KR100342383B1 - Isoxazolidine derivatives, method of preparing the same and antifungal composition comprising the same - Google Patents

Abstract

The present invention relates to isooxazolidine derivatives, which isooxazolidine derivatives have the following formula (1). This compound has a very good bactericidal effect against powdery mildew.

[Formula 1]

(Wherein

R ¹ is a hydrogen atom, C _1-6 alkyl, cyclohexyl, thioalkyl, thiophenyl, phenylsulfonyl, trifluoromethyl or pentafluoroethyl group,

R ² is a C _1-6 alkyl, phenyl, substituted phenyl, naphthyl or thiophene group, wherein substituted phenyl represents a phenyl group substituted with one to three halogen atoms, alkyl, alkoxy or trifluoromethyl groups,

X and Y are hydrogen atom, halogen atom, C _1-4 alkyl group, alkoxy group,

Z is a nitrogen atom or a methylene group.)

Description

Ixoxazolidine derivatives, preparation method thereof, and bactericidal composition comprising the same {ISOXAZOLIDINE DERIVATIVES, METHOD OF PREPARING THE SAME AND ANTIFUNGAL COMPOSITION COMPRISING THE SAME}

[Industrial use]

The present invention relates to an isoxoxazolidine derivative, a method for producing the same, and a bactericidal composition comprising the same, and more particularly to an isoxazolidine derivative having an excellent bactericidal effect.

[Prior art]

In order to be used as a disinfectant in agrohorticulture, it must have a low concentration and low dose. In addition, the target crop must be highly safe, and disinfectants must self-decompose or disappear from the soil so as not to contaminate the soil. In particular, low toxicity should not be harmful to humans and livestock.

Powdery mildew is a disease caused by powdery mildew fungi, and whitish white spots appear on the leaves, and the spots gradually spread to form white mold. Conventional fungicides for powdery mildew did not sufficiently satisfy the conditions of the fungicides described above. In particular, the sterilizing effect is not so large that an excessive amount should be used, which may cause soil pollution and may be harmful to humans and livestock.

The present invention is to solve the above problems, an object of the present invention is to provide an isoxoxolidine derivative which is excellent in bactericidal effect and can be used as a fungicide against powdery mildew.

Another object of the present invention is to provide a method for preparing the isooxazolidine derivative.

Still another object of the present invention is to provide a fungicide composition comprising the isooxazolidine derivative as an active ingredient.

In order to achieve the above object, the present invention provides an isoxazolidine derivative of the formula (1).

[Formula 1]

(Wherein

R ¹ is a hydrogen atom, C _1-6 alkyl, cyclohexyl, thioalkyl, thiophenyl, phenylsulfonyl, trifluoromethyl or pentafluoroethyl group,

R ² is a C _1-6 alkyl, phenyl, substituted phenyl, naphthyl or thiophene group, wherein substituted phenyl represents a phenyl group substituted with one to three halogen atoms, alkyl, alkoxy or trifluoromethyl groups,

X and Y are hydrogen atom, halogen atom, C _1-4 alkyl group, alkoxy group,

Z is a nitrogen atom or a methylene group.)

The present invention also provides a method for preparing the isooxazolidine derivative of Formula 1 comprising the step of condensation reaction of a compound of Formula 2 and a compound of Formula 3 in the presence of a base.

[Formula 2]

[Formula 3]

(In Chemical Formulas 2 and 3, R ¹ , R ² , X, Y, and Z are the same as defined in Formula 1 above.)

In addition, the present invention provides a fungicide composition comprising the isooxazolidine derivative of Formula 1 as an active ingredient.

Hereinafter, the present invention will be described in more detail.

The present invention relates to an isoxoxazolidine derivative of the formula (1) which is a novel compound having bactericidal effect against powdery mildew.

[Formula 1]

In Chemical Formula 1,

R ¹ is a hydrogen atom, C _1-6 alkyl, cyclohexyl, thioalkyl, thiophenyl, phenylsulfonyl, trifluoromethyl or pentafluoroethyl group,

R ² is a C _1-6 alkyl, phenyl, substituted phenyl, naphthyl or thiophene group, wherein substituted phenyl represents a phenyl group substituted with one to three halogen atoms, alkyl, alkoxy or trifluoromethyl groups,

X and Y are hydrogen atom, halogen atom, C _1-4 alkyl group, alkoxy group,

Z is a nitrogen atom or a methylene group.

In the compound of Formula 1, a more preferable compound is R ¹ is a hydrogen atom or a trifluoromethyl group, R ² is phenyl or substituted phenyl, X is a hydrogen atom or a halogen atom, Y is a halogen atom, Z Is a compound that is a nitrogen atom.

The isooxazolidine derivative of Chemical Formula 1 is a compound having a new structure in which a fluorine group-substituted olefin is introduced into an oxazoline compound including azole, and exhibits an excellent bactericidal effect against powdery mildew that damages various crops.

The isooxazolidine derivative of Chemical Formula 1 of the present invention may be prepared by the same method as in Scheme 1 below.

Scheme 1

(In the above Chemical Formulas 1, 2 and 3, R ¹ , R ² and X, Y, Z are as defined above.)

As shown in Scheme 1, the compound of Formula 1 of the present invention is 3-aryl-5-[(aryloxy) methyl] -3-[(azol-1-yl) methyl] -2-methyl Isooxazolidine derivatives are prepared by the condensation reaction of 1,1-difluorovinyl derivatives of Formula 3 in the presence of a base. As the base, any base that can be generally used in the condensation reaction can be used, and representative examples thereof include sodium carbonate (NaCO ₃ ), sodium hydride (NaH), caustic soda (NaOH), lithium hydroxide (LiOH), and the like. Can be used. It is preferable to mix the compounds of Formula 2 and Formula 3 in the same ratio, and when the compound of Formula 2 is used in excess of the compound of Formula 3, an undesired compound may be prepared, and the compound of Formula 3 may be The reaction does not proceed well when used in excess of the compound.

In the condensation reaction, well-dried acetonitrile, N, N-dimethylformamide, tetrahydrofuran, or the like may be used. As for the reaction temperature of the said condensation reaction, 0 degreeC-50 degreeC are preferable, and reaction time is suitable for 2 hours-10 hours. If the reaction temperature is less than 0 ° C, the reaction does not occur well, and 50 ° C is sufficient, so there is no need to increase the temperature anymore.

In Scheme 1, the compound of Formula 2 and the compound of Formula 3 used as starting materials may be prepared according to known literature.

Each compound prepared above may be separated and purified according to conventional methods such as crystallization and chromatography. In order to confirm whether the compound prepared in the preparation method of the present invention is the compound of Chemical Formula 1, the compound was identified through IR, NMR, mass spectrometry, and the like.

Since the isoxoxazolidine derivative of Formula 1 of the present invention exhibits excellent bactericidal effect against powdery mildew, it can be used as an active ingredient in fungicide compositions. The compound of the present invention is a new type of compound having a different structural skeleton from a conventional powdery mildew fungicide, and its medicinal effect is equivalent to flusilazole, a conventional powdery mildew fungicide, and exhibits superior activity than benomyl.

In the fungicide composition of the present invention comprising, as an active ingredient, an isooxazolidine compound derivative having a vinyl group containing a fluorine group represented by the above formula (1), the amount of the compound of formula (1) as an active ingredient is 0.01 to 90% by weight.

In addition to the excipients, the fungicide compositions of the present invention may further comprise suitable solid carriers, liquid carriers or other suitable auxiliaries such as surfactants, adhesives and the like. This fungicide composition may be used by formulating an agricultural composition by mixing the active ingredient with the excipient. As a method of formulating into an agricultural composition, any method generally used may be used. At this time, usable solid carriers include talc, clay, bentonite, pyrophyllite, kaolin, diatomaceous earth, silica and the like; Liquid carriers include xylene, toluene, methylnaphthalene, N-alkylpyrrolidone and the like; Surfactants include, but are not limited to, nonionic surfactants (eg, polyoxyethylene alkylphenylethers and polyoxyethylene fatty acid esters), anionic surfactants (eg, alkylbenzenesulfonates, ligninsulfonates, and dinaphthylmethanesulfonates). ) And the like; Polyvinyl alcohol, carboxymethyl cellulose, gum arabic and the like may be used as the adhesive.

In addition, the disinfectant composition containing the isooxazolidine derivative having a vinyl group containing a fluorine group represented by the formula (1) as an active ingredient is powder, hydrated powder, granules, emulsion concentrate, suspension solution, fumigant, gas, face, etc. It can be used to sterilize agricultural products, seedlings, seeds as well as soil. For example, an isooxazolidine derivative having a vinyl group substituted with a fluorine group represented by Chemical Formula 1 may be uniformly dissolved in a hydrocarbon, acetone or alcohol with a suitable surfactant to prepare an emulsion concentrate or suspension solution. In addition, the isooxazolidine derivative of Chemical Formula 1 may be mixed with an inorganic powder and a suitable surfactant, and pulverized and homogenized to obtain a fine powder to prepare a hydrated powder. The composition thus prepared may be diluted with water of a desired concentration, mixed with inorganic powder, crushed and mixed homogeneously, and used as dust. Finally, the composition is diluted so as to contain an effective amount of isooxazolidine derivative having a vinyl group containing a fluorine group represented by Chemical Formula 1 above. In addition, the composition may be combined with other agrochemicals such as insecticides, fungicides, herbicides, plant growth regulators, acaricides and the like. You can also mix them with nutrients.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited by the following examples.

Example 1 Cis-2-methyl-3-phenyl-5- [4- (1,3,3,3-tetrafluoro-2-phenyl-1-propenyloxy) phenoxymethyl] -3- Synthesis of ( 1H -1,2,4-triazol-1-ylmethyl) tetrahydroisoxazole

The title compound was prepared in the same manner as in Scheme 2 below.

Scheme 2

The synthesis method of the above formula is described in detail.

1) Cis-4- [2-methyl-3-phenyl-3- (1H-1,2,4-triazol-1-ylmethyl) tetrahydro-5-isoxazolylmethoxy] phenol of the formula Synthesis of

[Formula 2a]

51.7 g (0.26 mol) of 2-bromoacetophenone was dissolved in 250 ml of methanol, and then 19.18 g (0.28 mol) of 1,2,4-triazole and 40.2 ml (0.29 mol) of triethylamine were added. The mixture was stirred at reflux for 12 hours.

After the reaction, the obtained reaction mixture was poured into ethyl acetate, washed several times with water, dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the mixture was then mixed with tube chromatography (silica gel; n-hexane and ethyl acetate in an eluent ratio of 4: 1). 35.5g (yield 73%) of 2- (triazol-1-yl) acetophenones were obtained.

Then, 14.6 g (0.078 mol) of 2- (triazol-1-yl) acetophenone obtained above was dissolved in 300 ml of ethanol, and then N -methylhydroxylamine hydrochloride ?? 11.68 g (0.14 mole) and sodium acetate 24.1 g (0.23 mole) were added thereto, and the mixture was stirred under reflux for 48 hours. After the reaction, chloroform is poured, the organic layer is washed several times with water, dried over anhydrous magnesium sulfate, and the solvent is removed under reduced pressure. Then, tube chromatography (silica gel, eluent is used as a mixture of chloroform and methanol in a volume ratio of 10: 1) is used. 12.3 g (yield 73%) of 2- ( 1H -triazol-1-yl) -N -methyl-1-phenylethanimine N -oxides were obtained.

Subsequently, 10.8 g (0.05 mol) of 2- ( 1H -triazol-1-yl) -N -methyl-1-phenylethaneimine N -oxide was dissolved in 300 ml of toluene, followed by 8.25 (0.055 mol) of allyloxyphenol. It was stirred at reflux for 48 hours. After the reaction, the resulting solid was filtered. The filtered solid was recrystallized once more in toluene to give cis-4- [2-methyl-3-phenyl-3- ( 1H -1,2,4-triazol-1-ylmethyl) of the above formula 2a as a white powder. ) 5.4 g (50% yield) of tetrahydro-5-isoxazolylmethoxy] phenol were obtained.

2) cis-2-methyl-3-phenyl-5- [4- (1,3,3,3-tetrafluoro-2-phenyl-1-propenyloxy) phenoxymethyl]- Synthesis of 3- ( 1H -1,2,4-triazol-1-ylmethyl) tetrahydroisoxazole

[Formula 1a]

[Formula 3a]

168 mg (0.46 mmol) cis-4- [2-methyl-3-phenyl-3- ( 1H -1,2,4-triazol-1-ylmethyl) tetrahydro-5-isoxazolylmethoxy] phenol ) Was dissolved in 20 ml of acetonitrile, and then 36.8 mg of sodium hydride (0.69 mmol) was added at room temperature, and after about 30 minutes, 1,1,3,3,3-pentafluoro-2-phenylpropene of Formula 3a was added. 114.8 mg (0.55 mmol) was added and stirred at 50 ° C. for 12 hours. After the reaction was completed, the reaction mixture was poured into ethyl acetate at room temperature, washed several times with water and brine, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. Then, tube chromatography (silica gel; eluent was mixed with n-hexane and ethyl acetate in 4: 1). 121 mg (yield 47.5%) of the compound of Formula 1a was obtained.

(Example 2-190)

The compound of Formula 1 shown in Table 1-32 was prepared in the same manner as in Example 1, changing the starting material to suit the desired compound. In Formula 1, R ¹ , R ² , X, Y and Z are shown in Tables 1-32.

Melting points and NMR data values of the compounds prepared by the methods of Examples 1-190 were measured, and the results are shown in Table 1 below.

[Formula 1]

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ One H H N H Phenyl 7.79 (s, 1H), 6.99-7.47 (m, 15H), 5.65 (d, J = 6Hz, 1H), 4.9 (m, 1H), 4.67 (d, d, J = 36,14Hz, 2H), 4.31 (d, J = 4.4Hz, 2H), 2.85 (d, J = 7.4Hz, 2H), 2.58 (s, 3H) oil 2 H H N H 4-fluorophenyl 7.76 (s, 1H), 6.92-7.42 (m, 14H), 5.59 (d, J = 5.66Hz, 1H), 4.88 (m, 1H), 4.64 (d, d, J = 36.67,14Hz, 2H), 4.28 (d, J = 4.55Hz, 2H), 2.83 (d, J = 7.61Hz, 2H), 2.55 (s, 3H) 73-76 3 H H N H 4-methoxyphenyl 7.78 (s, 1H), 6.83-7.41 (m, 14H), 5.62 (d, J = 5.66Hz, 1H), 4.91 (m, 1H), 4.67 (d, d, J = 35.3,14Hz, 2H), 4.32 (d, J = 1.88Hz, 2H), 3.79 (s, 3H), 2.86 (d, J = 7.32HZ, 2H), 2.58 (s, 3H) oil 4 H H N H 4-methylphenyl 7.77 (s, 1H), 6.96-7.53 (m, 14H), 5.61 (d, J = 5.9Hz, 1H), 4.88 (m, 1H), 4.65 (d, d, J = 35.8,13.9Hz, 2H) , 4.28 (m, 2H), 2.83 (d, J = 7.41Hz, 2H), 2.56 (s, 3H), 2.31 (d, J = 4.68Hz, 3H) oil 5 H H N H 2,4,5-trimethyl-phenyl 7.76 (s, 1H), 6.93-7.32 (m, 12H), 5.69 (d, J = 6.2Hz, 1H), 4.88 (m, 1H), 4.65 (d, d, J = 34.7,14Hz, 2H), 4.28 (d, J = 4.64,2H), 2.83 (d, J = 7.61H ₃ , 2H), 2.56 (s, 3H), 2.18 (s, 3H), 2.16 (s, 3H), 2.14 (s, 3H ) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 6 H H N H 3-fluorophenyl 7.77 (s, 1H), 6.8-7.3 (m, 14H), 5.6 (d, J = 5.7Hz, 1H), 4.85 (m, 1H), 4.66 (d, d, J = 36,11Hz, 2H), 4.3 (d, J = 4Hz, 2H), 2.85 (d, J = 9Hz, 2H), 2.57 (s, 3H) oil 7 H H N H 4-ethylphenyl 7.7 (s, 1H), 6.8-7.3 (m, 14H), 5.6 (d, J = 5.8Hz, 1H), 4.8 (m, 1H), 4.6 (d, d, J = 24,4Hz, 2H), 4.2 (d, J = 4.7Hz, 2H), 2.76 (d, J = 7.1Hz, 2H), 2.54 (q, 2H), 2.51 (s, 3H), 1.13 (t, J = 7.5Hz, 3H) oil 8 H H N H 3-chlorophenyl 7.78 (s, 1H), 6.9-7.7 (m, 14H), 5.5 (d, J = 5.7Hz, 1H), 4.85 (m, 1H), 4.62 (d, d, 2H), 4.29 (d, 2H) , 2.84 (d, 2H), 2.56 (s, 3H), oil 9 H H N H 3-isopropoxy-phenyl 7.77 (s, 1H), 6.69-7.32 (m, 14H), 5.59 (d, J = 3.4Hz, 1H), 4.9 (m, 1H), 4.66 (d, d, J = 47,15Hz, 2H), 4.46 (m, 1H), 4.3 (d, J = 4Hz, 2H), 2.84 (d, J = 7Hz, 2H), 2.55 (s, 3H), 1.3 (d, 6H) oil 10 H Cl N H 3-isopropoxy-phenyl 7.78 (s, 1H), 6.69-7.46 (m, 13H), 5.59 (d, J = 6Hz, 1H), 4.85 (m, 1H), 4.6 (d, d, J = 25,12Hz, 2H), 4.47 (m, 1H), 4.27 (d, J = 6Hz, 2H), 2.83 (2H), 2.55 (s, 3H), 1.3 (d, 6H) oil 11 H H N H 3-methyl-4-chloro-phenyl 7.76 (s, 1H), 6.94-7.32 (m, 13H), 5.54 (d, J = 6Hz, 1H), 4.89 (m, 1H), 4.63 (d, d, J = 40,15Hz, 2H), 4.29 (m, 2H), 2.86 (m, 2H), 2.56 (s, 3H), 2.31 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 12 H H N H 3,4-methylenedioxyphenyl 7.77 (s, 1H), 6.71-7.34 (m, 13H), 5.92 (s, 2H), 5.57 (d, J = 4Hz, 1H), 4.9 (m, 1H), 4.65 (d, d, J = 38 , 14 Hz, 2H), 4.27 (d, J = 4 Hz, 2H), 2.84 (d, J = 10 Hz, 2H), 2.55 (s, 3H) oil 13 H Cl N H 3-methyl-4-chloro-phenyl 7.79 (s, 1H), 6.96-7.49 (m, 12H), 5.56 (d, J = 6Hz, 1H), 4.88 (m, 1H), 4.6 (d, d, J = 26,14Hz, 2H), 4.29 (m, 2H), 2.84 (m, 2H), 2.56 (s, 3H), 2.34 (s, 3H) oil 14 H H N H 4-ethoxyphenyl 7.74 (s, 1H), 6.77-7.33 (m, 14H), 5.57 (d, 1H), 4.86 (m, 1H), 4.63 (d, d, 2H), 4.27 (d, 2H), 3.99 (q, 2H), 2.81 (d, 2H), 2.54 (s, 3H), 1.36 (t, 3H) oil 15 H H N H 3-methoxyphenyl 7.76 (s, 1H), 6.71-7.3 (m, 14H), 5.6 (d, 1H), 4.8 (m, 1H), 4.64 (d, d, 2H), 4.28 (d, 2H), 3.73 (s, 3H), 2.82 (d, 2H), 2.55 (s, 3H) oil 16 H F N H Phenyl 6.85-7.51 (m, 15H), 5.62 (d, J = 6Hz, 1H), 4.8 (m, 1H), 3.77-4.63 (m, 4H), 2.7 (2H), 2.5 (s, 3H) oil 17 H Cl N H Phenyl 6.77-7.87 (m, 15H), 5.65 (d, J = 5.86Hz, 1H), 4.8 (m, 1H), 4.6 (d, d, J = 36.6,14.2Hz, 2H) 4.12 (m, 2H), 2.8 (m, 2H), 2.58 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 18 H H N H Naphthyl 6.91-7.84 (m, 18H), 6.23 (d, J = 5.8Hz, 1H), 4.86 (m, 1H), 4.65 (d, d, J = 40,15.2Hz, 2H), 4.25 (m, 2H) , 2.82 (t, J = 7.61Hz, 2H), 2.55 (s, 3H) oil 19 H Cl N H 4-methoxyphenyl 7.86 (s, 1H), 6.77-7.38 (m, 13H), 5.61 (d, J = 5.54Hz, 1H), 4.79 (m, 1H), 4.68 (d, d, J = 36.3,14.2Hz, 1H) , 4.12 (m, 2H), 3.79 (s, 3H), 2.83 (m, 2H), 2.58 (s, 3H) oil 20 H Cl N H 4-chlorophenyl 7.77 (s, 1H), 6.94-7.46 (m, 13H), 5.58 (d, J = 5.6Hz, 1H), 4.86 (m, 1H), 4.63 (d, d, J = 14.2,25.6Hz, 2H) 4.27 (m, 2H), 2.83 (m, 2H), 2.55 (s, 3H) oil 21 H Cl N H 3,4-methylenedioxyphenyl 7.79 (s, 1H), 6.7-7.47 (m, 12H), 5.93 (s, 2H), 5.57 (d, J = 6Hz, 1H), 4.8 (m, 1H), 4.63 (dd, J = 26,13Hz , 2H), 4.28 (m, 2H), 2.85 (m, 2H), 2.56 (s, 3H) oil 22 H OCH ₃ N H Phenyl 6.83-7.79 (m, 15H), 5.65 (d, J = 5.8Hz, 1H), 4.9 (m, 1H), 4.7 (d, d, J = 43.4,16Hz, 2H), 4.30 (m, 2H), 3.81 (s, 3H), 2.8 (d, J = 7.6Hz, 2H), 2.56 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 23 H OCH ₃ N H 4-methoxyphenyl 7.77 (s, 1H), 6.8-7.37 (m, 13H), 5.58 (d, J = 5.7Hz, 1H), 4.9 (m, 1H), 4.6 (m, 2H), 4.27 (m, 2H), oil 24 H OCH ₃ N H 4-chlorophenyl 7.82 (s, 1H), 6.85-7.42 (m, 13H), 5.61 (d, J = 5.66Hz, 1H), 5.9 (m, 1H), 4.65 (d, d, J = 39.8,13.8Hz, 2H) , 4.33 (t, 2H), 3.83 (s, 3H), 2.81 (m, 2H), 2.57 (s, 3H) oil 25 H OCH ₃ N H 3-fluorophenyl 7.79 (s, 1H), 6.81-7.78 (m, 13H), 5.61 (d, 1H), 4.83 (m, 1H), 4.63 (d, d, 2H), 4.31 (d, 2H), 3.79 (s, 3H), 2.79 (d, 2H), 2.54 (s, 3H) oil 26 H OCH ₃ N H 3-isopropoxy-phenyl 7.78 (s, 1H), 6.7-7.77 (m, 13H), 5.59 (d, 1H), 4.88 (m, 1H), 4.61 (d, d, 2H), 4.48 (m, 1H), 4.28 (d, 2H), 3.79 (s, 3H), 2.78 (d, 2H), 2.53 (s, 3H), 1.28 (d, 6H) oil 27 H OCH ₃ N H 3-chlorophenyl 7.81 (s, 1H), 6.83-7.8 (m, 13H), 5.57 (d, J = 5.66Hz, 1H), 4.91 (m, 1H), 4.64 (d, d, J = 39.8,14.2Hz, 2H) , 4.34 (m, 2H), 3.81 (s, 3H), 2.83 (m, 2H), 2.56 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 28 H OCH ₃ N H 3-methylphenyl 7.78 (s, 1H), 6.8-7.29 (m, 13H), 5.6 (d, J = 6.1Hz, 1H), 4.87 (m, 1H), 4.62 (d, d, J = 37,12.2Hz, 2H) 4.28 (d, J = 4.6Hz, 2H), 3.79 (s, 3H), 2.8 (d, 2H), 2.54 (s, 3H), 2.3 (s, 3H) oil 29 H OCH ₃ N H 4-ethylphenyl 7.78 (s, 1H), 6.81-7.37 (m, 13H), 5.63 (d, 1H), 4.83 (m, 1H), 4.63 (d, d, 2H), 4.29 (d, 2H), 3.8 (s, 3H), 2.79 (d, 2H), 2.59 (q, 2H), 2.54 (s, 3H), 1.21 (t, 3H) oil 30 H OCH ₃ N H 4-ethoxyphenyl 7.77 (s, 1H), 6.78-7.35 (m, 13H), 5.59 (d, 1H), 4.86 (m, 1H), 4.62 (d, d, 2H), 4.28 (d, 2H), 3.99 (q, 2H), 3.78 (s, 3H), 2.78 (d, 2H), 2.53 (s, 3H), 1.38 (t, 3H) oil 31 H OCH ₃ N H 3-methoxyphenyl 7.78 (s, 1H), 6.82-7.28 (m, 13H), 5.61 (d, J = 5.8Hz, 1H), 4.9 (m, 1H), 4.63 (d, d, J = 38.2,14Hz, 2H), 4.29 (m, 2H), 3.79 (s, 3H), 3.75 (s, 3H), 2.8 (d, J = 7.8Hz, 2H), 2.54 (s, 3H) oil 32 H OCH ₃ N H 3,5-dimethylphenyl 7.77 (s, 1H), 6.81-7.3 (m, 12H), 5.56 (d, 1H), 4.87 (m, 1H), 4.63 (d, d, 2H), 4.28 (d, 2H), 3.79 (s, 3H), 2.78 (d, 2H), 2.54 (s, 3H), 2.26 (s, 6H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 33 H OCH ₃ N H 3,4-methylenedioxyphenyl 7.78 (s, 1H), 6.71-7.28 (m, 12H), 5.92 (s, 2H), 5.57 (d, 1H), 4.9 (m, 1H), 4.67 (d, d, 2H), 4.29 (d, 2H), 3.79 (s, 3H), 2.79 (d, 2H), 2.54 (s, 3H) oil 34 Cl Cl N H 3,4-methylenedioxyphenyl 7.74 (s, 1H), 6.69-7.55 (m, 11H), 5.89 (s, 2H), 5.57 (d, 1H), 4.89 (m, 2H), 4.69 (m, 1H), 4.26 (m, 2H) , 3.01 (m, 2H), 2.68 (s, 3H) oil 35 H CH ₃ N H Phenyl 7.76 (s, 1H), 6.94-7.43 (m, 14H), 5.62 (d, J = 5.98Hz, 1H), 4.87 (m, 1H), 4.6 (d, d, J = 36.9,13.8Hz, 2H) , 4.28 (m, 2H), 2.79 (d, J = 7.2Hz, 2H), 2.53 (s, 3H), 2.318 (s, 3H) oil 36 H CH ₃ N H 4-chlorophenyl 7.78 (s, 1H), 6.92-7.4 (m, 13H), 5.6 (d, J = 5.8Hz, 1H), 4.9 (m, 1H), 4.6 (d, d, J = 38.1,13.9Hz, 2H) , 4.3 (m, 2H), 2.8 (d, J = 7.6Hz, 2H), 2.56 (s, 3H), 2.35 (s, 3H) oil 37 H CH ₃ N H 4-methylphenyl 7.77 (s, 1H), 6.9-7.33 (m, 13H), 5.6 (d, J = 5.9Hz, 1H), 4.87 (m, 1H), 4.63 (d, d, J = 36.2,13.8Hz, 2H) , 4.27 (d, J = 4.5Hz, 2H), 2.79 (d, J = 7.5Hz, 2H), 2.54 (s, 3H), 2.32 (s, 3H), 2.3 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 38 H CH ₃ N H 3-methylphenyl 7.77 (s, 1H), 6.8-7.2 (m, 13H), 5.6 (d, J = 5.9Hz, 1H), 4.87 (m, 1H), 4.63 (d, d, J = 37,17Hz, 2H), 4.28 (d, J = 4.6Hz, 2H), 2.79 (d, J = 7.3Hz, 2H), 2.48 (s, 3H), 2.33 (s, 3H), 2.30 (s, 3H) oil 39 H CH ₃ N H 3-chlorophenyl 7.78 (s, 1H), 6.91-7.45 (m, 14H), 5.57 (d, J = 5.54Hz, 1H), 4.9 (m, 1H), 4.76 (d, d, J = 37.6,14Hz, 2H), 4.3 (m, 2H), 2.84 (m, 2H), 2.57 (s, 3H), 2.35 (s, 3H) oil 40 H CH ₃ N H 4-methoxyphenyl 7.76 (s, 1H), 6.8-7.37 (m, 13H), 5.60 (d, J = 5.8Hz, 1H), 4.87 (m, 1H), 4.62 (d, d, J = 36.4,13.8Hz, 2H) 4.28 (d, J = 4.6Hz, 2H), 3.77 (s, 3H), 2.79 (d, J = 7.2Hz, 2H), 2.54 (s, 3H), 2.32 (s, 3H) oil 41 Cl Cl N H 3-methylphenyl 7.74 (s, 1H), 6.89-7.56 (m, 12H), 5.6 (d, 1H), 4.91 (m, 2H), 4.71 (m, 1H), 4.27 (m, 2H), 3.01 (m, 2H) , 2.7 (s, 3H), 2.32 (s, 3H) oil 42 Cl Cl N H 3-isopropoxyphenyl 7.73 (s, 1H), 6.69-7.54 (m, 12H), 5.58 (d, 1H), 4.89 (m, 2H), 4.7 (m, 1H), 4.46 (m, 1H), 4.26 (m, 2H) , 2.99 (m, 2H), 2.68 (s, 3H), 1.25 (d, 6H) oil 43 Cl Cl N H 3-fluorophenyl 7.75 (s, 1H), 6.83-7.74 (m, 12H), 5.59 (d, 1H), 4.9 (m, 2H), 4.73 (m, 1H), 4.29 (m, 2H), 3.07 (m, 2H) , 2.7 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 44 Cl Cl N H 4-fluorophenyl 7.74 (s, 1H), 6.76-7.73 (m, 12H), 5.6 (d, 1H), 4.91 (m, 2H), 4.74 (m, 1H), 4.26 (m, 2H), 3.02 (m, 2H) , 2.69 (s, 3H) oil 45 Cl Cl N H 4-methoxyphenyl 7.73 (s, 1H), 6.79-7.55 (m, 12H), 4.9 (m, 2H), 4.71 (m, 1H), 4.25 (m, 2H), 3.77 (s, 3H), 2.99 (m, 2H) , 2.68 (s, 3H) 71-75 46 Cl Cl N H 4-methylphenyl 7.74 (s, 1H), 6.84-7.56 (m, 12H), 5.61 (d, 1H), 4.86 (m, 2H), 4.73 (m, 1H), 4.27 (m, 2H), 3.0 (m, 2H) , 2.66 (s, 3H), 2.31 (s, 3H) oil 47 Cl Cl N H 3-chlorophenyl 7.74 (s, 1H), 6.74-7.73 (m, 12H), 5.54 (d, 1H), 4.94 (m, 2H), 4.72 (m, 1H), 4.24 (m, 2H), 3.02 (m, 2H) , 2.69 (s, 3H) 94-96 48 Cl Cl N H 4-ethylphenyl 7.73 (s, 1H), 6.93-7.44 (m, 12H), 5.61 (d, 1H), 4.89 (m, 2H), 4.73 (m, 1H), 4.26 (m, 2H), 3.01 (m, 2H) , 2.69 (s, 3H), 2.61 (q, 2H), 1.24 (t, 3H) oil 49 Cl Cl N H 4-n-butylphenyl 7.73 (s, 1H), 6.91-7.55 (m, 12H), 5.61 (d, 1H), 4.89 (m, 2H), 4.73 (m, 1H), 4.27 (m, 2H), 3.0 (m, 2H) , 2.69 (s, 3H), 2.55 (t, 2H), 1.55 (m, 2H), 1.3 (m, 2H) 0.9 (t, 3H) oil 50 Cl Cl N H 3,4-dimethylphenyl 7.73 (s, 1H), 6.93-7.56 (m, 11H), 5.58 (d, 1H), 4.9 (m, 2H), 4.72 (m, 1H), 4.26 (m, 2H), 3.01 (m, 2H) , 2.69 (s, 3H), 2.21 (s, 6H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 51 Cl Cl N H 3-methyl-4-chloro-phenyl 7.75 (s, 1H), 6.9-7.56 (m, 12H), 5.55 (d, 1H), 4.91 (m, 2H), 4.74 (m, 1H), 4.28 (m, 2H), 3.02 (m, 2H) , 2.7 (s, 3H), 2.35 (s, 3H) oil 52 Cl Cl N H 3,5-dimethylphenyl 7.74 (s, 1H), 6.83-7.56 (m, 11H), 5.56 (d, 1H), 4.91 (m, 2H), 4.73 (m, 1H), 4.27 (m, 2H), 3.01 (m, 2H) , 2.7 (s, 3H), 2.28 (s, 6H) oil 53 Cl Cl N H 2,4,5-trimethylphenyl 7.73 (s, 1H), 6.92-7.55 (m, 11H), 5.69 (d, 1H), 4.9 (m, 2H), 4.72 (m, 1H), 4.26 (m, 2H), 3.02 (m, 2H) , 2.69 (s, 3H), 2.17 (m, 9H) oil 54 H H N CF ₃ Phenyl 7.79 (s, 1H), 6.94-7.41 (m, 15H), 4.90 (m, 1H), 4.51 (d, d, J = 38.7,14Hz, 2H), 4.33 (m, 2H), 2.86 (m, 2H ), 2.58 (s, 3H) 90-92 55 H H N CF ₃ 4-methylphenyl 7.76 (s, 1H), 6.95-7.33 (m, 12H), 4.88 (m, 1H), 4.65 (d, d, J = 38,15.6Hz, 2H), 4.27 (d, J = 4.8Hz, 2H) , 2.83 (d, J = 7.2Hz, 2H), 2.56 (s, 3H), 2.34 (s, 3H) oil 56 H H N CF ₃ 4-ethylphenyl 7.76 (s, 1H), 6.902-7.271 (m, 14H), 4.847 (m, 1H), 4.64 (d, d, J = 37.8,14Hz, 2H), 4.25 (d, J = 3.8Hz, 2H), 2.82 (d, J = 6.6Hz ,, 2H), 2.61 (q, J = 6.2Hz, 2H), 2.534 (s, 3H), 1.21 (t, J = 7.2Hz ,, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 57 H H N CF ₃ 4-n-butylphenyl 7.74 (s, 1H), 6.9-7.3 (m, 14H), 4.84 (m, 1H), 4.62 (d, d, 2H), 4.25 (d, 2H), 2.8 (d, 2H), 2.56 (t, 2H), 2.52 (s, 3H), 1.56 (m, 2H), 1.3 (m, 2H), 0.9 (t, 3H) 90-92 58 H H N CF ₃ 4-methoxyphenyl 7.77 (s, 1H), 6.85-7.3 (m, 14H), 4.87 (m, 1H), 4.65 (d, d, J = 38,14Hz, 2H), 4.26 (d, J = 4.6Hz, 2H), 3.77 (s, 3H), 2.83 (d, J = 7.4Hz, 2H), 2.55 (s, 3H) oil 59 H H N CF ₃ 4-trifluoromethyl-phenyl 7.786 (s, 1H), 6.974-7.637 (m, 14H), 4.897 (m, 1H), 4.66 (d, d, J = 39.4,14Hz, 2H), 4.29 (d, J = 4.4Hz, 2H), 2.85 (d, J = 7.2 Hz, 2H), 2.576 (s, 3H) oil 60 H H N CF ₃ 4-fluorophenyl 7.778 (s, 1H), 6.914-7.335 (m, 14H), 4.884 (m, 1H), 4.66 (d, d, J = 39.2,13.8Hz, 2H), 4.28 (d, J = 4.4Hz, 2H) , 2.84 (d, J = 7.4Hz ,, 2H), 2.563 (s, 3H) oil 61 H H N CF ₃ 4-chlorophenyl 7.773 (s, 1H), 6.959-7.365 (m, 14H), 4.869 (m, 1H), 4.65 (d, d, J = 39.2,13.8Hz, 2H), 4.27 (d, J = 4.6Hz, 2H) , 2.83 (d, J = 7Hz ,, 2H), 2.547 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 62 H H N CF ₃ 4-bromophenyl 7.78 (s, 1H), 6.9-7.6 (m, 14H), 4.83 (m, 1H), 4.7 (d, d, 2H), 4.3 (d, 2H), 2.84 (d, 2H), 2.57 (s, 3H) oil 63 H H N CF ₃ 3-methylphenyl 7.76 (s, 1H), 6.95-7.31 (m, 14H), 4.86 (m, 1H), 4.64 (d, d, J = 38,14Hz, 2H), 4.26 (d, J = 4.6Hz, 2H), 2.82 (d, J = 6.6 Hz, 2H), 2.54 (s, 3H), 2.33 (s, 3H) 64 to 65 64 H H N CF ₃ 3-methoxyphenyl 7.77 (s, 1H), 6.87-7.3 (m, 14H), 4.87 (m, 1H), 4.65 (d, d, J = 38,14.2Hz, 2H), 4.27 (d, J = 4.2Hz, 2H) , 3.76 (s, 3H), 2.83 (d, J = 7Hz ,, 2H), 2.55 (s, 3H) oil 65 H H N CF ₃ 3-trifluoromethylphenyl 7.78 (s, 1H), 6.96-7.77 (m, 14H), 4.88 (m, 1H), 4.66 (d, d, 2H), 4.3 (d, 2H), 2.85 (d, 2H), 2.57 (s, 3H) oil 66 H H N CF ₃ 3-fluorophenyl 7.77 (s, 1H), 6.9-7.3 (m, 14H), 4.84 (m, 1H), 4.7 (d, d, 2H), 4.29 (d, 2H), 2.85 (d, 2H), 2.56 (s, 3H) oil 67 H H N CF ₃ 3-chlorophenyl 7.762 (s, 1H), 6.952-7.357 (m, 14H), 4.858 (m, 1H), 4.64 (d, d, J = 38.8,13.8Hz, 2H), 4.26 (d, J = 4.4Hz, 2H) , 2.82 (d, J = 6.6Hz ,, 2H), 2.538 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 68 H H N CF ₃ 3,4-dimethylphenyl 7.778 (s, 1H), 6.972-7.345 (m, 13H), 4.9 (m, 1H), 4.66 (d, d, J = 35,10.6Hz, 2H), 4.29 (m, 2H), 2.84 (d, J = 7.8Hz, 2H), 2.57 (s, 3H), 2.28 (s, 3H), 2.256 (s, 3H) oil 69 H H N CF ₃ 3,5-dimethylphenyl 7.77 (s, 1H), 6.96-7.33 (m, 13H), 4.88 (m, 1H), 4.65 (d, d, J = 37,13Hz, 2H), 4.29 (m, 2H), 2.83 (d, J = 7.4 Hz, 2H), 2.56 (s, 3H), 2.33 (s, 3H), 2.297 (s, 3H) 79-82 70 H H N CF ₃ 3,5-dichlorophenyl 7.791 (s, 1H), 6.995-7.41 (m, 13H), 4.91 (m, 1H), 4.67 (d, d, J = 40.4,14Hz, 2H), 4.32 (m, 2H), 2.86 (d, J = 7 Hz, 2H), 2.578 (s, 3H) oil 71 H H N CF ₃ 3,4-methylenedioxyphenyl 7.77 (s, 1H), 6.786-7.338 (m, 13H), 5.98 (s, 2H), 4.88 (m, 1H), 4.64 (d, d, J = 37.8,12.4Hz, 2H), 4.29 (m, 2H), 2.83 (d, J = 7.6Hz, 2H), 2.56 (s, 3H) oil 72 H H N CF ₃ Thiophene 7.783 (s, 1H), 6.82-7.4 (m, 13H), 4.887 (m, 1H), 4.66 (d, d, J = 39.2,14.2Hz, 2H), 4.291 (d, J = 4.2Hz, 2H) , 2.85 (d, J = 6.2Hz, 2H), 2.564 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 73 H H N CF ₃ n-hexyl 7.788 (s, 1H), 6.971-7.346 (m, 10H), 4.908 (m, 1H), 4.67 (d, d, J = 37.4,14Hz, 2H), 4.3 (d, J = 4.2Hz, 2H), 2.86 (d, J = 7.6Hz, 2H), 2.579 (s, 3H), 2.213 (m, 2H), 1.48 (m, 2H), 1.27 (m, 6H), 0.877 (t, J = 6Hz ,, 3H ) oil 74 H H N CF ₃ Cyclohexyl 7.76 (s, 1H), 6.94-7.3 (m, 9H), 4.87 (m, 1H), 4.65 (d, d, J = 37,14Hz, 2H), 4.29 (d, J = 4.4Hz, 2H), 2.83 (d, J = 8Hz, 2H), 2.55 (s, 3H), 2.34 (m, 1H), 1.1-1.79 (m, 10H) oil 75 H CH ₃ H CF ₃ 4-chlorophenyl 7.79 (s, 1H), 6.94-7.38 (m, 13H), 4.9 (m, 1H), 4.6 (d, d, J = 39.4,14Hz, 2H), 4.3 (m, 2H), 2.81 (d, J = 8Hz, 2H), 2.56 (s, 3H), 2.35 (s, 3H) oil 76 H CH ₃ H CF ₃ 3-methylphenyl 7.766 (s, 1H), 6.95-7.277 (m, 13H), 4.855 (m, 1H), 4.62 (d, d, J = 39.6,14Hz, 2H), 4.25 (d, J = 4.6Hz, 2H), 2.79 (d, J = 7.2Hz, 2H), 2.529 (s, 3H), 2.36 (s, 3H), 2.316 (s, 3H) oil 77 H CH ₃ H CF ₃ 3-methoxyphenyl 7.79 (s, 1H), 6.88-7.34 (m, 13H), 4.9 (m, 1H), 4.64 (d, d, J = 39.9,13.9Hz, 2H), 4.3 (m, 2H), 3.84 (s, 3H), 2.81 (m, 2H), 2.56 (s, 3H), 2.35 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 78 H CH3 N CF3 3-chlorophenyl 7.79 (s, 1H), 6.93-7.38 (m, 13H), 4.89 (m, 1H), 4.64 (d, d, J = 40.6,14Hz, 2H), 4.31 (m, 2H), 2.81 (m, 2H ), 2.56 (s, 3H), 2.35 (s, 3H) oil 79 H CH ₃ N CF ₃ 3,4-dimethylphenyl 7.796 (s, 1H), 6.978-7.259 (m, 12H), 4.88 (m, 1H), 4.65 (d, d, J = 38.8,14.6Hz, 2H), 4.28 (d, J = 4.6Hz, 2H) , 2.82 (d, J = 6.8Hz, 2H), 2.558 (s, 3H), 2.342 (s, 3H), 2.289 (s, 3H), 2.256 (s, 3H) oil 80 H CH ₃ N CF ₃ 3,5-dimethylphenyl 7.77 (s, 1H), 6.9-7.26 (m, 12H), 4.88 (m, 1H), 4.63 (d, d, J = 39,14Hz, 2H), 4.3 (m, 2H), 2.79 (d, J = 7.4 Hz, 2H), 2.54 (s, 3H), 2.33 (s, 3H), 2.29 (s, 3H) oil 81 H CH ₃ N CF ₃ 3,5-dichlorophenyl 7.77 (s, 1H), 6.86-7.367 (m, 12H), 4.87 (m, 1H), 4.63 (d, d, J = 41,14Hz, 2H), 4.27 (d, J = 4.4Hz, 2H), 2.8 (d, J = 7.4Hz ,, 2H), 2.53 (s, 3H), 2.32 (s, 3H) oil 82 H CH ₃ N CF ₃ Thiophene 7.79 (s, 1H), 6.82-7.35 (m, 12H), 4.88 (m, 1H), 4.64 (d, d, J = 40,14Hz, 2H), 4.29 (d, J = 3.8Hz, 2H), 2.81 (d, J = 7.2 Hz, 2H), 2.55 (s, 3H), 2.334 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 83 H CH ₃ N CF ₃ n-hexyl 7.78 (s, 1H), 6.961-7.27 (m, 9H), 4.886 (m, 1H), 4.65 (d, d, J = 38.2,13.8Hz, 2H), 4.3 (d, J = 4.4Hz, 2H) , 2.81 (d, J = 7.4Hz, 2H), 2.549 (s, 3H), 2.331 (s, 3H), 2.23 (m, 2H), 1.49 (m, 2H), 1.27 (m, 6H), 0.87 ( t, J = 6.3 Hz ,, 3H) oil 84 H CH ₃ N CF ₃ 3,4-methylenedioxyphenyl 7.771 (s, 1H), 6.719-7.232 (m, 12H), 5.935 (s, 2H), 4.863 (m, 1H), 4.63 (d, d, J = 39.4,13.8Hz, 2H), 4.26 (d, J = 4.8Hz, 2H), 2.79 (d, J = 7.2Hz, 2H), 2.53 (s, 3H), 2.318 (s, 3H) oil 85 H OCH ₃ N CF ₃ Cyclohexyl 7.76 (s, 1H), 6.8-7.3 (m, 9H), 4.83 (m, 1H), 4.6 (d, d, 2H), 4.29 (d, 2H), 3.78 (s, 3H), 2.8 (d, 2H), 2.53 (s, 3H), 2.33 (m, 1H), 1.1-1.9 (m, 10H) 80-82 86 H OCH ₃ N CF ₃ Phenyl 7.79 (s, 1H), 6.83-7.41 (m, 14H), 4.89 (m, 1H), 4.6 (d, d, J = 41.6,13.8Hz, 2H), 4.3 (m, 2H), 3.81 (s, 3H), 2.8 (m, 2H), 2.55 (s, 3H) 85-89 87 H OCH ₃ N CF ₃ 4-methylphenyl 7.781 (s, 1H), 6.81-7.256 (m, 13H), 4.869 (m, 1H), 4.62 (d, d, J = 41.2,14.4Hz, 2H), 4.27 (m, 2H), 3.788 (s, 3H), 2.78 (d, J = 7 Hz, 2H), 2.532 (s, 3H), 2.338 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 88 H OCH ₃ N CF ₃ 4-n-butylphenyl 7.78 (s, 1H), 6.8-7.3 (m, 13H), 4.83 (m, 1H), 4.63 (d, d, 2H), 4.27 (d, 2H), 3.8 (s, 3H), 2.79 (d, 2H), 2.6 (t, 2H), 2.53 (s, 3H), 1.23-1.43 (m, 4H), 0.94 (t, 3H) oil 89 H OCH ₃ N CF ₃ 4-methoxyphenyl 7.74 (s, 1H), 6.78-7.25 (m, 13H), 4.85 (m, 1H), 4.6 (d, d, J = 43,15.4Hz, 2H), 4.23 (m, 2H), 3.76 (s, 3H), 3.79 (s, 3H), 2.74 (m, 2H), 2.5 (s, 3H) oil 90 H OCH ₃ N CF ₃ 4-trifluoromethyl-phenyl 7.783 (s, 1H), 6.788-7.622 (m, 13H), 4.874 (m, 1H), 4.62 (d, d, J = 41.2,14Hz, 2H), 4.271 (d, J = 4Hz, 2H), 3.784 (s, 3H), 2.79 (d, J = 7.4 Hz, 2H), 2.532 (s, 3H) oil 91 H OCH ₃ N CF ₃ 4-fluorophenyl 7.78 (s, 1H), 6.81-7.35 (m, 13H), 4.86 (m, 1H), 4.62 (d, d, J = 41.8,14Hz, 2H), 4.27 (d, J = 4.4Hz, 2H), 3.78 (s, 3H), 2.78 (d, J = 7.2Hz, 2H), 2.53 (s, 3H) oil 92 H OCH ₃ N CF ₃ 4-chlorophenyl 7.79 (s, 1H), 6.83-7.38 (m, 13H), 4.9 (m, 1H), 4.64 (d, d, J = 43.4,14.4Hz, 2H), 4.31 (m, 2H), 3.82 (s, 3H), 2.82 (d, J = 7Hz, 2H), 2.55 (s, 3H) oil 93 H OCH ₃ N CF ₃ 3-methylphenyl 7.787 (s, 1H), 6.81-7.28 (m, 13H), 4.857 (m, 1H), 4.63 (d, d, J = 41,13.8Hz, 2H), 4.26 (d, J = 4.6Hz, 2H) , 3.769 (s, 3H), 2.78 (d, J = 7Hz, 2H), 2.527 (s, 3H), 2.33 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 94 H OCH ₃ N CF ₃ 3-chlorophenyl 7.79 (s, 1H), 6.83-7.8 (m, 13H), 4.9 (m, 1H), 4.64 (d, d, J = 40,15Hz, 2H), 4.32 (m, 2H), 3.81 (s, 3H ), 2.79 (m, 2H), 2.55 (s, 3H) oil 95 H OCH ₃ N CF ₃ 3-methoxyphenyl 7.79 (s, 1H), 6.83-7.34 (m, 13H), 4.9 (m, 1H), 4.64 (d, d, J = 41.8,13.8Hz, 2H), 4.3 (m, 2H), 3.8 (s, 3H), 3.85 (s, 3H), 2.98 (m, 2H), 2.55 (s, 3H) oil 96 H CH ₃ N CF ₃ 3,4-dichlorophenyl 7.77 (s, 1H), 6.86-7.367 (m, 12H), 4.87 (m, 1H), 4.63 (d, d, J = 41,14Hz, 2H), 4.27 (d, J = 4.4Hz, 2H), 2.8 (d, J = 7.4Hz ,, 2H), 2.53 (s, 3H), 2.32 (s, 3H) oil 97 H CH ₃ N CF ₃ Phenyl 7.77 (s, 1H), 6.93-7.45 (m, 14H), 4.87 (m, 1H), 4.62 (d, d, J = 40.2,13.8Hz, 2H), 4.37 (m, 2H), 2.8 (m, 2H), 2.55 (s, 3H), 2.34 (s, 3H) 89 98 H CH ₃ N CF ₃ 4-methylphenyl 7.786 (s, 1H), 6.956-7.275 (m, 12H), 4.9 (m, 1H), 4.64 (d, d, J = 40.6,15.8Hz, 2H), 4.28 (m, 2H), 2.8 (m, 2H), 2.556 (s, 3H), 2.36 (s, 3H), 2.349 (s, 3H) oil 99 H CH ₃ N CF ₃ 4-ethylphenyl 7.766 (s, 1H), 6.953-7.307 (m, 13H), 4.857 (m, 1H), 4.63 (d, d, J = 38.6,13.8Hz, 2H), 4.25 (d, J = 4.4Hz, 2H) 2.79 (d, J = 7.6Hz ,, 2H), 2.62 (q, J = 7Hz, 2H), 2.529 (s, 3H), 2.315 (s, 3H), 1.23 (t, J = 7.6Hz ,, 3H ) oil

Example number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 100 H CH ₃ N CF ₃ 4-methoxyphenyl 7.79 (s, 1H), 6.88-7.33 (m, 13H), 4.9 (m, 1H), 4.67 (d, d, J = 39.6,13.6Hz, 2H), 4.3 (m, 2H), 3.82 (s, 3H), 2.81 (m, 2H), 2.56 (s, 3H), 2.35 (s, 3H) oil 101 H CH ₃ N CF ₃ 4-trifluoromethyl-phenyl 7.78 (s, 1H), 6.91-7.63 (m, 13H), 4.88 (m, 1H), 4.64 (d, d, J = 38.6,13.8Hz, 2H), 4.27 (d, J = 4.4Hz, 2H) , 2.8 (d, J = 7.2Hz, 2H), 2.54 (s, 3H), 2.33 (s, 3H) oil 102 H CH ₃ N CF ₃ 4-fluorophenyl 7.78 (s, 1H), 6.91-7.36 (m, 13H), 4.84 (m, 1H), 4.64 (d, d, J = 40,13.8Hz, 2H), 4.28 (d, J = 4.8Hz, 2H) , 2.8 (d, J = 7.8Hz, 2H), 2.55 (s, 3H), 2.33 (s, 3H) oil 103 H OCH ₃ N CF ₃ 2-ethylphenyl 7.78 (s, 1H), 6.80-7.75 (m, 13H), 4.84 (m, 1H), 4.62 (d, d, J = 40.2,14.2Hz, 2H), 4.25 (d, J = 2.8Hz, 2H) , 3.74 (s, 3H), 2.77 (d, J = 13Hz, 2H), 2.6 (q, 2H), 2.51 (s, 3H), 1.20 (t, 3H) oil 104 H OCH ₃ N CF ₃ 3,5-dichlorophenyl 7.78 (s, 1H), 6.814-7.379 (m, 12H), 4.875 (m, 1H), 4.61 (d, d, J = 42.8,14.2Hz, 2H), 4.29 (m, 2H), 3.789 (s, 3H), 2.78 (d, J = 7.4Hz ,, 2H), 2.53 (s, 3H) oil

Example number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 105 H OCH ₃ N CF ₃ 3,5-dimethylphenyl 7.775 (s, 1H), 6.812-7.271 (m, 12H), 4.86 (m, 1H), 4.62 (d, d, J = 41.2,14Hz, 2H), 4.27 (d, J = 4.8Hz, 2H), 3.789 (s, 3H), 2.78 (d, J = 7.2Hz, 2H), 2.528 (s, 3H), 2.332 (s, 3H), 2.296 (s, 3H) oil 106 H OCH ₃ N CF ₃ 3,4-dimethylphenyl 7.764 (s, 1H), 6.804-7.244 (m, 12H), 4.87 (m, 1H), 4.6 (d, d, J = 42.2,15.4Hz, 2H), 4.27 (m, 2H), 3.781 (s, 3H), 2.786 (m, 2H), 2.518 (s, 3H), 2.266 (s, 3H), 2.233 (s, 3H) oil 107 H OCH ₃ N CF ₃ 3,4-methylenedioxyphenyl 7.79 (s, 1H), 6.74-7.27 (m, 12H), 5.96 (s, 2H), 4.88 (m, 1H), 4.63 (d, d, J = 41.8,14.6Hz, 2H), 4.29 (m, 2H), 3.79 (s, 3H), 2.79 (d, J = 7.6 Hz, 2H), 2.54 (3H) oil 108 H OCH ₃ N CF ₃ Thiophene 7.79 (s, 1H), 6.81-7.35 (m, 12H), 4.88 (m, 1H), 4.63 (d, d, J = 43,14.6Hz, 2H), 4.28 (d, J = 4.4Hz, 2H) , 3.782 (s, 3H), 2.79 (d, J = 7Hz, 2H), 2.532 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 109 H OCH ₃ N CF ₃ n-hexyl 7.748 (s, 1H), 6.781-7.244 (m, 9H), 4.845 (m, 1H), 4.6 (d, d, J = 41.4,14.8Hz, 2H), 4.26 (d, J = 4.4Hz, 2H) , 3.753 (s, 3H), 2.76 (d, J = 7.4Hz, 2H), 2.502 (s, 3H), 2.163 (m, 2H), 1.45 (m, 2H), 1.27 (m, 6H), 0.829 ( t, J = 6Hz ,, 3H) oil 110 H F N CF ₃ Phenyl 7.79 (s, 1H), 6.84-7.42 (m, 14H), 4.88 (m, 1H), 4.64 (d, d, J = 31,13.4, Hz, 2H), 4.28 (m, 2H), 2.86 (m , 2H), 2.56 (s, 3H) oil 111 H F N CF ₃ 3,4-methylenedioxyphenyl 6.7-7.775 (m, 13H), 5.93 (s, 2H), 5.57 (d, J = 6Hz, 1H), 4.88 (m, 1H), 4.6 (d, d, J = 22,12Hz, 2H), 4.28 (m, 2H), 2.8 (m, 2H), 2.54 (s, 3H) oil 112 H Cl N CF ₃ Phenyl 7.77 (s, 1H), 6.91-7.44 (m, 14H), 4.84 (m, 1H), 4.61 (d, d, J = 28.2,14.4Hz, 2H), 4.25 (m, 2H), 2.83 (m, 2H), 2.53 (s, 3H) oil 113 H Cl N CF ₃ 4-chlorophenyl 7.79 (s, 1H), 6.96-7.79 (m, 13H), 4.87 (m, 1H), 4.64 (d, d, J = 28,14.4Hz, 2H), 4.28 (m, 2H), 2.85 (m, 2H), 2.56 (s, 3H) oil 114 H Cl N CF ₃ 4-trifluoromethyl-phenyl 7.774 (s, 1H), 6.941-7.6 (m, 13H), 4.86 (m, 1H), 4.61 (d, d, J = 32,15.4Hz, 2H), 4.24 (d, J = 4.4Hz, 2H) , 2.84 (d, J = 4.8Hz, 2H), 2.537 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 115 H Cl N CF ₃ 3,4-dimethylphenyl 7.788 (s, 1H), 6.96-7.466 (m, 12H), 4.88 (m, 1H), 4.63 (d, d, J = 26,12.2Hz, 2H), 4.27 (m, 2H), 2.84 (m, 2H), 2.553 (s, 3H), 2.289 (s, 3H), 2.256 (s, 3H) oil 116 H Cl N CF ₃ 3,5-dichlorophenyl 7.784 (s, 1H), 6.936-7.446 (m, 12H), 4.86 (m, 1H), 4.62 (d, d, J = 28.6,13.6Hz, 2H), 4.27 (m, 2H), 2.835 (m, 2H), 2.543 (s, 3H) oil 117 Cl Cl N CF ₃ Phenyl 7.74 (s, 1H), 6.94-7.51 (m, 13H), 4.89 (m, 2H), 4.73 (m, 1H), 4.26 (m, 2H), 2.99 (m, 2H), 2.69 (s, 3H) oil 118 Cl Cl N CF ₃ 4-methylphenyl 7.75 (s, 1H), 6.91-7.74 (m, 12H), 4.9 (m, 2H), 4.73 (m, 1H), 4.28 (m, 2H), 3.03 (m, 2H), 2.7 (s, 3H) , 2.36 (s, 3H) oil 119 Cl Cl N CF ₃ 4-methoxyphenyl 7.74 (s, 1H), 6.86-7.52 (m, 12H), 4.9 (m, 2H), 4.71 (m, 1H), 4.28 (m, 2H), 3.8 (s, 3H), 2.99 (m, 2H) , 2.69 (s, 3H) oil 120 Cl Cl N CF ₃ 4-ethylphenyl 7.75 (s, 1H), 6.95-7.75 (m, 12H), 4.91 (m, 2H), 4.74 (m, 1H), 4.28 (m, 2H), 2.99 (m, 2H), 2.69 (s, 3H) , 2.66 (q, 2H), 1.25 (t, 3H) oil 121 Cl Cl N CF ₃ 4-chlorophenyl 7.74 (s, 1H), 6.91-7.75 (m, 12H), 4.9 (m, 2H), 4.72 (m, 1H), 4.28 (m, 2H), 3.03 (m, 2H), 2.69 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 122 Cl Cl N CF ₃ 4-trifluoromethyl-phenyl 7.75 (s, 1H), 6.95-7.74 (m, 12H), 4.9 (m, 2H), 4.72 (m, 1H), 4.28 (m, 2H), 3.04 (m, 2H), 2.69 (s, 3H) oil 123 Cl Cl N CF ₃ 4-fluorophenyl 7.74 (s, 1H), 6.91-7.51 (m, 12H), 4.89 (m, 2H), 4.74 (m, 1H), 4.27 (m, 2H), 2.99 (m, 2H), 2.69 (s, 3H) oil 124 Cl Cl N CF ₃ 3-methylphenyl 7.73 (s, 1H), 6.93-7.72 (m, 12H), 4.88 (m, 2H), 4.73 (m, 1H), 4.27 (m, 2H), 3.0 (m, 2H), 2.68 (s, 3H) , 2.34 (s, 3H) oil 125 Cl Cl N CF ₃ 3-methoxyphenyl 7.74 (s, 1H), 6.87-7.51 (m, 12H), 4.9 (m, 2H), 4.73 (m, 1H), 4.29 (m, 2H), 3.8 (s, 3H), 3.03 (m, 2H) , 2.69 (s, 3H) oil 126 Cl Cl N CF ₃ 3-trifluoromethylphenyl 7.74 (s, 1H), 6.92-7.71 (m, 12H), 4.9 (m, 2H), 4.72 (m, 1H), 4.28 (m, 2H), 3.02 (m, 2H), 2.69 (s, 3H) oil 127 Cl Cl N CF ₃ 3-fluorophenyl 7.73 (s, 1H), 6.91-7.5 (m, 12H), 4.9 (m, 2H), 4.72 (m, 1H), 4.26 (m, 2H), 3.0 (m, 2H), 2.68 (s, 3H) oil 128 Cl Cl N CF ₃ 3-chlorophenyl 7.74 (s, 1H), 6.91-7.51 (m, 12H), 4.89 (m, 2H), 4.73 (m, 1H), 4.28 (m, 2H), 2.99 (m, 2H), 2.69 (s, 3H) oil 129 Cl Cl N CF ³ 3,4-dimethylphenyl 7.74 (s, 1H), 6.95-7.52 (m, 11H), 4.9 (m, 2H), 4.73 (m, 1H), 4.27 (m, 2H), 3.03 (m, 2H), 2.69 (s, 3H) , 2.25 (s, 6H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 130 Cl Cl N CF ³ 3,5-dichlorophenyl 7.69 (s, 1H), 6.87-7.47 (m, 11H), 4.85 (m, 2H), 4.67 (m, 1H), 4.24 (m, 2H), 2.99 (m, 2H), 2.64 (s, 3H) 55 to 59 131 Cl Cl N CF ³ 3,5-dimethylphenyl 7.74 (s, 1H), 6.95-7.74 (m, 11H), 4.9 (m, 2H), 4.72 (m, 1H), 4.26 (m, 2H), 3.0 (m, 2H), 2.7 (s, 3H) , 2.31 (s, 6H) 52-54 132 Cl Cl N CF ³ 3,4-methylenedioxyphenyl 7.70 (s, 1H), 6.76-7.48 (m, 11H), 5.91 (s, 2H), 4.86 (m, 2H), 4.68 (m, 1H), 4.23 (m, 2H), 2.97 (m, 2H) , 2.65 (s, 3H) oil 133 Cl Cl N CF ₃ Thiophene 7.7 (s, 1H), 6.76-7.47 (m, 11H), 4.86 (m, 2H), 4.67 (m, 1H), 4.24 (m, 2H), 2.97 (m, 2H), 2.65 (s, 3H) oil 134 Cl Cl N CF ₃ n-hexyl 7.72 (s, 1H), 6.91-7.52 (m, 8H), 4.89 (m, 2H), 4.72 (m, 2H), 4.28 (m, 2H), 3.0 (m, 2H), 2.68 (s, 3H) , 2.2 (t, 2H), 1.18-1.52 (m, 8H), 0.87 (t, 3H) oil 135 Cl Cl N CF ₃ Cyclohexyl 7.74 (s, 1H), 6.93-7.54 (m, 8H), 4.91 (m, 2H), 4.73 (m, 1H), 4.28 (m, 2H), 3.04 (m, 2H), 2.7 (s, 3H) , 2.34 (m, 1H), 1.1-1.8 (m, 10H) oil 136 H H N C ₂ F ₅ Phenyl 7.78 (s, 1H), 6.67-7.76 (m, 15H), 4.88 (m, 1H), 4.68 (d, d, 2H), 4.26 (d, 2H), 2.83 (d, 2H), 2.56 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 137 H OCH ₃ N C ₂ F ₅ Phenyl 7.77 (s, 1H), 6.6-7.76 (m, 14H), 4.83 (m, 1H), 4.6 (d, d, 2H), 4.25 (d, 2H), 3.78 (s, 3H), 2.76 (d, 2H), 2.51 (s, 3H) oil 138 H CH ₃ N SPh 4-methylphenyl 7.78 (s, 1H), 6.95-7.78 (m, 18H), 4.87 (m, 1H), 4.63 (d, d, J = 36.6,13.8Hz, 2H), 4.27 (d, J = 4.8Hz, 2H) , 2.79 (d, J = 7.2Hz, 2H), 2.54 (s, 3H), 2.33 (s, 3H), 2.29 (s, 3H) oil 139 H H N SPh Phenyl 6.95-7.77 (m, 21H), 4.78 (m, 1H), 4.65 (d, d, J = 22.8, 14 Hz, 2H), 4.29 (m, 2H), 2.84 (d, J = 7.73 Hz, 2H), 2.56 (s _, 3H) oil 140 H H N SPh 4-methylphenyl 7.77 (s, 1H), 6.95-7.53 (m, 13H), 4.88 (m, 1H), 4.65 (d, d, J = 35.6,14Hz, 2H), 4.27 (d, J = 4Hz, 2H), 2.83 (d, J = 7Hz, 2H), 2.55 (s, 3H), 2.53 (s, 3H) oil 141 H Cl N SPh 4-methylphenyl 7.78 (s, 1H), 6.91-7.53 (m, 19H), 4.85 (m, 1H), 4.65 (d, d, J = 24.6,14.2Hz, 2H), 4.26 (d, J = 4.2Hz, 2H) , 2.84 (m, 2H), 2.55 (s, 3H), 2.28 (d, J = 6.6Hz, 3H) 105 to 106 142 H OCH ₃ N SPh 4-methylphenyl 7.78 (s, 1H), 6.81-7.53 (m, 19H), 4.84 (m, 1H), 4.6 (m, 2H), 4.28 (d, J = 4.2Hz, 2H), 3.79 (s, 3H), 2.79 (d, J = 7.8Hz, 2H), 2.54 (s, 3H), 2.3 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 143 H H N SPh methyl 7.79 (s, 1H), 6.9-7.4 (m, 15H), 4.92 (m, 1H), 4.7 (d, d, J = 36,14Hz, 2H), 4.3 (d, J = 4.4Hz, 2H), 2.87 (d, J = 8Hz ,, 2H), 2.6 (s, 3H), 1.9 (d, J = 3.6Hz, 3H) oil 144 H CH ₃ N SPh methyl 7.79 (s, 1H), 6.89-7.35 (m, 14H), 4.89 (m, 1H), 4.64 (d, d, J = 33,14.8Hz, 2H), 4.31 (d, J = 5Hz, 2H), 2.81 (d, J = 7.8Hz ,, 2H), 2.56 (s, 3H), 2.34 (s, 3H), 1.89 (d, J = 2.8Hz, 3H) oil 145 H OCH ₃ N SPh methyl 7.81 (s, 1H), 6.81-7.35 (m, 14H), 4.84 (m, 1H), 4.65 (d, d, J = 37,12Hz, 2H), 4.31 (d, J = 3.8Hz, 2H), 3.81 (s, 3H), 2.81 (d, J = 7Hz, 2H), 2.55 (s, 3H), 1.89 (d, J = 3.2Hz, 3H) oil 146 Cl Cl N SPh 4-methylphenyl 7.75 (s, 1H), 6.94-7.56 (m, 17H), 4.91 (m, 2H), 4.73 (m, 1H), 4.28 (m, 2H), 3.02 (m, 2H), 2.7 (s, 3H) , 2.29 (s, 3H) 72-75 147 H OCH ₃ N Ph Phenyl 7.78 (s, 1H), 6.8-7.33 (m, 19H), 4.86 (m, 2H), 4.62 (d, d, 2H), 4.27 (d, 2H), 3.78 (s, 3H), 2.78 (d, 2H), 2.53 (s, 3H) 53-57 148 H H CH H 4-chlorophenyl 6.42-7.39 (m, 16H), 5.61 (d, J = 5.86 Hz), 4.88 (m, 1H), 4.36 (m, 4H), 2.8 (m, 2H), 2.56 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 149 H H CH H 4-fluorophenyl 6.43-7.45 (m, 16H), 5.64 (d, J = 5.47Hz, 1H), 4.9 (m, 1H), 4.3 (m, 4H), 2.8 (m, 2H), 2.57 (s, 3H) oil 150 H H CH H 3-methyl-4-chloro-phenyl 6.43-7.36 (m, 15H), 5.68 (d, J = 6Hz, 1H), 4.89 (m, 1H), 4.19-4.4 (m, 4H), 2.8 (m, 2H), 2.57 (s, 3H), 2.34 (s, 3H) oil 151 H H CH H 3-isopropoxyphenyl 6.4-7.34 (m, 16H), 5.59 (d, J = 6Hz, 1H), 4.9 (m, 1H), 4.44 (m, 4H) 2.8 (m, 2H), 2.54 (s, 3H), 1.3 (d , 6H) oil 152 H Cl CH H 3-isopropoxyphenyl 6.47-7.3 (m, 15H), 5.59 (d, J = 6Hz, 1H), 4.84 (m, 1H), 4.46 (m, 1H), 4.3 (m, 4H), 2.74 (m, 2H), 2.55 ( s, 3H), 1.3 (d, 6H) oil 153 H Cl CH H 3-methyl-4-chloro-phenyl 6.47-7.32 (m, 14H), 5.57 (d, J = 7Hz, 1H), 4.6 (m, 1H), 4.23-4.49 (m, 4H), 2.52 (s, 3H), 2.52 (s, 3H), 2.33 (s, 3H) oil 154 H Cl CH H 3,4-dimethylphenyl 6.49-7.32 (m, 14H), 5.61 (d, J = 5.94Hz, 1H), 4.84 (m, 1H), 4.35 (d, d, J = 30.3,14Hz, 2H), 4.3 (m, 2H), 2.81,2.63 (t, d, J = 9.9,5.5Hz, 2H), 2.52 (s, 3H), 2.22 (s, 6H) oil 155 H Cl CH H 3-methoxyphenyl 6.49-7.28 (m, 15H), 5.6 (d, J = 5.86 Hz, 1H), 4.8 (m, 1H), 4.33 (d, d, J = 35.8, 13.8 Hz, 2H), 4.19 (m, 2H) , 3.71 (s, 3H), 2.78,2.58 (t, d, J = 12.8,5.49Hz, 2H), 2.49 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 156 H Cl CH H 3-fluorophenyl 6.49-7.29 (m, 15H), 5.58 (d, J = 5.78Hz, 1H), 4.83 (m, 1H), 4.36 (d, d, J = 36.3,13.5Hz, 2H), 4.22 (m, 2H) , 2.81,2.59 (t, d, J = 11.3,3.9Hz, 2H), 2.5 (s, 3H) oil 157 H Cl CH H 4-chlorophenyl 6.49-7.4 (m, 15H), 5.62 (d, J = 5.82 Hz, 1H), 4.87 (m, 1H), 4.39 (d, d, J = 28, 14.2 Hz, 2H), 4.26 (m, 2H) , 2.84,2.66 (t, m, J = 10.8Hz, 2H), 2.54 (s, 3H) oil 158 H Cl CH H 2-methylphenyl 6.46-7.31 (m, 15H), 5.85 (d, J = 4.5Hz, 1H), 4.85 (m, 1H), 4.34 (m, 4H), 2.7 (m, 2H), 2.52 (s, 3H), 2.36 (s, 3H) oil 159 H Cl CH H 4-methylphenyl 6.48-7.32 (m, 18H), 5.62 (d, J = 5.78,1H), 4.85 (m, 1H), 4.35 (d, d, J = 32.2,14Hz, 2H), 4.22 (m, 2H), 2.8 , 2.62 (t, m, J = 10.33Hz, 2H), 2.5 (s, 3H), 2.29 (s, 3H) oil 160 H Cl CH H 4-methoxyphenyl 6.5-7.38 (m, 15H), 5.63 (d, J = 5.86Hz, 1H), 4.86 (m, 1H), 4.38 (d, d, J = 30.1,14.4Hz, 2H), 4.28 (m, 2H) , 3.79 (s, 3H), 2.83,2.66 (t, m, J = 5.8Hz, 2H), 2.53 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 161 H Cl CH H Phenyl 6.49-7.44 (m, 16H), 5.64 (d, J = 5.82Hz, 1H), 4.83 (m, 1H), 4.36 (d, d, J = 31.1,14.1Hz, 2H), 4.22 (m, 2H) , 2.81,2.62 (t, d, J = 10.3,5.5Hz, 2H), 2.51 (s, 3H) oil 162 H Cl CH H 2,4,5-trimethyl-phenyl 6.5-7.38 (m, 13H), 5.71 (d, J = 6.43Hz, 1H), 4.88 (m, 1H), 4.4 (m, 4H), 2.6 (m, 2H), 2.53 (s, 3H), 2.28 (s, 3H) 2.19 (s, 3H), 2.16 (s, 3H) 97-104 163 H Cl CH H 3,5-dimethylphenyl 6.47-7.29 (m, 14H), 5.65 (d, J = 5.9Hz, 1H), 4.83 (m, 1H), 4.35 (d, d, J = 30.2,14Hz, 2H), 4.23 (m, 2H), 2.78,2.6 (t, d, J = 10.2, 5.5 Hz, 2H), 2.49 (s, 3H), 2.24 (s, 6H) oil 164 H Cl CH H 2,4,5-trimethyl-phenyl 6.5-7.38 (m, 13H), 5.71 (d, J = 6.43Hz, 1H), 4.88 (m, 1H), 4.4 (m, 4H), 2.6 (m, 2H), 2.53 (s, 3H), 2.28 (s, 3H) 2.19 (s, 3H), 2.16 (s, 3H) 97-104 165 H Cl CH H 3,4-methylenedioxyphenyl 6.5-7.31 (m, 14H), 5.91 (s, 2H), 5.58 (d, J = 5.86Hz, 1H), 4.84 (m, 1H), 4.35 (d, d, J = 33.1,13.9Hz, 2H) , 4.22 (m, 2H), 2.83,2.63 (t, d, J = 9.8Hz, 5.5Hz, 2H), 2.52 (s, 3H) oil 166 H Cl CH H Naphthyl 6.47-8.07 (m, 18H), 6.26 (d, J = 5.58Hz, 1H) 4.75 (m, 1H), 4.31 (d, d, J = 39.2,13.9Hz, 2H), 4.19 (m, 2H), 2.64 (m, 2H), 2.45 (s, 3H) 62-65

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 167 H H CH H 3,4-methylenedioxyphenyl 6.41-7.35 (m, 15H), 5.92 (s, 2H), 5.84 (d, J = 4Hz, 1H), 4.75 (m, 1H), 4.39 (d, d, J = 18,13Hz, 2H), 4.25 (m, 2H), 2.86 (m, 2H), 2.55 (s, 3H) oil 168 H H CH CF ₃ Phenyl 6.37-7.46 (m, 17H), 4.6 (m, 1H), 4.3 (m, 4H), 2.7 (m, 2H), 2.53 (s, 3H) oil 169 H H CH CF ₃ 4-methoxyphenyl 6.4-7.45 (m, 16H), 4.88 (m, 1H), 4.25 (m, 4H) 3.79 (s, 3H), 2.76 (m, 2H), 2.54 (s, 3H) oil 170 H H CH CF ₃ 4-fluorophenyl 6.37-7.34 (m, 16H), 4.85 (m, 1H), 4.3 (m, 4H), 2.85 (m, 2H), 2.53 (s, 3H) oil 171 H H CH CF ₃ 4-chlorophenyl 6.41-7.40 (m, 16H), 4.9 (m, 1H), 4.41 (m, 2H), 4.28 (m, 2H), 2.73 (m, 2H), 2.57 (s, 3H) oil 172 H H CH CF ₃ 4-methylphenyl 6.43-7.37 (m, 16H), 4.9 (m, 1H), 4.42 (m, 2H), 4.39 (m, 2H), 2.75 (m, 2H), 2.57 (s, 3H), 2.37 (s, 3H) oil 173 H H CH CF ₃ 4-ethylphenyl 6.38-7.33 (m, 16H), 4.86 (m, 1H), 4.3 (m, 4H), 2.8 (m, 2H), 2.6 (m, 2H), 2.53 (s, 3H), 1.22 (m, 3H) 114-116 174 H H CH CF ₃ 3,4-dimethylphenyl 6.41-7.35 (m, 15H), 4.86 (s, 1H), 4.23-4.2 (m, 4H), 2.74 (m, 2H), 2.55 (s, 3H), 2.29 (s, 3H) 2.26 (s, 3H ) oil 175 H H CH CF ₃ 3,5-dichlorophenyl 6.42-7.44 (m, 15H), 4.86 (m, 1H), 4.23-4.86 (m, 4H), 2.8 (m, 2H), 2.55 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 176 H Cl CH CF ₃ Phenyl 6.46-7.41 (m, 16H), 4.86 (m, 1H), 4.37 (m, 2H), 4.2 (m, 2H), 2.7 (m, 2H), 2.53 (s, 3H) oil 177 H Cl CH CF ₃ 4-methylphenyl 6.45-7.31 (m, 15H), 4.85 (m, 1H), 4.33 (m, 4H), 2.67 (m, 2H), 2.50 (s, 3H), 2.33 (s, 3H) oil 178 H Cl CH CF ₃ 3-methylphenyl 6.48-7.34 (m, 15H), 4.88 (m, 1H), 4.36 (m, 4H, 2.75 (m, 2H), 2.54 (s, 3H), 2.37 (s, 3H) oil 179 H Cl CH CF ₃ 3-chlorophenyl 6.48-7.37 (m, 15H), 4.85 (m, 1H), 4.3 (m, 4H), 2.8 (m, 2H), 2.52 (s, 3H) oil 180 H Cl CH CF ₃ 3,4-dimethylphenyl 6.49-7.31 (m, 14H), 4.85 (m, 1H), 4.36 (dd, J = 37.44,13.84HYz, 2H), 4.22 (m, 2H), 2.83,2.6 (t, mJ = 10.33Hz, 2H) , 2.52 (s, 3H), 2.28 (s, 3H), 2.27 (s, 3H) oil 181 H Cl CH CF ₃ 3-methoxyphenyl 6.45-7.31 (m, 15H), 4.85 (m, 1H), 4.33 (d, d, J = 36.8,16.8Hz, 2H), 4.22 (m, 2H), 3.77 (s, 3H), 2.8,2.6 ( t, m, J = 10Hz, 2H), 2.5 (s, 3H) oil 182 H Cl CH CF ₃ 3-fluorophenyl 6.46-7.36 (m, 15H), 4.82 (m, 1H), 4.4 (d, d, J = 37.65,14.28Hz, 2H), 4.22 (m, 2H), 2.82,2.58 (t, m, J = 10.4 Hz, 2H), 2.49 (s, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 183 H Cl CH CF ₃ 4-chlorophenyl 6.45-7.43 (m, 15H), 4.83 (m, 1H), 4.34 (d, d, J = 37,14.6Hz, 2H), 4.2 (m, 2H), 2.82,2.6 (t, m, J = 11Hz , 2H), 2.5 (s, 3H) oil 184 H Cl CH CF ₃ 4-fluorophenyl 6.44-7.32 (m, 15H), 4.82 (m, 1H), 4.32 (d, d, J = 35.9,13.9Hz, 2H), 4.19 (m, 2H), 2.79,2.58 (t, m, J = 15Hz , 2H), 2.48 (s, 3H) oil 185 H Cl CH CF ₃ 3,5-dimethylphenyl 6.46-7.29 (m, 14H), 4.85 (m, 1H), 4.34 (d, d, J = 36,15.8Hz, 2H), 4.2 (m, 2H), 2.81,2.59 (t, m, J = 12.6 Hz, 2H), 2.5 (s, 3H), 2.32 (s, 3H), 2.27 (s, 3H) oil 186 H Cl CH CF ₃ 3,4-methylenedioxyphenyl 6.49-7.35 (m, 14H), 6.0 (s, 2H), 4.88 (m, 1H), 4.38 (m, 4H), 2.76 (m, 2H), 2.54 (s, 3H) oil 187 H Cl CH SEt Phenyl 6.46-7.6 (m, 16H), 4.86 (m, 1H), 4.35 (d, d, J = 26.8,13.8Hz, 2H) 4.22 (m, 2H), 2.82,2.62 (t, m, J = 9.7Hz , 2H), 2.51 (s, 3H), 2.45 (q, J = 5.3Hz, 2H), 1.21 (t, J = 7.3Hz, 3H) oil

Example Number X Y Z R ¹ R ^{2 1} HNMR (ppm) m.p / ℃ 188 H Cl CH SPh 4-methylphenyl 6.5-7.56 (m, 20H), 4.88 (m, 1H), 4.38 (dd, J = 30.3,14.5Hz, 2H) 4.27 (m, 2H), 2.84,2.66 (t, d, J = 12.7,5.1Hz , 2H), 2.55 (s, 3H), 2.29 (s, 3H) 65-69 189 H Cl CH SPh Phenyl 6.47-7.64 (m, 21H), 4.84 (m, 1H), 4.37 (d, d, J = 29.8,14.7Hz, 2H), 4.24 (m, 2H), 2.82,2.6 (t, m, 2H), 2.52 (s, 3H) 58 to 60 190 H Cl CH SO ₂ Ph Phenyl 6.46-7.84 (m, 21H), 4.83 (m, 1H), 4.33 (d, d, J = 41.8, 14 Hz, 2H), 4.2 (m, 2H), 2.78, 2.58 (t, d, J = 15.4, 5.2Hz, 2H), 2.0 (s, 3H) 122-125

The bactericidal activity against barley powdery pathogens was examined using the following bioassay for the compounds prepared by the method of Example 1-190.

As a pathogen for investigating the protective effect of the compounds of the above example against phytopathogens, Erysiphe graminis f. sp. hordei was used. Erysiphe graminis f. sp. Since hordei is a biotic parasite, it was subcultured to barley seedlings in the laboratory and spores formed on barley seedlings were used as inoculum. In order to investigate the efficacy of the strain, barley seeds (variety: dongbori) of 5 grains were sown in disposable pots (diameter: 6.5 cm) and grown in a greenhouse for 8 days and grown until single-leaf season. 50 ml of fungicide compositions were sprayed on each of the barley which is the host plant of constant size which was obtained. The fungicide composition was prepared by dissolving the compound of Example in a 10% acetone solution and adding tween-20 to the solution so that the concentration of the drug was 2 ppm.

Barley coated with the fungicide composition was air-dried for 1 day and then inoculated with powdered powder spores on the treated barley. Inoculated barley seedlings were placed in a constant temperature and humidity room at 20-23 ° C and a relative humidity of 50% for 7 days, and then the lesion area ratio (measured lesion area (spot caused by disease) occupies the leaf area). Obtained from a table of disease area ratio).

The control value was calculated according to the following Equation 1 with respect to the experimental results in the experiment, the results are shown in Table 33. In the following Equation 1, the control refers to barley not treated with the fungicide composition of the present invention, the treatment means refers to barley treated with the fungicide composition of the present invention.

[Equation 1]

Bactericidal activity against powdery mildew Example number Treatment concentration (2 ppm) Example number Treatment concentration (2 ppm) Example number Treatment concentration (2 ppm) One 86 50 98 120 100 4 41 51 98 122 98 8 80 52 99 123 97 9 66 53 80 124 96 10 76 54 86 125 97 13 96 59 41 126 98 14 76 62 76 127 100 19 41 65 80 128 96 21 80 75 91 129 97 24 81 77 96 130 90 26 80 78 91 131 99 27 86 86 93 132 95 29 41 88 41 133 91 30 58 89 91 134 98 31 83 94 95 135 100 34 96 97 95 136 58 39 91 100 98 146 90 41 88 110 91 176 80 42 99 111 91 177 58 43 100 112 95 178 85 46 93 114 80 179 83 47 100 117 100 180 71 48 98 118 95 181 71 49 93 119 98 186 83

As shown in Table 33, it can be seen that the compound of Example 1-190 has excellent bactericidal activity against powdery mildew.

As described above, the isooxazolidine derivative of the present invention has a very good bactericidal effect against powdery mildew.

Claims (6)

Ioxoxazolidine derivatives of the general formula (1). [Formula 1] (Wherein R ¹ is a hydrogen atom, C _1-6 alkyl, cyclohexyl, thioalkyl, thiophenyl, phenylsulfonyl, trifluoromethyl or pentafluoroethyl group, R ² is a C _1-6 alkyl, phenyl, substituted phenyl, naphthyl or thiophene group, where substituted phenyl is a phenyl group having 1 to 3 substituted halogen atoms, alkyl, alkoxy or trifluoromethyl groups Indicates X and Y are hydrogen atom, halogen atom, C _1-4 alkyl group, alkoxy group, Z is a nitrogen atom or a methylene group.) The isoxa of claim 1, wherein R ¹ is a hydrogen atom or a trifluoromethyl group, R ² is phenyl, or substituted phenyl, X is a hydrogen atom or a halogen atom, Y is a halogen atom, and Z is a nitrogen atom. Zolidine derivatives. A method for preparing the isooxazolidine derivative of the general formula (1) comprising the step of condensation reaction of a compound of the formula (2) and a compound of the formula (3) in the presence of a base. [Formula 1] [Formula 2] [Formula 3] (Wherein R ¹ is a hydrogen atom, C _1-6 alkyl, cyclohexyl, thioalkyl, thiophenyl, phenylsulfonyl, trifluoromethyl or pentafluoroethyl group, R ² is a C _1-6 alkyl, phenyl, substituted phenyl, naphthyl or thiophene group, where substituted phenyl is a phenyl group having 1 to 3 substituted halogen atoms, alkyl, alkoxy or trifluoromethyl groups Indicates X and Y are hydrogen atom, halogen atom, C _1-4 alkyl group, alkoxy group, Z is a nitrogen atom or a methylene group.) The method of claim 3, wherein R ¹ is a hydrogen atom or a trifluoromethyl group, R ² is phenyl, or substituted phenyl, X is a hydrogen atom or a halogen atom, Y is a halogen atom, and Z is a nitrogen atom. . A bactericidal composition comprising an isoxazolidine derivative of formula 1 as an active ingredient. [Formula 1] (Wherein R ¹ is a hydrogen atom, C _1-6 alkyl, cyclohexyl, thioalkyl, thiophenyl, phenylsulfonyl, trifluoromethyl or pentafluoroethyl group, R ² is a C _1-6 alkyl, phenyl, substituted phenyl, naphthyl or thiophene group, wherein substituted phenyl represents a phenyl group substituted with one to three halogen atoms, alkyl, alkoxy or trifluoromethyl groups, X and Y are hydrogen atom, halogen atom, C _1-4 alkyl group, alkoxy group, Z is a nitrogen atom or a methylene group.) The method of claim 5, wherein R ¹ is a hydrogen atom or a trifluoromethyl group, R ² is phenyl, or substituted phenyl, X is a hydrogen atom or a halogen atom, Y is a halogen atom, Z is a nitrogen atom disinfectant composition.