RU2014320C1 - Method of synthesis of propenoic acid derivatives and their stereoisomers - Google Patents

Abstract

FIELD: organic chemistry. SUBSTANCE: derivatives of propenoic acid of the general formula (Z-X,A)-C₆H₂-K-C₆H₃-C(COOCH₃)=CHOCH₃, where K - oxygen or sulfur, A - hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, hydroxy, phenoxy or C₁-C₄-alkylcarbonyl. Reagent 1: compound of the general formula (A, W, L′)C₆H₃. Reagent 2: compound of the general formula (L″, Y)C₆H₄, where L, L′ - splitting off group. EFFECT: improved method of synthesis. 3 cl, 5 tbl

Description

и их стереоизомеров, где A - водород, галоген, С₁-С₄-алкил, С₁-С₄-алкокси, гидрокси, фенокси или С₁-С₄-алкилкарбонил; К представляет собой кислород или серу; Х - O, S(O)_n, NH, NR¹: CH₂, CHR², CO, CH₂CH₂, CH = CH, OCH₂, (CH₂)_mO, CHR¹O, OCH₂O, S(O)_nCH₂, S(O)CH₂O, NR¹CH₂, COO, OOC, SO₂O, COCH₂O, COCHR¹O, CONH, NHCO, NHSO₂, COS, SCO, N = N, CH₂OCO, CH₂SCO, CH₂NHCO, CH₂ON = CH₂, OCH₂CH₂O, NR¹N = CH, CH₂OCON, CH = CHCH₂O, (R₂)₂P⁺CH₂Q^-, N(COR¹), N = CH, CH(OH), CO₂CH₂, SCH₂O, NR¹CO, S(O)₂NH или CONR¹; R¹ - C₁-C₄-алкил; R² - фенил; n - 0,1 или 2; m - 1,2,3,4 или 5; Q - галоидный анион; Z - фенил (возможно монозамещенный С₁-С₆-алкилом, С₁-С₄-алкокси, С₁-С₄-галоидалкилом, фенокси,
фенилом, амино, гидрокси, 1-(С₁-С₄-алкоксикарбонил)-2-(С₁-С₄-алкокси)-винил, С₁-С_4-галоидалкокси или С₁-С₄-алкоксикарбонил, или моно- или дизамещенный галогеном, нитро, С₁-С₄-алкилом или цианогруппой); нафтил, хинолинил, пиридинил (возможно монозамещенный С₁-С₄-алкилом, С₁-С₄-алкоксикарбонилом, амино, галогеном, нитро, С₁-С₄-алкилкарбониламино, ди-(С₁-С₄-алкилсульфонил)амино или CH(O)NH, или моно- или дизамещенный С₁-С₄-галоидалкилом или цианогруппой, или дизамещенный аминогруппой и одной из циано, галоген или С₁-С₄-алкоксигруппы, или дизамещенный нитрогруппой и одной из циано, галоген, ди-(С₁-С₄-алкил)амино или С₁-С₄-алкоксигруппы, или замещенный цианогруппой и двумя С₁-С₄-алкильными группами); пиримидинил (возможно: монозамещенный С₁-С₄-алкилом, С₁-С₄-галоидалкилом, С₁-С₄-алкилтио, циано, нитро, фенилом, HO₂C, С₁-С₄-алкоксикарбонилом или С₁-С₄-алкилсульфонилом, или моно- или дизамещенный С₁-С₄-алкокси, или моно-, ди- или тризамещенный галогеном, или дизамещенный галогеном и одной из С_1-4 алкил или С_1-4 алкилтио, или дизамещенный С_1-4 алкил и С_1-4 галоалкил), пиразинил (возможно монозамещенный галогеном или циано, или дизамещенный С₁-С₄-алкилом), пиридазинил (возможно монозамещенный С₁-С₄-алкокси, фенилом или аминокарбонилом, или моно- или дизамещенный галогеном, или дизамещенный галогеном и С₁-С₄-алкилом), бензотиазолил, тиенил (возможно монозамещенный пиразолилом), который сам по себе дизамещен С₁-С₄-алкилом и С₁-С₄-галоидалкилом (или пиридинилом), который сам по себе, возможно, монозамещен нитро (или дизамещенный галогеном), 1,2,4-триазолил, хиноксалинил (монозамещенный галогеном), 1,3,5-триазинил (дизамещенный галогеном, или дизамещенный галогеном и С₁-С₄-алкокси), тиазолил (возможно монозамещенный нитро или моно-, или дизамещенный С₁-С₄-алкилом), бензоксазолил, пиридинил-N-оксид, тиено[2,3-d] пиримидинил, пирролил (возможно монозамещенный С₁-С₄-алкилом), изоксазолил (монозамещенный С₁-С₄-алкилом), 1,3,4,-тиадиазолил, пиразолил (замещенный галогеном и двумя С₁-С₄-алкильными группами) или 1,2,4-триазинил (монозамещенный фенилом); при условии, что, когда Z представляет собой незамещенный фенил, а Х и К оба представляют собой кислород, тогда A не является водородом; которые обладают фунгицидной активностью.The invention relates to the field of acids, in particular to a method for producing derivatives of propenic acid of the general formula

and their stereoisomers, where A is hydrogen, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, hydroxy, phenoxy or C ₁ -C ₄ -alkylcarbonyl; K represents oxygen or sulfur; X is O, S (O) _n , NH, NR ¹ : CH ₂ , CHR ² , CO, CH ₂ CH ₂ , CH = CH, OCH ₂ , (CH ₂ ) _m O, CHR ¹ O, OCH ₂ O, S (O) _n CH ₂ , S (O) CH ₂ O, NR ¹ CH ₂ , COO, OOC, SO ₂ O, COCH ₂ O, COCHR ¹ O, CONH, NHCO, NHSO ₂ , COS, SCO, N = N, CH ₂ OCO, CH ₂ SCO, CH ₂ NHCO, CH ₂ ON = CH ₂ , OCH ₂ CH ₂ O, NR ¹ N = CH, CH ₂ OCON, CH = CHCH ₂ O, (R ₂ ) ₂ P ⁺ CH ₂ Q ^- , N (COR ¹ ), N = CH, CH (OH), CO ₂ CH ₂ , SCH ₂ O, NR ¹ CO, S (O) ₂ NH or CONR ¹ ; R ¹ is C ₁ -C ₄ alkyl; R ² is phenyl; n is 0.1 or 2; m is 1,2,3,4 or 5; Q is a halide anion; Z is phenyl (possibly monosubstituted with C ₁ -C ₆ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkyl, phenoxy,
phenyl, amino, hydroxy, 1- (C ₁ -C ₄ alkoxycarbonyl) -2- (C ₁ -C ₄ alkoxy) vinyl, C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkoxycarbonyl, or mono - or disubstituted with halogen, nitro, C ₁ -C ₄ -alkyl or cyano); naphthyl, quinolinyl, pyridinyl (possibly monosubstituted with C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxycarbonyl, amino, halogen, nitro, C ₁ -C ₄ -alkylcarbonylamino, di- (C ₁ -C ₄ -alkylsulfonyl) amino or CH (O) NH, or a mono- or disubstituted C ₁ -C ₄ haloalkyl or cyano group, or a disubstituted amino group and one of cyano, halogen or a C ₁ -C ₄ alkoxy group, or disubstituted by a nitro group and one of cyano, halogen, di- (C ₁ -C ₄ alkyl) amino or C ₁ -C ₄ alkoxy groups, or substituted with a cyano group and two C ₁ -C ₄ alkyl groups); pyrimidinyl (possibly: monosubstituted With ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkylthio, cyano, nitro, phenyl, HO ₂ C, C ₁ -C ₄ -alkoxycarbonyl or C ₁ - C ₄ -alkylsulfonyl, either mono- or disubstituted C ₁ -C ₄ alkoxy, or mono-, di- or trisubstituted with halogen, or disubstituted with halogen and one of C _1-4 alkyl or C _1-4 alkylthio, or disubstituted C _{1 -4} alkyl and C _1-4 haloalkyl), pyrazinyl (possibly monosubstituted by halogen or cyano, or disubstituted with C ₁ -C ₄ alkyl), pyridazinyl (possibly monosubstituted C ₁ -C ₄ -alkoxy, phenyl, or aminocarbonyl, or m HO- or disubstituted by halogen, or disubstituted with halogen and C ₁ -C ₄ alkyl), benzothiazolyl, thienyl (possibly monosubstituted pyrazolyl), which itself is disubstituted with C ₁ -C ₄ -alkyl and C ₁ -C ₄ -galoidalkilom (or pyridinyl), which in itself is possibly monosubstituted by nitro (or disubstituted by halogen), 1,2,4-triazolyl, quinoxalinyl (monosubstituted by halogen), 1,3,5-triazinyl (disubstituted by halogen, or disubstituted by halogen and C ₁ - C ₄ -alkoxy), thiazolyl (possibly monosubstituted nitro or mono- or disubstituted by C ₁ -C ₄ alkyl), benzoxazolyl, pyr dinil-N-oxide, thieno [2,3-d] pyrimidinyl, pyrrolyl (possibly monosubstituted C ₁ -C ₄ alkyl), isoxazolyl (monosubstituted C ₁ -C ₄ alkyl), 1,3,4, thiadiazol, pyrazolyl (substituted with halogen and two C ₁ -C ₄ -alkyl groups) or 1,2,4-triazinyl (monosubstituted with phenyl); with the proviso that when Z is unsubstituted phenyl and X and K are both oxygen, then A is not hydrogen; which have fungicidal activity.

 Known fungicides - mankozeb, carboxin, pyroxyfur. However, their activity is not high enough.

 The aim of the invention is to develop a method for producing new compounds with fungicidal activity.

с соединением формулы

в присутствии основания, где одна из L' и L" представляет собой отщепляемую группу, тогда как другая представляет собой КН; W представляет собой ZX или группу, которую превращают в ZX путем:
(а) взаимодействия в присутствии основания соединения формулы
H

(i), когда Х представляет собой O, с соединением ZL; или
(ii), когда Х представляет собой SO₂O, с соединением ZSO₂O; или
(iii), когда Х представляет собой CH₂O, с соединением ZCH₂L; или
(iv), когда Х представляет собой CO.O, с соединением ZCO.Hal;
или (b) взаимодействия в присутствии основания соединения формулы
LCH

(i), когда Х представляет собой OCH₂, с соединением ZOH; или
(ii), когда Х представляет собой (C₆H₅)₂P + CH₂Q^- и L представляет собой галоид, с фосфином формулы Z(C₆H₅)₂P; или
(iii), когда Х представляет собой CO.OCH₂, с соединением ZCO.OH;
(с) когда Х представляет собой CH = CH, взаимодействие в присутствии основания соединения формулы
(R′O)

CH

где R¹ представляет собой С₁-С₆-алкил, с соединением формулы ZCHO; или
(d), когда Х представляет собой CH = CH, взаимодействие соединения формулы (I), где Х представляет собой (C₆H₅)₂P ⁺ CHR²Q^- последовательно с основанием и карбонильным соединением формулы ZCHO; или
(е), когда Х представляет собой CONH, взаимодействие соединения формулы

в присутствии основания с галоидом кислоты формулы ZCO.Q; или
(f), когда Х представляет собой СН(OH), взаимодействие альдегида формулы

с реактивом Гриньяра формулы ZMgHAI; или
(g), когда Х представляет собой O.CO, взаимодействие хлорида кислоты формулы

с соединением формулы ZOH в подходящем растворителе в присутствии основания; или
(h), когда Х представляет собой OCH₂, взаимодействие соединения формулы
HOCH

с соединением формулы ZL; или
(j), когда Х представляет собой N = N, взаимодействие формулы
H

с соединением формулы ZN⁺ = N Hal^-; или
(k), когда Х представляет собой NHSO₂, взаимодействие соединения формулы
ClSO

с соединением формулы ZNH₂; где: A, B, E, X, K и Z имеют значения, приведенные выше, L представляет собой отщепляющуюся группу, предпочтительно атом галогена, и Q представляет собой Hal; а Y представляет собой группу CH₃O.CH = C-(CO₂CH₃) или половину CH₂CO₂CH₃, которую можно превратить в подобную группу посредством взаимодействия с метилформиатом в присутствии основания и последующего метилирования в щелочных условиях.This goal is achieved by the proposed method for producing derivatives of propenic acid of the general formula I and their stereoisomers, the distinguishing feature of which is that the compounds of the formula

with a compound of the formula

in the presence of a base, where one of L 'and L "is a leaving group, while the other is KH; W is ZX or a group that is converted to ZX by:
(a) interactions in the presence of a base of a compound of the formula
H

(i) when X is O, with the compound ZL; or
(ii) when X is SO ₂ O, with a compound of ZSO ₂ O; or
(iii) when X is CH ₂ O, with the compound ZCH ₂ L; or
(iv) when X is CO.O, with the compound ZCO.Hal;
or (b) reacting in the presence of a base of a compound of the formula
Lch

(i) when X is OCH ₂ , with a ZOH compound; or
(ii) when X is (C ₆ H ₅ ) ₂ P + CH ₂ Q ^- and L is a halogen, with a phosphine of the formula Z (C ₆ H ₅ ) ₂ P; or
(iii) when X is CO.OCH ₂ , with the compound ZCO.OH;
(c) when X is CH = CH, reaction in the presence of a base of a compound of the formula
(R′O)

CH

where R ¹ represents a C ₁ -C ₆ -alkyl, with a compound of the formula ZCHO; or
(d) when X is CH = CH, the reaction of a compound of formula (I) wherein X is (C ₆ H ₅ ) ₂ P ⁺ CHR ² Q ^is sequentially with a base and a carbonyl compound of formula ZCHO; or
(e) when X is CONH, the interaction of the compounds of formula

in the presence of a base with an acid halide of the formula ZCO.Q; or
(f) when X represents CH (OH), the interaction of an aldehyde of the formula

with Grignard reagent of the formula ZMgHAI; or
(g) when X is O.CO, the interaction of an acid chloride of the formula

with a compound of formula ZOH in a suitable solvent in the presence of a base; or
(h) when X represents OCH ₂ , the interaction of the compounds of formula
HOCH

with a compound of formula ZL; or
(j) when X represents N = N, the interaction of the formula
H

with a compound of the formula ZN ⁺ = N Hal ^- ; or
(k) when X is NHSO ₂ , the interaction of the compounds of formula
Clso

with a compound of the formula ZNH ₂ ; where: A, B, E, X, K, and Z have the meanings given above, L represents a leaving group, preferably a halogen atom, and Q represents Hal; and Y represents a group CH ₃ O. CH = C- (CO ₂ CH ₃ ) or half CH ₂ CO ₂ CH ₃ , which can be converted into a similar group by reaction with methyl formate in the presence of a base and subsequent methylation under alkaline conditions.

где Y' представляет собой галоген, подвергают взаимодействию с фенолом общей формулы II

(II B) где A, X и Z имеют вышеуказанные значения в присутствии основания, или с солью фенола (IIb) в присутствии катализатора - соли меди или смесь соли меди и металлической меди.Desirable compounds of formula III

where Y 'is halogen, is reacted with phenol of the general formula II

(II B) where A, X and Z have the above meanings in the presence of a base, or with a phenol salt (IIb) in the presence of a catalyst — a copper salt or a mixture of a copper salt and metallic copper.

 The invention is illustrated by the compounds listed in the following tables I, II, III and IV. Everywhere in Tables I, II, III, and IV, the methyl-3-methoxypropenoate group has an (E) configuration.

 Tab. 3 includes 446 compounds of the above formula. For the first 445 compounds, all values of X, D, G, A, B, and E are shown in Table 1, i.e. compounds NN 1-445 are the same as in table 1, except for the value of K, which in table. 1 corresponds to oxygen, and in table 3 - sulfur. Compound N 446 corresponds to the above formula, where X is oxygen and A, B, D, E and G are all hydrogen. A description of the preparation of compound N 446 is given in Example 11.

 Tab. 4 includes 320 compounds of the above general formula, wherein all values of Z, X, A, B, and E are shown in Table 2, i.e. Compounds NN 1-320 are the same as in Table 2, except for the K value, to which oxygen corresponds in Table 2, and sulfur in Table 4.

Table 5 shows the data of proton NMR for some compounds of the table. 1,2,3 and 4. The chemical shifts in ppm refer ^-1 from tetramethylsilane, in all cases in deuterated chloroform is used as solvent. The column entitled “frequency” refers to the operating frequencies of the NMR spectrometers. In table 5, the following abbreviations are used:
Ush - widened strip
s - singlet
d - doublet
t - triplet
k - quartet
m - multiplet.

 The compounds of formula I are active fungicides and can be used to control the following pathogens: Pyricularia oryzae in rice, Puccinia recondita, puscinis herdei and other types of rust on barley and also rust on other cultivated plants, for example: coffee, pear, apples, peanuts, vegetables and ornamental plants. Erisiphe graminis (powdery mildew) on barley and wheat and other types of powdery mildew on various cultivated plants, such as Sphaerotheca macularis on hops, Sphaerotheca fuliginea on pumpkin (e.g. cucumbers), podosphaera feucolricha on apples and Uncinula Helminospor Phynchosporium, Septoria, pseudocercosprella herepotrichoides and Caeumannomyces graminis on cereals. Cercospora arachidieda and cerasporidium personata on peanuts and other Cercospora species on other cultivated plants, such as sugar beets, bananas, soy and rice.

 Botrytis cinerea (powdery mildew) on tomatoes, strawberries, vegetables and other cultivated plants.

 Alternaria on vegetables (e.g. cucumbers), rapeseed, apples, tomatoes and other cultivated plants.

 Vehtura inaegualis (scab) on apples.

 Plasmopara vitocola on the grape.

 Other types of downy mildew, such as Bremia lactucae on lettuce, peronospora on soy, tobacco, onions and other cultivated plants, pseudoperounospora on hops and pseudoperonuspora cubeusis on pumpkin. Phytophtora infestous - on potatoes and tomatoes, and other types of phytophtora - on vegetables, strawberries, avocados, peppers, ornamental plants, tobacco, cocoa and other cultivated plants. Thanatephorus cucumeris - rice and other Rhizoctonia species on various cultivated plants, such as wheat and barley, vegetables, cotton and grass for lawns.

 Some compounds exhibit a wide spectrum of activity against in vitro fungi. The compounds may also be active in fruit diseases following harvest (e.g., penicillium digitatum and italicum and Trichoderma viride on oranges, Gloesporium musarum on bananas, and Botrytis cinerea on grapes).

 In addition, individual compounds may be active in seed dressing against fungi of the species Fusarium, Septeria Tilletia (durum head in wheat seeds). Ustilago, Helminthosporium on cereals, Rhizochtonia solani on cotton and Pyriculare oryzae on rice.

 Compounds can undergo systematic promotion in plants. In addition, the compounds may be volatile enough to be active in the vapor phase against fungi on plants.

 Many compounds of formula I, including those compounds in which X = 0, are safer in relation to cultivated plants (for example, grapes), in comparison with the known compounds with similar structure.

 Thus, a method for controlling fungi is provided, which comprises applying to a plant, plant seeds or the place where the plant or seeds are located, an effective amount of a compound according to the above definition or composition containing it.

 The compounds may also be useful as industrial (as opposed to agricultural) fungicides, for example, for the prevention of fungal infections of wood, leather, leather products and especially paint films.

 The compounds can be used as fungicides, but usually using the carrier or diluent based on the compounds get the composition. Thus, fungicidal compositions are provided comprising a compound of general formula I and a fungicidally acceptable carrier or diluent.

 When used as fungicides, the compounds can be applied in a variety of ways. For example, they can be applied in the form of a composition and as such directly on the foliage of plants, seeds or the habitat of plants or growing plants, or they can be applied by spraying, in the form of dust, cream or paste, in the form of vapors or delayed-action granules. Any part of the plant can be treated, including foliage, trunk, branches or roots or the earth around the roots, or seeds before sowing, or the soil as a whole, as well as irrigation water or hydroponic plant growing systems. The compounds of the invention can be injected into plants or sprayed using electrodynamic spraying techniques or other low-cost methods.

 The term "plants" as used herein includes seedlings, shrubs and trees. The fungicidal method of the invention includes preventive, protective, preventive and extermination treatment.

 The compounds are recommended to be used as a composition for agricultural and horticultural purposes, and the type of composition used in each case depends on the specific purpose of use.

 The compositions may take the form of dustable powders or granules containing the active component (compound of the invention) and a solid carrier or diluent, for example, fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesium oxide, fuller’s earth, gypsum, diatom earth and chinese clay. Such granules may take the form of preformed granules suitable for use without further processing. Such granules can be prepared either by impregnating the tablet carrier with the active component, or by tabletting a mixture of the active component and the powder carrier. Seed treatment compositions may include an agent (eg, mineral oil) that facilitates pouring the composition onto the seeds. Alternatively, the active ingredient may be formulated for seed dressing using an organic solvent (e.g., N-methylpyrrolidone, propylene glycol or dimethylformamide). The compositions may also be in the form of wettable powders from water-dispersible granules containing a wetting or dispersing agent that facilitates dispersion in a liquid. Powders and granules may also contain fillers and suspending agents.

 Emulsifiable concentrates or emulsions can be prepared by dissolving the active component in an organic solvent, possibly containing a wetting or emulsifying agent, followed by adding the mixture to water, which may also contain a wetting or emulsifying agent. Suitable organic solvents include aromatic solvents, such as alkylbenzenes and alkylnaphthalenes, ketones, such as isophorone, cyclohexanone, methylcyclohexanone, chlorinated hydrocarbons, such as chlorobenzene and trichloroethane, alcohols, such as benzyl alcohol, furfuryl alcohol, butanol, ethers.

 Concentrated suspensions of almost insoluble solid products can be prepared by grinding in a ball mill in the presence of a dispersing agent with the inclusion of a suspending agent that prevents the precipitation of the solid product.

 Compositions intended for use as a spray may be in the form of aerosols, in which case the composition is contained in a container under pressure in the presence of a propellant, for example fluorotrichloromethane or difluorodichloromethane.

 The compounds of formula I can be mixed in a dry state with a pyrotechnic mixture to form a composition suitable for the formation in a confined space of smoke containing these compounds.

 Alternatively, the compounds may be used as microcapsules or may be formulated with biodegradable polymers to achieve a slow, controlled release of the active substance.

 The inclusion of appropriate additives, for example additives that facilitate the distribution of particles, increase the tackiness and resistance to rain on treated surfaces, i.e. different compositions may be better suited to various applications.

 The compounds of formula I can be used in a mixture with fertilizers (for example, nitrogen, potassium and phosphorus fertilizers). Recommended compositions containing only granules of fertilizer, including, for example, in the form of a coating compound of the invention. Such granules preferably contain up to 25 wt. % compound of the invention. Thus, the invention provides a composition consisting of a fertilizer and a compound of general formula I or a salt thereof, or a complex thereof with a metal.

 Wettable powders: emulsifiable concentrates and concentrated suspensions typically contain a surfactant, for example, a wetting agent, dispersing agent, emulsifier or suspending agent. These substances may be of the cationic, anionic or nonionic type.

 Suitable cationic surfactants are quaternary ammonium compounds, for example cetyltrimethylammonium bromide. Suitable cationic surfactants include: soaps, salts of aliphatic sulfuric acid monoesters (e.g. sodium lauryl sulfate) and salts of sulfonated aromatic compounds (e.g. sodium dodecylbenzenesulfonate, sodium, calcium or ammonium lignosulfonate, a mixture of sodium diisopropyl- and trisulfonate).

 Suitable nonionic surfactants are the condensation products of ethylene oxide with fatty alcohols, such as oleyl or cetyl alcohol, or with alkyl phenols, such as octyl or nonylphenol and octylcresol. Other non-ionic surfactants include partial esters formed by long chain fatty acids and hexite anhydrides, condensation products of these partial partial esters with ethylene oxide and lecithins. Suitable suspending agents include hydrophilic colloids (e.g. polyvinylpyrrolidone and sodium carboxymethyl cellulose), as well as swellable clays such as bentonite and attapulgite.

 Compositions intended for use in the form of aqueous dispersions or emulsions are generally supplied in the form of a concentrate with a high content of active component, such concentrates are diluted with water before use. These concentrates should preferably withstand long periods of storage and after such storage should retain the ability to form aqueous preparations that remain homogeneous for a sufficient time necessary for spraying using spraying equipment. Concentrates, as a rule, contain up to 95%, preferably 10-85%, for example, 25-60 wt. %, active component. After dilution with the formation of aqueous preparations, the resulting preparations may contain a different amount of the active component, depending on the intended use of the preparation; aqueous preparations containing 0.00055 or 0.01-10% by weight of the active component may be used.

 The compositions may contain other biologically active compounds, for example, compounds with similar or complementary fungicidal activity or with plant growth regulating, herbicidal or insecticidal activity.

 The fungicidal compound that may be present in the composition of the invention may be a compound capable of withstanding diseases of the ears of cereals (e.g. wheat) caused by pathogens such as Septoria, Gibberella and Helminthosporium, seed poisoning and soil poisoning, false and powdery mildew grapes, powdery mildew and scab on apples, etc. By incorporating another fungicide, the composition gains a wider spectrum of activity compared to using a compound of formula I alone. In addition, another herbicide may have a synergistic effect on the fungicidal activity of the compound of general formula I. Examples of fungicidal compounds that may be included in the composition of the invention include : carbendazim, benomyl, thiophanate-methyl, thiabendazole, fuberidazole, etridazole, dichlorofuanide, cymoxanil, oxadixyl, ofuras, metalaxyl, furalaxyl, benalaxyl, fosetyl-aluminum, fenarimol, iprodion, prothiocarb, procymidone, vinchlozolin, penconazole, mychlobutanil, propamocarb, diniconazole, pyrazofos, etirimol, ditalimphos, tridemorph, triforin, noarimol, propanazole, triazbutinium triazutinodiabutazinodiabutin triacetamide, triazutinodiabutin, triazutinodiabutin, triazutinodia , prochlorase, flutriafol, hexaconazole, (2RS, 5RS) -5- (2,4-dichlorophenyl) tetrahydro-5- (1H-1,2,4-triazol-1-ylmethyl) - 2-furyl-2,2, 2-trifluoroethyl ether, cyproconazole, terbukonazole, 1 - [(2P, 4P; 2RS; 4RS) -4-bromo-2- (2,4-dichlorophenyl) tetrahydrofurfuryl] -1H-1,2,4-triazole, pyrrolnitrin, 5-ethyl-5,8-dihydro-8-oxo (1,3) - dioxolo (4,5-o) quinoline-7-carboxylic acid, 3- (2,4-dichlorophenyl) -2- (1H, 1,2,4-triazol-1-yl) quinazolin-4- (3H) - he, (RS) -1-aminopropylphosphonic acid, fluzilazole, triadimefon, triademenol, dichlorobutrazole, fenpropimorph, pyrifenox, fenpropidin, chlorozolinate, imazalil, fenfuram, carboxin, hydroxycarboxin, metfuroxam, dodemorphine bazfenfazidazazbazdin BAS P, cycloheximide, phthalide, probenazole, isoprothiolane, tricyclazole, 4-chloro-P- (cyano (ethox i) methyl) benzamide, pyroquilon, hlorobenztiazon, neoazozin, polyoxin D, validamycin A, mepronil, flutolanil, pencycuron, dihlomezin, phenazine oxide, nikeldimetilditiokarbamid, tehloftalam, bitertanol, bupirimate, etakonazol, hydroxyisoxazole, streptomycin, tsiprofuram, biloksazol, chinomethionat, dimethyrimol, 1- (2-cyano-2-methoxyiminoacetyl) -3-ethylurea, fenapanil, tolchlofosmethyl, pyroxyfur, poliram, maneb, mancozeb, captafol, chlorothalonil, anilazine, tyram, captan, folpet, zineb, propine, propine dichlon, chloroneb, banacpril, nitrothalisopr saws, dodine, dithianon, fentigidroksid, fentin acetate, teknazem, quintozene, dihloran, copper-containing compounds such as copper oxychloride, copper sulphate and Bordeaux mixture, and organomercury compounds.

 The compounds of general formula I can be mixed with soil, peat or another root medium in order to protect plants from infecting seeds, infecting the soil or foliage of fungal infections.

 Suitable insecticides that may be included in the composition of the invention include: pyrimicarb, dimethoate, demethonsym.-methyl, formotion, carbaryl, isoprocarb, XMS, BRMS, carbofuran, carbosulfan, diazinon, fenthion, fentrotion, fentoate, chlorpyrifos, monocrotofas, buprofesin, etroproxyphene, cycloprotrin.

 Compounds that control plant growth include compounds that control the formation of weeds or seedlings, or selectively regulate the growth of less desirable vegetation (e.g. grass).

Examples of plant growth regulators suitable for use with the compounds of Formula I include: giberilins (e.g., GA ₃ , GA _4, or HA ₇ ), auxins (e.g., indoleacetic acid, indolebutyric acid, naphthoxyacetic acid or naphthylacetic acid), cytokinins (e.g. kinetin , diphenylurea, benzimidazole, benzyladeninine or benzylaminopurin), phenoxyacetic acids (e.g., 2,4-D or MPFC), substituted benzoic acids (e.g., triiodobenzoic acid), morphactins (e.g., chlorofluorocol), maleic hydrazide acids, glyphosate, glyphosine, long chain fatty alcohols and acids, dicegulac, paclobutrazole, fluoridamide, mefluidine, substituted quaternary ammonium or phosphonium derivatives (e.g. chloromequate chlorophonium or merquatchloride), ethephone, carbetamide, dlamide azide, 3-azide-aminoside, 3-azide , abscisic acid, isopyrimol, 1- (4-chlorophenyl) -4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylic acid, hydroxybenzonitriles (e.g. bromoxynil), diphenzenquat, benzoylpropetyl-3, 6-dichloropicolinic acid, fenpentesol, inabenfide, triapentenol and tech named.

The following examples are provided to illustrate the invention. In all examples, the term "ether" refers to diethyl ether, magnesium sulfate is used to dry solutions, and the solutions are concentrated under reduced pressure. Reactions involving moisture-sensitive intermediates are carried out in a nitrogen atmosphere and the solvents are dried before use where necessary. Unless otherwise indicated, chromatography is carried out on a column filled with silica gel. Where indicated, infrared and NMR spectroscopy data are selective without specifying all absorption bands in all cases. ¹ H-NMR spectra were recorded using CDCl ₃ as solvent, unless otherwise indicated. The following abbreviations are used everywhere:
DME - dimethoxyethane, THF - tetrahydrofuran, DMF - N, N-dimethylformamide, NMR - nuclear magnetic resonance, IR - infrared, s - singlet, d - doublet, t - triplet, m - multiplet.

mp - melting point
GC = gas chromatography
TLC = thin layer chromatography
HPLC = high performance liquid chromatography
Br = wide
ppm = parts per million.

 The invention is illustrated by the following examples.

 PRI me R 1. This example illustrates the preparation of (E) -methyl-2- [2- (3-benzyloxyphenoxy) phenyl] -3-methoxypropenoate (compound N 23, table 1).

 A mixture of 100 g (0.54 mol) of 2-bromobenzaldehyde, 67.03 g (1.08 mol) of ethylene glycol, 0.5 g of toluenesulfonic acid and toluene was heated to boiling point and kept at this temperature under reflux for 6 hours. During this time, 23 ml of an azeotropic mixture of water and ethylene glycol were distilled off. After that, the mixture was cooled and 1 l of ether was added to it. The ether solution was washed with saturated sodium bicarbonate solution (200 ml), then three times with water, 150 ml each and, finally, 150 ml of saturated sodium chloride solution. After drying and filtration and then evaporation of the ether solution, 121.96 g (98.6% yield) of 2- (2-bromophenyl) -1,3-dioxolane were obtained as an oily liquid.

¹ H NMR: (60 MHz), δ: 3.4 (4H, m), 6.0 (1H, s), 6.9-7.6 (4H, m), ppm.

 The resulting product was used in the next step without further purification.

35.2 g (0.63 mol) of granular potassium hydroxide was dissolved in 50 ml of water, and 78 g (0.63 mol) of 3-methoxyphenol with 250 ml of toluene was added to the resulting solution. The reaction mixture was heated to boiling point and kept at this temperature until the distillation of water stopped (65 ml of water was collected in total). Thereafter, the mixture was cooled to ⁸⁰ ° C and thereto was added 120 g (0.524 mol) of 2- (2-bromophenyl-1,3-dioxane, 200 ml of TMF and 0.2 g of cuprous chloride. The mixture was slowly heated to ^about 150-155 C and toluene was distilled off. Thereafter, it was kept for 6 hours at 150-155 ^{° C} and then cooled ^to 25 ° C and added to 500 ml of water. The mixture was filtered, the residue washed with 200 ml of ether, and the filter was extracted with ether (three times, in 150 ml portions.) The combined ether phases were washed twice with 2 N sodium hydroxide solution (150 ml each), four times with water (150 ml each) and then 150 ml brine. After drying and filtration, the ethereal solution was evaporated, to give 124.1 g (87.1% yield) of 2- [2- (3-methoxyphenoxy) phenyl] -1,3-dioxolane as an oily liquid.

 1 H NMR: (60 MHz), δ: 3.65 (3H, s), 3.95 (4H, d), 6.12 (1H, s), 6.6-7.6 (8H, m) m .d.

 The resulting product was used in the next step without further purification.

 32.7 g (0.12 mol) of 2- [2- (3-methoxyphenoxy) phenyl] -1,3-dioxolane was stirred in a mixture of 95 ml of water and 5 ml of concentrated hydrochloric acid at ambient temperature for 19 hours. Then the mixture was extracted twice with ether, in 60 ml portions, the combined ether phases were washed with 30 ml of a saturated aqueous solution of sodium bicarbonate, three times with water (in 30 ml portions) and, finally, 30 ml of brine. The resulting solution was dried, filtered and concentrated, resulting in 26.17 g (95.4% yield) of fairly pure 2- (3-methoxyphenoxy) benzaldehyde (A) as an oily liquid. The resulting product was used in the next step without further purification. A sample for analysis, however, was prepared by chromatography using a mixture of ether and hexane as eluent. The result was an amber-colored oily liquid.

¹ H NMR: (90 MHz), δ: 3.79 (3H, s), 6.58-7.97 (8H, m), 10.49 (1H, d) ppm.

IR _max (film): 1691, 1599 cm ^-1 .

 A mixture of 25.0 g (0.109 mol) of 2- (3-methoxyphenoxy) benzaldehyde, 13.64 g (0.11 mol) of methyl methylthiomethyl sulfoxide, 8.0 ml of a 30% solution of benzyltrimethylammonium hydroxide in methanol and 150 ml of THF stirred for 45 minutes at reflux temperature. The resulting solution was evaporated to dryness and the residue was chromatographed using a mixture of ether and hexane as eluent. The result was 27.67 g (75.3% yield) of sulfoxide (B) as an amber-colored resin.

¹ H NMR: (60 MHz), δ: 2.2 (3H, s), 2.55 (3H, s), 3.65 (3H, s), 6.35-8.15 (9H, m) ppm

20 ml of acetyl chloride was added dropwise over 15 minutes to 200 ml of absolute methanol, cooling the mixture in a water bath, and maintaining the temperature at 20-25 ^C. To the mixture was added in one portion a solution of 27.67 g (0.83 mol sulfoxide (B ) and 40 ml of methanol and the resulting solution was stirred at ambient temperature for 18 h. The methanol solution was evaporated to dryness under reduced pressure and the residue (22.78 g of a brown gum) was dissolved in 200 ml of ether.The ether solution was washed with saturated aqueous sodium bicarbonate filtered out the sky most of the insoluble matter was evaporated to dryness. The residue was chromatographed using a mixture of ether and hexane as eluent to give 15.62 g (yield 69.3%) of 2- (3-methoxyphenoxy) phenylacetate (C) as a viscous oily liquid.

12.89 g (0.051 mol) of boron tribromide dissolved in 50 ml of dichloromethane and the resulting solution was cooled to ^0-5 ° C and then added thereto dropwise over an hour, with stirring, a solution of 7.0 g (0.026 mole) of 2 - (3-methoxyphenoxy) phenylacetate in 80 ml of dichloromethane. After stirring for 20 minutes at ^0-5 ° C was added dropwise, with stirring, to 100 ml of absolute methanol, maintaining the temperature at 0-5 ° ^C. The resulting solution was poured into 250 ml of water with dissolved therein 12 g of sodium bicarbonate, and the mixture was extracted with 500 ml of ether. The organic phase was washed three times with water (in 200 ml portions), and then 150 ml of a saturated solution of sodium chloride. After drying, filtration and evaporation, 6.12 g (92.3% yield) of methyl 2- (3-hydroxyphenoxy) phenylacetate (D) were obtained in the form of a brown gum. The resulting product without further purification could be used in the next step. Using chromatography using a mixture of ether and hexane as an eluent, however, a high-purity product was obtained in the form of a viscous golden oily liquid, which quickly darkened upon exposure to air.

 In addition to the above, methyl 2- (3-hydroxyphenoxy) phenyl acetate (D) was prepared by the following method.

A mixture of 30 g (0.18 mol) of 2-chlorophenylacetic acid, 48.6 g (0.34 mol) of potassium carbonate and 43.5 (0.35 mole) of 3-methoxyphenol was heated with stirring at 140 ^{° C} in the presence of a catalytic amount of copper (I) chloride. After 3 hours according to gas and thin layer chromatography, the starting acid completely reacted. The reaction mixture was allowed to cool (adding 5 ml of dry DMF to it) to 70 ^° C so that it did not become too viscous, after which it was poured into water and acidified with hydrochloric acid. The resulting mixture was subjected to ether extraction, the combined ether phases were washed with water until neutral, dried and evaporated, resulting in a mixture of 3-methoxyphenol (49%) and 2- (3-methoxyphenoxy) phenylacetic acid (41%) as a brown mobile oily liquid that was used without further purification in the next stage.

The brown oily liquid was boiled for 2.5 hours under reflux in 70 ml of methanol supplemented with 2 ml of concentrated sulfuric acid. The reaction mixture was then cooled to room temperature and poured into water. The resulting mixture was extracted twice with ether, the ether phases were combined, washed first with a dilute aqueous solution of sodium hydroxide, and then with water until neutral and dried. After evaporation, 34.9 g of crude methyl 2- (3-methoxyphenoxy) phenylacetate was obtained as an orange-brown oily liquid (the target product content determined by gas chromatography was 86%). The resulting crude product was combined with another portion (8.2 g) of the same product obtained by the same method. After repeated molecular distillation (50-150 ° ^C under pressure of 4 x 10 ^-2 mbar) to give 37.1 g of purified (purity 95%, yield about 60% based on the 2-chlorophenylacetic acid) methyl-2- (3- methoxyphenoxy) phenyl acetate. Repeating the above operations, the desired amount of product was obtained.

97 g (0.36 mol) of methyl 2- (3-methoxyphenoxy) phenylacetate was heated for 8 hours at ¹¹⁰ ° C with 194 ml concentrated hydrobromic acid in 150 ml of acetic acid. The mixture was allowed to stand overnight at room temperature, followed by the addition thereto of 100 ml of concentrated hydrobromic acid and was again heated to 110 ^C. After holding the reaction mixture at this temperature for 7 hours all the starting material reacted. The reaction mixture was cooled to room temperature, poured into brine and extracted twice with dichloromethane. After distilling off the dichloromethane the oily liquid was obtained which was heated at ⁷⁰ ° C with 400 ml of methanol and 2 ml of concentrated sulfuric acid for 2 hours. The reaction mixture was then cooled to room temperature, poured into brine and extracted twice with dichloromethane. The combined extracts were washed with water until neutral, dried, filtered and evaporated to give 92.8 g of a brown oily liquid. After molecular distillation (at 150 ° ^C and a pressure of 1 x 10 ^-3 mbar) of the product (72.8 g) was obtained 41.4 g (yield 57% based on methyl 2- (3-methoxyphenoxy) phenylacetate) methyl -2- (3-hydroxyphenoxy) phenylacetate (D) as a golden syrup.

¹ H NMR: (60 MHz), δ: 3.57 (3H, s), 3.63 (2H, s), 5.82 (1H, s), 6.4-7.35 (8H, m) ppm

IR _max (film): 3408, 1713 cm ^-1 .

To a suspension of 0.558 g (0.023 mol) of sodium hydride in 20 ml of DMF was added dropwise a solution of 2.0 g (0.0077 mol) of methyl 2- (3-hydroxyphenoxy) phenylacetate (D) in 10 ml of DMF and 10 g ( 0.167 mol) methyl formate. After stirring for 45 minutes, 100 ml of water was added to the mixture and extraction was performed with 50 ml of ether. The aqueous layer was acidified with hydrochloric acid to pH 3-4 and the mixture was subjected to extraction twice with ether (in 40 ml portions). The combined ether extracts were washed three times with water (30 ml each), and then 30 ml of a saturated sodium chloride solution and dried. The ether was distilled off, and the residue was dissolved in 20 ml of DMF, and 0.64 g (0.0046 mol) of anhydrous potassium carbonate and 0.55 g (0.0044 mol) of dimethyl sulfate were added to the solution. The mixture was stirred at ambient temperature for one hour, after which 100 ml of water was added to it and extracted twice with ether (in 40 ml portions). The combined ether extracts were washed three times with water (20 ml each), and then 20 ml of a saturated sodium chloride solution, dried, filtered, evaporated to dryness and then chromatographed using an ether-hexane mixture as eluent. The result was (E) -methyl-2- / 2- (3-hydroxyphenoxy) phenyl / -3-methoxypropenoate (E) as an amber-colored resin. After trituration with a mixture of hexane and dichloromethane, 0.7 g (30% yield calculated as methyl 2- (3-hydroxyphenoxy) phenyl acetate (D)) of a white solid was obtained. Melting point 115-116 ^about C.

 In addition, (E) -methyl-2- [2- (3-hydroxyphenoxy) phenyl] -3-methoxypropenoate (E) was prepared as follows.

 A solution of 12 g (0.0465 mol) of methyl 2- (3-hydroxyphenoxy) phenylacetate (D) and 55.8 g (0.93 mol) of methyl formate in 35 ml of DMF was added dropwise over 45 minutes to a stirred suspension of sodium hydride (6.696 g of a 50% dispersion in oil, 0.1395 mol, previously washed with 40-60 petroleum ether) in 65 ml of DMF. The reaction mixture was stirred at room temperature for 2.5 hours, poured into 200 ml of water, acidified to pH 3 with concentrated hydrochloric acid, and then subjected to ether extraction twice (in 200 ml portions).

 The combined organic extracts were washed twice with brine (200 ml each), dried, filtered and evaporated, yielding 12.5 (0.0433 mol) of a yellow oily liquid.

12.5 g (0.0433 mol) of the resulting oily liquid was dissolved in 100 ml of DMF and 5.98 g (0.0433 mol) of sodium carbonate was added to the solution. After stirring for 10 minutes, 5.19 g (0.042 mol) of dimethyl sulfate in 10 ml of DMF was added to the mixture in one go. The resulting mixture was stirred overnight at room temperature, poured into 200 ml of water and subjected to extraction with ether (twice in 200 ml portions). The combined ether extracts were washed three times with brine (200 ml each), dried, filtered and evaporated to give an adhesive gum. Recrystallization from a mixture of dichloromethane and hexane gave 9.54 g (73%) of (E) -methyl-2- [2- (3-hydroxyphenoxy) phenyl] -2-methoxypropenoate (E). Mp 117-118 ^about S.

¹ H NMR (90 MHz), δ: 3.58 (3H, s), 3.75 (3H, s), 5.38 (1H, s), 6.39-7.33 (8H, m), 7.4 (1H, s) ppm.

IR _max (nujol): 3295, 1672, 1630 cm ^-1 .

 A mixture of 1.0 g (0.0033 mol) of (E) -methyl-2- [2- (3-hydroxyphenoxy) phenyl] -3-methoxypropenoate, 0.57 g (0.0033 mol) of benzyl bromide, 0.8 g (0.0053 mol) of potassium carbonate and 15 ml of dry DMF were stirred for 3 hours at ambient temperature. After that, 50 ml of water was added to the mixture and it was twice subjected to extraction with ether (in 30 ml portions). The combined organic extracts were washed twice with water (20 ml each) and, after drying and filtration, the ether solution was evaporated to dryness and chromatographed using a mixture of ether and hexane as eluent. The result was 1.11 g (yield 85%) of the target compound (F) as a colorless resin.

¹ H NMR: (90 MHz), δ: 3.55 (3H, s), 3.7 (3H, s), 4.97 (2H, s), 6.5-7.32 (13H, m) 7.44 (1H, s) ppm.

IR _max (film): 1710, 1638 cm ^-1 .

 Example 2. This example illustrates the preparation of (E) -methyl-3-methoxy-2- [2- (3-phenylsulfonyloxyphenoxy) phenyl] propenoate (compound N 51 of Table 1).

A mixture of 0.5 g (0.00166 mol) of (E) -methyl-2- [2- (3-hydroxyphenoxy) phenyl] -3-methoxypropenoate obtained using the method described in example 1, 0.36 g (0.002 mol) of benzenesulfonyl chloride and 10 ml of pyridine was stirred for 3 hours at 60-70 ^C. The mixture was cooled ^to 25 ° C, were added thereto 60 ml of water and twice extracted with ether (30 ml portions). The combined ether extracts were washed with 20 ml of water, 20 ml of diluted hydrochloric acid, three times with water (in 200 ml portions) and 20 ml of a saturated solution of sodium chloride. The ethereal solution was dried, filtered, concentrated and chromatographed using a mixture of chloroform and hexane as eluent. The result was 0.21 g (yield 28.7%) of the target compound as a colorless resin.

¹ H NMR (90 MHz), δ: 3.56 (3H, s), 3.75 (3H, s), 6.52-7.96 (13H, m), 7.40 (1H, s) m .d.

 Example 3. This example illustrates the preparation of (E) -methyl-3-methoxy-2- {2- [3- (4-nitrophenoxy) phenoxy] phenyl} - propenoate (compound N 133 from table 1) .

 A mixture of 1.2 g (0.004 mol) of E-methyl-2- [2- (3-hydroxyphenoxy) phenyl] -3-methoxypropenoate obtained as described in Example 1, 0.68 g (0.008 mol) of potassium carbonate and 15 ml DMF was stirred for 16 hours at ambient temperature, after which the mixture was poured into water (80 ml) and twice subjected to extraction with ether (30 ml). The combined organic extracts were washed three times with water (25 ml), and then 25 ml of a saturated solution of sodium chloride. After that, they were dried, filtered, concentrated and chromatographed using a mixture of chloroform and hexane as eluent. The result was 0.93 g (yield 55.2%) of the target compound.

¹ H NMR: (90 MHz), δ: 3.55 (3H, s), 3.72 (3H, s), 6.67-8.41 (12H, m), 7.44 (1H, s) ppm

 Example 4. This example illustrates the preparation of (E) -methyl-2- {2- [3- (4-fluorophenoxy) phenoxy] phenyl} -3-methoxy-propenoate (compound N 124 from table 1) .

 A mixture of 1.0 (0.0033 mol) of (E) methyl-2- / 2- (3-hydroxyphenoxy) phenyl / -3-methoxypropenoate obtained by the method described in example 1, 2.63 g (0.0069 mol) bis-4- (fluorophenyl) iodonium bromide, 0.5 ml of triethylamine, 0.5 g of copper powder and 15 ml of absolute methanol were refluxed for 6 hours. After that, another 1 g of (4-fluorophenyl) iodonium bromide was added to the mixture and it was refluxed for another 3 hours. After cooling and filtration, 80 ml of water was added to the filtrate and the mixture was subjected to extraction with ether twice (30 ml each). The combined ether extracts were washed three times with water (15 ml each), followed by 15 ml of a saturated sodium chloride solution.

 After drying and filtration, the ether solution was concentrated, resulting in 0.16 g (12.3% yield) of the target compound in the form of an amber-colored resin.

¹ H NMR: (60 MHz), δ: 3.42 (3H, s), 3.51 (3H, s), 6.35-7.30 (12H, m), 7.35 (1H, s) ppm

IR _max (film): 1710, 1641 cm ^-1 .

 Example 5. This example illustrates the preparation of (E) -methyl-2- [2- (3-benzoyloxyphenoxy) phenyl] -3-methoxypropenoate (compound N 49 from table 1).

A mixture of 0.5 g (0.00166 mol) of (E) -methyl-2- [2- (3-hydroxyphenoxy) phenyl] -3-methoxypropenoate obtained as described in Example 1, 0.26 g (0.00185 mol) of benzoyl chloride, 0.23 g (0.00166 mol) of potassium carbonate and 10 ml of DMF were stirred for 1.5 hours at ambient temperature. After that, another 0.26 g (0.00166 mol) of benzoyl chloride and 0.23 g (0.00166 mol) of potassium carbonate were added to the mixture and stirring was continued under the same conditions for another 16 hours. Then 80 ml of water was added to it. and extracted twice with ether (40 ml each). The combined ether extracts were washed three times with water (in 20 ml portions of water) and 20 ml of a saturated solution of sodium chloride, then they were dried, filtered, concentrated and chromatographed using a mixture of ether and hexane as eluent. The result is a more solid substance. After recrystallization from another aqueous methanol solution, 0.23 g (47.7% yield) of pure target compound was obtained as a white solid. Mp 94-95 ^about S.

¹ H NMR: (90 MHz), δ: 3.62 (3H, s), 3.74 (3H, s), 6.76-8.38 (13H, m), 7.46 (1H, s) ppm

IR _max (nujol): 1741, 1627 cm ^-1 .

 Example 6. This example illustrates the preparation of (E, E) -methyl-2- {2- [3- (4-chlorophenylazo) -4-hydroxyphenoxy] phenyl} -4-methoxypropenoate (compound N 282 from table .1).

2.5 ml of 1M hydrochloric acid was added to 6.64 ml of a 0.25M aqueous solution of 3-hloranilingidrohlorida and the mixture was cooled to a temperature below 10 ° ^C. Then, thereto was added dropwise 3.32 ml of 0.5M aqueous sodium nitrite solution and stirred for 10 minutes at a temperature below 10 ^C. The resulting solution of 3-hlordibenzoldiazoniya chloride was added dropwise with stirring to a mixture of 0.5 g (0.00166 mol) of (E) -methyl 2- [2- (4-hydroxyphenoxy) phenyl] -3-methoxypropenoate obtained in the same manner as described in Example 1 for the corresponding 3-hydroxy derivative in 16 ml of 0.1 M aqueous th solution of sodium hydroxide and 30 ml of acetone. Simultaneously continued to add sodium hydroxide solution to maintain the pH in the range 8-10 while maintaining the temperature below 10 ^C. After stirring for 20 minutes the mixture was twice extracted with ether (40 ml portions). The combined ether extracts were washed three times with water (15 ml each), and then 15 ml of a saturated sodium chloride solution, after which they were dried, filtered, concentrated and chromatographed using an ether and hexane mixture as eluent. As a result, an orange solid was obtained. After recrystallization from a mixture of hexane and dichloromethane, 99.3 mg (13.6% yield) of pure target compound are obtained; so pl. 143-144 ^about S.

 Example 7. This example illustrates the preparation of (E) -methyl-2- {2- [3- (3-methoxyphenoxy) phenoxy] phenyl} -3-methoxy-propenoate (compound N 129 from table 1) .

To a stirred solution of 0.61 g of sodium in 10 ml of methanol was added in one go 4.34 g of resorcinol. After stirring the resulting mixture for half an hour at room temperature, the excess methanol was distilled off under reduced pressure. To the residue, in the form of an oily orange liquid, 6.6 ml of pyridine, 14.74 g of 3-bromoanisole and 192 mg of copper chloride were added. The mixture was stirred for 66 hours at 125 ° ^C, then cooled and poured into dilute hydrochloric acid and then extracted with ether. The ether extracts were back-extracted with a dilute aqueous sodium hydroxide solution. The aqueous extracts were acidified with dilute hydrochloric acid and subjected to extraction with ether. The resulting ether extracts were washed successively with water and brine, and then dried and concentrated, resulting in 3.72 g of a red oily liquid. After distillation of this liquid (oven temperature 170 ^C, pressure 0.05 mmHg) gave 1.71 g of 3- (3-methoxyphenoxy) phenol as an oil viscous pale yellow.

¹ H NMR, δ: 3.78 (3H, s), 4.93 (1H, s) ppm.

To a stirred solution of 0.18 g of sodium in 4 ml of methanol was added 1.70 g of 3- (3-methoxyphenoxy) phenyl in one portion. After stirring the resulting mixture for half an hour at room temperature, the excess methanol was distilled off under reduced pressure. To the residue as an oil orange in color was added 0.85 g of o-bromophenylacetic acid and 40 mg of copper chloride and the reaction mixture was stirred for one hour at 130 ° ^C. Thereafter, thereto was further added 0.4 g of o-bromophenylacetic acid and 0 13 g of sodium ethoxide was added and stirring continued at 130 ^{° C} for a further 3 hours.

The mixture was then cooled, acidified with dilute hydrochloric acid and subjected to extraction with ether. The ether extracts were washed successively with water and brine, then dried and concentrated, to give 3.12 g of a red oily liquid containing 2- [3- (3-methoxyphenoxy) phenoxy] phenylacetic acid. To 3.12 g of this acid was added 40 g of methanol and 3 drops of concentrated sulfuric acid. The reaction mixture was stirred for one hour at ⁹⁰ ° C, then slowly cooled, poured into water and extracted with ether. The ether extracts were washed sequentially with a dilute aqueous solution of sodium hydroxide, water and brine, dried and concentrated, resulting in 1.33 g of a yellow oily liquid. After distilling it (oven temperature 160 ^C, pressure 0.07 mmHg) gave 1.03 g (yield 36%) based on the 3- (3-methoxyphenoxy) phenol 2- [3- (3-methoxyphenoxy ) -phenoxy] phenylacetate.

¹ H NMR, δ: 3.62 (3H, s), 3.68 (2H, s), 3.78 (3H, s) ppm.

A mixture of 1.00 g of methyl [3- (3-methoxyphenoxyl) phenoxy] phenylacetate and 3.34 ml of methyl formate in 1 ml of DMF was added dropwise over 10 minutes and to a stirred suspension of 0.13 g of sodium hydride in 10 ml of DMF cooled with ice to a temperature below 10 ^{° C} (with effervescence occurred). Upon completion of the addition, the reaction mixture was stirred for 2 hours at room temperature, then poured into water, acidified with dilute hydrochloric acid and subjected to extraction with ether. The extracts were washed with water, dried and concentrated, resulting in 1.09 g of a yellow oily liquid. 0.76 g of potassium carbonate and 0.33 g of dimethyl sulfate were added to a stirred solution of this liquid in 20 ml of DMF, and the resulting mixture was stirred at room temperature for 2.5 hours, then it was poured into water and subjected to extraction with ether. The extracts were washed with water, dried, concentrated, and chromatographed using a mixture of ether and gasoline (1: 1) as eluent. The result was 0.61 g (55% yield based on methyl 2- [3- (3-methoxyphenoxy) phenoxy] phenylacetate of the target compound as a colorless viscous oily liquid.

¹ H NMR, δ: 3.60 (3H, s), 3.75 (3H, s), 3.78 (3H, s), 6.55-6.72 (5H, m), 6.97 ( 1H, d), 7.10-7.30 (6H, m), 7.48 (1H, s) ppm.

IR _max (nujol): 1713, 1638 cm ^-1 .

 EXAMPLE 8. This example illustrates the preparation of (E) -methyl-3-methoxy-2- {2- [3- (phenoxymethyl) phenoxy] phenyl} -propenoate (compound N 21 from table 1) .

 0.50 g of (E) -methyl-3-methoxy-2- [2- (3-methylphenoxy) phenyl] propenoate obtained from 3-methylphenol and 2-bromobenzaldehyde as described in Example 1, and 0.30 g of N β-bromosuccinimide was refluxed in 25 ml of carbon tetrachloride with traces of azobisisobutyronitrile (AIBN) for 4.5 hours, adding traces of AIBN every 1.5 hours. The progress of the reaction was monitored by gas chromatography. After this, the reaction mixture was left to stand overnight at room temperature, more trace amounts of AIBN were added and continued to boil it until gas chromatography showed an almost complete absence of starting material (1 h). After this, the reaction mixture was filtered through celite, washed with water and evaporated, yielding 0.69 g of a pale yellow gum. According to gas chromatography and NMR, this resin consisted of (E) methyl 2- [2- (3-bromomethylphenoxy) phenyl] 3-methoxypropenoate (80%), the corresponding dibromomethyl derivative (11%), and unreacted starting material (propenoate , 8%).

¹ H NMR, data for the main component, δ, 3.61 (3H, s), 3.77 (3H, s), 4.42 (2H, s), 6.90-7.40 (3H, m) 7.48 (1H, s), ppm.

 The resulting material was used further without further purification.

Part of this crude material (0.42 g, 80% concentration) was mixed with 0.105 g of phenol, and 0.077 g of potassium carbonate in 20 ml of DMF and heated for one hour at 60 ^C. The mixture was then allowed to stand overnight at room temperature, then heated at ⁶⁰ ° C for another hour, cooled, poured into water and extracted with ethyl acetate. The organic fraction was washed with water, dried and evaporated, yielding 0.42 g of a pale yellow oily liquid. After purification using high performance liquid chromatography using a 3: 1 mixture of gasoline and ethyl acetate as eluent, 0.13 g of the target compound are obtained in the form of a colorless resin containing 20% (E) -methyl-2- as an impurity [2- (3-dibromomethylphenoxy) phenyl] -3-methoxypropenoate.

¹ H NMR, data for the target compound: δ: 3.58 (3H, s), 3.70 (3H, s), 4.98 (2H, s), 6.88-7.36 (s), ( 13H, m), 7.46 (1H, s). ppm

 Example 9. This example illustrates the preparation of (E) methyl-2- [2- (2-acetyl-5-phenoxyphenoxy) phenyl] -3-methoxypropenoate and (E) -methyl-2- / 2- ( 4-acetyl-3-phenoxyphenoxy) phenyl / -3-methoxypropenoate (compound N 366 and 365, respectively, from table 1).

Methyl 2- (3-phenoxyphenoxy) phenyl acetate was prepared from 3-phenoxyphenol and 2-bromobenzaldehyde in the same manner as described in Example 1 to obtain methyl 2- (3-methoxyphenoxy) phenyl acetate. The resulting product was converted to (E) -methyl-3-methoxy-2- [2- (3-phenoxyphenoxy-si) phenyl] propenoate ( ¹ H NMR (250 MHz) 3.61 (3H, s), 3.78 (3H, s), 6.68-7.35 (13H, m), 7.48 (1H, s) m, d.) Using sodium hydride and methyl formate, and then potassium carbonate and dimethyl sulfate, according to the method described in Example 1, to obtain (E) -methyl-2- [2- (3-hydroxyphenoxy) phenyl] -3-methoxypropenoate, with the difference that in this case two equivalents of sodium hydride were used.

To a stirred solution of 0.722 g (1.92 mmol) of (E) -methyl 3-methoxy-2- / 2- (3-phenoxyphenoxy) phenyl / propenoate in 20 ml of dry dichloromethane was added at 0-5 ^C. 0.512 g (3 , 84 mmol) of powdered aluminum chloride, and then dropwise, over 10 minutes, a solution of 0.151 g (1.92 mmol) of acetyl chloride in 3 ml of dry dichloromethane. The resulting mixture was stirred overnight and allowed to warm to ambient temperature. The reaction mixture was then diluted with 125 ml of ether, washed twice with 2n. hydrochloric acid, a 10% aqueous solution of sodium carbonate and finally water. The residue obtained after distillation of the solvent was purified by flash chromatography using a mixture of ether and gasoline as eluent. The result was 0.424 g of a mixture of two target compounds in an approximate ratio of 3: 1. (separation into individual components was not carried out) in the form of a colorless resin. A part of this resin (0.400 g) was separated using high-performance silica gel chromatography liquid, using a mixture of hexane, dichloromethane and methyl tert-butyl ether with a component ratio of 70: 25: 5 as eluent. As a result, (I) regioisomer A (0.179 g) was obtained, which was the first to be released and which was the main component of the mixture, as a white crystalline substance. Mp 90-92 ^about S.

¹ H NMR, (250 MHz), δ: 2.52 (3H, s), 3.56 (3H, s), 3.72 (3H, s), 6.48 (1H, d), 6.64 (1H, q), 6.9-7.4 (9H, m), 7.43 (1H, s), 7.84 (1H, d) ppm. and (II) regioisomer B (0.061 g, with an admixture of about 5% regioisomer A), leaving the second and contained in the mixture in a smaller amount, in the form of a white crystalline substance; so pl. 82-85 ^about S.

¹ H NMR (250 MHz), δ: 2.51 (3H, s), 3.60 (3H, s), 3.75 (3H, s), 6.45 (1H, d), 6.59 ( 1H, q), 6.9-7.4 (9H, m), 7.48 (1H, s), 7.82 (1H, d) ppm.

 PRI me R 10. This example illustrates the preparation of (E) -methyl-3-methoxy-2- [2- (3-pyrimidin-2-yl-hydroxyphenoxy) phenyl] propenoate (compound N 22 from table 2) .

A mixture of 0.5 g of (E) -methyl-2- [2- (3-hydroxyphenoxy) phenyl] -3-methoxypropenoate obtained as described in Example 1, 0.46 g of potassium carbonate, 0.23 g of 2-chloropyrimidine and 0.01 g of copper chloride in 15 ml of DMF was boiled for 4 hours under reflux. After cooling, the mixture was poured into water and filtered. The filtrate was subjected to extraction with ether. The combined ether extracts were washed successively with water and brine, dried, concentrated and chromatographed using a mixture of ether and hexane as eluent. The result was 0.26 (yield 41%) of the target compound, IR (film): 1707, 1633 cm ^-1 .

¹ H NMR (90 MHz), δ: 3.54 (3H, s), 3.68 (3H, s), 6.74-7.34 (9H, m), 7.38 (1H, s), 8.28 (2H, d) ppm.

 Example 11. This example describes the preparation of (E) -methyl-3-methoxy-2- [2- (3-phenoxyphenylthio) phenyl] propenoate (compound N 446 from table 3).

2-Меркаптофенилуксусную кислоту получали описанным в литературе способом (см.D.Papa и др., J.Org.Chem. 1949, 24.723, R.H.Glauert, F.G.Mann, J. Chem. Soc. 1952, 2127 и ссылки в этой статье). 1,68 г 2-меркаптофенилуксусной кислоты добавляли к перемешиваемому раствору 0,8 г гидроксида натрия в 10 мл метанола (сравни D, C.Atkinson и др. J.Med.Chem., 1983, 26, 1361). Образующийся оранжевый раствор перемешивали при комнатной температуре в течение 90 мин, затем концентрировали при пониженном давлении, удаляя остатки метанола путем азеотропной перегонки с толуолом. В результате получали желтое твердое вещество. К перемешиваемому раствору этого желтого вещества в 20 мл ДМФ добавляли 0,2 г хлорида меди и раствор 2,49 г 3-феноксибромбензола, полученного из 3-феноксифенола и трифенилфосфиндибромида по способу, описанному J.P.Schaefer и др. Org.Synth., Coll, т.5, 142) в 10 мл ДМФ. Образующуюся смесь нагревали при 95^оС в течение часа, при 125^оС в течение 2 ч и затем при температуре кипения в течение еще 2 ч. После охлаждения реакционную смесь выливали в водный раствор гидроксида натрия и трижды промывали эфиром. Водный раствор подкисляли концентрированной соляной кислотой и трижды подвергали экстракции эфиром.

2-Mercaptophenyl acetic acid was prepared as described in the literature (see D. Papa et al., J. Org. Chem. 1949, 24.723, RHGlauert, FGMann, J. Chem. Soc. 1952, 2127 and references therein). 1.68 g of 2-mercaptophenylacetic acid was added to a stirred solution of 0.8 g of sodium hydroxide in 10 ml of methanol (cf. D, C. Atkinson et al. J. Med. Chem., 1983, 26, 1361). The resulting orange solution was stirred at room temperature for 90 minutes, then concentrated under reduced pressure, removing residual methanol by azeotropic distillation with toluene. The result was a yellow solid. To a stirred solution of this yellow substance in 20 ml of DMF was added 0.2 g of copper chloride and a solution of 2.49 g of 3-phenoxybromobenzene obtained from 3-phenoxyphenol and triphenylphosphine dibromide according to the method described by JPSchaefer et al. Org. Synth., Coll, t .5, 142) in 10 ml of DMF. The resulting mixture was heated at ⁹⁵ ° C for one hour, at ¹²⁵ ° C for 2 hours and then at reflux temperature for a further 2 hours. After cooling, the reaction mixture was poured into aqueous sodium hydroxide solution and washed with ether. The aqueous solution was acidified with concentrated hydrochloric acid and extracted three times with ether.

 The extracts were washed with water, dried and concentrated, resulting in 2.2 g of an oily purple liquid, consisting mainly of 2- (3-phenoxyphenylthio) phenylacetic acid. A solution of this oily liquid in 20 ml of methanol was added to acidic methanol obtained by careful treatment of 30 ml of methanol with 3.5 ml of acetyl chloride, and the resulting mixture was stirred for 90 min at room temperature. The reaction mixture was then concentrated and the residue was partitioned between ether and aqueous sodium bicarbonate. The organic layer was separated and washed successively with an aqueous solution of sodium hydroxide (twice) and three times with water, after which it was dried and concentrated to obtain 2.06 g of crude 2- (3-phenoxyphenylthio) phenylacetate as a purple oily liquid.

IR _max (film): 1740 cm ^-1 , purity 94% (determined by gas chromatography). The crude methyl 2- (3-phenoxyphenylthio) phenylacetate was converted to the target compound in 53% yield in two steps, in the same manner as described in Example 7 for the conversion of methyl 2- [3- (3-methoxyphenoxy) phenoxy] phenylacetate in (E) -methyl-2- [2- (3-methoxyphenoxy) phenoxy) phenyl] -3-methoxypropenoate, namely by formation with methyl formate and sodium hydride and subsequent O-methylation with dimethyl sulfate and potassium carbonate. The resulting product was an orange resin (purity determined by gas chromatography, 98%), which crystallized upon standing. Mp 48-51.5 ^about S.

IR _max (film): 1710 and 1632 cm ^-1 .

¹ H NMR (270 MHz), δ: 3.62 (3H, s), 3.73 (3H, s), 6.78 (1H, dd), 6.88-7.00 (4H, m), 7.05-7.36 (7H, m), 7.42 (1H, d), 7.48 (1H, s) ppm.

 PRI me R 12. This example illustrates the preparation of (E) -methyl-2- [2- (3-pyrimidin-2-yl-hydroxyphenylthio) phenyl] -3-methoxypropenoate (compound N 22 from table 4).

 A mixture of 3-methoxythiophenol sodium salt obtained by treating 2.8 g of 3-methoxythiophenol 0.8 g of sodium hydroxide in 20 ml of methanol, followed by evaporation of the solution to dryness, 4.3 g of 2-bromophenylacetic acid and 0.4 g of copper chloride (I ) in 25 ml of dry DMF was boiled overnight under reflux. The reaction mixture was then cooled, poured into water and acidified with dilute hydrochloric acid. The aqueous mixture was extracted three times with ether, and the combined ether extracts, in turn, were twice extracted with a dilute sodium hydroxide solution. The combined aqueous hydroxide extracts were acidified with dilute hydrochloric acid and reextracted with ether three times.

 The combined ether extracts were washed three times with water, dried and evaporated, yielding 3.5 g (96.8% determined by gas chromatography) of an orange oily liquid. The resulting oily liquid was kept overnight at room temperature with acidic methanol. After ordinary processing, 2.9 g (91% determined by gas chromatography) of methyl 2- (3-methoxyphenylthio) phenylacetate were obtained as a yellow liquid, which was used in the next step without further purification.

¹ H NMR, δ: 3.64 (3H, s), 3.74 (3H, s), 3.86 (2H, s) ppm.

IR _max (film): 1739 cm ^-1 .

0.86 g of methyl 2- (3-methoxyphenylthio) phenylacetate and 2.08 g (excess) piridiniygidrohlorida heated at 200 ^{° C} under a nitrogen atmosphere. After 3 hours, the reaction mixture was cooled and partitioned between dilute hydrochloric acid and ethyl acetate. The acidic aqueous layer was extracted twice with ethyl acetate and the combined organic phases were extracted three times with a dilute sodium hydroxide solution. The combined alkaline phases were acidified with concentrated hydrochloric acid and extracted three times with ethyl acetate. These organic extracts were combined, washed three times with water, dried and evaporated, yielding 0.64 g of an off-white solid. The obtained off-white solid was treated with a methanolic solution of hydrogen chloride and, after standard processing, 0.44 g of methyl 2- (3-hydroxyphenylthio) phenylacetate was obtained as a red oily liquid (purity determined by gas chromatography, 90.5%) which was used without further purification in the next step.

IR _max .: 3384, 1738 cm ^-1 .

A solution of 0.44 g of crude metal 2- (3-hydroxyphenylthio) phenylacetate and 1.92 ml of methyl formate in 2 ml of dry DMF was added dropwise to a stirred suspension of 0.21 g (55% dispersion in oil, pre-washed with petroleum ether ) sodium hydride in 3 ml of dry DMF at 0-5 ° ^C. After 15 minutes the mixture was allowed to warm to room temperature. After 2.5 hours, the reaction mixture was poured into water, acidified with concentrated hydrochloric acid and extracted three times with ether. The combined ether extracts were washed three times with water, dried and evaporated, yielding 0.49 g of a red gum. The resulting red gum was dissolved in 5 ml of DMF and cooled to 0 C. To ^the prepared solution was added 0.132 g of potassium carbonate and then dropwise a solution of 0.111 g of dimethyl sulphate in DMF. After stirring for 4.5 hours, the reaction mixture was poured into water and extracted three times with ether. The combined ether extracts were washed three times with water, dried and evaporated, yielding 0.45 g of methyl 2- [2- (3-hydroxyphenylthio) phenyl] -3-methoxypropenoate as a red gum.

IR _max 3240, 1709, 1665 cm ^-1 , M ⁺ 316.

¹ H NMR, δ: 3.65 (3H, s), 3.76 (3H, s), 7.47 (1H, s) ppm.

0.4 g of crude (E) -methyl-2- [2- (3-hydroxyphenylthio) phenyl] -3-methoxypropenoate was treated with 0.45 g of 2-chloropyrimidine and 0.17 g of potassium carbonate in 10 ml of dry DMF at 80- 90 ^about With nitrogen atmosphere. According to the results of gas chromatographic analysis, after 4.5 h, one reaction product was present in the reaction mixture, the reaction mixture was cooled, poured into water and subjected to extraction with ether four times. The combined yellow ethers were washed twice with water, dried and evaporated, yielding 0.39 g of an orange gum. Chromatography using ether as the eluent gave 0.34 g of the target compound as a viscous orange resin.

IR _max 1706, 1632 cm ^-1 .

¹ H NMR, δ: 3.64 (3H, s), 3.75 (3H, s), 6.97-7.06 (3H, m), 7.08-7.12 (1H, d), 7.25-7.35 (4H, m), 7.46-7.48 (1H, d), 7.49 (1H, s), 8.53-8.56 (2H, d) ppm .

 Example 13. This example illustrates the preparation of (E) -methyl-2- / 2- (3-phenylthiophenoxy) phenyl] -3-methoxypropenoate (compound N 1 from table 1).

2.02 g (0.01 mol) of 3-hydroxydiphenyl sulfide, 1.35 g (0.005 mol) of (E) -methyl-2- (2-bromophenyl) -3-methoxypropenoate obtained from o-bromophenyl acetate, methyl formate and sodium hydride followed by the addition of potassium carbonate and dimethyl sulphate in the two steps following the procedure described in example 7 for a similar conversion, 0.69 g (0.005 mol) of anhydrous potassium carbonate and a catalytic amount of cuprous chloride were mixed and heated with stirring to 175 ^C. After 10 hours, the reaction mixture was cooled to ambient temperature and dissolved in 50 ml of DMF. The resulting solution was poured into 100 ml of water and the resulting emulsion was extracted twice with ether (in 100 ml portions). The combined ether extracts were washed sequentially with water (twice, in 100 ml portions), twice with 2M sodium hydroxide solution (in 100 ml portions) and twice with water (100 ml portions). The ethereal solution obtained after washing was dried, filtered and evaporated to dryness under reduced pressure. Chromatography using chloroform as eluent gave 0.83 g of the target compound as a viscous oily liquid.

¹ H NMR (60 MHz), δ: 3.52 (3H, s), 3.64 (3H, s), 6.5-7.3 (13H, m), 7.42 (1H, s) m .d.

 Example 14. This example illustrates the preparation of (E) -methyl-2- [2- (3-phenylthiophenoxy) phenyl] -3-methoxypropenoate-S, S-dioxide (compound N 3 from table 1).

3.66 g (0.0156 mol) of 3-hydroxydiphenyl sulfonate, 1.5 g (0.0055 mol) of (E) -methyl-2- (2-bromophenyl) -3-methoxypropenoate obtained by the method described in example 13, and 1.1 g (0.0079 mol) of anhydrous potassium carbonate was mixed with a catalytic amount of copper chloride and copper bronze. The mixture was heated for 10 hours at 170 ^{° C} under a nitrogen atmosphere. After that, the melt was cooled to ambient temperature and the residue was dissolved in 50 ml of DMF. The resulting solution was diluted with 100 ml of ether and filtered to remove inorganic salts. The solution was washed successively with 100 ml of water, twice with 2M sodium hydroxide solution (in 100 ml portions), again with 100 ml of water and 100 ml of a saturated solution of sodium chloride. The ethereal solution was dried, filtered and evaporated to dryness under reduced pressure. Chromatography of the residue using hexane and chloroform as eluent gave 0.66 g of the target compound.

¹ H NMR (60 MHz), δ: 3.46 (3H, s), 3.57 (3H, s), 6.6-8.0 (14H, m) ppm.

 PRI me R 15. This example illustrates the preparation of (E) -methyl-2- / 2- (3-anilinophenoxy) phenyl / -3-methoxypropenoate (compound N 4 from table 1).

1.355 g (0.0074 mol) of 3-oxydiphenylamine, 1 g (0.0037 mol) of 2- (2-bromophenyl) -3-methoxypropenoate obtained by the method described in example 13, and 0.517 g (0.0037 mol) of anhydrous carbonate potassium was mixed with catalytic amounts of copper chloride and copper bronze. The mixture was heated for 9 hours at 170 ^{° C,} then cooled and dissolved in 20 ml of DMF. The resulting solution was partitioned between ether and water. The ether layer was washed with water (twice in 100 ml portions) and twice with 1M sodium hydroxide solution (in 100 ml portions), after which it was dried, filtered and evaporated to dryness under reduced pressure. The resin residue was purified by chromatography using hexane and dichloromethane as eluents. The result was 0.40 g of the target compound.

¹ H NMR (60 MHz), δ: 3.57 (3H, s), 3.67 (3H, s), 5.75 (1H, broad), 6.3-7.4 (13H, m), 7.44 (1H, s) ppm.

 Example 16. This example illustrates the preparation of (E) -methyl-2- [2- (3-N-methylanilinphenoxy) phenyl] -3-methoxypropenoate (compound No. 5 of Table 1).

 300 mg (0.01 mol) of an 80% dispersion of sodium hydride in oil was washed twice with hexane (in 50 ml portions) to remove the oil, and then suspended in 10 ml of dry DMF. To the resulting suspension was added a solution of (290 mg) of (E) -methyl-2- [2- (3-aniline phenoxy) phenyl] -3-methoxypropenoate obtained in the manner described in Example 15 in 10 ml of DMF at such a rate that ensure uniform release of gas bubbles. After gas evolution ceased, the mixture was stirred for another 15 minutes and 2 ml (a larger excess) of iodomethane was added to it over 5 minutes. Stirring was continued for another 30 minutes, after which the suspension was carefully diluted with 50 ml of water. The aqueous emulsion was extracted twice with ether (50 ml each), dried, filtered and evaporated to dryness under reduced pressure, to give 211 mg of the target compound as a viscous oily liquid.

¹ H NMR (60 MHz), δ: 3.20 (3H, s), 3.54 (3H, s), 3.65 (3H, s), 6.3-7.4 (12, m) 7.44 (1H, s) ppm.

 Example 17. This example illustrates the preparation of (E) -methyl-3-methoxy-2- {2- [3- (α-hydroxybenzyl) phenoxy] phenyl} propenoate (compound N 380 from table. 1).

31.0 g of 3-hydroxybenzyl alcohol was finely ground and mixed with 34.6 g of potassium carbonate, 26.9 g of 2-bromophenylacetic acid and copper chloride (large spatula) in a nitrogen atmosphere. The mixture was heated to ¹⁴⁰ ° C and vigorously stirred at this temperature for 3.5 hours. Then, to the stirred melt was added 60 ml of DMF, the solution was cooled, poured into water and acidified with dilute hydrochloric acid. The aqueous layer was extracted with ether, the ether extracts were washed with water, dried and evaporated, yielding 42.03 g of 2- (3-hydroxymethylphenoxy) phenylacetic acid and as a brown oily liquid, which was used without further purification in the next step.

 41.0 g of the obtained crude acid was boiled for 3.5 hours under reflux in 600 ml of methanol with the addition of 2.5 ml of concentrated sulfuric acid. After distilling off methanol, the residue was dissolved in ethyl acetate, washed with a dilute aqueous solution of sodium hydroxide, and then with water, dried and evaporated, resulting in 26.31 g of a brown oily liquid. 1.31 g of it was purified by high performance liquid chromatography using a 1: 1 mixture of ethyl acetate and hexane as the eluent. As a result, pure 2- (3-hydroxymethylphenoxy) phenylacetate was obtained as a pale yellow oily liquid.

¹ H NMR (400 MHz), δ: 2.12 (1H, s), 3.60 (3H, s), 3.69 (3H, s), 4.62 (2H, s), 6.95 ( 1H, s), 6.85-6.90 (2H, t), 7.04-7.14 (2H, m), 7.21-7.32 (3H, m) ppm.

IR (film): 3450, 1742 cm ^-1 .

A mixture of 25.0 g of crude methyl-2- / 3-oksimetilfenoksi / phenylacetate and 56 ml of methyl formate in 50 mL of dry DMF was added dropwise over 30 minutes at ⁵ ° C to sodium hydride (7.35 g of 60% dispersion in oil washed with hexane). After stirring for another 30 minutes at 5 ° C., ^the mixture was allowed to warm to room temperature for several hours and then left to stand overnight. After that, the reaction mixture was poured into water and subjected to extraction with ether. The aqueous layer was acidified with dilute hydrochloric acid and subjected to extraction with ether. The ether extracts were dried and evaporated, yielding 32.19 g of crude methyl 2- [2- (3-hydroxymethylphenoxy)] phenylpropenoate as an orange oily liquid. 32.10 g of crude methyl ether was stirred in 80 ml of DMF at 5-10 ^about 25.4 g of potassium carbonate and a solution of 11.6 g of dimethyl sulfate in 20 ml of DMF was added dropwise to the mixture over 10 minutes. The mixture was allowed to warm to room temperature for several hours and left to stand overnight. After that, it was poured into water, acidified with dilute hydrochloric acid and subjected to extraction with ether. The ether extracts were washed with water, dried and evaporated, yielding 14.38 g of an orange-brown oily liquid. After purification by high performance liquid chromatography, 7.8 g of (E) -methyl-3-methoxy-2- [2- (3-hydroxymethylphenoxy) phenyl] propenoate was obtained as a pinkish crystalline solid.

¹ H NMR (270 MHz), δ: 2.55 (1H, s), 3.58 (3H, s), 3.74 (3H, s), 4.55 (2H, s), 6.8- 7.28 (8H, m), 7.44 (1H, s) ppm.

IR _max ., (Nujol): 3515, 1705, 1625 cm ^-1 .

 A portion of the obtained alcohol (0.314 g) was stirred in 5 ml of dry methylene chloride, 0.564 g of pyridinium dichromate was added, and the mixture was stirred for 4 hours at room temperature. Then it was filtered and the precipitate was washed with ether. After washing, the methylene chloride and ether were combined and evaporated, yielding 0.309 g of (E) -methyl-3-methoxy-2- [2- (3-formylphenoxy) phenyl] propenoate as a brown oily liquid.

¹ H NMR (270 MHz), δ: 3.59 (3H, s), 3.65 (3H, s), 6.98 (1H, d), 7.17-7.36 (4H, m), 7.40-7.47 (3H, m), 7.47 (1H, s), 7.55 (1H, d) ppm.

IR _max (film): 1710, 1640 cm ^-1 .

0.50 g of (E) -methyl 3-methoxy-2- [2- (3-formylphenoxy) phenyl] propenoate was stirred in 20 ml of dry THF at ^-20 ° C under a nitrogen atmosphere. Phenylmagnesium bromide (0.53 ml of a 3M ether solution) was slowly added dropwise to the prepared mixture as a dilute solution in dry THF (5 ml). Upon completion of addition, the reaction mixture was stirred at ^-20 ° C for 30 min and then slowly for one hour, warmed to room temperature and then left to stand overnight. The mixture was then cooled ^to 5 ° C, water was added thereto and extracted with ethyl acetate. After washing with brine and drying, the ethyl acetate solution was evaporated, yielding a yellow oily liquid, which was purified by high performance liquid chromatography using a 2: 1 mixture of hexane and ether as eluent. The result was 0.340 g of the target compound as a colorless oily liquid.

¹ H NMR (400 MHz), δ: 2.30 (1H, d), 3.57 (3H, s), 3.72 (3H, s), 5.78 (1H, d), 6.82 ( 1H, d), 6.91 (1H, d), 7.02-7.08 (2H, m), 7.10-7.16 (1H, m), 7.20-7.38 (8H, m), 7.45 (1H, s) ppm.

IR _max (film): 3460, 1715, 1635 cm ^-1 .

 Example 18. This example illustrates the preparation of (E) -methyl-3-methoxy-2- {2- [3- (2-pyridyloxymethyl) phenoxy] phenyl} propenoate (compound N 6 from table 2).

 0.28 g of silver carbonate was added to 0.75 g (70% purity) of (E) -methyl-3-methoxy-2- [2- (3-bromomethylphenoxy) phenyl] propenoate obtained by the method described in example 8, and 0.19 g of 2-pyridone in hexane. The mixture was refluxed for 3 hours in the dark, for which the reaction flask was wrapped in foil, and then left to stand overnight. After this, hexane was distilled off, and the residue was dissolved in an aqueous solution of sodium bicarbonate, and then with water, dried and evaporated, resulting in 0.72 g of an orange resin. The obtained resin was purified using high-performance liquid chromatography using a mixture of ether and hexane taken in the ratio 1: 1 as eluent. The result was 0.188 g of the target compound as a colorless resin.

¹ H NMR (270 MHz), δ: 3.60 (3H, s), 3.76 (3H, s), 5.32 (2H, s), 6.78 (1H, d), 6.84- 6.96 (3H, m), 7.04-7.16 (1H, m), 7.21-7.31 (3H, m), 7.48 (1H, s), 7.52-7, 60 (1H, m), 8.15 (1H, d), ppm.

IR _max (film): 1715, 1670, 1645, 1600 cm ^-1 .

 PRI me R 19. This example illustrates the preparation of (E) -methyl-3-methoxy-2- [2- (3-pyrimidin-2-yl-hydroxymethylphenoxy) phenyl] propenoate (compound N 85 from table 2) .

 0.5 g of (E) -methyl-3-methoxy- [2- (3-hydroxymethylphenoxy) phenyl] propenoate obtained by the method described in example 17 in several ml of DMF was added to sodium hydride (0.072 g of a 60% dispersion in oil washed with hexane) and stirred in 10 ml of dry DMF at room temperature. Upon completion of the addition, the mixture was stirred for 5 minutes, 0.92 g of 2-chloropyrimidine was added to it and left to stand overnight. Then it was poured into water, acidified and subjected to extraction with ether. The ether extracts were dried and evaporated, yielding 0.95 g of a yellow oily liquid. After purification using high-performance liquid chromatography using a 1: 1 mixture of ethyl acetate and hexane as the eluent, 0.104 g of the pure target compound was obtained in the form of an oily liquid.

¹ H NMR (270 MHz), δ: 3.60 (3H, s), 3.75 (3H, s), 5.39 (2H, s), 6.86-6.96 (3H, m), 7.03-7.31 (6H, m), 7.49 (1H, s), 8.50 (2H, d) ppm.

IR _max (film): 1713, 1640 cm ^-1 .

 Example 20. This example illustrates the preparation of (E, E) - and (E, Z) -methyl-3-methoxy-2- {2 [3- (4-nitrostyryl) phenoxy] phenoxy} phenylpropenoate (mixture of compounds N 403 from table 1).

1.39 g of dimethyl phosphite in 5 ml of dry DMF was added dropwise to a stirred suspension of sodium hydride (0.61 g of 50% dispersion in oil, washed with hexane) in 10 ml of dry DMF at 20 ^o C. After the addition and stirring the mixture over another 20 minutes, 7.0 g (70% purity) of (E) -methyl-3-methoxy-2- [2- (3-bromomethylphenoxy) phenyl] propenoate obtained by the method described in Example 8 was added dropwise thereto. . The reaction mixture was allowed to stand for 60 hours, then heated ^at 55 ° C for 10 hours, poured into water and extracted with ethyl acetate. The extract was dried and evaporated, yielding a yellow viscous gum which was purified by flash chromatography using 5% methanol in ethyl acetate as eluent. The result was 1.50 g of (E) -methyl-3-methoxy-2- (3- / dimethylphosphonomethyl / phenoxy) -phenylpropenoate phosphonate as an almost colorless oily liquid.

¹ H NMR (400 MHz), δ: 3.13 (2H, d), 3.62 (3H, s), 3.66 (3H, s), 3.68 (3H, s), 3.78 ( 3H, s), 6.85 (1H, d), 6.92 (2H, d), 7.00 (1H, d), 7.13 (1H, t), 7.20-7.31 (4H , m) 7.48 (1H, s) ppm.

IR _max (film): 1715, 1645 cm ^-1 .

0.61 g of the resulting phosphonate in 5 ml of dry DMF was added dropwise to sodium hydride (0.072 g of 50% dispersion in oil, washed with hexane) stirred in 10 ml dry DMF at ⁵ ° C under a nitrogen atmosphere. Upon completion of the addition, the reaction mixture was warmed to room temperature and stirred for 15 minutes. Thereafter, 0.227 g of N-nitrobenzaldehyde in 5 ml of dry DMF was slowly added dropwise to it and stirred overnight at room temperature, then adding water, and subjected to extraction with ether. The ether layer was dried and evaporated, resulting in a viscous yellow liquid, which was purified using high-performance liquid chromatography using a mixture of hexane and ethyl acetate taken in the ratio 3: 1 as eluent. The result was 0.20 g of the target compound in the form of a yellow resin, which is a mixture (in a ratio of 5: 1) of / Z / - and / E / -stilbene isomers.

¹ H NMR (270 MHz), δ: (data for the / Z / -isomer) 3.57 (3H, s), 3.74 (3H, s), 6.58 (1H, d), 6.72 ( 1H, d), 6.72-6.98 (3H, m), 7.05-7.36 (7H, m), 7.45 (1H, s), 8.06 (2H, d) m. d.

 By boiling the mixture under reflux in toluene with traces of iodine, a mixture was obtained with a ratio of (E) - and (Z) -isomers of 85:15.

¹ H NMR (400 MHz), δ (data for the (E) -isomer): 3.62 (3H, s), 3.78 (3H, s), 6.92-7.35 (10H, m), 7.49 (1H, s), 7.61 (2H, d), 8.22 (2H, d) ppm.

 Example 21. This example illustrates the preparation of (E) -methyl-3-methoxy-2- [2- (3-benzoyloxymethylphenoxyl) phenyl] propenoate (compound 398 from table 1).

 0.5 g (purity 75%) of (E) -methyl-3-methoxy-2- (3-bromomethylphenoxy) phenylpropenoate obtained by the method described in example 8, 0.13 g of benzoic acid and 0.076 g of potassium carbonate were mixed overnight at room temperature in dry DMF. After that, water was added to the mixture and subjected to extraction with a dilute aqueous bicarbonate solution, dried and evaporated, yielding 0.49 g of a yellow viscous oily liquid, which was purified by high-performance liquid chromatography using a mixture of hexane and ethyl acetate taken as an eluent. 5: 2 ratio. The result was 0.120 g of the target compound.

¹ H NMR (400 MHz), δ: 3.60 (3H, s), 3.75 (3H, s), 5.31 (2H, s), 6.93 (1H, d), 6.96 ( 1H, d), 7.06 (1H, s), 7.12 (1H, d), 7.16 (1H, d), 7.44 (2H, t), 7.25-7.32 (2H , m), 7.47 (1H, s), 7.55 (1H, d), 8.05 (2H, d).

 Example 22. This example illustrates the preparation of the bromide salt of (E) -methyl-3-methoxy-2- {2- [3- (triphenylphosphorophoniummethyl) phenoxy] phenyl} propenoate (compound N 404 from table. 1).

4.58 g (70% purity) of (E) -methyl-3-methoxy-2 [2- (3-bromomethylphenoxy) phenyl] propenoate obtained by the method described in example 8 were stirred for 4 hours and 2 , 33 g of triphenylphosphine in 40 ml of dry DMF and the resulting mixture was left to stand overnight. After that, the solvent was distilled off and a thick residue was obtained, which was triturated in a mixture of ether and ethyl acetate, thereby obtaining 4.38 g of the target compound as a yellow-white crystalline substance; so pl. 176-177 ^about S.

¹ H NMR (270 MHz), δ: 3.56 (3H, s), 3.74 (3H, s), 5.28 (2H, d), 6.48 (1H, s), 6.62 ( 1H, d), 6.77 (1H, d), 6.97 (1H, d), 7.04 (1H, t), 7.10-7.28 (3H, m), 7.40 (1H , s), 7.54-7.80 (15H, m) ppm.

 Example 23. This example illustrates the preparation of (E, E) -methyl-3-methoxy-2- [2- (3-styrylphenoxy) phenyl] propenoate (compound N 18 from table 1).

1.0 g of the bromide salt of (E) -methyl-3-methoxy-2- [2- (3-triphenylphosphoniummethyl) phenoxy] phenylpropenoate obtained by the method described in Example 22 in 5 ml of dry DMF was added dropwise to sodium hydride (0.075 g of a 50% dispersion in oil washed with hexane) in 5 ml of dry DMF. The result was an orange solution. Upon completion of hydrogen evolution (2 h) was added thereto, 0.66 g of benzaldehyde in 5 mL of dry DMF and the reaction mixture was stirred at room temperature for 20 hours and then heated for 2 hours at 60 ^C. Thereafter, to this was added water and subjected to extraction with ethyl acetate. The organic layer was dried and evaporated, resulting in 1.3 g of a yellow oily liquid, which was purified using high-performance liquid chromatography using a mixture of THF and hexane taken in the ratio 1: 4 as eluent. The result was 0.362 g of a mixture of the target compound and the corresponding (Z) -styryl isomer in a ratio of 1: 1.

 By boiling this mixture and refluxing for several hours in toluene with the addition of crystalline iodine, the (E) -isomer was obtained in the form of a colorless resin.

¹ H NMR (270 MHz), δ: 3.64 (3H, s), 3.77 (3H, s), 6.88 (1H, d), 6.96-7.40 (10H, m), 7.49 (1H, s), 7.48 (2H, m), ppm.

IR _max (film): 1710, 1640 cm ^-1 .

 Example 24. This example illustrates the preparation of (E) -methyl-3-methoxy-2- [2- (3-phenoxycarbonylphenoxy) phenyl] propenoate (compound N 50 from table 1).

To 2.43 g of (E) -methyl 3-methoxy-2- [2- (3-oksimetilfenoksi) phenyl] propenoate, prepared in Example 17, a method of stirring in 100 ml of acetone at 5-10 ^{° C,} was added chromic acid obtained by dissolving 6.5 g of chromium trioxide in 18.5 ml of water with the addition of 5.5 ml of concentrated sulfuric acid, until a stable reddish color is obtained and the entire amount of the starting alcohol enters the reaction (according to gas chromatography). After that, the mixture was poured into water and subjected to extraction with ether. The ether extracts were washed with water, dried and evaporated, yielding 2.495 g of (E) -methyl-3-methoxy-2- [2- (3-carboxyphenoxy) phenylpropenoate] as a pale yellow oily liquid.

¹ H NMR (270 MHz), δ: 3.60 (3H, s), 3.76 (3H, s), 6.95 (1H, d), 7.14-7.40 (5H, m), 7.50 (1H, s), 7.66 (1H, s), 7.78 (1H, d), 9.35 (1H, broad s) ppm.

IR _max (film): 3500-2500, 1725, 1640 cm ^-1 .

 0.33 g of the carboxylic acid obtained in the previous step was stirred in 10 ml of dry DMF and treated with 0.11 ml of oxalyl chloride and one drop of dry DMF. The reaction mixture was stirred for 45 minutes, allowed to stand overnight and evaporated to give crude (E) -methyl-3-methoxy-2- [2- (3-chlorocarbonylphenoxy) phenyl] propenoate as an orange-yellow oily liquid.

IR _max (film): 1760, 1715, 1640 cm ^-1 .

 To the acid chloride obtained in the previous step, in 15 ml of dry THF, 0.090 g of phenol and 0.096 g of triethylamine in 5 ml of dry DMF were added. The reaction mixture was stirred at room temperature for 1.5 hours, poured into water and subjected to extraction with ether. The ether extracts were washed with dilute sodium hydroxide solution and then with water, dried and evaporated, to give 136 mg of the target compound as an orange oily liquid.

¹ H NMR (270 MHz), δ: 3.60 (3H, s), 3.77 (3H, s), 6.94 (1H, d), 7.14 (2H, t), 7.23- 7.38 (3H, m), 7.47 (1H, s), 7.61 (1H, t), 7.72 (1H, d) ppm.

IR _max (film): 1755, 1710, 1640 cm ^-1 .

 Example 25. This example illustrates the preparation of (E) -methyl-2- {2- [3- (6-chloropyrimidin-4-yloxy) phenoxy] phenyl} -3-methoxypropenoate (compound N 89 from table. 2).

 To a stirred solution of 1.0 g of (E) -methyl-2- [2- (3-hydroxyphenoxy) phenyl] -3-tag-sipropenoate obtained by the method described in Example 1, 0.46 g of potassium carbonate were successively added in 10 ml , 0.027 g of copper chloride and 0.41 g of 4,6-dichloropyrimidine, and the resulting mixture was stirred for 10 hours at room temperature. Then it was diluted with water and subjected to extraction with ether. The extracts were washed sequentially with aqueous sodium bicarbonate and water, dried, concentrated and chromatographed using 1: 1 ether and hexane as an eluent. As a result, 0.39 g (28% yield) of the target compound was obtained as a colorless oily liquids.

¹ H NMR (270 MHz), δ: 3.60 (2H, s), 3.76 (3H, s), 6.74 (1H, t), 6.81 (1H, dd), 6.90 ( 2H, m), 7.03 (1H, m), 7.17 (1H, t), 7.26-6.36 (3H, m), 7.49 (1H, s), 8.59 (1H , s) ppm

 Example 26. This example illustrates the preparation of (E) -methyl-3-methoxy-2- [2- (3-pyrimidin-4-yloxyphenoxy) phenyl] propenoate (compound N 92 from table 2).

 A solution of 0.27 g of sodium hypophosphite in 5 ml of water was added dropwise with stirring to a mixture of 0.4 g of (E) -methyl-2- {2- [3- (6-chloropyrimidin-4-yloxy) phenoxy] phenyl} - 3-methoxypropenoate obtained as described in Example 25, 0.2 g of potassium carbonate and 0.08 g of 5% palladium on charcoal in 4 ml of THF. The resulting mixture was stirred for 2 hours at room temperature, filtered through Hyflo and washed with ethyl acetate and water. The combined filtrate and washings were separated into aqueous and organic layers. The latter was dried, concentrated and chromatographed using a mixture of ether and hexane taken in the ratio 1: 1 as eluent. The result was 0.19 g (yield 52%) of the target compound as a colorless oily liquid.

¹ H NMR (270 MHz), δ: 3.61 (3H, s), 3.75 (3H, s), 7.75 (1H, t), 7.48 (1H, s), 8.56 ( 1H, d), 8.76 (1H, s) ppm.

 Example 27. This example illustrates the preparation of (E) -methyl-3-methoxy-2- {2- [3- (3-nitrophenoxy) phenoxy] phenyl} propenoate (compound N 132 from table 1) .

A mixture of 1.7 g of 3- (3-nitrophenoxy) phenol, 2.09 g of (E) -methyl-2- (2-bromophenyl) -3-methoxypropenoate obtained by the method described in example 13, 1.0 g of potassium carbonate and 1.0 g of cuprous chloride was stirred for 5 hours at 170-180 ^{° C,} then cooled, diluted with water and extracted with ether. The extracts were washed successively with an aqueous solution of sodium hydroxide and brine, dried and concentrated, resulting in 3.12 g of a brown oily liquid. Chromatography using mixtures with different ratios of ether (up to 20%) and hexane as eluent gave 1.06 g (34% yield) of the target compound as a yellow oily liquid.

¹ H NMR (270 MHz), δ: 3.60 (3H, s), 3.76 (3H, s), 6.66-6.83 (3H, m), 7.02 (1H, d), 7.18 (1H, d), 7.22-7.38 (3H, m), 7.45-7.52 (1H, m), 6.49 (1H, s), 7.78 (1H, m), 7.92-7.97 (1H, m) ppm.

 Example 28. This example illustrates the preparation of (E) -methyl-3-methoxy-2- {2- [3- (3-methoxyphenoxymethyl) phenoxy] phenyl} propenoate (compound N 372 from table 1 )

0.50 g of (E) -methyl-3-methoxy-2- (2- [3-methylphenoxy] phenyl) propenoate obtained as described in Example 8, 0.32 g of 1,3-dibromo-5,5-dimethylhydantoin and 0.033 g of azobutyronitrile was refluxed in 40 ml of carbon tetrachloride by irradiation with a 400 W tungsten lamp. After an hour, the mixture was cooled and poured into water. The organic layer was separated, washed with water, dried and evaporated, yielding 0.825 g of a yellow, viscous oily liquid containing about 65% of (E) -methyl-2-methoxy-2- [2- (3-bromomethylphenoxy) phenyl] propenoate, which was used further without further purification (see Example 8, ¹ H NMR data).

 A solution of 0.41 g of crude bromide in 4 ml of dry DMF was added to a solution of 3-methoxyphenoxide (obtained from 3-methoxyphenol and sodium hydride) in 6 ml of dry DMF and the mixture was stirred for 4 hours, after which it was left to stand overnight. The reaction mixture was then poured into a dilute aqueous hydrochloric acid solution and subjected to extraction with ethyl acetate. The organic fractions were dried and evaporated, resulting in a brown oily liquid, which was purified using high-performance liquid chromatography using a mixture of petroleum ether 40/60 and ethyl acetate taken in the ratio of 7: 3 as eluent. The result was 0.20 g of the target compound as a colorless resin.

IR _max (film): 1715, 1640 cm ^-1 .

¹ H NMR (400 MHz), δ: 3.60 (3H, s), 3.73 (3H, s), 3.77 (3H, s), 4.99 (3H, s), 6.50- 6.55 (3H, m), 6.88-6.95 (2H, m), 7.05 (1H, s), 7.09-7.20 (3H, m), 7.24-7, 31 (3H, m), 7.47 (1H, s) ppm.

 Example 29. This example illustrates the preparation of (E) -methyl-3-methoxy-2- [2- (3-benzoylphenoxy) phenyl] propenoate (compound N 12 from table 1).

 10.0 g of methyl 2- (3-hydroxymethylphenoxy) phenylacetate obtained as described in Example 17 and 10 g of celite were mixed in 100 ml of methylene chloride and 15.85 g of pyridinium chlorochromate was added to the mixture in one go. After the mixture was stirred at room temperature for 2.5 hours, it was filtered and the filtrate was evaporated, yielding 8.48 g of methyl 2- (3-formylphenoxy) phenylacetate as an orange oily liquid that was pure enough to be able to Use without further cleaning.

IR _max (film): 1740, 1700 cm ^-1 .

¹ H NMR (270 MHz), δ: 3.59 (3H, s), 3.69 (2H, s), 6.92 (1H, d), 7.14-7.20 (1H, t), 7.23-7.37 (3H, m), 7.43 (1H, m), 7.50 (1H, t), 7.60 (1H, dd), 9.95 (1H, s) m. d.

To 2.30 g of the cooled stirred solution of the aldehyde obtained in the previous step in THF was added dropwise phenylmagnesium bromide (2.84 ml of a 3M solution in ether) at such a rate that the temperature did not rise above - 30 ^C. After complete addition (35 min) the reaction mixture was slowly warmed to room temperature, stirred overnight and then cooled in an ice bath, carefully adding water. After that, dilute hydrochloric acid was added to it and subjected to extraction with ethyl acetate. The extracts were dried and evaporated, resulting in a yellow oily liquid, which was purified using flash chromatography using a mixture of hexane and ethyl acetate taken in a 2: 1 ratio as eluent. The result was 1.69 g of 2 - [(3-α-hydroxy) benzylphenoxy] phenylacetate as a pale yellow oily liquid.

¹ H NMR (270 MHz), δ: 3.57 (3H, s), 8.68 (2H, s), 5.79 (1H, s), 6.79-6.90 (2H, m), 7.05-7.13 (3H, m), 7.18-7.40 (9H, m) ppm.

 0.91 g of the hydroxyether obtained in the previous step was stirred at room temperature in 25 ml of methylene chloride with the addition of two celite spatulas. Then, 0.65 g of pyridinium chlorochromate was added to the mixture and it was stirred for 3 h, then it was filtered, the filtrate was evaporated and purified by high performance liquid chromatography using a mixture of hexane and ethyl acetate taken in the ratio 3: 1 as eluent. The result was 0.56 g of methyl 2- (3-benzoylphenoxy) phenyl acetate as a pale yellow gum.

¹ H NMR (270 MHz), δ: 3.60 (3H, s), 3.70 (2H, s), 6.93 (1H, d), 7.10-7.63 (10H, m), 7.81 (2H, d) ppm.

IR _max (film): 1740, 1660 cm ^-1 .

 The resulting product was transferred to the target compound by treatment with sodium hydride and methyl formate, followed by the addition of potassium carbonate and dimethyl sulfate, the treatment was washed in two stages, as described in example 7 for a similar conversion.

IR _max (film): 1710, 1660, 1635 cm ^-1 .

¹ H NMR (270 MHz), δ: 3.60 (3H, s), 3.75 (3H, s), 6.98 (1H, d), 7.12-7.20 (2H, m), 7.26-7.52 (8H, m), 7.47 (1H, s), 7.55-7.63 (1H, m), 7.80 (2H, dd) ppm.

 Example 30. This example illustrates the preparation of (E) -methyl-3-methoxy-2- [2- (3-benzylphenoxy) phenyl] propenoate (compound No. 9 of Table 1).

To 1.68 g of methyl 2 - {[3- (oxy) benzyl] phenoxy} phenyl acetate, prepared as described in Example 29 method, was added dropwise at ⁵ ° C and stirred 3.28 g of trifluoroacetic acid. At the end of the addition, 2.24 g of triethylsilane was slowly added dropwise to the resulting mixture. The resulting clear solution was stirred overnight, diluted with an aqueous sodium bicarbonate solution, dried, concentrated, and purified using high performance liquid chromatography using a 4: 1 mixture of hexane and ether as eluent. As a result, 1.03 g of methyl 2- (3-benzylphenoxy) phenylacetate was obtained as a colorless oily liquid.

IR _max (film): 1742 cm ^-1 .

 The resulting product was transferred to the target compound by treating sodium hydride and methyl formate and then adding potassium carbonate and dimethyl sulfate. The treatment was carried out in two stages, as described for a similar transformation in example 7.

IR _max (film): 1708, 1635 cm ^-1 .

¹ H NMR (270 MHz), δ: 3.56 (3H, s), 3.72 (3H, s), 3.93 (2H, s), 6.76-6.93 (4H, m), 7.08-7.31 (10H, m), 7.47 (1H, s) ppm.

 Example 31. This example illustrates the preparation of (E) -methyl-3-methoxy-2- {2- [3- (N-phenylsulfonamido) phenoxy] phenyl} - propenoate (compound N 78 from the table. 1).

A mixture of 21.5 g of 2-bromophenylacetic acid, 29.2 g of 3-nitrophenol, 27.6 g of potassium carbonate and 0.5 g of copper chloride was heated for 6 hours with stirring at 130 ^about C.

After cooling, the mixture was poured into 500 ml of water, acidified with concentrated hydrochloric acid and extraction was performed three times with ethyl acetate (in 200 ml portions). The extracts were dried, filtered and concentrated to give a dark oily liquid, which was dissolved in 400 ml of methanol with the addition of 4 ml of concentrated sulfuric acid and the resulting solution was boiled for 3 hours. After that, the reaction mixture was concentrated and the residue was dissolved in 300 ml of ethyl acetate. The resulting solution was washed successively with a 1M aqueous sodium hydroxide solution (twice, in 100 ml portions) and brine, dried, filtered and concentrated to give a dark oily liquid. After distilling it (oven temperature 220 ^{° C,} pressure 0.2 mm Hg. V.) Was obtained 16.74 g (yield 58% based on 2-bromophenylacetic acid) methyl-2- (3-nitrophenoxy) phenylacetic acid as a clear, pale, oily liquid.

¹ H NMR (270 MHz), δ: 3.60 (3H, s), 3.70 (2H, s), 6.9-8.0 (8H, m) ppm.

IR _max (film): 1739 cm ^-1 .

 A mixture of 15 g of methyl 2- (3-nitrophenoxy) phenylacetate, 100 ml of methanol, 100 ml of glacial acetic acid and 15.0 g of iron powder was gently heated with stirring to boiling point. After 30 minutes, the mixture was cooled and excess iron powder was filtered off. The filtrate was poured into 700 ml of water and extracted twice with ether. The ether extracts were neutralized by stirring with an aqueous solution of sodium bicarbonate, then dried, filtered and concentrated, resulting in 13.0 g (yield 97%) of 2- (3-aminophenoxy) phenylacetate as a pale yellow oily liquid.

¹ H NMR (270 MHz), δ: 3.63 (3H, s), 3.68 (2H, s), 3.9 (1H, broad s), 6.2-7.3 (8H, m) ppm

IR _max (film): 3400, 3373, 1733 cm ^-1 .

A mixture of 11.54 g of methyl 2- (3-aminophenoxy) phenylacetate and 27.7 ml of methyl formate in 25 mL of DMF was added dropwise with stirring to the cooled with ice to a temperature below 10 ^{° C} slurry of 3.25 g of sodium hydride in 50 ml DMF (evolution of gas bubbles). Upon completion of the addition, the reaction mixture was stirred at room temperature for 3 hours, poured into water, acidified with concentrated hydrochloric acid, and subjected to extraction with ethyl acetate. The extracts were washed with brine, dried and concentrated to give a yellow viscous oily liquid. To a stirred solution of this liquid in 50 ml of DMF, 12.4 g of potassium carbonate and 4 ml of dimethyl sulfate were successively added. The resulting mixture was stirred for 3 hours at room temperature, then poured into water and subjected to extraction with ethyl acetate. The extracts were washed with water, dried and concentrated, yielding 13.67 g (93% yield) of (E) -methyl-2- [2- (3-formamidophenoxy) phenyl] -3-methoxypropenoate as a clear green resin.

¹ H NMR (270 MHz), δ: 3.60 (3H, s), 3.78 (3H, s), 7.47 (1H, s) ppm.

IR _max (film): 3309, 1702, 1606 cm ^-1 .

To a stirred solution of (E) -methyl-2- [2- (3-formamidophenoxy) phenyl] -3-methoxypropenoate (13.67 g) in 100 ml of methanol was added dropwise 7.8 ml of phosphoryl chloride, maintaining the temperature during the addition of using a cooling bath below 50 ^C. After stirring for 20 min, the reaction mixture was poured into 500 ml of water, neutralized with sodium bicarbonate and extracted with ether. The extracts were dried and concentrated, obtaining a yellow oily liquid, which was subjected to chromatography using ether as an eluent. The result was 8.57 g (68% yield) of (E) -methyl-2- [2- (3-aminophenoxy) phenyl] -3-methoxypropenoate as a yellow solid. Mp 83-85 ^about S.

¹ H NMR (270 MHz), δ: 3.6 (2H, broad s), 3.62 (3H, s), 3.77 (3H, s), 6.2-6.4 (3H, m) 6.9-7.3 (5H, m), 7.48 (1H, s), ppm.

IR _max (film): 3450, 3370, 1703, 1632 cm ^-1 .

A solution of (E) -methyl 2- [2- (3-aminophenoxy) phenyl] -3-methoxypropenoate (0.4 g) in 2 ml of glacial acetic acid was treated at - 10 ^C. 1 ml 5,8M HCl. Thereafter, the stirred solution was treated at - 10 ^{° C} 0.1 N solution. sodium nitrite in 2 ml of water. After 20 minutes, the resulting solution (containing the diazonium salt) was added to a stirred mixture of 0.5 ml of glacial acetic acid saturated with sulfur dioxide, with the addition of 0.1 g of copper chloride (evolution of gas bubbles). After 30 minutes, the reaction mixture was poured into water and subjected to extraction with ether. The ether extracts were neutralized with saturated aqueous sodium bicarbonate, dried, concentrated, resulting in 0.14 g of (E) -methyl-2- [2- (3-chlorosulfonylphenoxy) phenyl] -3-methoxypropenoate as a yellow oily liquid.

IR _max (film): 1710, 1636 cm ^-1 .

 To a solution of 0.14 g of methyl 2- [2- (3-chlorosulfonylphenoxy) phenyl] -3-methoxypropenoate in 0.5 ml of pyridine was added dropwise at room temperature with 0.05 ml of aniline.

 After 3 hours, the reaction mixture was poured into water, 2M hydrochloric acid was added to it until the reaction was weakly acid and it was extracted with ether. The ether extracts were washed with brine, dried, concentrated and chromatographed using ether as eluent. The result was 0.145 g of the target compound in the form of a clear oily liquid.

IR _max (film): 3240, 1693, 1935, 1600 cm ^-1 .

¹ H NMR (270 MHz), δ: 3.55 (3H, s), 3.69 (3H, s), 6.53 (1H, broad s), 6.8 (1H, m), 7.0 -7.4 (12H, m), 7.43 (1H, s) ppm.

 Example 32. This example illustrates the preparation of (E) -methyl-2- {2- [3- (3-bromobenzoylamino) phenoxy] phenyl} -3-methoxypropenoate (compound N 421 from table 1).

 To a stirred solution of 0.5 g of (E) -methyl-2- [2- (3-aminophenoxy) phenyl] -3-methoxypropenoate, obtained as described in Example 31, in 20 ml of dichloromethane with the addition of 0.17 g of triethylamine 0.37 g of 3-bromobenzoyl chloride was added. After 3 hours, the reaction mixture was poured into water and extracted twice with dichloromethane (in 50 ml portions). The extracts were dried, concentrated and chromatographed using ether as eluent. The result was 0.61 g of the target compound as a pale yellow foam.

IR _max (nujol): 1710, 1680, 1640, 1605 cm ^-1 .

¹ H NMR (270 MHz), δ: 3.62 (3H, s), 3.78 (3H, s), 6.73-8.0 (13H, m), 7.47 (1H, s) m .d.

 PRI me R 33. This example illustrates the preparation of (E) -methyl-2- [2- (3-pyridin-2-yloxyphenoxy) phenyl] -3-methoxypropenoate (compound N 1 from table 2).

To a stirred solution of 2.0 g of (E) -methyl-2- [2- (3-hydroxyphenoxy) phenyl] -3-methoxypropenoate obtained as described in Example 1 in 0.2 ml of DMF was successively added 0.2 g of carbonate potassium, a catalytic amount of copper chloride and 1.94 g of 2-fluoropyridine. The resulting mixture was stirred for 3 hours at 130 ^C. After cooling, it was diluted with water and extracted twice with ether. The combined extracts were washed sequentially with an aqueous solution of sodium hydroxide, water and brine, then dried and concentrated. Chromatography using an ether / hexane mixture as eluent gave 1.68 g (67% yield) of the target compound as an orange-yellow oily liquid.

¹ H NMR (270 MHz), δ: 3.60 (3H, s), 3.73 (3H, s), 6.72-7.32 (10H, m), 7.48 (1H, s), 7.67 (1H, m), 8.19 (1H, m) ppm.

 PRI me R 34. This example illustrates the preparation of (E) -methyl-2- {2- [3- (6-chloropyridazin-3-yloxy) phenoxy] phenyl} -3-methoxypropenoate (compound N 130 from the table. 2).

To a stirred solution of 2.01 g of (E) -methyl-2- [2- (3-hydroxyphenoxy) phenyl] -3-methoxypropenoate, obtained as described in Example 1, in 30 ml of DMF was added successively 0.93 g of carbonate potassium, a catalytic amount of copper chloride and 1.0 g of 3,6-dichloropyridazine. The obtained mixture was stirred for 1 hour at 95 ^C. After cooling, it was diluted with water and extracted (twice) with ether. The combined extracts were washed sequentially with an aqueous solution of sodium hydroxide, water and brine, then dried and concentrated. Chromatography using an ether / hexane mixture as eluent gave 1.71 g (yield 62%) of the target compound as a yellow gum.

¹ H NMR (270 MHz), δ: 3.60 (3H, s), 3.73 (3H, s), 6.73-7.36 (9H, m), 7.46 (1H, m), 7.50 (1H, s) ppm.

 The following are examples of compositions prepared on the basis of the compounds in accordance with the present invention, which can be used for processing agricultural and horticultural crops. Such compositions are also the subject of the present invention. Percentages quoted are massive.

 PRI me R 35. An emulsion concentrate was prepared by mixing and then mixing the components until they are dissolved (%).

Compound N 212 from table 1 10
Benzene alcohol 30
Dodecylbenzenesulfonate
calcium 5
Nonylphenol Ethoxylate
(13 mol of ethylene oxide) 10
Alkylbenzenes 45
PRI me R 36. The active component was dissolved in methylene chloride and the resulting solution was sprayed onto granules of attappulgite clay (%). After evaporation of the solvent, a granular preparation was obtained.

Compound N 212 from table 1 5
Attapulgite granulate 95
PRI me R 37. The composition for dressing seeds was obtained by grinding and mixing the three components (%). Compound N 212 from table 1 50 Mineral oil 2 Kaolin 48
PRI me R 38. Powder for spraying was obtained by grinding and mixing the active component with talc (%). Compound N 212 from table 1 5 Talc 95
PRI me R 39. A suspension concentrate was prepared by grinding components in a ball mill with the formation of an aqueous suspension of the ground mixture (%) Compound N 212 from table 1 40 Sodium lignosulfonate 10 Bentonite clay 1 Water 49
The resulting composition can be used directly for spraying the seed material or for spraying after preliminary dilution with water.

 PRI me R 40. Wettable powder was obtained by mixing and subsequent grinding of the components to form a homogeneous mixture (%).

Compound N 212 from table 1 25
Sodium Lauryl Sulfate 2
Sodium Lignosulfonate 5
Silicon dioxide 25
Kaolin 43
PRI me R 41. The compounds of formula I were tested in relation to various fungal diseases of plant leaves. The tests were carried out as follows.

 The plants were grown in John Innes Potting Compost (N 1 or 2) in pots with a diameter of 4 cm. Preparations of the test compounds were prepared either by grinding in a ball mill with aqueous dispersol T, or by dissolving in acetone, or a mixture of acetone and ethanol and then diluting to the desired concentration immediately before use. In the case of leaf diseases with compositions (concentration of the active component, if not specified, 100 ppm), the leaves were sprayed or applied to the soil. When spraying the composition was applied in the maximum amount retained on the leaves. When they were introduced into the soil to the root system, the final concentration corresponded to approximately 40 ml of the active component calculated on dry soil. When processing cereals, Tween 20 was added to the compositions in such an amount that its final concentration was 0.05%.

 In most cases, the test compound was applied to the soil or the leaves were sprayed one or two days before the infection of the plant with the pathogen. The exception was experiments with Erysi phegraminis. In this case, the plants were infected 24 hours before treatment. Infection with leaf pathogens was carried out by spraying the leaves of test plants with spore suspensions. After infection, the plants were kept under conditions favorable for the development of the disease, until its obvious signs appeared, by which it was possible to assess the degree of its development. The time between infection and assessment of the degree of development of the disease ranged from 4 to 14 days, depending on the disease and environmental conditions.

 The degree of development of the disease was evaluated in points according to the following system: 4 = absence of the disease; 3 = disease from traces to 5% of untreated plants; 2 = disease 6-25% of untreated plants; 1 = disease 26-59% of untreated plants; 0 = disease 60-100% of untreated plants. The results are shown in table 6, the standards in table 7.

Claims (3)

1. The method of obtaining derivatives of propenic acid of the General formula

where A is hydrogen, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, hydroxy, phenoxy or C ₁ -C ₄ -alkylcarbonyl;
K is oxygen or sulfur;
X is oxygen, S (O) _n , NH, NR ₁ , CH ₂ , CHR ₂ , CO, CH ₂ CH ₂ , CH = CH, OCH ₂ , (CH ₂ ) _m O, CHR ₁ O, OCH ₂ O, S (O) _n CH ₂ , S (O) CH ₂ O, NR ₁ CH ₂ , COO, OOC, SO ₂ O, COCH ₂ O,
COCHR ₁ O, CONH, NHCO, NHSO ₂ , COS, SCO, N = N, CH ₂ OCO, CH ₂ SCO, CH ₂ NHCO, CH ₂ ON = CH, OCH ₂ CH ₂ O, NR ₁ N = CH, CH ₂ OCONH, CH = CHCH ₂ O, (R ₂ ) ₂ P ⁺ CH ₂ Q-, N (COR ₁ ), N = CH, CH (OH), CO ₂ CH ₂ , SCH ₂ O, NR ₁ CO, S (O) ₂ NH or CONR ₁ ;
R ₁ is C ₁ -C ₄ alkyl;
R ₂ is phenyl;
n is 0.1 or 2;
m is 1-5;
Q is a halide anion;
Z is phenyl (possibly monosubstituted with C ₁ -C ₆ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkyl, phenoxy, phenyl, amino, hydroxy, 1- (C ₁ -C ₄ alkoxycarbonyl) -2- (C ₁ -C ₄ alkoxy) vinyl, C ₁ -C ₄ alkalo halide,
or C ₁ -C ₄ alkoxycarbonyl, or mono- or disubstituted with halogen, nitro, C ₁ -C ₄ -alkyl or cyano), naphthyl, quinolinyl, pyridinyl (possibly monosubstituted with C ₁ -C ₄ -alkyl, C ₁ -C _4- alkoxycarbonyl, amino, halogen, nitro, C ₁ -C ₄ -alkylcarbonylamino, di- (C ₁ -C ₄ -alkylsulfonyl) amino or CH (O) NH, or mono- or disubstituted C ₁ -C ₄ -haloalkyl or a cyano group, or a disubstituted amino group and one of the cyano, halogen or C ₁ -C ₄ alkoxy groups, or a disubstituted nitro group and one of the cyano, halogen, di- (C ₁ -C ₄ -alkyl) amino or C ₁ -C ₄ - alkoxy groups, or substituted cyano group and two C ₁ -C ₄ -alkyl groups), pyrimidinyl (possibly monosubstituted with C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkylthio, cyano, nitro, phenyl, HO ₂ C, C ₁ -C ₄ alkoxycarbonyl or C ₁ -C ₄ alkylsulfonyl, or mono- or disubstituted C ₁ -C ₄ alkoxy, or mono-, di- or trisubstituted with halogen, or disubstituted with halogen and one of C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkylthio, or disubstituted C ₁ -C ₄ -alkyl and C ₁ -C ₄ haloalkyl), pyrazinyl (possibly monosubstituted with halogen or cyano or disubstituted with C ₁ -C ₄ -alkyl) , pyridazinyl (possibly monosubstituted C ₁ -C ₄ alkoxy, phenyl or aminocarbonyl, or mono- or disubstituted with halogen, or disubstituted with halogen and C ₁ -C ₄ -alkyl), benzothiazolyl, thienyl (possibly monosubstituted with pyrazolyl, which itself is disubstituted with C ₁ -C _4- alkyl and C ₁ -C ₄ -haloalkyl, or pyridinyl, which itself may be monosubstituted by nitro, or disubstituted by halogen), 1,2,4-triazolyl, quinoxaline (monosubstituted by halogen), 1,3,5- triazinyl (disubstituted by halogen or disubstituted by halogen and C ₁ -C ₄ -alkoxy), thiazolyl (possibly monosubstituted by nitro, or mono- or Disa eschenny C ₁ -C ₄ alkyl), benzoxazolyl, pyridinyl-N-oxide, thieno [2,3-d] pyrimidinyl, pyrrolyl (possibly monosubstituted C ₁ -C ₄ alkyl), isoxazolyl (monosubstituted C ₁ -C ₄ -alkyl), 1,3,4-thiadiazolyl, pyrazolyl (substituted with halogen and two C ₁ -C ₄ -alkyl groups) or 1,2,4-triazinyl (monosubstituted with phenyl), provided that when Z is unsubstituted phenyl, and X and K are both oxygen, then A is not hydrogen;
and their stereoisomers, characterized in that they interact in the presence of a base of compounds of the general formula

with a compound of the general formula

where one of L 'and L''is a leaving group and the other is KH;
W is ZX or a group that is converted to ZX by
a) interactions in the presence of a base of a compound of general formula
H

when X is oxygen, with a compound of the formula ZL;
or, when X is SO ₂ O, with a compound of the formula ZS O ₂ O;
or,
when X is CH ₂ O, with a compound of the formula ZCH ₂ L;
or,
when X is CO · O, with a compound of the formula ZCO · Hal;
or
b) interactions in the presence of a base of a compound of the formula
Lch

when X is OCH ₂ , with a compound of the formula ZOH;
or
when X is (C ₆ H ₅ ) ₂ P ⁺ CH ₂ O ^- and L is a halogen, with a phosphine of the formula Z (C ₆ H ₅ ) ₂ P;
or
when X is CO · OCH ₂ , with a compound of the formula Z CO · OH;
c) when X is CH = CH, reaction in the presence of a base of a compound of general formula
(R ₁ O) ₂ -

-CH

where R ₁ is C ₁ -C ₆ alkyl,
with a compound of formula Z CHO;
or
d) when X is CH = CH, the reaction of a compound of formula I, where X is (C ₆ H ₅ ) ₂ P ⁺ CHR ₂ Q ^- , is in series with a base and a carbonyl compound of formula Z CHO;
or
d) when X is CONH, interactions of a compound of the general formula

in the presence of a base with an acid halide of the formula Z CO · Q;
or
e) when X is CH (OH), an aldehyde reaction of the general formula

with Grignard reagent of formula Z MgHal;
or
g) when X is O · CO, the interaction of an acid chloride of the general formula

with a compound of formula Z OH in a suitable solvent in the presence of a base;
or
h) when X is OCH ₂ , the interaction of the compounds of General formula
HOCH

with a compound of formula ZL;
or
i) when X is N = N, interactions of a compound of the general formula
H

with a compound of the formula ZN ⁺ = NHal ^- ;
or
j) when X is NHSO ₂ , interactions of a compound of the general formula
Clso

with a compound of the formula
Z NH ₂ ;
where A, K and Z have the indicated meanings;
L is a cleaving group, preferably a halogen and oxygen atom, is HaI;
l) is a group of CH ₃ O. CH = C- (CO ₂ CH ₃ ) or half of CH ₂ CO ₂ CH ₃ , which can be converted into a similar group by reaction with methyl formate in the presence of a base and subsequent methylation under alkaline conditions. 2. The method according to claim 1, characterized in that the compounds of General formula

where Y 'is halogen,
subjected to interaction with phenol of the General formula

where A, X and Z have the indicated meanings,
in the presence of a base, or with a phenol salt of the specified formula in the presence of a catalyst, a copper salt or a mixture of a copper salt and metallic copper Priorities by feature:
01/22/88 at A - hydroxy, phenoxy, C ₁ -C ₄ -alkylcarbonyl; X is CH (C ₆ H ₅ ), C (= O) CH ₂ O, CH (OH), CO ₂ CH ₂ , COCH (C ₁ -C ₄ alkyl) O-, SCH ₂ O; K is oxygen; Z is unsubstituted phenyl or substituted with halogen;
03/17/88 at K - sulfur; X is oxygen, A is hydrogen, K is phenyl, Z is pyrimidinyl;
06/21/08 at A - hydrogen, X - Ph ₂ P ⁺ CH ₂ Br ^- , CH ₂ OCO; CH ₂ NHCO, CH ₂ SCO; K is oxygen; Z is phenyl;
09/08/08 at A - hydrogen, X - OCH ₂ O, S (O) CH ₂ O, CH ₂ ON = CH, (CH ₂ ) ₃ O, (CH ₂ ) ₅ O, OCH ₂ CH ₂ O, CH ₂ OCONH; K is oxygen, Z is phenyl.  09/15/87 - the remaining values of the radicals.