴ , R ⁵ and R 'or R ⁷ and R ^{8 may} together form another ring containing either a cycloalkyl or a

Heterocyclyl, or ii) when ρ is O and A is CH ₂ or CHMe, R ³ and R ^s together can form a bond or R ⁴ and R ⁵ together

or iii) when ρ is 1, R ³ and R ⁷ or R ⁸ and R ^{7 may} together form a bond or R ⁴ and R ⁸ or R ⁵ and R ⁸ together may form a fused ring,

b) optionally substituted benzothioadiazinyl or

c) optionally substituted tetrahydroazepinyl.

Particularly preferred values of U as a ring are substituted 1,3-thiazin-2-yl, substituted thiazol-2-yn-2-yl and optionally substituted 3,1-benzothiazinyl.

When R ^{1 is} an alkyl, it preferably has 5 to 15 carbon atoms and is optionally substituted, e.g. By halogen, alkoxy, alkylthio, alkoxycarbonyl or aryl. Otherwise, alkyl, alkoxy or alkylthio groups preferably have 1 to 4 carbon atoms, in particular a carbon atom. Heteroaryl groups are aromatic rings, which are preferably five- or six-membered and generally have 1 to 3 heteroatoms, ζ. As oxygen, sulfur or nitrogen. These rings may be substituted and / or carry a fused ring, in particular a benzo ring. Examples of these groups include thienyl, furyl, pyrrolyl, pyridyl, pyrimidinyl, pyrazolyl, thiazolyl, oxazolyl, benzimidazolyl, tetrazolyl, benzoxazolyl, thiadiazolyl, triazolyl, imidazolyl or benzothiazolyl. Non-aromatic heterocycles are generally five to eight membered rings, typically containing one to three heteroatoms such as oxygen, nitrogen or sulfur, and / or bearing fused rings. Examples of these groups include pyrrolidinyl, morpholinyl, thiomorpholinyl or fully or partially hydrogenated thienyl, furanyl, pvrrolyl, thiazolyl, oxazolyl, oxazinyl, thiazinyl, pyridinyl and azepinyl. Cycloalkyl groups usually have 3 to 8 carbon atoms. Aryl groups can be hoteroaryl groups, but are preferably phenyl, optionally substituted, for example by halogen, hydroxy, alkoxy group, alkyl, trifluoromethyl or nitro group.

R 'is preferably a methylthio group or methyl.

A particularly preferred group of compounds is that in which η is 1, m is 0, and X is S. Compounds of the invention exist as structural isomers and the invention includes single isomers as well as mixtures thereof. Preferred compounds are those in which the thio-propenoate or (methoxyimino) -acetate bonded directly to the benzene ring, as shown in Formula I, is in the Ε-configuration. The compounds according to the invention are particularly valuable as fungicides, especially against fungal diseases of plants, eg. As powdery mildew and especially cereal powdered mildew (Eryslphe gramlnls), downy mildew (Plasmopara vitlcola), rice blast (Pyricularia oryzae), cereal eye patch (Pseudocercosporelln herpotrlchoides), Reisscheidonfiiule (Pelllcularia sasakii), gray mold (Botrvtls cinerea), musty (Rhlzoctonia solani), wheat brown rust ( Pucclnla recondlta), potato blight (Phytophthora infectans), apple scab (Venturis inaequils) and Septoria ssp., E.g. B. Septorla trltlcl and Septorla nodorum. Other fungi against which the compounds may be used include other powdery mildew diseases, other rust diseases, and general pathogens of deuteromycete, ascomycet, phycycet, or basidiomycete origin.

The compounds of the invention also have insecticidal, acaricidal and nematocidal activity and are particularly useful in controlling a number of economically important insects, acarids and plant nematodes, including animal ectoparasites and especially Diptera such as sheep's fly, Lucllia sericata, and domestic flies, Musca domestica; Lepidoptera, including Plutella xylostella, Spodoptera littoralls, Heliothis armigera and Pleris brassicae; Homoptera, including aphids, such as Megoura vlciae; Coleoptera, including cereal root worms (Diabrotica spp., Eg Diabrotica undeclunctata) and spider mites such as Tetranychus ssp.

The invention thus provides a method of controlling pests (ie fungi, insects, nematodes and acarids) at an affected site or a site susceptible to infestation by them, which is to associate with that site Apply Formula I. The agricultural composition of the invention consists of a compound of formula I in admixture with an agriculturally acceptable diluent or carrier. Of course, the composition of the invention may contain more than one compound of the invention. In addition, the composition may contain one or more other active ingredients, for example, compounds known to have plant growth regulating, herbicidal, fungicidal, insecticidal or acaricidal properties. Alternatively, the compounds of the invention can be used in sequence with the other active ingredients.

The diluent or carrier in the composition of the invention may be a solid or a liquid, optionally in association with a surfactant, for example a dispersant, an emulsifier or a wetting agent. Suitable surfactants include those anionic compounds such as a carboxylate, for example a metal carboxylate of a long chain fatty acid: an N-acyl sarcosinate, mono- or diesters 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; petroleum sulfonates; Alkyl arylsulfonates, such as alkyl-benzenesulfonates or lower alkylnaphthalenesulfonates, e.g. Butyl-naphthalenesulfonates; Salts of sulfonated naphthalene-formaldehyde condensates; Salts of sulfonated phenol-formaldehyde condensates, or more complex sulfonates, such as the amide sulfonates, z. Example, the sulfonated condensation product of oleic acid and N-methyl taurine, or the Dialkylsulfosukzinate, z. For example, the sodium sulfonate of dioctyl succinate. The 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 esters, e.g. B. sorbitan fatty acid esters, condensation products of these esters with ethylene oxide, ζ. Β. Polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylene glycols such as 2,4,7,9-tetramethyl-5-decyn-4,7-diol, ethoxylated acetylene glycols or ethoxylated tristyrylphenols.

Examples of cationic surfactants include u. a. an aliphatic mono-, di- or polyamine such as an acetate, naphthenate or oleate; an oxygen-containing amine such as an amine oxide or polyoxyethylalkylamine; an amide-bonded amine prepared by condensation of a carboxylic acid with a di- or polyamine, or a quaternary ammonium salt.

The compositions of the invention may take any form known in the art for the preparation of agrochemicals, e.g. A solution, a dispersion, an aqueous emulsion, a dusting powder, a seed dressing (including coatings to form a seed pellet), a disinfectant, a mist, a bait, a dispersible powder, an emulsifiable concentrate or granules, e.g. water-dispersible granules. In addition, they may have a form suitable for direct application or may be present as a concentrate or primary composition which must be diluted with an appropriate amount of water or other diluent prior to use.

An emulsifiable concentrate consists of a compound of the invention which is dissolved in a water-immiscible solvent from which an emulsion is made with water in the presence of an emulsifying agent.

A dusting powder consists of a compound according to the invention, which intimately with a solid, powdery!

Diluent, such as kaolin, mixed and ground.

A granulated solid material consists of a compound according to the invention, to which are added diluents similar to those used in dusting powders, but the mixture is granulated by known methods. Alternatively, it consists of the active ingredient which is absorbed or adsorbed to a pre-granulated diluent, for example Fuller's earth, attapulgite or limestone sand.

Wettable powders, granules or granules typically consist of the active ingredient in admixture with a suitable ozone surfactant and an inert powder diluent such as kaolin.

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

The concentration of the active ingredient in the composition of the present invention when applied to plants is preferably in the range of 0.0001 to 3.0%, preferably 0.001 to 1.0%. In a primary composition, the amount of the active ingredient may vary widely, for example between 5 and 95% of the weight of the composition.

In the method of the invention, the compound is generally applied to seeds, plants or their location. Thus, the composition can be applied directly to the soil before or after drilling, so that the presence of the active compound in the soil can combat the growth of fungi that can attack the seeds. When the soil is treated directly, the active compound may be applied so that it is intimately mixed with the soil, for example by spraying, by puffing a solid form of granules or by applying the active ingredient simultaneously with the drilling. Introduce into the same Saatrille as the seed. A suitable rate of application may be between 0.005 and 10 kg / ha, preferably between 0.05 and 1 kg / ha.

Alternatively, the active compound may be applied directly to the plant, for example by spraying or dusting either at the time the fungus begins to appear on the plant or as a precautionary measure against the appearance of the fungus. The preferred form of application in these two cases is foliar spraying. In general, it is important to achieve good control of the fungi in the early stages of plant growth, as the plant can be most severely damaged at this time. However, it can also be beneficial to apply it later in order to treat later diseases such as Septoria ssp. to fight. The spray material or dust may advantageously contain a pre-emergence or a post-emergence herbicide, if deemed 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, the appropriate application rate is between 0.001 and 5 kg per hectare, preferably between 0.005 and 1 kg / ha.

The compounds of the invention can be prepared in different ways when η is 1, e.g. B. by reaction of a compound of formula II

ZCH ₂

(II)

0-C-OMe wherein Z is a residual group such as halogen, with a compound of formula III or its tautomer

Q- (CH ₂ ) ₂ -XH (III)

or, if Q is R ² -N = C- and m is 0, with

a compound of formula IV

R ² -NH-C = X (IV)

When Q is a non-aromatic heterocyclic ring as defined above, a number of the compounds of formula III are novel, and these novel compounds constitute one aspect of the invention.

embodiment

The invention is illustrated in the following examples. Structures of isolated novel compounds were confirmed by elemental and / or other suitable analyzes. Temperatures are given in ⁰ C.

Example!

Methyl o-tolyl acetate (100 g) was dissolved in a mixture of methyl formate (450 ml) and dimethylformamide (200 ml). The solution was added to a benzene-washed suspension of sodium hydride (from 36.5 g of an 80% dispersion in oil) in dimethylformamide (100 mL) with cooling. Then the mixture was stirred at room temperature overnight. Excess methyl formate and most of the dimethylformamide were evaporated and water (500 ml) was added. The mixture was treated with ether and the aqueous phase separated, acidified and extracted with ether. The extract was worked up in a conventional manner to give a brown oil. This was dissolved in tetrahydrofuran and the solution was added dropwise to sodium hydride (16.5 g of an 80% dispersion in oil) in tetrahydrofuran (50 mL) with cooling. After the evolution of hydrogen ceased, methyl iodide (35 ml) was added and the mixture was heated to reflux for five hours. Methanol (5 ml) was added and the solvent was evaporated. The resulting oil was partitioned between ether and water, and the organic phase was worked up in a conventional manner to give methyl (Z) -3-methoxy-2- (ot) -yl) -prop-2-enoate, mp 68 ° C. 70 ° C. This product (185g) was dissolved in carbon tetrachloride (1 250ml). N-bromosuccinimide (159.3 g) was added and the mixture was heated at reflux for 3 hours. Then, the reaction mixture was cooled and worked up to give a light brown oil. The crude product was triturated with a 10% solution of diisopropyl ether in petroleum ether to give methyl (E) -3-methoxy-2- [2- (bromomethyl) phenyl] prop-2-enoate, m.p. 87 ° C-90 ° C (Intermediate A).

To a mixture of (1S, 2R) - (+) - norephedrine (5 g) and aqueous sodium hydroxide (50 ml of a 15% solution) was added carbon disulfide (27 ml) and the mixture was stirred for 24 hours. Excess carbon disulfide was evaporated under reduced pressure and the residue was poured into water and extracted with ethyl acetate. The extracts were washed with water, dried and evaporated. The residue was purified by silica gel chromatography (eluent ether / hexane, 1: 1) to give 4-methyl-5-phenylthiazolidine-2-thione and 4-methyl-5-phenyloxazlidine-2-thione. A solution of the first of these thiones (0.80 g) in dimethylformamide was treated with sodium hydride (0.12 g of an 80% dispersion of oil). At the end of hydrogen evolution, Intermediate A (1.2 g) was added, for one hour, and the mixture was allowed to stand for 60 hours. The mixture was poured into water and extracted with ether. The extracts were worked up in a conventional manner to give methyl (E; -2- [2 - [[(4-methyl-5-phenylthiazol-2-yn-2-yl) thio] methyl] phenyl] -3-methoxy 2-propenoate in the form of a gum (Compound 1).

Similarly, the other thione gave methyl (E) -2-l2 - [[(4-methyl-5-phenyloxazol-2-yn-2-yl) thiolmethyl] phenyl) -3-methoxy-2-propenoate in the form of a rubber (compound 2).

Example 2

Methyl chlorooxoacetate (22.5 mL) in tetrahydrofuran (60 mL) was added dropwise over one hour to a stirred solution of imidazole (33.35 g) in tetrahydrofuran (500 mL) kept at 0 ° C and under nitrogen. Then, the mixture was stirred for an additional hour at this temperature. The reaction mixture was filtered and the precipitate washed with tetrahydrofuran. The filtrate and washings, containing methyl alpha-oxo-1 H-imidazol-1-acetate contained were cooled to -65 ⁰ C, and there was added a solution of a Grignard reagent, which (42 g of o-Bromotoluen ), 1,2-dibromoethane (3.6 ml) and magnesium (7 g) was prepared in tetrahydrofuran over 45 minutes, keeping the temperature between -6O ⁰ C and -70 ⁰ C was maintained. Then, the mixture was stirred at this temperature for 15 minutes and then at room temperature for 2.5 hours. It was then poured into ice / water, extracted with ether, the extracts washed with brine, dried and concentrated. The residue was distilled under reduced pressure to give methyl oxo (o-tolyl) acetate, b.p. 92 ° C-97 ° C / 0.5mm. A solution of this product (5g) in methanol (100ml) was heated at reflux with methoxyamine hydrochloride (2.55g) for 3 hours. The mixture was cooled, evaporated, triturated with diisopropyl ether, filtered and the filtrate evaporated to give methyl (methoxyimino) (o-tolyl) acetate. This compound was then treated with N-bromosuccinimide in carbon tetrachloride on reflux under a 300 W lamp with the addition of benzoyl peroxide (0.005 g every 10 minutes). Conventional work-up gave the bromomethyl compound (Intermediate B), which was then reacted with substituted thiazolidinethione derived from (1S, 2R) - (+) - norephedrine as in Example 1 and in a similar manner to Example 1, which gave methyl (methoxy-imino) [2- [(4-methyl-5-phenylthiazol-2-yn-2-yl) thio] methyl] -phenyl] acetate as a pale yellow gum (Compound 3).

Example 3

Methyl 4-methoxyphenyl dithiocarbamate (4.5 g) was added to a suspension of sodium hydride (700 mg of an 80% dispersion in oil) in tetrahydrofuran (50 ml). After completion of the hydrogen evolution, Intermediate A of Example 1 (5.0 g) was added over one hour and the mixture allowed to stand for 36 hours. Aqueous sodium hydroxide was added and the mixture was extracted with diethyl ether and the extracts worked up in a conventional manner to give methyl (E) -3-methoxy-2 [2 - [[(4-methoxyphenylimino) (methylthio) methyl] thiomethyllphenyl]. -2-propenoate in the form of a pale yellow gum (Compound 4).

Example 4

Intermediate B from Example 2 was methylated with methyl-chlorophenyl dithiocarbamate in a manner similar to Example 1 to give methyl [2 - [((4-chlorophenylimino) (methylthio) methyl) thiomethyl] phenyl (methoxyimino) acetate, mp 74 ° C-76 ° C (compound 5).

Example 5

Methyl pyridin-3-yl dithiocarbamate (1.85 ml) was added to a suspension of sodium hydride (350 mg of an 80% dispersion in oil) in tetrahydrofuran (50 ml). After completion of hydrogen evolution, Intermediate A from Example 1 (2.5 g) was added over a period of one hour and the mixture was allowed to stand for 24 hours. The mixture was extracted with ethyl acetate and the extracts were worked up in a conventional manner to give methyl (E) -3-methoxy-2- [2 - [((pyridin-3-ylmino) (methylthio) methyl] thiomethyl] phenyl ] -2-propenoate in the form of a yellow gum (Compound 6).

Belspie (6

Intermediate B of Example 2 was reacted with methylbenzothioazol-2-yl dithiocarbamate in the same manner as in Example 1 to give methyl [2- [z (benzothiazol-2-ylmino) methylthio) methyl] thiomethyl-phenyl) (methoxyimino) acetate. Melting point 106 ° C-108 ° C (Compound 7).

Example 7

2-Aminopyrimidine (10.27g) was dissolved in dimethylsulfoxide (DMSO) (100ml). While stirring and cooling to less than 20 ° C, a solution of sodium hydroxide (9.0g) in water (20ml) was added. After ten minutes on ten Minute'i carbon disulfide was added dropwise (7.1 ml) was added, the temperature was kept by cooling in ice between 10 ⁰ C and 20 ⁰ C. After stirring for an additional 15 minutes, iodomethane (6.7 ml) was added dropwise at 10 ° C-20 ° C.

The reaction mixture was stirred at room temperature for a further 20 minutes and then poured into water (2000 ml). The solution was acidified with 2 M hydrogen chloride. After a thirty-minute rest, a solid substance was precipitated and filtered. Trituration with ethyl acetate gave <ithylpynmidin-2-yl-dithiocarbamate M, melting point 171 ⁰ C-173 ° C (decomposition) (airtightly sealed tube) in low yield.

This intermediate (0.5g) was dissolved in dry DMSO (6ml). A solution of Intermediate A from Example 1 (0.77 g) in dry DMSO (4 ml) was added. The mixture was heated to 50 ^° C. to give a clear solution, which was then allowed to cool to room temperature and stirred for 3 hours. Subsequently, Ν, Ν-diisopropylethylamine (2 ml) was added and the mixture stirred at room temperature for a further 2 hours before pouring onto water (200 ml).

The mixture was extracted three times with ethyl acetate (80 ml). The extracts were combined, washed three times with 2M sodium hydroxide solution (80 ml) and then dried over magnesium sulfate.

Filtering and evaporation gave the crude product as a viscous, brown oil which crystallized on standing overnight. The product was dissolved in diisopropyl ether containing about ethyl acetate. Decolorizing charcoal (possibly g) was added and the solution filtered hot.

After the filtrate was quenched, a solid was precipitated. Filtering gave methyl (E) -3-methoxy-2- {2 - [(methylthio) pyrimidin-2-ylimino) methylthiomethyl] phenyl} -2-propenoate, mp 109.5 ° C-111 ⁰ C (compound 8th).

Example 8

In a similar manner as in any of the preceding examples, the following compounds were prepared. Unless otherwise stated, the connections are in the E-form.

Q-S-CH,

W-OMe

MeOCO

Verb. Q W melting No. pkt.CC) 9 5- (4-MeO-phenyl) -thiazol-2-ynyl N oil 10 4-Me-5-Ph-thiazol-2-yn-2-yl CH rubber 11 4-Me-5-Ph-oxazol-2-yn-2-yl CH rubber 12 5-Ph-thiazol-2-ynyl CH rubber 13 4,5-Ph ₂ -oxazol-2-yn-2-yl CH rubber *. 4-Et-Thia. '. Ol-2-in-2-yl CH rubber 15 2-Me-1,1-dioxo-2H-1,2,4-benzothiadiazin-3-yl CH 125-127 16 4H-3,1-Benzothiazin-2-yl CH rubber 17 4,5,6,7-tetrahydro-3H-azepin-2-yl CH rubber 18 4-Me-5- (3-hydroxyphenyl) thiazole-2-yn-2-yl CH rubber 19 3,4,5,6-tetrahydropyridin-2-yl CH rubber 20 4-Ph-thiazol-2-yn-2-yl CH rubber 21 4-Me-5-Ph-oxazol-2-yn-2-yl N lummi 22 4H-3,1-benzothiazin-2-yl N rubber 23 5-phenylthiazol-2-yn-2-yl N rubber 24 (4-methylphenylimino) (MeS) methyl CH rubber

Verb Q no.

W melting pkUV.) CH rubber CH rubber CH rubber CH rubber CH rubber CH rubber CH 57-59 CH oil N oil N oil CH 67-69 CH 143-145 CH oil CH oil CH oil CH rubber CH oil CH oil CH oil CH oil CH oil CH oil CH oil CH oil CH oil CH oil CH oil CH oil CH oil CH 81-83 CH oil CH oil CH oil CH oil CH oil CH oil CH oil CH oil CH 95-97 CH 78-83 CH oil CH oil CH oil CH oil CH 109.5 to 111 CH 136-137 CH oil CH oil CH oil CH 112-114 CH oil CH oil CH rubber CH rubber CH 65 CH rubber CH Oil N oil CH 83-84 CH 101-102 CH 140-143 CH 95-98 CH 104-105 CH 111-112 CH oil CH 141-142

25 (4-chlorophenylimino) (MeS) methyl

26 (3-trifluoromethylphenylimino) (MeS) methyl

27 (3-methoxyphenylimino) (MeS) methyl

28 (4-methoxycarbonylphenylimino) (MeS) methyl

29 (4-phenoxyphenylimino) (MeS) methyl

30 (4-t-butylphenylimino) (MeS) methyl

31 (4-propylphenylimino) (MeS) methyl

32 {3-chlorophenylimino) (MeS) methyl

33 1- (phenylimino) propyl

34 (phenylimino (MeS) methyl

35 4-Me-5- (3-hydroxyphenyl) oxazol-2-yn-2-yl

36 (4-CI-benzothiazol-2-ylmino) (MeS) methyl

37 (1,3-dimethylbutylimino) (MeS) methyl

38 (decylimino) (MeS) methyl

39 (Dodezyliminol (MeS) methyl

40 (octyliminoHMeS) methyl

41 (hexahydroazepine-1-ylimino) (MeS) methyl

42 (pyridin-4-ylmino) (MeS) methyl

43 4ethoxycarbonylthiazol-2-yn-2-yl

44 4-Butyloxazol-2-yn-2-yl

45 (morpholinoimino) (MeS) methyl

46 (2,2-dimethylpropylimino) (MeS) methyl

47 (ö-chloropyridine) -yliminoKMeSlmethyl

48 5-Phenyloxazol-2-yn-2-yl

49 4-butylthiazol-2-yn-2-yl

50 3 a, 4,5,6,7,7 a-hexahydrobenzoxazol-2-yl

51,5,5-dimethyl-4-ethoxy-carbonyl-thiazole-2-yn-2-yl

52,5-dimethyl-4-butoxycarbonylthiazol-2-yn-2-yl

53 (3,4-dichlorophenyl-imino) (MeS) methyl

54 4-butoxycarbonylthiazol-2-yn-2-yl

55 4-Otyloxycarbonythiazol-2-yn-2-yl

56,5,5-dimethyl-4-octyloxycarbonylthiazol-2-yn-2-yl

57 5-t-butyloxazole -? - in-2-yl

58 (1,2,3,4-tetrahydronyl-1-ylmino) (MeS) methyl

59 (2,4-difluorophenylimino) (MeS) methyl

60 4-octylthiazol-2-yn-2-yl

61 (4-butylphenylmono) (MeS) methyl

62 (2,5-difluorophenylimino) (MeS) methyl

63 pyrrol-1-yn-2-yl

64,4,4,6-Me ₃ -4H-1,3-thiazin-2-yl

65 3-methylpyrrol-1-ynyl

66 | (N-methylanilino) iminol (MeS) methyl

67 4- (4-Cl-phenyl) pyrrol-1-yn-2-yl

68 (3-methylisothiazol-5-ylmino) (MeS) methyl

69 (pyrimidin-2-ylmino) (MeS) methyl

70 (5-methyl-1,3,4-thiadiazol-2-ylmino) (MeS) methyl

71 1- (4-chlorophenylimino) ethyl

72 i- (pyridin-2-ylmino) ethyl

73 1- (3-methylphenylmono) ethyl

74 4,6,6-Me ₃ -6H-1,3-thiazin-2-yl

75 cis-4,5-dimethoxyoxazol-2-yn-2-yl

76 5- (4-methoxyphenyl) thiazole-2-yn-2-yl

77 (pyridin-2-ylmino) (MeS) methyl

78 (benzothiazol-2-ylmino) (MeS) methyl

79 (cyclohexylimino) (MeS) methyl

80 (thiazol-2-ylmino) (MeS) methyl

81 (hexylimino) (MeS) methyl

82 (hexylimino) (MeS) mothyl

83 (piperidin-1-ylmino) (MeS) methyl

84 (quinolin-8-ylimino) (MeS) methyl

85 (6-MeO-benzothiazol-2-ylmino) (MeS) methyl

86 (3-Me-imidazol-1-yn-2-ylmino) (MeS) methyl

87 (3-Me-isoxazol-5-ylmino) (MeS) methyl-

88 (4 _/ 5,6,7-tetrahydrobenzothiazol-2-ylmino) - (MeS) methyl

89 (4,6-dimethylpyridin-2-ylmino) (MeS) methyl

90 (6-Me-benzothiazol-2-ylmino) (MeS) methyl-

Verb Q no.

91 (2, e-dimethylpiperidinoimino) (MeS) methyl

92 1,1-dioxo-2,3,4, B, -tetrahydrothien-3-yl

93 1-Phimidazol-2-yn-1-yl · HCl

94 (4- (4-chlorophenyl) thiazol-2-ylmino] (MeS) methyl

95 1- (pyridin-2-ylmino) ethyl

96 (2-methylphenylimino (MeS) methyl

97 (2-methoxymethylpyrrolidinoimino) (MeS) methyl

98 4-Butyloxazo! -2-yn-2-yl

99 5-methylpyrrol-1-yn-2-yl

100 1-Phimidazol-2-yn-2-yl

101 (6-MeO-pyridin-3-ylmino) (MeO) methyl

102 (4-Me-pyrimidin-2-ylmino) (MeS) methyl

103 (6-F-benzothiazol-2-ylmino) (MeS) methyl

104 (3-phenyl-1,2,4-thiadiazol-5-ylmino) (MeS) methyl

105 1- (3,4-dimethylphenyl) -mino) ethyl

106 (4,5,6,7-tetrahydro-3H-azepin-2-yl-limino) - (MeS) methyl

107 4-butoxycarbonylthiazol-2-yn-2-yl

108 (4-bromo-3-methylphenylimino) (Mer>) methyl

109 (4-Me-benzothiazol-2-ylmino) (MeS) methyl

110 1- (4,6-dimethylpyrimidin-2-ylmino) ethyl

111 (3-phenyl-1,2,4-thiadiazol-5-ylmino) (MeS) methyl

112 (6-F-benzothiazol-2-ylmino) (MeS) methyl

113,4,4-Me2-4H-3,1-Benzoxazin-2-yl

114 5,6-dihydro-4,4,6-Me ₃ -4 H -1,3-oxazin-2-y I

115 (morpholinoimono) (MeS) methyl (isomer 1)

116 (morpholinoimino) (MeS) methyl (isomer 2)

117 1,1-dioxo-2,3,4,5-tetrahydrothien-3-yl (isomer 1)

118 1,1-dioxo-2,3,4,5-tetrahydrothien-3-yl (isomer 2)

119 5,6-dihydro-4,4,6-Me ₃ -4H-1,3-oxazin-2-yl

120 4.4-M9 ₂ -4H-3,1-benzoxazin-2-yl

121 (5-CF3-1,3,4-thidiazol-2-ylmino) (MeS) methyl

122 2,5-methylpyrrol-1-yn-2-yl

123 5-hexylthiazol-2-yn-2-yl

124 (3-Me-isoxazol-5-ylmino) (MeS) methyl

125 (5-CF ₃ -1,3,4-thiadiazol-2-ylmino) (MeS) methyl

126 (Quinoline-S-ylmino-XMeSlmethyl

127 (5-CF ₃ -pyridin-2-ylmino) (MeS) methyl

128 (5-Br-pyridin-2-ylmino) (MeS) methyl

129 (quinoline) -yliminoMMeS-methyl

130 trans-4,5-Me ₂ -oxazol-2-yn-2-yl

131 5-hexylthiazol-2-yn-2-yl

132 4-Benzylthiazol-2-yn-2-yl

133 4-benzyloxazol-2-yn-2-yl

134 (5- (3,4-dichlorophenyl) thiazole-2-yn-2-yl

135 5- (3,4-dichlorophenyl) oxazol-2-ynyl

136 4-Et-5-Ph-oxazol-2-yn-2-yl

137 4-MeOCH ₂ -5-Ph-oxazol-2-yn-2-yl

138 [5- (4-chlorophenyl) -1,3,4-oxadiazol-2-yl-imino] (MeS) -methyl

Notes: Compounds 10, 11 and 21 were derived from (1R, 2S) - (-) - norephedrine).

Example 9

Allylamine and carbon disulfide were reacted together in the presence of triethylamine, followed by reaction with the intermediate of Example 1 to give crude methyl 2- (2 - [(allylaminothiocarbonyl) thiomethyl) phenyl} 3-methoxy-2-propenoate. This product (2.0g) was dissolved in dichloromethane (10ml) and triethylamine (0.85ml) added. The mixture was cooled to -6 ° C in an ice / sau bath and phenyllsulphuric chloride (0.87 g) was added. The temperature rose to 3 ° C and the mixture was stirred in ice / salt bath for 3 hours. Dichloromethane (15 ml) and 1M hydrogen chloride (20 ml) were added. The organic phase was separated and washed with aqueous sodium bicarbonate (20 ml), then dried over MgSO ₄ and evaporated. Purification by column chromatography on silica gel using ethyl acetate / hexane (3: 1) as eluent gave methyl 2- {2 - [[(allylimirio) (phenyldithio) methyl] thiomethyl] phenyl} -3-methoxy-2-propenoate. A solution of this product (0.1 g) in xylene (5 ml) was refluxed and irradiated by a UV lamp for 5 hours. Purification by preparative layer chromatography gave methyl 3-methoxy-2- {2 - [(5-phenylthiomethylthiazol-2-yn-2-yl) thiomethyl-phenyl} -2-propenoate as an oil (Compound 139).

W enamel pts. ( 'C) CH oil CH oil CH 177-178 CH 116-118 CH 100-102 CH oil CH oil N oil CH oil CH rubber CH oil CH oil CH 125-127 CH 134-136 CH 92-94 N   oil N 66-68 CH oil CH 120-121 CH 122-124 N 125-130 N 134-135 N 95-97 N 95-97 N 115-117 N oil N 131-133 N oil CH 81-84 CH oil N N oil N oil N 134-135 CH 79-80 CH 116-117 CH 68-69 CH 88-89 N 95-97 CH oil CH oil CH oil CH oil CH oil CH oil CH oil CH oil CH oil

Intermediate Examples Example A

This example demonstrates an alternative method of homologation. Methyloxo (o-toly!) Azotate, which is used as an intermediate in the preparation of compounds in which W is N.

To a stirred solution of o-toluoyl chloride (38.86g) in dichloromethane (250ml) at room temperature was added water (20.0ml) followed immediately by tetrabutylammonium bromide (0.15g) and sodium cyanide (13.0g). The reaction mixture was stirred vigorously for 1.5 hours, then filtered. The filtrate was washed with water (2 x 100 ml). dried (MgSO ₄ ) and evaporated under reduced pressure to give a golden oil. Distillation under vacuum gave 2-methylbenzoyl cyanide as a colorless oil, b.p. 47 ° C-50 ° C / 0.05 mm. To an 85% sulfuric acid (140 mL) at room temperature was added sodium bromide (20 g) followed immediately by the dropwise addition of 2-methylbenzoyl cyanide (34.8 g). Then, the reaction mixture was gently heated until the exothermic reaction started, and then kept at 70 ° C for 10 minutes with cooling. Methanol (400 mL) was added and the mixture was heated at reflux for 1 h, cooled and diluted with ice / water (500 mL). Extraction with diethyl ether gave a golden oil which was distilled under vacuum to give methyl oxo (o-tolyl) acetate as a colorless oil (bp 75 ° C-85 ° C / 0.4 mm).

Example B

This example illustrates the preparation of certain novel starting materials.

Method 1

To a stirred solution of 3- (N-phthalimido) butan-2-one (17g) in 13% aqueous propan-2-ol (400 ml) was added portionwise sodium borohydride (14.7 g). The temperature was kept below 30 ° C. The clear solution was stirred at room temperature for 24 hours. Excess sodium borohydride was decomposed by the dropwise addition of glacial acetic acid, and the solvent was decomposed under glacial acetic acid, and the solvent was evaporated under reduced pressure. The residue was dissolved in water (500ml) and the solution extracted with ethyl acetate (3x 200ml). The combined organic extracts were dried over sodium sulfate Filtering and evaporation gave 2-hydroxymethyl-N- (2-hydroxy-1-methylpropyl) benzamide. This was dissolved in 20% aqueous ethanol (200 ml) containing sodium hydroxide (4 g) and the solution was refluxed for 5 hours and cooled. Hydrogen chloride (36%, 20 mL) was added and the solvent was pre-evaporated under reduced pressure. The residue was suspended in water (200 ml) and extracted with ethyl acetate (3x 200 ml). The combined organic extract j were discarded. The aqueous phase, after evaporation under reduced pressure to a volume of about 80%, gave a solution of 3-aminobutan-2-ol hydrochloride. With stirring wuroen sodium hydroxide (30g) added in portions, it was cooled to ^r 20 C and stirred for 15 minutes. Carbon disulfide (100 ml) was then added and the mixture was heated under reflux with vigorous stirring for 6 hours. The cooled reaction mixture was evaporated under reduced pressure to remove the excess carbon sulfide. The residue was diluted to 300 ml with water, then extracted with diethyl ether (3x 250 ml). The combined organic extracts were dried over sodium sulfate and evaporated to give a mixture of the geometric isomers of 4,5-dimethyloxazolidin-2-thiones in the form of an oil. The aqueous phase was adjusted to pH 2 with hydrogen chloride (36%) and then extracted with ethyl acetate (3x 100 ml). The combined organic extracts were dried over sodium sulfate. Filtering and evaporation gave an oil which was dissolved in diethyl ether (100 ml) and filtered through a pad of silica gel (20 mm χ 40 mm). The pad was gowajchon with diethyl ether (100 ml) and the combined filtrates were evaporated to give a second crop of 4,5-dimethyloxazolidin-2-thiones. The combined 4,5-dimethyloxazolidin-2-thiones were durcl. Relaxation chromatography on a Kioselgolkolonne separated, wherein a mixture of diethyl ether and petroleum ether in the ratio of 4: 1 was used as the eluent, and the products were recrystallized from this solvent mixture, which trans-4,5-Dimethyloxa2olidin-2-thione, melting point 82 ° C-84 ° C, and cis ^ .B-dimethyloxazolidine ^ -thione, m.p. 108 ° C-109 ° C.

Method 2

To a stirred, cold solution of DL-2-amino-i-hexanol (1.1 ml) in dry THF (10 ml) was added triethylamine (2.8 mm) followed by the dropwise addition of thiophosgene (0.81 i) in dry THF (9 ml). Then, the mixture was stirred at 20 ° C for 18 hours, evaporated under reduced pressure, and the residue was separated with water and diethyl ether. The ether extract was dried with sodium sulfate, filtered and evaporated. The residue was dissolved in a minimum of 1: 1 hot dimethyl ether hexane and crystallized on cooling to yield 4-butyloxazolidin-2-thione. Melting point 7rC-72 ° C.

In a manner similar to one of these two methods, the following novel thiones were obtained:

Thione for Compound No. Melting p. ( ⁰ C)

43 4-Ethoxycarbonylthiazolidine-2-thione oil

52 5,5-dimethyl-4-butoxy carbonyl thiazolidine-2-thione! M-96

54 4-Butoxy carbonyl thiazoliilin-2-thione oil

55 4-octyloxycarbonylthia.7olidin-2-thione oil

56,5-dimethyl-4-octyloxycarbonyl-thiazolidine-2-thione oil

57 5-t-Butyloxazolidine-2-thione 143-144 60 4-octyl-thiazolidine-2-thione oil

131 5-hexylthiazolidine-2-thione 84-85

133 4-benzyloxazolidine-2-thione oil

134 5 ~ (3,4-dichlorophenyl) thiazolidine-2-thione oil

135 S (3,4-dichlorophenyl) oxazolidine-2-thione 113-115

136 4-Et-5-Ph-oxazolidine-2-thione 124-125

Magnhot nuclear resonance reconstitution data for compounds of the invention having kelon characteristic melting odor boiling point

Chemical shifts are reported in Tellchen / Mulll. Measured in tetramethylsilane (TMS). Unless otherwise stated, the solvent used was deuteriochloroform. The abbreviation habon following Bodo:

wide

d Dublott

m multiply

q Quartet

Singled

t triplet

Vbdg. Magnetic nuclear magnetic resonance data (δ relative to TMS)

1.35 (3H, d, Me), 3.66 (3H, β, OMe), 3.77 (3H, s, OMe), 4.31 (2H, s, CH ₂ ), 4 , 4-4.7 (2H, m, 2-CH), 7.0-7.55 OH, m, 9ArH), 7.58 (1H, s, CH).

2 0.78 (3H, d, Me), 3.66 (3H, i, OMe), 3.8 (3H, s, OMo), 4.24 (2H, s, CH ₂ ), 4.35-4.65 (1H, m, CH), 5.66 (1H, d, CH), 7.05-7.80 (9H, m, 9-ArH), 7.81 ( 1H, s, CH).

3, 1.33 (3H, d, Me), 3.83 (3H, s, OMe), 4.04 (3H, s, OMe), 4.25 (2H, s, CH ₂ ), 4 , 30 to 4.70 (4 H, m, CH _2, 2-CH), 7.05 to 7.60 (9 H, m, 9-ArH).

4 2.40 (3H, s, SMe), 3.01 (3H, s, OMe), 3.72 (6H, d, 2-0Me), 4.22 (2H, s, CH ₂ ), 6.8 (1H, s, 4-ArH), 7.0-7.45 (4H, m, 4-ArH), 7.53 (1H, s, CH).

6, 2.53 (3H, s, SMe), 3.61 (3H, s, OMe), 3.71 (3H, s, OMe), 4.23 (2H, s, CH ₂ ), 7.1-7.5 (6H, m, Ar), 7.56

(1H, s, HC = C (Ar) CO ₂ Me), 8.20 (1H, br, pyr-H), 8.31 (1H, t, pyr-H). 9.82 (3H, s, OCH ₃ ), 3.90 (3H, s, CO ₂ CH ₃ ), 4.09 (3H, s, NOCH ₃ ), 4.24-4.38 (1H, obscured m, Hot-CH), 4.29

(2H, 8, SCH ₂ ), 4.48 (1H, dd, Het-CH), 5.06 (1H, dt, Hot-CH), 6.8-6.9 (2H, m , ArH), 7.1-7.45 (5H, m, ArH), 7.55 (1H, m, ArH)

10, 1.37 (3H, d, Me), 3.67 (3H, s, OMe), 3.80 (3H, s, OMe), 4.32 (2H, s, CH ₂ ), 4.50-4.70 (2H, m, 2-CH), 7.05-7.55 (9H, m, 9-ArH), 7.60 (1H, s, CH).

11 .77 (3H, d, Me), 3.66 (3H, s, OMe). 3.78 (3 H, s, OMe), 4.23 (2 H, s, CH _2), 4.35 to 4.6 (1 H, m, CH), 5.65 (1 H, d, CH), 7.0-7.45 (9H, m, 9 ArH), 7.48 (1H, s, CH).

12 3.66 (3H, s, OMe), 3.76 (3 H, s, OMo), 4.25 to 4.6 (4 H, m, 2-CH _2), 5.04 (1 H, t, CH), 7.0-7.5 (9H, m, 9-ArH), 7.56 (1H, S, CH).

13 3.66 (3H, s, OMe), 3.76 (3H, s, OMe), 4.35 (2H, s, _CH2), 5.53 (1 H, d, CH), 5.87 (1H, d, CH), 6.7-7.5 (14H, m, 14-ArH), 7.6 (1H, s, CH).

14 Solvents: Acetone-d _e 1,10 (3H, t, Me), 1.4-1.9 (2H, m, CH ₂ ), 3.1 (1H, q, CH), 3.59 (3H , s, OMe), 3.8 (3H, s, OMe), 4.28 (2H, s, CH ₂ ), 6.95-7.55 (4H, m, 4-ArH), 7, 6 (1H, s, CH).

16 3.67 (3 H, s, OMe), 3.76 (3 H, s, OMe), 3.83 (2 H, s, CH _2), 4.44 (2 H, s, CH ₂₎ , 6.9-7.4 (8H, m, 8-ArH), 7.53 (1H, s, CH).

17 1.2-1.9 (8H, m, 4-CH _2), 2.3-2.5 (2H, m, CH _2), 3.67 (3 H, s, OMe), 3 , 81 (3H, s, OMe), 4.07 (2H, s, CH ₂ ), 7.0-7.5 (4H, m, 4-AiH), 7.55 (1H, s, CH).

18 1.5-1.85 (6H, m, 3-CH ₂ ), 2.1-2.35 (2H, m, CH ₂ ), 3.68 (3H, s, OMo), 3 , 81 (3 H, s, OMe), 4.09 (2 H, s, CH _2), 7.0-7.5 (4H, m, 4-ArH), 7.35 (1H, s, CH ).

19 1.71 (2 H, m, Het-CH _2), 2.26 (2 H, t, Het-CH _2), 3.7 (3 H, s, OCH _3), 3.7 (2 H , obscured t, Het-CHj), 3.85 (3H, s, CO ₂ CH ₃ ), 4.09 (2H, s, SCH ₂ ), 7.0-7.5 (4H, m, ArH), 7.56 (1H, s, = CH).

20 3.5-3.85 (8H, m, 2-OMe, CH ₂ ), 4.35 (2H, s, CH ₂ ), 5.45 (1H, t, CH), 7.0 -7.45 (9H, m, 9-ArH), 7.52 (1H, s, CH).

21, 0.77 12H, d, Me), 3.82 (3H, s, OMe), 4.04 (3H, s, OMe), 4.18 (2H, s, CH ₂ ), 4.25 -4.7 (1H, m, CH), 5.65 (1H, d, CH), 7.0-7.7 (9H, m, 9-ArH).

22 3.81 (3 H, s, OMe), 3.84 (2 H, s, CH _2), 4.05 (3 H, s, OMe), 4.39 (2 H, s, CH ₂₎ , 6.95-7.7 (8H, m, 8-ArH).

23 3.78 (3H, s, OMe), 3.99 (3H, s, OMe), 4.15-4.50 (4H, m, 2-CH ₂ ), 5.0 (1H, t, CH), 7.05-7.60 (OH, m, 9-ArH).

24 2.28 (3H, s, SMe), 2.41 (3H, s, Me), 3.63 (3H, s, OMe), 3.73 (3H, s, OMe), 4.24 (2 H, s, CH ₂ ), 6.75-7.50 (CH, m, 8-ArH), 7.57 (1 H, s, CH).

25 2.41 (3H, s, SMe), 3.62 (3H, s, OMe), 3.72 (3H, s, OMe), 4.21 (2H, s, CH ₂ ), 6.7- 7, '5 (8H, m, 8-ArH), 7.54 (1H, s, CH).

26 2.41 (3H, s, SMe), 3.61 (3H, s, OMe), 3.70 (3H, s, OMe), 4.23 (2 H, s, CH _2), 6.95 -7.55 (8H, m, 8-ArH), 7.57 (1H, s, Ch).

27 2.42 (3H, s, SMe), 3.53 (3H, s, OMe), 3.63 (3H, s, OMe), 3.66 (3H, s, OMe), 4 , 22 (2 H, s, CH _2), 6.4-6.7 (2 H, m, ArH).

28, 2,42 (3H, s, SMe), 3,63 (3H, s, OMe), 3,71 (3H, s, OMe), 4,24 (2H, s, CH ₂ ), 6 , 8-7.0 (2H, d, 2-ArH), 7.0-7.55 (4H, m, 4-ArH), 7.58 (1H, s, CH) 7.9-8 , 1 (2H, d, 2-ArH).

29 2.42 (3H, s, SMe), 3.63 (3H, s, OMe), 3.73 (3H, s, OMe), 4.25 (2H, s, CH ₂ ), 6.75-7.55 (13H, m, 1U-ArH), 7.59 (1H, s, CH).

30 1.27 (9H, s, Bu ¹ ), 2.41 (3H, s, SMe), 3.62 (3H, s, OMe), 3.70 (3H, s, OMe), 4.24 (2H, s, CH ₂ ), 6.7-7.5 (8H, m, ArH), 7.54 (1H, s, CH).

32.42 (3H, s, SMe), 3.64 (3H, s, OMe), 3.74 (3H, s, OMe), 4.23 (2H, s, CH ₂ ), 6 , 65-7.45 (8H, m, ArH), 7.56 (1H, s, CH).

33 1.03 (3 H, m, CH ₃ CH _2), 2.28 (2 H, m, CH ₃ CH _2), 3.74 (3 H, s, OMe), 4.01 (3 H, s, OMe), 4.12 (2H, s, CH ₂ S), 6.71 (2H, br d, ArH), 6.9-7.5 (7H, br m, ArH). ,

34 Solvent: acetone-de

2.41 (3 H, s, SMe), 3.70 (3 H, s, OMe), 3.94 (3 H, s, OMe), 4.23 (2 H, s, CH _2), 6 , 75-7.65 (9H, m, ArH). 37 Mixture of E and Z iminoisomerone 0.9 (6H, m, CH (CH ₃ J ₂ , 1.0 & 1.1 (3 H, 2 d, CH ₃ ), 1.3 (1H, m, CH), 1.5

(2 H, m, CH _2), 2.35 & 2.5 (3 H, 2 s, SCH _3), 3.7 (3 H, s, OCH _3), 3.8 (1H, m, NCH ), 3.85 (3H, s, CO ₂ CH ₃ ), 4.15 & 4.25 (2H, 2 s, SCH ₂ ), 7.1 (1H, m, ArH), 7.25 ( 2 H, m, ArH), 7.45 (1H, m, ArH), 7.55 & 7.6 (1H, 2 s, = CH).

Continued TaIiMIo

Nuclear Magnetic Resonance Daton (δ relative to TMS)

Mixture of E and Z imine isomers, 0.9 (3H, t, CH ₁ 1,1,2 (16H, br m, 8x CH ₂ ), 2,35 & 2,45 (3H, 2 s, SCH _3), 3.4 (2H, m, NCH _l), 3.7 (3H _l 8 _/ OCH,), 3.85 (3H, 8, CO ₂ CH _3), 4.16 & 4.25 (2H, 2s , SCH _J ), 7.1 (1H, m, ArH), 7.25 (2H, m, ArH), 7.45 (1H, m, ArH), 7.55 & 7.6 (1H, 2 s, = CH).

Mixture of E and Z imino isomers, 0.9 (3H ₁ 1, CH ₃ ), 1.2 (20H, br m, 10X CH ₂ ), 2.35 & 2.45 (3H, 2 s, SCH ₃ ), 3,4 (2H, m, NCH ₂ ), 3,7 (3H, d, OCH ₃ ), 3,85 (3H, d, CO ₂ CH ₃ ), 4,2 (2H, d, SCH ₂ ), 7.1 (1H, m, ArH), 7.25 (2H, m, ArH), 7.45 (iH, m, A (H), 7, e (1H, d , = CH).

Mixture of E- and Z-Imlnoisomoren, 0.9 (3H, m, CH _3), 1.2 (12 H, br s, 6x CH _2), 2.35 & 2.45 (3H, 2s, SCH ₃ ), 3,4

2 H, m, NCH ₁ ), 3.7 (3H, s, OCH ₃ ), 3.85 (3H, s, CO ₂ CH ₃ ), 4.15 & 4.25 (2H, 2 s , SCH ₂ ), 7.1 (1H, m, ArH), 7.25 (2H, m, ArH), 7.45 (1H, m, ArH), 7.6 (1H, d, = CH).

Mixture of E and Z iminoisomerone, 1.65 (BH br, m, 4x CH ₂ ), 2.3F & 2.45 (3H, 2 s, SCH ₃ ), 2.95 (4H, m, 2x NCH ₂ ), 3.7 (3H, s, OCH ₃ ), 3.85 (3H, s, CO ₂ CH ₃ ), 4.1 ft 4.2E (2H, 2 s, SCH ₂ ), 7 , 15 (1H, m, ArH), 7.3 (2H ₁ m, ArH), 7.5 (1H, m, ArH), 7.6 (1H, d, = CH).

2.5 (3H, s, SCH ₃ ), 3.75 (3H, s, OCH ₃ ), 3.8 (3H, s, CO ₂ CH ₃ ), 4.25 (2H, br , SCH ₂ ), 6.8 (2H, m, ArH) ₁ 7.15 (1H, m, ArH), 7.3 (2H, m, ArH), 7.45 (1H, m, ArH ), 7.6 (1H, s, = CH), 8.5 (2H, in. ArH).

1.35 (3 H, t, CH _3), 3.65 (2 H, m, Het-CH _2), 3.7 (3 H, s, OCH _3), 3.82 (3 H, s; CO ₂ CH ₃ ), 4.28 (2H, q, OCH ₂ CH ₃ ), 4.35 (2H, s, SCHtAr), 5.02 (1H, t, Het-CH), 7.1 -7.5 (4H, m, ArH), 7.6 (1H, s, = CH).

0.95 (3 H, t, CH _3), 1.38 to 1.7 (6 H, m, 3 x CH,), 3.7 (3 H, s, OCH _3), 3.8 (3 H , s, CO ₂ CH ₃ ), 3.95 (1H, dd, Het-CH), 4.14 1H, m, Het-CH), 4.2 (2H, s, SCH ₁ Ar), 4, 4 (1H, dd, Het-CH), 7.15 (4H, m, ArH), 7.6 (1H ₁ s, = CH).

Mixture of E- and Z-Iminoisomeren, 2.35 & 2.45 (3H, 2s, SCH _3), 2.8 (4H, m, 2x _NCH2), 3.7 (3H, d, OCH _3), 3.8 (4H, m, 2xOCH ₂ ), 3.9 (3H, d, CO ₂ CH ₃ ), 4.1 8 (4.2 (2H, 2 s, SCH ₂ ), 7.15 (1 H, m, ArH), 7.3 (2H, m, ArH), 7.5 (1H, m, ArH), 7.6 (1H, d, = CH).

Mixture of E- and Z-Iminoisomeren, 0.95 & 1.0 (9H, 2 s, C (CH ₃ I _3), 2.4 & 2.5 (3 H, 2 s, SCH _3), 3, C5 & 3.1 (2H, 2S, NCH ₂ ), 3.7 (3H, s, OCH ₃ ), 3.8 (3H, d, CO ₂ CH ₃ ), 4.25 (2H , br s, SCH ₂ ), 7.15 (1H, m, ArH), 7.3 (2H, m, ArH), 7.5 (1H, m, ArH), 7.6 (1H, d , = CH).

2.5 (.1H, 3, SCH ₃ ), 3.7 (3H, s, OCH ₃ ), 3.8 (3H, s, CO ₂ CH ₃ ), 4.3 (2H, br s, SCH ₂ ), 6.95 (1H, d, ArH), 7.15 (1h, m, ArH), 7.25 (2H, m, ArH), 7.35 (1H, m, ArH), 7.6 (2H, m, ArH), 8.4 (1H, s, = CH).

3.73 (3H, a, OCH ₃ ), 3.77-3.93 (4H, m, Het-CH & CO ₂ Cf ¹ ,), 4.2-4.42 (3H, m, Het-CH & SCH ₂ ), 5.6 (1H, t, OCH), 7.1-7.6 9H, m, ArH), 7.62IIH, s, = CH).

0.95 (3H, t, CH _3), 1.4-1.8 (6H, m, 3x CH _2), 3.06 (1H, dd, Het-CH), 3.5 (1H, m, Het-CH), 3.75 (3H, s, OCH ₃ ), 3.82 (3H, 8, CO ₂ CH ₃ ), 4.3 (2H, s, SCH ₂ Ar) ₁ 4.4 ( 1H _1m , Het-CH), 7.1-7.5 (4H, m, ArH), 7.6 (1H, s, = CH).

1.35-2.35 (8H, m, 4X CH ₂ ), 3.24 (1H, dt, Het-CH), 3.7 (1H, m, Het-CH), 3.7 (3 H, s, OCH ₃ ), 3.8 (3 rs, CO ₂ CH ₃ ), 4.22 (2 H, q, SCH ₂ Ar), 7.1-7.5 (4 H, m, ArH), 7.6 (1H, s, = CH).

1.35 (3 H, t, CO ₂ CH ₂ CH,), 1.42 (3 H, s, CH ₃ ), 1.75 (3 H, 8, CH ₃ ), 3.7 (3 H, s, OCH _3), 3.84 (3 H, 8, CO ₂ CH _3), 4.28 (2H, q, CO ₂ CH ₂ CH _3), 4.34 (2 H, s, SCH ₂ Ar ), 4.65 (1H, s, Het-CH), 7.15 to 7.54 (4 H ₁ m, ArH), 7.6 (1H, s, = CH).

0.95 (3 H, t, CO ₂ (CH ₂ ) ₃ CH,), 1.4 (3 H, s, CH ₃ ), 1.44 (2 H, m, CO ₂ (CH ₂ I ₂ CHiCH ₃ ), 1.68 (2H, m, CO ₂ (CH ₂ I ₂ CH ₂ CH ₂ CH ₃ ), 1.7 (3H, s, CH ₃ ), 3.68 (3H, s, OCH ₃ ) , 3.84 (3H, s, CO ₂ CH ₃ ), 4.2 (2H, m, CO ₂ CH ₂ (CH ₂ I ₂ CH ₃ ), 4.34 (2H, s, SCH ₂ Ar), 4.66 (1H, s, Het-CH), 7.12-7.5 (4H, m, ArH), 7.6 (1H, s, = CH).

2.5 (3H, s, SCH ₃ ), 3.7 (3H, s, OCH ₃ ), 3.8 (3H ₁ s, CO ₂ CH ₃ ), 4.25 (2H, br s, SCH ₂ ), 6.7 (1H, m, ArH), 7.0 (1H, m, ArH), 7.1 (1H, m, ArH), 7.3 (3H, m, ArH), 7.5 (1H, m.ArH), 7.6 (1H, s, = CH).

0.9513H, t, (CH ₂ I ₇ CHj), 1.35 (1OH, m, CH ₂ CH ₂ (CHj) ₅ CHj), 1.72 (2H, m, CH ₂ CH ₂ (CH ₂ I ₅ CH ₃ ), 3.54 (2H, m, Het-CH ₂ ), 3.7 (3H, s, OCH ₃ ), 3.84 (3 H, s, CO ₂ CH ₃ ), 4.22 ( 2 H, t, CHj (CH ₂ I ₆ (CH ₃ )), 4.35 (2 H, s, SCH ₂ Ar), 5.06 (1 H, t, Het-CH), 7.01-7 , 5 (4H, m, ArH), 7.6 (1H, s, = CH).

0.95 (3H, t, (CHj) ₇ CH _3), 1.3 (1 OH, m, CH ₂ CH ₂ (CHj) ₅ CH _3), 1.44 (3H, s, CH _3), 1, 68 (2H, m, CH ₂ CH ₂ (CH ₂ I ₅ CH _3), 1.74 (3 H, s, CH _3), 3.7 (3 H, s, OCH _3), 3.84 (3 H, s, CO ₂ CH ₃ ), 4.22 (2H, t, CH, (CH ₂ ) ₆ CH ₃ ), 4.35 (2H, s, SCH ₂ Ar), 4.68 (1H , s, Het-CH), 7, 12-7, 51 (4H, m, ArH), 7.6 (1H, s, = CH).

0.95 (9H, s, 3x _CH3), 3.64 (1H, m, Het-CH), 3.7 (3H, s, OCH _3), 3.8 (1H, m, Het-CH) , 3.84 (3H, m, Het-CH), 3.84 (3H, s, CO ₂ CH ₃ ), 4.18 (2H, s, SCH ₂ Ar), 4.36 (1H, m, Het -CH 7.1-7.5 (4H, m, ArH), 7.6 (1H, s, = CH).

Mixture of E and Z iminoisomers, 1.6-2.1 (4 H, m, 2 CH ₂ ), 2.4 & 2.5 (3 H, 2 s, SCH ₃ ), 2.9 (2 H, m, ArCH ₂ ), 3.7

3 H, s, OCH ₃ ), 3.75 & 3.85 (3H, 2s, CO ₂ CH ₃ ), 4.2 & 4.3 (2H, 2 s, SCH ₂ ), 5.0 ( 1 H, m.A.NCHN), 7.0-7.4 (8H, m, ArH), 7.55 & 7.65 (1H, s, = CH).

2.5 (3H, br s, SCH ₃ ), 3.7 (3H, s, OCH ₃ ), 3.8 (3H, s, CO ₂ CH ₃ ), 4.3 (2H, br s, SCH ₂ ), 6.8-7.5 (7H, m, ArH), 7.6 (1H, s, = CH).

0.95 (3 H, t, (CHj) ₇ CH _3), 1.3-1.8 (14 H, m, (CHj) ₇ CH _3), 3.04 (1 H, m, Het-CH ), 3.44 (1 H, m, Het-CH), 3.7 (3 H, s, OCH _3), 3.84 (3H, s, CO ₂ CH _3), 4.28 (2 H, s, SCH ₂ Ar), 4.37 (1 H, m, Het-CH), 7.1-7.5 (4 H, m, ArH). 7.6 (1H, s, = CH).

0.9 (3 H, t, CH _3), 1.3 (2 H, m, CH _2), 1.6 (2 H, m, CH _2), 2.4 (3 H, br s, SCH ₃ ), 2.5 (2H, t, NCH ₂ ), 3.7 (3H ₁ s, OCH ₃ ), 3.8 (3H, s, CO ₂ CH ₃ ), 4.25 (2H , br s, SCH ₂ ), 6.8 (2H, d, ArH), 7.1 (3H, m, ArH), 7.3 (2H, d, ArH), 7.45 (1H, br s, ArH), 7.5 1H, s, = CH),

2.5 (3H, s, SCH ₃ ), 3.7 (3H, 8, OCH ₃ ), 3.8 (3H, 8, CO ₂ CH ₃ ), 4.3 (2H, s, SCH ₂ ), 6.65 (1H, m, ArH), 6.75 (1H, m, ArH), 7.0 (1H, m, ArH), 7.1 (1H, m, ArH), 7.3 (2H, m, ArH), 7.45 (1H, m, ArH), 7.6 (1H, s, = CH).

1.15 (3H, d, CH _3), 1,62,2,27 & 2.86 (1H, each, m, Het-CH), 3.71 (3 H, s, OCH ₃₎ 3, 76 (1H, m, Het-CH), 3.92 (1H, m, Het-CH), 3.84 (3H, s, CO ₂ CH ₃ ), 4.21 (2H, s, SCH ₂ ) , 7.0-7.5 (4H, m, ArH), 7.55 (1H, s, = CH).

Mixture of E and Z iminoisomers, 2.35 & 2.6 (3H, 2s, SCH ₃ ), 3.05 & 3.1 (3H, 2s, NCH ₃ ), 3.65 & 3.7 (3 H, 2 s, OCH ₃ ), 3.7 & 3.8 (3H, 2 s, CO ₂ CH ₃ ), 4.1 8t 4.4 (2H, 2 s, SCHj), 6.9- 7.5 (9H, m, ArH), 7.55 & 7.65 (1H, 2s, = CH).

2.68,305 8 »3.59 (each 1 H, m, Het-CH), 3.71 (3 H, s, OCH ₃ ), 3.85 (3 H, s, CO ₂ CH ₃ ), 3, 88 (1H, m, 1 let-CH), 4,3 (2H, s, SCH ₂ ), 4,38 (1H, m, HetCH), 7,0-7,55 (4H, m, ArH ), 7.61 (1H, s, = CH).

Continued table

Verb. Magnetic resonance data (δ relative to TMS)

2.43 (3 H, 8, CHj), 2.57 (3H, 8, _SCH3), 3.70 (3 H, s, OCH _3), 3.84 (31 i ε. CO ₂ CH ₃ ), 4.36 (2H, s, CH ₂ ), 6.72 (1H, s, Het-CH), 7.10-7.48 (4H, m, ArH), 7.60 (1 H, 8, = CH).

1.98 (3H, 8, N = CCH _3), 3.73 (3 H, s, OCH _3), 3.82 (3 H, s, CO ₂ CH _3), 4.25 (2 H, br s, SCH ₂ ), 6.75 (2H, d, ArH), 7.15 (1H, t, ArH), 7.30 (4H, m, ArH), 7.46 (1H, t, ArH ), 7.59 ('H, s, = CH).

2.12 (3H, br s, N = C-CH ₃ ), 3.70 (3H, s, OCH ₃ ), 3.80 (3H, s, CO ₂ CH ₃ ), 4.25 (2H, br s, SCH ₂ ), 6.82 (1H, d, ArH), 7.00 (1H, m, ArH), 7.15 (1H, m.ArH), 7.28 (2H, m , ArH), 7.52 (1H, m, ArH), 7.60 (1H, s, = CH), 7.68 (1H, t, ArH), 8.40 (1H, d, ArH ).

7Γ. '2.0 (3 H, s, N = CCH _3), 2.36 (3 H, s, ArCH _3), 3.70 (3 H, s, OCH _3), 3.82 (3 H, s , CO ₂ CH ₃ ), 4.25 (2 H, br s, SCH ₂ ), 6.60

(2H, d, ArH), 6.90 (1H, d, ArHI, 7.1-7.35 (4H, m, ArH), 7.52 (1H, m, ArH), 7.6 ( 1H, s, = CH).

7! I 1.18 (3 H, d, CH _3), 1.3 (3 H, d, CH _3), 3.72 (3H, s, OCH _3), 3.85 (3H, s, CO ₂ CH ₃ ), 4.1 (1H, m, Het-CH), 4.15

(2H, s, SCH ₂ Ar), 4.78 (1H, m, Hot CH), 7.12-7.5 (4H, m, ArH), 7.6 (1H, s, = CH).

3.7 (3H, s, OCH ₃ ), 3.8 (3H, s, ArOCH ₃ ), 3.84 (3H, s, CO ₂ CH ₃ ), 4.3 (1H, m, Het -CH), 4.35 (2H, s, SCH ₂ Ar), 4.5 (1H, m, Het-CH), 5.06 (1H, m, Het-CH), 6.85- 7.5 (8H, m, ArH), 7.6 (1H, s, = CH).

2.47 (3H s, SMe), 3.63 (3H, s, OMe), 3.76 (3H, s, OMe), 4.29 (2H, s, CH ₂ ), 6 , 9-7.7 (7H, br m, Ar), 7.57 (1H, s, HC = C (Ar) CO ₂ Me), 8.40 (1H, br d, pyr-H).

2.53 (3H, s, SMe), 3.65 (3H, s, OMe), 3.78 (3H, s, OMe), 4.35 (2H, s, CH ₂ ), 7.05- 7.55 (6H, br m, ArH), 7.58 (1H, s, HC = C (Ar) CO ₂ Me), 7.7-7.8 (2H, br m, ArH).

2.52 (3H, s, SMe), 3.67 (3H, s, OMe), 3.80 (3H, s, OMe), 4.34 (2H, s, CH ₂ ), 6 , 5-7.5 (6H, br m, ArH), 7.49 (1H, s, HC = C (Ar) CO ₂ Me).

Mixture of isomers: 0.87 (3H, brt, CH ₃ CH ₂ -), 1.1-1.5 (6H, br m, (CH ₂ I ₃ ), 1.5-1.8 (2H, br m, CH ₂ ), 2.33 and 2.43 3H, 2xs, SMe), 3.39 (2H, brt, CH ₂ N), 3.66 (3H, s, OMe), 3.78 (3H, s, OMe), 4.17 and 4.20 (2H, 2xbr s, SCH ₂ Ar), 7.0-7.5 (4H, m, Ph), 7.53 and 7.58 (1H, 2 xs, HC = C- (Ar) CO ₂ Me).

Mixture of isomers: 0.86 (3H, br t, CH ₃ CH ₂ -), 1,1-1,45 (6H, br m, (CH ₂ I ₃ ), 1,45-1,8 (2H , br m, CH ₂ ), 2.33 and 2.43 (3H, 2xs, SMe), 3.38 (2H, t, CH ₂ N), 3.82 (3H, s, OMe), 4 , 01 (3H, s, OMe), 4,11 and 4,15 (2H, 2 xbr, s, SCH ₂ Ar), 6,9-7,6 (4H, br m, Ph).

2.32 (3H, s, CH ₃ ), 2.51 (6H, s, 2xCH ₃ ), 3.71 (3H, s, OCH ₃ ), 3.81 (3H, s, CO ₂ CH ₃ ) , 6.57 (1H, d, pyridine ring, CH), 6.72 (1H, d, pyridine ring CH), 7.08-7.53 (4H, m, ArH), 7.60 (1H, s , = CH).

0.9 (6H, d, 2x CH _3), 1.4-1.7 (6H, m, 3xCH _2), 2.3 (3H, s, SCH _3), 2.5 (2H, brs, N -CH), 3.7 (3H, s, OCH ₃ ), 3.85 (3H, s, CO ₂ CH ₃ ), 4.25 (2H, s, SCH ₂ ), 7.1 (1H, m , ArH), 7.3 (2H, m, ArH), 7.55 (1H, m, ArH), 7.6 (1H, s, = CH).

2.36, 2.79 and 2.97 (each 1H, m, Het-CH), 3.1-3.4 (3H, m, 3x Het-CH), 3.70 (2H, s, CH ₂ ), 3.75 (3H, s, OCH ₃ ), 3.7-3.8 (1H, indistinct m, Het-CH), 3.88 (3H, s, CO ₂ CH ₃ ), 7, 14 (1H, m, ArH), 7.30 (2H, m, ArH), 7.44 (1H, m, ArH), 7.61 (1H, s, = CH).

2.1 (3 H, s, ArCH _3), 2.5 (3 H, s, SCH _3), 3.65 (3 H, s, OCH _3), 3.8 (3 H, s, CO ₂ CH ₃ ), 4.3 (2H, br s, SCH ₂ ), 6.8 (1H, m, ArH), 7.0 (1H, m, ArH), 7.1 (3H, m, ArH ), 7.3 (2H, m, ArH), 7.5 (1H, m, ArH), 7.6 (1H, s, = CH).

Mixture of E and Z iminoisomers, 165-2.05 (4H, m, 2xCH ₂ ), 2.2 & 2.25 (3H, 2 s, SCH ₃ ), 2.5 (1H, m, NCH), 3.2-3.45 (4H, m, NCH ₂ & OCh ₂ ), 3.4 (3H, d, OCH ₃ ), 3.7 (3H, s, OCH ₃ ), 3 , 85 (3H, s, CO ₂ CH ₃ ), 7.1 (1H, m, ArH), 7.25 (2H, m, ArH), 7.5 (1H, m, ArH), 7, 6 (1H, d, = CH).

0.94 (3H, t, CH _3), 1.1E-1,8 (6H, m, 3x CH _2), 3.86 (3H, s, CO ₂ CH _3), 3.93 (1 H, t, Het-CH), 4.0-4.2 (1 H, m abscured, Het-CH), 4.08 (3H, s, NOCH _3), 4.15 (2 H, s, CH ₂ S ), 4.41 (1H, t, Het-CH), 7.14 (1H, dd, ArH), 7.3-7.45 (2H, m, ArH), 7.58 (1H , dd, ArH).

1.30 (3H, d, CH _3), 1,53,2,20 (each 1H, m, Het-CH), 2.62 (2 H, m, Het-CH), 3.71 (3 H , s, OCH ₃ ), 3.85 (3H, s, CO ₂ CH ₃ ), 4.11 (1H, m, Het-CH), 4.26 (2H, q, CH ₂ S), 7 , 0-7.5 (4H, m, ArH), 7.59 (1H, s, = CH).

10O 3.62 (3 H, s, OCH _3), 3.76 (3 H, s, CO ₂ Me), 3.95 (4H, t, Het-CH), 4.29 (2 H, s , CH ₂ S), 7.0-7.5 (9 H, m, ArH), 7.56 (1H, s, = CH).

2.50 (3H, s, SCH ₃ ), 3.68 (3H, s, OCH ₃ ), 3.80 (3H, s, CO ₂ CH ₃ ), 3.90 (3H, s, ArOCH ₃ ), 4.29 (2H, s, SCH ₂ ), 6.70 (1H, d, pyridineH), 7.05-7.5 (5H, m, 4xArH and pyridineH), 7.6C (1H, s , = CH), 7.77 (1H, s, PyridinH).

2.54 (6 H, s, SCH ₃ CH _3), 3.70 (3 H, s, OCH _3), 3.82 (3 H, s, CO ₂ CH _3), 4.26 (2 H , s, SCH ₂ ), 6.84 (1H, d, Py rimidine H), 7.0-7.5 (4H, m, ArH), 7.60 (1H, s, = CHj, 8.52 (1H, d, pyrimidine H).

1.45-1.65 (4H, m, 2x Het-CH _2), 1.74 to 1.86 (2H, m, Het-CH _2), 2.35-2.45 (2H, m, Het -CH ₂ ), 3.67 (2H, m, HOt-CH ₁ N), 3.87 (3 H, 8, CO ₂ CH ₃ ), 4.03 (2 H, s, SCH ₂ ), 4, 09 (3H, s, NOCH ₃ ), 7.11 (1H, m, ArH), 7.2-7.4 (2H, m, ArH), 7.46 (1H, m, ArH)

2.37 (3 H, s, ArCH _3), 2.47 (3 H, s, SCH _3), 3.7 (3 H, s, OCH _3), 3.8 (3 H, s, CO ₂ CH ₃ ), 4.26 (2H, br s, SCH ₂ ), 6.6 (1H, d, ArH), 6.8 (1H, s, ArH), 7.14 (1H, br d, ArH), 7.23-7.35 (2H, m, ArH), 7.4-7.55 (2H, m, ArH), 7.58 (1H, s, = CH). 2 / .5 (3 K, s, CH ₃ S), 2.7-2.85 (4 H, m, Het-CH), 3.68 to 3.84 (4H, m, Het-CH) , 3.86 (3H, s, CO ₂ CH ₃ ), 4.06 (5H, br s, SCH ₂ & NOCH ₃ ), 7.1-7.18 (1H, m, ArH), 7, 25-7.55 (3H, m, ArH). 2.0 (1H, m, Het-CH), 2.2 (1H, brM, Het-CH), 2.77 (1H, q, Het-CH), 2.85-3.3 (4H , m, Het-CH), 3.8 (2H, s, SCH ₂ ), 3.94 (3H, s, CO ₂ CH ₃ ), 4.08 (3H, s, NOCH ₃ ), 7, 17 (1H, m, ArH), 7.3-7.5 (3H, m, ArH). 1.63 (6H, S, 2 x CH ₃ ), 3.72 (3H, s, OCH ₃ ), 3.88 (3H, s, CO ₂ CH ₃ ), 4.30 (2H, s, CH ₂ S), 7.05-7.35 (7H, m, ArH), 7.60 (1H, m, ArH), 7.64 (1H, s, = CH)

As a mixture of diastereoisomers obtained by -getrennt Kolonnenchromatografie, MKR for Hauptdiastereoisomere: 1.3 (3H, d, CH _3), 1.52 (1 H, m, Het-CH), 2,22Ί H, m, Het-CH ), 2.6 (2H, m, 2x Het-CH), 3.86 (3H, s, CO ₂ CH ₃ ), 4.06 (3H, s, NOCH ₃ ), 4.0-4.2 ( 1H, indistinct m, Het-CH), 4,22 (2H, s, SCH ₂ ), 7,14 (1H, m, ArH), 7,24-7,32 (2H, m, ArH), 7.54 (1H, m, ArH).

Continued table Nuclear Magnetic Resonance Data (δ relative to TMS)

123 0.9 (3H, brt, CH _3), 1.18 to 1.45 (8H, m, 4xCH2) .1,70 (2H, m, CHj), 3.82 to 4.36 (5H, undeutlichesm , CH, Sund

3x Het-CH), 3.88 (3H, indistinct, CO ₂ CHj), 4.06 (3H, indistinct, NOCH,), 7.14 (1H, m, ArH), 7.23-7.46 (2H, m, ArH), 7.53 (1H, m, ArH).

130 1.3 (3 H, d, CH _3), 1.38 (3 H, d, CH _3), 3.7 (3 H, s, OCH _3), 3.74 (1 H, m, Het -CH), 3.84 (3H, s, CO ₂ CH ₃ ), 4.2 (2H, s, SCH ₂ Ar), 4.25 (1H, m, Het-CH), 7.15 -7.52 (4H, m, ArH), 7.6 (1H, s, = CH)

131.95 (3 H, t, (CH ₂ J ₆ CH,), 1.3 (8 H, s, CH ₂ (CHj) ₄ CH ₃ ), 1.64 (2 H, m, CH ₂ ( CH ₂ I ₄ CH ₃ ), 3.7 (3H, s, OCH ₃ ), 3.85 (3H, s, CO ₂ CH ₃ ), 3.95 (2H, m, Het-CH), 4 , 2 (1 H, m, Het-CH), 4.3 (2H, s, _SCH2 Ar), 7.14 to 7.45 (4H, m, ArH), 7.6 (1H, s , = CH)

132 2.82 and 3.16 (2 \ I,? Dd, not equivalent _ArCH2), 3.35 (1 H, m, Het-CH), 3.7 (3 H, s, OCH ₃₎ 3, 84 (3H, s, CO ₂ CH ₃ ), 4.35 (2H, s, SCH ₂ Ar), 4.72 (1H, m, Het-CH), 7.14-7.48 (9H, m, ArH), 7.6 (1H, s, = CH)

133, 2.7 and 3.15 (2 H, 2 dd, non-equivalent ArCH ₂ ), 3.7 (3 H, s, OCH ₃ ), 3.84 (3H, s, CO ₂ CH ₃ ), 4.1 (1 H, m. Het-CH), 4.22 (2 H, s, _SCH2 Ar), 4.3 (1 H, m, Het-CH), 4.44 (1 H, m, Het- CH), 7.14-7.55 (9H, m, ArH), 7.6 (1H, s, = CH)

134. 3.72 (3H, s, OCH ₃ ), 3.84 (3H, s, CO ₂ CH ₃ ), 4.34 (1H, m, Het-CH), 4.38 (2H, s , SCH ₂ Ar), 4.55 (1H, m, Het-CH), 5.00 (1H, m, Het-CH), 7.15-7.5 (7H, m, ArH), 7 , 6 (1H, s, = CH)

135 3.7 (3H, s, OCH ₃ ), 3.78 (1H, m, Het-CH), 3.86 (3H, s, CO ₂ CH ₃ ), 4.25 (2H, s, SCH ₂ Ar), 4.32 (1H, m, Het-CH), 5.5 (1H, m Het-CH), 7.1-7.52 (7H, m, ArH), 7 , 6 (1H, s, = CH)

136 1.03 (3H, br s, CH ₂ CH ₃ ), 1.75 (2H, br s, CH ₃ ), 3.7 (3H, s, OCH ₃ ), 3.84 (3H, s , CO ₂ CH ₃ ), 3.95 (1H, m, Het-CH), 4.28 (2H, s, SCH ₂ Ar), 5.1 (1H, m, Het-CH), 7, 14-7.54 (9H, m, ArH), 7.6 (1H, s, = CH)

137 3.45 (3 H, s, CH ₂ OCH _3), 3.54 (2 H, m, CH ₂ OCH _3), 3.72 (3 H, s, OCH _3), 3.84 (3 H , s, CO ₂ CH ₃ ), 4.2 (1H, m, Het-CH), 4.28 (2H, s, SCH ₂ Ar), 5.4 (1H, d, Het-CH), 7 , 15-7.54 (9H, m, ArH), 7.6 (1H, s, = CH)

138 2.66 (3H, s, CH ₃ S), 3.73 (3 H, s, OCH _3), 3.89 (3 H, s, CO ₂ CH _3), 4.43 (2 H, s , CH ₂ S), 7.1-7.53 (6H, m, ArH), 7.62 (1H, s, = CH), 7.97 (1H, d, ArH), 8.07 (1H , s, ArH)

139 3.12 (2H, m, PhCH ₂ ), 3.71 (3H, s, OCH ₃ ), 3.87 (3H, s, CO ₂ CH ₃ ), 4.03 (1H, m, Het-CH), 4.15 (2 H, m, Het-CH), 4.38 (2H, m, SCH _2), 7.14 (1 H, m, ArH), 7.2-7.55 (8H, m, ArH), 7.60 (1H, s, = CH),

Experimental Example A Compounds are tested for activity against one or more of the following species:

a) foliage

Phytophthora infectans: late tomato rot (Pl) Plasmopara vltlcola: downy mildew (PV) Eryslphe gramlnis: cereal powdery mildew (EC) Pyricularla oryzae: Rice Flame (PO) Pelllcularla sasakli: rice sheath blight (PS) Botrytls clnerea: gray mold of tomato (BC) Venturia inaequalls: apple scab (Vl)

Aqueous solutions or dispersions of the compounds were applied in the desired concentration, including wetting agents, by spraying or soaking the stem base of the test plants. These plants were then inoculated with the appropriate experimental pathogens and kept under controlled environmental conditions suitable for the maintenance of plant growth and the development of the disease. After an appropriate time, the degree of infection of the leaf surface was visually determined.

The compounds have been considered active if they control the disease by more than 50% at a concentration of 125 particles / mill. (Weight / volume) or less.

Soil pathogen test b)

In this experiment, the compounds were determined for activity against Rhlzoctonla solanl (RS). Flasks containing cornmeal / sand were inoculated with the testis and then incubated. The maize meal / sand cultures were used to infect plant compost, which was then placed in plastic pots. To the pots were added aqueous solutions or dispersions of compounds, including a wetting agent, in the desired concentration of the compound in the individual pots. Control pots were prepared with similar solutions or dispersions without the test compound. Immediately after application of the test compound, some cabbage seeds were sown in each pot. The seeds were covered with treated, infected soil and the pots were incubated under controlled environmental conditions suitable for plant growth and disease development. The number of emerging cabbage seedlings is counted and the percent control of disease is calculated by comparison with the untreated, infected pots.

The compounds were considered active when control of the disease resulted in greater than 50% at a concentration of 100 parts by weight of the compound or less per mil volume of the soil.

The following activities were detected (+ = active). PI PI> EG PO PS BC Vl RS

No

19 +

31 + +

34 +

37 + + +

39 +++

40 + +

46 y . + +

55 + +

56 + +

57 + + +

58 +

59 + I- + +

63 +

66 + + + f

Continued table

PI PI> EG PO PS BC Vl RS

nn

69 + +

70+

71 +++

72 + +

73 + + +

74 + +

75 + + +

76 + +

84 + +

85 4 + + + +

88 ++ +

91 + + +

92 +

93 + +

Experimental Example B

This example illustrates the insecticidal activity of compounds of the invention.

Aliquots of 1 ml of an acetone solution containing the test compound at different concentrations were applied to 1 cm Dental 2 cm cotton dental rolls placed in glass ampoules 2 cm in diameter χ 5 cm in length. After drying, the material treated with 1 ml of a nutrient solution was impregnated, was infected with larvae of the first instar of sheep blowfly (Lucilia serlcata), the vials were sealed with a cotton plug and held for 24 hours at 25 ⁰ C. For the controls, the mortality was <5%, while the compounds of Examples 1,4,6,10,12,13,20,24-26,30-32,38-41,46,49, 51,53,56 , 60, 61, 64, 81 and 90 had an LC ₆₀ value of less than 300 particles per mill.

Claims (1)

1. Agricultural composition, characterized by a content of a compound of the formula I. (D in which X is oxygen or sulfur, W is CH or N, m is 0 or 1 and either a) η is 1 and Q is a non-aromatic heterocyclic ring of 3 to 10 ring atoms containing one to three heteroatoms selected from oxygen, sulfur and nitrogen which may be substituted and fused to another ring, provided that a) Q, if it is thiazole-2-ynyl, but is not substituted by methylene, and b) Q is not a six-membered ring with only two nitrogen atoms, or b) η is 0 or 1 and