CN1153779A - 2-(4-pyrazoloxy-pyrimidin-5-yl) acetic acid derivatives - Google Patents

Abstract

The present invention relates to novel formula (I) 2-(4-pyrazolyloxy-pyrimidin-5-yl) acetic acid derivatives (in the formula, R ₁ , R ₂ , R ₃ , R ₄ and X are defined in the description) . Use of such compounds for controlling phytopathogenic fungi, compositions facilitating said use and processes for the preparation of compounds of formula (I).

Description

2-(4-Pyrazolyloxy-pyrimidin-5-yl)acetic acid derivatives

The present invention relates to novel 2-(4-pyrazolyloxy-pyrimidin-5-yl)acetic acid derivatives, their synthesis and the use of said compounds in controlling phytopathogenic bacteria.

式中R₁是氢，C_1-4烷基，C_1-4烷氧基，C_1-4烷硫基，C_3-6环烷基或二-C_1-4烷基氨基，R₂是氢，C_1-4烷基，C_1-4烷氧基，C_1-4烷硫基或二-C_1-4烷基氨基，R₃是氢或甲基，R₄是芳基，芳基-C_1-4烷基，杂芳基或杂芳基-C_1-4烷基，其中每个芳环均可任选地被取代，和X是CH或氮。It has now been found that the following compounds of formula (I) are surprisingly effective against phytopathogenic bacteria:

In the formula, R ₁ is hydrogen, C _1-4 alkyl, C _1-4 alkoxyl, C _1-4 alkylthio, C _3-6 cycloalkyl or di-C _1-4 alkylamino, R ₂ is hydrogen, C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio or di-C _1-4 alkylamino, R ₃ is hydrogen or methyl, R ₄ is aryl, Aryl-C _1-4 alkyl, heteroaryl or heteroaryl-C _1-4 alkyl, wherein each aromatic ring can be optionally substituted, and X is CH or nitrogen.

In the definition of a group of formula (I), alkyl is understood to include straight-chain and branched-chain alkyl. For example alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or sec-butyl. Alkoxy includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy or sec-butoxy. Alkylthio is methylthio, ethylthio, isopropylthio, propylthio, n-butylthio, isobutylthio, t-butylthio or sec-butylthio. Cycloalkyl means, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Dialkylamino means for example dimethylamino, diethylamino, dipropylamino, ethylmethylamino, ethylpropylamino, methylbutylamino, methylpropylamino or ethylbutylamino Amino. Aryl represents an aromatic hydrocarbon radical such as phenyl or naphthyl, preferably phenyl. The aryl groups may also be optionally substituted. Heteroaryl represents a 5- or 6-membered aromatic ring containing one, two or three ring atoms selected from nitrogen, oxygen and sulfur, which may also be fused to another heteroaryl or aryl. Heteroaryl groups are attached to oxygen bridges through ring carbon atoms. The heteroaryl can also be optionally substituted. Examples of heteroaryl are pyridyl, pyrimidinyl, thienyl, oxazolyl, oxadiazolyl, triazolyl, thiadiazolyl, furyl, isoxazolyl, thiazolyl, imidazolyl, pyridazinyl , quinolinyl, quinazolinyl, benzothienyl, benzofuryl, benzimidazolyl, pyrazolyl, benzothiazolyl, benzoxazolyl, etc. Arylalkyl preferably means phenylalkyl such as benzyl, phenylethyl, phenylpropyl or 1-phenylethyl. The aryl groups may also be optionally substituted. Heteroarylalkyl means containing one, two or three ring atoms selected from nitrogen, oxygen and sulfur and through an alkylene group such as -CH ₂ -, -CH ₂ -CH ₂ - or -CH(CH ₃ )-a 5- or 6-membered aromatic ring group connected to an oxygen bridge. The heteroaryl is attached to the alkylene group through a ring carbon atom. Examples of heteroarylalkyl groups are thienylmethyl, thienylethyl, furylmethyl, pyridylmethyl, pyrrolylmethyl and the like. The pyrazolyl ring can be attached to an oxygen bridge through the 3- or 4-position. However 3-pyrazolyl is preferred.

In groups combined with various other definitions, each definition has the meaning respectively assigned to the definition for that moiety.

The aforementioned aryl and heteroaryl groups may also be substituted. If aryl or heteroaryl is substituted, it is preferably substituted with one, two or three groups selected from the group consisting of: halogen, C _1-4 alkyl, C _1-4 alkoxy, C _1-4 haloalkane radical, C _1-4 haloalkoxy, C _2-8 acyl, benzoyl, C _1-4 alkylthio, cyano, phenyl, phenoxy, nitro, or the group -C(CH ₃ ) =NOC _1-4 alkyl. Halogen means fluorine, chlorine, bromine and iodine, with fluorine and chlorine being preferred. Haloalkyl refers to a linear or branched alkyl group that is monohalogenated to perhalogenated. Preferred alkyl groups are linear lower alkyl groups. Perfluorinated linear lower alkyl groups are preferred alkyl groups. Fluoro and chlorine are preferred halogens. Examples are trifluoromethyl, difluoromethyl, 2,2,2-trifluoroethyl or 2,2,3,3,3-pentafluoropropyl. Haloalkoxy refers to monohalogenated to perhalogenated alkoxy groups. Examples are difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy or 1,1,2,2-tetrafluoroethoxy. Examples of acyl groups are acetyl, propionyl, butyryl, isopropionyl, hexanoyl or octanoyl.

Preferred classes of compounds of formula (I) are compounds of formula (I) in which the substituents are defined as follows: a) _R is methyl, ethyl or cyclopropyl; or b) _R is methyl or methoxy or c) the pyrazole ring is connected to the oxygen bridge at the 3- or 4-position; or d) R ₄ is chlorophenyl, dichlorophenyl, fluorophenyl, methyl-chlorophenyl, trifluoromethylbenzene base,

Trifluoromethyl-chlorophenyl, difluoromethoxyphenyl, trifluoromethoxyphenyl, methylphenyl

or dimethylphenyl.

A further preferred class of compounds of formula (I) are compounds of formula (I) in which the substituents are defined as follows: R _{and R} are methyl, and _R is chlorophenyl, dichlorophenyl, fluorophenyl, Methyl-chlorophenyl, trifluoromethylphenyl, trifluoromethyl-chlorophenyl, difluoromethoxyphenyl, trifluoromethoxyphenyl, methylphenyl or dimethylphenyl.

Among such compounds of formula (I), those wherein X is CH are preferred.

Preferred specific compounds of formula (I) are: 2-[2,4-dimethyl-6-(1-(3-trifluoromethylphenyl)-1H)pyrazol-3-yloxy)pyrimidine -5-yl]-3-methoxymethyl acrylate; 2-[2,4-dimethyl-6-(1-(3,5-dimethylphenyl)-1H-pyrazole-4- 2-[2,4-dimethyl-6-(1-(5-chloro-2-methylphenyl)-1H -pyrazol-3-yloxy)pyrimidin-5-yl]-3-methoxymethyl acrylate; and 2-[2-methyl-4-methoxy-6-(1-(5-chloro -2-methylphenyl)-1H-pyrazol-3-yloxy)pyrimidin-5-yl]-3-methoxymethyl acrylate.

The double bond in the acrylic acid structure of the compound of formula (I) can be of E or Z formula. In this text, formulas E and Z are defined where specifically indicated. In all other cases a mixture of the two isomers is meant. As for the E and Z isomers obtained during the synthesis, they can be separated by known techniques such as crystallization, chromatography or distillation. Formula E is preferably obtained in the preparation described.

Compounds of formula (I) can be obtained by O-methylation of compounds of formula (II): In the formula, R ₁ , R ₂ , R ₃ , R ₄ and X are as defined above.

The O-methylation (II→I) can be carried out by methods known per se for the preparation of 3-methoxyacrylates with customary methylating agents. Examples of suitable methylating agents include methyl iodide and dimethyl sulfate. O-methylation is preferably carried out in the presence of a base. The reaction temperature is conveniently in the range of 0°C to the boiling point of the reaction mixture, for example about ambient temperature. Inert solvents can be used if desired. Examples of suitable bases include alkali metal hydrides such as sodium hydride, alkali metal alcoholates such as sodium methoxide or alkali metal carbonates. Examples of suitable inert solvents include aromatic hydrocarbons such as benzene and toluene; ethers such as diethyl ether, tetrahydrofuran and 1,2-dimethoxyethane; polar solvents such as dimethylformamide, dimethylsulfoxide, Alcohols such as methanol; acetone or mixtures of two or more thereof. The desired end product is isolated and purified according to known techniques, eg by evaporation of the solvent, chromatography and crystallization.

The compounds of formula (I) are only slightly basic in nature and they form salts with sufficiently strong acids such as HCl and HBr.

X is the compound of formula (II) CH can be obtained by reaction of compound of formula (III) with formylating agent such as N,N-diformylmethylamine or methyl formate in the presence of a base; said compound of formula (III) as follows: In the formula, R ₁ , R ₂ , R ₃ and R ₄ are as defined above, and the alkyl group is a C _1-10 alkyl group.

This reaction is essentially a Claisen reaction and can be performed under known conditions for such reactions. The reaction [(III)→(II)] can be carried out in an inert solvent. Examples of suitable solvents are as described for the O-methylation of compounds of formula (II). Examples of suitable bases are bases commonly used in Claisen reactions, eg alkali metal alcoholates such as sodium methoxide, alkali metal hydrides such as sodium hydride, and lithium or sodium amides such as lithium diethylamide. The reaction temperature can vary within a wide range, for example from 0°C to the boiling point of the reaction mixture, preferably around ambient temperature.

式中R₁、R₂和R₃的定义同上。In another method, the compound of formula (II) can also be obtained by reacting the compound of formula (III) with a 1:1 adduct of dimethylformamide and dimethyl sulfate in the presence of a strong base such as t-BuOK , and the obtained intermediate of formula (IIIa) is hydrolyzed:

In the formula, R ₁ , R ₂ and R ₃ have the same definitions as above.

A variant of this reaction is preferably carried out in an inert solvent at a temperature of from -70°C to -30°C, most preferably from -60°C to -40°C. Suitable solvents are ethers such as tetrahydrofuran, dioxane, diethyl ether or glyme. Suitable bases are, for example, alkali metal alcoholates such as t-BuOK; or basic hydrides such as NaH, KH. The hydrolysis step is generally carried out in a two-phase system by adding water and at a temperature between 0°C and +40°C, preferably at room temperature.

Compounds of formula (II) where X is nitrogen can be obtained by reacting compounds of formula (III) with an alkyl nitrite in the presence of a base and optionally an inert solvent. In a variant of this process, the compound of formula (II) where X is N can also be obtained by reacting the compound of formula (III) with an alkyl nitrite in the presence of hydrochloric acid and optionally an inert solvent. The reaction temperature is preferably in the range of -40°C to +30°C, for example about -20°C to 0°C. Inert solvents can be used, if desired. Examples of suitable bases include alkali metal hydrides such as sodium hydride and alkali metal alcoholates such as potassium t-butoxide. Examples of suitable inert solvents include aromatic hydrocarbons such as benzene and toluene; ethers such as diethyl ether, tetrahydrofuran and 1,2-dimethoxyethane; polar solutions such as dimethylformamide, dimethylsulfoxide, alcohols such as tert-butanol; or mixtures of two or more thereof.

In a variant of the two-step process [(III)→(II)→(I)], the compound of formula (I) can be obtained from the compound of formula (III) through a one-pot reaction without going through the intermediate of formula (II) Isolation and purification of compounds.

式中R₃和R₄的定义同上。适宜的碱和溶剂与用于[(II)→(I)]的相同。Formula (III) acetate can be by formula (IV) compound (In the formula, R _{and R} are as defined above), and obtained by reacting with the following formula (V) or (VI) hydroxy-pyrazole in the presence of a base and an inert solvent:

In the formula, _R3 and _R4 are as defined above. Suitable bases and solvents are the same as for [(II)→(I)].

Compounds of formula (IV) in which R ₂ is hydrogen, alkyl, alkoxy or dialkylamino are known, see EP-A-634495 and EP-A-667343.

_R Be the formula (IV) compound of alkylthio group and obtain by making formula (VII) compound react with formula (VIII) thiol in the presence of base; Said formula (VII) is as follows: In the formula, R ₁ is defined as above; the formula (VIII) is as follows:

R ₂ in formula HSR ₂ (VIII) is as defined above.

The reaction is best carried out in an inert solvent such as an ether such as glyme (dimethoxyethane). Suitable bases are sodium hydride, sodium methoxide and the like. In a preferred variant, the base is first reacted with the thiol to form the sodium salt, which can then be reacted with the compound of formula (VII) in the absence of the base.

式中R₁、R₃和R₄的定义同上；所述式(X)化合物如下：Alternatively, R ₂ is C _1-4 alkoxy or di-C _1-4 alkylamino formula (III) intermediates can be obtained by first making the starting material formula (VII) dichloropyrimidinyl acetate with Formula (V) or (VI) hydroxypyrazole reaction, then make the resulting formula (IX) intermediate react with the formula (X) compound in the presence of a base; the formula (IX) is as follows:

In the formula, R ₁ , R ₃ and R ₄ have the same definitions as above; the compound of formula (X) is as follows:

In the formula HR ₂ (X), R ₂ is C _1-4 alkoxy or di-C _1-4 alkylamino.

The reaction conditions of this synthetic variant method [(VII)+(V)/(VI)→(IX)+(X)→(III)] are similar to those used for the reaction of (VII) and (VIII).

Intermediates of formula (II), (III) and (IX) have been especially developed for the synthesis of compounds of formula (I). They therefore form part of the present invention.

The starting materials of the formulas (IV), (V), (VI), (VII) and (VIII) are known or can be prepared analogously to known methods.

Compounds of formula (V) in which R ₄ is optionally substituted aryl or heteroaryl are best obtained by using novel oxidation methods which have been specially developed for the synthesis of compounds of formula (I). It is therefore part of the invention.

A novel oxidation process for the preparation of compounds of formula (V) in which R ₄ is an optionally substituted aryl or heteroaryl group involves the use of a parent aryl- or heteroaryl pyrazolidinone of formula (XI) by H _{2 O} and oxidant oxidation prepared in situ by catalyst; the formula (XI) is as follows: where _R4 is optionally substituted aryl or heteroaryl.

This oxidation step [(XI)→(V)] is best carried out in an inert solvent such as formic acid or acetic acid at low temperature. Preferably, the exothermic oxidation process is controlled by cooling, or by adding an oxidizing agent. The temperature is preferably kept below +50°C, especially in the range of 0°C to +30°C. _A suitable oxidizing agent is _H2O2 in the presence of an oxidation catalyst. Suitable oxidation catalysts are vanadyl acetylacetonate, copper(II) acetylacetonate, manganese oxide (MnO ₂ ), selenium oxide (SeO ₂ ), nickel oxide (NiO ₂ ), and the like.

The compounds of formula (I) are effective against phytopathogenic bacteria, including phytopathogenic fungi.

Its beneficial fungicidal activity was confirmed by in vivo tests with test concentrations of 0.1-500 mg a.i./l against the following fungi: Puccinia triticina on bean, Puccinia triticina on wheat, monofilament husk on cucumber , Erysiophora graminearum on wheat and barley, Erysiophora graminearum on apples, L. viticola on grape vines, Leptosphaeria nodorum on wheat, Sporosphaeria graminearum and Sclerotinia tritici on barley, Scrub apples on apples, Phytophthora infestans on tomatoes, and Plasmopara viticola on grapevines.

Many compounds of formula (I) have excellent plant tolerance and systemic action. The compounds according to the invention are therefore suitable for the treatment of plants, seeds and soil against phytopathogenic fungi, for example of the order Basidiomycetes of the order Rusts (rusts) such as Puccinia, Camelopsis, Monocystis; and Erysiphales of the class Ascomycetes (Erysimycetes) such as Erysipha spp., Monocystica spp., Unceria spp., Septoria spp.; and the spp. Coccomycetes; Micrococcomyces; Deuteromycetes such as Pyricularia, Thinicoderma (Poororium), Botrytis; and Oomycetes such as Phytophthora, Plasmodium.

The compounds of formula (I) are particularly effective against powdery mildew and rust, Sclerotinia and Chlorococcus fungi, especially against pathogens of monocotyledonous plants such as cereals including wheat and barley.

The amount of the compound according to the invention depends on various factors, such as the compound used, the object to be treated (plant, soil, seed), the form of the treatment (for example spraying, powdering, seed dressing), the purpose of the treatment (preventive or curative), The type of fungus to be treated and the time of application.

In general, in the case of plants or soil treatments, satisfactory results are obtained if the compounds of the invention are applied at rates of about 0.01-2.0 kg/ha, preferably about 0.02-1 kg/ha; 0.04-0.500 kg active ingredient (a.i.) per hectare for field crops such as cereal crops, or 4-50 ga.i. per well for crops such as fruit, grapes and vegetables (application volume 300-1000 l/ha, depending Depending on the size of the crop or leaf volume, this corresponds to an application rate of approximately 30-500 g/ha). If desired, repeated treatments may be performed, eg, at intervals of 8-30 days.

When the compounds of the present invention are used for seed treatment, satisfactory results are generally obtained when the compounds of the present invention are used in an amount of about 0.05-0.5 g/kg seed, preferably about 0.1-0.3 g/kg seed.

The term "soil" as used herein is intended to include any conventional growing medium, whether natural or man-made.

The compounds of the present invention can be used in various crops, such as soybeans, coffee, ornamental plants (especially geraniums, Rosaceae), vegetables (such as peas, cucumbers, celery, tomato and leguminous plants), sugar beets, sugar cane, Cotton, flax, corn, vineyards, pome and stone fruits (eg apples, pears, plums) and cereals (eg wheat, oats, barley, rice).

The present invention also provides a fungicidal composition comprising a compound of formula (I) as a fungicide and an agriculturally acceptable diluent (hereinafter referred to as diluent). They are obtained in a conventional manner, for example by mixing the compounds according to the invention with diluents and optionally additional ingredients such as surfactants.

The term "diluent" as used herein means an agriculturally acceptable liquid or solid substance which may be added to the active substance in order to make the active substance into an easier or better application form, respectively, the active substance The ingredients are diluted to the usable or desired active concentration. Examples of such diluents are talc, kaolin, diatomaceous earth, xylene or water.

In particular, formulations for use in spray form, such as water-dispersible concentrates or wettable powders, may contain surfactants, such as wetting and dispersing agents, such as condensation products of formaldehyde with naphthalenesulfonates, alkylarylsulfonates, salts, lignosulfonates, aliphatic alkyl sulfates, ethoxylated alkylphenols and ethoxylated fatty alcohols.

Generally, the formulations comprise 0.01-90% by weight active substance, 0-20% agriculturally acceptable surfactant and 10-99.99% diluent. Compositions in concentrated form, such as concentrated emulsions, will generally contain between about 2-90%, preferably 5-70%, by weight of active material. The application forms of the formulations generally contain 0.0005-10% by weight of the compound according to the invention as active substance. Typical spray suspensions may, for example, contain 0.0005-0.05, eg 0.0001, 0.002 or 0.005% by weight of active substance.

In addition to the usual diluents and surfactants, the composition of the invention can also contain additives for special purposes, such as stabilizers, deactivators (for solid preparations or carriers with active surfaces), for enhancing the resistance to plants. Adhesion agents, corrosion inhibitors, antifoam agents and colorants. In addition, fungicides with similar or auxiliary fungicidal activity may also be present in the formulation, such as sulfur, chlorothalonil, fenzamid; guanidine fungicides such as biguanide salts; dithiocarbamates Such as mancozeb, maneb, zinc, zinc methyl; trichloromethane sulphenyl-phthalimides (trichloromethane sulphenyl-phthalimides) and the like Dan and folpet; benzimidazole systemic fungicides such as carbendazim and benomyl; pyrroles such as cyproconazole, flusilazole, flutriafol, hexaconazole, propiconazole, tebuconazole, epoxiconazole, triticonazole, prochloraz; morpholine systemic Sexual fungicides such as fenpropimorph, fenpropidine or other substances that facilitate action such as cymoxanil, oxadixyl, metalaxyl; or insecticides.

Examples of phytofungicidal formulations are as follows: a. Wettable powder formulations

10 parts of a compound of formula (I) were mixed and ground to an average particle size of about 5 microns: 4 parts of synthetic fine silica, 3 parts of sodium lauryl sulfate, 7 parts of sodium lignosulfonate and 66 parts of finely divided Kaolin and 10 parts diatomaceous earth. Before use, the obtained wettable powder is diluted with water to form a spray liquid, and the spray liquid can be used by spraying on leaves and root irrigation. b. Granules

Spray 0.5 parts by weight of binder (nonionic surfactant) into 94.5 parts by weight of quartz sand in a drum mixer, and mix the whole material thoroughly. Then add 5 parts by weight of the compound of formula (I) of the present invention and continue to mix well to obtain granules with a particle size in the range of 0.3-0.7 mm (if desired, the granules can be made by adding 1-5% (by weight) of talcum powder) dry). The granules can be applied by incorporation into the soil surrounding the plants to be treated. c. Concentrated emulsion

10 parts by weight of the compound of formula (I) are mixed with 10 parts by weight of emulsifier and 80 parts by weight of xylene. The concentrated emulsion thus obtained is diluted with water to obtain an emulsion of the desired concentration before application. d. Seed dressing agent

45 parts of the compound of formula (I) were mixed with 1.5 parts of diamylphenol decaethylene glycol ether ethylene oxide adduct, 2 parts of spindle oil, 51 parts of fine talc and 0.5 part of colorant rhodamine B. The mixture was ground in a contraplex mill at 10000 rpm until a powder with an average particle size of less than 20 microns was obtained. The resulting dry powder has good adhesion and can be applied to seeds, for example by mixing in a slowly rotating container for 2-5 minutes.

The following examples further illustrate the invention. All temperatures are in degrees Celsius.

Example 1

2-[2,4-Dimethyl-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl]-3-methoxymethyl acrylate a) 2-[2,4-Dimethyl-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl]acetic acid methyl ester

Methyl (4-chloro-2,6-dimethyl-5-pyrimidinyl)acetate (5.0 g, 23 mmol), 1-phenyl-1H-pyrazol-3-one (3.73 g, 23 mmol) and carbonic acid A mixture of potassium (5.5 g, 40 mmol) in dimethylformamide (30 ml) was heated at +120°C for 2 hours. Water was added, extracted with ether and dried to give intermediate 2-[2,4-dimethyl-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl]acetic acid Methyl ester, as a yellow oil. ¹ H-NMR (CDCl ₃ ): 7.86 (d, 1H); 7, 67-7.20 (m, 5H); 6.32 (d, 2H); 3.80 (s, 2H); 3.70 (s, 3H); 2.57 ( s,3H); 2.36(s,3H).b)

The intermediate 2-[2,4-dimethyl-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl]acetic acid methyl ester (6.8g, 20mmol), A mixture of NaH (0.8 g, 80% suspension in oil, 25 mmol) and N,N-diformylmethylamine (5 ml) in dimethylformamide (40 ml) was stirred at 45°C for 2 hours. Dimethyl sulfate (2.4ml, 25mmol) was added at room temperature and stirring was continued for a further 2 hours. Diluted with ether, washed with brine, dried, and chromatographed on silica gel (eluent: ethyl acetate/hexane 1:1) to give 2-[2,4-dimethyl-6-(1-benzene Methyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl]-3-methoxyacrylate as a colorless oil. ¹ H-NMR (CDCl ₃ ): 7.86(d, 1H); 7.63(s, 1H); 7.67-7.20(m, 5H); 6.32(d, 1H); 3.88(s, 3H); 3H); 2.57(s, 3H); 2.36(s, 3H).

Example 2

a)2-[2-甲基-4-二甲氨基-6-(1-苯基-1H-吡唑-3-基氧基)-嘧啶-5-基]乙酸甲酯 2-Methoxyimino-[2-methyl-4-dimethylamino-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl]acetic acid methyl ester

a) 2-[2-Methyl-4-dimethylamino-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl]acetic acid methyl ester

Methyl (4,6-dichloro-2-methyl-pyrimidin-5-yl)acetate (5.43g, 23mmol), 1-phenyl-1H-pyrazol-3-one (3.73g, 23mmol) and A mixture of potassium carbonate (5.5 g, 40 mmol) in dimethylformamide (30 ml) was heated at +120°C for 30 minutes. Dimethylamine (10ml, 25% aqueous solution) was added at room temperature, stirred for 20 hours and worked up to give the intermediate 2-[2-methyl-4-dimethylamino-6-(1-phenyl-1H- Pyrazol-3-yloxy)-pyrimidin-5-yl]acetic acid methyl ester as an oil. b) 2-oximino-2-[2-methyl-4-dimethylamino-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl]acetic acid methyl ester 2-[2-Methyl-4-dimethylamino-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl]acetic acid methyl ester (8.0 g, 22 mmol) A solution of dimethoxyethane (20ml) was added to a solution of t-BuOK (7.3g, 65mmol) and t-BuONO (8ml) in dimethoxyethane (80ml) at -40°C. After stirring for 30 minutes, the mixture was quenched with ammonium chloride (aq, 75ml). The mixture was stirred for 2 hours, dried and chromatographed on silica gel (eluent: ethyl acetate/hexane 1:1) to give crystalline 2-oximino-2-[2-methyl-4-dimethyl amino-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl]acetic acid methyl ester. c)

2-oximino-2-[2-methyl-4-dimethylamino-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl]acetic acid methyl ester ( 3.5 g, 8.8 mmol) was added to a suspension of NaH (0.3 g, 10 mmol) in dimethylformamide (30 ml) and dimethyl sulfate (0.9 ml, 9.7 mmol). The mixture was stirred at room temperature for 2 hours. Diluted with ether, washed with brine, dried, and chromatographed on silica gel (eluent: ethyl acetate/hexane 1:1) to give 2-methoxyimino-2-[2-methyl-4 - Dimethylamino-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl]acetic acid methyl ester.

¹ H-NMR (CDCl ₃ ): 7.82 (d, 1H); 7.67-7.20 (m, 5H); 6.22 (d, 2H); 4.06 (s, 3H); 3.88

(s, 3H); 3.03(s, 6H); 2.41(s, 3H).

Example 3

a)2-[2，4-二甲基-6-(1-(2，6-二氯苄基)-1H-吡唑-3-基氧基)-嘧啶-5-基]乙酸甲酯

2-[2,4-Dimethyl-(1-(2,6-dichlorobenzyl)-1H-pyrazol-3-yloxy)-pyrimidin-5-yl]-3-methoxyacrylic acid methyl ester

a) 2-[2,4-Dimethyl-6-(1-(2,6-dichlorobenzyl)-1H-pyrazol-3-yloxy)-pyrimidin-5-yl]acetic acid methyl ester

Methyl (2,4-dimethyl-6-chloro-5-pyrimidinyl)acetate (0.5 g, 23 mmol), 1-(2,6-dichlorobenzyl)-1H-pyrazol-3-one (5.80g, 23mmol) and potassium carbonate (10.0g, 70mmol) in dimethylformamide (30ml) was heated at +130°C for 2 hours. Water was added, extracted with ether and dried to give the intermediate 2-[2,4-dimethyl-6-(1-(2,6-dichlorobenzyl)-1H-pyrazol-3-yloxy) -pyrimidin-5-yl]methyl acetate as a yellow oil. b)

The intermediate 2-[2,4-dimethyl-6-(1-(2,6-dichlorobenzyl)-1H-pyrazol-3-yloxy)-pyrimidin-5-yl]acetic acid methyl The ester (9.6g, 23mmol) was dissolved in dimethylformamide (20ml) and added to NaH (1.3g, 80% suspension in oil, 46mmol) and N,N-diformyl A suspension of methylamine (10ml) in dimethylformamide (40ml). The mixture was stirred at +45°C for 2 hours. Dimethyl sulfate (2.4ml, 25mmol) was added under cooling at room temperature and stirring was continued for a further 2 hours. Diluted with ether, washed with brine, dried, and chromatographed on silica gel (eluent: ethyl acetate/hexane 3:1) to give 2-[2,4-dimethyl-6-(1-( Methyl 2,6-dichlorobenzyl)-1H-pyrazol-3-yloxy)-pyrimidin-5-yl]-3-methoxyacrylate as a colorless oil (4.8 g).

¹ H-NMR (CDCl ₃ ): 7.59 (s, 1H); 7.39-7.23 (m, 3H); 7.19 (d, 1H); 6.04 (d, 1H);

5.54(s, 2H); 3.83(s, 3H); 3.67(s, 3H); 2.53(s, 3H); 2.33(s, 3H).

Example 4

2-[2,4-Dimethyl-6-(1-(2-methylphenyl)-1H-pyrazol-4-yloxy)-pyrimidin-5-yl]-3-methoxyacrylic acid methyl ester a) 2-[2,4-dimethyl-6-(1-(2-methylphenyl)-1H-pyrazol-4-yloxy)-pyrimidin-5-yl]acetic acid methyl ester

Methyl (4-chloro-2,6-dimethyl-5-pyrimidinyl)acetate (4.6 g, 21 mmol), 1-(2-methylphenyl)-1H-pyrazol-4-one (4.1 g, 23 mmol) and potassium carbonate (6.4 g, 46 mmol) in dimethylformamide (50 ml) was heated at +120°C for 2 hours. Water was added, extracted with ether and dried to give the intermediate 2-[2,4-dimethyl-6-(1-(2-methylphenyl)-1H-pyrazol-4-yloxy)-pyrimidine -5-yl] methyl acetate as an oil. ¹ H-NMR (CDCl ₃ ): 7.23-7.96 (m, 6H); 3.78 (s, 2H); 3.73 (s, 3H); 2.58 (s, 3H); 2.47 (s, 3H); 3H).b)

The intermediate 2-[2,4-dimethyl-6-(1-(2-methylphenyl)-1H-pyrazol-4-yloxy)-pyrimidin-5-yl]acetic acid methyl ester ( 6.0g, 17mmol), sodium hydride (0.9g, 37mmol) and N, N-diformylmethylamine (6ml) in dimethylformamide (20ml) and 1,2-dimethoxyethane (20ml ) was stirred at 45°C for 3 hours. Iodomethane (4.2 g, 30 mmol) was added at room temperature and stirring was continued for a further 16 hours. Diluted with ether, washed with brine, dried, and chromatographed on silica gel (eluent: ethyl acetate/hexane 3:7) to give 2-[2,4-dimethyl-6-(1-( Methyl 2-methylphenyl)-1H-pyrazol-4-yloxy)-pyrimidin-5-yl]-3-methoxyacrylate as a colorless oil. ¹ H-NMR (CDCl ₃ ): 7.26-7.95 (m, 6H); 3.90 (s, 3H); 3.74 (s, 3H); 2.59 (s, 3H); 2.38 (s, 3H); 3H).

Example 5

a)1-(2，5-二氯苯基)-3-吡唑烷酮

1-(2,5-Dichlorophenyl)-2-pyrazolone

a) 1-(2,5-dichlorophenyl)-3-pyrazolidinone

2,5-Dichlorophenylhydrazine hydrochloride (240 g, 1.1 mol) and acrylamide (100 g, 1.4 mol) in a solution of sodium (56 g, 2.4 mol) in ethanol (1000 ml) and toluene (1000 ml) were refluxed for 3 hours . The solvent was evaporated, acidified with acetic acid, diluted with water, filtered and dried (high vacuum, +100°C) to give 1-(2,5-dichlorophenyl)-3-pyrazolidinone. b)

Hydrogen peroxide (30% in water, 120ml) was added slowly to well stirred 1-(2,5-dichlorophenyl)-3-pyrazolidinone (200g, 0.86mol) and selenium dioxide (3.0g) Suspension in acetic acid (1000ml). Control the temperature by cooling so that it does not exceed +50°C. After stirring at this temperature for 1 hour, crushed ice and water were added. The product was filtered and dried to give 1-(2,5-dichlorophenyl)-3-pyrazolone, m.p. 201-202°C.

Example 6

1-Phenyl-3-pyrazolidinone

Phenylhydrazine (10.8 g, 0.1 mol) and acrylamide (7.8 g, 0.11 mol), powdered potassium hydroxide (12.5 g, 0.22 g) and a catalytic amount of tetrabutylammonium bromide were refluxed for 30 minutes. The precipitate was filtered off and washed with toluene. The crystalline solid was dissolved in water, acidified with acetic acid, filtered and dried to give 1-phenyl-3-pyrazolidinone.

 化合物序号  R₁  R₂  R₃  R₄ 物理数据¹H-NMR(CDCl₃)或/和m.p.  1.01  CH₃  CH₃  CH₃  2，3-二氯苯基 7.58(s，1H)；7.57-7.27(m，3H)；6.17(s，1H)；3.85(s，3H)；3.70(s，3H)；2.62(s，3H)；2.32(s，3H)；2.18(s，3H).m.p.169-171℃  1.02  CH₃  CH₃  CH₃  2-氯苯基 7.58(s，1H)；7.54-7.30(m，4H)；6.17(s，1H)；3.85(s，3H)；3.70(s，3H)；2.58(s，3H)；2.35(s，3H)；2.18(s，3H).m.p.135-137℃  1.03  CH₃  CH₃  CH₃ 2，4-二氯苯基 7.59(s，1H)；7.55-7.25(m，3H)；6.12(s，1H)；3.85(s，3H)；3.65(s，3H)；2.58(s，3H)；2.33(s，3H)；2.17(s，3H).  1.04  CH₃  CH₃  CH₃  2，5-二氯苯基 7.59(s，1H)；7.49-7.35(m，3H)；7.24(s，1H)；6.14(s，1H)；3.85(s，3H)；3.68(s，3H)；2.58(s，3H)；2.32(s，3H)；2.18(s，3H).m.p.142-144℃  1.05  CH₃  CH₃  CH₃  2，6-二氯苯基 7.59(s，1H)；7，47-7.23(m，3H)；6.18(s，1H)；3.83(s，3H)；3.68(s，3H)；2.57(s，3H)；2.33(s，3H)；2.12(3，3H).  1.06  CH₃  CH₃  CH₃  2，4，5-三氯苯基 7.65(s，1H)；7.62-7.40(m，2H)；6.14(s，1H)；3.86(s，3H)；3.69(s，3H)；2.58(s，3H)；2.34(s，3H)；2.18(s，3H).  1.07  CH₃  CH₃  CH₃  2，4，6-三氯苯基 7.59(s，1H)；7.43(s，2H)；6.18(s，1H)；3.84(s，3H)；3.68(s，3H)；2.55(s，3H)；2.33(s，3H)；2.12(s，3H).  1.08  CH₃  CH₃  CH₃  2-CF₃-苯基 7.52(s，1H)；7.76-7.34(m，3H)；6.06(s，1H)；3.79(s，3H)；3.63(s，3H)；2.52(s，3H)；2.29(s，3H)；2.04(s，3H).m.p.143-144℃  1.09  CH₃ CH₃  CH₃ 2-氟苯基 7.59(s，1H)；7.52-7.18(m，3H)；6.13(s，1H)；3.87(s，3H)；3.70(s，3H)；2.59(s，3H)；2.34(s，3H)；2.22(s，3H).  1.10  CH₃  CH₃  CH₃  2-甲基-5-氯苯基 7.59(s，1H)；7.34-7.22(m，3H)；6.10(s，1H)；3.86(s，3H)；3.69(s，3H)；2.58(s，3H)；2.33(s，3H)；2.09(s，3H).m.p.139-141℃  1.11  CH₃  CH₃  CH₃  苯基 7.59(s，1H)；7.48-7.32(m，5H)；6.09(s，1H)；3.85(s，3H)；3.69(s，3H)；2.58(s.3H)；2.33(s，3H)；2.22(s，3H).

 1.19  CH₃  CH₃  H  3-甲氧基苄基 7.59(s，1H)；7.24(d，1H)；7.22-6.78(m，4H)；6.07(d，1H)；5.17(s，2H)；3.84(s，3H)；3.78(s，3H)；3.70(s，3H)；2.57(s，3H)；2.35(s，3H).  1.20  CH₃  CH₃  H  4-甲氧基苄基 7.60(s，1H)；7.24(d，1H)；7.22-6.84(m，4H)；6.07(d，1H)；5.15(s，2H)；3.85(s，3H)；3.80(s，3H)；3.70(s，3H)；2.56(s，3H)；2.35(s，3H).  1.21  CH₃  N(CH₃)₂  H  苯基  1.22  CH₃  CH₃  CH₃  2-氰基苯基 7.80-7.48(m，4H)；7.59(s，1H)；6.20(s，1H)；3.85(s，3H)；3.70(s，3H)；2.58(s，3H)；2.37(s，3H)；2.30(s，3H).m.p.154-156℃  1.23  CH₃  CH₃  CH₃  3-氯苯基 7.60(s，1H)；7.52-7.32(m，4H)；6.10(s，1H)；3.85(s，3H)；3.69(s，3H)；2.58(s，3H)；2.39(s，3H)；2.37(s，3H).m.p.135-136℃  1.24  CH₃  CH₃  CH₃ 3-CF₃-苯基 7.79-7.57(m，4H)；7.59(s，1H)；6.13(s，1H)；3.87(s，3H)；3.70(s，3H)；2.58(s，3H)；2.40(s，3H)；2.37(s，3H).  1.25  CH₃  CH₃  CH₃  2-硝基苯基 8.00(dd，1H)；7.75-7.54(m，3H)；7.59(s，1H)；6.16(s，1H)；3.85(s，3H)；3.70(s，3H)；2.59(s，3H)；2.37(s，3H)；2.22(s，3H).m.p.110-111℃  1.26  CH₃  CH₃  CH₃ 2-甲氧基-5-氯苯基 7.59(s，1H)；7.40-6.91(m，3H)；6.08(s，1H)；3.86(s，3H)；3.80(s，3H)；370(s，3H)；2.60(s，3H)；2.37(s，3H)；2.18(s，3H).m.p.140-141℃   1.27   CH₃   CH₃   H   2-甲基苯基 7.62(s，1H)；7.50(d，1H)；7.38-7.22(m，4H)；6.33(d，1H)；3.85(s，3H)；3.70(s，3H)；2.57(s，3H)；2.36(s，3H)；2.31(s，3H).m.p.160-161℃   1.28   CH₃   CH₃   CH₃   3，4二氯苯基 7.63-7.33(m，3H)；7.62(s，1H)；6.12(s，1H)；3.86(s，3H)；3.70(s，3H)；2.58(s，3H)；2.40(s，3H)；2.37(s，3H).m.p.126-129℃   1.29   CH₃   CH₃   CH₃   3-硝基苯基 8.38-7.62(m，4H)；7.60(s，1H)；6.17(s，1H)；3.88(s，3H)；3.73(s，3H)；2.60(s，3H)；2.47(s，3H)；2.37(s，3H).m.p.146-147℃   1.30   CH₃   CH₃   CH₃   3-CF₃-4-氯苯基 7.83-7.57(m，3H)；7.60(s，1H)；6.14(s，1H)；3.85(s，3H)；3.70(s，3H)；2.58(s，3H)；2.40(s，3H)；2.37(s，3H).m.p.125-128℃   1.31   CH₃   OCH₃   H   2-氯苯基 7.82(d，1H)；7.63-7.23(m，4H)；7.56(s，1H)；6.30(d，1H)；3.97(s，3H)；3.82(s，3H)；3.67(s，3H)；2.50(s，3H)m.p.123-125℃   1.32   CH₃   OCH₃   CH₃ 2-氯苯基 7.55(s，1H)；7.54-7.30(m，4H)；6.07(s，1H)；3.93(s，3H)；3.80(s，3H)；3.64(s，3H)；2.50(s，3H)；2.15(s，3H).m.p.141-142℃   1.33   CH₃   OCH₃   H   2-甲氧基苄基 7.53(s，1H)；7.33-6.84(m，5H)；6.02(d，1H)；5.20(s，2H)；3.93(s，3H)；3.83(s，3H)；3.80(s，3H)；3.67(s，3H)；2.47(s，3H).m.p.110-112℃

 1.73   CH₃   OCH₃   H   3-CF₃-苯基 7.96-7.47(m，6H)；6.33(d，1H)；3.96(s，3H)；3.86(s，3H)；3.70(s，3H)；2.50(s，3H).m.p.152-154℃.  1.74   CH₃   OCH₃   H   2，5-二氯苯基 7.90(d，1H)；7.70-7.23(m，4H)；6.33(d，1H)；3.96(s，3H)；3.84(s，3H)；3.70(s，3H)；2.53(s，3H).  1.75   H   CH₃   H 3-CF₃-苯基 8.64(s，1H)；7.95(d，1H)；7.82-7.50(m，5H)；6.33(d，1H)；3.93(s，3H)；3.73(s，3H)；2.42(s，3H).m.p.153-155℃.  1.76   CH₃   OCH₃   H   5-氯-2-甲基苯基 7.57(s，1H)；7.50(d，1H)；7.40-7.18(m，3H)；6.28(d，1H)；3.95(s，1H)；3.83(s，3H)；3.70(s，3H)；2.50(s，3H)；2.32(s，3H).m.p.102-106℃.  1.77   CH₃   CH₃   CH₃ 3-氯-2-甲基苯基 7.60(s，1H)；7.46-7.19(m，3H)；6.08(s，1H)；3.83(s，3H)；3.70(s，3H)；2.58(s，3H)；2.37(s，3H)；2.10(2s，6H).m.p.157-159℃.  1.78   CH₃   CH₃   CH₃   4-氯-2-甲基苯基 7.60(s，1H)；7.32-7.20(m，3H)；6.04(s，1H)；3.84(s，3H)；3.70(s，3H)；2.57(s，3H)；2.36(s，3H)；2.10(2s，6H).  1.79   CH₃   OCH₃   CH₃   3-氯苯基 7.56(s，1H)；7.50-7.26(m，4H)；6.04(s，1H)；3.93(s，3H)；3.83(s，3H)；3.68(s，3H)；2.53(s，3H)；2.38(s，3H).  1.80   CH₃   OCH₃   CH₃   4-氯苯基 7.52(s，1H)；7.38(s，4H)；6.03(s，1H)；3.94(s，3H)；3.82(s，3H)；3.66(s，3H)；2.51(s，3H)；2.36(s，3H). 1.81  CH₃  OCH₃  CH₃  3，4-二氯苯基 7.63-7.30(m，4H)；6.05(s，1H)；3.93(s，3H)；3.82(s，3H)；3.67(s，3H)；2.53(s，3H)；2.38(s，3H).m.p.147-148℃. 1.82  CH₃  OCH₃  CH₃  2，3-二氯苯基 7.60-7.27(m，4H)；6.08(s，1H)；3.92(s，3H)；3.81(s，3H)；3.64(s，3H)；2.50(s，3H)；2.15(s，3H).m.p.147-150℃. 1.83  CH₃  OCH₃  CH₃  3,5-二氯苯基 7.52(s，1H)；7.40-7.28(m，3H)；6.03(s，1H)；3.93(s，3H)；3.80(s，3H)；3.66(s，3H)；2.48(s，3H)；2.38(s，3H).m.p.160-161℃. 1.84  CH₃  OCH₃  CH₃  4-氯-2-甲基苯基 7.52(s，1H)；7.32-7.20(m，3H)；6.02(s，1H)；3.90(s，3H)；3.83(s，3H)；3.67(s，3H)；2.50(s，3H)；2.15(2s，6H).m.p.140-143℃. 1.85  CH₃  OCH₃  CH₃  3-氯-2-甲基苯基 7.52(s，1H)；7.45-7.20(m，3H)；6.03(s，1H)；3.93(s，3H)；3.82(s，3H)；3.68(s，3H)；2.50(s，3H)；2.15(s，3H)；2.14(s，3H).m.p.147-149℃ 1.86  CH₃  OCH₃  CH₃  2，4-二氯苯基 7.52-7.30(m，4H)；6.08(s，1H)；3.95(s，3H)；3.80(s，3H)；3.68(s，3H)；2.53(s，3H)；2.17(s，3H). 1.87  CH₃  OCH₃  CH₃ 5-氯-2-甲基苯基 7.54(s，1H)；7.34-7.20(m，3H)；6.03(s，1H)；3.92(s，3H)；3.80(s，3H)；3.67(s，3H)；2.52(s，3H)；2.15(2s，6H). 1.88  CH₃  CH₃  CH₃ 3-溴苯基 7.65-7.30(m，5H)；6.10(s，1H)；3.87(s，3H)；3.70(s，3H)；2.59(s，3H)；2.38(s，3H)；1.36(s，3H)；m.p.141-142℃. 1.89  CH₃  CH₃  CH₃  4-溴苯基 7.60(s，1H)；7.57-7.30(m，4H)；6.10(s，1H)；3.85(s，3H)；3.70(s，3H)；2.58(s，3H)；2.38(2s，6H). 1.90  CH₃  OCH₃  CH₃ 3-溴苯基 7.64-7.26(m，5H)；6.06(s，1H)；3.97(s，3H)；3.83(s，3H)；3.69(s，3H)；2.53(s，3H)；2.38(s，3H). 1.91  CH₃  OCH₃  H 3-溴苯基 7.86-7.24(m，5H)；6.30(d，1H)；3.97(s，3H)；3.86(s，3H)；3.70(s，3H)；2.53(s，3H).m.p.144-145℃. 1.92  CH₃  OCH₃  H 4-甲基苯基 7.78(d，1H)；7.57-7.17(m，5H)；6.23(d，1H)；3.97(s，3H)；3.88(s，3H)；3.70(s，3H)；2.52(s，3H)；2.38(s，3H). 1.93  CH₃  CH₃  H  4-溴苯基 7.80(d，1H)；7.57(s，1H)；7.55(s，4H)；6.28(d，1H)；3.97(s，3H)；3.86(s，3H)；3.70(s，3H)；2.53(s，3H). 1.94  CH₃  OCH₃  H 2，5-二甲基苯基 7.56(s，1H)；7.48(d，1H)；7.08-7.02(m，3H)；6.23(d，1H)；3.96(s，3H)；3.84(s，3H)；3.70(s，3H)；2.52(s，3H)；2.38(s，3H)；2.25(s，3H).m.p.86-87℃. 1.95  CH₃  CH₃  H  3-溴苯基 7.84(d，1H)；7.62(s，1H)；7.57-7.26(m，4H)；6.33(d，1H)；3.87(s，3H)；3.70(s，3H)；2.58(s，3H)；2.38(s，3H).m.p.120-122℃. 1.96  CH₃  CH₃  H  4-溴苯基 7.83(d，1H)；7.63(s，1H)；7.53(s，4H)；6.33(d，1H)；3.87(s，3H)；3.70(s，3H)；2.58(s，3H)；2.38(s，3H).m.p.141-142℃.   1.97   CH₃   CH₃   H   4-甲基苯基   7.81(d，1H)；7.62(s，1H)；7.50-7.19(m，4H)；6.29(d，1H)；3.87(s，3H)；3.70(s，3H)；2.58(s，3H)；2.38(2s，6H)，m.p.121-122℃.   1.98   CH₃   CH₃   H 2，5-二甲基苯基   7.60(s，1H)；7.52(d，1H)；7.17-7.03(m，3H)；6.28(d，1H)；3.84(s，3H)；3.70(s，3H)；2.58(s，3H)；2.38(s，3H)；2.37(s，3H)；2.30(s，3H).   1.99   CH₃   CH₃   CH₃ 3，5-二甲基苯基   7.60(s，1H)；7.06(s，2H)；6.96(s，1H)；6.06(s，1H)；3.84(s，3H)；3.70(s，3H)；2.59(s，3H)；2.37(4s；12H).m.p.143-144℃. 表2

化合物序号  R₁  R₂  R₃  R₄ 物理数据¹H-NMR(CDCl₃)或/和m.p. 2.01  CH₃  CH₃  CH₃  2，3-二氯苯基 2.02  CH₃  CH₃  CH₃  2-氯苯基 2.03  CH₃  CH₃  CH₃  2，4-二氯苯基 表3 化合物序号 R₁  R₂  R₄ 物理数据¹H-NMR(CDCl₃)或/和m.p. 3.01  CH₃  CH₃ 2，3-二氯苯基 7.22-8.19(m，5H)；3.92(s，3H)；3.76(s，3H)；2.62(s，3H)；2.37(s，3H). 3.02  CH₃  CH₃ 2-氯苯基 7.26-8.21(m，6H)；3.93(s，3H)；3.76(s，3H)；2.62(s，3H)；2.38(s，3H). 3.03  CH₃  CH₃ 2，4-二氯苯基 7.28-8.20(m，5H)；3.91(s，3H)；3.77(s，3H)；2.61(s，3H)；2.38(s，3H). 3.04  CH₃  CH₃ 2，5-二氯苯基 7.24-8.23(m，5H)；3.93(s，3H)；3.78(s，3H)；2.59(s，3H)；2.37(s，3H). 3.05  CH₃  CH₃ 2，6-二氯苯基 7.26-7.97(m，5H)；3.88(s，3H)；3.75(s，3H)；2.60(s，3H)；2.37(s，3H). 3.06  CH₃  CH₃  2-甲基苯基 7.26-7.95(m，6H)；3.90(s，3H)；3.74(s，3H)；2.59(s，3H)；2.38(s，3H)；2.33(s，3H). 3.07  CH₃  CH₃  2-异丙基苯基 7.24-7-96(m，6H)；3.94(s，3H)；3.77(s，3H)；3.03(m，1H)；2.59(s，3H)；2.38(s，3H)；1.23(s，3H)；1.20(s，3H).   3.08  CH₃  CH₃  2-CF₃-苯基 7.56-8.18(m，6H)；3.92(s，3H)；3.73(s，3H)；2.63(s，3H)；2.37(s，3H).   3.09  CH₃  CH₃  2-甲氧基苯基 7.03-8.28(m，6H)；3.90(s，3H)；3.77(s，3H)；2.60(s，3H)；2.38(s，3H)；2.04(s，3H).   3.10  CH₃  CH₃  2-甲基-5-氯苯基 7.22-7-93(m，5H)；3.90(s，3H)；3.74(s，3H)；2.61(s，3H)；2.38(s，3H)；2.31(s，3H).   3.11  CH₃  CH₃  苯基 7.24-8.21(m，7H)；3.92(s，3H)；3.75(s，3H)；2.61(s，3H)；2.38(s，3H).   3.12  CH₃  CH₃  3-甲基苯基 6.84-7.59(m，6H)；3.90(s，3H)；3.74(s，3H)；2.51(s，3H)；2.38(s，3H).   3.13  CH₃  CH₃ 2-氯-4-甲基苯基 7.16-8.13(m，5H)；3.94(s，3H)；3.78(s，3H)；2.59(s，3H)；2.50(s，3H)；2.39(s，3H).   3.14  CH₃  CH₃  2-氰基-4-氯苯基 7.63-8.59(m，5H)；3.81(s，3H)；3.76(s，3H)；2.62(s，3H)；2.53(2，3H).   3.15  CH₃  CH₃  3-CF₃-苯基 7.49-8.21(m，6H)；3.92(s，3H)；3.74(s，3H)；2.63(s，3H)；2.38(s，3H).   3.16  CH₃  CH₃  4-氯苯基 7.39-8.12(m，6H)；3.89(s，3H)；3.72(s，3H)；2.61(s，3H)；2.37(s，3H).   3.17  CH₃  CH₃ 2-氰基苯基 7.40-8.58(m，6H)；3.92(s，3H)；3.75(s，3H)；2.62(s，3H)；2.37(s，3H).   3.18  CH₃  CH₃ 2-甲基-3-氯苯基 7.20-7.89(m，5H)；3.92(s，3H)；3.74(s，3H)；2.59(s，3H)；2.37(s，3H)；2.28(s，3H). 3.19  CH₃  CH₃ 2-甲基-4-氯苯基 7.22-7.87(m，5H)；3.93(s，3H)；3.76(s，3H)；2.60(s，3H)；2.39(s，3H)；2.34(s，3H). 3.20  CH₃  CH₃ 2，3-二甲基苯基 7.17-7.86(m，5H)；3.91(s，3H)；3.76(s，3H)；2.60(s，3H)；2.38(s，6H)；2.15(s，3H). 3.21  CH₃  CH₃  2，6-二甲基苯基 7.06-7.64(m，5H)；3.91(s，3H)；3.73(s，3H)；2.44(s，3H)；2.37(s，3H)；2.08(s，6H). 3.22  CH₃  CH₃ 2-甲基-6-氯苯基 7.28-7.91(m，5H)；3.94(s，3H)；3.76(s，3H)；2.61(s，3H)；2.39(s，3H)；2.17(s，3H). 3.23  CH₃  CH₃  4-甲基苯基 7.23-8.11(m，6H)；3.91(s，3H)；3.75(s，3H)；2.61(s，3H)；2.39(s，3H)；2.36(s，3H). 3.24  CH₃  CH₃ 2-乙基苯基 6.98-7.63(m，6H)；3.89(s，3H)；3.74(s，3H)；2.71(s，3H)；2.48(s，3H)；2.37(s，3H)；1.12(t，3H). 3.25  CH₃  CH₃ 2-氟苯基 7.20-8.27(m，6H)；3.93(s，3H)；3.74(s，3H)；2.61(s，3H)；2.38(s，3H). 3.26  CH₃  CH₃ 2-联苯基 7.17-7.64(m，11H)；3.83(s，3H)；3.62(s，3H)；2.47(s，3H)；2.30(s，3H). 3.27  CH₃  CH₃ 3，4-二氯苯基 7.55-8.32(m，5H)；3.91(s，3H)；3.73(s，3H)；2.62(s，3H)；2.37(s，3H). 3.28  CH₃  CH₃  3，5-二氯苯基 7.23-8.18(m，5H)；3.91(s，3H)；3.73(s，4H)；2.63(s，3H)；2.38(s，3H) 3.29  CH₃  CH₃  4-甲基-3-氯苯基 7.19-8.08(m，5H)；3.87(s，3H)；3.72(s，3H)；2.63(s，3H)；2.36(s，3H)；2.30(s，3H). 3.30  CH₃  CH₃  3-氰基苯基 7.58-8.22(m，6H)；3.91(s，3H)；3.75(s，3H)；2.63(s，3H)；2.39(s，3H). 3.31  CH₃  CH₃  3-氯苯基 7.25-8.17(m，6H)；3.92(s，3H)；3.74(s，3H)；2.61(s，3H)；2.39(s，3H). 3.32  CH₃  CH₃  3-氟苯基 6.96-8.18(m，6H)；3.91(s，3H)；3.74(s，3H)；2.62(s，3H)；2.39(s，3H). 3.33  CH₃  CH₃  3-甲氧基苯基 6.82-8.17(m，6H)；3.92(s，3H)；3.89(s，3H)；3.75(s，3H)；2.60(s，3H)；2.38(s，3H). 3.34  CH₃  OCH₃  2-甲基苯基 6.98-7.60(m，6H)；3.96(s，3H)；3.87(s，3H)；3.70(s，3H)；2.61(s，3H)；2.18(s，3H). 3.35  CH₃  OCH₃ 2，5-二氯苯基 7.24-8.19(m，5H)；3.98(s，3H)；3.87(s，3H)；3.73(s，3H)；2.54(s，3H). 3.36  CH₃  CH₃ 2，4，5-三氯苯基 7.63-8.24(m，4H)；3.91(s，3H)；3.75(s，3H)；2.61(s，3H)；2.37(s，3H). 3.37  CH₃  CH₃  3-乙基苯基 7.11-8.16(m，6H)；3.90(s，3H)；3.74(s，3H)；2.72(t，2H)；2.62(s，3H)；2.37(s，3H)；1.28(t，4H). 3.38  CH₃  CH₃ 2-苄基苯基 7.29-7.96(m，11H)；4.02(s，2H)；3.94(s，3H)；3.76(s，3H)；2.59(s，3H)；2.38(s，3H). 3.39  CH₃  CH₃  2-苯氧基苯基 7.00-8.38(m，11H)；3.85(s，3H)；3.68(s，3H)；2.49(s，3H)；2.34(s，3H). 3.40  CH₃  CH₃  3，5-二甲基苯基 6.92-8.11(m，5H)；3.91(s，3H)；3.76(s，3H)；2.62(s，3H)；2.40(s，6H)；2.38(s，3H). 3.41  CH₃  CH₃  1-萘基 7.52-8.11(m，9H)；3.93(s，3H)；3.77(s，3H)；2.62(s，3H)；2.39(s，3H). 表4

化合物序号  R₁  R₂  R₄ 物理数据 4.01  CH₃  CH₃  2，3-二氯苯基 4.02  CH₃  CH₃  2-氯苯基 4.03  CH₃  CH₃  2，4-二氯苯基 4.04  CH₃  CH₃  2，5-二氯苯基 4.05  CH₃  CH₃  2，6-二氯苯基 4.06  CH₃  CH₃  2-甲基苯基 4.07  CH₃  CH₃  2-异丙基苯基 4.08  CH₃  CH₃  2-CF₃-苯基 4.09  CH₃  CH₃  2-甲氧基苯基 4.10  CH₃  CH₃  2-甲基-5-氯苯基 4.11  CH₃  CH₃  苯基 4.12  CH₃  CH₃  3-甲基苯基 4.13  CH₃  CH₃  2-氯-4-甲基苯基 4.14  CH₃  CH₃  2-氰基-4-氯苯基 4.15  CH₃  CH₃  3-CF₃-苯基 4.16  CH₃  CH₃  4-氯苯基 4.17  CH₃  CH₃  2-氰基苯基 4.18  CH₃  CH₃  2-甲基-3-氯苯基 4.19  CH₃  CH₃  2-甲基-4-氯苯基 4.20  CH₃  CH₃  2，3-二甲基苯基 4.21  CH₃  CH₃  2，6-二甲基苯基 4.22  CH₃  CH₃  2-甲基-6-氯苯基 4.23  CH₃  CH₃  4-甲基苯基 4.24  CH₃  CH₃  2-乙基苯基 4.25  CH₃  CH₃  2-氟苯基 4.26  CH₃  CH₃  2-联苯基 4.27  CH₃  CH₃  3，4-二氯苯基 4.28  CH₃  CH₃  3，5-二氯苯基 4.29  CH₃  CH₃  4-甲基-3-氯苯基 4.30  CH₃  CH₃  3-氰基苯基 4.31  CH₃  CH₃  3-氯苯基 4.32  CH₃  CH₃  3-氟苯基 4.33  CH₃  CH₃  3-甲氧基苯基 4.34  CH₃  OCH₃  2-甲基苯基 4.35  CH₃  OCH₃  2，5-二氯苯基 4.36  CH₃  CH₃  2，4，5-三氯苯基 表5

化合物序号  R₁  R₂  R₃  R₄ 物理数据 5.01  CH₃  CH₃  CH₃  2，3-二氯苯基 5.02  CH₃  CH₃  CH₃  2-氯苯基 5.03  CH₃  CH₃  CH₃  2，4-二氯苯基 5.04  CH₃  CH₃  CH₃  2，5-二氯苯基 5.05  CH₃  CH₃  CH₃  2，6-二氯苯基 5.06  CH₃  CH₃  CH₃  2，4，5-三氯苯基 5.07  CH₃  CH₃  CH₃  2，4，6-三氯苯基 5.08  CH₃  CH₃  CH₃  2-CF₃-苯基 5.09  CH₃  CH₃  CH₃  2-氟苯基 5.10  CH₃  CH₃  CH₃  2-甲基-5-氯苯基 5.11  CH₃  CH₃  CH₃  苯基 5.12  CH₃  CH₃  H  苯基 5.13  CH₃  CH₃  H  2-氯苯基 5.14  CH₃  CH₃  H  2，4-二氯苯基 5.15  CH₃  CH₃  H  2-氟苯基 5.16  CH₃  CH₃  H  苄基 5.17  CH₃  CH₃  H  2，6-二氯苄基

  5.80   CH₃   OCH₃   CH₃   4-氯苯基   5.81   CH₃   OCH₃   CH₃   3，4-二氯苯基   5.82   CH₃   OCH₃   CH₃   2，3-二氯苯基   5.83   CH₃   OCH₃   CH₃   3，5-二氯苯基   5.84   CH₃   OCH₃   CH₃   4-氯-2-甲基苯基   5.85   CH₃   OCH₃   CH₃   3-氯-2-甲基苯基   5.86   CH₃   OCH₃   CH₃   2，4-二氯苯基   5.87   CH₃   OCH₃   CH₃   5-氯-2-甲基苯基   5.88   CH₃   CH₃   CH₃   3-溴苯基   5.89   CH₃   CH₃   CH₃   4-溴苯基   5.90   CH₃   OCH₃   CH₃   3-溴苯基   5.91   CH₃   OCH₃   H   3-溴苯基   5.92   CH₃   OCH₃   H   4-甲基苯基   5.93   CH₃   CH₃   H   4-溴苯基   5.94   CH₃   CH₃   H   4-溴苯基   5.95   CH₃   CH₃   H   3-溴苯基   5.96   CH₃   CH₃   H   4-溴苯基   5.97   CH₃   CH₃   H   4-甲基苯基   5.98   CH₃   CH₃   H   2，5-二甲基苯基   5.99   CH₃   CH₃   CH₃   3，5-二甲基苯基 表6

  化合物序号   R₁   R₂   R₃   R₄ 物理数据   6.01   CH₃   CH₃   CH₃   2，3-二氯苯基   6.02   CH₃   CH₃   CH₃   2-氯苯基   6.03   CH₃   CH₃   CH₃   2，4-二氯苯基   6.04   CH₃   CH₃   CH₃   2，5-二氯苯基   6.05   CH₃   CH₃   CH₃   2，6-二氯苯基   6.06   CH₃   CH₃   CH₃   2，4，5-三氯苯基   6.07   CH₃   CH₃   CH₃   2，4，6-三氯苯基   6.08   CH₃   CH₃   CH₃   2-CF₃-苯基   6.09   CH₃   CH₃   CH₃   2-氟苯基   6.10   CH₃   CH₃   CH₃   2-甲基-5-氯苯基   6.11   CH₃   CH₃   CH₃   苯基   6.12   CH₃   CH₃   H   苯基   6.13   CH₃   CH₃   H   2-氯苯基   6.14   CH₃   CH₃   H   2，4-二氯苯基   6.15   CH₃   CH₃   H   2-氟苯基   6.16   CH₃   CH₃   H   苄基   6.17   CH₃   CH₃   H   2，6-二氯苄基

表7 化合物序号 R₁ R₂ R₄ 物理数据 7.01  CH₃  CH₃  2，3-二氯苯基 7.02  CH₃  CH₃  2-氯苯基 7.03  CH₃  CH₃  2，4-二氯苯基 7.04  CH₃  CH₃  2，5-二氯苯基 7.05  CH₃  CH₃  2，6-二氯苯基 7.06  CH₃  CH₃  2-甲基苯基 7.07  CH₃  CH₃  2-异丙基苯基 7.08  CH₃  CH₃  2-CF₃-苯基 7.09  CH₃  CH₃  2-甲氧基苯基 7.10  CH₃  CH₃  2-甲基-5-氯苯基 7.11  CH₃  CH₃  苯基   7.12   CH₃   CH₃   3-甲基苯基   7.13   CH₃   CH₃   2-氯-4-甲基苯基   7.14   CH₃   CH₃   2-氰基-4-氯苯基   7.15   CH₃   CH₃   3-CF₃-苯基   7.16   CH₃   CH₃   4-氯苯基   7.17   CH₃   CH₃   2-氰基苯基   7.18   CH₃   CH₃   2-甲基-3-氯苯基   7.19   CH₃   CH₃   2-甲基-4-氯苯基   7.20   CH₃   CH₃   2，3-二甲基苯基   7.21   CH₃   CH₃   2，6-二甲基苯基   7.22   CH₃   CH₃   2-甲基-6-氯苯基   7.23   CH₃   CH₃   4-甲基苯基   7.24   CH₃   CH₃   2-乙基苯基   7.25   CH₃   CH₃   2-氟苯基   7.26   CH₃   CH₃   2-联苯基   7.27   CH₃   CH₃   3，4-二氯苯基   7.28   CH₃   CH₃   3，5-二氯苯基   7.29   CH₃   CH₃   4-甲基-3-氯苯基   7.30   CH₃   CH₃   3-氰基苯基   7.31   CH₃   CH₃   3-氯苯基   7.32   CH₃   CH₃   3-氟苯基   7.33   CH₃   CH₃   3-甲氧基苯基   7.34   CH₃   OCH₃   2-甲基苯基   7.35   CH₃   OCH₃   2，5-二氯苯基   7.36   CH₃   CH₃   2，4，5-三氯苯基 表8

  化合物序号 R₁ R₂ R₄ 物理数据   8.01  CH₃  CH₃   2，3-二氯苯基   8.02   CH₃   CH₃   2-氯苯基   8.03   CH₃   CH₃   2，4-二氯苯基   8.04   CH₃   CH₃   2，5-二氯苯基   8.05   CH₃   CH₃   2，6-二氯苯基   8.06   CH₃   CH₃   2-甲基苯基   8.07   CH₃   CH₃   2-异丙基苯基   8.08   CH₃   CH₃   2-CF₃-苯基   8.09   CH₃   CH₃   2-甲氧基苯基   8.10   CH₃   CH₃   2-甲基-5-氯苯基   8.11   CH₃   CH₃   苯基   8.12   CH₃   CH₃   3-甲基苯基   8.13   CH₃   CH₃   2-氯-4-甲基苯基   8.14   CH₃   CH₃   2-氰基-4-氯苯基   8.15   CH₃   CH₃   3-CF₃-苯基   8.16   CH₃   CH₃   4-氯苯基   8.17   CH₃   CH₃   2-氰基苯基   8.18   CH₃   CH₃   2-甲基-3-氯苯基   8.19   CH₃   CH₃   2-甲基-4-氯苯基   8.20   CH₃   CH₃   2，3-二甲基苯基   8.21   CH₃   CH₃   2，6-二甲基苯基   8.22   CH₃   CH₃   2-甲基-6-氯苯基   8.23   CH₃   CH₃   4-甲基苯基   8.24   CH₃   CH₃   2-乙基苯基   8.25   CH₃   CH₃   2-氟苯基   8.26   CH₃   CH₃   2-联苯基   8.27   CH₃   CH₃   3，4-二氯苯基   8.28   CH₃   CH₃   3，5-二氯苯基   8.29   CH₃   CH₃   4-甲基-3-氯苯基   8.30   CH₃   CH₃   3-氰基苯基   8.31   CH₃   CH₃   3-氯苯基   8.32   CH₃   CH₃   3-氟苯基   8.33   CH₃   CH₃   3-甲氧基苯基   8.34   CH₃   OCH₃   2-甲基苯基   8.35   CH₃   OCH₃   2，5-二氯苯基   8.36   CH₃   CH₃   2，4，5-三氯苯基 表9

化合物序号  R₁  R₂  R₃  R₄ 物理数据 9.01  CH₃  CH₃  CH₃  2，3-二氯苯基 9.02  CH₃  CH₃  CH₃  2-氯苯基 9.03  CH₃  CH₃  CH₃  2，4-二氯苯基 9.04  CH₃  CH₃  CH₃  2，5-二氯苯基 9.05  CH₃  CH₃  CH₃  2，6-二氯苯基 9.06  CH₃  CH₃  CH₃ 2，4，5-三氯苯基 9.07  CH₃  CH₃  CH₃  2，4，6-三氯苯基 9.08  CH₃  CH₃  CH₃  2-CF₃-苯基 9.09  CH₃  CH₃  CH₃  2-氟苯基 9.10  CH₃  CH₃  CH₃  2-甲基-5-氯苯基 9.11  CH₃  CH₃ CH₃  苯基 9.12  CH₃  CH₃  H  苯基 9.13  CH₃  CH₃  H  2-氯苯基 9.14  CH₃  CH₃  H  2，4-二氯苯基 9.15  CH₃  CH₃  H  2-氟苯基

  9.81   CH₃   OCH₃   CH₃   3，4-二氯苯基   9.82   CH₃   OCH₃   CH₃   2，3-二氯苯基   9.83   CH₃   OCH₃   CH₃   3，5-二氯苯基   9.83   CH₃   OCH₃   CH₃   2，4-二氯苯基   9.84   CH₃   OCH₃   CH₃   4-氯-2-甲基苯基   9.85   CH₃   OCH₃   CH₃   3-氯-2-甲基苯基   9.86   CH₃   OCH₃   CH₃   2，4-二氯苯基   9.87   CH₃   OCH₃   CH₃   5-氯-2-甲基苯基   9.88   CH₃   CH₃   CH₃   3-溴苯基   9.89   CH₃   CH₃   CH₃   4-溴苯基   9.90   CH₃   OCH₃   CH₃   3-溴苯基   9.91   CH₃   OCH₃   H   3-溴苯基   9.92   CH₃   OCH₃   H   4-甲基苯基   9.93   CH₃   CH₃   H   4-溴苯基   9.94   CH₃   OCH₃   H   2，5-二甲基苯基   9.95   CH₃   CH₃   H   3-溴苯基   9.96   CH₃   CH₃   H   4-溴苯基   9.97   CH₃   CH₃   H   4-溴苯基   9.98   CH₃   CH₃   H   2，5-二甲基苯基   9.99   CH₃   CH₃   CH₃   3，5-二甲基苯基 表10   化合物序号   R₁   R₂   R₄ 物理数据   10.01   CH₃   CH₃   2，3-二氯苯基   10.02   CH₃   CH₃   2-氯苯基   10.03   CH₃   CH₃   2，4-二氯苯基   10.04   CH₃   CH₃   2，5-二氯苯基   10.05   CH₃   CH₃   2，6-二氯苯基   10.06   CH₃   CH₃   2，4，5-三氯苯基   10.07   CH₃   CH₃   2，4，6-三氯苯基   10.08   CH₃   CH₃   2-CF₃-苯基   10.09   CH₃   CH₃   2-氟苯基   10.10   CH₃   CH₃   2-甲基-5-氯苯基   10.11   CH₃   CH₃   苯基   10.12   CH₃   N(CH₃)₂   苯基   10.13   CH₃   CH₃   2-氰基苯基   10.14   CH₃   CH₃   3-氯苯基   10.15   CH₃   CH₃   3-CF₃-苯基   10.16   CH₃   CH₃   2-硝基苯基   10.17   CH₃   CH₃   2-甲氧基-5-氯苯基   10.18   CH₃   CH₃   2-甲基苯基   10.19   CH₃   CH₃   3，4-二氯苯基   10.20   CH₃   CH₃   3-硝基苯基   10.21   CH₃   CH₃   3-CF₃-4-氯苯基   10.22   OCH₃   CH₃   2-氯苯基 表11

表12

化合物序号 R₁ R₄ 物理数据 12.01  CH₃  苯基 12.02  CH₃  2-甲基苯基 12.03  CH₃  2，5-二氯苯基 Obtain the compounds in the following table in a similar manner: Table 1

Compound No. R ₁ R ₂ R ₃ R ₄ Physical data ¹ H-NMR (CDCl ₃ ) or/and mp 1.01 _{CH3 CH3 CH3} 2,3-Dichlorophenyl 7.58(s, 1H); 7.57-7.27(m, 3H); 6.17(s, 1H); 3.85(s, 3H); 3.70(s, 3H); 2.62(s, 3H); 2.32(s, 3H) ;2.18(s,3H).mp169-171℃ 1.02 _{CH3 CH3 CH3} 2-Chlorophenyl 7.58(s, 1H); 7.54-7.30(m, 4H); 6.17(s, 1H); 3.85(s, 3H); 3.70(s, 3H); 2.58(s, 3H); 2.35(s, 3H) ;2.18(s,3H).mp135-137℃ 1.03 _{CH3 CH3 CH3} 2,4-Dichlorophenyl 7.59(s, 1H); 7.55-7.25(m, 3H); 6.12(s, 1H); 3.85(s, 3H); 3.65(s, 3H); 2.58(s, 3H); 2.33(s, 3H) ;2.17(s, 3H). 1.04 _{CH3 CH3 CH3} 2,5-Dichlorophenyl 7.59(s, 1H); 7.49-7.35(m, 3H); 7.24(s, 1H); 6.14(s, 1H); 3.85(s, 3H); 3.68(s, 3H); 2.58(s, 3H) ;2.32(s, 3H); 2.18(s, 3H).mp142-144℃ 1.05 _{CH3 CH3 CH3} 2,6-Dichlorophenyl 7.59(s, 1H); 7, 47-7.23(m, 3H); 6.18(s, 1H); 3.83(s, 3H); 3.68(s, 3H); 2.57(s, 3H); 3H); 2.12(3,3H). 1.06 _{CH3 CH3 CH3} 2,4,5-Trichlorophenyl 7.65(s, 1H); 7.62-7.40(m, 2H); 6.14(s, 1H); 3.86(s, 3H); 3.69(s, 3H); 2.58(s, 3H); 2.34(s, 3H) ;2.18(s, 3H). 1.07 _{CH3 CH3 CH3} 2,4,6-Trichlorophenyl 7.59(s, 1H); 7.43(s, 2H); 6.18(s, 1H); 3.84(s, 3H); 3.68(s, 3H); 2.55(s, 3H); 2.33(s, 3H); 2.12 (s, 3H). 1.08 _{CH3 CH3 CH3} 2-CF ₃ -phenyl 7.52(s, 1H); 7.76-7.34(m, 3H); 6.06(s, 1H); 3.79(s, 3H); 3.63(s, 3H); 2.52(s, 3H); 2.29(s, 3H) ;2.04(s,3H).mp143-144℃ 1.09 _{CH3 CH3 CH3} 2-fluorophenyl 7.59(s, 1H); 7.52-7.18(m, 3H); 6.13(s, 1H); 3.87(s, 3H); 3.70(s, 3H); 2.59(s, 3H); 2.34(s, 3H) ; 2.22(s, 3H). 1.10 _{CH3 CH3 CH3} 2-Methyl-5-chlorophenyl 7.59(s, 1H); 7.34-7.22(m, 3H); 6.10(s, 1H); 3.86(s, 3H); 3.69(s, 3H); 2.58(s, 3H); 2.33(s, 3H) ;2.09(s,3H).mp139-141℃ 1.11 _{CH3 CH3 CH3} Phenyl 7.59(s, 1H); 7.48-7.32(m, 5H); 6.09(s, 1H); 3.85(s, 3H); 3.69(s, 3H); 2.58(s.3H); 2.33(s, 3H) ; 2.22(s, 3H).

1.19 _{CH3 CH3} h 3-methoxybenzyl 7.59(s, 1H); 7.24(d, 1H); 7.22-6.78(m, 4H); 6.07(d, 1H); 5.17(s, 2H); 3.84(s, 3H); 3.78(s, 3H) ;3.70(s,3H);2.57(s,3H);2.35(s,3H). 1.20 _{CH3 CH3} h 4-methoxybenzyl 7.60(s, 1H); 7.24(d, 1H); 7.22-6.84(m, 4H); 6.07(d, 1H); 5.15(s, 2H); 3.85(s, 3H); 3.80(s, 3H) ;3.70(s,3H);2.56(s,3H);2.35(s,3H). 1.21 _CH3 N(CH ₃ ) ₂ h Phenyl 1.22 _{CH3 CH3 CH3} 2-cyanophenyl 7.80-7.48(m, 4H); 7.59(s, 1H); 6.20(s, 1H); 3.85(s, 3H); 3.70(s, 3H); 2.58(s, 3H); 2.37(s, 3H) ;2.30(s,3H).mp154-156℃ 1.23 _{CH3 CH3 CH3} 3-Chlorophenyl 7.60(s, 1H); 7.52-7.32(m, 4H); 6.10(s, 1H); 3.85(s, 3H); 3.69(s, 3H); 2.58(s, 3H); 2.39(s, 3H) ;2.37(s,3H).mp135-136℃ 1.24 _{CH3 CH3 CH3} 3-CF ₃ -phenyl 7.79-7.57(m, 4H); 7.59(s, 1H); 6.13(s, 1H); 3.87(s, 3H); 3.70(s, 3H); 2.58(s, 3H); 2.40(s, 3H) ;2.37(s, 3H). 1.25 _{CH3 CH3 CH3} 2-nitrophenyl 8.00(dd, 1H); 7.75-7.54(m, 3H); 7.59(s, 1H); 6.16(s, 1H); 3.85(s, 3H); 3.70(s, 3H); 2.59(s, 3H) ;2.37(s, 3H); 2.22(s, 3H).mp110-111℃ 1.26 _{CH3 CH3 CH3} 2-methoxy-5-chlorophenyl 7.59(s, 1H); 7.40-6.91(m, 3H); 6.08(s, 1H); 3.86(s, 3H); 3.80(s, 3H); 370(s, 3H); 2.60(s, 3H) ;2.37(s, 3H); 2.18(s, 3H).mp140-141℃ 1.27 _{CH3 CH3} h 2-Methylphenyl 7.62(s, 1H); 7.50(d, 1H); 7.38-7.22(m, 4H); 6.33(d, 1H); 3.85(s, 3H); 3.70(s, 3H); 2.57(s, 3H) ;2.36(s, 3H); 2.31(s, 3H).mp160-161℃ 1.28 _{CH3 CH3 CH3} 3,4 dichlorophenyl 7.63-7.33(m, 3H); 7.62(s, 1H); 6.12(s, 1H); 3.86(s, 3H); 3.70(s, 3H); 2.58(s, 3H); 2.40(s, 3H) ;2.37(s,3H).mp126-129℃ 1.29 _{CH3 CH3 CH3} 3-nitrophenyl 8.38-7.62(m, 4H); 7.60(s, 1H); 6.17(s, 1H); 3.88(s, 3H); 3.73(s, 3H); 2.60(s, 3H); 2.47(s, 3H) ;2.37(s,3H).mp146-147℃ 1.30 _{CH3 CH3 CH3} 3-CF ₃ -4-chlorophenyl 7.83-7.57(m, 3H); 7.60(s, 1H); 6.14(s, 1H); 3.85(s, 3H); 3.70(s, 3H); 2.58(s, 3H); 2.40(s, 3H) ;2.37(s,3H).mp125-128℃ 1.31 _CH3 OCH ₃ h 2-Chlorophenyl 7.82(d, 1H); 7.63-7.23(m, 4H); 7.56(s, 1H); 6.30(d, 1H); 3.97(s, 3H); 3.82(s, 3H); 3.67(s, 3H) ;2.50(s,3H)mp123-125℃ 1.32 _CH3 OCH _{3 CH3} 2-Chlorophenyl 7.55(s, 1H); 7.54-7.30(m, 4H); 6.07(s, 1H); 3.93(s, 3H); 3.80(s, 3H); 3.64(s, 3H); 2.50(s, 3H) ;2.15(s,3H).mp141-142℃ 1.33 _CH3 OCH ₃ h 2-methoxybenzyl 7.53(s, 1H); 7.33-6.84(m, 5H); 6.02(d, 1H); 5.20(s, 2H); 3.93(s, 3H); 3.83(s, 3H); 3.80(s, 3H) ;3.67(s, 3H); 2.47(s, 3H).mp110-112℃

1.73 _CH3 OCH ₃ h 3-CF ₃ -phenyl 7.96-7.47(m, 6H); 6.33(d, 1H); 3.96(s, 3H); 3.86(s, 3H); 3.70(s, 3H); 2.50(s, 3H).mp152-154℃. 1.74 _CH3 OCH ₃ h 2,5-Dichlorophenyl 7.90(d, 1H); 7.70-7.23(m, 4H); 6.33(d, 1H); 3.96(s, 3H); 3.84(s, 3H); 3.70(s, 3H); 2.53(s, 3H) . 1.75 h _CH3 h 3-CF ₃ -phenyl 8.64(s, 1H); 7.95(d, 1H); 7.82-7.50(m, 5H); 6.33(d, 1H); 3.93(s, 3H); 3.73(s, 3H); 2.42(s, 3H) .mp153-155℃. 1.76 _CH3 OCH ₃ h 5-Chloro-2-methylphenyl 7.57(s, 1H); 7.50(d, 1H); 7.40-7.18(m, 3H); 6.28(d, 1H); 3.95(s, 1H); 3.83(s, 3H); 3.70(s, 3H) ;2.50(s, 3H); 2.32(s, 3H).mp102-106℃. 1.77 _{CH3 CH3 CH3} 3-Chloro-2-methylphenyl 7.60(s, 1H); 7.46-7.19(m, 3H); 6.08(s, 1H); 3.83(s, 3H); 3.70(s, 3H); 2.58(s, 3H); 2.37(s, 3H) ;2.10(2s,6H).mp157-159℃. 1.78 _{CH3 CH3 CH3} 4-Chloro-2-methylphenyl 7.60(s, 1H); 7.32-7.20(m, 3H); 6.04(s, 1H); 3.84(s, 3H); 3.70(s, 3H); 2.57(s, 3H); 2.36(s, 3H) ;2.10(2s,6h). 1.79 _CH3 OCH _{3 CH3} 3-Chlorophenyl 7.56(s, 1H); 7.50-7.26(m, 4H); 6.04(s, 1H); 3.93(s, 3H); 3.83(s, 3H); 3.68(s, 3H); 2.53(s, 3H) ;2.38(s, 3H). 1.80 _CH3 OCH _{3 CH3} 4-Chlorophenyl 7.52(s, 1H); 7.38(s, 4H); 6.03(s, 1H); 3.94(s, 3H); 3.82(s, 3H); 3.66(s, 3H); 2.51(s, 3H); 2.36 (s, 3H). 1.81 _CH3 OCH _{3 CH3} 3,4-Dichlorophenyl 7.63-7.30(m, 4H); 6.05(s, 1H); 3.93(s, 3H); 3.82(s, 3H); 3.67(s, 3H); 2.53(s, 3H); 2.38(s, 3H) .mp147-148℃. 1.82 _CH3 OCH _{3 CH3} 2,3-Dichlorophenyl 7.60-7.27(m, 4H); 6.08(s, 1H); 3.92(s, 3H); 3.81(s, 3H); 3.64(s, 3H); 2.50(s, 3H); 2.15(s, 3H) .mp147-150℃. 1.83 _CH3 OCH _{3 CH3} 3,5-dichlorophenyl 7.52(s, 1H); 7.40-7.28(m, 3H); 6.03(s, 1H); 3.93(s, 3H); 3.80(s, 3H); 3.66(s, 3H); 2.48(s, 3H) ;2.38(s,3H).mp160-161℃. 1.84 _CH3 OCH _{3 CH3} 4-Chloro-2-methylphenyl 7.52(s, 1H); 7.32-7.20(m, 3H); 6.02(s, 1H); 3.90(s, 3H); 3.83(s, 3H); 3.67(s, 3H); 2.50(s, 3H) ;2.15(2s,6H).mp140-143℃. 1.85 _CH3 OCH _{3 CH3} 3-Chloro-2-methylphenyl 7.52(s, 1H); 7.45-7.20(m, 3H); 6.03(s, 1H); 3.93(s, 3H); 3.82(s, 3H); 3.68(s, 3H); 2.50(s, 3H) ;2.15(s, 3H); 2.14(s, 3H).mp147-149℃ 1.86 _CH3 OCH _{3 CH3} 2,4-Dichlorophenyl 7.52-7.30(m, 4H); 6.08(s, 1H); 3.95(s, 3H); 3.80(s, 3H); 3.68(s, 3H); 2.53(s, 3H); 2.17(s, 3H) . 1.87 _CH3 OCH _{3 CH3} 5-Chloro-2-methylphenyl 7.54(s, 1H); 7.34-7.20(m, 3H); 6.03(s, 1H); 3.92(s, 3H); 3.80(s, 3H); 3.67(s, 3H); 2.52(s, 3H) ;2.15(2s, 6H). 1.88 _{CH3 CH3 CH3} 3-Bromophenyl 7.65-7.30(m, 5H); 6.10(s, 1H); 3.87(s, 3H); 3.70(s, 3H); 2.59(s, 3H); 2.38(s, 3H); 1.36(s, 3H) ;mp141-142℃. 1.89 _{CH3 CH3 CH3} 4-Bromophenyl 7.60(s, 1H); 7.57-7.30(m, 4H); 6.10(s, 1H); 3.85(s, 3H); 3.70(s, 3H); 2.58(s, 3H); 2.38(2s, 6H) . 1.90 _CH3 OCH _{3 CH3} 3-Bromophenyl 7.64-7.26(m, 5H); 6.06(s, 1H); 3.97(s, 3H); 3.83(s, 3H); 3.69(s, 3H); 2.53(s, 3H); 2.38(s, 3H) . 1.91 _CH3 OCH ₃ h 3-Bromophenyl 7.86-7.24(m, 5H); 6.30(d, 1H); 3.97(s, 3H); 3.86(s, 3H); 3.70(s, 3H); 2.53(s, 3H).mp144-145℃. 1.92 _CH3 OCH ₃ h 4-Methylphenyl 7.78(d, 1H); 7.57-7.17(m, 5H); 6.23(d, 1H); 3.97(s, 3H); 3.88(s, 3H); 3.70(s, 3H); 2.52(s, 3H) ;2.38(s, 3H). 1.93 _{CH3 CH3} h 4-Bromophenyl 7.80(d, 1H); 7.57(s, 1H); 7.55(s, 4H); 6.28(d, 1H); 3.97(s, 3H); 3.86(s, 3H); 3.70(s, 3H); 2.53 (s, 3H). 1.94 _CH3 OCH ₃ h 2,5-Dimethylphenyl 7.56(s, 1H); 7.48(d, 1H); 7.08-7.02(m, 3H); 6.23(d, 1H); 3.96(s, 3H); 3.84(s, 3H); 3.70(s, 3H) ;2.52(s, 3H); 2.38(s, 3H); 2.25(s, 3H).mp86-87℃. 1.95 _{CH3 CH3} h 3-Bromophenyl 7.84(d, 1H); 7.62(s, 1H); 7.57-7.26(m, 4H); 6.33(d, 1H); 3.87(s, 3H); 3.70(s, 3H); 2.58(s, 3H) ;2.38(s,3H).mp120-122℃. 1.96 _{CH3 CH3} h 4-Bromophenyl 7.83(d, 1H); 7.63(s, 1H); 7.53(s, 4H); 6.33(d, 1H); 3.87(s, 3H); 3.70(s, 3H); 2.58(s, 3H); 2.38 (s,3H).mp141-142℃. 1.97 _{CH3 CH3} h 4-Methylphenyl 7.81(d, 1H); 7.62(s, 1H); 7.50-7.19(m, 4H); 6.29(d, 1H); 3.87(s, 3H); 3.70(s, 3H); 2.58(s, 3H) ; 2.38(2s, 6H), mp121-122℃. 1.98 _{CH3 CH3} h 2,5-Dimethylphenyl 7.60(s, 1H); 7.52(d, 1H); 7.17-7.03(m, 3H); 6.28(d, 1H); 3.84(s, 3H); 3.70(s, 3H); 2.58(s, 3H) ;2.38(s,3H);2.37(s,3H);2.30(s,3H). 1.99 _{CH3 CH3 CH3} 3,5-Dimethylphenyl 7.60(s, 1H); 7.06(s, 2H); 6.96(s, 1H); 6.06(s, 1H); 3.84(s, 3H); 3.70(s, 3H); 2.59(s, 3H); 2.37 (4s; 12H).mp143-144℃. Table 2

Compound No. R ₁ R ₂ R ₃ R ₄ Physical data ¹ H-NMR (CDCl ₃ ) or/and mp 2.01 _{CH3 CH3 CH3} 2,3-Dichlorophenyl 2.02 _{CH3 CH3 CH3} 2-Chlorophenyl 2.03 _{CH3 CH3 CH3} 2,4-Dichlorophenyl table 3 Compound No. R ₁ R ₂ R ₄ Physical data ¹ H-NMR (CDCl ₃ ) or/and mp 3.01 _{CH3 CH3} 2,3-Dichlorophenyl 7.22-8.19(m, 5H); 3.92(s, 3H); 3.76(s, 3H); 2.62(s, 3H); 2.37(s, 3H). 3.02 _{CH3 CH3} 2-Chlorophenyl 7.26-8.21(m, 6H); 3.93(s, 3H); 3.76(s, 3H); 2.62(s, 3H); 2.38(s, 3H). 3.03 _{CH3 CH3} 2,4-Dichlorophenyl 7.28-8.20(m, 5H); 3.91(s, 3H); 3.77(s, 3H); 2.61(s, 3H); 2.38(s, 3H). 3.04 _{CH3 CH3} 2,5-Dichlorophenyl 7.24-8.23(m, 5H); 3.93(s, 3H); 3.78(s, 3H); 2.59(s, 3H); 2.37(s, 3H). 3.05 _{CH3 CH3} 2,6-Dichlorophenyl 7.26-7.97(m, 5H); 3.88(s, 3H); 3.75(s, 3H); 2.60(s, 3H); 2.37(s, 3H). 3.06 _{CH3 CH3} 2-Methylphenyl 7.26-7.95(m, 6H); 3.90(s, 3H); 3.74(s, 3H); 2.59(s, 3H); 2.38(s, 3H); 2.33(s, 3H). 3.07 _{CH3 CH3} 2-isopropylphenyl 7.24-7-96(m, 6H); 3.94(s, 3H); 3.77(s, 3H); 3.03(m, 1H); 2.59(s, 3H); 2.38(s, 3H); 3H); 1.20(s, 3H). 3.08 _{CH3 CH3} 2-CF ₃ -phenyl 7.56-8.18(m, 6H); 3.92(s, 3H); 3.73(s, 3H); 2.63(s, 3H); 2.37(s, 3H). 3.09 _{CH3 CH3} 2-methoxyphenyl 7.03-8.28(m, 6H); 3.90(s, 3H); 3.77(s, 3H); 2.60(s, 3H); 2.38(s, 3H); 2.04(s, 3H). 3.10 _{CH3 CH3} 2-Methyl-5-chlorophenyl 7.22-7-93(m, 5H); 3.90(s, 3H); 3.74(s, 3H); 2.61(s, 3H); 2.38(s, 3H); 2.31(s, 3H). 3.11 _{CH3 CH3} Phenyl 7.24-8.21(m, 7H); 3.92(s, 3H); 3.75(s, 3H); 2.61(s, 3H); 2.38(s, 3H). 3.12 _{CH3 CH3} 3-Methylphenyl 6.84-7.59(m, 6H); 3.90(s, 3H); 3.74(s, 3H); 2.51(s, 3H); 2.38(s, 3H). 3.13 _{CH3 CH3} 2-Chloro-4-methylphenyl 7.16-8.13(m, 5H); 3.94(s, 3H); 3.78(s, 3H); 2.59(s, 3H); 2.50(s, 3H); 2.39(s, 3H). 3.14 _{CH3 CH3} 2-cyano-4-chlorophenyl 7.63-8.59(m, 5H); 3.81(s, 3H); 3.76(s, 3H); 2.62(s, 3H); 2.53(2, 3H). 3.15 _{CH3 CH3} 3-CF ₃ -phenyl 7.49-8.21(m, 6H); 3.92(s, 3H); 3.74(s, 3H); 2.63(s, 3H); 2.38(s, 3H). 3.16 _{CH3 CH3} 4-Chlorophenyl 7.39-8.12(m, 6H); 3.89(s, 3H); 3.72(s, 3H); 2.61(s, 3H); 2.37(s, 3H). 3.17 _{CH3 CH3} 2-cyanophenyl 7.40-8.58(m, 6H); 3.92(s, 3H); 3.75(s, 3H); 2.62(s, 3H); 2.37(s, 3H). 3.18 _{CH3 CH3} 2-Methyl-3-chlorophenyl 7.20-7.89(m, 5H); 3.92(s, 3H); 3.74(s, 3H); 2.59(s, 3H); 2.37(s, 3H); 2.28(s, 3H). 3.19 _{CH3 CH3} 2-Methyl-4-chlorophenyl 7.22-7.87(m, 5H); 3.93(s, 3H); 3.76(s, 3H); 2.60(s, 3H); 2.39(s, 3H); 2.34(s, 3H). 3.20 _{CH3 CH3} 2,3-Dimethylphenyl 7.17-7.86(m, 5H); 3.91(s, 3H); 3.76(s, 3H); 2.60(s, 3H); 2.38(s, 6H); 2.15(s, 3H). 3.21 _{CH3 CH3} 2,6-Dimethylphenyl 7.06-7.64(m, 5H); 3.91(s, 3H); 3.73(s, 3H); 2.44(s, 3H); 2.37(s, 3H); 2.08(s, 6H). 3.22 _{CH3 CH3} 2-Methyl-6-chlorophenyl 7.28-7.91(m, 5H); 3.94(s, 3H); 3.76(s, 3H); 2.61(s, 3H); 2.39(s, 3H); 2.17(s, 3H). 3.23 _{CH3 CH3} 4-Methylphenyl 7.23-8.11(m, 6H); 3.91(s, 3H); 3.75(s, 3H); 2.61(s, 3H); 2.39(s, 3H); 2.36(s, 3H). 3.24 _{CH3 CH3} 2-Ethylphenyl 6.98-7.63(m, 6H); 3.89(s, 3H); 3.74(s, 3H); 2.71(s, 3H); 2.48(s, 3H); 2.37(s, 3H); 1.12(t, 3H) . 3.25 _{CH3 CH3} 2-fluorophenyl 7.20-8.27(m, 6H); 3.93(s, 3H); 3.74(s, 3H); 2.61(s, 3H); 2.38(s, 3H). 3.26 _{CH3 CH3} 2-biphenyl 7.17-7.64(m, 11H); 3.83(s, 3H); 3.62(s, 3H); 2.47(s, 3H); 2.30(s, 3H). 3.27 _{CH3 CH3} 3,4-Dichlorophenyl 7.55-8.32(m, 5H); 3.91(s, 3H); 3.73(s, 3H); 2.62(s, 3H); 2.37(s, 3H). 3.28 _{CH3 CH3} 3,5-Dichlorophenyl 7.23-8.18(m, 5H); 3.91(s, 3H); 3.73(s, 4H); 2.63(s, 3H); 2.38(s, 3H) 3.29 _{CH3 CH3} 4-methyl-3-chlorophenyl 7.19-8.08(m, 5H); 3.87(s, 3H); 3.72(s, 3H); 2.63(s, 3H); 2.36(s, 3H); 2.30(s, 3H). 3.30 _{CH3 CH3} 3-cyanophenyl 7.58-8.22(m, 6H); 3.91(s, 3H); 3.75(s, 3H); 2.63(s, 3H); 2.39(s, 3H). 3.31 _{CH3 CH3} 3-Chlorophenyl 7.25-8.17(m, 6H); 3.92(s, 3H); 3.74(s, 3H); 2.61(s, 3H); 2.39(s, 3H). 3.32 _{CH3 CH3} 3-fluorophenyl 6.96-8.18(m, 6H); 3.91(s, 3H); 3.74(s, 3H); 2.62(s, 3H); 2.39(s, 3H). 3.33 _{CH3 CH3} 3-methoxyphenyl 6.82-8.17(m, 6H); 3.92(s, 3H); 3.89(s, 3H); 3.75(s, 3H); 2.60(s, 3H); 2.38(s, 3H). 3.34 _CH3 OCH ₃ 2-Methylphenyl 6.98-7.60(m, 6H); 3.96(s, 3H); 3.87(s, 3H); 3.70(s, 3H); 2.61(s, 3H); 2.18(s, 3H). 3.35 _CH3 OCH ₃ 2,5-Dichlorophenyl 7.24-8.19(m, 5H); 3.98(s, 3H); 3.87(s, 3H); 3.73(s, 3H); 2.54(s, 3H). 3.36 _{CH3 CH3} 2,4,5-Trichlorophenyl 7.63-8.24(m, 4H); 3.91(s, 3H); 3.75(s, 3H); 2.61(s, 3H); 2.37(s, 3H). 3.37 _{CH3 CH3} 3-Ethylphenyl 7.11-8.16(m, 6H); 3.90(s, 3H); 3.74(s, 3H); 2.72(t, 2H); 2.62(s, 3H); 2.37(s, 3H); 1.28(t, 4H) . 3.38 _{CH3 CH3} 2-Benzylphenyl 7.29-7.96(m, 11H); 4.02(s, 2H); 3.94(s, 3H); 3.76(s, 3H); 2.59(s, 3H); 2.38(s, 3H). 3.39 _{CH3 CH3} 2-Phenoxyphenyl 7.00-8.38(m, 11H); 3.85(s, 3H); 3.68(s, 3H); 2.49(s, 3H); 2.34(s, 3H). 3.40 _{CH3 CH3} 3,5-Dimethylphenyl 6.92-8.11(m, 5H); 3.91(s, 3H); 3.76(s, 3H); 2.62(s, 3H); 2.40(s, 6H); 2.38(s, 3H). 3.41 _{CH3 CH3} 1-Naphthyl 7.52-8.11(m, 9H); 3.93(s, 3H); 3.77(s, 3H); 2.62(s, 3H); 2.39(s, 3H). Table 4

Compound No. R ₁ R ₂ R ₄ physical data 4.01 _{CH3 CH3} 2,3-Dichlorophenyl 4.02 _{CH3 CH3} 2-Chlorophenyl 4.03 _{CH3 CH3} 2,4-Dichlorophenyl 4.04 _{CH3 CH3} 2,5-Dichlorophenyl 4.05 _{CH3 CH3} 2,6-Dichlorophenyl 4.06 _{CH3 CH3} 2-Methylphenyl 4.07 _{CH3 CH3} 2-isopropylphenyl 4.08 _{CH3 CH3} 2-CF ₃ -phenyl 4.09 _{CH3 CH3} 2-methoxyphenyl 4.10 _{CH3 CH3} 2-Methyl-5-chlorophenyl 4.11 _{CH3 CH3} Phenyl 4.12 _{CH3 CH3} 3-Methylphenyl 4.13 _{CH3 CH3} 2-Chloro-4-methylphenyl 4.14 _{CH3 CH3} 2-cyano-4-chlorophenyl 4.15 _{CH3 CH3} 3-CF ₃ -phenyl 4.16 _{CH3 CH3} 4-Chlorophenyl 4.17 _{CH3 CH3} 2-cyanophenyl 4.18 _{CH3 CH3} 2-Methyl-3-chlorophenyl 4.19 _{CH3 CH3} 2-Methyl-4-chlorophenyl 4.20 _{CH3 CH3} 2,3-Dimethylphenyl 4.21 _{CH3 CH3} 2,6-Dimethylphenyl 4.22 _{CH3 CH3} 2-Methyl-6-chlorophenyl 4.23 _{CH3 CH3} 4-Methylphenyl 4.24 _{CH3 CH3} 2-Ethylphenyl 4.25 _{CH3 CH3} 2-fluorophenyl 4.26 _{CH3 CH3} 2-biphenyl 4.27 _{CH3 CH3} 3,4-Dichlorophenyl 4.28 _{CH3 CH3} 3,5-Dichlorophenyl 4.29 _{CH3 CH3} 4-methyl-3-chlorophenyl 4.30 _{CH3 CH3} 3-cyanophenyl 4.31 _{CH3 CH3} 3-Chlorophenyl 4.32 _{CH3 CH3} 3-fluorophenyl 4.33 _{CH3 CH3} 3-methoxyphenyl 4.34 _CH3 OCH ₃ 2-Methylphenyl 4.35 _CH3 OCH ₃ 2,5-Dichlorophenyl 4.36 _{CH3 CH3} 2,4,5-Trichlorophenyl table 5

Compound No. R ₁ R ₂ R ₃ R ₄ physical data 5.01 _{CH3 CH3 CH3} 2,3-Dichlorophenyl 5.02 _{CH3 CH3 CH3} 2-Chlorophenyl 5.03 _{CH3 CH3 CH3} 2,4-Dichlorophenyl 5.04 _{CH3 CH3 CH3} 2,5-Dichlorophenyl 5.05 _{CH3 CH3 CH3} 2,6-Dichlorophenyl 5.06 _{CH3 CH3 CH3} 2,4,5-Trichlorophenyl 5.07 _{CH3 CH3 CH3} 2,4,6-Trichlorophenyl 5.08 _{CH3 CH3 CH3} 2-CF ₃ -phenyl 5.09 _{CH3 CH3 CH3} 2-fluorophenyl 5.10 _{CH3 CH3 CH3} 2-Methyl-5-chlorophenyl 5.11 _{CH3 CH3 CH3} Phenyl 5.12 _{CH3 CH3} h Phenyl 5.13 _{CH3 CH3} h 2-Chlorophenyl 5.14 _{CH3 CH3} h 2,4-Dichlorophenyl 5.15 _{CH3 CH3} h 2-fluorophenyl 5.16 _{CH3 CH3} h Benzyl 5.17 _{CH3 CH3} h 2,6-Dichlorobenzyl

5.80 _CH3 OCH _{3 CH3} 4-Chlorophenyl 5.81 _CH3 OCH _{3 CH3} 3,4-Dichlorophenyl 5.82 _CH3 OCH _{3 CH3} 2,3-Dichlorophenyl 5.83 _CH3 OCH _{3 CH3} 3,5-Dichlorophenyl 5.84 _CH3 OCH _{3 CH3} 4-Chloro-2-methylphenyl 5.85 _CH3 OCH _{3 CH3} 3-Chloro-2-methylphenyl 5.86 _CH3 OCH _{3 CH3} 2,4-Dichlorophenyl 5.87 _CH3 OCH _{3 CH3} 5-Chloro-2-methylphenyl 5.88 _{CH3 CH3 CH3} 3-Bromophenyl 5.89 _{CH3 CH3 CH3} 4-Bromophenyl 5.90 _CH3 OCH _{3 CH3} 3-Bromophenyl 5.91 _CH3 OCH ₃ h 3-Bromophenyl 5.92 _CH3 OCH ₃ h 4-Methylphenyl 5.93 _{CH3 CH3} h 4-Bromophenyl 5.94 _{CH3 CH3} h 4-Bromophenyl 5.95 _{CH3 CH3} h 3-Bromophenyl 5.96 _{CH3 CH3} h 4-Bromophenyl 5.97 _{CH3 CH3} h 4-Methylphenyl 5.98 _{CH3 CH3} h 2,5-Dimethylphenyl 5.99 _{CH3 CH3 CH3} 3,5-Dimethylphenyl Table 6

Compound No. R ₁ R ₂ R ₃ R ₄ physical data 6.01 _{CH3 CH3 CH3} 2,3-Dichlorophenyl 6.02 _{CH3 CH3 CH3} 2-Chlorophenyl 6.03 _{CH3 CH3 CH3} 2,4-Dichlorophenyl 6.04 _{CH3 CH3 CH3} 2,5-Dichlorophenyl 6.05 _{CH3 CH3 CH3} 2,6-Dichlorophenyl 6.06 _{CH3 CH3 CH3} 2,4,5-Trichlorophenyl 6.07 _{CH3 CH3 CH3} 2,4,6-Trichlorophenyl 6.08 _{CH3 CH3 CH3} 2-CF ₃ -phenyl 6.09 _{CH3 CH3 CH3} 2-fluorophenyl 6.10 _{CH3 CH3 CH3} 2-Methyl-5-chlorophenyl 6.11 _{CH3 CH3 CH3} Phenyl 6.12 _{CH3 CH3} h Phenyl 6.13 _{CH3 CH3} h 2-Chlorophenyl 6.14 _{CH3 CH3} h 2,4-Dichlorophenyl 6.15 _{CH3 CH3} h 2-fluorophenyl 6.16 _{CH3 CH3} h Benzyl 6.17 _{CH3 CH3} h 2,6-Dichlorobenzyl

Table 7 Compound No. R ₁ R ₂ R ₄ physical data 7.01 _{CH3 CH3} 2,3-Dichlorophenyl 7.02 _{CH3 CH3} 2-Chlorophenyl 7.03 _{CH3 CH3} 2,4-Dichlorophenyl 7.04 _{CH3 CH3} 2,5-Dichlorophenyl 7.05 _{CH3 CH3} 2,6-Dichlorophenyl 7.06 _{CH3 CH3} 2-Methylphenyl 7.07 _{CH3 CH3} 2-isopropylphenyl 7.08 _{CH3 CH3} 2-CF ₃ -phenyl 7.09 _{CH3 CH3} 2-methoxyphenyl 7.10 _{CH3 CH3} 2-Methyl-5-chlorophenyl 7.11 _{CH3 CH3} Phenyl 7.12 _{CH3 CH3} 3-Methylphenyl 7.13 _{CH3 CH3} 2-Chloro-4-methylphenyl 7.14 _{CH3 CH3} 2-cyano-4-chlorophenyl 7.15 _{CH3 CH3} 3-CF ₃ -phenyl 7.16 _{CH3 CH3} 4-Chlorophenyl 7.17 _{CH3 CH3} 2-cyanophenyl 7.18 _{CH3 CH3} 2-Methyl-3-chlorophenyl 7.19 _{CH3 CH3} 2-Methyl-4-chlorophenyl 7.20 _{CH3 CH3} 2,3-Dimethylphenyl 7.21 _{CH3 CH3} 2,6-Dimethylphenyl 7.22 _{CH3 CH3} 2-Methyl-6-chlorophenyl 7.23 _{CH3 CH3} 4-Methylphenyl 7.24 _{CH3 CH3} 2-Ethylphenyl 7.25 _{CH3 CH3} 2-fluorophenyl 7.26 _{CH3 CH3} 2-biphenyl 7.27 _{CH3 CH3} 3,4-Dichlorophenyl 7.28 _{CH3 CH3} 3,5-Dichlorophenyl 7.29 _{CH3 CH3} 4-methyl-3-chlorophenyl 7.30 _{CH3 CH3} 3-cyanophenyl 7.31 _{CH3 CH3} 3-Chlorophenyl 7.32 _{CH3 CH3} 3-fluorophenyl 7.33 _{CH3 CH3} 3-methoxyphenyl 7.34 _CH3 OCH ₃ 2-Methylphenyl 7.35 _CH3 OCH ₃ 2,5-Dichlorophenyl 7.36 _{CH3 CH3} 2,4,5-Trichlorophenyl Table 8

Compound No. R ₁ R ₂ R ₄ physical data 8.01 _{CH3 CH3} 2,3-Dichlorophenyl 8.02 _{CH3 CH3} 2-Chlorophenyl 8.03 _{CH3 CH3} 2,4-Dichlorophenyl 8.04 _{CH3 CH3} 2,5-Dichlorophenyl 8.05 _{CH3 CH3} 2,6-Dichlorophenyl 8.06 _{CH3 CH3} 2-Methylphenyl 8.07 _{CH3 CH3} 2-isopropylphenyl 8.08 _{CH3 CH3} 2-CF ₃ -phenyl 8.09 _{CH3 CH3} 2-methoxyphenyl 8.10 _{CH3 CH3} 2-Methyl-5-chlorophenyl 8.11 _{CH3 CH3} Phenyl 8.12 _{CH3 CH3} 3-Methylphenyl 8.13 _{CH3 CH3} 2-Chloro-4-methylphenyl 8.14 _{CH3 CH3} 2-cyano-4-chlorophenyl 8.15 _{CH3 CH3} 3-CF ₃ -phenyl 8.16 _{CH3 CH3} 4-Chlorophenyl 8.17 _{CH3 CH3} 2-cyanophenyl 8.18 _{CH3 CH3} 2-Methyl-3-chlorophenyl 8.19 _{CH3 CH3} 2-Methyl-4-chlorophenyl 8.20 _{CH3 CH3} 2,3-Dimethylphenyl 8.21 _{CH3 CH3} 2,6-Dimethylphenyl 8.22 _{CH3 CH3} 2-Methyl-6-chlorophenyl 8.23 _{CH3 CH3} 4-Methylphenyl 8.24 _{CH3 CH3} 2-Ethylphenyl 8.25 _{CH3 CH3} 2-fluorophenyl 8.26 _{CH3 CH3} 2-biphenyl 8.27 _{CH3 CH3} 3,4-Dichlorophenyl 8.28 _{CH3 CH3} 3,5-Dichlorophenyl 8.29 _{CH3 CH3} 4-methyl-3-chlorophenyl 8.30 _{CH3 CH3} 3-cyanophenyl 8.31 _{CH3 CH3} 3-Chlorophenyl 8.32 _{CH3 CH3} 3-fluorophenyl 8.33 _{CH3 CH3} 3-methoxyphenyl 8.34 _CH3 OCH ₃ 2-Methylphenyl 8.35 _CH3 OCH ₃ 2,5-Dichlorophenyl 8.36 _{CH3 CH3} 2,4,5-Trichlorophenyl Table 9

Compound No. R ₁ R ₂ R ₃ R ₄ physical data 9.01 _{CH3 CH3 CH3} 2,3-Dichlorophenyl 9.02 _{CH3 CH3 CH3} 2-Chlorophenyl 9.03 _{CH3 CH3 CH3} 2,4-Dichlorophenyl 9.04 _{CH3 CH3 CH3} 2,5-Dichlorophenyl 9.05 _{CH3 CH3 CH3} 2,6-Dichlorophenyl 9.06 _{CH3 CH3 CH3} 2,4,5-Trichlorophenyl 9.07 _{CH3 CH3 CH3} 2,4,6-Trichlorophenyl 9.08 _{CH3 CH3 CH3} 2-CF ₃ -phenyl 9.09 _{CH3 CH3 CH3} 2-fluorophenyl 9.10 _{CH3 CH3 CH3} 2-Methyl-5-chlorophenyl 9.11 _{CH3 CH3 CH3} Phenyl 9.12 _{CH3 CH3} h Phenyl 9.13 _{CH3 CH3} h 2-Chlorophenyl 9.14 _{CH3 CH3} h 2,4-Dichlorophenyl 9.15 _{CH3 CH3} h 2-fluorophenyl

9.81 _CH3 OCH _{3 CH3} 3,4-Dichlorophenyl 9.82 _CH3 OCH _{3 CH3} 2,3-Dichlorophenyl 9.83 _CH3 OCH _{3 CH3} 3,5-Dichlorophenyl 9.83 _CH3 OCH _{3 CH3} 2,4-Dichlorophenyl 9.84 _CH3 OCH _{3 CH3} 4-Chloro-2-methylphenyl 9.85 _CH3 OCH _{3 CH3} 3-Chloro-2-methylphenyl 9.86 _CH3 OCH _{3 CH3} 2,4-Dichlorophenyl 9.87 _CH3 OCH _{3 CH3} 5-Chloro-2-methylphenyl 9.88 _{CH3 CH3 CH3} 3-Bromophenyl 9.89 _{CH3 CH3 CH3} 4-Bromophenyl 9.90 _CH3 OCH _{3 CH3} 3-Bromophenyl 9.91 _CH3 OCH ₃ h 3-Bromophenyl 9.92 _CH3 OCH ₃ h 4-Methylphenyl 9.93 _{CH3 CH3} h 4-Bromophenyl 9.94 _CH3 OCH ₃ h 2,5-Dimethylphenyl 9.95 _{CH3 CH3} h 3-Bromophenyl 9.96 _{CH3 CH3} h 4-Bromophenyl 9.97 _{CH3 CH3} h 4-Bromophenyl 9.98 _{CH3 CH3} h 2,5-Dimethylphenyl 9.99 _{CH3 CH3 CH3} 3,5-Dimethylphenyl Table 10 Compound No. R ₁ R ₂ R ₄ physical data 10.01 _{CH3 CH3} 2,3-Dichlorophenyl 10.02 _{CH3 CH3} 2-Chlorophenyl 10.03 _{CH3 CH3} 2,4-Dichlorophenyl 10.04 _{CH3 CH3} 2,5-Dichlorophenyl 10.05 _{CH3 CH3} 2,6-Dichlorophenyl 10.06 _{CH3 CH3} 2,4,5-Trichlorophenyl 10.07 _{CH3 CH3} 2,4,6-Trichlorophenyl 10.08 _{CH3 CH3} 2-CF ₃ -phenyl 10.09 _{CH3 CH3} 2-fluorophenyl 10.10 _{CH3 CH3} 2-Methyl-5-chlorophenyl 10.11 _{CH3 CH3} Phenyl 10.12 _CH3 N(CH ₃ ) ₂ Phenyl 10.13 _{CH3 CH3} 2-cyanophenyl 10.14 _{CH3 CH3} 3-Chlorophenyl 10.15 _{CH3 CH3} 3-CF ₃ -phenyl 10.16 _{CH3 CH3} 2-nitrophenyl 10.17 _{CH3 CH3} 2-methoxy-5-chlorophenyl 10.18 _{CH3 CH3} 2-Methylphenyl 10.19 _{CH3 CH3} 3,4-Dichlorophenyl 10.20 _{CH3 CH3} 3-nitrophenyl 10.21 _{CH3 CH3} 3-CF ₃ -4-chlorophenyl 10.22 OCH _{3 CH3} 2-Chlorophenyl Table 11

Table 12

Compound No. R ₁ R ₄ physical data 12.01 _CH3 Phenyl 12.02 _CH3 2-Methylphenyl 12.03 _CH3 2,5-Dichlorophenyl

Example A

Active monofilament shells against powdery mildew:

7-day-old (cotyledon stage) Cucumis sativus (cucumber) plants were sprayed close to overflow with a suspension containing 63 mg/l active ingredient. The deposited layer was then allowed to dry naturally. One day later, the treated plants were inoculated with a spore suspension containing 1 x 10 ⁵ /ml of conidia of freshly collected monofilament shells and incubated for 7 days in a greenhouse at +24°C and 60% relative humidity.

The efficacy of the test compound is determined by comparison with the degree of fungal infection of untreated, similarly inoculated control plants. In this test, compounds 1.03, 1.06, 1.09, 1.10, 1.12, 1.13, 1.38, 1.39, 1.40, 1.41, 1.43, 1.44, 1.45, 1.48, 1.51, 1.64, 1.65, 1.66, 1.67, 1.68, 1.69, 1.70, 1.71, 1.73, 1.74, 1.75, 1.76, 1.78, 1.79, 1.80, 1.81, 1.83, 1.86, 1.88, 1.89, 1.90, 1.92, 1.93, 1.94, 1.95, 1.96, 1.97, 1.98, 3.01, 3.02, 3.03, 3.04, 3.07, 3.08, 3.15, 3.16, 3.31, 3.35, 3.36, 3.37, 3.39, 3.40, 3.41 showed greater than 90% potency.

The compounds were tested in the same way for their efficacy against the following pathogens: Unicola graminis on apples, Erysipha graminearum (dry inoculation) on wheat and barley, Acaria viticola on grapes.

Example B

Activity against Rust, Scab, Sclerotinia, Microglobulina Verrucous:

14-day-old (2-leaf stage) Phaseolus vulgaris (bean) plants were sprayed close to overflow with a suspension containing 63 mg/l active ingredient. The deposited layer was then allowed to dry naturally. One day later, the treated plants were inoculated with a spore suspension containing 1×10 ⁵ /ml freshly collected spores of P. verrucae, and incubated in a high humidity chamber at +23°C and >95% relative humidity for 3 days. days, and then cultivated at +24°C and 60% relative humidity for 10 days.

The efficacy of the test compound is determined by comparison with the degree of fungal infection of untreated, similarly inoculated control plants. In this test, compounds 1.01, 1.02, 1.03, 1.04, 1.06, 1.08, 1.09, 1.10, 1.11, 1.12, 1.13, 1.17, 1.37, 1.38, 1.39, 1.40, 1.41, 1.43, 1.44, 1.45, 1.48, 1.51, 1.64,1.65,1.66,1.67,1.68,1.69,1.70,1.71,1.73,1.74,1.75,1.76,1.77,1.78,1.79,1.80,1.81,1.83,1.84,1.86,1.88,1.89,1.90,1.92,1.93, 1.94, 1.95, 1.96, 1.97, 1.98, 1.99, 3.01, 3.02, 3.03, 3.04, 3.06, 3.07, 3.08, 3.09, 3.15, 3.16, 3.25, 3.31, 3.33, 3.35, 3.37, 3.38, 3.39, 3.40 and 3.41 display at least 90% efficacy.

In the same way, the compounds were tested for their efficacy against the following pathogenic bacteria:

Puccinia triticina on wheat (10-day-old plants), Sclerotinia triticina on barley, Leptosphaeria nodorum on wheat, Sclerotina apples on apples (21-day-old plants, spore suspension with 1% malt).

Example C

Activity against downy mildew

Lycopersicon esculentum (tomato) plants with 6 leaves were sprayed close to overflow with a spray suspension containing 63 mg/l active ingredient. The deposited layer was then allowed to dry naturally. One day later, the treated plants were inoculated with a spore suspension containing 1×10 ⁵ /ml freshly collected sporangia of Phytophthora infestans and then incubated in a high humidity chamber at +18°C and >95% relative humidity for 7 sky. The efficacy of the test compound is determined by comparison with the degree of fungal infection of untreated, similarly inoculated control plants. In this test, compounds 1.02, 1.03, 1.04, 1.06, 1.09, 1.10, 1.12, 1.17, 1.37, 1.38, 1.40, 1.41, 1.51, 1.65, 1.67, 1.69, 1.71, 1.73, 1.76, 1.78, 1.93, 1.95, 1.96, 1.97, 1.98, 3.01, 3.05, 3.06, 3.09, 3.40 and 3.41 showed at least 90% potency.

The compounds were tested in the same way for their efficacy against Plasmopara viticola on grapevines.

Example D

Activity after seed treatment

The compounds according to the invention can also be used in seed treatment. Its beneficial fungicidal activity was confirmed by in vitro tests with the following pathogenic bacteria: Sclerotinia tritici, Ustilago smut, Gerlachianivalis and Leptoshpaeria nodorum.

Autoclaved wheat seeds were inoculated with spores or mycelium of the pathogen and coated with test compounds at different concentrations at a final dose of 50 g a.i./100 kg of seeds. The treated seeds were then placed on agar plates and the pathogen was grown for 3-8 days at +24°C in the dark.

The efficacy of test compounds was determined by comparing the fungal growth of treated and untreated inoculated seeds.

To evaluate crop plant tolerance of the compounds, healthy wheat and barley seeds were coated with the above-mentioned doses. The seeds were then germinated in Petri dishes on wet filter paper at +18° C. for 10 days in high humidity. Plant damage was recorded and growth of treated and untreated seedlings was compared.

In this test, the compound of formula (I) showed an efficacy of at least 90% against Sclerotinia sativae.

Claims (16)

1. The compound of formula (I): In the formula, _R is hydrogen, C _1-4 alkyl, C _1-4 alkoxy, C _3-6 cycloalkyl, C _1-4 alkylthio, or two-C _1-4 alkylamino, R ₂ is hydrogen, C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio or di-C _1-4 alkylamino, R ₃ is hydrogen or methyl, R ₄ is aryl , aryl-C _1-4 alkyl, heteroaryl or heteroaryl-C _1-4 alkyl, wherein each aromatic ring may be optionally substituted, and X is CH or nitrogen. 2. The compound according to claim 1, wherein the aromatic ring in _R is optionally substituted by one, two or three groups selected from the group consisting of: halogen, C _1-4 alkyl, C _1-4 alkane Oxygen, C _1-4 haloalkyl, C _1-4 haloalkoxy, C _1-4 alkylthio, cyano, phenyl, phenoxy, nitro or the group -C(CH ₃ )=NOC _{1 -4} alkyl. 3. A compound according to claim 1 or 2, wherein _R1 is methyl, ethyl or cyclopropyl. 4. A compound according to claim 1 or 2, wherein _R2 is methyl or methoxy. 5. A compound according to claim 1 or 2, wherein the pyrazole ring is attached to an oxygen bridge at the 3 or 4 position. 6. according to the compound of claim 1 or 2, wherein R _Be chlorophenyl, dichlorophenyl, fluorophenyl, methyl-chlorophenyl, trifluoromethylphenyl, trifluoromethyl-chlorophenyl , difluoromethoxyphenyl, trifluoromethoxyphenyl, methylphenyl or dimethylphenyl. 7. according to the compound of claim 1, wherein R ₁ and R ₂ are methyl, R ₄ are chlorophenyl, dichlorophenyl, fluorophenyl, methyl-chlorophenyl, trifluoromethylphenyl, three Fluoromethyl-chlorophenyl, difluoromethoxyphenyl, trifluoromethoxyphenyl, methylphenyl or dimethylphenyl. 8. A compound according to claim 7, wherein X is CH. 9. The compound according to claim 1, selected from the group consisting of: 2-[2,4-dimethyl-6-(1-(3-trifluoromethylphenyl)-1H-pyrazol-3-yloxy) Pyrimidin-5-yl]-3-methoxymethyl acrylate; 2-[2,4-Dimethyl-6-(1-(3,5-dimethylphenyl)-1H-pyrazole-4 -yloxy)pyrimidin-5-yl]-3-methoxymethyl acrylate; 2-[2,4-dimethyl-6-(1-(5-chloro-2-methylphenyl)- 1H-pyrazol-3-yloxy)pyrimidin-5-yl]-3-methoxymethyl acrylate; and 2-[2-methyl-4-methoxy-6-(1-(5- methyl chloro-2-methylphenyl)-1H-pyrazol-3-yloxy)pyrimidin-5-yl]-3-methoxyacrylate. 10. A method of killing phytopathogenic fungi, comprising applying a fungicidally effective amount of a compound of formula (I) according to claim 1 to said fungus or its habitat. 11. A fungicidal composition comprising a compound of formula (I) as claimed in claim 1 and an agriculturally acceptable diluent. 12. according to the preparation method of the formula (I) compound of claim 1, it comprises with following formula (II) compound O-methylation:

The definitions of R ₁ , R ₂ , R ₃ , R ₄ and X in the formula are the same as those in claim 1. 13. Compounds of formula (II)

The definitions of R ₁ , R ₂ , R ₃ , R ₄ and X in the formula are the same as those in the formula (I) of claim 1. 14. Compounds of formula (III) The definitions of R ₁ , R ₂ , R ₃ and R ₄ in the formula are the same as those in the formula (I) of claim 1. 15. Compounds of formula (IX) The definitions of R ₁ , R ₃ and R ₄ in the formula are the same as those in the formula (I) of claim 1. 16. The preparation method of the compound of formula (V):

In the formula, R ₄ is optionally substituted aryl or heteroaryl as defined in claim 1; the method comprises the use of aryl- or heteroaryl pyrazolidinone of formula (XI) by H _{2 O} and oxidant oxidation prepared in situ by catalyst; the formula (XI) is as follows: where _R4 is optionally substituted aryl or heteroaryl.